КАТАЛИТИЧЕСКАЯ СИСТЕМА

Описывается каталитическая система, состоящая из соединения общей формулы I или его соли, объединяемого с металлом VIIIB группы, где А1 и А2, а также А3, А4 и A5 (когда присутствуют), К, D, Е, X1-X4, Q1, Q2, M, L1 имеют значения, указанные в формуле изобретения. Система пригодна для карбонилирования этиленовых ненасыщенных соединений. 10 н. и 35 з.п.ф-лы, 9 табл.

КАТАЛИЗАТОР ДЛЯ ПОЛУЧЕНИЯ 1-АЛКОКСИ-2,3-ДИФЕНИЛАЛЮМАЦИКЛОПРОПЕНОВ

Изобретение относится к области катализаторов, в частности к катализатору для получения 1-алкокси-2, 3-дифенилалюмациклопропенов. Получаемый катализатор состоит из двухлористого кобальта, активирующей добавки трифенилфосфина и алкоксиалюминийхлорида в качестве восстановителя, взятых в мольном соотношении 1: (1,5-2,5): (2-6) соответственно. Преимуществом катализатора является его доступность. 1 табл.

СПОСОБ ПОЛУЧЕНИЯ АЛЬДЕГИДОВ ГИДРОФОРМИЛИРОВАНИЕМ С МОДИФИКАЦИЕЙ ЛИГАНДОВ АЦЕТАЛИЗАЦИЕЙ

Изобретение относится к способу получения альдегидов гидроформилированием с модификацией лигандов ацетализацией. Предлагаемый способ включает следующие стадии:- смешивание в автоклаве этилового спирта (А), ацетилацетоната дикарбонила родия Rh(acac)(CO)(Б), при соотношении Б:А от 1:6000 до 1:10000 в массовых долях, лиганда, содержащего остаток ароматического фосфина и по меньшей мере две гидроксильные группы (В), при соотношении В:Б от 1:1 до 5:1 в мольных долях, линейного олефина ряда С-С, (Г) при соотношении Г:Б от 500:1 до 5000:1 в мольных долях и катионита в кислой форме (Д), взятого в 10-20-кратном избытке по отношению к лиганду (В);- создание в автоклаве давления синтез-газа (СО/Н=1:1) 0,1-10 МПа, нагрев смеси до 30-120°C, при этом синтез ведут при перемешивании магнитной мешалкой при 500-1000 об/мин в течение 3-10 часов с образованием альдегида и каталитического комплекса родия с объемным лигандом;- отделение катионита посредством фильтрации и отделение каталитического комплекса родия ...

СПОСОБ ПОЛУЧЕНИЯ АЦЕТИЛАМИДИНИОФЕНИЛАЛАНИЛЦИКЛОГЕКСИЛГЛИЦИЛПИРИДИНИОАЛАНИНАМИДОВ

Изобретение относится к способу получения ацетиламидиниофенилаланилциклогексилглицилпиридинио-аланинамидов формулы (I), в которой анионы Х являются физиологически приемлемыми анионами, и их аналогов, которые являются эффективными ингибиторами фактора Ха свертывания крови и которые могут быть использованы, например, для предотвращения тромбозов. Способ согласно изобретению включает сочетание 2-[2-ацетиламино-3-(4-амидинофенил)-пропиониламино]-2-циклогексилуксусной кислоты, которую получают из 2-[2-ацетил-амино-3-(4-цианофенил)акрилоиламино]-2- циклогексилуксусной кислоты путем асимметрического гидрирования и превращения цианогруппы в амидин, или ее соли, с 3-(2-амино-2-карбамоилэтил)-1-метилпиридиниевой солью, или ее солью. Кроме того, изобретение относится к исходным материалам и промежуточным продуктам для этого способа, способам их получения и ацетил-(S)-4-амидиниофенилаланил-(S)-циклогексилглицил-(S)-(1-метил-3-пиридинио)аланинамид в виде дитозилата. Технический результат: упрощение ...

КАТАЛИЗАТОР ДЛЯ ПОЛУЧЕНИЯ 1-ДИАЛКИЛАМИН-2,3-ДИФЕНИЛАЛЮМАЦИКЛОПРОПЕНОВ

Катализатор для получения 1-диалкиламин-2,3-дифенилалюмациклопропенов получен взаимодействием двухлористого кобальта СоСl2, активирующей добавки трифенилфосфина Ph3P и диалкиламиналюминийдихлорида R2N-AlCl2, где R - Et, n-Bu, n-Hex, в качестве восстановителя при следующем мольном соотношении компонентов: СоСl2: Ph3P:R2N-AlCl2=1:(1.5-2.5):(2-6). В присутствии указанного катализатора образуются 1-диалкиламин-2,3-дифенилалюмациклопропены с выходами 62-79%. 1 табл.

СПОСОБ КАРБОНИЛИРОВАНИЯ, ПРЕДНАЗНАЧЕННЫЙ ДЛЯ ПРОИЗВОДСТВА УКСУСНОЙ КИСЛОТЫ С ПРИМЕНЕНИЕМ МЕТАЛЛИЧЕСКИХ КАТАЛИЗАТОРОВ С КЛЕШНЕОБРАЗНЫМИ ЛИГАНДАМИ

Изобретение относится к усовершенствованному способу получения уксусной кислоты путем карбонилирования метанола и/или его реакционноспособного производного, выбранного из метилацетата, метилиодида, диметилового простого эфира и их смеси, монооксидом углерода в присутствии катализатора в жидкой реакционной смеси, включающей метилиодид и воду в концентрации от 0,1 до 30% мас., в котором катализатор включает комплекс металла с клешнеобразным лигандом, соответствующий общей формуле (I), в которой Z представляет собой углерод, каждый из L1 и L2 представляет собой координирующую группу, содержащую донорный атом Р, либо донорный атом N; каждый R3 независимо выбирают из водорода или C1-С6алкильной группы, и М выбирают из Rh и Ir; или общей формуле (II), в которой Z представляет собой углерод, и каждый из L3 и L4 представляет собой координирующую группу, содержащую донорный атом Р либо донорный атом N, а М выбирают из Rh и Ir. Способ позволяет получить высокую селективность образования уксусной ...

СПОСОБ ПОЛУЧЕНИЯ АРОМАТИЧЕСКИХ АМИНОВ В ПРИСУТСТВИИ КОМПЛЕКСА ПАЛЛАДИЯ, ВКЛЮЧАЮЩЕГО ФЕРРОЦЕНИЛБИФОСФИНОВЫЙ ЛИГАНД

Изобретение относится к улучшенному способу получения соединений формулы I ! ! где группа R1 является группой A1, в которой группы R2, R3, R4 и R5 являются каждая водородом. Указанные соединения являются промежуточными продуктами для синтеза фунгицидов. Способ заключается в том, что соединение формулы II ! ! где группы R1 и R2 определены как указано для формулы 1, и X является хлором, взаимодействует с аммиаком в присутствии основания и каталитического количества, по меньшей мере, одного комплексного соединения палладия, где комплексное соединение палладия включает, по меньшей мере, один ферроценилбифосфиновый лиганд, выбранный из R(-)-ди-тpeт-бyтил[1-[(S)-2-(дициклогексилфосфинил)ферроценил]этил]-фосфина и рацемического ди-трет-бутил[1-[2-(дициклогексилфосфинил)ферроценил]этил]-фосфина. Реакцию проводят в инертном растворителе. При этом комплексное соединение палладия предпочтительно используют при соотношении от 1:10000 до 1:10 по отношению к соединению формулы II, а соединение формулы ...

Новый ахиральный дифосфиновый лиганд, комплексы на его основе и способ его получени

Изобретение относится к новым ахиральным дифосфиновым лигандам бигетероарильного типа. Описывается новый ахиральный дифосфиновый лиганд Также описываются дифосфиновые комплексы переходных металлов формул IIa и IIIa. и способ синтеза соединения Ia. Технический результат – получено новое соединение и дифосфиновые комплексы на его основе, которые могут быть использованы в каталитических процессах: аминировании, кросс-сочетании, гидроформилировании, гидроцианировании, гидрировании, аллильном алкилировании, полимеризации α-олефинов и других реакциях, приводящих к образованию С-С и C-N связей. 3 с.п. ф-лы, 2 табл.

СПОСОБ ПОЛУЧЕНИЯ ОПТИЧЕСКИ АКТИВНЫХ СПИРО-ГОМОФУЛЛЕРЕНОВ

Изобретение относится к способу получения оптически активных спиро-гомофуллеренов формулы (1) и (2) ! ! характеризующийся тем, что С60-фуллерен взаимодействует с оптически активными диазосоединениями, генерируемыми in situ окислением гидразонов (-)-ментона и D-(+)-камфоры с помощью MnO2, в о-дихлорбензоле в присутствии трехкомпонентной каталитической системы Pd(асас)2-PPh3-Et3Al, взятыми в мольном соотношении С60: оптически активный гидразон: Pd(acac)2:PPh3:Et3Al=0.01:(0.01-0.02):(0.0015-0.0025):(0.003-0.005):(0.006-0.01), при комнатной температуре (~20°С) в течение 1-2 ч. Способ отличается от известных высокими выходами целевых продуктов и селективностью реакции, использованием палладиевого комплекса в каталитических количествах, а также меньшими энергозатратами. 8 пр., 1 табл.

СПОСОБ ПОЛУЧЕНИЯ 1,3-АЛКАНДИОЛОВ И 3-ГИДРОКСИАЛЬДЕГИДОВ

Способ получения 1,3-алкандиолов и 3-гидроксиальдегидов посредством гидроформилирования оксирана монооксидом углерода и водородом в присутствии одного или более катализаторов гидроформилирования на основе металла VIII группы, который может содержать до 50 мол. % в расчете на металл фосфинмодифицированного катализатора, в котором концентрация оксирана в начале реакции составляет менее 15 вес.% в расчете на общий вес реакционной жидкой смеси. Технический результат состоит в повышении выхода 1,3-пропандиола, а также избирательности процесса. 15 з.п. ф-лы, 1 ил, 1 табл.

СПОСОБ ПОЛУЧЕНИЯ АЛЬДЕГИДОВ C3-C5

Использование: в производстве альдегидов, в частности C3-C5-альдегидов. Сущность изобретения: продукт C3-C5-альдегиды. Реагент 1: олефин. Реагент 2: монооксид углерода и водород. Условия реакции: в способе гидроформилирования олефинов синтез газом предусматривается абсорбция при 0 60°С и давлении 3,45 9,4 атм с последующей отгонкой непрореагировавшего олефина из абсорбента продувкой синтез газом под давлением 7 35 атм и температуре 0 130°С с отделением смеси непрореагировавшего отогнанного олефина и газообразной смеси синтез-газа. Последнюю рециркулируют в реактор гидроформилирования. 4 з.п. ф-лы, 1 ил.

КАТАЛИТИЧЕСКАЯ КОМПОЗИЦИЯ ДЛЯ СОПОЛИМЕРИЗАЦИИ ОКИСИ УГЛЕРОДА С АЛЬФА-ОЛЕФИНАМИ И СПОСОБ ПОЛУЧЕНИЯ СОПОЛИМЕРОВ ОКИСИ УГЛЕРОДА С АЛЬФА-ОЛЕФИНАМИ

Использование: для получения пластмасс. Сущность: проводят сополимеризацию олефинов с окисью углерода на каталитической композиции, состоящей из соли паладия и карбоновой кислоты, кислоты с РКа менее 4, бисфосфина и органического растворителя. Бисфосфин имеет формулу R2P-CH2-CH(R')-CH2-PR2, где R-2-алкоксифенил, R'-алкилгидроксиалкил, бензил, бензилокси или триалкилбензилокси. 2 с. п. ф-лы.

СПОСОБ ИЗВЛЕЧЕНИЯ БЛАГОРОДНОГО МЕТАЛЛА ИЗ НЕОРГАНИЧЕСКОГО И/ИЛИ ОРГАНИЧЕСКОГО ОСТАТКА

Изобретение относится к способам извлечения благородного металла из неорганического и/или органического остатка в форме теллуровой амальгамы, отличающимся тем, что добавляют растворитель, имеющий температуру кипения выше 120oC, в остаток, удаляют при помощи отгонки воду и другие остаточные растворители, имеющие температуры кипения ниже температуры кипения добавляемого растворителя, добавляют теллур или восстанавливаемое соединение теллура, а затем подвергают дефлегмации при атмосферном давлении перед отведением амальгамы благородного металла. Способ изобретения позволяет также осуществить одновременное извлечение третичного фосфина в виде его окисла из остатка, содержащего третичный фосфин, при помощи дополнительных стадий концентрирования маточных жидкостей, оставшихся после отделения амальгамы благородного металла, извлечения добавленного растворителя с высокой температурой кипения и извлечения третичного фосфина в виде его окиси при помощи осаждения водой. 7 з.п. ф-лы.

КАТАЛИТИЧЕСКАЯ СИСТЕМА

... 1. Каталитическая система, способная катализировать карбонилирование этилен-ненасыщенного соединения, эта система может быть получена посредством объединенияa) металла группы VIB или группы VIIIB, или его соединения,b) бидентатного фосфинового, арсинового или стибинового лиганда иc) кислоты,где указанный лиганд присутствует в молярном избытке, по меньшей мере, 2:1, по сравнению с указанным металлом или указанным металлом в соединении указанного металла, и указанная кислота присутствует в молярном избытке, по меньшей мере, 2:1, по сравнению с указанным лигандом.2. Каталитическая система по п.1, в которой соотношение указанного лиганда к указанному металлу находится в пределах 5:1-750:1.3. Каталитическая система по п.1, в которой соотношение указанного лиганда к указанному металлу находится в пределах 10:1-500:1.4. Каталитическая система по п.1, в которой соотношение указанного лиганда к указанному металлу находится в пределах 20:1-40:1,5. Каталитическая система по п.1, в которой соотношение ...

ИНТЕГРИРОВАННЫЕ ХИМИЧЕСКИЕ СПОСОБЫ ПРОМЫШЛЕННОГО ПРИМЕНЕНИЯ РАСТИТЕЛЬНЫХ МАСЕЛ ИЗ СЕМЯН

... 1. Композиция на основе жирных кислот или сложных эфиров жирных кислот, содержащая одну или более ненасыщенных жирных кислот или сложных эфиров ненасыщенных жирных кислот, характеризующаяся тем, что содержит менее 3,0 миллиэквивалентов примеси(ей), отравляющей катализатор метатезиса, на килограмм композиции на основе жирных кислот или сложных эфиров жирных кислот. 2. Композиция на основе жирных кислот или сложных эфиров жирных кислот по п.1, содержащая менее приблизительно 2,5 мэкв./кг примеси(ей), отравляющей катализатор метатезиса. 3. Композиция на основе жирных кислот или сложных эфиров жирных кислот по п.1, содержащая менее приблизительно 1,0 мэкв./кг примеси(ей), отравляющей катализатор метатезиса. 4. Композиция на основе жирных кислот или сложных эфиров жирных кислот по п.1, где примесь, отравляющая катализатор метатезиса, содержит одну или более органических гидроперекисей. 5. Композиция на основе жирных кислот или сложных эфиров жирных кислот по п.1, содержащая более приблизительно ...

ПЕРЕКРЕСТНОЕ СОЧЕТАНИЕ УГЛЕРОД-УГЛЕРОД, КАТАЛИЗИРУЕМОЕ ПЕРЕХОДНЫМИ МЕТАЛЛАМИ НА ТВЕРДЫХ НОСИТЕЛЯХ

... 1. Способ сочетания углеродсодержащих соединений, включающий реакцию (i) первого углеродсодержащего соединения со (ii) вторым углеродсодержащим соединением в присутствии (iii) металла палладия или никеля на твердом катализаторе, включающем соль щелочноземельного металла, и (iv) растворителя, включающего спирт. 2. Способ согласно п.1, в котором указанным первым углеродсодержащим соединением является арилгалогенид и указанным вторым углеродсодержащим соединением является арилборная кислота. 3. Способ согласно п.1, в котором указанным первым углеродсодержащим соединением является арилгалогенид и указанным вторым углеродсодержащим соединением является соединение, включающее винильную группу. 4. Способ согласно п.1, в котором указанным первым углеродсодержащим соединением является алкилгалогенид и указанным вторым углеродсодержащим соединением является соединение, включающее винильную группу. 5. Способ согласно п.1, в котором указанным первым углеродсодержащим соединением является арилгалогенид ...

СПОСОБ ПОЛУЧЕНИЯ КАТАЛИЗАТОРОВ НА ОСНОВЕ ПЕРЕХОДНОГО МЕТАЛЛА И ФОСФИНА

... 1. Способ получения катализаторов, содержащих по меньшей мере один переходный металл со степенью окисления 0 или 1, ассоциированный по меньшей мере с одним монодентатным или бидентатным водорастворимым фосфином, отличающийся тем, что осуществляют обработку водородом, при отсутствии моноокиси углерода, водного раствора, содержащего по меньшей мере одно соединение переходного металла и по меньшей мере один монодентатный или бидентатный водорастворимый фосфин. 2. Способ по п. 1, отличающийся тем, что используемый водорастворимый фосфин представляет собой монодентатный фосфин общей формулы I P(Ar1)a(Ar2)b(Ar3)c(D1)d(D2)e(D3)f где Ar1, Ar2 и Ar3, одинаковые или разные, означают арильные группы или арильные группы, содержащие один или несколько заместителей, таких, как алкильный или алкоксильный радикал с 1-4 атомами углерода, атом галогена, нитрильная группа, нитрогруппа, гидрофильная группа, такая, как COOM, -SO3M, -PO3M, где М означает минеральный или органический катионный остаток, выбираемый ...

СПОСОБ ПОЛУЧЕНИЯ ДИНИТРИЛОВ

Изобретение относится к способу гидроцианирования нитрилов с этиленовой ненасыщенностью до насыщенных динитрилов, особенно гидроцианирования пентен-нитрилов до адипонитрила, одного из основных соединений для получения полиамида-66. Более конкретно, оно представляет собой способ гидроцианирования алифатического нитрила с этиленовой ненасыщенностью путем взаимодействия с циановодородом в присутствии водного раствора катализатора, содержащего соединение переходного металла и сульфированный фосфин, отличающийся тем, что вышеуказанный раствор содержит также сокатализатор, состоящий по крайней мере из одной кислоты Льюиса.

ОДНОСТАДИЙНЫЙ СПОСОБ ПОЛУЧЕНИЯ 1,3-ПРОПАНДИОЛА ИЗ ЭТИЛЕНОКСИДА И СИНТЕЗ-ГАЗА С КАТАЛИЗАТОРОМ С ФОСФОЛАНОАЛКАНОВЫМ ЛИГАНДОМ

... 1. Каталитическая композиция, включающая а) кобальтовый компонент, включающий одно или более не лигированных соединений кобальта; и b) рутениевый компонент, включающий в основном соединение карбонила рутения лигированное с фосфоланоалкановым лигандом. 2. Каталитическая композиция по п.1, растворенная в эфирном растворителе. 3. Композиция по п.1 или 2, где фосфоланоалкан представляет собой где, в обеих формулах I и II, R является низшим алкилом, трифторметилом, фенилом, замещенным фенилом, аралкилом или замещенным в кольце аралкилом; и n равно целому числу от 1 до 12; и А в формуле II является ССН3, СН, N или Р. 4. Композиция по п.3, в которой в обеих формулах I и II R является низшим алкилом С1-С6 алкилом, и n равно от 1 до 3. 5. Композиция по п.4, в которой в формулах I и II R является метилом. 6. Композиция по п.1, в которой фосфоланоалкан выбирают из группы, включающей 1,2-бис(фосфолано)этан; 1,2-бис(2,5-диметилфосфолано)этан; 1, 2-бис[(2R,5R)-2,5-диметилфосфолано]этан; 1,2-бис[(2S,5S ...

ОДНОСТАДИЙНЫЙ СПОСОБ ПОЛУЧЕНИЯ 1,3-ПРОПАНДИОЛА ИЗ ЭТИЛЕНОКСИДА И СИНТЕТИЧЕСКОГО ГАЗА С ПОМОЩЬЮ КАТАЛИЗАТОРА НА ОСНОВЕ КОБАЛЬТА-ЖЕЛЕЗА

... 1. Композиция катализатора, содержащая a) компонент кобальта; и b) компонент железа, лигированный лигандом, выбранным из группы, состоящей из остатков N-гетероцикла, фосфина и порфорина. 2. Композиция по п.1, где компонент кобальта выбирается из солей кобальта, которые восстановлены до состояния нулевой валентности путем тепловой обработки в присутствии синтетического газа. 3. Композиция по п.1 или 2, где компонент железа представляет собой карбонил железа или металлоорганическое соединение железа. 4. Композиция по п.1 или 2, где лиганд выбирается из группы, состоящей из монодентатных, бидентатных и мультидентатных N-гетероциклических лигандов. 5. Композиция по п.1 или 2, где лиганд представляет собой лиганд третичного дифосфина общей формулы RRP-Q-PR'R', где каждая группа R и R', независимо или в сочетании, представляет собой углеводородный остаток, содержащий до 30 атомов углерода, и Q представляет собой органическую мостиковую группу из 2-4 атомов в длину. 6. Композиция по п.1 или 2, ...

Катализатор для получения 4-метилпиридина

Изобретение относится к каталитической химии, в частности к катализатору для получения 4-метиллиридина. С целью повышения селективности катализатора он содержит следующее соотношение компонентов, мас.%: дихлоро-бис(трифе- нилфосфин)-медь (2+) 0.37-1,48; оксид алюминия остальное. Новый катализатор работает в более мягких условиях с выходом 4-метилпиридина 84,9%. 2 табл.

СПОСОБ ПОЛУЧЕНИЯ ТРИФЕНИЛФОСФИНКАРБОНИЛЬНОГО КОЛШЛЕКСА ПЛАТИНЫ

Каталитическая система для гидрирования непредельных альдегидов

Способ борьбы с нежелательной растительностью

Способ получения 6-метил-3,4-дигидро-1,2,3-оксатиазин-4-он-2,2-диоксида или его калиевой соли и способ получения аммоний ацетоацетамид-N-сульфонатов

Изобретение касается гетероциклических соединений, в частности 6- метил-3,4-дигидро-1,2,З-оксатиазин-4- он-2,2-диоксида и его калиевой соли (ОТА), которые как обладающие сладким вкусом находят применение в пищевой промьшшенности, также новьгх промежуточных продуктов - аммоний ацетоацетамид-К-сульфонатов (ААС) формулы CHj-C(0)CH2-C(0)-NH-SO R,(, где R,. Н, или R, - Н, низший алкил; R - низший алкил; R, - И, низший алкил, фенил, бензил. Упрощение процесса, повышение выхода ОТА достигается использованием других исходных промежуточных продуктов - ААС, и их циклизацией в других условиях. Получение ОТА ведут из аммониевой соли амидосульфокислоты (АСК) формулы H N-Sof R,(R,JjRjN , и 4-30 мол.%-ного избытка декетена в среде растворителя (ледяная , и/или дихлорметилен) при температуре в пределах 0-30°С, возможно в присутствии амина. Последующую циклизацию промежуточного ААС ведут обработкой 4-20 кратным мольным избытком SOj в среде органического () или неорганического (жидкий SOj) растворителя , ...

Способ получения гептенов

Способ получения альдегидов С @ -С @

Изобретение относится к кислородсодержащим соединениям, в частности к получению альдегидов C4- C11. Цель - увеличение селективности процесса по н-альдегиду. Получение ведут путем гидроформилирования олефинов C3-C10окисью углерода и водородом при 60-120°С, общем давлении 3,5-11,2 атм, парциальном давлении водорода 1,4-6,69 атм, парциальном давлении окиси углерода 0,7-8,4 атм в присутствии родийсодержащей каталитической системы, включающей дикарбонилацетилацетонат родия (112-400 PPM в расчете на родий) и фосфорсодержащий лиганд-бисфосфитный лиганд общей фор-лы (мольное соотношение лиганда и родия 4-58,8:1). @ , где R1- R4- вместе или раздельно H или OCH3, или третбутил Z - CH3, C6H5, N-нонил C6H5, N=CLC6H5, O-толил, N-C6H5- C9H19. 12 табл.

VERFAHREN ZUR HERSTELLUNG VON GERADKETTIGEN FETTSAEUREN ODER IHRER ESTER

KATALYSIERTE GASPHASENISOMERISIERUNG VON NICHT KONJUGIERTEN 2-ALKYL-3-MONOALKENNITRILEN

VERFAHREN ZUR HERSTELLUNG VON 1,3-ALKANDIOLEN UND 3-HYDROXYALDEHYDEN

VERBESSERTES VERFAHREN ZUR REDUKTIVEN HYDROLISE VON NITRILEN

Verfahren zur Herstellung arylsubstituierter aminoacylierter Phosphohnsäurederivate mit Hilfe von Metallkomplexen chiraler amphiphiler Liganden

Reaktivierung von Hydroformylierungskatalysatoren.

Fluor enthaltende Organosiliziumverbindung und Verfahren zu deren Herstellung

VERFAHREN ZUR HERSTELLUNG VON 1,4-BUTANDIAL

TETRAENE, ITS PREPARATION AND ITS USE

KATALYTISCHE ASYMMETRISCHE HYDRIERVERFAHREN

Verfahren zur Karbonylierung von Olefin.

Verfahren zur Karbonylierung von Olefin.

KATALYSATORSYSTEM ZUR UMWANDLUNG VON UNGESAETTIGTEN KOHLENWASSERSTOFFEN, VERFAHREN ZU SEINER HERSTELLUNG UND DESSEN VERWENDUNG

Verfahren zur Herstellung von Alkenylphosphonsäure-Derivaten

VERFAHREN ZUR HERSTELLUNG VON N-OCTADIENOL

Verfahren zur Herstellung von Benzylketonen.

ACRYLIC DIMERIZATION USING SUPPORTED CATALYSTS

Verfahren zur Herstellung von optisch aktivem 3-Chinuclidinol

Prodn. of carbonyl cpd. by oxidn. of alcohol with chloro-aromatic cpd.

Prodn. of carbonyl cpds. (I) comprises reacting the corresp. prim. or sec. alcohols (II) with a chlorinated aromatic cpd. (III) in presence of a complex transition metal catalyst (IV).

Ruthenium-Phosphin-Komplexe.

HYDROFORMYLIERUNGSVERFAHREN UNTER VERWENDUNG NIEDRIG FLUECHTIGER PHOSPHORLIGANDEN

Neue Diphosphinverbindung, Zwischenprodukte für deren Herstellung, Übergangsmetallkomplex enthaltend die Verbindung als Ligand und Katalysator für asymmetrische Hydrierungen, welcher den Komplex enthält

CHIRALE RHODIUM-DIPHOSPHINKOMPLEXE FUER ASYMMETRISCHE HYDRIERUNGEN.

VERFAHREN ZUR HERSTELLUNG VON ALPHA-(4-ISOBUTYL-PHENYL)PROPIONSAEURE.

VERFAHREN ZUR HERSTELLUNG VON 6,7-DIHYDRO-5,8-DIMETHYL-9-FLUOR-1-OXO-1H,5H-BENZO(I,J)CHINOLIZIN-2-CARBONSAEURE.

ORGANISCHE VERBINDUNGEN UND VERFAHREN ZU DEREN HERSTELLUNG

HERSTELLUNGSVERFAHREN VON ALKYLIDENDIESTERN.

VERFAHREN ZUR HERSTELLUNG VON 4-DEMETHOXYDAUNOMYCINON.

VERFAHREN ZUR HERSTELLUNG VON NABUMETON.

PROCESS FOR DIMERIZING LOWER ALPHA-OLEFINS

Katalysator umfassend einen Komplex eines Metalls der VIII. Nebengruppe auf Basis eines Heterophosphacyclohexanliganden

The invention relates to a catalyst, comprising at least one complex of a platinate metal of the VIII. sub-group with at least one heterophosphacyclohexane ligand, a method for hydroformylation in the presence of such a catalyst and the use thereof.

Verfahren zur Herstellung von Aldehyden und Alkoholen

NICHT-LINEARES POLYMERISAT ALS KATALYSATORVORLAEUFER UND DEREN VERWENDUNG IN EINER KATALYSATORZUSAMMENSETZUNG

Aminosäurekomplexe und ihre Verwendung zur Herstellung von Olefinpolymerisaten

Aminosäurekomplex der allgemeinen Formel I, DOLLAR F1 wobei M ausgewählt wird aus Fe, Co, Ni, Pd, Pt oder Ir, vorzugsweise Ni, bedeutet; Verfahren zu ihrer Herstellung sowie Verwendung zur Polymerisation von Olefinen.

Verfahren zur Herstellung von aromatischen Acetylenen mit Palladazyklen als Katalysatoren

VERFAHREN ZUR OXIDATION VON ACYCLISCHEN UND CYCLISCHEN MONOOLEFINEN UND DIOLEFINEN

Verfahren zur Herstellung von Ruthenium-Hydrogenierungskatalysatoren und deren Verwendung

HYDRIERUNG VON GLYCERIN

Optisch aktive Diphosphine, diese enthaltende Übergangsmetallkomplexe und ein Verfahren zur Darstellung einer optisch aktiven Verbindung, in dem diese Komplexe eingesetzt werden

Valeraldehyd und Verfahren zu seiner Herstellung

Die Erfindung betrifft einen zweizähnigen Phosphinligand der allgemeinen Formel DOLLAR F1 sowie ein Verfahren zur Herstellung linearer Aldehyde durch Hydroformylierung interner Olefine unter Verwendung solcher Phosphinliganden.

Verfahren zur Herstellung von an der Doppelbindung mit Ethylen verlängerten Styrol-Derivaten mit in der gebildeten Verlängerungskette verbleibender Doppelbindung und neue mit Ethylen verlängerte Styrol-Derivate

Verfahren zur Herstellung von Carbonsäurevinylestern

PROCESS FOR PREPARING RHODIUM (I) CARBONYL COMPLEXES

VERFAHREN ZUR HERSTELLUNG VON ALKOHOLEN UND/ODER ALDEHYDEN AUS OLEFINEN

VERFAHREN ZUR KATALYTISCHEN HERSTELLUNG VON N-ACYLGLYCINDERIVATEN

Verfahren zur Herstellung von 2,6-Pyridindicarbonsäureestern

VERFAHREN ZUR HERSTELLUNG VON CYANVALERIANSÄURE ODER -ESTERN

Verfahren zur Herstellung fluorierter cyclischer aliphatischer Verbindungen

Die vorliegende Erfindung betrifft ein neuartiges Verfahren zur Herstellung fluorierter cyclischer aliphatischer Verbindungen aus den analogen aromatischen Verbindungen durch Hydrierung mit einem Rh-Katalysatorsystem.

Verfahren zur Herstellung von optisch aktiven aliphatischen Hydroxycarbonsäureestern.

PROCESS FOR THE PRODUCTION OF AROMATIC CARBOXYLIC-ACID CHLORIDES

Katalysatorsysteme auf der Basis von Rhodium-Komplexverbindungen mit Diphosphin-Liganden und ihre Verwendung bei der Herstellung von Aldehyden

New phosphine compounds for use as ligands in metal complex catalysts

Phosphine compounds of formula (I) are new. m = 1-1000;x = 0-4; W = -CH2CH2-, -CHMeCH2- or -CH2CHMe-; R = H, 1-5C alkyl or a group of formula (A) or (B); a-e = 0-1000; at least one of the numbers a-e is more than 0; R<5>-R<9> = H, 1-5C alkyl or a group of formula (C); R<1>, R<2> = linear, branched or cyclic 1-30 alkyl or 6-10C aryl (optionally substituted with 1-5 1-3C alkyl groups), or R<1> + R<2> + P = a dibenzo-phosphoryl or 3,4-dimethyl-phosphoryl group of formula (D) or (E); L = 1-5C alkyl or alkoxy, NO2 or NR<3>R<4> (with R<3>, R<4> = H, 1-4C alkyl, Cl or OH). Also claimed is a process for the production of (I) from the corresponding phenol, by deprotonation with base followed by reaction with a compound of formula X-(W-O)m-R, in which X is a nucleophilically substitutable leaving group.

Water soluble transition metal complexes useful for preparation of linear alternating carbon monoxide copolymers

Water soluble transition metal complexes suitable as active constituents of the catalyst system for the preparation of linear, alternating carbon monoxide alpha -olefin copolymers in aqueous medium are new. Water soluble transition metal complexes, of formula (I), suitable as active constituents of the catalyst system for the preparation of linear, alternating carbon monoxide alpha -olefin copolymers in aqueous medium are new. G = (CRb2)r-, (-CRb2)s-Si(Ra)2-(CRb2)t- A'-O-B'-, or A'-Z(R<5>)-B'-, R<5> = H, 1-28C alkyl, 3-14C cycloalkyl, 6-15C aryl, or alkylaryl with 1-20C in alkyl and 6-15C in aryl part optionally substituted with group IVA, VA, VIA, or VIIA elements, N(Rb)2, -Si(Rc)3, or a residue of formula (II): A', B', -(CRb2)r-(CRb2)s-Si(Ra)2-(CRb2)t, -N(Rb)- = an r', s-, or t-atom constituent of a ring system, or together with Z = an (r+1) or (t+1) constituent of a heterocyclic ring, Ra = 1-20C alkyl, 3-10C cycloalkyl, 6-15C aryl, or alkylaryl with 1-10C in the alkyl and 6-15C in the ...

Verfahren zur katalytischen Umsetzung olefinisch ungesättigter Verbindungen mit Wasserstoff und/oder Kohlenmonoxid

CHIRALE PHOSPHINE, DEREN KOMPLEXE MIT ÜBERGANGSMETALLEN UND DEREN VERWENDUNG IN ASYMMETRISCHEN SYNTHESEREAKTIONEN

VERFAHREN ZUR SELEKTIVEN HYDRIERUNG UNGESAETTIGTER VERBINDUNGEN

VERFAHREN ZUM CARBONYLIEREN VON PENTENNITRIL

PROCESS FOR THE PRODUCTION OF PURE ADIPINIC-ACID MONOESTERS

HYDROFORMYLIERUNG VON ALLYL-ALKOHOLEN

Verfahren zur Herstellung von Essigsäure

PROCESS FOR THE PRODUCTION OF METHYL FORMATE

VERFAHREN ZUR HERSTELLUNG EINES ALDEHYDS

Hydroformylation von Dien enthaltenden olefinischen Speiseströmen

KATALYTISCHE TRIMERISATION UND TETRAMERISATION VON OLEFINISCHEN MONOMEREN

Verwendung von molekulargewichtsvergrößerten Katalysatoren in einem Verfahren zur asymmetrischen kontinuierlichen Hydrierung, neue molekulargewichtsvergrößerte Liganden und Katalysatoren

Die vorliegende Erfindung richtet sich auf eine Verwendung von molekulargewichtsvergrößerter homogen löslicher Katalysatoren Verfahren zur asymmetrischen kontinuierlichen Hydrierung von C=C-, C=N- oder C=O-Doppelbindungen mittels molekulargewichtsvergrößerter homogen löslicher Katalysatoren in einem Membranreaktor. DOLLAR A Bisherige im Stand der Technik vorgeschlagene Hydrierverfahren liefen diskontinuierlich ab. Die kontinuierliche Fahrweise hilft dagegen Prozeßkosten zu sparen. DOLLAR A Angegeben werden auch neue molekulargewichtsvergrößerte Liganden und Katalysatoren.

Chirale Diphosphin-Verbindung, Zwischenprodukte zu ihrer Herstellung, Übergangsmetall-Komplexe davon und asymmetrischer Hydrierungskatalysator

Preparation of dialkyl ketones, e.g. 3-pentanone, used as solvent or intermediate e.g. in synthesis of trimethylphenol and vitamin E, uses amide in palladium phosphine catalyst system in reductive carbonylation of olefin

Preparation of dialkyl ketones (I) by reductive carbonylation of alpha -olefins with carbon monoxide (CO) and hydrogen (H2) is carried out in the presence of a catalyst system containing: (a) palladium (Pd) or a Pd compound; (b) a phosphine; (c) a protonic acid with a pKa value \- 4.5, measured in aqueous solution at 25 deg C; and (d) a solubilizable carboxamide.

Organic chlorohydrosilane and method for preparing them

Provided is an organic chlorohydrosilane, a useful starting material for preparing silicon polymers and a method for preparing the same. More particularly, the present invention enables the synthesis of various novel organic chlorohydrosilanes in high yield by an exchange reaction between an Si—H bond of a chlorosilane which can be obtained in an inexpensive and easy manner and an Si—Cl bond of an another organic chlorosilane using a quaternary organic phosphonium salt compound as a catalyst. Since the catalyst can be recovered after its use and reused, the present invention is very economical and thus effective for mass-producing silicon raw materials.

Method for producing formic acid

An object of the present invention is providing a method for producing formic acid under mild reaction conditions and by a simple procedure. As a means for achieving the object, the method for producing formic acid of the present invention is characterized by a reaction between carbon dioxide and hydrogen in the presence of an ionic liquid. According to the present invention, it is possible to generate formic acid effectively, because the method does not require that carbon dioxide be brought into a supercritical state and because no basic substances are required to be added to the reaction system.

Method for producing substituted fluorine-containing olefin

This invention relates to a method of reacting fluoroolefin with an organic magnesium compound in the presence of a catalyst comprising nickel or palladium so as to efficiently produce fluoroolefin, such as TFE, in which a fluorine (F) atom or atoms bonded to the sp 2 hybridized carbon atom are substituted with an organic group.

CONVERSION OF ALCOHOLS

A method is described for use in a process for the conversion of an alcohol, the method including the step of contacting a composition comprising a first alcohol with a catalyst composition. Catalyst composition described comprises: i) a source of a Group VIII transition metal; ii) a phosphine ligand of formula PRRR, wherein R, Rand Rare the same or different; and iii) a base. In examples described, the alcohol which is converted comprises ethanol and the product comprises butanol. 1. A method for use in a process for the conversion of an alcohol into a product , the method including the step of contacting a composition comprising a first alcohol with a catalyst composition , in which the catalyst composition comprises:i) a source of a Group VIII transition metal, wherein the Group VIII transition metal is selected from one or more of the group comprising Fe, Ru, Os;{'sup': 1', '2', '3', '1', '2', '3', '1', '2', '3, 'ii) a phosphine ligand of formula PR, RR, wherein R, Rand Rare the same or different, and wherein one or more of R, R, and Rinclude a heteroatom-substituted hydrocarbon group; and'}iii) abase.2. A method according to claim 1 , wherein the phosphine ligand of formula PR claim 1 , RRis a multi-dentate ligand with respect to the Group VIII metal.3. A method according to claim 1 , wherein the heteroatom comprises one or more selected from the group comprising O claim 1 , S claim 1 , N and P.4. A method according to claim 3 , wherein the heteroatom comprises one or more selected from the group comprising N and P.5. A method according to claim 1 , wherein only one of R claim 1 , R claim 1 , and Rinclude a heteroatom-substituted hydrocarbon group.6. A method according to claim 1 , wherein the phosphine ligand comprises a bi-dentate ligand with respect to the Group VIII metal.7. A method according to claim 1 , wherein the phosphine ligand comprises a diphosphine group —[P{link}P]— wherein a linking group {link} has a backbone including fewer than two atoms.8. A ...

PROCESS FOR PREPARING FORMIC ACID BY REACTION OF CARBON DIOXIDE WITH HYDROGEN

The invention relates to a process for preparing formic acid by reaction of carbon dioxide with hydrogen in a hydrogenation reactor in the presence of a transition metal complex as a catalyst comprising at least one element from group 8, 9 or 10 of the Periodic Table and at least one phosphine ligand with at least one organic radical having at least 13 carbon atoms, of a tertiary amine and of a polar solvent to form a formic acid-amine, adduct, which is subsequently dissociated thermally to formic acid and the corresponding tertiary amine. on unit. 115.-. (canceled)16. A process for preparing formic acid , comprising the steps of [{'br': None, 'sup': 1', '2', '3, 'NRRR\u2003\u2003(A1)'}, 'in which', {'sup': 1', '2', '3, 'R, R, Rare each independently an unbranched or branched, acyclic or cyclic, aliphatic, araliphatic or aromatic radical having in each case 1 to 16 carbon atoms, where individual carbon atoms may each independently also be substituted by a hetero group selected from the —O— and >N— groups, and two or all three radicals may also be joined to one another to form a chain comprising at least four atoms in each case,'}, 'in the presence of at least one transition metal complex as a catalyst, comprising at least one element selected from groups 8, 9 and 10 of the Periodic Table and at least one phosphine ligand with at least one organic radical having at least 13 carbon atoms,', 'in a hydrogenation reactor', 'to obtain, optionally after addition of water, a biphasic hydrogenation mixture (H) comprising', 'an upper phase (U1) comprising the catalyst and the tertiary amine (A1), and', {'br': None, 'sup': 1', '2', '3, 'i': '*x', 'sub': 'i', 'NRRRHCOOH\u2003\u2003(A2)'}, 'a lower phase (L1) comprising the at least one polar solvent, residues of the catalyst and a formic acid-amine adduct of the general formula (A2)'}, 'in which', {'sub': 'i', 'xis in the range from 0.4 to 5 and'}, {'sup': 1', '2', '3, 'R, R, Rare each as defined above,'}], '(a) homogeneously ...

Metal Complex Compound and Process for Producing Amides Utilizing the Metal Complex Compound

A catalyst contains a metal complex compound represented by the following general formula (I). In the formula (I), M is a metal ion such as ruthenium, Lis a cyclic or acyclic, neutral or minus 1-valent unsaturated hydrocarbon group of 1 to 30 carbon atoms which may have a substituent, Land Lare each independently chlorine or the like, and Lis a compound bonded to M through phosphorus or arsenic and represented by the following general formula (IIa) or (IIb). In the formulas (IIa) and (IIb), E is phosphorus or arsenic, Yis oxygen or sulfur, Y, Yand Yare each independently a hydrogen atom, an aryl group or the like, and H is a hydrogen atom. 3. The hydration catalyst as claimed in claim 1 , wherein Lis cyclic diene claim 1 , triene or tetraene of 1 to 30 carbon atoms which may have a substituent and is a neutral or minus 1-valent unsaturated hydrocarbon group.4. The hydration catalyst as claimed in claim 1 , wherein Lis acyclic diene claim 1 , triene or tetraene of 1 to 30 carbon atoms which may have a substituent and is a neutral or minus 1-valent unsaturated hydrocarbon group.5. The hydration catalyst as claimed in claim 1 , wherein the compound represented by the general formula (IIa) or (IIb) is any one of secondary phosphine oxide claim 1 , an aliphatic phosphoric acid ester claim 1 , an aliphatic phosphorous acid ester claim 1 , an aromatic phosphoric acid ester and an aromatic phosphorous acid ester of 1 to 30 carbon atoms which may have a substituent.6. The hydration catalyst as claimed in claim 1 , wherein the compound represented by the general formula (IIa) or (IIb) is any one of diarylphosphine oxide which may have a substituent claim 1 , dialkylphosphine oxide which may have a substituent claim 1 , secondary phosphine oxide having a phenyl group which may have a substituent and having an alkyl group which may have a substituent claim 1 , a phosphorous acid dialkyl ester of 1 to 30 carbon atoms claim 1 , a phosphorous acid diphenyl ester which may have a ...

NICKEL FORM FOR PREPARATION OF CATALYTIC NICKEL-LIGAND COMPLEXES

A novel nickel particulate form is provided that efficiently forms a zero-valent nickel complex with a phosphorus-containing ligands in an organic liquid to form a hydrocyanation catalyst. Particles in the nickel particulate form comprise nickel crystallites. For example, the nickel particulate form can have a BET Specific Surface Area of at least about 1 m/gm; an average crystallite size less than about 20-25 nm, the nickel particulate form can have at least 10% of the crystallites in the nickel form can have can have a diameter (C10) of less than about 10 nm, and/or there are on average at least about 10surface crystallites per gram nickel. A ratio of BET SSA to C50 for the nickel particulate form can be at least about 0.1×10m/gm and preferably at least about 0.4×10m/gm. Methods of preparation and use are also provided. 1. A nickel particulate form comprising nickel crystallites , wherein the nickel particulate form has a BET Specific Surface Area of at least about 1 m/gm; at least 10% of the nickel crystallites have a size (C10) that is less than about 20 nm; the nickel crystallites have an average crystallite size of no greater than about 100 nm; and the nickel crystallite size distribution span is greater than about 1.0.2. The nickel particulate form of claim 1 , wherein the nickel particulate form has a BET Specific Surface Area/C50 ratio of not less than 0.07×10m/gm.3. The nickel particulate form of claim 1 , wherein the nickel particulate form on average has at least about 10surface crystallites per gram of nickel.4. The nickel particulate form of claim 1 , wherein at least 10% of the particles of the form have a size (D10) of no greater than about 6 μm.5. The nickel particulate form of claim 1 , which has a Laser Diffraction Specific Surface Area of at least about 0.4 m/gm.6. The nickel particulate form of claim 1 , which has a BET Specific Surface Area to D10 ratio of about 0.3×10m/gm to about 10.0×10m/gm.7. The nickel particulate form of claim 1 , which ...

Polyhedral oligomeric silsesquioxane (poss) bonded ligands and the use thereof

The present invention relates to POSS-modified ligands and to the use thereof in catalytically effective compositions in hydroformylation.

Chelating Carbene Ligand Precursors and Their Use in the Synthesis of Metathesis Catalysts

Chelating ligand precursors for the preparation of olefin methathesis catalysts are disclosed. The resulting catalysts are air stable monomeric species capable of promoting various methathesis reactions efficiently, which can be recovered from the reaction mixture and reused. Internal olefin compounds, specifically beta-substituted styrenes, are used as ligand precursors. Compared to terminal olefin compounds such as unsubstituted styrenes, the beta-substituted styrenes are easier and less costly to prepare, and more stable since they are less prone to spontaneous polymerization. Methods of preparing chelating-carbene methathesis catalysts without the use of CuCl are disclosed. This eliminates the need for CuCl by replacing it with organic acids, mineral acids, mild oxidants or even water, resulting in high yields of Hoveyda-type methathesis catalysts. The invention provides an efficient method for preparing chelating-carbene metathesis catalysts by reacting a suitable ruthenium complex in high concentrations of the ligand precursors followed by crystallization from an organic solvent.

NOVEL CATALYSTS

The present invention provides novel compounds and ligands that are useful in transition metal catalyzed cross-coupling reactions. For example, the compounds and ligands of the present invention are useful in palladium or gold catalyzed cross-coupling reactions. 2. The compound of claim 1 , wherein both of Rand Rare tert-butyl claim 1 , cyclohexyl claim 1 , 2-tolyl claim 1 , or 1-adamantyl.3. The compound of claim 2 , wherein both of Rand Rare tert-butyl or 1-adamantyl.4. (canceled)5. (canceled)6. The compound of claim 1 , wherein R claim 1 , R claim 1 , and the nitrogen atom to which they are attached form an optionally substituted 4-10 membered heterocyclic ring.9. The compound of claim 1 , wherein each of Xand Xis C—R claim 1 , and each of Xand Xis C—R claim 1 , wherein each Ris independently selected from —H claim 1 , —CH claim 1 , —OCH claim 1 , halogen claim 1 , or —CF claim 1 , and each Ris independently selected from —H claim 1 , —CH claim 1 , —OCH claim 1 , —N(CH) claim 1 , halogen claim 1 , or —CF; or a vicinal Rgroup and Rgroup together with the carbon atoms to which they are attached form an optionally substituted 5-7 membered heterocyclic or carbocyclic ring.10. The compound of claim 9 , wherein each of X claim 9 , X claim 9 , X claim 9 , and Xis C—H.12. (canceled)13. The compound of claim 11 , wherein R claim 11 , R claim 11 , and the nitrogen atom to which they are attached form an optionally substituted 4-10 membered heterocyclic ring.16. The compound of claim 11 , wherein each of Xand Xis C—R claim 11 , and each of Xand Xis C—R claim 11 , wherein each Ris independently selected from —H claim 11 , —CH claim 11 , —OCH claim 11 , halogen claim 11 , or —CF claim 11 , and each Ris independently selected from —H claim 11 , —CH claim 11 , —OCH claim 11 , —N(CH) claim 11 , halogen claim 11 , or —CF; or a vicinal Rgroup and Rgroup together with the carbon atoms to which they are attached form an optionally substituted 5-7 membered heterocyclic or ...

METHODS FOR RECOVERY AND RECYCLE OF RUTHENIUM HOMOGENOUS CATALYSTS

Disclosed is a process for the extractive recovery of a homogeneous ruthenium catalyst from the reaction product of the hydrogenation of glycolic acid, glycolate esters, and/or glycolic acid oligomers with an extractant comprising a hydrophobic solvent and an optional hydrophilic solvent. The ruthenium catalyst, which can include 1,1,1-tris(diaryl- or dialkylphosphinomethyl)alkane ligands, can be recovered from the hydrophobic extract phase by back extraction with a hydrophilic solvent and recycled to a process for the preparation of ethylene glycol by the hydrogenation of glycolic acid and glycolic acid derivatives. 1. A process for recovering a homogeneous catalyst , comprising(A) contacting an aqueous mixture comprising glycolic acid, glycolate esters, methyl glycolate, oligomers of glycolic acid, or mixtures thereof, with hydrogen in the presence of a catalyst composition comprising ruthenium and tris-1,1,1-(diphenylphosphinomethyl)ethane to form a glycolic acid hydrogenation product comprising about 50 to about 90 weight percent, based on the total weight of said glycolic acid hydrogenation product, ethylene glycol, about 0.5 to about 25 weight percent water, and about 0.5 to about 30 weight percent of one or more reaction by-products selected from glycolic acid, oligomers of glycolic acid, and glycolate esters of ethylene glycol, and said catalyst composition;(B) extracting said glycolic acid hydrogenation product with a first extractant, comprising about 60 to 100 weight percent, based on the total weight of said first extractant, 2-ethylhexanol and about 0 to about 40 weight percent of a hydrocarbon having 5 to 20 carbon atoms to form a first raffinate phase comprising a major amount of said ethylene glycol contained in said glycolic acid hydrogenation product and a first extract phase comprising a major amount of said catalyst composition contained in said glycolic acid hydrogenation product;(C) separating said first raffinate and extract phases;(D) ...

CATALYST COMPOSITIONS FOR HYDROFORMYLATION REACTION AND HYDROFORMYLATION PROCESS USING THE SAME

Disclosed are a catalyst composition for hydroformylation of olefin compounds, comprising a specific phosphine ligand and a transition metal catalyst, and a hydroformylation process using the same. Through a hydroformylation process using the catalyst composition according to the present invention, a suitable selectivity of iso-aldehyde can be maintained, catalyst stability can be improved, the amount of used ligand can be reduced and superior catalyst activity can be obtained. 1. A catalyst composition for hydroformylation comprising a monodentate phosphine ligand and a transition metal catalyst ,wherein the monodentate phosphine ligand is at least one selected from cyclohexyldiphenylphosphine, cyclohexylditolylphosphine and cycloheptyldiphenylphosphine.2. The catalyst composition according to claim 1 , wherein the content of the monodentate phosphine ligand is 0.5 to 200 moles claim 1 , with respect to one mole of the central metal of the transition metal catalyst claim 1 ,{'sub': 2', '8', '2', '3', '2', '3, 'wherein the transition metal catalyst is at least one selected from the group consisting of cobaltcarbonyl [Co(CO)], acetylacetonatodicarbonylrhodium [Rh(AcAc)(CO)], acetylacetonatocarbonyltriphenylphosphinerhodium [Rh(AcAc)(CO)(TPP)], hydridocarbonyltri(triphenylphosphine)rhodium [HRh(CO)(TPP)], acetylacetonatodicarbonylirridium [Ir(AcAc)(CO)] and hydridocarbonyltri(triphenylphosphine)iridium [HIr(CO)(TPP)].'}3. The catalyst composition according to claim 1 , wherein the catalyst composition comprises 1.6 to 3.0% by weight of cyclohexyldiphenylphosphine as the monodentate phosphine ligand claim 1 , with respect to the total weight of the catalyst composition.4. The catalyst composition according to claim 1 , wherein the catalyst composition comprises 1.5 to 1.8% by weight of cyclohexyldiphenylphosphine as the monodentate phosphine ligand claim 1 , with respect to the total weight of the catalyst composition.5. The catalyst composition according to claim 1 , ...

Novel Compound, Novel Ligand, Novel Transition Metal Complex, and Catalyst Including Novel Transition Metal Complex

The invention provides novel ligands for transition metal complexes which exhibit high coordination power with respect to metals by being free of substituents at the positions ortho to phosphorus or arsenic and which have electron-withdrawing power comparable to the highest level known in conventional ligands. A ligand of the invention includes a compound represented by General Formula (1): RRRA or General Formula (2): RRA-Y-ARRand having a total of 15 to 110 carbon atoms. In the formulae, A is phosphorus or arsenic; R, R, Rand Rare each independently a substituted pyridyl group having optionally different electron-withdrawing groups bonded to the positions meta to the atom A as well as hydrogen atoms bonded to the positions ortho to the atom A; and Y is a divalent group derived from a C, optionally substituted and optionally heteroatom-containing, aliphatic, alicyclic or aromatic compound or from ferrocene. 1. A compound represented by General Formula (1) or (2) and having a total of 15 to 110 carbon atoms:{'br': None, 'sup': 1', '2', '3, 'RRRA\u2003\u2003(1)'}{'br': None, 'sup': 1', '2', '3', '4, 'RRA-Y-ARR\u2003\u2003(2)'}{'sup': 1', '2', '3', '4, 'sub': '2-20', '(wherein A is phosphorus or arsenic; R, R, Rand Rare each independently a substituted pyridyl group having optionally different electron-withdrawing groups bonded to the positions meta to the atom A as well as hydrogen atoms bonded to the positions ortho to the atom A; and Y is a divalent group derived from a C, optionally substituted and optionally heteroatom-containing, aliphatic, alicyclic or aromatic compound or from ferrocene).'}2. The compound according to claim 1 , wherein the electron-withdrawing group is at least one selected from the group consisting of a perhaloalkyl group having 1 to 4 carbon atoms claim 1 , a halogen claim 1 , nitro group claim 1 , cyano group claim 1 , pentafluorophenyl group claim 1 , tetrafluoropyridyl group claim 1 , heptafluorotolyl group claim 1 , 2 claim 1 ,6- ...

METHOD FOR MANUFACTURING RUTHENIUM CARBENE COMPLEXES

The invention is directed to aryl alkylidene ruthenium complexes and the use of these complexes as catalysts in metathesis reactions. 112-. (canceled)14. The Ru-carbene complex according to claim 13 , wherein L and L′ are selected independently from the group consisting of triphenylphosphane claim 13 , triisopropylphosphane claim 13 , tricyclohexylphosphane and 9-cyclohexyl-9-phosphabicyclo[3.3.1]nonane.15. The Ru-carbene complex according to claim 13 , wherein L is a heterocyclic carbene and L′ is selected from the group consisting of triphenylphosphane claim 13 , triisopropylphosphane claim 13 , tricyclohexylphosphane and 9-cyclohexyl-9-phospha-bicyclo[3.3.1]nonane.16. The Ru-carbene complex according to claim 13 , wherein Ar is a furyl or thienyl radical.17. (canceled)1830. A metathesis reaction which comprises utilizing the Ru-carbene complex according to claim as a catalyst in the metathesis reaction.19. The Ru-carbene complex according to claim 13 , wherein X is halogen claim 13 , pseudo-halogen claim 13 , carboxylate claim 13 , sulphate or diketonate.20. The Ru-carbene complex according to claim 13 , wherein X is bromine or chlorine.21. The Ru-carbene complex according to claim 13 , wherein X is chlorine.22. The Ru-carbene complex according to claim 19 , wherein L is a heterocyclic carbene and L′ is selected from the group consisting of triphenylphosphane claim 19 , triisopropylphosphane claim 19 , tricyclohexylphosphane and 9-cyclohexyl-9-phospha-bicyclo[3.3.1]nonane.23. The Ru-carbene complex according to claim 22 , wherein Ar is a furyl or thienyl radical.24. The Ru-carbene complex according to claim 21 , wherein L is a heterocyclic carbene and L′ is selected from the group consisting of triphenylphosphane claim 21 , triisopropylphosphane claim 21 , tricyclohexylphosphane and 9-cyclohexyl-9-phospha-bicyclo[3.3.1]nonane.25. The Ru-carbene complex according to claim 24 , wherein Ar is a furyl or thienyl radical. This application is a Division of application ...

PROCESS FOR PREPARING A PROPIOLIC ACID OR A DERIVATIVE THEREOF

The invention relates to a process for preparing a propiolic acid or a derivative thereof by reacting a terminal alkyne with carbon dioxide, which comprises performing the reaction in the presence of a base and a copper complex, especially a copper (I) complex having at least one ligand, at least one of the ligands of the copper complex being selected from monodentate ligands which have an aminic or iminic nitrogen atom capable of coordination with copper, and polydentate ligands having at least two atoms or atom groups which are capable of simultaneous coordination with copper and are selected from nitrogen, oxygen, sulfur, phosphorus and carbene carbon. 1: A process for preparing a propiolic acid or a derivative thereof , the process comprising:reacting a terminal alkyne with carbon dioxide in the presence of a base and a copper complex comprising a ligand, whereinthe ligand is a monodentate ligand or a polydentate ligandthe monodentate ligand comprises an amine or imine nitrogen atom, and is capable of coordinating to copper,the polydentate ligand comprises at least two atoms or atom groups, which are capable of coordinating simultaneously to copper, andthe atoms or atom groups are at least one selected from the group consisting of nitrogen, oxygen, sulfur, phosphorus and carbene carbon.2: The process according to claim 1 , wherein the terminal alkyne is a compound of formula:{'br': None, 'sup': 'x', 'R—C≡C—H,'}wherein{'sup': x', 'x1', 'x3', 'x3', 'x4', 'x4', 'x4', 'x4', 'x2, 'sub': '3', 'Ris selected from the group consisting of a hydrogen, a COOR, an alkyl optionally substituted by one or more substituents R, an alkenyl optionally substituted by one or more substituents R, a cycloalkyl optionally substituted by one or more substituents R, a heterocycloalkyl optionally substituted by one or more substituents R, an aryl optionally substituted by one or more substituents R, a hetaryl optionally substituted by one or more substituents R, and a (R)Si,'}{'sup': x1', ...

CYCLOPROPENYLIDENE-STABILIZED PHOSPHENIUM CATIONS

Phosphenium compounds with the general formula I: 2. The phosphenium compound as claimed in claim 1 , wherein R claim 1 , R claim 1 , Rand R claim 1 , each independently of one another claim 1 , are chosen from isopropyl and tert-butyl.3. The phosphenium compound as claimed in wherein Xis chosen from BF claim 1 , PF claim 1 , SbFand/or BPh.5. The process as claimed in claim 4 , wherein X represents chlorine.6. A metal complex comprising the phosphenium compound with the general formula I as claimed in as a ligand.8. The metal complex as claimed in claim 7 , wherein the ligands L are chosen from halogen claim 7 , CN claim 7 , CO claim 7 , alkenes claim 7 , cycloalkenes and/or alkynes.9. The metal complex as claimed in claim 7 , wherein MLrepresents AuCl claim 7 , AuCl claim 7 , PdCl(allyl) claim 7 , RhCl(cod) claim 7 , RhCl(CO) claim 7 , CuCl claim 7 , RhCland/or BH.10. A cycloisomerization reaction catalyzed by the metal complex as claimed in . The present invention relates to novel stabilized cyclopropenylylidene cations and their use as ligands in metal catalysts.Phosphenium cations of the general formula [RP:]are isolobal with singlet carbenes and can be stabilized, for example, by donation of electron density in their empty orbital. This stabilization can, for example, be achieved by incorporation of the phosphorus atom in a heterocyclic backbone A or by reaction with bases with the formation of the corresponding Lewis adduct B (scheme 1).In both cases, the presence of a free electron pair on the phosphorus atom suggests the use of these compounds as ligands, though their intrinsic positive charge results in them being weak a donors and strong Π acceptors. In particular, in the adducts of type B, the resonance structure of Bdominates in the basic structure, if D is a phosphine, so that transition metal complexes, which can be derived from these compounds, are rare. Even in cases in which D is an N-heterocyclic carbene (NHC), the coordination properties of the ...

Synthesis and Characterization of Open Metal Clusters

The present invention is directed to the synthesis of novel stable open metal clusters by selective oxidation of bound ligands. The synthesis comprises, for example, using an amine based oxidant for decarbonylation of specific carbonyl ligands. The synthesis can also comprise further removal of a bound amine group by an acid. The resulting metal cluster contains a coordinatively unsaturated site comprising a carbonyl vacancy. The resulting metal cluster can be used as a catalyst in a variety of chemical transformations. 1. A method for preparing an open metal carbonyl cluster comprising chemically reacting a closed metal carbonyl cluster and an opening agent , with the opening agent reacting with a bound carbonyl group so as to unbind it from the cluster and leave behind a CO-labile ligand on the cluster.2. The method of claim 1 , wherein the opening agent is an oxidant.3. The method of claim 2 , wherein the oxidant is trimethylamine oxide.4. The method of claim 1 , wherein the CO-labile ligand is a nitrogen-containing compound coordinating through nitrogen or an oxygen-containing compound coordinating through oxygen.5. The method of claim 1 , wherein the CO-labile ligand is an ether claim 1 , amine claim 1 , dioxygen or nitrogen.6. The method of claim 1 , wherein the open metal carbonyl cluster obtained comprises CO-labile ligands or vacant CO sites.7. The method of claim 1 , wherein the closed metal carbonyl cluster is an Ircarbonyl cluster.8. The method of claim 1 , wherein the closed metal carbonyl cluster is bound with three sterically protective ligands.9. The method of claim 8 , wherein the ligands are calixarene phosphine ligands.10. The method of claim 1 , wherein the closed metal carbonyl cluster is an Ircarbonyl cluster bound with three calixarene phosphine ligands claim 1 , and the opening agent is trimethylamine oxide.11. The method of claim 6 , wherein the open metal carbonyl cluster prepared comprises CO-labile ligands in vacated CO sites.12. The ...

MARKOVNIKOV-SELECTIVE PALLADIUM CATALYST FOR CARBONYLATION OF ALKYNES WITH HETEROARENES

Markovnikov-selective palladium catalyst for carbonylation of alkynes with heteroarenes. 2. Use of a compound according to claim 1 ,for catalysing a carbonylation reaction.3. A process comprising the following process steps:a) initially charging an alkyne,{'claim-ref': {'@idref': 'CLM-00001', 'claim 1'}, 'b) adding a compound according to and a substance including Pd,'}c) feeding in N-methylpyrrole and CO,d) heating the reaction mixture, with conversion of the alkyne to the product. The invention relates to Markovnikov-selective palladium catalyst for carbonylation of alkynes with heteroarenes.The development of ligands plays a key role and provides significant innovations in homogenous catalysis and organic synthesis. Illustrative examples include polymerizations, organometallic coupling reactions, carbonylations, hydrogenations and metathesis. Although a plethora of nitrogen- and phosphorous-based ligands have been developed over the last decades, their rational design to afford highly active catalyst systems, which can easily be prepared and modified, continues to be an important topic in this area.Among the privileged ligand classes known, especially bi- and multidentate derivatives create highly stable and selective organometallic complexes.The problem addressed by the invention was that of providing a compound which is to have good properties as ligands in palladium catalyst for carbonylation of alkynes and reaches a good result regarding the yield of the carbonylation reaction.The problem is solved by a compound according to claim ,Compound having the structure (1):Additionally claimed is the use of the compound as ligand in a ligand-metal complex for catalysis of a carbonylation reaction.Use of a compound described above in a ligand-metal complex for catalysis of a carbonylation reaction.The process in which the compound is used as ligand in a ligand-metal complex for conversion of an olefin to an aldehyde is likewise claimed.A process comprising the ...

CATALYTIC COMPOSITION COMPRISING NICKEL, A PHOSPHINE-TYPE LIGAND AND A LEWIS BASE, AND USE THEREOF IN AN OLEFIN OLIGOMERISATION METHOD

The invention concerns a catalytic composition comprising: at least one nickel precursor with an oxidation number of (+II), at least one phosphine ligand with formula PRRRin which the groups R, Rand R, which may be identical or different and which may or may not be bonded together, and at least one Lewis base, said composition having a molar ratio of the phosphine ligand to the nickel precursor of less than or equal to 5 and a molar ratio of the Lewis base and phosphine ligand together to the nickel precursor of greater than or equal to 5. 1. A catalytic composition comprising:at least one nickel precursor with an oxidation number of (+II),{'sup': 1', '2', '3', '1', '2', '3, 'claim-text': 'aromatic groups which may or may not be substituted and which may or may not contain heteroelements,', 'at least one phosphine ligand with formula PRRRin which the groups R, Rand R, which may be identical or different, and which may or may not be bonded together, are selected from'}and/or from hydrocarbyl groups, which may or may not be cyclic, which may or may not be substituted and which may or may not contain heteroelements,and at least one Lewis base,said composition having a molar ratio of the phosphine ligand to the nickel precursor of less than or equal to 5 and a molar ratio of the Lewis base and phosphine ligand together to the nickel precursor of greater than or equal to 5.2. The composition as claimed in claim 1 , in which the molar ratio of the phosphine ligand to the nickel precursor is in the range 2 and 5.3. The composition as claimed in claim 1 , in which the nickel precursor is selected from nickel(II) chloride; nickel(II) (dimethoxyethane) chloride;nickel(II) bromide; nickel(II) (dimethoxyethane) bromide; nickel(II) fluoride; nickel(II) iodide; nickel(II) sulphate; nickel(II) carbonate; nickel(II) dimethylglyoxime; nickel(II) hydroxide; nickel(II) hydroxyacetate; nickel(II) oxalate; nickel(II) carboxylates selected from the group formed by nickel(II) 2- ...

PROCESS OF PRODUCTION OF 2,5-DIMETHYLPHENOL

The present invention relates to a new method to produce 2,5-dimethylphenol (2,5-DMP). 2. Process according to claim 1 , wherein the catalyst is an Au(I) complex.6. A process according claim 3 , wherein the Au(I) complex is added to reaction mixture as such.7. Process according to claim 3 , wherein the Au(I) complex is formed in situ in the reaction mixture.8. Process according to claim 1 , wherein the substrate to catalyst ratio is 2:1 to 10000:1 claim 1 , preferably are 10:1 to 3000:1 The present invention relates to a new method to produce 2,5-dimethylphenol (2,5-DMP).2,5-dimethylphenol, which is also called 2,5 xylenol, can be used for example as an intermediate in the production of vitamin E.Xylenols are organic compounds with the formula (I)They are volatile colorless solids or oily liquids. They are derivatives of phenol with two methyl groups and a hydroxyl group. Six isomers are existing.Together with many other compounds, xylenols are traditionally extracted from coal tar, the volatile materials obtained in the production of coke from coal. These residues contain a few percent by weight of xylenols as well as cresols and phenol.Together with cresols and cresylic acid, xylenols are an important class of phenolics with great industrial importance. They are used in the manufacture of antioxidants. Xylenol orange is a redox indicator built on a xylenol skeleton. 2,5-DMP, which is the compound of formula (Ia)is an intermediate in the production of the 2,3,6-trimethylphenol (2,3,6-TMP) which is the compound of formula (II)2,3,6-TMP is usually produced by a gasphase methylation of 2,5-DMP.2,3,6-TMP can be used as such (for example in cosmetic formulations) as well as intermediate in the production of other organic compounds, such as for example vitamin E.Due to fact that of 2,5-DMP is obtained from not renewable resources, an alternative, more sustainable production of 2,5-DMP is desirable.We now found a new way for the production of 2,5-DMP, which is carried out ...

ALKANE DEHYDROGENATION PROCESS

Disclosed herein are processes for dehydrogenation of an alkane to an alkene using an iridium pincer complex. In the dehydrogenation reactions, hydrogen that is co-formed during the process must be removed for the chemical reaction to proceed and to prevent the excess hydrogen from poisoning the catalyst. In one embodiment the process comprises providing an alkane feedstock comprising at least one alkane and contacting the alkane with an iridium pincer complex in the presence of a hydrogen acceptor selected from the group consisting of ethylene, propene, or mixtures to form an alkene product. The processes disclosed herein can accomplish facile, low-temperature transfer dehydrogenation of alkanes with unprecedented selectivities and TONs at a reasonable rate of conversion. 1. A process for preparing alpha-olefins from an at least one alkane , comprising the steps of:providing an alkane feedstock in a gaseous phase comprising the at least one alkane;contacting the at least one alkane in the gaseous phase with an iridium pincer complex in the presence of a gaseous hydrogen acceptor selected from the group consisting of ethylene, propene, and mixtures thereof; andrecovering an alpha-olefin product.2. The process of claim 1 , wherein the at least one alkane in the gaseous phase is selected from the group consisting of a butane claim 1 , a pentane claim 1 , an octane claim 1 , a nonane claim 1 , a decane claim 1 , a dodecane claim 1 , and mixtures thereof.5. The process of claim 1 , wherein the iridium pincer complex is (PCP)Ir(CH) or (p-OK-PCP)Ir(CH).6. The process of claim 1 , wherein the iridium pincer complex is unsupported.7. The process of claim 1 , wherein the iridium pincer complex is immobilized on a solid support.8. The process of claim 7 , wherein the solid support is selected from the group consisting of a silica claim 7 , a γ-alumina claim 7 , a basic alumina claim 7 , a florisil claim 7 , and a neutral alumina.9. The process of claim 8 , wherein the solid ...

METHOD FOR REDUCTION OF ORGANIC MOLECULES

A method for the reduction organic molecules comprising a Ruthenium-Triphosphine complex with aromatic ligands at the phosphors which are ortho or meta substituted. 1. A method for the reduction of organic molecules , comprising the step ofa) hydrogenating at least one organic molecule in the presence of a Ruthenium-Triphosphine-complex whereby the triphosphine-complex comprises at least one aryl and/or heteroaryl moeity bound to a phosphine which is substituted in ortho and/or meta position to the phosphine.2. The method according to claim 1 , wherein the Ruthenium-Triphosphine-complex comprises a phosphororganic compound where two or all three phosphors have an aryl and/or heteroaryl moeity which is substituted in ortho and/or meta position to the phosphine bound thereto.4. The method according to claim 1 , wherein step a) is performed under acidic conditions.5. The method according to claim 1 , wherein step a) is performed under acidic conditions whereby the (initial) concentration of acid is ≧0.5 to ≦20 times the concentration of Ruthenium (in mol:mol).6. The method according to claim 5 , wherein step a) is performed under acidic conditions whereby the acid is selected out of the group comprising sulfonic acids claim 5 , especially methanesulfonic acid claim 5 , trifluormethansulfonic acid claim 5 , p-toluolsulfonic acid claim 5 , p-bromobenzosulfonic acid claim 5 , p-nitrobenzosulfonic acid claim 5 , sulfuric acid claim 5 , hydrochloric acid claim 5 , hydrofluoric acid claim 5 , trifluoracetic acid claim 5 , perchloric acid claim 5 , bis(trifluoromethane)sulfonimide or mixtures thereof7. The method according to claim claim 5 , wherein step a) is carried out at an initial hydrogen pressure of ≧1 bar.8. The method according to claim 1 , wherein step a) is carried out in a dipolar protic or aprotic solvent or in CO The present invention relates to a method for reducing organic molecules, especially by using Ruthenium-Triphosphine-complexes.In the prior art, e.g. ...

METHOD FOR PRODUCING HYDROGEN GAS FROM FORMIC ACID

A method for producing A hydrogen gas from formic acid, characterized in that at least one heterogeneous catalyst is used to transform the formic acid into hydrogen gas. The at least one heterogeneous catalyst contains heterogenised ruthenium. According to a first aspect of the invention, the at least one heterogeneous catalyst contains at least one hydrophilic phosphine ligand which is m-TPPTS (meta-trisulfonated triphenylphosphine). The at least one heterogeneous catalyst is preferably obtained by mixing an aqueous solution of RuClwith hydrophilic phosphine, firstly activated by carrying out a homogeneous reaction with formic acid and by adding at least one solid structure. 113-. (canceled)14. A method of producing hydrogen gas from formic acid , the method comprising:using at least one heterogeneous catalyst to transform formic acid to hydrogen gas.15. The method according to claim 14 , further comprising the at least one heterogeneous catalyst containing heterogenised ruthenium.16. The method according to claim 14 , further comprising the at least one heterogeneous catalyst containing at least one hydrophilic phosphine ligand.17. The method according to claim 16 , further comprising using m-TPPTS (meta-trisulfonated triphenylphosphine) as the at least one hydrophilic phosphine ligand.18. The method according to claim 14 , further comprising obtaining the at least one heterogeneous catalyst by mixing an aqueous solution of RuClwith hydrophilic phosphine claim 14 , firstly activated by carrying out a homogeneous reaction with formic acid and by adding at least one solid structure.19. The method according to claim 14 , further comprising the at least one heterogeneous catalyst containing silica modified with phosphine ligands.20. The method according to claim 19 , further comprising preparing linkers from parent bromoalkenes and coupled with PPhnucleophile and the ligand is covalently bonded to the silica surface and the ruthenium phosphine complex is anchored in a ...

Synthesis of (S)-6-Hydroxytryptophan and Derivatives Thereof

The present invention relates to novel methods and compounds for synthesizing amanitin derivatives. The invention in particular relates to methods for synthesizing (S)-6-hydroxy-tryptophan derivatives which can be used as building blocks for synthesizing amanitin derivatives or amatoxin drug conjugates. The invention further relates to intermediate compounds of said synthesis pathways for use in amanitin derivative and amatoxin drug conjugate synthesis, and to the use of particular catalysts suited for mediating said synthesis pathways.

PROCESS FOR THE CARBONYLATION OF ETHYLENICALLY UNSATURATED COMPOUNDS, NOVEL CARBONYLATION LIGANDS AND CATALYST SYSTEMS INCORPORATING SUCH LIGANDS

A novel bidentate ligand of general formula (I) 2. A process for the carbonylation of ethylenically unsaturated compounds comprising reacting said compound with carbon monoxide in the presence of a source of hydroxyl groups , optionally , a source of anions and of a catalyst system , the catalyst system obtainable by combining:(a) a metal of Group 8, 9 or 10 of the Periodic Table or a compound thereof; and{'claim-ref': {'@idref': 'CLM-00001', 'claim 1'}, '(b) the bidentate ligand of formula (I) according to'}3. The bidentate ligand according to claim 1 , wherein the group Xis selected from a cyclic structure which is unsaturated claim 1 , saturated or part unsaturated.4. The bidentate ligand according to claim 3 , wherein the group Xis selected from a cyclic structure which is unsaturated.5. The bidentate ligand according to claim 4 , wherein the groups Xis aromatic.6. The bidentate ligand according to claim 1 , wherein the group Xis selected from an aromatic nitrogen heterocycle having 3-14 ring atoms.7. The bidentate ligand according to claim 1 , wherein the group Xis selected from an aziridine claim 1 , azirine claim 1 , azetidine claim 1 , azete claim 1 , pyrrolidone claim 1 , pyrrole claim 1 , pyridine claim 1 , piperidine claim 1 , azepane claim 1 , azepine claim 1 , azocane claim 1 , azocine imidazolidine claim 1 , pyrazolidine claim 1 , imidazole claim 1 , benzimidazole claim 1 , imidazoline claim 1 , pyrazole claim 1 , indazole claim 1 , pyrazoline claim 1 , pyrazine claim 1 , pyrimidine claim 1 , pyridazine claim 1 , piperazine claim 1 , hexahydro-pyrimidine claim 1 , hexahydro-pyridazine claim 1 , indole claim 1 , isoindole claim 1 , quinoline claim 1 , isoquinoline claim 1 , quinazoline claim 1 , benzopyrazine claim 1 , acridine or benzoquinoline radical.8. The bidentate ligand according to claim 1 , wherein the group Xis an alkyl amine claim 1 , aryl amine claim 1 , dialkylamine claim 1 , or trialkyl amine radical.9. The bidentate ligand according to ...

ETHYLENE TETRAMERIZATION CATALYST SYSTEM AND METHOD FOR PREPARING 1-OCTENE USING THE SAME

Disclosed herein is a method of preparing 1-octene at high activity and high selectivity while stably maintaining reaction activity by tetramerizing ethylene using a chromium-based catalyst system comprising a transition metal or a transition metal precursor, a cocatalyst, and a P—C—C—P backbone structure ligand represented by (R)(R)P—(R)CHCH(R)—P(R)(R). 110.-. (canceled)12. The method of preparing 1-hexene by trimerizing ethylene of claim 11 , wherein the method is operated at a temperature of −20˜250° C.13. The method of preparing 1-hexene by trimerizing ethylene of claim 11 , wherein the method is operated at a temperature of 15˜130° C.14. The method of preparing 1-hexene by trimerizing ethylene of claim 11 , wherein the method is operated at a temperature of 30˜70° C.15. The method of preparing 1-hexene by trimerizing ethylene of claim 11 , wherein the method is operated at a pressure of atmospheric pressure to 500 bar.16. The method of preparing 1-hexene by trimerizing ethylene of claim 11 , wherein the method is operated at a pressure of 10-70 bar.17. The method of preparing 1-hexene by trimerizing ethylene of claim 11 , wherein the method is operated at a pressure of 30-50 bar.18. The method of preparing 1-hexene by trimerizing ethylene of claim 11 , wherein the method is operated using inactive solvent selected from saturated aliphatic hydrocarbons claim 11 , unsaturated aliphatic hydrocarbons claim 11 , aromatic hydrocarbons claim 11 , halogenated hydrocarbons claim 11 , or a combination thereof.19. The method of preparing 1-hexene by trimerizing ethylene of claim 11 , wherein the inactive solvent selected from benzene claim 11 , toluene claim 11 , xylene claim 11 , cumene claim 11 , heptanes claim 11 , cyclohexane claim 11 , methylcyclohexane claim 11 , methylcyclopentane claim 11 , n-hexane claim 11 , 1-hexene or a combination thereof.20. The method of preparing 1-hexene by trimerizing ethylene of claim 11 , wherein the aluminum of alkylaluminoxane: ...

Chelating Carbene Ligand Precursors and Their Use in the Synthesis of Metathesis Catalysts

Chelating ligand precursors for the preparation of olefin methathesis catalysts are disclosed. The resulting catalysts are air stable monomeric species capable of promoting various methathesis reactions efficiently, which can be recovered from the reaction mixture and reused. Internal olefin compounds, specifically beta-substituted styrenes, are used as ligand precursors. Compared to terminal olefin compounds such as unsubstituted styrenes, the beta-substituted styrenes are easier and less costly to prepare, and more stable since they are less prone to spontaneous polymerization. Methods of preparing chelating-carbene methathesis catalysts without the use of CuCl are disclosed. This eliminates the need for CuCl by replacing it with organic acids, mineral acids, mild oxidants or even water, resulting in high yields of Hoveyda-type methathesis catalysts. The invention provides an efficient method for preparing chelating-carbene metathesis catalysts by reacting a suitable ruthenium complex in high concentrations of the ligand precursors followed by crystallization from an organic solvent. 2. The chelating carbene complex of claim 1 , wherein the chelating carbene complex is prepared by a method comprising contacting a metathesis-active metal carbene complex of the formula XXLLM=CRRwith a beta-substituted styrene ligand precursor claim 1 , wherein{'sup': 1', '2', '1, 'claim-ref': {'@idref': 'CLM-00001', 'claim 1'}, 'X, X, L, and M are as defined in ;'}{'sup': 2', '1', '2', '1', '2, 'Lis any neutral electron donor, and wherein any of two or three of X, X, L, and Lmay form a multidentate ligand; and'}{'sup': 1', '2', '1', '2, 'Rand Rare each, independently, selected from hydrogen or a substituent selected from the group consisting of alkyl, alkenyl, alkynyl, aryl, alkylcarboxylate, arylcarboxylate, alkoxy, alkenyloxy, alkynyloxy, aryloxy, alkoxycarbonyl, alkylthio, alkylsulfonyl, alkylsulfinyl, or trialkylsilyl, wherein each of the substituents is substituted or ...

Complexes

The present invention provides a complex of formula (1), 2. The complex of claim 1 , wherein M is palladium.3. The complex of claim 1 , wherein Rand Rare tert-butyl.4. The complex of claim 1 , wherein Rand Rare cyclohexyl.5. The complex of claim 4 , wherein Rand Rare phenyl.6. The complex of claim 1 , wherein Rand Rare linked to form a 4- to 7-membered ring.7. The complex of claim 1 , wherein Ris phenyl claim 1 , 2-dimethylaminophenyl claim 1 , 3-dimethylaminophenyl claim 1 , or 4-dimethylaminophenyl.8. The complex of claim 1 , wherein Ris furanyl claim 1 , thiophenyl claim 1 , pyrrolyl claim 1 , pyridinyl claim 1 , or quinolinyl.9. The complex of claim 1 , wherein X is Cl.10. The complex of claim 1 , wherein each Ris independently methyl claim 1 , phenyl claim 1 , or substituted phenyl.12. A method for performing a carbon-carbon coupling reaction or a carbon-nitrogen coupling reaction in the presence of a catalyst claim 1 , the method comprising using a catalyst that is a complex of .13. A method for performing a carbon-carbon coupling reaction or a carbon-nitrogen coupling reaction in the presence of a catalyst claim 2 , the method comprising using a catalyst that is a complex of . This application is a divisional of U.S. patent application Ser. No. 13/806,575, filed Mar. 11, 2013, which is the National Stage of International Patent Application No. PCT/GB2011/051171, filed Jun. 22, 2011, which claims priority from U.S. Provisional Patent Application No. 61/357,744, filed Jun. 23, 2010, the disclosures of each of which are incorporated herein by reference in their entireties for any and all purposes.The present invention relates to transition metal complexes and, in particular, to π-allyl complexes, such as π-allylpalladium and π-allylnickel complexes. The invention also relates to the use of the transition metal complexes in coupling reactions.In many transitions metal mediated reactions, the active catalyst is formed in situ by the additional of a transition ...

Cross-Coupling Reaction Catalysts, and Methods of Making and Using Same

The present invention provides novel transition-metal precatalysts that are useful in preparing active coupling catalysts. In certain embodiments, the precatalysts of the invention are air-stable and moisture-stable. The present invention further provides methods of making and using the precatalysts of the invention. 2. The precatalyst of claim 1 , wherein each occurrence of M is independently selected from the group consisting of Pd claim 1 , Ni claim 1 , and Pt.3. The precatalyst of claim 1 , wherein at least one applies:(a) the two occurrences of M in (I) are identical;(b) the two ligands comprising 5-membered rings are identical;(c) each occurrence of Z is independently selected from the group consisting of CH and CR.46-. (canceled)7. The precatalyst of claim 1 , wherein each occurrence of X is independently selected from the group consisting of triflate claim 1 , pentafluoroethanesulfonate claim 1 , heptafluoropropanesulfonate claim 1 , and nonafluorobutanesulfonate.8. (canceled)11. The precatalyst of claim 9 , wherein M is selected from the group consisting of Pd claim 9 , Ni claim 9 , and Pt.12. (canceled)13. The precatalyst of claim 9 , wherein each occurrence of Z is independently selected from the group consisting of CH and CR.14. The precatalyst of claim 9 , wherein X is selected from the group consisting of triflate claim 9 , pentafluoroethanesulfonate claim 9 , heptafluoropropanesulfonate claim 9 , and nonafluorobutanesulfonate.15. (canceled)16. The precatalyst of claim 9 ,wherein L is selected from the group consisting of 1,3-bis(2,6-diisopropyl phenyl)-1,3-dihydro-2H-imidazol-2-ylidene and 1,3-bis(2,6-bis-(diphenylmethyl)-4-methoxyphenyl)imidazol-2-ylidene, orwherein L is a bidentate phosphine ligand.17. (canceled)18. The precatalyst of claim 16 , wherein L is a bidentate phosphine ligand selected from the group consisting of AmPhos (di-t-butylphosphino-4-dimethylaminobenzene) claim 16 , DavePhos (2-dicyclohexylphosphino-2′-(N claim 16 ,N- ...

BENZENE-BASED DIPHOSPHINE LIGANDS FOR ALKOXYCARBONYLATION

The invention relates to compounds of formula (I) 3. Compound according to claim 1 ,{'sup': 1', '2', '3', '4, 'sub': 3', '20, 'where at least two of the R, R, R, Rradicals are a —(C-C)-heteroaryl radical.'}4. Compound according to claim 1 ,{'sup': 1', '3, 'sub': 3', '20, 'where the Rand Rradicals are each a —(C-C)-heteroaryl radical.'}5. Compound according to claim 1 ,{'sup': 1', '3, 'sub': 3', '20, 'where the Rand Rradicals are each a —(C-C)-heteroaryl radical;'}{'sup': 2', '4, 'sub': 1', '12', '3', '12', '3', '12', '6', '20, 'and Rand Rare each independently selected from —(C-C)-alkyl, —(C-C)-cycloalkyl, —(C-C)-heterocycloalkyl, —(C-C)-aryl.'}6. Compound according to claim 1 ,{'sup': 1', '3, 'sub': 3', '20, 'where the Rand Rradicals are each a —(C-C)-heteroaryl radical;'}{'sup': 2', '4, 'sub': 1', '12, 'and Rand Rare each independently selected from —(C-C)-alkyl.'}7. Compound according to claim 1 ,{'sup': 1', '2', '3', '4, 'where R, R, R, R, if they are a heteroaryl radical, are each independently selected from furyl, thienyl, pyrrolyl, oxazolyl, isoxazolyl, thiazolyl, isothiazolyl, imidazolyl, pyrazolyl, furazanyl, tetrazolyl, pyridyl, pyridazinyl, pyrimidyl, pyrazinyl, benzofuranyl, indolyl, isoindolyl, benzimidazolyl, quinolyl, isoquinolyl.'}9. Complex comprising Pd and a compound according to .11. Process according to claim 10 ,wherein the ethylenically unsaturated compound comprises 2 to 30 carbon atoms and optionally one or more functional groups selected from carboxyl, thiocarboxyl, sulpho, sulphinyl, carboxylic anhydride, imide, carboxylic ester, sulphonic ester, carbamoyl, sulphamoyl, cyano, carbonyl, carbonothioyl, hydroxyl, sulphhydryl, amino, ether, thioether, aryl, heteroaryl or silyl groups and/or halogen substituents.12. Process according to claim 10 ,wherein the ethylenically unsaturated compound is selected from ethene, propene, 1-butene, cis- and/or trans-2-butene, isobutene, 1,3-butadiene, 1-pentene, cis- and/or trans-2-pentene, 2-methyl-1- ...

PALLADIUM CATALYSTS WITH IMPROVED PERFORMANCE IN BIOLOGICAL ENVIRONMENTS

Provided herein are palladium (Pd) catalysts with improved performance in biological environments. In particular, formulations, methods of preparations, and storage conditions are provided that provide improved performance of Pd catalysts under protein-rich conditions. 1. A Pd catalyst composition comprising phosphine-coordinated palladium ions , wherein phosphine ligand is present at 6-12 fold excess over palladium in the composition.2. The Pd catalyst composition of claim 1 , wherein the phosphine ligand is a strong π-acceptor aryl phosphine.3. (canceled)4. The Pd catalyst composition of claim 3 , wherein the phosphine ligand is selected from the group consisting of DANPHOS claim 3 , o-DANPHOS claim 3 , p-DANPHOS claim 3 , DAN2PHOS claim 3 , o-DAN2PHOS p-DAN2PHOS claim 3 , and DANPHOS/DAN2PHOS derivatives with alternative solubilizing groups.5. The Pd catalyst composition of claim 4 , wherein the phosphine ligand is o-DANPHOS.6. The Pd catalyst composition of claim 1 , wherein the palladium is provided as a Palladium(II) salt selected from the group consisting of: Palladium acetate (Pd(OAc)) claim 1 , Palladium trifluoroacetate (Pd(TFA)) claim 1 , Palladium nitrate (Pd(NO)) claim 1 , Palladium chloride (PdCl) claim 1 , Palladium bromide (PdBr) claim 1 , Sodium tetrachloropalladate (NaPdCl) claim 1 , Potassium tetrachloropalladate (KPdCl) claim 1 , Lithium tetrachloropalladate (LiPdCl) claim 1 , Sodium tetrabromopalladate (NaPdBr) claim 1 , Potassium tetrabromopalladate (KPdBr) claim 1 , Pd(dibenzylideneacetone) claim 1 , Pd(dibenzylideneacetone) claim 1 , and Buchwald precatalysts.7. The Pd catalyst composition of claim 1 , wherein the phosphine-coordinated palladium ions are in aqueous solution.8. The Pd catalyst composition of claim 1 , wherein the phosphine-coordinated palladium ions are lyophilized.910.-. (canceled)11. A method for the preparation of a Pd catalyst claim 1 , comprising combining a palladium(II) salt with a phosphine ligand in buffered or un- ...

PROCESS FOR THE CATALYTIC REVERSIBLE ALKENE-NITRILE INTERCONVERSION

The present invention refers to processes for catalytic reversible alkene-nitrile interconversion through controllable HCN-free transfer hydrocyanation. 2. Process according to claim 1 , wherein R claim 1 , R claim 1 , Rand Rcan be the same or different and each independently represents H claim 1 , aryl claim 1 , aralkyl claim 1 , heteroaryl claim 1 , heteroaralkyl claim 1 , each being optionally substituted by one or more groups selected from straight chain or branched chain alkyl claim 1 , cycloalkyl claim 1 , heterocycloalkyl claim 1 , alkenyl claim 1 , alkynyl claim 1 , aryl claim 1 , aralkyl claim 1 , heteroaryl claim 1 , heteroaralkyl or a heterosubstituent claim 1 , or a heterosubstituent claim 1 , or Rand Rform a bond; wherein at least one of R claim 1 , R claim 1 , Rand Ris not hydrogen.3. Process according to claim 1 , wherein R claim 1 , R claim 1 , Rand Rcan be the same or different and each independently represents H claim 1 , straight chain or branched chain alkyl claim 1 , cycloalkyl claim 1 , heterocycloalkyl claim 1 , each being optionally substituted by one or more groups selected from straight chain or branched chain alkyl claim 1 , cycloalkyl claim 1 , heterocycloalkyl claim 1 , alkenyl claim 1 , alkynyl claim 1 , aryl claim 1 , aralkyl claim 1 , heteroaryl claim 1 , heteroaralkyl or a heterosubstituent claim 1 , or a heterosubstituent claim 1 , or at least two of R claim 1 , R claim 1 , Rand Rmay each form a cyclic 3 to 20 membered hydrocarbon ring structure which may further be substituted by one or more groups selected from alkyl claim 1 , cycloalkyl claim 1 , heterocycloalkyl claim 1 , aryl claim 1 , heteroaryl or heterosubstituent claim 1 , and optionally having any of O claim 1 , S claim 1 , N in the straight chain claim 1 , branched chain or cyclic structure claim 1 , wherein optionally at least one of R claim 1 , R claim 1 , Rand Ris not hydrogen.4. Process according to claim 3 , wherein R claim 3 , R claim 3 , Rand Rcan be the same or ...

SYNTHESIS AND CHARACTERIZATION OF RU ALKYLIDENE COMPLEXES

This invention relates generally to olefin metathesis catalyst compounds, to the preparation of such compounds, compositions comprising such compounds, methods of using such compounds, articles of manufacture comprising such compounds, and the use of such compounds in the metathesis of olefins and olefin compounds. The invention has utility in the fields of catalysts, organic synthesis, polymer chemistry, and industrial and fine chemicals industry. 8. The olefin metathesis catalyst according to claim 7 , wherein{'sup': '1', 'Xis Cl;'}{'sup': '2', 'Xis Cl;'}{'sup': '1', 'Ris morpholino, thiomorpholino, 1-methyl-piperazino, piperidino, N-acetyl-piperazino, di-benzyl-amino, N-ethylcarboxylate-piperazino, diethylamino, methyl-phenylamino, or di-iso-propylamino;'}{'sup': '2', 'Ris phenyl, morpholino, thiomorpholino, 1-methyl-piperazino, piperidino, N-acetyl-piperazino, di-benzyl-amino, N-ethylcarboxylate-piperazino, diethylamino, methyl-phenylamino, or di-iso-propylamino; and'}{'sup': '3', 'Ris phenyl or morpholino.'}11. The method according to claim 10 , wherein:{'sup': '1', 'Xis Cl;'}{'sup': '2', 'Xis Cl;'}{'sup': '1', 'Ris morpholino, thiomorpholino, 1-methyl-piperazino, piperidino, N-acetyl-piperazino, di-benzyl-amino, N-ethylcarboxylate-piperazino, diethylamino, methyl-phenylamino, or di-iso-propylamino;'}{'sup': '2', 'Ris phenyl, morpholino, thiomorpholino, 1-methyl-piperazino, piperidino, N-acetyl-piperazino, di-benzyl-amino, N-ethylcarboxylate-piperazino, diethylamino, methyl-phenylamino, or di-iso-propylamino; and'}{'sup': '3', 'Ris phenyl or morpholino'}{'sup': '5', 'Ris 2,4,6-trimethylphenyl;'}{'sup': '6', 'Ris 2,4,6-trimethylphenyl;'}{'sup': 'd', 'Ris phenyl;'}{'sup': 'e', 'Ris phenyl; and'}{'sup': 'f', 'Ris phenyl, methyl, p-(OMe)phenyl, or iso-propyl.'}13. The method according to claim 12 , wherein:{'sup': '1', 'Ris morpholino, thiomorpholino, 1-methyl-piperazino, piperidino, N-acetyl-piperazino, di-benzyl-amino, N-ethylcarboxylate-piperazino, diethylamino, ...

HOMOGENEOUS IRON CATALYSTS FOR THE CONVERSION OF METHANOL TO METHYL FORMATE AND HYDROGEN

Iron-based homogeneous catalysts, supported by pincer ligands, are employed in the catalytic dehydrocoupling of methanol to produce methyl formate and hydrogen. As both methanol and methyl formate are volatile materials, they can be readily separated from the catalyst by applying vacuum at room temperature. The hydrogen by-product of the reaction may be isolated and utilized as a feedstock in other chemical transformations. 4. The process according to claim 1 , wherein one or more of R claim 1 , R claim 1 , R claim 1 , and Rare substituted with one or more groups selected from ethers claim 1 , esters claim 1 , and amides.5. The process to claim 1 , wherein R claim 1 , R claim 1 , R claim 1 , and Rare each independently a methyl claim 1 , ethyl claim 1 , propyl claim 1 , isopropyl claim 1 , butyl claim 1 , pentyl claim 1 , isopentyl claim 1 , cyclopentyl claim 1 , hexyl claim 1 , cyclohexyl claim 1 , or phenyl group.6. The process according to claim 5 , wherein each of R claim 5 , R claim 5 , R claim 5 , and Ris isopropyl.7. The process according to claim 5 , wherein each of R claim 5 , R claim 5 , R claim 5 , and Ris phenyl.8. The process according to claim 1 , wherein each of Rand Ris —(CHCH)—.9. The process according to claim 1 , wherein E is phosphorus.10. The process according to claim 1 , wherein L is carbon monoxide claim 1 , a phosphine claim 1 , an amine claim 1 , a nitrile claim 1 , or an N-containing heterocyclic ligand.11. The process according to claim 2 , wherein Lis an ether claim 2 , an ester claim 2 , an amide claim 2 , a nitrile claim 2 , or an N-containing heterocyclic ligand.12. The process according to claim 1 , wherein the contacting step is conducted at a temperature of 40 to 160° C.13. The process according to claim 1 , wherein the contacting step is conducted in the presence of a solvent.14. The process according to claim 1 , wherein the contacting step is conducted in the absence of a solvent.15. The process according to claim 1 , wherein ...

2,3-BISPHOSPHINOPYRAZINE DERIVATIVE, METHOD FOR PRODUCING SAME, TRANSITION METAL COMPLEX, ASYMMETRIC CATALYST, AND METHOD FOR PRODUCING ORGANIC BORON COMPOUND

Provided is a 2,3-bisphosphinopyrazine derivative represented by the following general formula (1), wherein R, R, R, and Rrepresent an optionally substituted straight-chain or branched alkyl group having 1 to 10 carbon atoms, an optionally substituted cycloalkyl group, an optionally substituted adamantyl group, or an optionally substituted phenyl group, Rrepresents an optionally substituted alkyl group having 1 to 10 carbon atoms or an optionally substituted phenyl group, each Rmay be the same group or a different group, Rrepresents a monovalent substituent, n denotes an integer of 0 to 2. An optically active form of the 2 ,3-bisphosphinopyrazine derivative represented by general formula (1).5. The optically active form of the 2 claim 3 ,3-bisphosphinopyrazine derivative according to claim 3 , wherein Rand Rin the formula of general formula (2) are a combination of groups of the following (i) or (ii):{'sup': 1', '2, 'Rand Rare a combination of a tert-butyl group and a methyl group;'}{'sup': 1', '2, 'Rand Rare a combination of an adamantyl group and a methyl group;'}{'sup': 1', '2, 'Rand Rare a combination of a 1,1,3,3-tetramethylbutyl group and a methyl group.'}6. The optically active form of the 2 claim 4 ,3-bisphosphinopyrazine derivative according to claim 4 , wherein R claim 4 , R claim 4 , and Rin the formula of general formula (3) are a combination of groups of any of the following (1) to (9):{'sup': 1', '3', '4, '(1) Ris a tert-butyl group, and Rand Rare a combination of a tert-butyl group and a methyl group;'}{'sup': 1', '3', '4, '(2) Ris a tert-butyl group, and Rand Rare a combination of a 1,1,3,3-tetramethylbutyl group and a methyl group;'}{'sup': 1', '3', '4, '(3) Ris a tert-butyl group, and Rand Rare a combination of an adamantyl group and a methyl group;'}{'sup': 1', '3', '4, '(4) Ris an adamantyl group, and Rand Rare a combination of a tert-butyl group and a methyl group;'}{'sup': 1', '3', '4, '(5) Ris an adamantyl group, and Rand Rare a combination of ...

Materials and methods for immobilization of catalysts on surfaces and for selective electroless metallization

A method of rendering a substrate catalytic to electroless metal deposition comprising the steps of: (a) depositing a ligating chemical agent on the substrate, which is capable of both binding to the substrate and ligating to an electroless plating catalyst; and (b) ligating the electroless plating catalyst to the ligating chemical agent, wherein the ligating chemical agent has the chemical structure: wherein n and m are each between about 1 and about 100.

PROCESS FOR THE DIASTEREOSELECTIVE PREPARATION OF RUTHENIUM COMPLEXES

The present invention relates to a process for the preparation of a compound of formula (I), wherein X is —CH—, —CH—CH—, —CH—CH—CH— or —CH—CH—CH—CH—; Yis —CH—; —CH2—CH— or —NH—; Yis NHR, or SH; wherein Ris hydrogen, C-Calkyl or phenyl; R—and R, independently from each other, represent aliphatic or aromatic groups; Rand R, independently from each other, represent aliphatic or aromatic groups; Rand Rare each hydrogen or represent together with the carbon atoms to which they are bonded, a phenyl ring; which process comprises reacting a compound of formula II [RuCI(R)n]m (II), wherein n is 1 and m is >1 which represents a polymeric structure if Ris a molecule containing two alkene or alkyne moieties coordinating in an hapto-2 coordination mode to the metal; or n is 4 and m is 1 if Ris a nitrogen, oxygen or sulfur containing molecule in which said nitrogen, oxygen or sulfur coordinate to the metal; in the presence of an inert solvent which boiling point is from 112° C. to 165° C. with a compound of formula (III), wherein R, R, Yand Yare as defmed under formula I, and a phosphane of formula IV R3R4P—X—PRR(iv), wherein R, R, R, Rand X are as defined under formula I. 2. A process according to for the preparation of a compound of formula I claim 1 , wherein{'sub': 2', '2', '2', '2, 'X is —CH—CH—CH—CH—.'}3. A process according to for the preparation of a compound of formula I claim 2 , wherein{'sub': '8', 'Ris cyclooctadiene or bicyclo[2.2.1]hepta-2,5-diene if n is 1 and m >1; or is dimethylsulfoxide if n is 4 and m is 1.'}4. A process according to for the preparation of a compound of formula I claim 2 , wherein{'sub': 1', '2', '3', '4, 'R, R, Rand Rare phenyl and'}{'sub': 5', '6, 'Rand Rare hydrogen or together represent with the carbon atoms to which they are bonded, a phenyl ring;'}{'sub': 1', '2, 'Yis —CH—, and'}{'sub': 2', '2, 'Yis NH.'}6. A process according to performed as a one pot procedure. The present invention relates to a process for the diastereoselective ...

Methods of Activating Metal Complexes for Catalysts

The present invention is directed to the activation of metal carbonyl clusters by an oxidative agent to prepare a stable metal cluster catalyst exhibiting catalytic rate enhancement. The activation comprises, for example, using oxygen for decarbonylation of carbonyl ligands and changing the oxidation state of the other ligands. In one aspect, treatment of the metal cluster catalyst under oxidative conditions in a flow reactor leads to removal of CO ligands and oxidation of bound calixarene phosphine ligands, and results in a stable activated open metal cluster that is more active for ethylene hydrogenation catalysis. The resulting metal cluster contains coordinatively unsaturated sites comprising carbonyl vacancies. In one aspect, the resulting activated open metal cluster can be used as a catalyst in a variety of chemical transformations.

Alkane-Alkene Coupling Via Tandem Alkane-Dehydrogenation/Alkene-Dimerization Catalyzed by Pincer Iridium Catalyst Heterogenized on Solid Supports

Disclosed herein are processes for tandem alkene dehydrogenation/alkene dimerization using an iridium pincer complex catalyst on a support comprising magnesium silicates (e.g., Florisil®). The reaction process comprises providing an iridium pincer complex bound to a solid support comprising magnesium silicates; providing a gaseous alkane feedstock comprising at least one alkane; and contacting the gaseous alkane feedstock with the iridium pincer complex bound to the solid support in the presence of a hydrogen acceptor to form dimerized alkenes. The processes disclosed herein can accomplish facile, low-temperature tandem transfer dehydrogenation of alkanes and dimerization of alkenes with unprecedented TONs at a reasonable rate of conversion. 1. A process for preparing dimerized alkenes in a tandem dehydrogenation/alkene dimerization reaction comprising:providing an iridium pincer complex bound to a solid support comprising magnesium silicates;providing a gaseous alkane feedstock comprising at least one alkane;contacting the gaseous alkane feedstock with the iridium pincer complex bound to the solid support in the presence of a hydrogen acceptor to form the dimerized alkenes; andrecovering the dimerized alkenes as recovered dimerized alkenes.2. The process of claim 1 , wherein the at least one alkane of the gaseous alkane feedstock comprises 4 or 5 carbons.3. The process of claim 1 , wherein the recovered dimerized alkenes comprise Cdimerized alkenes.4. The process of claim 3 , wherein the recovered dimerized alkenes comprise Cdimerized alkenes.5. The process of claim 1 , wherein the hydrogen acceptor comprises ethylene claim 1 , propene or mixtures thereof.6. The process of claim 1 , wherein the iridium pincer complex is (p-OM-PCP)Ir(CH) bound to the solid support comprising magnesium silicate claim 1 , where M is K or the solid support.7. The process of claim 1 , wherein the process has a TON for Cproducts of at least 100 at 10 minutes.8. The process of claim 1 , ...

METHOXYCARBONYLATION WITH FORMIC ACID AS CO SOURCE

Process for methoxycarbonylation with formic acid as the CO source. 2. Process according to claim 1 ,wherein no CO gas is supplied to the reaction mixture,3. Process according to claim 1 ,wherein HCOOH serves as the only CO source for the reaction,4. Process according to claims 1 ,wherein the compound in process step b) is selected from:{'sub': 2', '2', '3', '3', '2', '2', '3', '2, 'Pd(acac), PdCl, Pd(dba)*CHCl (dba=dibenzylideneacetone), Pd(OAc), Pd(TFA), Pd(CHCN)Cl.'}5. Process according to claim 1 ,wherein the process comprises additional process step f):f) addition of an acid.6. Process according to claim 5 ,{'sub': 2', '4', '3', '3', '3', '3, 'wherein the acid is selected from: HSO, CHSOH, CFSOH, PTSA.'}7. Process according to claim 1 ,wherein the MeOH/HCOOH ratio based on the employed volume is in the range from 1.5:0.5 to 1.2:0.8.8. Process according to claim 1 ,{'sup': 1', '2', '3', '4, 'sub': 1', '12', '1', '12', '4', '14', '4', '14', '1', '12', '1', '12', '3', '14', '3', '14', '2, 'wherein R, R, R, Rare each independently selected from: —(C-C)-alkyl, —O—(C-C)-alkyl, —(C-C)-aryl, —O—(C-C)-aryl, cycloalkyl, —(C-C)-heteroalkyl, —O—(C-C)-heteroalkyl, —(C-C)-heteroaryl, —O—(C-C)-heteroaryl, —COO-alkyl, —COO-aryl, —C—O-alkyl, —C—O-aryl, NH, halogen and the residues are also capable of forming a larger condensed ring;'}wherein the recited alkyl groups, aryl groups, cycloalkyl, heteroalkyl groups, heteroaryl groups may be substituted as follows:{'sub': 1', '12', '1', '12, '—(C-C)-alkyl, —O—(C-C)-alkyl, halogen;'}{'sup': 1', '2', '3', '4, 'and at least one of the radicals R, R, R, Rdoes not represent phenyl.'}9. Process according to claim 1 ,{'sup': 1', '2', '3', '4, 'sub': 1', '12', '4', '14', '1', '12', '3', '14, 'wherein R, R, R, Rare each independently selected from: —(C-C)-alkyl, —(C-C)-aryl, cycloalkyl, —(C-C)-heteroalkyl, —(C-C)-heteroaryl, halogen and the residues are also capable of forming a larger condensed ring;'}wherein the recited alkyl groups, aryl ...

METHOXYCARBONYLATION WITH FORMIC ACID AND METHANOL

Process for methoxycarbonylation with formic acid and methanol. 2. Process according to claim 1 ,wherein no CO gas is supplied to the reaction mixture.3. Process according to claim 1 ,wherein HCOOH serves as the only CO source for the reaction.4. Process according to claim 1 ,wherein the compound in process step b) is selected from:{'sub': 2', '2', '3', '3', '2', '2', '3', '2, 'Pd(acac), PdCl, Pd(dba)*CHCl (dba=dibenzylideneacetone), Pd(OAc), Pd(TFA), Pd(CHCN)Cl.'}5. Process according to claim 1 ,wherein the process comprises the additional process step g):g) addition of an acid.6. Process according to claim 5 ,{'sub': 2', '4', '3', '3', '3', '3, 'wherein the acid is selected from: HSO, CHSOH, CFSOH, PTSA.'}7. Process according to claim 1 ,wherein the employed volume of HCOOH based on 2 mmol of olefin is in the range from 0.4 ml to 0.6 ml.8. Process according to claim 1 ,{'sup': 1', '2', '3', '4, 'sub': 1', '12', '1', '12', '4', '14', '4', '14', '1', '12', '1', '12', '3', '14', '3', '14', '2, 'wherein R, R, Rand Rare each independently selected from: —(C-C)-alkyl, —O—(C-C)-alkyl, —(C-C)-aryl, —O—(C-C)-aryl, cycloalkyl, —(C-C)-heteroalkyl, —O—(C-C)-heteroalkyl, —(C-C)-heteroaryl, —O—(C-C)-heteroaryl, —COO-alkyl, —COO-aryl, —C—O-alkyl, —C—O-aryl, NH, halogen and the residues are also capable of forming a larger condensed ring;'}wherein the recited alkyl groups, aryl groups, cycloalkyl, heteroalkyl groups, heteroaryl groups may be substituted as follows:{'sub': 1', '12', '1', '12, '—(C-C)-alkyl, —O—(C-C)-alkyl, halogen;'}{'sup': 1', '2', '3', '4, 'and at least one of the radicals R, R, R, Rdoes not represent phenyl.'}9. Process according to claim 1 ,{'sup': 1', '2', '3', '4, 'sub': 1', '12', '4', '14', '1', '12', '3', '14, 'wherein R, R, Rand Rare each independently selected from: —(C-C)-alkyl, —(C-C)-aryl, cycloalkyl, —(C-C)-heteroalkyl, —(C-C)-heteroaryl, halogen and the residues are also capable of forming a larger condensed ring;'}wherein the recited alkyl groups, ...

METHODS TO REJUVENATE A DEACTIVATED HYDROFORMYLATION CATALYST SOLUTION

Disclosed herein are methods to rejuvenate a deactivated hydroformylation catalyst solution wherein the solution comprises rhodium, polydentate phosphine ligands, and polydentate phosphine ligand degradation products. In one embodiment, such methods comprise adding a peroxide to the deactivated hydroformylation catalyst solution. 1. A method to rejuvenate a deactivated hydroformylation catalyst solution comprising rhodium , polydentate phosphine ligands , and polydentate phosphine ligand degradation products , the method comprising: adding a peroxide to the deactivated hydroformylation catalyst solution.2. The method of claim 1 , further comprising adding additional polydentate phosphine ligand to the catalyst solution after the addition of peroxide.3. The method of claim 1 , wherein the temperature of the deactivated hydroformylation catalyst solution is between 0° C. and 40° C. when the peroxide is added.4. The method of claim 1 , wherein the deactivated hydroformylation catalyst solution further comprises at least one product aldehyde claim 1 , and further comprising removing a majority of the product aldehyde prior to adding the peroxide.5. The method of claim 4 , wherein a majority of the product aldehyde is removed by vaporization.6. The method of claim 4 , wherein the temperature of the deactivated hydroformylation catalyst solution is 70° C. or greater when the peroxide is added.7. The method of claim 4 , wherein the temperature of the deactivated hydroformylation catalyst solution is 100° C. or greater when the peroxide is added.8. The method of claim 4 , wherein the peroxide comprises hydrogen peroxide claim 4 , peroxy esters claim 4 , peroxydicarbonates claim 4 , dialkyl peroxides claim 4 , hydroperoxides claim 4 , peroxyketals claim 4 , or a combination thereof. The present disclosure relates generally to methods for rejuvenating deactivated hydroformylation catalyst solutions and in particular, to methods for rejuvenating deactivated hydroformylation ...

N-SUBSTITUTED PYRIDINIOPHOSPHINES, PROCESSES FOR THEIR PREPARATION AND THEIR USE

The present invention deals with the synthesis and applications of new cationic compounds being useful as metal ligands. Specifically, N-alkyl/aryl substituted pyridiniophosphines are prepared and used as ligands for transition metals. The so-obtained metal complexes and their use as catalysts in chemical synthesis is also described. It also worth mentioning that N-alkyl/aryl pyridiniophosphines can be synthesized through a short, scalable and highly modular route. 2. N-substituted pyridiniophosphine of the general formula (I) according to claim 1 , wherein R claim 1 , Rand Reach represent hydrogen and Rrepresents halogen claim 1 , a linear claim 1 , cyclic or branched C-C-alkyl claim 1 , -alkenyl or -alkynyl group or C-C-aryl or -heteroaryl group claim 1 , which can have suitable substituents selected from halogen claim 1 , ═O claim 1 , —OH claim 1 , —OR claim 1 , —NH claim 1 , —NHR claim 1 , —NR claim 1 , aryl or Ris bound to the pyridinio ring via —O— or —NR—; and{'sup': 5', '6', '7', '−, 'claim-ref': {'@idref': 'CLM-00001', 'claim 1'}, 'R, R, R, R and X have the meaning as given in .'}3. N-substituted pyridiniophosphine of the general formula (I) according to claim 1 , wherein X is an anion selected from Cl claim 1 , Br claim 1 , I claim 1 , PF claim 1 , SbF claim 1 , BF claim 1 , ClO claim 1 , FCCOO claim 1 , TfN claim 1 , (Tf=trifluoromethanesulfonyl) claim 1 , TfO claim 1 , tosyl claim 1 , [B[3 claim 1 ,5-(CF)CH]] claim 1 , [B(CF)] claim 1 , and [Al(OC(CF))].5. A metal complex comprising as a ligand a N-substituted pyridiniophosphine of the general formula (I) according to .7. The metal complex as claimed in claim 6 , wherein the ligand L can be chosen from halogen claim 6 , CN claim 6 , CO claim 6 , alkenes claim 6 , cycloalkenes and/or alkynes claim 6 , arenes claim 6 , nitriles claim 6 , phosphines claim 6 , amines claim 6 , pyridines or carboxylates.8. The metal complex as claimed in claim 6 , wherein M is selected from Ag claim 6 , Au claim 6 , Ru claim ...

ORGANORUTHENIUM CARBIDE COMPLEXES AS PRECATALYSTS FOR OLEFIN METATHESIS

Embodiments in accordance with the present invention encompass an organoruthenium compound of the formula (I) or formula (II): 2. The compound according to claim 1 , wherein:X is chlorine or iodine;{'sub': 1', '1, 'Rand Arare both substituted phenyl; and'}{'sub': '3', 'L is PR, where each R is independently selected from the group consisting of isopropyl, sec-butyl, tert-butyl, cyclohexyl and phenyl.'}3. The compound according to claim 1 , wherein:X is chlorine;{'sub': 1', '1, 'Rand Arare independently selected from the group consisting of phenyl, 2-methylphenyl, 2,4-dimethylphenyl, 2,6-dimethylphenyl, 2,4,6-trimethylphenyl, 2-ethylphenyl, 2,4-diethylphenyl, 2,6-diethylphenyl, 2,4,6-triethylphenyl, 2-isopropylphenyl and 2,6-diisopropylphenyl; and'}L is tri(isopropyl)phosphine or tricyclohexylphosphine.4. The compound according to claim 1 , wherein:X is chlorine;{'sub': 1', '1, 'Rand Arare independently selected from the group consisting of phenyl, 2,4-dimethylphenyl, 2,6-dimethylphenyl, 2,4,6-trimethylphenyl, 2,4-diethylphenyl, 2,6-diethylphenyl, 2,4,6-triethylphenyl, 2-isopropylphenyl and 2,6-diisopropylphenyl; and'}L is tricyclohexylphosphine.5. The compound according to claim 1 , wherein:X is iodine;{'sub': 1', '1, 'Rand Arare independently selected from the group consisting of 2,6-dimethylphenyl, 2,4,6-trimethylphenyl, 2,6-diethylphenyl, 2,4,6-triethylphenyl and 2,6-diisopropylphenyl; and'}L is tricyclohexylphosphine.7. A process for carrying out a metathesis reaction of olefins claim 1 , comprising contacting at least one olefin with the compound of as a procatalyst.8. The process according to claim 7 , wherein the metathesis reaction is carried out in an organic solvent.9. The process according to claim 8 , wherein the organic solvent is selected from the group consisting of dichloromethane claim 8 , dichloroethane claim 8 , toluene claim 8 , ethyl acetate and a mixture in any combination thereof.10. The process according to claim 7 , wherein the metathesis ...

Catalyst and process for the co-dimerization of ethylene and propylene

Disclosed are novel catalyst solutions comprising an organic complex of nickel, an alkyl aluminum compound, a solvent, and a phosphine compound, that are useful for the preparation of butenes, pentenes and hexenes by the co-dimerization or cross-dimerization of ethylene and propylene. Also disclosed are processes for the dimerization of ethylene and propylene that utilize these catalyst solutions. The catalyst systems described herein demonstrate that, depending on the choice of phosphine compound used with the catalytically active nickel, it is indeed possible to lower the concentration of hexene olefins relative to butenes and pentenes, even in the presence of excess propylene. The selectivity to the linear or branched pentene product can also be controlled by the selection of the phosphine compound. The catalyst solutions may be used with mixtures of olefins.

CO-FEEDING ETHYLENE WITH ALLYL ALCOHOL IN HYDROFORMYLATION TO MAKE 1,4-BUTANEDIOL AND N-PROPANOL

A process of co-feeding gaseous ethylene with liquid allyl alcohol in the presence of a catalyst to produce 1,4-butanediol and n-propanol may include: introducing a gaseous mixture of ethylene, carbon monoxide and hydrogen into a reactor in the presence of a hydroformylation catalyst in a solvent; introducing liquid allyl alcohol (AA) into the reactor; and carrying out hydroformylation reaction at a temperature between 50 and 100° C. to obtain hydroformylation products. 1. A method for producing an alcohol in a hydroformylation process , comprising the steps of:a) introducing a gaseous mixture of ethylene, carbon monoxide and hydrogen into a reactor in the presence of a hydroformylation catalyst in a solvent;b) introducing liquid allyl alcohol (AA) into the reactor; andc) carrying out hydroformylation reaction at a temperature between 50 and 100° C. to obtain hydroformylation products.2. The method of claim 1 , wherein the molar ratio of ethylene to allyl alcohol ranges from 1:3 to 1:7.3. The method of claim 1 , wherein the molar ratio of ethylene to allyl alcohol ranges from 1:4 to 1:5.5. The method of claim 1 , wherein molar ratio of ethylene:carbon monoxide:hydrogen is (0.18-0.35):(2.7-4.1):(5-7).6. The method of claim 5 , wherein the molar ratio of ethylene:carbon monoxide:hydrogen is about 1:13:22.7. The method of claim 1 , wherein in step c) the hydroformylation reaction is carried out at a moderate pressure in the range of from about 137.9 kPa to about 1378.95 kPa.8. The method of claim 1 , wherein in step c) the hydroformylation reaction is carried out at a moderate pressure in the range of from about 689.48 kPa to about 1034.21 kPa.9. The method of claim 1 , wherein in step c) the hydroformylation reaction is carried out at a moderate pressure in the range of from about 896.32 kPa to about 965.27 kPa.10. The method of claim 1 , wherein the hydroformylation catalyst is a mixture of rhodium and a ligand selected from the group consisting of trans-1 claim 1 ,2 ...

Method for converting carbon dioxide and bicarbonates into formic acid derivatives using a cobalt complex as a catalytic system

The invention relates to a method for converting carbon dioxide or bicarbonates into formic acid derivatives, i.e. formate salts, formate esters, and formamides, using molecular hydrogen and a catalytic system comprising a cobalt complex of cobalt salt and at least one tripodal, tetradentate ligand. The catalyst complex can be used as a homogeneous catalyst. The invention further relates to the cobalt complexes per se.

Purified cenicriviroc and purified intermediates for making cenicriviroc

The disclosure includes high purity compounds having CCR5 and/or CCR2 antagonism, or salts thereof, high purity intermediates thereto and processes for synthesizing the same. 130.-. (canceled)31. A composition of 8-(4-(2-butoxyethoxy)phenyl)-1-isobutyl-N-(4-(2-(1-propyl-1H-imidazol-5-yl)acetyl)phenyl)-1 ,2 ,3 ,4-tetrahydrobenzo[b]azocine-5-carboxamide methanesulfonate (Compound I-MsOH) , or an enantiomer , a stereoisomer , or a combination thereof , with a purity of ≥96.0% or ≥98.5% or higher , wherein said compound comprises one or more of the following:(a) about ≤0.50% to about ≥0.30% of 8,8′-(4-(2-butoxyethoxy)-1,3-phenylene)bis(1-isobutyl-1,2,3,4-tetrahydrobenzo[b]azocine-5-carboxylic acid) (Compound VIII);(b) about ≤0.50% to about ≥0.30% of 8-(4-(2-butoxyethoxy)phenyl)-1-butyl-1,2,3,4-tetrahydrobenzo[b]azocine-5-carboxylic acid (Compound IX);(c) about ≤0.50% to about ≥0.30% of 8-(4-(2-ethoxyethoxy)phenyl)-1-isobutyl-N-(4-(((1-propyl-1H-imidazol-5-yl)methyl)sulfinyl)phenyl)-1,2,3,4-tetrahydrobenzo[b]azocine-5-carboxamide methanesulfonate (Compound I-MsOH-A);(d) about ≤0.50% to about ≥0.30% of 1-isobutyl-8-(4-(2-propoxyethoxy)phenyl)-N-(4-(((1-propyl-1H-imidazol-5-yl)methyl)sulfinyl)phenyl)-1,2,3,4-tetrahydrobenzo[b]azocine-5-carboxamide methanesulfonate (Compound I-MsOH-B);(e) about ≤0.50% to about ≥0.45% of 8-(4-butoxyphenyl)-1-isobutyl-N-(4-(((1-propyl-1H-imidazol-5-yl)methyl)sulfinyl)phenyl)-1,2,3,4-tetrahydrobenzo[b]azocine-5-carboxamide methanesulfonate (Compound I-MsOH-C);(f) about ≤0.50% to about ≥0.45% of 8-(4-(2-butoxyethoxy)phenyl)-1-isobutyl-N-(4-(((1-propyl-1H-imidazol-5-yl)methyl)thio)phenyl)-1,2,3,4-tetrahydrobenzo[b]azocine-5-carboxamide methanesulfonate (Compound I-MsOH-E);(g) about ≤0.50% to about ≥0.45% of 8-(4-(2-butoxyethoxy)phenyl)-1-butyl-N-(4-(((1-propyl-1H-imidazol-5-yl)methyl)sulfinyl)phenyl)-1,2,3,4-tetrahydrobenzo[b]azocine-5-carboxamide methanesulfonate (Compound I-MsOH-F); and(h) about ≤0.50% to about ≥0.45% of 8,8′-(4-(2- ...

PROCESS FOR PREPARING 1,4-DIBENZODIAZEPINES VIA BUCHWALD-HARTWIG CHEMISTRY

The present application provides a one-pot catalytic process which involves the formation of 1,4-dibenzodiazepines from o-haloaldimines (either pre-formed or formed in situ) of formula (I) and o-haloanilines of formula (II) via a palladium catalyzed Buchwald-Hartwig reaction and a cyclization sequence, to afford the 1,4-dibenzodiazepine products of formula (III). The present application describes the preparation of the 1,4-dibenzodiazepine products of formula (III) from simple commercial raw materials by efficient processes. 2. The process according to claim 1 , wherein the active catalyst is prepared by adding the ligand to the palladium complex in a dry solvent claim 1 , under an inert atmosphere and allowing the mixture to stir up to 24 h with a temperature range from 50 to 130° C.3. The process according to claim 1 , wherein the palladium complex used is selected from the group consisting of Pd(OAc) claim 1 , PEPPSI-iPr catalyst claim 1 , Pd(dba).CHCl claim 1 , [Pd(TFA)] claim 1 , PdCl(dppf) claim 1 , Pd(PPh) claim 1 , cationic palladium (II) complexes and Pd—NHCs.4. The process according to claim 1 , wherein the reaction solvent used is selected from the group consisting of: toluene claim 1 , dimethyl ether claim 1 , diethyl ether claim 1 , 1 claim 1 ,4-dioxane claim 1 , acetonitrile claim 1 , chloroform claim 1 , DMF claim 1 , DMA and NMP.5. The process according to claim 1 , wherein the ligand is a monophosphane type ligand.6. The process according to claim 1 , wherein the base is selected from the group consisting of triethylamine claim 1 , KCO claim 1 , NaCO claim 1 , CaCO claim 1 , Ba(OH) claim 1 , KOAc claim 1 , DIPA claim 1 , KPO claim 1 , NMM claim 1 , DBU claim 1 , KOH claim 1 , KF claim 1 , CsCO claim 1 , and KOtBu.7. The process according to claim 1 , wherein the substrate of formula (I) is pre-formed or formed in situ.8. The process according to claim 1 , wherein the reaction is run under an inert atmosphere.9. The process according to claim 1 , ...

Novel ruthenium complex and process for producing optically active alcohol compound using same as catalyst

The present invention provides a novel ruthenium complex which has an excellent catalytic activity in terms of reactivity for an asymmetric reduction of a carbonyl compound and enantioselectivity, a catalyst using the ruthenium complex, and a method for preparing optically active alcohol compounds using the ruthenium complex. The present invention relates to a ruthenium complex having a ruthenacycle structure, a catalyst for an asymmetric reduction consisting of the ruthenium complex, and a method for preparing optically active alcohol compounds using the ruthenium complex.

CONJUGATED POLYMER AND PEROVSKITE SOLAR CELL INCLUDING SAME

The present disclosure relates to a conjugated polymer and a perovskite solar cell including the same, more particularly to a conjugated polymer capable of improving moisture stability and thermal stability. When the conjugated polymer according to the present disclosure is used in an organic electronic device, superior efficiency can be maintained for a long period of time. 2. The method for preparing a conjugated polymer according to claim 1 , wherein claim 1 , in the step 1) claim 1 , the compound represented by Chemical Formula a and the compound represented by Chemical Formula b are mixed at a molar ratio of 1:1.3. The method for preparing a conjugated polymer according to claim 1 , wherein the solvent is any one or more selected from a group consisting of toluene claim 1 , benzene claim 1 , hexane claim 1 , naphthalene claim 1 , ethylbenzene claim 1 , chlorobenzene claim 1 , dichlorobenzene claim 1 , dichloromethane claim 1 , trichloromethane claim 1 , tetrachloromethane claim 1 , cyclohexane and carbon tetrachloride.4. The method for preparing a conjugated polymer according to claim 1 , wherein the complex catalyst is any one or more selected from a group consisting of tris(dibenzylideneacetone)dipalladium(0) (Pd(dba)) claim 1 , bis(dibenzylideneacetone)palladium(0) (Pd(dba)) and tetrakis(triphenylphosphine)palladium(0) (Pd(PPh)).5. The method for preparing a conjugated polymer according to claim 1 , wherein the cocatalyst is any one or more selected from a group consisting of tri(o-tolyl)phosphine (P(o-tolyl)) claim 1 , triphenylphosphine (PPh) and tricyclohexylphosphine tetrafluoroborate (PCyHBF). This application claims, under 35 U.S.C. § 119, the priority of Korean Patent Application No. 10-2019-0134733 filed on Oct. 28, 2019 in the Korean Intellectual Property Office, the disclosure of which is incorporated herein by reference in its entirety.The present disclosure relates to a conjugated polymer and a perovskite solar cell including the same, more ...

ORGANORUTHENIUM CARBIDE COMPLEXES AS PRECATALYSTS FOR OLEFIN METATHESIS

Embodiments in accordance with the present invention encompass an organoruthenium compound of the formula (I) or formula (II): 2. The compound according to claim 1 , wherein:X is chlorine or iodine;{'sub': 2', '3', '4', '5, 'each R, R, Rand Ris independently selected from the group consisting of methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, tert-butyl and phenyl;'}{'sub': '2', 'Aris substituted phenyl; and'}{'sub': '3', 'L is PR, where each R is independently selected from the group consisting of isopropyl, sec-butyl, tert-butyl, cyclohexyl and phenyl.'}3. The compound according to claim 1 , wherein:X is chlorine;{'sub': 2', '3, 'Rand Rtaken together with the carbon atom to which they are attached to form a cyclopentyl, cyclohexyl or cycloheptyl ring;'}{'sub': 4', '5, 'each Rand Ris independently selected from the group consisting of hydrogen, methyl, ethyl and iso-propyl;'}{'sub': '2', 'Aris selected from the group consisting of phenyl, 2-methylphenyl,'}2,4-dimethylphenyl, 2,6-dimethylphenyl, 2,4,6-trimethylphenyl, 2-ethylphenyl,2,4-diethylphenyl, 2,6-diethylphenyl, 2,4,6-triethylphenyl, 2-isopropylphenyl and2,6-diisopropylphenyl; andL is tri(isopropyl)phosphine or tricyclohexylphosphine.4. The compound according to claim 1 , wherein:X is chlorine;{'sub': 2', '3', '4', '5, 'each R, R, Rand Rindependently is methyl or ethyl;'}{'sub': '2', 'Aris selected from the group consisting of phenyl, 2,4-dimethylphenyl,'}2,6-dimethylphenyl, 2,4,6-trimethylphenyl, 2,4-diethylphenyl, 2,6-diethylphenyl,2,4,6-triethylphenyl, 2-isopropylphenyl and 2,6-diisopropylphenyl; andL is tricyclohexylphosphine.5. The compound according to claim 1 , wherein:X is iodine;{'sub': 2', '3', '4', '5, 'each R, R, Rand Rindependently is methyl or ethyl;'}{'sub': '2', 'Aris selected from the group consisting of 2,6-dimethylphenyl,'}2,4,6-trimethylphenyl, 2,6-diethylphenyl, 2,4,6-triethylphenyl and2,6-diisopropylphenyl; andL is tricyclohexylphosphine.14. A process for carrying out a ...

PLATINUM COMPLEXES HAVING BINAPHTHYL-BASED DIPHOSPHINE LIGANDS FOR THE SELECTIVE CATALYSIS OF THE HYDROXYCARBONYLATION OF ETHYLENICALLY UNSATURATED COMPOUNDS

Platinum complexes having binaphthyl-based diphosphine ligands for the selective catalysis of the hydroxycarbonylation of ethylenically unsaturated compounds. 2. Complex according to claim 1 ,{'sup': 1', '2', '3', '4, 'sub': 6', '20, 'wherein at least two of the R, R, R, Rradicals are a —(C-C)-heteroaryl radical having at least six ring atoms.'}3. Complex according to claim 1 ,{'sup': 1', '3, 'sub': 6', '20, 'wherein the Rand Rradicals are each a —(C-C)-heteroaryl radical having at least six ring atoms.'}4. Complex according to claim 1 ,{'sup': 1', '3, 'wherein the Rand Rradicals are each 2-pyridyl.'}5. Complex according to claim 1 ,{'sup': 2', '4, 'sub': 1', '12, 'wherein Rand Rare —(C-C)-alkyl.'}6. Complex according to claim 1 ,{'sup': 2', '4, 'wherein Rand Rare tert-butyl.'}9. Process according to claim 8 ,wherein the ethylenically unsaturated compound is selected from: ethene, propene, 1-butene, cis- and/or trans-2-butene, isobutene, 1,3-butadiene, 1-pentene, cis- and/or trans-2-pentene, 2-methyl-1-butene, 3-methyl-1-butene, 2-methyl-2-butene, hexene, tetramethylethylene, heptene, 1-octene, 2-octene, di-n-butene, or mixtures thereof.10. Process according to claim 8 ,wherein the acid in process step c) is selected from acetic acid, perchloric acid, sulfuric acid, phosphoric acid, methylphosphonic acid, methanesulfonic acid, trifluoromethanesulfonic acid, tert-butanesulfonic acid, p-toluenesulfonic acid, 2-hydroxypropane-2-sulfonic acid, 2,4,6-trimethylbenzenesulfonic acid, dodecylsulfonic acid, camphorsulfonic acid.11. Process according to claim 8 ,wherein the acid in process step c) is acetic acid.12. Process according to claim 8 ,{'sub': 2', '2', '2', '2', '2', '2', '3', '2', '2', '2, 'wherein the substance comprising Pt is selected from: platinum dichloride (PtCl), platinum(II) acetylacetonate [Pt(acac)], platinum(II) acetate [Pt(OAc)], dichloro(1,5-cyclooctadiene)platinum(II) [Pt(cod)Cl], bis(dibenzylideneacetone)platinum [Pt(dba)], bis(acetonitrile) ...

PLATINUM COMPLEXES HAVING 1,2-SUBSTITUTED BENZYL-BASED DIPHOSPHINE LIGANDS FOR THE CATALYSIS OF THE ALKOXYCARBONYLATION OF ETHYLENICALLY UNSATURATED COMPOUNDS

Platinum complexes having 1,2-substituted benzyl-based diphosphine ligands for the catalysis of the alkoxycarbonylation of ethylenically unsaturated compounds. 2. Complex according to claim 1 ,{'sup': 1', '2', '3', '4, 'sub': 6', '20, 'wherein at least two of the R, R, R, Rradicals are a —(C-C)-heteroaryl radical having at least six ring atoms.'}3. Complex according to claim 1 ,{'sup': 1', '3, 'sub': 6', '20, 'wherein the Rand Rradicals are each a —(C-C)-heteroaryl radical having at least six ring atoms.'}4. Complex according to claim 1 ,{'sup': 1', '3, 'wherein the Rand Rradicals are each 2-pyridyl.'}5. Complex according to claim 1 ,{'sup': 2', '4, 'sub': 1', '12, 'wherein Rand Rare —(C-C)-alkyl.'}6. Complex according to claim 1 ,{'sup': 2', '4, 'wherein Rand Rare tert-butyl.'}9. Process according to claim 8 ,wherein the ethylenically unsaturated compound is selected from: ethene, propene, 1-butene, cis- and/or trans-2-butene, isobutene, 1,3-butadiene, 1-pentene, cis- and/or trans-2-pentene, 2-methyl-1-butene, 3-methyl-1-butene, 2-methyl-2-butene, hexene, tetramethylethylene, heptene, 1-octene, 2-octene, di-n-butene, or mixtures thereof.10. Process according to claim 8 ,wherein the alcohol in process step c) is selected from: methanol, ethanol, 1-propanol, 1-butanol, 1-pentanol, 1-hexanol, 2-propanol, tert-butanol, 3-pentanol, cyclohexanol, phenol.11. Process according to claim 8 ,wherein the alcohol in process step c) is methanol.12. Process according to claim 8 ,{'sub': 2', '2', '2', '2', '2', '2', '3', '2', '2', '2, 'wherein the substance comprising Pt is selected from: platinum dichloride (PtCl), platinum(II) acetylacetonate [Pt(acac)], platinum(II) acetate [Pt(OAc)], dichloro(1,5-cyclooctadiene)platinum(II) [Pt(cod)Cl], bis(dibenzylideneacetone)platinum [Pt(dba)], bis(acetonitrile)dichloroplatinum(II) [Pt(CHCN)Cl], (cinnamyl)platinum dichloride [Pt(cinnamyl)Cl].'}13. Process according to claim 8 ,{'sub': 2', '2', '2, 'wherein the substance comprising Pt is ...

PLATINUM COMPLEXES HAVING BINAPHTHYLDIPHOSPHINE LIGANDS FOR THE CATALYSIS OF THE HYDROXYCARBONYLATION OF ETHYLENICALLY UNSATURATED COMPOUNDS

Platinum complexes having binaphthyldiphosphine ligands for the catalysis of the hydroxycarbonylation of ethylenically unsaturated compounds. 2. Complex according to claim 1 , wherein at least two of the R claim 1 , R claim 1 , R claim 1 , Rradicals are a -(C-C)-heteroaryl radical having at least six ring atoms.3. Complex according to Claim 1 , wherein the Rand Rradicals are each a -(C6-C20)-heteroaryl radical having at least six ring atoms.4. Complex according to Claim 1 , wherein the Rand Rradicals are each 2-pyridyl.5. Complex according to Claim 1 , wherein Rand Rare -(C-C12)-alkyl.6. Complex according to Claim 1 , wherein Rand Rare tent-butyl.9. Process according to claim 8 , wherein the ethylenically unsaturated compound is selected from: ethene claim 8 , propene claim 8 , 1-butene claim 8 , cis- and/or trans-2-butene claim 8 , isobutene claim 8 , 1 claim 8 ,3-butadiene claim 8 , 1-pentene claim 8 , cis- and/or trans-2-pentene claim 8 , 2-methyl-1-butene claim 8 , 3-methyl-1-butene claim 8 , 2-methyl-2-butene claim 8 , hexene claim 8 , tetramethylethylene claim 8 , heptene claim 8 , 1-octene claim 8 , 2-octene claim 8 , di-n-butene claim 8 , or mixtures thereof.10. Process according to claim 8 , wherein the acid in process step c) is selected from: acetic acid claim 8 , perchloric acid claim 8 , sulfuric acid claim 8 , phosphoric acid claim 8 , methylphosphonic acid claim 8 , methanesulfonic acid claim 8 , trifluoromethanesulfonic acid claim 8 , tert-butanesulfonic acid claim 8 , p-toluenesulfonic acid (PTSA) claim 8 , 2-hydroxypropane-2-sulfonic acid claim 8 , 2 claim 8 ,4 claim 8 ,6-trimethylbenzenesulfonic acid claim 8 , dodecylsulfonic acid claim 8 , camphorsulfonic acid.11. Process according to any of to claim 8 , wherein the acid in process step c) is acetic acid.12. Process according to any of to claim 8 , wherein the substance comprising Pt is selected from: platinum dichloride (PtC1) claim 8 , platinum(II) acetylacetonate [Pt(acac)] claim 8 , platinum( ...

Vanadium Containing Hydrosilylation Catalysts And Compositions Containing The Catalysts

A composition contains (A) a hydrosilylation reaction catalyst and (B) an aliphatically unsaturated compound having an average, per molecule, of one or more aliphatically unsaturated organic groups capable of undergoing hydrosilylation reaction. The composition capable of reacting via hydrosilylation reaction to form a reaction product, such as a silane, a gum, a gel, a rubber, or a resin. Ingredient (A) contains a metal-ligand complex that can be prepared by a method including reacting a metal precursor and a ligand. 2. (canceled)3. The method of claim 1 , further comprising (2) combining the reaction product with an ionic activator.5. (canceled)6. The method of claim 4 , further comprising (2) combining the reaction product with a reducing agent.7. The method of claim 1 , where the reaction product comprises a V-ligand complex and a by-product of reaction of the V precursor and the ligand or of a side reaction therein.8. The method of claim 7 , further comprising removing all or a portion of the by-product.9. The method of claim 3 , further comprising using the product prepared by the method as a hydrosilylation catalyst.10. A composition comprising:{'claim-ref': {'@idref': 'CLM-00003', 'claim 3'}, '(A) a product prepared by the method of ;'}(B) an aliphatically unsaturated compound having an average, per molecule, of one or more aliphatically unsaturated organic groups capable of undergoing hydrosilylation reaction; and{'sup': 4', '4, 'sub': e', 'f, '(C) a silane of formula RSiH, where subscript e is 0, 1, 2, or 3; subscript f is 1, 2, 3, or 4, with the proviso that a sum of (e+f) is 4, and each Ris independently a halogen atom or a monovalent organic group.'}11. The composition of claim 10 , where the composition further comprises one or more additional ingredients claim 10 , which are distinct from ingredients (A) claim 10 , (B) claim 10 , and (C) claim 10 , and which are selected from the group consisting of (D) a spacer; (E) an extender claim 10 , a ...

AIR-STABLE Ni(0)-OLEFIN COMPLEXES AND THEIR USE AS CATALYSTS OR PRECATALYSTS

The present invention relates to air stable, binary Ni(0)-olefin complexes and their use in organic synthesis. 2. An air-stable Ni(R)—complex according to claim 1 ,wherein Ni represents Ni(0),wherein R is the same or different and represents a trans-stilbene of the Formula (I);{'sup': 1', '5', '6', '10', '1', '10', '11', '12, 'sub': 1', '8', '3', '6', '1', '8', '3', '6', '1', '8', '3', '6, 'wherein in Formula (I), at least one of Rto Rand at least one of Rto Rare the same or different and are selected from Cl, Br, F, CN, Cto Calkyl, or Cto Ccycloalkyl, which alkyl or cycloalkyl is optionally substituted by one or more halogens, and the others of Rto Rare hydrogen, and Rto Rare the same or different and are selected from H, Cto Calkyl, Cto Ccycloalkyl, —O—Cto Calkyl, or —O—Cto Ccycloalkyl.'}3. An air-stable Ni(R)—complex according to claim 1 ,wherein Ni represents Ni(0),wherein R is the same or different and represents a trans-stilbene of the Formula (I);{'sup': 3', '8', '1', '10', '11', '12, 'sub': 1', '8', '1', '6', '1', '6', '3', '6', '3', '6, 'wherein in Formula (I), Rand Rare the same or different and are selected from Cto Calkyl which is optionally substituted by one or more halogens, and the others of Rto Rare hydrogen, and Rto Rare the same or different and are selected from H, Cto Calkyl, —O—Cto Calkyl, Cto Ccycloalkyl or —O—Cto Ccycloalkyl.'}4. An air-stable Ni(R)—complex according to claim 1 ,wherein Ni represents Ni(0),wherein R is the same or different and represents a trans-stilbene of the Formula (I);{'sup': 3', '8', '1', '10', '11', '12, 'sub': 1', '8', '1', '6', '1', '6', '3', '6', '3', '6, 'wherein in Formula (I), Rand Rare the same or different and are selected from Cto Cperfluoro alkyl and the others of Rto Rare hydrogen, and Rto Rmay be the same or different and are selected from H, Cto Calkyl, O—Cto Calkyl, Cto Ccyclolkyl or —O—Cto Ccycloalkyl.'}5. An air-stable Ni(R)—complex according to claim 1 ,wherein Ni represents Ni(0),wherein R is the ...

OLEFIN HYDROFORMYLATION METHODS FOR OBTAINING BRANCHED ALDEHYDES

The present technology relates to methods of hydroformylating allyl alcohol to 4-hydroxybutanal and 2-methyl-3-hydroxypropanal, comprising (i) admixing allyl alcohol with CO and Hto form a starting material mixture, and (ii) reacting the starting material mixture in the presence of a catalyst under conditions capable of forming a product mixture comprising 4-hydroxybutanal and 2-methyl-3-hydroxypropanal, wherein the catalyst is a transition metal complex comprising a transition metal ion and a diphosphine ligand with a bite angle from about 70° to about 100°, and wherein the ratio of 4-hydroxybutanal to 2-methyl-3-hydroxypropanal in the product mixture is less than 1.5:1. 1. A method comprising:{'sub': '2', '(i) admixing allyl alcohol with CO and Hto form a starting material mixture; and'}(ii) reacting the starting material mixture in the presence of a catalyst under conditions capable of forming a product mixture comprising 4-hydroxybutanal and 2-methyl-3-hydroxypropanal;wherein the catalyst is a transition metal complex comprising a transition metal ion and a diphosphine ligand with a bite angle from about 70° to about 100°, and wherein the ratio of 4-hydroxybutanal to 2-methyl-3-hydroxypropanal in the product mixture is less than 1.5:1.2. The method of claim 1 , wherein the diphosphine ligand has a bite angle from about 85° to about 95°.3. The method of claim 1 , wherein the ratio of 4-hydroxybutanal to 2-methyl-3-hydroxypropanal is less than 0.75:1.4. The method of claim 1 , wherein the transition metal is a Rh claim 1 , Re claim 1 , or Co ion.5. The method of claim 4 , wherein the transition metal ion is a Rh ion.6. The method of claim 1 , wherein the reaction of step (ii) occurs at a temperature from about 20° C. to about 120° C. and at a pressure from about 20 psi to about 600 psi (about 140 to about 4 claim 1 ,100 kPa).7. The method of claim 1 , wherein the starting material mixture further comprises a solvent.8. The method of claim 7 , wherein the amount of ...

PROCESS FOR THE ISOMERISATION OF SUBSTITUTED ALKENES

The invention relates to a process for the isomerization of unsaturated fatty acids or esters or amides thereof, said process comprising reacting: 1. A process for the isomerization of unsaturated fatty acids and/or an ester and/or an amide thereof , said process comprising reacting:(a) an unsaturated fatty acid and/or ester and/or amide thereof;(b) a source of Pd; {'br': None, 'R1R2>P1-R-P2P1-R-P2 Подробнее

NICKEL PRE-CATALYSTS AND RELATED COMPOSITIONS AND METHODS

Described herein are nickel pre-catalysts and related compositions and methods. The nickel pre-catalysts may be activated to form catalysts which may be utilized in organic reactions. 1. A pre-catalyst , comprising:a nickel (II) atom, wherein the nickel (II) atom is associated with at least one phosphine ligand; at least one aryl ligand; and at least one leaving group.2. The pre-catalyst of claim 1 , wherein the pre-catalyst comprises two phosphine ligands.3. The pre-catalyst of claim 1 , wherein the pre-catalyst comprises two phosphine ligands claim 1 , one aryl ligand claim 1 , and one leaving group.4. The pre-catalyst of claim 2 , wherein the two phosphine ligands are trans.5. The pre-catalyst of claim 2 , wherein the two phosphine ligands are cis.6. The pre-catalyst claim 2 , the two phosphine ligands are monodentate.10. A pre-catalyst claim 2 , comprising:a nickel (II) atom, wherein the nickel (II) atom is associated with at least one N-heterocyclic carbene ligand; at least one aryl ligand; and at least one leaving group.11. The pre-catalyst of claim 10 , wherein the pre-catalyst further comprises at least one phosphine ligand.12. The pre-catalyst of claim 10 , wherein the pre-catalyst comprises one heterocyclic carbene ligand claim 10 , one phosphine ligand claim 10 , one aryl ligand claim 10 , and one leaving group.13. The pre-catalyst of claim 11 , wherein the phosphine ligand is monodentate.14. The pre-catalyst of claim 1 , wherein each monodentate phosphine ligand is the same or different and has the structure P(R) claim 1 , wherein each Ris independently optionally substituted alkyl claim 1 , optionally substituted cycloalkyl claim 1 , or optionally substituted aryl.15. The pre-catalyst of claim 1 , wherein the pre-catalyst comprises a bidentate phosphine ligand.16. The pre-catalyst of claim 15 , wherein the bidentate phosphine ligand has the structure (R)P—(R)—P(R) claim 15 , wherein each Ris independently optionally substituted alkyl claim 15 , ...

PROCESS FOR PREPARING AN UNSATURATED CARBOXYLIC ACID SALT

A catalytic process for preparing an α,β-ethylenically unsaturated carboxylic acid salt from an alkene, carbon dioxide and an alkoxide having a secondary or tertiary carbon atom directly bound to a [O—] group is described. The alcohol byproduct is distilled off after an intermediate phase separation. This provides pure β,β-ethylenically unsaturated carboxylic acid salt at minimum effort. 1. A catalytic process for preparing an α ,β-ethylenically unsaturated carboxylic acid salt , the process comprising:{'sup': '−', 'a) contacting an alkene and carbon dioxide with a carboxylation catalyst and an alkoxide, the alkoxide having a secondary or tertiary carbon atom directly bound to a [O] group, to obtain a crude reaction product comprising the α,β-ethylenically unsaturated carboxylic acid salt and an alcohol byproduct which is a conjugate acid of the alkoxide,'}b) contacting at least part of the crude reaction product with a polar solvent such that a first liquid phase in which the α,β-ethylenically unsaturated carboxylic acid salt is enriched, and a second liquid phase in which the carboxylation catalyst is enriched, are obtained, andc) distilling an alcohol byproduct off from the first liquid phase.2. The catalytic process according to claim 1 , wherein further comprising:d) contacting at least part of the alcohol byproduct recovered in c) with an alkaline material in order to regenerate the alkoxide.3. The catalytic process according to claim 2 , wherein at least part of the alkoxide obtained in d) is recycled to a).4. The catalytic process according to claim 1 , wherein at least part of the second liquid phase obtained in b) is recycled to a).5. The catalytic process according to claim 1 , wherein the polar solvent is at least one polar solvent that has a boiling temperature of less than 150° C. at a pressure of 1 bar.6. The catalytic process according to claim 1 , wherein the polar solvent comprises at least 90% by weight of water.7. The catalytic process according ...

Compound, Manufacturing Method Therefor, and Method for Manufacturing Optically Active alpha-Aminophosphonate Derivative

A method for producing a compound represented by General Formula (1), the method including: 5. The method according to claim 4 , wherein the reacting is performed using a catalyst containing an asymmetric ligand.6. The method according to claim 5 , wherein the catalyst containing an asymmetric ligand is a copper-optically active phosphine complex. The present invention relates to a method for efficiently synthesizing an optically active α-aminophosphonic acid derivative which is useful as a starting material of a candidate substance of a drug. Specifically, the present invention relates to a novel compound, a method for efficiently synthesizing the novel compound, a method for synthesizing the optically active α-aminophosphonic acid derivative using the novel compound, and a novel optically active α-aminophosphonic acid derivative.Optically active α-aminophosphonic acid derivatives are useful for the synthesis of candidate compounds of pharmaceutical drugs such as antibacterial agents, anti-HIV drugs, and enzyme inhibitors (see, for example, NPLs 1 to 5).Generally employed methods for producing optically active α-aminophosphonic acid derivatives are, for example, methods using chiral auxiliary groups for increasing stereoselectivity (see, for example, NPLs 6 to 9).These techniques, however, use expensive chiral auxiliary groups in a large amount (an equimolar amount or more) and the chiral auxiliary groups cannot be recovered after use, having a problem that they are not economical.Other proposed production methods include a method using, as a catalyst, Cinchona Alkaloid such as quinine, adding diphenyl phosphate to a specific ketimine to obtain an adduct, and synthesizing an optically active α-aminophosphonic acid derivative from the adduct (see, for example, NPL 10).This technique, however, has a problem that stereoselectivity is low unless at least one of two substituents binding to carbon of the C═N bond of the ketimine is an aromatic hydrocarbon group, which ...

Ligand, Oligomerization Catalyst Comprising Same, and Method for Producing Ethylene Oligomer by Using Oligomerization Catalyst

The present invention relates to a ligand, an ethylene oligomerization catalyst including the ligand, and a method for selectively producing 1-hexene or 1-octene from ethylene by using the catalyst. The ligand according to the present invention is a bis(diphenylphosphino)ethene with a phosphorus atom substituted with a fluoro-substituted phenyl, and when the ligand is used for ethylene oligomerization, the high temperature activity of the catalyst can be increased. 4. The ligand of claim 3 , wherein Ris C1-C7alkyl or C6-C12aryl.5. An ethylene oligomerization catalyst comprising:{'claim-ref': {'@idref': 'CLM-00001', 'claim 1'}, 'the ligand of ; and'}a transition metal.6. The ethylene oligomerization catalyst of claim 5 , wherein the ethylene oligomerization catalyst is mononuclear or binuclear.7. The ethylene oligomerization catalyst of claim 5 , wherein the transition metal is a Group 4 claim 5 , Group 5 claim 5 , or Group 6 transition metal.8. The ethylene oligomerization catalyst of claim 7 , wherein the transition metal is chromium claim 7 , molybdenum claim 7 , tungsten claim 7 , titanium claim 7 , tantalum claim 7 , vanadium claim 7 , or zirconium.9. The ethylene oligomerization catalyst of claim 8 , wherein the transition metal is chromium.10. A method for producing an ethylene oligomer claim 5 , comprising contacting a catalyst composition including the ethylene oligomerization catalyst of with ethylene.11. The method of claim 10 , wherein the catalyst composition further includes a cocatalyst.12. The method of claim 11 , wherein the cocatalyst is an organoaluminum compound claim 11 , organoaluminoxane claim 11 , an organoboron compound claim 11 , an organic salt claim 11 , or a mixture thereof.13. The method of claim 12 , wherein the cocatalyst is one or a mixture of two or more selected from the group consisting of methylaluminoxane (MAO) claim 12 , modified methylaluminoxane (mMAO) claim 12 , ethyl aluminoxane (EAO) claim 12 , tetraisobutyl aluminoxane ( ...

Purified cenicriviroc and purified intermediates for making cenicriviroc

The disclosure includes high purity compounds having CCR5 and/or CCR2 antagonism, or salts thereof, high purity intermediates thereto and processes for synthesizing the same. 130-. (canceled)31. A composition of 8-(4-(2-butoxyethoxy)phenyl)-1-isobutyl-N-(4-(2-(1-propyl-1H-imidazol-5-yl)acetyl)phenyl)-1 ,2 ,3 ,4-tetrahydrobenzo[b]azocine-5-carboxamide methanesulfonate (Compound I-MsOH) , or an enantiomer , a stereoisomer , or a combination thereof , with a purity of ≥96.0% or ≥98.5% or higher , wherein said compound comprises one or more of the following:(a) about ≤0.50% to about ≥0.30% of 8,8′-(4-(2-butoxyethoxy)-1,3-phenylene)bis(1-isobutyl-1,2,3,4-tetrahydrobenzo[b]azocine-5-carboxylic acid) (Compound VIII);(b) about ≤0.50% to about ≥0.30% of 8-(4-(2-butoxyethoxy)phenyl)-1-butyl-1,2,3,4-tetrahydrobenzo[b]azocine-5-carboxylic acid (Compound IX);(c) about 0.50% to about ≥0.30% of 8-(4-(2-ethoxyethoxy)phenyl)-1-isobutyl-N-(4-(((1-propyl-1H-imidazol-5-yl)methyl)sulfinyl)phenyl)-1,2,3,4-tetrahydrobenzo[b]azocine-5-carboxamide methanesulfonate (Compound I-MsOH-A);(d) about ≤0.50% to about ≥0.30% of 1-isobutyl-8-(4-(2-propoxyethoxy)phenyl)-N-(4-(((1-propyl-1H-imidazol-5-yl)methyl)sulfinyl)phenyl)-1,2,3,4-tetrahydrobenzo[b]azocine-5-carboxamide methanesulfonate (Compound I-MsOH-B);(e) about ≤0.50% to about ≥0.45% of 8-(4-butoxyphenyl)-1-isobutyl-N-(4-(((1-propyl-1H-imidazol-5-yl)methyl)sulfinyl)phenyl)-1,2,3,4-tetrahydrobenzo[b]azocine-5-carboxamide methanesulfonate (Compound I-MsOH-C);(f) about ≤0.50% to about ≥0.45% of 8-(4-(2-butoxyethoxy)phenyl)-1-isobutyl-N-(4-(((1-propyl-1H-imidazol-5-yl)methyl)thio)phenyl)-1,2,3,4-tetrahydrobenzo[b]azocine-5-carboxamide methanesulfonate (Compound I-MsOH-E);(g) about ≤0.50% to about ≥0.45% of 8-(4-(2-butoxyethoxy)phenyl)-1-butyl-N-(4-(((1-propyl-1H-imidazol-5-yl)methyl)sulfinyl)phenyl)-1,2,3,4-tetrahydrobenzo[b]azocine-5-carboxamide methanesulfonate (Compound I-MsOH-F); and(h) about ≤0.50% to about ≥0.45% of 8,8′-(4-(2-butoxyethoxy ...

CHEMICAL PROCESS FOR THE SYNTHESIS OF HERBICIDAL PYRAZOLIDINEDIONE COMPOUNDS

The present invention relates to a novel process for the synthesis of herbicidal pyrazolidinedione compounds. In particular, a process for the preparation of a compound of formula (I), wherein R, Rand Rare as defined herein. The present invention further relates to novel intermediate compounds utilized in said process, and methods for preparing said intermediate compounds. 2. A process according to claim 1 , wherein X is Br.3. A process according to claim 1 , wherein each Rand Rare ethyl.4. A process according to wherein Ris methyl.5. A process according to claim 1 , wherein the π-allylpalladium complex is selected from the group consisting of allylpalladium chloride claim 1 , allylpalladium trifluoroacetate claim 1 , (2-Butenyl)chloropalladium claim 1 , palladium (π-cinnamyl) chloride and (2-methylallyl)palladium chloride.6. A process according to claim 1 , wherein the π-allylpalladium complex is allylpalladium chloride or (2-Butenyl)chloropalladium.7. A process according to claim 1 , wherein the π-allylpalladium complex is present in the amount of from 1 to 10 mol % based on the compound of formula (II).8. A process according to wherein the molar ratio of π-allylpalladium complex to phosphine ligand or phosphine ligand salt is 1:4.9. A process according to claim 1 , wherein the π-allylpalladium complex is provided with a phosphine ligand as defined herein in a pre-formed complex.10. A process according to claim 1 , wherein the phosphine ligand of formula (IV) is 4-di-tent-butylphosphanyl-N claim 1 ,N-dimethyl-aniline.11. A process according to claim 1 , wherein the organic solvent is 1 claim 1 ,4-dioxane or toluene.12. A process according to claim 1 , wherein the base is KPO.13. A process according to claim 1 , wherein the reaction of a compound of formula (II) with a compound of formula (III) is at a temperature of from 80° C. to 110° C.15. A process according to claim 1 , wherein a compound of formula (I) is further converted to pinoxaden. The present invention ...

PROCESS FOR THE MANUFACTURE OF A SATURATED ALCOHOL

The present invention relates to a process for the manufacture of a saturated primary alcohol from an unsaturated aliphatic ester comprising the steps of: a) Providing an aliphatic ester having at least one carbon-carbon double bond; b) Carrying out a metathesis of said ester in the presence of a ruthenium carbene-based catalyst thereby obtaining a first reaction mixture; c) Adding a ligand and a base to the first reaction mixture, wherein the ligand comprises at least one donor atom chosen from the group consisting of a nitrogen atom and a phosphorus atom thereby obtaining a second reaction mixture comprising an ester product resulting from the metathesis reaction; d) Carrying out a homogeneous hydrogenation of the ester-product resulting from the metathesis, thereby obtaining a saturated primary alcohol. Further, the present invention relates to a catalyst for the hydrogenation of esters and to a process for the hydrogenation of esters using said catalyst. 1. Process for the manufacture of a saturated primary alcohol from an unsaturated aliphatic ester comprising the steps of:a) Providing an aliphatic ester having at least one carbon-carbon double bond;b) Carrying out a metathesis of said ester in the presence of a ruthenium carbene-based catalyst thereby obtaining a first reaction mixture;c) Adding a ligand and a base to the first reaction mixture, wherein the ligand comprises at least one donor atom chosen from the group consisting of a nitrogen atom and a phosphorus atom thereby obtaining a second reaction mixture comprising an ester product resulting from the metathesis reaction;d) Carrying out a homogeneous hydrogenation of the ester-product resulting from the metathesis, thereby obtaining a saturated primary alcohol.2. Process according to claim 1 , wherein a second compound having at least one carbon-carbon double bond is provided in step a) together with the aliphatic ester having at least one carbon-carbon double bond.3. Process according to claim 1 , ...

SELECTIVE REDUCTION OF ESTERS TO ALCOHOLS

The present invention relates to a selective reduction of esters to their corresponding alcohols. 2. Process according to claim 1 , wherein the process is carried out in the presence of at least one base.3. Process according to claim 1 , wherein the process is carried out in the presence of at least one base of formula (VIII){'br': None, 'sup': '1', 'sub': 1', '5, 'M(OC—Calkyl)\u2003\u2003(VIII),'}{'sup': '1', 'wherein Mis an alkali metal, is used.'}4. Process according to claim 1 , wherein the process is carried out in the presence of at least one base of formula (VIII′) claim 1 ,{'br': None, 'sup': '1', 'sub': 3', '5, 'M(OC—Calkyl)\u2003\u2003(VIII′)'}wherein{'sup': '1', 'Mis Li, Na or K.'}5. Process according to claim 1 , wherein the process is carried out in the presence of at least one base selected form the group consisting of KOtBu claim 1 , NaOtBu and LiOtBu.8. Process according to claim 1 , whereinthe catalyst of formula (III) is used in an amount of 0.001-0.5 mol-% (based on the number of moles of the compounds of formula (I)).9. Process according to claim 1 , wherein the reduction is a transfer hydrogenation.10. Process according to claim 1 , wherein the process is carried out with Hgas.11. Process according to claim 10 , wherein the process is carried out at a pressure of 10-50 bar.12. Process according to claim 1 , wherein the process is carried out at a temperature of 30-150° C. The present invention relates to a selective reduction of esters to their corresponding alcohols.Reduction of an ester into the corresponding alcohol is a fundamental and very important reaction in organic chemistry, and is used in a large number of chemical processes. The obtained alcohols are used as such or are important intermediates in further chemical processes.To reduce such esters, usually harsh reaction conditions have to be applied.Furthermore, the reduction of esters usually requests the use of highly reactive reducing agents such as LiAIHor NaBH, which are not easy ...

METHOD FOR HYDROSILYLATION OF ALIPHATICALLY UNSATURATED ALKOXYSILANES AND HYDROGEN TERMINATED ORGANOSILOXANE OLIGOMERS TO PREPARE ALKOXYSILYL TERMINATED POLYMERS USEFUL FOR FUNCTIONALIZING POLYORGANOSILOXANES USING A RHODIUM CATALYST

A method for preparing a product includes combining starting materials including, A) a siloxane oligomer having silicon bonded hydrogen atoms, B) an alkoxysilane having at least one aliphatically unsaturated group capable of undergoing hydrosilylation reaction and C) a dirhodium complex catalyst. The method can be used to produce a compound of formula (Formula (F)). This compound can be used in a hydrosilylation reaction with a vinyl-functional polyorganosiloxane. The resulting product includes an ethyltrimethoxysilyl functional polyorganosiloxane useful in condensation reaction curable sealant compositions. 2. The method of claim 1 , where (C) the rhodium diphosphine chelate has a formula selected from (C1) and (C2) claim 1 , where{'sup': 4', '5', '6', '4', '5', '6, 'sub': 2', '2', '2, '(C1) is [(R(RP))RhR], where each Ris independently a divalent hydrocarbon group, each Ris independently a monovalent hydrocarbon group, and each Ris a negatively charged ligand; and'}{'sup': 4', '5', '7', '4', '5', '7, 'sub': 2', '2, '(C2) is [(R(RP))Rh(X)] R, where R, and R, are as described above, and Ris an anion, and X is a donor ligand.'}6. The method of claim 1 , where (A) the polyorganohydrogensiloxane oligomer has unit formula:{'sup': 1', '1', '1, 'sub': 2', '1/2', '3', '2', '2/2', 'q', '3/2, '(HRSiO)(RSiO)(RSiO), where subscript q is 0 to 3.'}9. The method of claim 1 , where the organohydrogensiloxane oligomer is a cyclic organohydrogensiloxane oligomer of unit formula: (RHSiO) claim 1 , where subscript s is at least 3.16. The method of claim 15 , where the condensation reaction catalyst comprises a titanate catalyst.17. The method of claim 15 , where the composition further comprises one or more additional starting materials claim 15 , where the one or more additional starting materials are selected from the group consisting of (iii) a filler; (iv) a filler treating (v) a crosslinker; (vi) an adhesion promoter claim 15 , (vii) a drying agent; (viii) an extender claim 15 , ...

METHOD FOR PREPARING ORGANIC CARBOXYLIC ESTER BY USING COMBINED CATALYST OF ARYL BIDENTATE PHOSPHINE LIGAND

Disclosed is a method for preparing an organic carboxylic ester by using a combined catalyst of an aryl bidentate phosphine ligand. The method includes subjecting a terminal olefin, carbon monoxide, and an alcohol to a hydroesterification reaction in the presence of a combined catalyst of a palladium compound, an aryl bidentate phosphine ligand, and an acidic additive, to generate an organic carboxylic ester having one more carbon atom than the terminal olefin. 1. A method for preparing an organic carboxylic ester , comprising the step of:subjecting a terminal olefin, carbon monoxide, and an alcohol to a hydroesterification reaction in an organic solvent in the presence of a combined catalyst to generate an organic carboxylic ester having one more carbon atom than the terminal olefin,wherein the combined catalyst comprises a palladium compound, an aryl bidentate phosphine ligand, and an acidic additive.2. The method as claimed in claim 1 , wherein:a molar ratio of the aryl bidentate phosphine ligand to the palladium compound ranges from 0.1:1 to 100:1; anda molar ratio of the acidic additive to the palladium compound ranges from 0.1:1 to 100:1.3. The method as claimed in claim 2 , wherein:the molar ratio of the aryl bidentate phosphine ligand to the palladium compound ranges from 2:1 to 10:1; andthe molar ratio of the acidic additive to the palladium compound ranges from 2:1 to 20:1.5. The method as claimed in claim 4 , wherein claim 4 , in the substituted Caryl and substituted Cheteroaryl claim 4 , a substituent is selected from the group consisting of —Calkyl claim 4 , —Ccycloalkyl claim 4 , —Cheterocycloalkyl claim 4 , —Caryl claim 4 , —Cheteroaryl claim 4 , —O—Calkyl claim 4 , —O—Calkyl-Caryl claim 4 , —O—Ccycloalkyl claim 4 , —S—Calkyl claim 4 , —S—Ccycloalkyl claim 4 , —COO—Calkyl claim 4 , —COO—Ccycloalkyl claim 4 , —CONH—Calkyl claim 4 , —CONH—Ccycloalkyl claim 4 , —CO—Calkyl claim 4 , —CO—Ccycloalkyl claim 4 , —N—(Calkyl) claim 4 , —Caryl claim 4 , —Caryl- ...

Butadiene telomerization catalyst precursor preparation

Use a solvent blend that contains 1methoxy-2,7-octadiene and an alkanols rather than the alkanols by itself to prepare a catalyst precursor suitable for use in butadiene telomerization.

PREPARATION OF ALKYLAROMATIC COMPOUNDS

Described herein are methods useful for preparing alkylaromatics. 1. A method of preparing p-xylene , comprising converting 3-methyleneheptane or 3-methylheptane to p-xylene.2. The method of comprising converting 3-methyleneheptane top-xylene.3. The method of claim 1 , wherein the 3-methyleneheptane or 3-methylheptane is contacted with a catalyst.4. (canceled)5. The method of claim 3 , wherein the catalyst is a transition metal catalyst.6. The method of claim 3 , wherein the catalyst is an iridium catalyst.7. The method of claim 3 , wherein the catalyst is a pincer-ligated catalyst.89-. (canceled)10. The method of claim 3 , wherein the catalyst is (PCOP)Ir or (PCP)Ir.11. (canceled)12. The method of claim 3 , wherein the step of contacting 3-methyleneheptane or 3-methylheptane with the catalyst is performed in the presence of an H-acceptor.13. The method of claim 12 , wherein the H-acceptor is t-butylethylene (TBE).1415-. (canceled)16. The method of claim 1 , wherein the conversion is performed in a solvent.1719-. (canceled)20. A method of preparing p-xylene claim 1 , comprising converting 1-butene or 2-butene or a mixture thereof to p-xylene.21. The method of characterized in that conversion comprises the use of a catalyst.22. The method of characterized in that the 1-butene is first converted to an intermediate compound which intermediate is contacted with a catalyst.23. (canceled)24. The method of claim 21 , wherein the catalyst is a transition metal catalyst.25. The method of claim 21 , wherein the catalyst is an iridium catalyst.2628-. (canceled)29. The method of claim 21 , wherein the catalyst is any species containing the unit (PCOP)Ir or (PCP)Ir or other pincer-ligated iridium species.3032-. (canceled)33. The method of claim 1 , wherein the p-xylene is obtained in greater than 30% yield.34. The method of claim 1 , wherein the p-xylene is obtained in greater than 50% yield.3530. The method of any one of - claims 1 , wherein the p-xylene is obtained in greater ...

YLIDE-FUNCTIONALISED PHOSPHANES FOR USE IN METAL COMPLEXES AND HOMOGENEOUS CATALYSIS

The invention relates to ylide-functionalized phosphane ligands, the production of same and use in transition metal compounds, as well as the use of same as catalysts in organic reactions. 1. (canceled)2. The method of claim 8 , wherein in the phosphane ligands{'sub': 1-10', '1-6', '4-10', '6-14', '2-10', '6-14, '(i) the alkyl groups are selected from linear, branched-chain or cyclic Calkyl groups, preferably from Calkyl groups or C-cycloalkyl groups, the aryl groups are selected from Caryl groups, the alkenyl groups are selected from mono- or polyunsaturated linear, branched-chain or cyclic Calkenyl groups, and the heteroaryl groups are selected from Cheteroaryl groups; and/or'}{'sup': 11', '12', '3', '11', '11', '11', '11', '11, 'sub': 1-6', '6-10', '2', '2', '1-6, '(ii) the functional groups are selected from alkyl (—R), especially Calkyl groups, Caryl (—R), halogen (—Hal), hydroxy (—OH), cyano (—CN), alkoxy (—OR), amino (—NR, —NHR, —NH), mercapto (—SH, —SR), wherein R, independently of further Rresidues, is selected from Calkyl residues.'}4. The method of claim 8 , wherein in the phosphane ligands R claim 8 , Rand Rare independently selected from the group consisting of methyl claim 8 , ethyl claim 8 , butyl claim 8 , cyclohexyl claim 8 , phenyl claim 8 , and combinations thereof.5. The method of claim 8 , wherein in the phosphane ligands claim 8 , R claim 8 , Rand Rare the same and are selected from the group consisting of methyl claim 8 , ethyl claim 8 , butyl claim 8 , cyclohexyl claim 8 , phenyl claim 8 , and combinations thereof claim 8 , especially cyclohexyl and phenyl.6. The method of claim 8 , wherein in the phosphane ligands claim 8 , X is selected from the group consisting of methyl claim 8 , ethyl claim 8 , cyclohexyl claim 8 , phenyl claim 8 , p-tolyl claim 8 , trimethylsilyl claim 8 , p-tolylsulfonyl claim 8 , or combinations thereof.7. The method of claim 8 , wherein in the phosphane ligands claim 8 , Rand Rare independently selected from the ...

Novel phosphorus 2-pyrone derivative and preparation method thereof

Provided are a novel phosphorus 2-pyrone derivative and a preparation method thereof. The phosphorus 2-pyrone derivative according to the present invention is capable of being efficiently synthesized by treating an alkyl hydrogen alkynylphosphonate derivative and an alkyne derivative with a minimal amount of a gold catalyst.

Synthesis and characterization of metathesis catalysts

This invention relates generally to olefin metathesis catalysts, to the preparation of such compounds, compositions comprising such compounds, methods of using such compounds, and the use of such compounds in the metathesis of olefins and in the synthesis of related olefin metathesis catalysts. The invention has utility in the fields of catalysis, organic synthesis, polymer chemistry, and in industrial applications such as oil and gas, fine chemicals, and pharmaceuticals.

PRODUCTION METHOD OF POLYMER COMPOUND

The invention provides a production method of a polymer compound having a constitutional unit represented by the formula (3-1) and a constitutional unit represented by the formula (3-2), which contains a step of reacting a compound represented by the formula (1) and a compound represented by the formula (2) in the presence of a transition metal complex, a base and an organic solvent having a peroxide amount of 15 ppm by weight or less: 2. The polymer compound production method according to claim 1 , wherein a radical chain inhibitor is further used in said reaction step.3. The polymer compound production method according to claim 1 , wherein said transition metal complex is a palladium complex.4. The polymer compound production method according to any one of claim 1 , wherein said organic solvent is an organic solvent obtained by contacting with an adsorbent. The present invention relates to a production method of a polymer compound.As the material of organic electroluminescent devices and the like, for example, polymer compounds are used, and there is a correlation between the size of the molecular weight of the polymer compound and device characteristics, and it is desired to increase the molecular weight of the polymer compound.Such a polymer compound can be synthesized, for example, by reacting a diboronic acid of an aromatic compound and a dihalide of an aromatic compound in the presence of a transition metal complex by the Suzuki Coupling method. Specifically, for example, a method of reacting a diboronic acid of fluorene and a dibromo form of carbazole by the Suzuki Coupling method is known (Non-Patent Document 1).Non-Patent Document 1: Journal of Materials Chemistry C, 2015, 3, 9664-9669In the above-described method, however, it was difficult to obtain a polymer compound having sufficiently large molecular weight.Then, the present invention has an object of providing a polymer compound production method capable of obtaining a polymer compound having ...

CATALYST COMPLEX WITH CARBENE LIGAND

Catalytic complexes including a metal atom having anionic ligands, at least one nucleophilic carbene ligand, and an alkylidene, vinylidene, or allenylidene ligand. The complexes are highly stable to air, moisture and thermal degradation. The complexes are designed to efficiently carry out a variety of olefin metathesis reactions. 2. The catalytic complex of claim 1 , wherein Ris a C-Calkyl claim 1 , where the C-Calkyl is substituted with a functional group selected from hydroxyl claim 1 , thiol claim 1 , thioether claim 1 , ketone claim 1 , aldehyde claim 1 , ester claim 1 , amide claim 1 , amine claim 1 , imine claim 1 , nitro claim 1 , carboxylic acid claim 1 , disulfide claim 1 , carbonate claim 1 , isocyanate claim 1 , carbodiimide claim 1 , carboalkoxy claim 1 , carbamate claim 1 , and halogen.3. The catalytic complex of claim 1 , wherein Ris a C-Calkyl claim 1 , where the C-Calkyl is substituted with a functional group selected from thioether and imine.4. The catalytic complex of claim 3 , wherein Ris a cyclic isomer.5. The catalytic complex of claim 4 , wherein the cyclic isomer is a multiply unsaturated variant.6. The catalytic complex of claim 5 , wherein R is selected from the group consisting of hydrogen claim 5 , C-Calkyl claim 5 , and aryl; L is selected from the group consisting of phosphines claim 5 , phosphites claim 5 , phosphinites claim 5 , phosphonites claim 5 , and pyridines; Y and Yare each independently an aryl group substituted with C-Calkyl groups; and Z and Zare independently selected from the group consisting of hydrogen and C-Calkyl.7. The catalytic complex of claim 5 , wherein R is selected from the group consisting of hydrogen claim 5 , methyl claim 5 , ethyl claim 5 , n-propyl claim 5 , iso-propyl claim 5 , n-butyl claim 5 , iso-butyl claim 5 , sec-butyl claim 5 , and phenyl; X and Xare each halide claim 5 , CFCO claim 5 , CHCO claim 5 , CFHCO claim 5 , (CH)CO claim 5 , (CF)(CH)CO claim 5 , (CF)(CH)CO claim 5 , PhO claim 5 , MeO claim ...

CATALYST COMPOSITION COMPRISING PHOSPHORUS-BASED LIGAND AND HYDROFORMYLATION PROCESS USING THE SAME

Disclosed are a catalyst composition containing a phosphorous-based ligand and a hydroformylation process using the same. More specifically, disclosed are a catalyst composition containing a monodentate phosphite ligand, a monodentate phosphine ligand and a transition metal catalyst, wherein the total content of the entire ligand including the monodentate phosphite ligand and the monodentate phosphine ligand is 1 to 33 moles, based on 1 mole of the transition metal catalyst, and a hydroformylation method using the same. 2. The catalyst composition according to claim 1 , wherein the content of each of the monodentate phosphite ligand and the monodentate phosphine ligand is 0.5 to 32.5 moles claim 1 , based on 1 mole of the transition metal catalyst.3. The catalyst composition according to claim 1 , wherein a mix ratio of the monodentate phosphite ligand and the monodentate phosphine ligand is 5:1 to 1:5 claim 1 , based on weight.4. The catalyst composition according to claim 1 , wherein the monodentate phosphite ligand comprises one or more selected from the group consisting of triphenyl phosphite claim 1 , tris(2 claim 1 ,6-triisopropyl)phosphite claim 1 , tris(2 claim 1 ,6-di-tert-butyl-4-methoxyphenyl)phosphite claim 1 , tris(2-tert-butyl-4-methylphenyl)phosphite and tris(2 claim 1 ,4-di-tert-butylphenyl)phosphite (TDTBPP).5. The catalyst composition according to claim 1 , wherein the monodentate phosphine ligand comprises one or more selected from the group consisting of tri-m-tolylphosphine (TMTP) claim 1 , tri-p-tolylphosphine (TPTP) claim 1 , diphenyl(p-tolyl)phosphine (DPPTP) claim 1 , cyclohexyldiphenylphosphine (CHDP) claim 1 , tris(2 claim 1 ,6-dimethoxyphenyl)phosphine (TDMPP) claim 1 , tris(4-methoxyphenyl)phosphine (TMPP) claim 1 , trimesitylphosphine (TMSTP) claim 1 , tris-3 claim 1 ,5-xylylphosphine (TXP) claim 1 , tricyclohexylphosphine (TCHP) claim 1 , tribenzylphosphine (TBP) claim 1 , benzyl diphenylphosphine (BDPP) and diphenyl-n-propylphosphine ...

IRIDIUM PINCER COMPLEX FOR ALKANE DEHYDROGENATION PROCESS

Disclosed herein are processes for dehydrogenation of an alkane to an alkene using an iridium pincer complex and iridium pincer complexes. In the dehydrogenation reactions, hydrogen that is co-formed during the process must be removed for the chemical reaction to proceed and to prevent the excess hydrogen from poisoning the catalyst. In one embodiment the process comprises providing an alkane feedstock comprising at least one alkane and contacting the alkane with an iridium pincer complex in the presence of a hydrogen acceptor selected from the group consisting of ethylene, propene, or mixtures to form an alkene product. The processes disclosed herein can accomplish facile, low-temperature transfer dehydrogenation of alkanes with unprecedented selectivities and TONs at a reasonable rate of conversion 1. An iridium pincer complex of the formula (PCP)Ir(CH).2. The iridium pincer complex of claim 1 , wherein the iridium pincer complex is unsupported.3. The iridium pincer complex of claim 1 , wherein the iridium pincer complex is immobilized on a solid support.4. An iridium pincer complex of the formula (p-OK-PCP)Ir(CH).5. The iridium pincer complex of claim 4 , wherein the iridium pincer complex is unsupported.6. The iridium pincer complex of claim 4 , wherein the iridium pincer complex is immobilized on a solid support. This application is a Divisional of U.S. application Ser. No. 14/638,997 filed Mar. 4, 2015 entitled “Alkane Dehydrogenation Process” which claims priority to U.S. Provisional No. 61/947,915 filed Mar. 4, 2014 entitled “Alkane Dehydrogenation Process”, the contents of both of which are herein incorporated by reference in their entireties.Provided is a process for generating olefins (i.e., alkenes) from alkanes. More specifically, the process uses iridium pincer complex catalysts for generating olefins from alkanes.Olefins are an important and versatile feedstock for fuels and chemicals, but they are not as widely available naturally as alkanes. The ...

PROCESS FOR PRODUCING POLYISOCYANURATE PLASTICS BY MEANS OF PHOSPHINE CATALYSIS

The present invention relates to process for producing polyisocyanurate plastics, comprising the following steps: a) providing a polyisocyanate composition A) which comprises oligomeric polyisocyanates and is low in monomeric diisocyanates, “low in monomeric diisocyanates” meaning that the polyisocyanate composition A) has a content of monomeric diisocyanates of not more than 20% by weight, b) catalytically trimerizing the polyisocyanate composition A) using at least one tertiary organic phosphine catalyst B). The invention further relates to polyisocyanurate plastics obtainable by the process according to the invention, to coatings, films, semifinished products and mouldings comprising or consisting of the polyisocyanurate plastic according to the invention, and to the use of the polyisocyanurate plastics according to the invention for production of coatings, films, semifinished products and mouldings. 115-. (canceled)16. A process for producing a polyisocyanurate plastic , comprising the following steps:a) providing a polyisocyanate composition A) which comprises oligomeric polyisocyanates and is low in monomeric diisocyanates, “low in monomeric diisocyanates” meaning that the polyisocyanate composition A) has a content of monomeric diisocyanates of not more than 20% by weight, andb) catalytically trimerizing the polyisocyanate composition A) using at least one tertiary organic phosphine catalyst B).18. The process according to claim 16 , wherein the tertiary organic phosphine catalyst B) is selected from the group consisting of trimethylphosphine claim 16 , triethylphosphine claim 16 , tri-n-propylphosphine claim 16 , tripropylphosphine claim 16 , dibutylethylphosphine claim 16 , tri-n-butylphosphine claim 16 , triisobutylphosphine claim 16 , tri-tert-butylphosphine claim 16 , pentyldimethylphosphine claim 16 , pentyldiethylphosphine claim 16 , pentyldipropylphosphine claim 16 , pentyldibutylphosphine claim 16 , pentyldihexylphosphine claim 16 , ...

Process of production of 1-(5,5-dimethylcyclohex-1-en-1-yl)ethanone and 1-(5,5-dimethylcyclohex-6-en-1-yl )ethanone

The present invention relates to an improved method for producing of 1-(5,5-dimethylcyclohex-1-en-1-yl)ethanone and 1-(5,5-dimethylcyclohex-6-en-1-yl)ethanone.

PROCESS FOR PREPARING AN UNSATURATED CARBOXYLIC ACID SALT

Catalytic process for preparing an α,β-ethylenically unsaturated carboxylic acid salt, comprising reacting an alkene and carbon dioxide in the presence of a carboxylation catalyst and releasing the α,β-ethylenically unsaturated carboxylic acid salt with a base, the carboxylation catalyst being a transition metal complex, which comprises a structurally constrained bidentate P,X ligand, wherein X is selected from the group consisting of P, N, O, and carbene, the P and X atom are separated by 2 to 4 bridging atoms, and wherein the bridging atoms are part of at least one 5- to 7-membered cyclic substructure. A further catalytic processes for preparing α-βethylenically unsaturated carboxylic acid derivatives from COand an alkene is provided. 1: A catalytic process for preparing an α ,β-ethylenically unsaturated carboxylic acid salt , the process comprising reacting an alkene and carbon dioxide in the presence of a carboxylation catalyst and releasing the α ,β-ethylenically unsaturated carboxylic acid salt with a base ,wherein:the carboxylation catalyst is a transition metal complex comprising a structurally constrained bidentate P,X ligand:X is selected from the group consisting of P, N, O, and a carbene;the P and X atoms of the P,X ligand are separated by 2 to 4 bridging atoms; andthe bridging atoms are contained in at least one 5- to 7-membered cyclic substructure.2: The catalytic process according to claim 1 , wherein the structurally constrained bidentate ligand is a P claim 1 ,X ligand is a P claim 1 ,P ligand in which:each bridging atom is directly linked to a P atom, together with the P atom to which it is linked, and the bridging atoms are contained in a 5 to 7-membered cyclic substructure; ortwo neighboring bridging stomas are contained in a 5- to 7-membered cyclic substructure.4: The catalytic process according to claim 3 , wherein:the structurally constrained bidentate P,X ligand is a ligand of formula (IIa); and{'sup': 6', '7, 'sub': '3', 'Ris CR.'}6: The ...

NOVEL CATALYTIC COMPOSITION COMPRISING NICKEL AND A PHOSPHINE-TYPE LIGAND, AND USE THEREOF IN AN OLEFIN OLIGOMERISATION METHOD

The invention concerns a process for the dimerization of ethylene to 1-butene, carried out with a catalytic composition comprising: at least one nickel precursor with an oxidation number of (+II), at least one phosphine ligand with formula PRRRin which the groups R, Rand Rmay be identical or different and which may or may not be bonded together, and at least one activating agent selected from the group formed by chlorinated and brominated hydrocarbylaluminium compounds, used alone or as a mixture, said composition having a molar ratio of the phosphine ligand to the nickel precursor in the range 5 to 30 and a molar ratio of the activating agent to the phosphine ligand greater than or equal to 1. 1. A process for the dimerization of ethylene to 1-butenes , comprising bringing ethylene into contact with a catalytic composition comprising:at least one nickel precursor with an oxidation number of (+II),{'sup': 1', '2', '3', '1', '2', '3, 'at least one phosphine ligand with formula PRRR, in which the groups R, Rand R, which may be identical or different, and which may or may not be bonded together, are selected from'}aromatic groups, which may or may not be substituted and which may or may not contain heteroelements,and/or hydrocarbyl groups, which may or may not be cyclic, which may or may not be substituted and which may or may not contain heteroelements,and at least one activating agent selected from the group formed by chlorinated and brominated hydrocarbylaluminium compounds, used alone or as a mixture, said composition having a molar ratio of the phosphine ligand to the nickel precursor in the range 5 to 30 and a molar ratio of the activating agent to the phosphine ligand which is greater than or equal to 1,the process being carried out at a temperature in the range from a value of more than 20° C. to +250° C.2. The process according to claim 1 , in which the groups R claim 1 , Rand Rof said phosphine ligand are identical.3. The process according to claim 1 , in ...

METAL COMPLEX AND SUPPORTED METAL COMPLEX HAVING DISILOXANE AS LIGAND, METHOD FOR PRODUCTION THEREFOR, AND SUPPORTED METAL CATALYST PREPARED BY USING THE SAME

A metal complex represented by the following Formula (1): 23.-. (canceled)4. A method for producing the metal complex as defined in claim 1 , comprising reacting a metal complex LMX(wherein M represents palladium or platinum; L represents a ligand selected from carbon monoxide claim 1 , an olefin compound claim 1 , an amine compound claim 1 , a phosphine compound claim 1 , an N-heterocyclic carbene compound claim 1 , a nitrile compound and an isocyanide compound; n represents an integer of 0 to 2 showing the number of the ligand; and X represents halogen or a hydroxyl group) with a disiloxane compound HO—(R)(R)Si—O—(R)(R)Si—OH (each of Rto Rrepresents an organic group) in the presence of an alkaline metal hydride.5. (canceled)7. A catalyst for hydrogenation reaction of olefins claim 6 , comprising the supported metal catalyst as defined in .8. The catalyst for hydrogenation reaction according to claim 7 , wherein a central metal of the catalyst is platinum.9. A catalyst for hydrosilylation reaction of olefins claim 1 , comprising the metal complex compound as defined in .10. (canceled)11. The catalyst for hydrosilylation reaction according to claim 9 , wherein a central metal of the catalyst is platinum.12. The supported metal catalyst according to claim 6 , wherein the inorganic oxide of the supported metal complex is silica or a composite oxide containing silicon. Technical FieldThe present invention relates to a metal complex having a skeletal structure in which a disiloxane group is coordinated as a chelate to a central metal. Further, the present invention relates to a supported metal complex obtained by fixing the metal complex on an inorganic oxide while retaining a skeletal structure thereof, and a method for producing the same.Also, the present invention relates to a method for producing a supported metal catalyst by calcining the supported metal complex.Background ArtA reaction system in which a catalyst containing a metal component as a catalytically ...

Process for the Preparation of Alcohols from Alfa, Beta-Unsaturated Aldehydes and Ketones

A chemoselective process for producing alcohols from α,β-unsaturated aldehydes and ketones is described. 2. The process according to wherein the base is an alkali metal compound.3. The process according to wherein the temperature is increased after at least 88% of the compound of formula (II) has been converted to the respective alcohol of formula (III).4. The process according to claim 1 , wherein the catalyst is a homogeneous ruthenium (II) catalyst.5. The process according to wherein the homogeneous ruthenium (II) catalyst is a Ru complex comprising two triarylphosphines claim 4 , a diamine and two electronegative ligands.6. The process according to claim 1 , wherein the ruthenium catalyst is RuCl(PPh)(ethylene-diamine) or RuCl(P(para-methyl phenyl))(ethylene-diamine).7. A process according to wherein the α claim 1 ,β-unsaturated double bond of the compound of formula (II) is in E- configuration.8. A process according to wherein:{'sup': '1', 'Ris hydrogen;'}{'sup': '2', 'Ris hydrogen;'}{'sup': '3', 'Ris methyl;'}{'sup': '4', 'Ris methyl; and'}R is selected from the group consisting of 3-methyl but-2-enyl, 3,7-dimethylocta-2,6-dieneyl, 2,3-dimethylbut-2-enyl, but-2-enyl, 2,4,7-trimethylocta-2,6-dieneyl, and 2-methylpent-2-enyl.10. A process according to wherein R is 3-methyl but-2-enyl. The present invention relates to fragrance ingredients and to methods of forming same. In particular the present invention relates to a method for producing alcohols from ,β-unsaturated aldehydes and ketones.The reduction of ,β-unsaturated aldehydes is an important reaction, because the possible products, such as saturated aldehydes, and saturated or unsaturated alcohols, have found many uses in fragrances, cosmetics, and pharmaceutical industries; also they constitute relevant intermediates in the synthesis of various fine chemicals. Due to the presence of two or more moieties with similar reactivity the reaction is complicated, in particular, when it is desired that not all ...

CATALYST CAPABLE OF FORMING 2,5-DIMETHYLHEXENES

A process of making a catalyst and the catalyst composition made by that process comprising a multinuclear metal compound of the formula M(PCy)(H)(CO)(OR)(HO)with molar ratios a:b:c:d:e:f, wherein a is in the range from 2 to 2000, b is in the range from 0 to 4000, c is in the range from 0 to 6000 and d is in the range from 0 to 2000, e is in the range from 1 to 2000, and f is in the range from 0 to 100; wherein PCyindicates tricyclohexylphosphine, H indicates hydride, R is an alkyl group determined by the alcohol utilized and HO is water from the reaction; and a is at least twice w. A method of making one or more 2,5-dimethylhexenes is described. A method of making p-xylene using one or more 2,5-dimethylhexenes is also described. 1. A process for manufacturing a catalyst composition which comprises:{'sub': w', '3', 'x', 'y', 'z', '3, 'a) making a mixture by blending one molar part of a metal compound comprising a core species M(PCy)(H)(CO), wherein PCyindicates tricyclohexylphosphine and wherein H indicates a hydride, in a molar ratio of w:x:y:z, with at least about one molar part of an alcohol; and with at least about one molar part isobutylene; and'} wherein M is selected from the group consisting of ruthenium, platinum, rhodium, palladium, osmium, and iridium;', 'wherein the metal compound can be charged from 2− to 2+;', 'wherein w is in a range from 1 to 6, x is in a range from 0 to 12, y is in a range from 0 to 18 and z is in a range from 0 to 6; and', 'wherein the alcohol is selected from the group consisting of methanol, ethanol, n-propanol, n-butanol, isobutyl alcohol, n-pentanol, n-hexanol, n-heptanol and n-octanol., 'b) heating the mixture to a temperature in the range of 50° to about 200° C. for at least about 10 minutes;'}2. The process of wherein the metal compound is [(CH)(PCy)(CO)RuH]BF claim 1 , and w=x=y=z=1.3. The process of wherein the metal compound is {[PCy)(CO)RuH](μ-O)(μ-OH)(μ-OH)} and w=x=y=z=4.4. The process of wherein the metal compound is ...

CATALYST COMPOSITIONS FOR HYDROFORMYLATION AND METHODS OF USE THEREOF

Disclosed are highly active cationic cobalt phosphine complexes, both mono- and bimetallic, that can catalyze hydroformylation reactions. The disclosed catalysts can be utilized in methods that provide reaction processes that are hundreds of times faster than high pressure HCo(CO)or phosphine-modified HCo(CO)(PR) catalysts and operate at considerably lower pressures and temperatures. Also disclosed are methods of hydroformylation using the described transition metal complexes. This abstract is intended as a scanning tool for purposes of searching in the particular art and is not intended to be limiting of the present disclosure. 2. The compound of claim 1 , wherein X is CRR.3. The compound of claim 1 , wherein Rand Rare each C-Calkyl.4. The compound of claim 1 , wherein Rand Rare each ethyl.5. The compound of claim 1 , wherein Ris phenyl.6. The compound of claim 1 , wherein Y is 1 claim 1 ,2-phenylene.7. The compound of claim 1 , wherein Mand Mare each independently selected from the group consisting of Co and Rh.8. The compound of claim 1 , wherein p is 2.9. The compound of claim 1 , wherein Land Lare each independently selected from the group consisting of acetoacetonate claim 1 , acetonitrile claim 1 , pyridine claim 1 , and cyclooctadiene.12. The compound of claim 11 , wherein M is Rh or Co.13. The compound of claim 11 , wherein L is acetylacetonate.14. The compound of claim 11 , wherein Rand Rare each C-Calkyl claim 11 , phenyl claim 11 , or cycloalkyl; each of which may be optionally substituted.15. The compound of claim 11 , wherein Z is 1 claim 11 ,2-phenylene claim 11 , 1 claim 11 ,2-ethylene claim 11 , or 1 claim 11 ,3-propylene.16. The compound of claim 11 , wherein q is 1.18. A method of preparing an aldehyde-containing compound claim 1 , the method comprising contacting an alkene-containing compound with the compound of in the presence of hydrogen (H) and carbon monoxide (CO) claim 1 , whereby the alkene is converted to an aldehyde.19. The method of ...

Selective catalysts for spinetoram production

This invention is based on the discovery that homogeneous catalysts, [Rh(C 2 H 4 ) 2 Cl] 2 and/or [Rh(COD) 2 ][BF 4 ], can be used to produce spinetoram in higher yields at lower catalyst loadings as compared to previous methodologies. In addition, one or more phosphorus ligand donors can also be added to further increase yields/efficiency. The methods and/or systems provided herein enable cost-effective ways to produce spinetoram in large quantity with relatively simple procedures.

PLATINUM COMPLEXES HAVING BENZYL-BASED DIPHOSPHINE LIGANDS FOR THE CATALYSIS OF THE ALKOXYCARBONYLATION OF ETHYLENICALLY UNSATURATED COMPOUNDS

Platinum complexes having benzyl-based diphosphine ligands for the catalysis of the alkoxycarbonylation of ethylenically unsaturated compounds. 2. Complex according to claim 1 ,{'sup': 1', '2', '3', '4, 'sub': 5', '20, 'wherein at least two of the R, R, R, Rradicals are a -(C-C)-heteroaryl radical having at least six ring atoms.'}3. Complex according to claim 1 ,{'sup': 1', '3, 'sub': 6', '20, 'wherein the Rand Rradicals are each a -(C-C)-heteroaryl radical having at least six ring atoms.'}4. Complex according to claim 1 ,{'sup': 1', '3, 'wherein the Rand Rradicals are each 2-pyridyl.'}5. Complex according to claim 1 ,{'sup': 2', '4, 'sub': 1', '12, 'wherein Rand Rare -(C-C)-alkyl.'}6. Complex according to claim 1 ,{'sup': 2', '4, 'wherein Rand Rare Cert-butyl.'}9. Process according to claim 8 ,wherein the ethylenically unsaturated compound is selected from: ethene, propene, 1-butene, cis- and/or trans-2-butene, isobutene, 1,3-butadiene, 1-pentene, cis- and/or trans-2-pentene, 2-methyl-1-butene, 3-methyl-1-butene, 2-methyl-2-butene, hexene, tetramethylethylene, heptene, 1-octene, 2-octene, di-n-butene, or mixtures thereof.10. Process according to claim 8 ,wherein the alcohol in process step c) is selected from: methanol, ethanol, 1-propanol, 1-butanol, 1-pentanol, 1-hexanol, 2-propanol, tert-butanol, 3-pentanol, cyclohexanol, phenol.11. Process according to any of to claim 8 ,wherein the alcohol in process step c) is methanol.12. Process according to claim 8 ,{'sub': 2', '2', '2', '2', '2', '2', '3', '2', '2', '2, 'wherein the substance comprising Pt is selected from: platinum dichloride (PtCl), platinum(II) acetylacetonate [Pt(acac)], platinum(II) acetate [Pt(OAc)], dichloro(1,5-cyclooctadiene)platinum(II) [Pt(cod)Cl], bis(dibenzylideneacetone)platinum [Pt(dba)], bis(acetonitrile)dichloroplatinum(II) [Pt(CHCN)Cl], (cinnamyl)platinum dichloride [Pt(cinnamyl)Cl].'}13. Process according to claim 8 ,{'sub': 2', '2', '2, 'wherein the substance comprising Pt is selected ...

CATALYSTS FOR THE PRODUCTION OF METHANOL FROM CARBON DIOXIDE

Catalysts for the reduction of COare described herein. More specifically, catalysts of Formula I and Formula II: 1422-. (canceled)23. The process of claim 13 , wherein the hydrogen source is a hydroborane.24. The process of claim 23 , wherein the hydroborane is selected from the group consisting of HBCat claim 23 , HBPin claim 23 , 9-BBN and BH—SMe.2527-. (canceled)3338-. (canceled)4052-. (canceled) The present application claims the benefit of priority from U.S. Provisional Application No. 61/815,066 filed on Apr. 23, 2013. The entire text of the above-referenced disclosure is specifically incorporated herein by reference.The present disclosure broadly relates to the production of methanol. More specifically but not exclusively, the present disclosure relates to catalysts for the production of methanol from carbon dioxide. The present disclosure also relates to a process for the production of methanol from carbon dioxide using such catalysts.It is widely known that carbon dioxide is a green-house gas and considered one of the most important contributors to global warming. Many initiatives have been put forward by a great number of countries with the aim of reducing carbon dioxide emissions. The transformation of carbon dioxide into valuable chemicals, such as energy vectors like methane or methanol, is a highly desirable objective having received considerable interest in recent years. Most of the current systems capable of catalyzing the reduction of COinto valuable products, including notably the inverse water-gas shift reaction to generate carbon monoxide which in turn can be transformed into several useful chemicals, call upon the use of transition metals.Recently, some organometallic systems have shown promise in generating valuable chemicals in one pot under mild conditions. For example, Milstein described a ruthenium pincer complex to reduce CO-derived carbamates, carbonates and formates to methanol using Has a hydrogen source.Methanol has also been obtained ...

BUTADIENE TELOMERIZATION CATALYST PRECURSOR PREPARATION

Use a solvent blend that contains 1-methoxy-2,7-octadiene and an alkanols rather than the alkanols by itself to prepare a catalyst precursor suitable for use in butadiene telomerization. 1. A process for preparing a telomerization catalyst precursor used in telomerization of butadiene that comprises dissolving one equivalent of palladium acetyl acetonate and from one to three equivalents of a phosphine in a solvent blend that comprises methanol and 1-methoxy-2 ,7-octadiene under conditions sufficient to yield a catalyst precursor solution that comprises an aryl phosphine-palladium octadienyl complex represented formulaically either as [(ArPR)PdY] or as [(ArPR)PdY] wherein R is an alkyl or heteroatom-containing alkyl moiety with 1 to 12 carbon atoms , Ar is an aryl moiety or substituted aryl moiety , x=1 or 2 , n=1 , 2 or 3 , and Y is a ligand derived from methoxyoctadiene and wherein illustrative ligands include 1-methoxy-2 ,7-octadiene (MOD-1) where no charge is present or octadienyl when a positive charge is present.2. The process of claim 1 , wherein the conditions include a temperature within a range of from 0 degrees centigrade to 100 degrees centigrade.3. The process of claim 1 , wherein the conditions include a temperature within a range of from 5 degrees centigrade to 60 degrees centigrade.4. The process of any of through claim 1 , wherein the number of equivalents of a phosphine is one or two.5. The process of claim 1 , wherein the solvent blend has a 1-methoxy-2 claim 1 ,7-octadiene content within a range of from 0.1 weight percent to 50 weight percent claim 1 , based upon total solvent blend weight.6. The process of claim 5 , wherein the solvent blend has a 1-methoxy-2 claim 5 ,7-octadiene content within a range of from 10 weight percent to 25 weight percent claim 5 , based upon total solvent blend weight.7. The process of claim 1 , wherein the catalyst precursor solution has a palladium concentration that ranges from 0.02 weight percent to 2 weight ...

METAL-CATALYZED ALKOXYCARBONYLATION OF A LACTONE

The metal-catalyzed alkoxycarbonylation of a lactone is a method of alkoxycarbonylating a δ-lactone, specifically 3-ethylidene-6-vinyltetrahydro-2H-pyran-2-one. The method includes combining the δ-lactone with an alcohol in an organic solvent in the presence of a catalyst system that includes palladium or a salt thereof to form a reaction mixture, which is heated to 110-130° C. at a pressure of 20-50 bar for between 3-5 hours under flow of carbon monoxide gas. The product of the reaction is a substituted 2-octendioate diester. The alcohol may be methyl alcohol, n-butyl alcohol, 2-ethylhexanol, isobutyl alcohol, isopropyl alcohol, benzyl alcohol, or phenol. The solvent may be toluene, acetonitrile, or tetrahydrofuran. The method may include adding an acid to the reaction mixture, which may be dilute (about 5 mol %) sulfuric or p-toluenesulfonic acid. The catalyst system may also include a phosphine ligand. 1. A method for metal-catalyzed alkoxycarbonylation of a δ-lactone , the δ-lactone being 3-ethylidene-6-vinyletetrahydro-2H-pyran-2-one , the method comprising the steps of:adding an alcohol and a catalyst system including palladium or a salt thereof to a solution of the δ-lactone in an organic solvent to form a reaction mixture;placing the reaction mixture under pressure of carbon monoxide (CO) gas;heating the reaction mixture to a temperature of at least 110° C.; andrecovering a 2-octendioate diester product.2. The method for metal-catalyzed alkoxycarbonylation according to claim 1 , wherein the catalyst system further comprises a phosphine ligand.3. The method for metal-catalyzed alkoxycarbonylation according to claim 2 , wherein the phosphine ligand is selected from the group of phosphine ligands having the formulas shown in L1 claim 2 , L2 claim 2 , L3 claim 2 , L4 claim 2 , L5 claim 2 , L6 claim 2 , L7 claim 2 , L8 claim 2 , L9 claim 2 , L10 claim 2 , L11 claim 2 , L12 claim 2 , L13 claim 2 , L14 claim 2 , L15 claim 2 , L16 claim 2 , L17 claim 2 , L18 claim 2 ...

LIGANDS OF THE BENZO QUINOLINE CLASS AND TRANSITION METAL COMPLEXES CONTAINING THEM AND USE OF SAID COMPLEXES AS CATALYSTS

A new class of ligands derived from benzo[h]quinoline are described and these ligands are used to prepare several novel transition metal complexes. The complexes are preferably of the group VIII transition metals iron, ruthenium or osmium, with the benzo[h]quinolone ligands acting as tridentate ligands. The complexes described are proved to be very active catalysts for the reduction of ketones and aldehydes to alcohols, via hydrogen transfer and hydrogenation reactions. These compounds hence can be usefully employed as catalysts in said reduction reactions. 2. The transition metal complex of claim 1 , wherein M is Ru.3. The transition metal complex of claim 1 , wherein L is PPhand X is Cl.4. The transition metal complex of claim 1 , wherein Ris H.5. The transition metal complex of claim 2 , wherein L is PPhand X is Cl.6. The transition metal complex of claim 2 , wherein L is PPhand X is Cl and Ris H.8. The transition metal complex of claim 7 , wherein L is PPh(CH))PPh.9. The transition metal complex of claim 7 , wherein X is Cl and Ris H.10. The transition metal complex of claim 7 , wherein X is H and Ris H.11. The transition metal complex of claim 7 , wherein X is OCH (p-CHF)and Ris H.12. The transition metal complex of claim 7 , wherein M is Ru claim 7 , X is Cl claim 7 , and Ris methyl.13. The transition metal complex of claim 7 , wherein M is Ru claim 7 , X is Cl claim 7 , and Ris tert-butyl.14. The transition metal complex of claim 8 , wherein X is Cl and Ris H.15. The transition metal complex of claim 8 , wherein X is H and Ris H.16. The transition metal complex of claim 8 , wherein X is OCH (p-CHF)and Ris H.18. The transition metal complex of claim 17 , wherein Ris methyl.19. The transition metal complex of claim 17 , wherein Ris tert-butyl.26. The transition metal complex of claim 25 , wherein Ris methyl.27. The transition metal complex of claim 25 , wherein Ris tert-butyl.29. The transition metal complex of claim 28 , wherein Ris methyl.30. The transition ...

Method For Synthesising Esters And Catalyst For Said Synthesis

A method for synthesising esters from alcohols by dehydrogenating coupling in the presence of a catalyst of formula 1 as well as to the use of catalysts of formula 1 for synthesising esters. The method according to the invention can be used in particular for the production of dihydrogen. The invention also relates to novel catalysts as well as to the uses thereof. 15-. (canceled)7. The method as claimed in claim 6 , wherein said synthesis produces gaseous dihydrogen claim 6 , H.8. The method as claimed in claim 7 , wherein said method comprises a step of capturing said gaseous dihydrogen.9. The method as claimed in claim 6 , wherein said at least one alcohol is a crude alcohol.10. The method as claimed in claim 6 , wherein said at least one alcohol is a branched or non-branched primary alcohol comprising a number of carbon atoms ranging from 1 and 30.11. The method as claimed in claim 6 , wherein that the reaction of said at least one alcohol and said catalyst is carried out in the absence of a hydrogen acceptor compound and in the absence of base.12. The method as claimed in claim 6 , wherein that said reaction is carried out in the absence of solvent.13. The method as claimed in claim 6 , wherein that the catalyst loading used is selected from a range extending from 10 000 ppm to 1 ppm.14. The method as claimed in claim 6 , wherein that the pressure of the reaction medium is atmospheric pressure or a lower pressure claim 6 , and that the temperature of the reaction medium is selected from a range extending from 200° C. to 15° C. claim 6 ,15. The method as claimed in claim 6 , wherein that the alcohol reacted with the catalyst of formula 1 is an alcohol selected from the group consisting of ethanol claim 6 , butanol claim 6 , octan-1-ol claim 6 , 2-ethyl-1-hexanol claim 6 , nonan-1-ol claim 6 , decan-1-ol claim 6 , undecanol claim 6 , lauryl alcohol claim 6 , myristyl alcohol claim 6 , cetyl alcohol claim 6 , stearyl alcohol claim 6 , docosanol claim 6 , ...

Amine Derivatives of The Beta-Farnesene

The invention provides a process for preparing farnesylamines by reacting β-farnesene with one or more amines in the presence of a transition metal catalyst from transition group 10 at a temperature in the range from 60 to 150° C.

A solid heterogeneous catalyst for olefin hydroformylation reaction and production method and use thereof

A solid heterogeneous catalyst consisting of a metal component and an organic ligand polymer, wherein the metal component is one or more of Rh, Ir or Co, the organic ligand polymer is a polymer having a large specific surface area and hierarchical porosity formed by polymerizing an organic ligand monomer containing P and alkenyl group and optional N via a solvothermal polymerization process, the metal component forms coordinated bond with the P atom or N in backbone of the organic ligand polymer and exists in a monoatomic dispersion state; when the catalyst is used in an olefin hydroformylation reaction, the metal component and the P and/or N atom form in situ an intermediate active species similar to homogeneous catalyst due to the coordination effect, and the catalyst has an excellent catalytic property, can be easily separated, and has a relatively high stability. 1. A solid heterogeneous catalyst for olefin hydroformylation reaction , wherein the solid heterogeneous catalyst consists of a metal component and an organic ligand polymer , wherein the metal component is one or more of Rh , Ir or Co , the organic ligand polymer is a polymer having a large specific surface area and hierarchical porosity formed by polymerizing an organic ligand monomer containing P and alkenyl group and optional N via a solvothermal polymerization process , the metal component forms coordinated bonds with the P atom or N in backbone of the organic ligand polymer and exists in a monoatomic dispersion state.2. The solid heterogeneous catalyst according to claim 1 , wherein the metal component accounts for 0.005 to 5.0% based on the total weight of the solid heterogeneous catalyst.3. The solid heterogeneous catalyst according to claim 1 , wherein the organic ligand monomer is an organic phosphine ligand monomer containing P and vinyl group and optional N.4. The solid heterogeneous catalyst according to claim 1 , wherein the organic ligand polymer has a specific surface area of 100 to 3000 ...

Method for olefin hydroformylation reaction using solid heterogeneous catalyst

A method for an olefin hydroformylation reaction comprising subjecting olefins and CO/H2 mixed gas to the olefin hydroformylation reaction in a reactor in the presence of a solid heterogeneous catalyst, which consisting of a metal component and an organic ligand polymer with hierarchical porosity, in which the metal component is one or more of Rh, Ir or Co, the organic ligand polymer is a polymer formed by polymerization of an organic ligand monomer containing P and alkenyl group and optional N, and in the solid heterogeneous catalyst, the metal component forms coordinated bonds with the P atom or N in the backbone of the organic ligand polymer and exists in a monoatomic dispersion state; the reaction technique and device are simple, and the catalyst has a stable hydroformylation property with a high activity and yield.

Process for Preparing 2,6-Substituted Phenols

The present invention relates to a process for preparing 2,6-substituted phenols, and in particular to a process for preparing 2,6-diphenylphenol. This process is a doubling coupling of a boronic acid and a 2,6-dihalogenphenol in a Suzuki-Miyaura reaction on sterically hindered ortho positions. In a preferred embodiment, this process takes place in a continuous flow system. The present invention further relates to the composition obtained by this process, and to the use of this composition for preparing poly(2,6-diphenylphenylene oxide), for the manufacture of dyes, drugs, plastics, insulating materials and/or insecticides, and for use in medical applications and material research.

HYDROGENATION OF ESTERS WITH FE/TRIDENTATE LIGANDS COMPLEXES

The present invention relates to the field of catalytic hydrogenation and, more particularly, to the use of Fe complexes with tridentate ligands, having one amino or imino coordinating group and two phosphino coordinating groups, in hydrogenation processes for the reduction of ketones, aldehydes, esters or lactones into the corresponding alcohol or diol, respectively. 1. A process for the reduction by hydrogenation , using molecular H , of a C-Csubstrate containing one or two carbonyl or carboxylic functional group into the corresponding alcohol , or diol , characterized in that said process is carried out in the presence of a base and at least one catalyst or pre-catalyst in the form of a iron complex of formula{'br': None, 'sub': a', 'b, '[Fe(L3)(L′)Y](Z)\u2003\u2003(1)'}wherein L3 represents a tridentate ligand wherein the coordinating groups consist of one amino or imino group and two phosphino groups;{'sub': '1-11', 'L′ represents a CO or Cisonitrile compound;'}{'sub': 1', '6', '4', '4, 'each Y represents, simultaneously or independently, a hydrogen or halogen atom, a hydroxyl group, or a C-Calkoxy or carboxylic radical or a BHor AlHgroup;'}{'sub': 1', '6', '4', '4, 'each Z represents, simultaneously or independently, a halogen atom, a hydroxyl group, or a C-Calkoxy or carboxylic radical or a BHor AlHgroup; and'}(a+b)=2 with a being 1 or 2.2. A process according to claim 1 , wherein said complex is of formula{'br': None, 'sub': '2', '[Fe(L3)(L′)Y]\u2003\u2003(2)'}{'claim-ref': {'@idref': 'CLM-00001', 'claim 1'}, 'wherein L3 L′ and Y have the same meaning as in .'}6. A process according to claim 5 , characterized in that said substrate is a compound of formula (I) wherein Rrepresent a hydrogen atom or a Rgroup claim 5 , and each R claim 5 , when taken separately claim 5 , represent simultaneously or independently a linear claim 5 , branched or cyclic C-Caromatic claim 5 , alkyl claim 5 , alkenyl or alkanedienyl group optionally substituted; or Rand Rare bonded ...

1,3-BUTADIENE SYNTHESIS

The invention relates to a process for preparing 1,3-butadiene by means of ene-yne metathesis over at least one transition metal catalyst of the element ruthenium. 1. A process for preparing 1 ,3-butadiene , the process comprising contacting ethene and ethyne in the presence of at least one transition metal catalyst of the element ruthenium.2. The process as claimed in claim 1 , the contacting is carried out in liquid phase using at least one solvent.3. The process as claimed in claim 2 , wherein the solvent is a haloalkane which is liquid at room temperature claim 2 , preferably dichloromethane.4. The process as claimed in claim 1 , wherein the contacting is carried out at a temperature of −70 to 50° C.5. The process as claimed in claim 1 , wherein the contacting is carried out without superatmospheric pressure.7. The process as claimed in claim 6 , wherein:{'sub': 1', '30', '3', '20', '2', '20', '2', '20', '6', '24', '1', '20', '1', '2D', '2', '20', '2', '20', '2', '24', '2', '20', '1', '30', '1', '30', '6', '24', '1', '20', '1', '20', '1', '6', '1', '6, 'R is, in each case, independently of one another, hydrogen, C-C-alkyl, C-C-cycloalkyl, C-C-alkenyl, C-C-alkynyl, C-C-aryl, C-C-carboxylate, C-C-alkoxy, C-C-alkenyloxy, C-C-alkynyloxy, C-C-aryloxy, C-C-alkoxycarbonyl, C-C-alkylamino, C-C-alkylthio, C-C-arylthio, C-C-alkylsulfonyl or C-C-alkylsulfinyl, where these radicals can, in each case, optionally be substituted by one or more C-C-alkyl, halogen, C-C-alkoxy, preferably i-propoxy, aryl, preferably phenyl, or heteroaryl radicals, or, as an alternative, the two radicals R are bridged with inclusion of the common carbon atom to which they are bound to form a cyclic group which can be aliphatic or aromatic in nature and is optionally substituted and can contain one or more heteroatoms; and'}L is, in each case, independently of one another, a phosphine, sulfonated phosphine, phosphate, phosphinite, phosphonite, ether, amine, amide, sulfoxide, carboxyl, nitrosyl, ...

Palladium Catalyst System Comprising Zwitterion And/Or Acid-Functionalyzed Ionic Liquid

The present invention concerns a catalyst system in particular a catalyst system comprising Palladium (Pd), a zwitterion and/or an acid-functionalized ionic liquid, and one or more phosphine ligands, wherein the Pd catalyst can be provided by a complex precursor, such as Pd(CH 3 COO) 2 , PdCl 2 , Pd(CH 3 COCHCOCH 3 ), Pd(CF 3 COO) 2 , Pd(PPh 3 ) 4 or Pd 2 (dibenzylideneacetone) 3 . Such catalyst systems can be used for e.g. alkoxycarbonylation reactions, carboxylation reactions, and/or in a co-polymerization reaction, e.g. in the production of methyl propionate and/or propanoic acid, optionally in processes forming methyl methacrylate and/or methacrylic acid. Catalyst systems according to the invention are suitable for reactions forming separable product and catalyst phases and supported ionic liquid phase SILP applications.