СИНТЕЗ 1,3-БУТАДИЕНА

Изобретение относится к способу получения 1,3-бутадиена. Способ характеризуется тем, что этен и этин взаимодействуют друг с другом в присутствии по меньшей мере одного катализатора на основе переходного металла, содержащего элемент рутений, причем в качестве катализатора на основе переходного металла, содержащего элемент рутений, используют по меньшей мере одно вещество из группы следующих: M1 = бензилиден[1,3-бис(2,4,6-триметилфенил)-2-имидазолидинилиден]дихлор(трициклогексил-фосфин)рутений, M2 = бис(трициклогексилфосфин)-[(фенилтио)метилен]рутений(II) дихлорид, M3 = 1,3-бис(2,4,6-триметилфенил)-4,5-дигидроимидазол-2-илиден[2-(изо-пропокси)-5-(N,N-ди-MeNHSO)фенил]метиленрутений(II) дихлорид, M4 = бис(трициклогексилфосфин)-3-фенил-1H-инден-1-илиденрутений(II) дихлорид, M5 = бензилиден-бис(трициклогексилфосфин)дихлоррутений, M6 = дихлор(o-изопропоксифенилметилен)(трициклогексилфосфин)рутений(II), M7 = (1,3-бис-(2,4,6-триметилфенил)-2-имидазолидинилиден)дихлор(o-изопропоксифенилметилен)рутений ...

СПОСОБ СИНТЕЗА ПРОИЗВОДНЫХ 9-АЛЛИЛКАМПТОТЕЦИНА

Изобретение относится к производным 9-аллилкамптотецина, включая соединение формулы 14 в качестве важнейшего промежуточного продукта для получения соединения формулы 1 и его гидрохлорида формулы 1Н, который обладает противоопухолевым действием. Изобретение также относится к способу получения соединения формулы 14 и способу получения соединений 1 и 1Н. Технический результат - высокий общий выход продуктов. 3 н. и 7 з.п. ф-лы, 8 пр.

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 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 ...

КАТАЛИТИЧЕСКИЕ СИСТЕМЫ ДЛЯ ТЕТРАМЕРИЗАЦИИ ЭТИЛЕНА И СПОСОБ ПОЛУЧЕНИЯ 1-ОКТЕНА С ИХ ПРИМЕНЕНИЕМ

... 1. Каталитическая система для тетрамеризации этилена, содержащая переходный металл или предшественник переходного металла, сокатализатор и лиганд со структурой главной цепи Р-С-С-Р, представленный следующей формулой 1 ! [Формула 1] ! ! где R1, R2, R3 и R4 представляет собой каждый независимо углеводородную группу, замещенную углеводородную группу, гетероуглеводородную группу и замещенную гетероуглеводородную группу, каждый из R1, R2, R3 и R4 не имеет заместитель на атомах, соседних с атомами, связанными с атомами Р. ! 2. Каталитическая система для тетрамеризации этилена по п.1, где каталитическая система содержит лиганд со структурой мульти-Р-С-С-Р, в которой два или более лигандов со структурой главной цепи Р-С-С-Р связаны друг с другом. ! 3. Каталитическая система для тетрамеризации этилена по п.1, где в лиганде со структурой главной цепи Р-С-С-Р, представленном указанной выше формулой 1, R1, R2, R3 и R4 выбран каждый независимо из группы, состоящей из фенила, бензила, нафтила, антраценила ...

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 ОЛИГОМЕРИЗАЦИИ ЭТИЛЕНА В СРЕДЕ ОРГАНИЧЕСКОГО РАСТВОРИТЕЛЯ В ПРИСУТСТВИИ ХРОМОВОГО КАТАЛИЗАТОРА И АЛЮМИНИЙОРГАНИЧЕСКОГО АКТИВАТОРА

Изобретение относится к области промышленного получения гексена-1 и октена-1 олигомеризацией этилена и может быть использовано в нефтехимической промышленности и в органическом синтезе. Предложен способ получения гексена-1 и октена-1. Олигомеризацию этилена осуществляют при умеренно повышенных температурах (30-60°С) и давлении (2-5 мПа) в присутствии катализатора, полученного на основе смесей соли хрома(III) и конформационно жестких хелатных дифосфиновых лигандов, активированных матилалюмоксаном, при этом в качестве лигандов используются соединения нового структурного типа на основе 5,6-дигидродибензо[с,е][1,2]азафосфинина общей формулы: где R1 - алкильный или арильный заместитель, a R2 – орто-замещенный фенильный фрагмент. Продукты реакции выделают ректификацией под атмосферным давлением. Предпочтительно в качестве лиганда использовать дифосфиновые лиганды, содержащие трет-бутильный заместитель или орто-метоксифенильный заместитель R1 и орто-метоксифенильные заместители R2. Технический ...

СПОСОБ ПОЛУЧЕНИЯ СОЕДИНЕНИЯ ПИРАЗОЛАМИДА

КОМПЛЕКСЫ

СИНТЕЗ 1,3-БУТАДИЕНА

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, ...

CПOCOБ PEГEHEPAЦИИ ЧACTИЧHO ДEЗAKTИBИPOBAHHOГO COЛЮБИЛИЗИPOBAHHOГO POДИЙTPETИЧHOГO OPГAHOФOCФИHOBOГO KOMПЛEKCHOГO KATAЛИЗATOPA ГИДPOФOPMИЛИPOBAHИЯ

Способ получения масляного альдегида

Изобретение касается производства альдегидов, в частности масляного альдегида , который используют для синтеза бутиловых спиртов, Цель - увеличение активности катализатора. Процесс ведут реакцией гидИзобретение относится к способу получения масляного альдегида и касается способа обработки реакционной среды реакции гидроформилирования пропилена при получении масляного альдегида т.е к способу селективного превращения алкилзамещен- ных фосфинов, содержащихся в реакционной среде реакции гидроформирования пропилена , в соответствующие окислы фосфинов роформилирования пропилена моноокисью углерода и водородом в присутствии катализатора , представляющего собой смесь родия с трифенилфосфином, с образованием реакционной массы, содержащей масляный альдегид, высококипящие побочные продукты конденсации масляного альдегида, пропилдифенилфосфин, трифенилфосфин и остальную часть, содержащую комплексный родиевый катализатор, трифенилфосфинок- сид и высококипящие органические компоненты , с последующей ...

Способ димеризации низших @ -олефинов

Способ получения гептенов

VERFAHREN ZUR HERSTELLUNG VON GERADKETTIGEN FETTSAEUREN ODER IHRER ESTER

Reaktivierung von Hydroformylierungskatalysatoren.

KATALYTISCHE ASYMMETRISCHE HYDRIERVERFAHREN

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).

Verfahren zur Rückgewinnung eines Gruppe-VIII-Metall-Komplexes und Hydroformylationsverfahren.

Katalytische Metall-Rückgewinnung aus nichtpolaren organischen Lösungen.

PROCESS FOR DIMERIZING LOWER ALPHA-OLEFINS

Verfahren zur Herstellung von Aldehyden und Alkoholen

Verfahren zur Herstellung von Ruthenium-Hydrogenierungskatalysatoren und deren Verwendung

VERFAHREN ZUR HERSTELLUNG VON CARBONSAEUREN

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

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

VERFAHREN ZUM CARBONYLIEREN VON PENTENNITRIL

New supported transition metal complex useful as catalyst in the transition metal catalyzed reaction, and in olefin metathesis reaction

Supported transition metal complex (T) based on a polystyrene matrix or silica gel matrix comprising a phenyl compound (I) or a phenyl-ketone compound (II), respectively, is new. Supported transition metal complex (T) based on a polystyrene matrix or silica gel matrix comprising a phenyl compound of formula (I) or a phenyl-ketone compound of formula (II), respectively, is new. X : a direct bond, O, S, -N(R 1>)-, -C(=O)O-, -O(O=)C-, -N(R 1>)(O=)C-, -C(=O)N(R 1>)-, -O-CHR 1>-O-, -OC(=O)N(R 1>)-, -N(R 1>)C(=O)O-, =C(=O) or =C(=S); R 1>, R 3>H or 1-4C alkyl; K 1>a transition metal complex; Z : a bond or a spacer; m, n, x, y : 1-5000; q : 2-5; and z : 3-20. An independent claim is included for a procedure for the transition metal catalyzed conversion of a reactant to a product in the presence of a supercritical carbon dioxide comprising using (T), as the catalyst. [Image] [Image].

New ruthenium- and osmium-carbene-complex catalysts, which are bonded with chiral carbon atoms or over double bonds at a catalyst base skeleton, useful e.g. in metathesis-reactions, preferably in ring closing metathesis reactions

Ruthenium- and osmium-carbene-complex catalysts (I), which are bonded with chiral carbon atoms or over one or more double bonds at a catalyst base skeleton, are new. Ruthenium- and osmium-carbene-complex catalysts of formula (I), which are bonded with chiral carbon atoms or over one or more double bonds at a catalyst base skeleton, is new. Either R 1>-R 8> : alkyl, cycloalkyl, alkenyl, alkynyl, aryl, carboxylate, alkoxy, alkenyloxy, alkynyloxy, aryloxy, alkoxycarbonyl, alkyl amino, alkylthio, arylthio, alkylsulfonyl, alkylsulfinyl, dialkylamino, alkylsilyl or alkoxysilyl (all optionally substituted by one or more alkyl, halo, alkoxy or (hetero)aryl), H, halo, OH, aldehyde, keto, thiol, CF 3, NO 2, nitroso, CN, thiocyano, isocyanato, carbodiimide, carbamate, thiocarbamate, dithiocarbamate, amino, amido, imino, silyl, SO 3 ->, OSO 3 ->, PO 3 ->or OPO 3 ->; or CR 1>R 8> : cyclic group, preferably aromatic system, where R 8>is bridged with other ligand of (I); m : 0-1; A : O, S, C(R 9>R 10> ...

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.

MEMBRANE SEPARATION PROCESS

... 1,260,733. Dialysis. BRITISH PETROLEUM CO. Ltd. 3 June, 1970 [17 June, 1969], No. 30575/69. Heading B1X. Organic metal compounds are separated by reverse osmosis using a polyolefinic membrane. A membrane 10 in pressurised cell is supported on a steel plate 11 in Fig. 2. In Figure 3 a membrane 11 cushioned by filter paper 18 rests on a steel plate 12. To create turbulence feedstock enters through a 1 mm. orifice 16.

DIMETHYL OMEGA-CARBOXYALKYLPHOSPHINES AND THEIR ALKYL ESTERS

... 1355565 Organic phosphines and complexes thereof; oxo process BADISCHE ANILIN- & SODA-FABRIK AG 7 Sept 1971 [8 Sept 1970] 41633/71 Headings C2P and C2C The invention comprises compounds of Formula I where R is hydrogen or C 1-12 alkyl and n is 8 to 14. Compounds of Formula I in which R is hydrogen may be prepared by reacting dimethyl phosphine with a suitable omega-alkenoic acid under free radical conditions. Compounds of Formula I in which R is alkyl may be prepared by reacting the corresponding compound in which R is hydrogen with a C 1-4 alkanol and optionally transesterifying with a C 5-12 alkanol, or by reacting phosphine with an omega-alkenoic acid under free radical conditions, esterifying the product with a C 1-4 alkanol, reacting this product, after isolation by distillation, with methyl iodide or methyl bromide, reacting the quaternary phosphine formed with alcoholic alkali solution and optionally transesterifying with a C 5-12 alkanol. The compounds of Formula I may be reacted ...

PROCESS FOR PRODUCING ETHANOL

Metal complexes comprising a fullerite

A process for the preparation of a fullerite, said process comprising the admixture of metal complex MLwL'x(wherein M is a non-group 1 metal, each L and L' is a ligand and w and x are selected from 0 to 8), a fullerene or derivative thereof, a first solvent in which the fullerene or derivative is substantially soluble and a second solvent in which the fullerene or derivative is substantially insoluble, to precipitate the fullerite. In another aspect, the use of the above process for the preparation of particles of ML'ywherein y is 0 to 9, preferably by dissolving fullerites prepared according to the above mentioned process. Additionally, fullerites and particles prepared by the above processes, to matrices incorporating said fullerites and/or- particles, and to their uses. The preferred metal is Palladium and the preferred ligand is triphenylphosphine.

HYDROGENATING CYCLIC OLIGOMERS OF BUTADIENE

... 1382012 Hydrogenation catalyst INSTITUT FRANCAIS DU PETROLE 20 Feb 1973 [24 Feb 1972]. 8241/73 Heading B1E [Also in Division C5] A hydrogenation catalyst comprises: (a) an iron salt (b) a reducing agent which has the formula MR 1 R 2 R 3 (where M is Al or B and each of R 1 R 2 and R 3 is H or a monovalent hydrocarbyl group) or is a complex hydride of Al and Na or Li; and (c) a phosphine. A hydrocarbon solvent may be present. Catalyst components used in the Examples are:-(a) iron octoate or stearate (b) Et 3 Al (c) Ph 3 P, bis (diphenyl phosphine) ethane and tricyclohexyl phosphine.

Complexes

Catalytic olefin metathesis reaction method

A method for performing an olefin metathesis or cross-coupling reaction is characterised by the catalyst system comprising: [a] a source of a d-block metal, such as Group VIII metal, iron, cobalt, copper, ruthenium, rhodium, nickel, palladium or platinum [b] optionally a promoter, an activator and/or a base, and [c] a source of a 3-membered carbocyclic ligand. Also disclosed is catalysing olefin metathesis or cross-coupling reactions, comprising the catalyst system and a method of producing the catalyst system wherein [b] optionally a promoter, an activator and/or a base is a further reagent.

Process for the preparation of aldehydes and/or alcohols

An aldehyde and/or an alcohol is obtained by reacting an olefin with carbon monoxide and hydrogen in the presence of a complex containing in the molecule a transition metal having an atomic number from 23 to 32, 40 to 51, or 57 to 84 and at least one molecule of a biphyllic ligand containing trivalent phosphorus, arsenic or antimony as a catalyst. The preferred transition metals are iron, nickel, ruthenium, rhodium, palladium, osmium, iridium, platinum and, particularly, cobalt. A preferred class of catalysts are those having the formula [(Rz1A)x-L-Ry]pM(CO)n in which (Rz1A)x-L-Ry represents the biphyllic ligand, M is a transition element as defined above, L is phosphorus, arsenic or antimony, R and R1 are alkyl, aryl, aralkyl or alkaryl groups, A is oxygen, nitrogen or sulphur, x is 0-3, y is 3-x, p varies from 1 to the co-ordination member of the transition metal, n + p is equal to the co-ordination number and z is 1 where A is oxygen or sulphur or 2 when A is nitrogen. The olefines used ...

Complexes

A palladium (II) complex of formula (1) or (3). R1 and R2 are organic groups having 1-20 carbon atoms or form a ring with E; R3, R4, R5, R6, R7, R8, R9, R10 and R11 is -H or an organic group having 1-20 carbon atoms; or R1/R3 or R2/R3 forms a ring and R4/R5, R5/R6, R7/R8, R8/R9, R9/R10 or R10/R11 may form a ring; R12 is an organic group having 1-20 carbon atoms; m is 0, 1,2,3,4 or 5; E is P or As; X is a non-coordinated anionic ligand; R18 and R19 are Me, -Et, -nPr, -iPr, -nBu, -iBu, cyclohexyl or cycloheptyl; R12 is an organic group having 1-20 carbon atoms; R20, R21, R22, R23 and R24 are H or organic groups having 1-20 carbon atoms; or one or both of R20/R21 or R22/R23 may form a ring. The complexes find use in carbon-carbon and carbon-heteroatom coupling reactions.

Cationic pi-allyl palladium complexes and their use in coupling reactions

A novel catalytic formulation and its preparation technical field

PREPARATION OF CARBOXYLIC ACID ANHYDRIDES

CARBONYLATION OF OLEFINICALLY UNSATURATED HYDROCARBONS

... 1328850 Carbonylation MOBIL OIL CORP 30 Dec 1970 [20 Feb 1970 17 Aug 1970] 61912/70 Heading C2C Carboxylic acids and esters are prepared by the liquid phase carbonylation of olefinically unsaturated hydrocarbons with carbonmonoxide and hydroxylic compounds in the presence of a palladium salt catalyst of formula L m PdX y in which L is an organic phosphine, X is an anion, m an integer of 1-4, and y is 1 or 2, and a tin cocatalyst. The ligand may be triphenyl, tri-ptolyl, tri-p-trifluoromethyl phenyl, tri-p-anisyl and tri-n-butyl phosphines or palladium dichloride-1,2-diphenyl phosphino ethane and the tin cocatalyst may be stannous chloride dihydrate, anhydrous stannous chloride, stannic chloride, stannic chloride pentahydrate, and triphenyl tin chloride. Examples describe the treatment of propylene, 1-butene, 1-pentene, 2- pentene, 1-hexene, 1-octene, cis-2-hexene, and 1-octadecene with various catalysts to yield the corresponding esters.

AROMATIC CARBONATES

PRODUCTION OF -HYDROXYMETHYL-ALKYL CYCLOALKYL AND ARALKYL PHOSPHINES

... 1468491 Preparation of hydroxymethyl phosphines HOECHST AG 17 March 1975 [22 March 1974] 11012/75 Heading C2P Phosphines of Formula I where n is 1 or 2 and each R is optionally substituted alkyl, cycloalkyl or aralkyl having up to 18 carbon atoms, are prepared by reacting a corresponding phosphine R n P(H) 3-n with formaldehyde, paraformaldehyde or trioxane at atmospheric pressure at less than 40‹ C. in the presence of an inert, polar, organic solvent, and separating the solvent from the reaction product. Suitable solvents are alcohols, glycols, ethers, alkylated formamides, aliphatic and aromatic nitriles, halogenated aliphatic and aromatic hydrocarbons, cyclic and linear sulphones, carboxylic anhydrides and esters and N- alkylated carboxylic acid amides. A catalyst which is a salt or complex of a group II or VIII metal or a phosphate, phosphite, hypophosphite or phosphonium compound may also be used. The reaction is preferably carried out in a protective gas atmosphere. The process may ...

Complexes

PROCEDURE FOR THE PRODUCTION OF ALDEHYDES

PROCEDURE FOR THE PRODUCTION OF DERIVATIVES OF CHIRALER BETA AMINO ACIDS BY ASSEMBLY-METRIC HYDROGENATION

BISPHOSPHINE AS BIDENTAT LIGANDS

VERFAHREN ZUR REGENERIERUNG UND ABTRENNUNG VON RHODIUM ODER IRIDIUM ENTHALTENDEN KATALYSATOREN

VERFAHREN ZUR HERSTELLUNG VON OPTISCH AKTIVEN ALFA-N-ACYLAMINO-PROPIONSAUREN

MIKROVERKAPSELTES CATALYST LIGAND SYSTEM, MANUFACTURING PROCESS FOR IT AND PROCEDURES FOR THE USE OF IT

USING A THERMALLY ACTIVATED NHETEROCYCLI CARBENE FORERUNNER EDUCATION HIGH-ACTIVITY ONE METALLCARBENMETATHESEKATALYSATOREN

VERFAHREN ZUR HERSTELLUNG EINES NEUEN STABILEN HOMOGENEN RHODIUM-HYDRIERUNGS-KATALYSATORS UND DESSEN ANWENDUNG

VERFAHREN ZUR ABTRENNUNG UND REGENERIERUNG VON RHODIUMKOMPLEXKATALYSATOREN

PROCEDURE FOR THE SEPARATION AND RECOVERY OF RHODIUM COMPLEX CATALYSTS

PROCEDURE FOR THE PRODUCTION OF OPTICALLY ACTIVE ONE ALFA N ACYLAMINO PROPIONSAUREN

RUTHENIUM COMPLEXES OF PHOSPHINAMINOPHOSPHINLIGANDEN

PROCEDURE FOR THE PRODUCTION OF NEW POLYMERS RHODIUM, IRIDIUM AND RUTHENIUM PHOSPHINKOMPLEXVERBINDUNGENUND THEIR USE

PROCEDURE FOR ENANTIOSELEKTIVEN THE HYDROGENATION THE CARBONYLGRUPPE USING RUTHENIUM COMPLEXES WITH BIPHOSPHINELIGANDEN

PROCEDURE FOR THE PRODUCTION OF ALDEHYDES.

PROCEDURE FOR THE RECUPERATION OF RHODIUM.

PROCEDURE FOR THE RECUPERATION OF RHODIUM FROM RHODIUM COMPLEX CONNECTIONS ABSTENTION WAESSRIGEN LOESUNGEN.

AMIDIERUNG OF PYRIDINEN.

PROCEDURE FOR THE REACTIVATION OF WATER-SOLUBLE HYDROFORMYLIERUNGSKATALYSATOREN.

HYDROFORMYLATION OF OLEFINEN UNDER WEAK PRESSURE WITH A RHODIUM CATALYST.

PROCEDURE AND COMPOSITION FOR THE PROMOTION OF HYDROSILYLIERUNGSREAKTIONEN USING STERISCH PREVENT NITROGEN AND PHOSPHORHALTIGER CONNECTIONS

PROCEDURE FOR THE PRODUCTION OF ALDEHYDES THROUGH HYDROFORMYLIERUNG.

PROCEDURE FOR THE PRODUCTION OF POLYKETONEN

PROCEDURE FOR THE PRODUCTION OF A NICKEL/CPHOSPHORUS LIGAND CATALYST FOR THE OLEFIN HYDROCYANIERUNG

Procedure for the recovery of cobalt and organic Phosphinen, which do not form water-soluble salts, from distillation residues of the Oxo synthesis

Procedure for the electro-chemical production of CO-free metal-organic complexes of transition metals

PROCEDURE FOR THE PRODUCTION OF OPTICALLY ACTIVE ONE ALFA N ACYLAMINO PROPIONSAUREN

PROCEDURE FOR THE RECOVERY OF RHODIUM FROM THE PRODUCTS OF THE HYDROFORMYLIERUNG

PROCEDURE FOR THE PRODUCTION OF OPTICALLY ACTIVE ONES ALKANE AND ALKENE-MONOCARBON-SOUR

PROCEDURE FOR THE PRODUCTION OF METAL COMPLEXES, THE HYDROXYALKOXYCARBONYLCYCLOPENTADIEN LIGANDS CONTAINING

PROCEDURE FOR THE PRODUCTION OF NEW DIPHOSPHINEN

HYDROFORMYLIERUNGSVERFAHREN

PROCEDURE FOR THE CARBONYLIEREN OF AETHYLENISCH INSATIATED CONNECTIONS

Production method for pyrazole-amide compound

The present invention is a production method for a compound represented by formula [I] or a pharmaceutically acceptable salt thereof, or a hydrate of said compound or salt.

PROCESS FOR PREPARING [(3-HYDROXYPYRIDINE-2-CARBONYL)AMINO]ALKANOIC ACIDS, ESTERS AND AMIDES

Disclosed are processes for preparing [(3-hydroxypyridine-2-carbonyl)amino] alkanoic acids, derivatives, inter alia, 5-aryl substituted and 5- heteroaryl substituted [(3-hydroxypyridine-2-carbonyl]amino}acetic acids. Further disclosed are methods for making prodrugs of [(3-hydroxypyridine-2-carbonyl)-amino]acetic acids, for example, [(3-hydroxypyridine-2-carbonyl]amino}acetic acid esters and {[3 hydroxypyridine-2-carbonyl]amino}acetic acid amides. The disclosed compounds are useful as prolyl hydroxylase inhibitors or for treating conditions wherein prolyl hydroxylase inhibition is desired.

Processes for the preparation of a diarylthiohydantoin compound

Disclosed are processes and intermediates for the preparation of compound (X), which is currently being investigated for the treatment of prostate cancer. NC N CONHMe 0 (X) ...

PROCESS FOR PREPARING [(3-HYDROXYPYRIDINE-2-CARBONYL)AMINO]ALKANOIC ACIDS, ESTERS AND AMIDES

Disclosed are processes for preparing [(3-hydroxypyridine-2-carbonyl)amino] alkanoic acids, derivatives, inter alia, 5-aryl substituted and 5- heteroaryl substituted [(3 -hydroxypyridine-2-carbonyl] amino } acetic acids. Further disclosed are methods for making prodrugs of [(3-hydroxypyridine-2-carbonyl)-amino]acetic acids, for example, [(3-hydroxypyridine-2-carbonyl] amino } acetic acid esters and {[3 hydroxypyridine-2-carbonyl] amino } acetic acid amides. The disclosed compounds are useful as prolyl hydroxylase inhibitors or for treating conditions wherein prolyl hydroxylase inhibition is desired.

CATALYTIC COMPOSITION FOR ALKENE-CARBON MONOXIDE POLYMERISATION

Carbonylation of ethylenically unsaturated compounds

A process for the carbonylation of ethylenically unsaturated compounds including vinyl esters and a process for the production of 3-hydroxy propanoate esters or acids. The process comprises reacting said compound with carbon monoxide in the presence of a source of hydroxyl groups and of a catalyst system. The catalyst system is obtainable by combining: (a) a metal of Group 8, 9 or 10 or a compound thereof: and (b) a bidentate ligand of general formula (I): X(X)- Q - A - R- B - Q - X(X).

MIXTURES OF CHIRAL MONOPHOSPHORUS COMPOUNDS USED AS LIGAND SYSTEMS FOR ASYMMETRIC TRANSITION METAL CATALYSIS

Process for the preparation of chiral beta amino acid derivatives by asymmetric hydrogenation

Carbonylation catalyst system

Metathesis of unsaturated fatty acid esters or unsaturated fatty acids with lower olefins

HOMOGENOUS PROCESS FOR THE HYDROGENATION OF CARBOXYLIC ACIDS AND DERIVATIVES THEREOF

Method for producing endo-9-azabicyclo[3.3.1]nonane-3-ol derivative

Provided is a method that makes it possible to obtain an endo-9-azabicyclo[3.3.1]nonane-3-ol derivative that is useful as an intermediate of agricultural and horticultural chemicals or pharmaceuticals at a low cost by reacting a 9-azabicyclo[3.3.1]nonane-3-on derivative with hydrogen under the presence of a catalyst comprising a ruthenium complex.

Transfer Hydrogenation of Cyclopamine Analogs

Provided herein is a process for the transfer-hydrogenation of ketone analogs of members of the jervine type of Veratrum alkaloids, such as cyclopamine. Also provided herein are novel ruthenium transfer-hydrogenation catalysts.

Tetramerization ligands

An ethylene oligomerization catalyst which contains a bridged diphosphine ligand having the formula (R 1 ) m (X 1 ) n P 1 -bridge-P 2 (R 2 )X 2 wherein R 1 and R 2 are independently selected from the group consisting of hydrocarbyl and heterohydrocarbyl; X 1 is selected from the group consisting of halogen, hydrocarbyl and heterohydrocarbyl; m is 1 or 2; n is 0 or 1; m+n=2; bridge is a divalent bridging group bonded to P 1 and P 2 ; and X 2 is halogen. The present ligands differ from prior diphosphine ligands used in olefin oligomerization processes in that at least one halide substituent is directly bonded to at least one P atom of the ligand.

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.

Highly Active and Selective Ethylene Oligomerization Catalyst and Method of Preparing Hexene or Octene Using the Same

This invention relates to a chromium complex compound for selective ethylene oligomerization including a chiral ligand, and to a method of selectively preparing 1-hexene or 1-octene from ethylene using the same.

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 ...

Metal-ligand catalyst formation

As described herein, nickel treated with sulfur provides a surprisingly effective source of nickel atoms for generating nickel-phosphorus-containing ligand complexes useful as hydrocyanation catalysts.

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.

Method for producing alcohol and/or amine from amide compound

Disclosed herein is a method for producing an alcohol and an amine from an amide under an atmosphere of hydrogen with the use of, as a catalyst, a ruthenium complex that is easily prepared, easy to handle, and relatively cheaply obtained. Specifically, the method is a method for producing an alcohol and/or an amine from an amide compound under an atmosphere of hydrogen with the use of as a catalyst, a ruthenium carbonyl complex represented by the following general formula (1): RuXY(CO)(L) (1) wherein X and Y may be the same or different from each other and each represents an anionic ligand and L represents a tridentate aminodiphosphine ligand containing two phosphino groups and a —NH— group.

HYDROFORMYLATION PROCESS

A combination of calixarene bisphosphite ligand and an organophosphine ligand. The combination can be employed with a catalytic metal to form a complex catalyst. The catalyst can be employed in a hydroforaiylation process for producing a mixture of aldehydes. 1. A composition comprising a calixarene bisphosphite ligand and an organophosphine ligand.6. The composition of the organophosphine is triphenylphosphine.7. A catalytic complex comprising a transition metal complexed with the ligands of .8. A process comprising contacting CO claim 1 , Hand at least one olefin in the presence of a catalytic complex claim 1 , the complex comprising a calixarene bisphosphite ligand and an organophosphine ligand of claim 1 , under hydroformylation conditions sufficient to form at least one aldehyde product.9. A process comprising contacting CO claim 1 , Hand at least one olefin under hydroformylation conditions sufficient to form at least one aldehyde product in the presence of a catalyst having as components a transition metal claim 1 , a calixarene bisphosphite ligand and an organophosphine ligand claim 1 , wherein the molar ratio of organophosphine to catalytic metal is greater than 150:1 claim 1 , and the reaction rate is at least 0.2 g-mol/l-hr.10. The process of wherein the ratio of normal to branched products (the N/I ratio) is at least 13.11. The process of wherein the process is conducted in a reaction vessel claim 9 , and the concentration of the transition metal is greater than about 1 part per million (ppm) and less than about 1 claim 9 ,000 ppm claim 9 , based on the weight of hydroformylation reaction fluid in the vessel.12. The process of wherein the process temperature is greater than about −25° C. and less than about 200° C. claim 9 , wherein the total gas pressure comprising carbon monoxide claim 9 , hydrogen claim 9 , and olefinic reactant(s) ranges from greater than about 25 psia (173 kPa) to less than about 2 claim 9 ,000 psia (14 claim 9 ,000 kPa) claim 9 , ...

PHOSPHINE LIGANDS FOR CATALYTIC REACTIONS

The disclosure is directed to: (a) phosphacycle ligands; (b) catalyst compositions comprising phosphacycle ligands; and (c) methods of using such phosphacycle ligands and catalyst compositions in bond forming reactions. 2. The phosphine ligand of claim 1 , wherein Vand Vare CR claim 1 , wherein Ris alkoxy.3. The phosphine ligand of claim 1 , wherein Vand Vare CR claim 1 , wherein Ris methoxy.4. The phosphine ligand of claim 1 , wherein Vand Vare CR claim 1 , wherein Ris hydrogen.5. The phosphine ligand of claim 1 , wherein V claim 1 , Vand Vare CR claim 1 , wherein Ris alkyl.6. The phosphine ligand of claim 1 , wherein V claim 1 , Vand Vare CR claim 1 , wherein Ris isopropyl.7. The phosphine ligand of claim 1 , wherein Vand Vare CR claim 1 , wherein Ris hydrogen.10. The phosphine ligand of claim 1 , wherein the ligand is selected from the group consisting of:2,2,6,6-tetramethyl-1-(2′,4′,6′-triisopropylbiphenyl-2-yl)phosphinane;2,2,6,6-tetramethyl-1-(2′,4′,6′-triisopropylbiphenyl-2-yl)phosphinan-4-one;2,2,6,6-tetramethyl-1-(2′,4′,6′-triisopropylbiphenyl-2-yl)phosphinan-4-ol;7,7,9,9-tetramethyl-8-(2′,4′,6′-triisopropylbiphenyl-2-yl)-1,4-dioxa-8-phosphaspiro[4.5]decane;8,8,10,10-tetramethyl-9-(2′,4′,6′-triisopropylbiphenyl-2-yl)-1,5-dioxa-9-phosphaspiro[5.5]undecane;3,3,8,8,10,10-hexamethyl-9-(2′,4′,6′-triisopropylbiphenyl-2-yl)-1,5-dioxa-9-phosphaspiro[5.5]undecane;1-(2′-(dimethylamino)-6′-methoxybiphenyl-2-yl)-2,2,6,6-tetramethylphosphinan-4-one;1-(2′,6′-bis(dimethylamino)biphenyl-2-yl)-2,2,6,6-tetramethylphosphinan-4-one;1-(2′,6′-dimethoxybiphenyl-2-yl)-2,2,6,6-tetramethylphosphinan-4-one;1-(2′,6′-diisopropoxybiphenyl-2-yl)-2,2,6,6-tetramethylphosphinan-4-one;1-(2′-(dimethylamino)biphenyl-2-yl)-2,2,6,6-tetramethylphosphinan-4-one;1-(biphenyl-2-yl)-2,2,6,6-tetramethylphosphinan-4-one;1-(1,1′-binaphthyl-2-yl)-2,2,6,6-tetramethylphosphinan-4-one;1-(2′-methoxy-1,1′-binaphthyl-2-yl)-2,2,6,6-tetramethylphosphinan-4-one;1-(3,6-dimethoxybiphenyl-2-yl)-2,2,6,6- ...

CHIRAL SPIRO-PYRIDYLAMIDOPHOSPHINE LIGAND COMPOUND, SYNTHESIS METHOD THEREFOR AND APPLICATION THEREOF

The present invention relates to a chiral spiro-pyridylamidophosphine ligand compound, synthesis method therefor and application thereof. The chiral spiro-pyridylamidophosphine compound is a compound having a structure of Formula (I), a racemate or optical isomer thereof, or a catalytically acceptable salt thereof, and is mainly characterized by having a chiral spiro-dihydro-indene skeleton in its structure. The chiral spiro-pyridylamidophosphine compound may be synthesized with optical active 7-diaryl/alkylphosphino-7′-amino-1,1′-spiro-dihydro-indene or substituted 7-diaryl/alkylphosphino-7′-amino-1,1′-spiro-dihydro-indene having a spiro-skeleton as chiral starting material. The chiral spiro-pyridylamidophosphine compound may be used as a chiral ligand in asymmetric hydrogenation of a carbonyl compound catalyzed by iridium, in which the reaction activity is very high, the amount of the catalyst may be 0.0001 mol %, and the enantioselectivity of the reaction is up to 99.9% ee. 2. The chiral spiro-pyridylamidophosphine compound according to claim 1 , or the racemate or optical isomer thereof claim 1 , or the catalytically acceptable salt thereof claim 1 , which is characterized by that in the structural formula of said compound claim 1 , R claim 1 , R claim 1 , R claim 1 , R claim 1 , R claim 1 , R claim 1 , R claim 1 , Rare H simultaneously claim 1 , and Ris phenyl or substituted phenyl claim 1 , and the substituent on said substituted phenyl is halogen claim 1 , C-Calkyl or alkoxy claim 1 , with a substituent amount of 1-5; Ris H claim 1 , halogen claim 1 , C-Calkyl claim 1 , C-Calkoxy claim 1 , phenyl claim 1 , substituted phenyl claim 1 , 1-naphthyl claim 1 , 2-naphthyl claim 1 , heteroaryl claim 1 , furyl or thienyl claim 1 , and the substituent on said substituted phenyl is halogen claim 1 , C-Chydrocarbyl or alkoxy claim 1 , with a substituent amount of 1-5 claim 1 , and said heteroaryl is pyridyl claim 1 , and m=0-3; or when m≧2 claim 1 , adjacent Rgroups can ...

Metal Complex Compound, Hydrogen Production Catalyst and Hydrogenation Reaction Catalyst Each Comprising the Metal Complex Compound, and Hydrogen Production Method and Hydrogenation Method Each Using the Catalyst

Provided is a catalyst for producing hydrogen, which catalyst has higher performance than conventional catalysts since, for example, it exhibits a certain high level of activity in an aqueous formic acid solution at high concentration even without addition of a solvent, amine and/or the like. The metal phosphine complex is a metal phosphine complex represented by General Formula (1): MH(CO)L, wherein M represents an iridium, iron, rhodium or ruthenium atom; in cases where M is an iridium or rhodium atom, m=3 and n=2, and in cases where M is an iron or ruthenium atom, m=2 and n=3; and the number n of Ls each independently represent a tri-substituted phosphine represented by General Formula (2): PRRR. The catalyst for producing hydrogen comprises the metal phosphine complex as a constituent component. 2. The metal phosphine complex according to claim 1 , wherein the tri-substituted phosphine represented by the General Formula (2) comprises at least one optionally substituted cyclohexyl group or 4-dialkylaminophenyl group.3. The metal phosphine complex according to claim 1 , wherein the tri-substituted phosphine represented by the General Formula (2) is at least one selected from the group consisting of tri(4-dialkylaminophenyl)phosphine claim 1 , di(4-dialkylaminophenyl)phenylphosphine claim 1 , 4-dialkylaminophenyldiphenylphosphine claim 1 , trimethylcyclohexylphosphine claim 1 , methylcyclohexyldicyclohexylphosphine claim 1 , dicyclohexyl(4-dialkylaminophenyl)phosphine and cyclohexyldi(4-dialkylaminophenyl)phosphine.4. A catalyst for producing hydrogen by the formic acid decomposition reaction (HCOOH→H+CO) claim 1 , the catalyst comprising as a constituent component the metal phosphine complex according to .5. The catalyst for producing hydrogen according to claim 4 , further comprising as a constituent component an amine or a phosphine.6. The catalyst for producing hydrogen according to claim 5 , wherein the amine is at least one amine selected from the group ...

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) ...

Novel ruthenium complexes and their uses in processes for formation and/or hydrogenation of esters, amides and derivatives thereof

The present invention relates to novel Ruthenium catalysts and related borohydride complexes, and the use of such catalysts, inter alia, for (1) hydrogenation of amides (including polyamides) to alcohols and amines; (2) preparing amides from alcohols with amines (including the preparation of polyamides (e.g., polypeptides) by reacting dialcohols and diamines and/or by polymerization of amino alcohols); (3) hydrogenation of esters to alcohols (including hydrogenation of cyclic esters (lactones) or cyclic di-esters (di-lactones) or polyesters); (4) hydrogenation of organic carbonates (including polycarbonates) to alcohols and hydrogenation of carbamates (including polycarbamates) or urea derivatives to alcohols and amines; (5) dehydrogenative coupling of alcohols to esters; (6) hydrogenation of secondary alcohols to ketones; (7) amidation of esters (i.e., synthesis of amides from esters and amines); (8) acylation of alcohols using esters; (9) coupling of alcohols with water to form carboxylic acids; and (10) dehydrogenation of beta-amino alcohols to form pyrazines. The present invention further relates to the novel uses of certain pyridine Ruthenium catalysts.

PALLADIUM CATALYST, METHOD FOR ITS PREPARATION AND ITS USE

The invention relates to palladium(0)-tris{tri-[3,5-bis(trifluoromethyl)-phenyl]-phosphine} complex of formula (I), as well as to its preparation and use. 2. The composition of in a solid form.3. The composition of having a melting point of 220° C. as determined by DSC in inert atmosphere.4. The composition of claim 1 , having a decomposition point of 169.5° C. as determined by DSC in air under atmospheric pressure.5. A palladium(0) complex comprising three fluorinated phosphine compounds.6. The palladium(0) complex of exhibiting a stability characterized by no measurable decomposition on the basis of P claim 5 , F claim 5 , C and H NMR spectra following 4 months of storage in air at a temperature of 25° C.7. The palladium(0) complex of exhibiting a stability characterized by no measurable decomposition on the basis of P claim 5 , F claim 5 , C and H NMR spectra following 20 months of storage in air at room temperature.8. The palladium(0) complex of having a melting point in inert atmosphere of 220° C.9. The palladium(0) complex of exhibiting stability at any temperature below its melting point.10. The palladium(0) complex of exhibiting insolubility in water at industrially relevant temperatures and stability when stored in water.11. The palladium(0) complex of comprising a yellow solid.12. The palladium(0) complex of that dissolves at around 90° C. in aqueous alcohols.13. The palladium(0) complex of having catalytic activity in cross coupling reactions at a concentration of from 0.1 to 0.3 mole % of the substrate.14. A method for catalysing a C—C claim 5 , C-heteroatom claim 5 , or hydrogenation reaction comprising carrying out the C—C claim 5 , C-heteroatom or hydrogenation reaction in the presence of the palladium(0) complex of .15. The method of claim 14 , wherein the reaction is a C—C cross-coupling reaction.16. The method of claim 14 , wherein the C—C cross-coupling reaction is selected from the group consisting of: Suzuki coupling claim 14 , Heck coupling and ...

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 , ...

CATALYST AND METHOD HAVING SELECTIVITY TO ISOBUTYRALDEHYDE VIA CATALYST INDUCTION

Industrially relevant product selectivities and reaction rates are obtained from rhodium catalyzed hydroformylation of propylene via the use of a novel induction period in which the supramolecular ligand assembly, the rhodium precatalyst and an initial substrate are allowed to form a hydroformylation catalyst that is more selective toward branched aldehydes. Upon heating this incubated mixture and addition of propylene, iso-butyraldehyde is obtained in higher concentrations and rates that are otherwise unattainable. 1. A process for producing aldehydes , comprising:a) contacting a catalyst composition and a first olefin under hydroformylation conditions to prepare a catalyst ligand composition; andb) contacting a second olefin, hydrogen and carbon monoxide in the presence of said catalyst ligand composition to produce aldehydes wherein the second olefin is propylene,wherein the first olefin has a longer carbon chain than the second olefin, andwherein said catalyst ligand composition comprises tris(3-pyridyl)phosphine, a magnesium centered tetraphenylporphyrin coordination complex and a ligand formed in situ via insertion of the first olefin into a rhodium carbonyl bond.2. A process according to claim 1 , wherein the aldehydes are produced in an N:I ratio of from about 1.2:1 to about 0.01:1.3. A process according to claim 2 , wherein the N:I ratio is from about 1.0:1 to about 0.1:1.4. A process according to claim 2 , wherein the N:I ratio is from about 0.6:1 to about 0.1:1.5. The process according to claim 3 , wherein the N:I ratio is from about 0.4:1 to about 0.25:1.6. The process according to claim 1 , wherein the first olefin is a butene claim 1 , a pentene claim 1 , a hexene claim 1 , a heptene claim 1 , an octene claim 1 , a nonene claim 1 , a decene claim 1 , an undecene claim 1 , or a dodecene.7. The process according to claim 1 , wherein a mole ratio of magnesium centered tetraphenylporphyrin coordination complex to tris(3-pyridyl)phosphine is from about 1000 ...

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', ...

New palladium catalyst, method for its preparation and its use

The invention relates to palladium(0) tris{tri-[3,5-bis(trifluoromethyl)-phenyl]-phosphine} complex of formula (I), as well as to its preparation and use. This compound is outstandingly stable, and can be used as catalyst with excellent results.

CATALYST FOR ASYMMETRIC HYDROGENATION OF IMINE, SYNTHESIS METHOD AND APPLICATION THEREOF

A chiral hydrogenated H-BINOL bisphosphine compound is provided, with the structure shown as the following formula (I), wherein both Rand Rare halogen, H or C-Caliphatic group; Ris H or C-Caliphatic group; Ris halogen, amino, nitro, H, C-Caliphatic group or C-Caromatic group; and X is phenyl, substituted phenyl, cyclohexyl, substituted cyclohexyl, C-Caromatic group, or C-Cheterocyclic aromatic group containing one or more heteroatoms selected from N, S, O. The present invention further provides a catalyst for an asymmetric catalytic hydrogenation reaction which contains the compound, wherein the catalyst can produce more than % of enantiomers and efficiency with the turnover number of greater than in the asymmetric hydrogenation reaction of imines. 4. A catalyst for an asymmetric catalytic hydrogenation reaction claim 1 , characterized by comprising a coordination compound which is an iridium-containing coordination compound formed by the compound as claimed in as a ligand and an iridium-cyclooctadiene complex based on a molar ratio of 0.5-5:1.5. The catalyst as claimed in claim 4 , characterized in that the iridium-cyclooctadiene complex is any one of [IrCl(COD)] claim 4 , [IrBr(COD)]or [Ir(COD)]BF.6. The catalyst as claimed in claim 4 , characterized by further comprising a halogen-containing additive claim 4 , a molar ratio of which to the iridium--containing coordination compound catalyst is 0.001-10:1.7. The catalyst as claimed in claim 6 , characterized in that the halogen-containing additive is selected from an alkali metal salt of a halogen family element claim 6 , a halogen-containing C1-C60 quaternary ammonium salt claim 6 , or a halogen-containing C1-C60 aromatic hydrocarbon or aliphatic hydrocarbon.8. The catalyst as claimed in claim 7 , characterized in that the halogen is chlorine claim 7 , bromine or iodine.9. The catalyst as claimed in claim 7 , characterized in that the halogen-containing additive is selected from iodobenzene claim 7 , tetrabutyl ...

Method for Producing Unsaturated Compounds

The invention relates to a method for producing compositions containing unsaturated compounds, wherein (A) one or more unsaturated monocarboxylic acids having 10 to 24 C-atoms or esters of said monocarboxylic acids and optionally (B) one or more compounds having at least one C═C double bond (wherein the compounds (B) are different from the compounds (A)) are subjected to a tandem isomerization/metathesis reaction sequence in the presence of a palladium catalyst and a ruthenium catalyst, providing that the palladium catalysts used are compounds that contain at least one structural element Pd—P(R 1 R 2 R 3 ), wherein the radicals R 1 to R 3 , independently of one another, each comprise 2 to 10 C-atoms, which may be aliphatic, alicyclic, aromatic or heterocyclic respectively, providing that at least one of the radicals R 1 to R 3 contains a beta-hydrogen, wherein the palladium catalyst is used as such or is produced in situ, providing that the method is carried out in the absence of substances that have a pKa value of 3 or less.

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 ...

Immobilized Ruthenium-Triphos Catalysts for Selective Hydrogenolysis of Amides

A compound represented by the structure of formula (I): 5. The compound of claim 4 , wherein L comprises trimethylenemethane.7. The method of claim 6 , wherein the Ru-containing compound comprises [Ru(COD)(methylallyl)].8. A catalyst composition comprising:(a) an oxidic support; and{'claim-ref': {'@idref': 'CLM-00004', 'claim 4'}, '(b) the compound of immobilized on the support.'}9. The catalyst composition of claim 8 , wherein the oxidic support comprises silica claim 8 , magnesia claim 8 , titania claim 8 , or alumina.10. The catalyst composition of claim 8 , wherein the oxidic support comprises silica.11. The catalyst composition of claim 8 , wherein L comprises trimethylenemethane.13. The process of claim 12 , wherein the oxidic support comprises silica claim 12 , magnesia claim 12 , titania claim 12 , and alumina.14. The process of claim 12 , wherein the oxidic support comprises silica.15. The process of claim 12 , wherein L comprises trimethylenemethane.16. The process of claim 13 , wherein L comprises trimethylenemethane.17. The process of claim 14 , wherein L comprises trimethylenemethane.18. The process of claim 12 , wherein the amide comprises a lactam.19. The process of claim 13 , wherein the amide comprises a lactam.20. The process of claim 17 , wherein the amide comprises a lactam. This is application claims the benefit of Provisional Application No. 62/691,936 filed on Jun. 29, 2018 under 35 U.S.C. § 119(e)(1); the entire content of the provisional application is hereby incorporated by reference.The invention generally relates to the field of organic chemistry. It particularly relates to silyl ether triphos compounds, organometallic complexes containing the silyl ether triphos compounds, catalysts containing the organometallic complexes immobilized on oxidic supports, methods of making, and/or methods of using the compounds, complexes, and catalysts.The hydrogenolysis of amides to amines under mild reaction conditions represents a challenging chemical ...

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 ...

Photocatalytic Conversion of Carbon Dioxide and Water Into Substituted or Unsubstituted Hydrocarbon(s)

A method for the production of hydrocarbon(s), such as methane, substituted hydrocarbons, such as methanol, or the production of hydrogen, the method comprising the steps of contacting a first catalyst with water in order to photocatalyse the splitting of at least some of the water into hydrogen and oxygen; and contacting a second catalyst with a gas stream comprising carbon dioxide and at least some of the hydrogen produced from step (a) in order to photocatalyse the reaction between the hydrogen and carbon dioxide to produce hydrocarbon(s), such as methane, and/or substituted hydrocarbons, such as methanol. In an embodiment, the catalyst comprises gold and or ruthenium nanoclusters supported on a substrate. 1. A method for the production of hydrocarbon(s) , such as methane , or substituted hydrocarbons , such as methanol , the method comprising the steps of:contacting a catalyst with water and carbon dioxide in the presence of light in order to photocatalyse:(i) the splitting of at least some of the water into hydrogen and oxygen; and(ii) the reaction between hydrogen and carbon dioxide to produce at least one of a hydrocarbon and/or substituted hydrocarbons;wherein the catalyst comprises at least gold and ruthenium, in the form of at least one nanocluster supported by a substrate.2. The method according to claim 1 , wherein support substrate is selected from the group comprising graphene claim 1 , graphite claim 1 , carbon black claim 1 , nanotubes claim 1 , fullerenes claim 1 , zeolites claim 1 , carbon nitrides claim 1 , metal nitrides and or oxides including zinc oxide or titanium oxide.3. The method according to claim 1 , wherein the gold and ruthenium nanocluster has at least one Au—Ru bond having a distance in the range of from about 2.5 to 3.0 Å.4. The method according to claim 1 , wherein the gold and ruthenium nanocluster comprise an average cluster size less than about 2 nm.5. A method for the production of hydrocarbon(s) claim 1 , such as methane claim ...

Processes for the preparation of a diarylthiohydantoin compound

Disclosed are processes and intermediates for the preparation of compound (X), which is currently being investigated for the treatment of prostate cancer.

SYNTHESIS OF COELENTERAZINE

Disclosed herein are synthesis methods for coelenterazine. Also disclosed are articles including the coelenterazine and coelenterazine derivatives. Representative absorbent articles include disposable diapers and adult incontinence products. 1. A method of making coelenterazine , comprising:(a) reacting 3-benzylpyrazin-2-amine (25) with N-bromosuccinimide to provide 3-benzyl-5-bromopyrazin-2-amine (2);(b) reacting the 3-benzyl-5-bromopyrazin-2-amine (2) in two sequential steps to provide 4-(5-amino-6-benzylpyrazin-2-yl)phenol (7) (coelenteramine); and(c) coupling the 4-(5-amino-6-benzylpyrazin-2-yl)phenol (7) with silyl-protected 1,1-diethoxy-3-(4-hydroxyphenyl)propan-2-one to provide coelenterazine, or a salt thereof.2. The method of claim 1 , wherein (a) provides 3-benzyl-5-bromopyrazin-2-amine (2) in a yield of 60% to 85% relative to 3-benzylpyrazin-2-amine (25) and in a purity of at least 85%.3. The method of claim 1 , wherein (b) comprises a first step of reacting the 3-benzyl-5-bromopyrazin-2-amine (2) with 4-methoxyphenyl boronic acid (4) in the presence of a palladium catalyst to provide 3-benzyl-5-(4-methoxyphenyl)pyrazin-2-amine (5).4. The method of claim 3 , wherein the palladium catalyst is tetrakis(triphenylphosphine)palladium(0).5. The method of or claim 3 , wherein the palladium catalyst is present in an amount of 5 to 10 percent by weight relative to the 3-benzyl-5-bromopyrazin-2-amine (2).6. The method of any one of to claim 3 , wherein the first step in (b) comprises 1:1 to 1:1.3 molar equivalent of the 3-benzyl-5-bromopyrazin-2-amine (2) to 4-methoxyphenyl boronic acid (4).7. The method of any one of to claim 3 , wherein the first step in (b) comprises reacting the 3-benzyl-5-bromopyrazin-2-amine (2) and the 4-methoxyphenyl boronic acid (4) for a duration of 120 minutes to 300 minutes.8. The method of any one of to claim 3 , wherein the first step in (b) comprises reacting the 3-benzyl-5-bromopyrazin-2-amine (2) and the 4-methoxyphenyl boronic ...

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 ...

WATER-INSOLUBLE RUTHENIUM CATALYST COMPOSITION FOR USE IN AQUEOUS HYDROGENATION REACTIONS

The invention relates to a method for converting a precatalyst complex to an active catalyst complex, wherein the precatalyst complex and the active catalyst complex comprise a ruthenium atom and an optically active ligand that is insoluble in water, and the active catalyst complex furthermore comprises a monohydride and a water molecule. The method comprises the steps of providing water as an activation solvent system with a pH value equal or below 2, and solving said precatalyst complex, an acid, and hydrogen therein. The invention further relates to a method for manufacturing a catalyst composition, a method for hydrogenating a substrate molecule and a reaction mixture. 1. A method for converting a precatalyst complex to an active catalyst complex ,wherein said precatalyst complex and said active catalyst complex comprise a ruthenium atom and an optically active ligand that is insoluble in water, andwherein said active catalyst complex comprises a monohydride and a water molecule,said method comprising the steps of:a) providing an activation solvent system comprising water, said precatalyst complex,', 'a solubilizer,', 'an acid, and', 'hydrogen,, 'b) adding to, particularly solving in, said activation solvent system'}characterized in thatthe pH value of said activation solvent system is equal or below 2 after addition of said acid.2. The method according to claim 1 , wherein said activation solvent system comprises ≧50% (v/v) claim 1 , ≧75% (v/v) claim 1 , ≧80% (v/v) claim 1 , ≧90% (v/v) claim 1 , ≧99% (v/v) or 100% water.3. The method according to claim 1 , wherein said solubilizer is a surfactant that is capable of forming micelles in water and that is resistant to hydrolysis at pH≦2.4. A method for obtaining a catalyst composition claim 1 , comprising the steps ofa) providing water as a preparation solvent system, andb) adding to, particularly solving in, said preparation solvent system an optically active ligand, wherein said optically active ligand is ...

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 ...

METHOD FOR ALKYLATION OF AMINES

The present invention provides a simple, efficient, and industrially advantageous method for the alkylation of amines. The present invention relates to a production method for N-alkylamines whereby an amine is reacted with an alcohol in the presence of a ruthenium complex represented by general formula (1): RuXY(CO)(L) (wherein X and Y can be the same or different and represent a monovalent anionic ligand, and L represents a tridentate aminodiphosphine ligand). 3. The production method according to claim 1 , wherein the N-alkylamine has the following general formula (4):{'br': None, 'sup': 'A', 'R—NH—R\u2003\u2003(4)'}wherein, in the general formula (4),{'sup': 'A', 'Rrepresents an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, a heterocyclic group, an alkenyl group, an alkynyl group, a cycloalkenyl group, an alkyloxy group, a cycloalkyloxy group, an aryloxy group, an aralkyloxy group, a hydroxyl group, an alkoxycarbonyl group, a cycloalkyloxycarbonyl group, an aryloxycarbonyl group, an aralkyloxycarbonyl group, an alkenyloxycarbonyl group, an alkynyloxycarbonyl group, a cycloalkenyloxycarbonyl group, a carboxamide group or an alkoxysulfonyl group, which groups may comprise substituent(s); and'}R represents an optionally substituted hydrocarbon group, an optionally substituted aryl group or an optionally substituted heterocyclic group, {'br': None, 'sup': 'A', 'sub': '2', 'R—NH\u2003\u2003(5)'}, 'wherein the amine has the following general formula (5){'sup': 'A', 'wherein, in the general formula (5), Rrepresents the same group as in the definition in the general formula (4), and'} {'br': None, 'R—OH\u2003\u2003(6)'}, 'the alcohol has the following general formula (6)wherein, in the general formula (6), R represents the same group as in the definition in the general formula (4).6. The method according to claim 1 , wherein the alcohol is a primary or secondary alcohol.7. The method according to claim 1 , wherein the alcohol is methanol or ethanol.8. ...

Platinum metallacycles comprising n, p, or as ringatoms and their use as catalysts in 1,2-hydrosilylation reactions of dienes

Described herein are platinum complexes of Formula (I) for hydrosilylation of 1,3-dienes. Methods of using the platinum complexes for selective 1,2-hydrosilylation of 1,3-dienes are also provided.

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.

METHOD FOR CATALYTIC PREPARATION OF HYDROMORPHONE, HYDROCODONE, AND OTHER OPIATES

Methods are provided for efficient preparation of hydromorphone or hydrocodone by redox isomerization of morphine or codeine allylic alcohols, respectively, using transition metal aminophosphine catalysts formed in situ. 2. The method of claim 1 , wherein Ris H or Calkyl; Ris H claim 1 , Calkyl claim 1 , Calkenyl claim 1 , or Ccycloalkyl; and Ris H claim 1 , or —OH.3. The method of claim 2 , wherein Ris H or CH; Ris CH claim 2 , allyl claim 2 , or cyclopropylmethyl; and Ris H or —OH.4. The method of claim 3 , wherein Ris H or CH; Ris CH; and Ris H or —OH.5. The method of claim 4 , wherein Ris H or CH; Ris CH; and Ris H.6. The method of claim 5 , wherein Ris H; Ris CH; and Ris H.7. The method of claim 5 , wherein Ris CH; Ris CH; and Ris H.8. The method of claim 7 , wherein the compound of formula (II) is codeine base or a hydrate thereof or concentrated poppy straw-codeine (CPS-C).9. The method of claim 1 , wherein X is halo; and R claim 1 , R claim 1 , R claim 1 , R claim 1 , R claim 1 , R claim 1 , Rand Rare each optionally substituted aryl.10. The method of claim 9 , wherein M is Rh; R claim 9 , R claim 9 , R claim 9 , R claim 9 , R claim 9 , R claim 9 , Rand Rare each phenyl; m is 1; and n is 1.11. The method of claim 1 , wherein the exposing comprises adding 0.05-0.3 mol % of the compound of formula (III) to the compound of formula (II) claim 1 , to transform the compound of formula (II) into the compound of formula (I) or salt or solvate thereof.12. The method of claim 11 , wherein the transformation of compound (II) into the compound of formula (I) is greater than 97% claim 11 , 99% claim 11 , 99.5% claim 11 , or 99.9% by HPLC.13. The method of claim 1 , further comprising dissolving the compound of formula (II) in a solvent selected from the group consisting of methanol claim 1 , ethanol claim 1 , isopropanol claim 1 , n-propanol claim 1 , water claim 1 , methylene chloride/methanol claim 1 , tetrahydrofuran claim 1 , and acetone prior to the exposing step.14 ...

ENANTIOSELECTIVE HYDROGENATION OF 4-SUBSTITUTED 1,2-DIHYDROQUINOLINES IN PRESENCE OF A CHIRAL IRIDIUM CATALYST

The invention relates to a process for preparing optically active 4-substituted 1,2,3,4-tetrahydroquinolines comprising enantioselective hydrogenation of the corresponding 4-substituted 1,2-dihydroquinolines in presence of a chiral iridium (P,N)-ligand catalyst. 2: The process according to claim 1 , wherein{'sup': '1', 'sub': 1', '6', '6', '14', '1', '4, 'claim-text': {'sub': 6', '14', '6', '14', '1', '4', '1', '4', '1', '4', '1', '4', '1', '4, 'wherein C-C-aryl in the C-C-aryl-C-C-alkyl moiety is unsubstituted or substituted by one to five substituents selected from the group consisting of halogen, C-C-alkyl, C-C-haloalkyl, C-C-alkoxy and C-C-haloalkoxy'}, 'Ris C-C-alkyl or C-C-aryl-C-C-alkyl,'}{'sup': 2', '3, 'sub': 1', '4, 'Rand Rare the same and are selected from C-C-alkyl,'}{'sup': '4', 'sub': 1', '4', '1', '4', '1', '4', '1', '4, 'Ris C-C-alkyl, C-C-haloalkyl, C-C-alkoxy, C-C-haloalkoxy, phenyl or benzyl,'}n is 0, 1 or 2, and{'sup': '5', 'sub': 1', '6', '1', '6, 'each substituent R, if present, is independently selected from the group consisting of halogen, C-C-alkyl and C-C-haloalkyl.'}3: The process according to claim 1 , wherein{'sup': '1', 'Ris methyl, ethyl or n-propyl,'}{'sup': 2', '3, 'Rand Rare methyl,'}{'sup': '4', 'sub': 1', '4, 'Ris C-C-alkyl,'}n is 0, 1 or 2, and{'sup': '5', 'sub': 1', '6, 'each substituent R, if present, is independently selected from the group consisting of halogen and C-C-alkyl.'}6: The process according to claim 1 , wherein the hydrogenation is conducted using hydrogen gas at a pressure of from 1 to 300 bar.7: The process according to claim 1 , wherein the amount of iridium catalyst used is within the range of from 0.001 mol % to 5 mol % claim 1 , based on the amount of the compound of the formula (II).8: The process according to claim 1 , wherein the hydrogenation is conducted at a temperature within the range of from 20° C. to 130° C.9: The process according to claim 1 , wherein the hydrogenation is conducted in presence of a ...

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 ...

CATALYST SYSTEM CONTAINING A METATHESIS CATALYST AND AT LEAST ONE PHENOLIC COMPOUND AND A PROCESS FOR METATHESIS OF NITRILE-BUTADIENE RUBBER (NBR) USING THE CATALYST SYSTEM

The present invention relates to a catalyst system containing a metathesis catalyst containing at least one N-heterocyclic carbene ligand and at least one phenolic compound and to a process for performing the metathesis on nitrile rubbers for reducing their molecular weight using a metathesis catalyst containing at least one N-heterocyclic carbene ligand (NHC ligand) and at least one phenolic compound. 2. The catalyst system of claim 1 , wherein the metathesis catalyst is selected from the group consisting of:dichloro(fluorenylidene)(1,3-dimesityldihydroimidazolylidene)(triphenylphosphino)ruthenium,1,3-bis(2,4,6-trimethylphenyl)-2-imidazolidinylidene)dichloro(o-isopropoxyphenylmethylene)ruthenium,[1,3-bis(2,4,6-trimethylphenyl)-2-imidazolidinylidene]dichloro(phenylmethylene)bis(3-bromopyridine)ruthenium(II), and,1,3-bis(2,4,6-trimethylphenyl)-2-imidazolidinylidene)(2-isopropoxy-5-nitrobenzylidene)ruthenium(II)chloride.3. The catalyst system of wherein the phenolic compound of general formula (Z1) is selected from the group consisting of:2,2′-methylene-bis(4-methyl-6-tert-butylphenol),2,6-di-tert-butyl-4-methylphenol, and,2,2′-methylenebis(4-methyl-6-nonylphenol).4. The catalyst system of claim 1 , wherein the molar ratio of metathesis catalyst to phenolic compound of general formula (Z1) or (Z2)=1:(0.01-1000).5. A process of performing a metathesis of nitrile rubber claim 1 , the process comprising the use of the catalyst system of .6. A process of reducing the molecular weight of nitrile rubbers claim 1 , in which nitrile rubber is subjected to a metathesis reaction in the presence of a complex catalyst system of .7. The process of claim 6 , wherein the amount of metathesis catalyst is 1 to 1000 ppm of noble metal claim 6 , based on the employed nitrile rubber.8. The process of claim 6 , wherein the amount of phenolic compound of general formula (Z1) or (Z2) is 0.0001 phr to 5 phr claim 6 , based on the nitrile rubber to be degraded.9. The process of claim 6 , ...

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: ...

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.

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- ...

INTEGRATED CAPTURE AND CONVERSION OF CO2 TO METHANOL OR METHANOL AND GLYCOL

A process for producing methanol includes combining a hydrogenation catalyst, hydrogen, and COwith a condensed phase solution comprising an amine under conditions effective to form methanol and water. A process for coproduction of methanol and a glycol includes combining an epoxide, a hydrogenation catalyst, hydrogen, and COwith a condensed phase solution comprising an amine under conditions effective to form methanol and a glycol. 1. A process , comprising:{'sub': 2', '2, 'producing methanol and a glycol by combining an epoxide, a hydrogenation catalyst, hydrogen, and COwith a condensed phase comprising an amine under conditions effective to provide a reaction between the epoxide, hydrogen, and COto form methanol and the glycol, wherein at least 10 mol % of the epoxide is consumed in the reaction.'}2. The process of claim 1 , wherein the condensed phase is a condensed phase solution further comprising the CO.3. The process of claim 2 , further comprising preparing the condensed phase solution by contacting a gas stream comprising COwith an amine-containing solvent or solution prior to combining the epoxide claim 2 , the hydrogenation catalyst claim 2 , and the hydrogen with the condensed phase solution.4. The process of claim 3 , wherein contacting the gas stream with the amine-containing solvent or solution is performed:(i) at a temperature T′ within a range of from 20° C. to 60° C.; or(ii) at an initial pressure P′ within a range of from 0.1 MPa to 5 MPa; or(iii) both (i) and (ii).5. The process of claim 1 , wherein the conditions effective to form methanol and the glycol comprise:{'sub': 'MG', '(i) a temperature Twithin a range of from 50° C. to 170° C.; or'}{'sub': 'MG', '(ii) an initial pressure Pwithin a range of from 3 MPa to 10 MPa; or'}{'sub': 'MG', '(iii) a time twithin a range of from 3 seconds to 36 hours; or'}(iv) any combination of (i), (ii), and (iii).6. The process of claim 1 , further comprising:{'sub': '2', '(i) combining the epoxide, the CO, and ...

Metallorganocatalysis For Asymmetric Transformations

A ligand having the structure or its enantiomer; (I) wherein: each one of R a , R b , R c and R d is selected from alkyl, cycloalkyl, and aryl; the bridge group is selected from CH 2 NH; *CH(CH 3 )NH(C*,R); and the organocatalyst is an organic molecule catalyst covalently bound to the bridge group. Also, a catalyst having the structure or its enantiomer: (II) wherein: each one of R a , R b , R c and R d is selected from alkyl, cycloalkyl, and aryl; the bridge group is selected from CH 2 NH; *CH(CH 3 )NH(C*,R); and *CH(CH 3 )NH(C*,S); the organocatalyst is an organic molecule catalyst covalently bound to the bridge group; and M is selected from the group consisting of Rh, Pd, Cu, Ru, Ir, Ag, Au, Zn, Ni, Co, and Fe.

P-CHIROGENIC ORGANOPHOSPHORUS COMPOUNDS

Novel P-chirogenic organophosphorus compounds of general formula (I), a process for the synthesis of the compounds of formula (I), and intermediate products of general formulae (II), (III) and (IV), as shown below, are involved in the synthesis of compounds (I). 2. The process according to claim 1 , wherein the electrophile is selected from the group consisting of boronate reagents claim 1 , aldehydes claim 1 , ketones claim 1 , acyl chlorides claim 1 , halosilanes claim 1 , haloalkanes claim 1 , and Michael acceptors such as α claim 1 ,β-insaturated ester claim 1 , α claim 1 ,β-insaturated ketones claim 1 , and α claim 1 ,β-insaturated phosphine derivatives.3. The process according to claim 1 , wherein the oxidative reagent is selected from the group consisting of transition metal salts and transition metal complexes claim 1 , wherein the metal is selected from the group comprising iron claim 1 , copper.4. The process according to claim 1 , wherein compound (VII) is chiral. The present invention relates to novel P-chirogenic organophosphorus compounds of general formula (I). The present invention also provides a process for the synthesis of said compounds of formula (I). The present invention also relates to intermediate products of general formulae (II), (III) and (IV), as shown below, which are involved in the synthesis of compounds (I).Compounds of general formula (I) may useful as agrochemical and therapeutic substances, or as reagents or intermediates for fine chemistry.Further, the invention relates to metal complexes comprising compounds (I) as ligands. The novel compounds and complexes of the present invention are useful in asymmetric catalysis by transition metal complexes or organocatalysis, especially for asymmetric hydrogenation or allylation.During the past decades, asymmetric organocatalysis and organometallic catalysis made a breakthrough and became methodologies of choice for the synthesis of chiral substances on laboratory as well as on industrial ...

COMPLEX CATALYSTS BASED ON AMINO-PHOSPHINE LIGANDS FOR HYDROGENATION AND DEHYDROGENATION PROCESSES

The present application discloses novel PWNN and PWNWP metal catalysts for organic chemical syntheses including hydrogenation (reduction) of unsaturated compounds or dehydrogenation of substrates. The range of hydrogenation substrate compounds includes esters, lactones, enals, enones, enolates, oils and fats, resulting in alcohols, enols, diols, and triols as reaction products. The catalysts of current application can be used to catalyze a hydrogenation reaction under solvent free conditions. The present catalysts also allow the hydrogenation to proceed without added base, and it can be used in place of the conventional reduction methods employing hydrides of the main-group elements. Furthermore, the catalysts of the present application can catalyze a dehydrogenation reaction under homogenous and/or acceptorless conditions. As such, the catalysts provided herein can be useful in substantially reducing cost and improving the environmental profile of manufacturing processes for a variety of chemicals. 2. The compound of claim 1 , wherein when R′ is PR claim 1 , R is H claim 1 , or when Rand R′ do not form part of a heteroaryl Ris H.3. The compound of claim 1 , wherein R′ taken together with Rand the atoms to which they are attached forms a substituted or unsubstituted heteroaryl claim 1 , such as pyridyl claim 1 , furanyl claim 1 , imidazolyl claim 1 , pyrazolyl or oxazolyl.54. The compound of any one of - claims 1 , wherein n is 1 claims 1 , or m is 1 or both n and m are 1.76. The compound of any one of - coordinated to a transition metal.8. The compound of claim 7 , wherein the transition metal is a group 7 (manganese group) metal claim 7 , a group 8 (iron group) metal claim 7 , group 9 (cobalt group) metal claim 7 , or group 10 (nickel group) metal.9. The compound of claim 7 , wherein the transition metal is Ru or Os.11. The metal complex of claim 10 , which comprises the PWNN ligand wherein R′ taken together with Rand the atoms to which they are attached forms a ...

PHENANTHROLINE BASED PINCER COMPLEXES USEFUL AS CATALYSTS FOR THE PREPARATION OF METHANOL FROM CARBONDIOXIDE

The present invention relates to a novel phenonthroline based pincer complexes and process for preparation thereof. The present invention also provides a one pot process for the conversion of carbon dioxide to methanol in the presence of a molecularly defined pincer-type single-site Ru-catalyst and secondary amine. Further the present invention provides the use of phenonthroline based pincer complexes for the esterification of alcohols and hydrogenation of esters under mild conditions. 3. The phenanthroline based pincer complexes of formula (I) as claimed in claim 1 , wherein the said catalyst is used for hydrogenation of lactones to diols and esters to alcohols4. The phenanthroline based pincer complexes of formula (I) as claimed in claim 1 , wherein the said catalyst is used for dehydrogenation of diols to lactones claim 1 , alcohol to esters and secondary alcohols to ketones.6. The process as claimed in claim 8 , wherein solvent used in step (a) is selected from hexane claim 8 , heptane claim 8 , tetrahydrofuran (THF) claim 8 , diethyl ether claim 8 , toluene claim 8 , and etheylbenzene.8. The process as claimed in claim 1 , wherein catalyst of formula 1 used in step (i) is selected from HCl(CO)Ru(Phen-(Bu)PNN) (3); H(CO)Ru-(Phen-(Bu)PNN) (4); H(CO)Ru(η1BH4)(Phen-(tBu)PNN) (5a); HCl(CO)Ru(BPy-PNN); [H(CO)Ru(BPy-PNN)]; and H(CO) Ru(Py-PNN)].9. The process as claimed in claim 7 , wherein said steps (ii) and (vi) are absent when [H(CO)Ru(BPy-PNN)] catalyst is used. The present invention relates to phenonthroline based pincer complex of formula (I) and process for preparation thereof. Particularly the present invention relates to use of phenonthroline based pincer complex of formula (I) as catalyst for the esterification of alcohols and hydrogenation of esters including lactones under mild conditions. More particularly the present invention relates to a one pot process for the conversion of carbon dioxide to methanol in the presence of a pincer based catalyst and a ...

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- ...

Butyl-bridged diphosphine ligands for alkoxycarbonylation

The invention relates to compounds of formula (I) where R 1 , R 2 , R 3 , R 4 are each independently selected from —(C 1 -C 12 )-alkyl, —(C 3 -C 12 )-cycloalkyl, —(C 3 -C 12 )-heterocycloalkyl, —(C 6 -C 20 )-aryl, —(C 3 -C 20 )-heteroaryl; at least one of the R 1 , R 2 , R 3 , R 4 radicals is a —(C 3 -C 20 )-heteroaryl radical; and R 1 , R 2 , R 3 , R 4 , if they are —(C 1 -C 12 )-alkyl, —(C 3 -C 12 )-cycloalkyl, —(C 3 -C 12 )-heterocycloalkyl, —(C 6 -C 20 )-aryl or —(C 3 -C 20 )-heteroaryl, may each independently be substituted by one or more substituents selected from —(C 1 -C 12 )-alkyl, —(C 3 -C 12 )-cycloalkyl, —(C 3 -C 12 )-heterocycloalkyl, —O—(C 1 -C 12 )-alkyl, —O—(C 1 -C 12 )-alkyl-(C 6 -C 20 )-aryl, —O—(C 3 -C 12 )-cycloalkyl, —S—(C 1 -C 12 )-alkyl, —S—(C 3 -C 12 )-cycloalkyl, —COO—(C 1 -C 12 )-alkyl, —COO—(C 3 -C 12 )-cycloalkyl, —CONH—(C 1 -C 12 )-alkyl, —CONH—(C 3 -C 12 )-cycloalkyl, —CO—(C 1 -C 12 )-alkyl, —CO—(C 3 -C 12 )-cycloalkyl, —N—[(C 1 -C 12 )-alkyl] 2 , —(C 6 -C 20 )-aryl, —(C 6 -C 20 )-aryl-(C 1 -C 12 )-alkyl, —(C 6 -C 20 )-aryl-O—(C 1 -C 12 )-alkyl, —(C 3 -C 20 )-heteroaryl, —(C 3 -C 20 )-heteroaryl-(C 1 -C 12 )-alkyl, —(C 3 -C 20 )-heteroaryl-O-(C 1 -C 12 )-alkyl, —COOH, —OH, —SO 3 H, —NH 2 , halogen; and to the use thereof as ligands in alkoxycarbonylation.

MONOPHOSPHINE COMPOUNDS AND PALLADIUM CATALYSTS BASED THEREON FOR THE ALKOXYCARBONYLATION OF ETHYLENICALLY UNSATURATED COMPOUNDS

The invention relates to compounds of formula (I) 2. Compound according to claim 1 ,{'sup': '1', 'sub': 1', '12, 'where Ris —(C-C)-alkyl.'}3. Compound according to claim 1 ,{'sup': '2', 'sub': 6', '20', '3', '20, 'where Ris selected from —(C-C)-aryl and —(C-C)-heteroaryl.'}4. Compound according to claim 1 ,{'sup': '2', 'where Ris selected from phenyl, pyrimidyl and imidazolyl.'}5. Compound according to claim 1 ,{'sup': '3', 'where Ris selected from heteroaryl groups having five or six ring atoms.'}6. Compound according to claim 1 ,{'sup': '3', 'where Ris selected from pyrimidyl and imidazolyl.'}7. Compound according to claim 1 ,{'sup': 1', '2', '3, 'sub': 1', '12, 'where R, Rand Rmay each independently be substituted by one or more substituents selected from —(C-C)-alkyl.'}9. Complex comprising Pd and a compound according to .11. Process according to claim 10 , wherein the ethylenically unsaturated compound is selected from ethene claim 10 , propene claim 10 , 1-butene claim 10 , cis- and/or trans-2-butene claim 10 , isobutene claim 10 , 1 claim 10 ,3-butadiene claim 10 , 1-pentene claim 10 , cis- and/or trans-2-pentene claim 10 , 2-methyl-1-butene claim 10 , 3-methyl-1-butene claim 10 , 2-methyl-2-butene claim 10 , hexene claim 10 , tetramethylethylene claim 10 , heptene claim 10 , 1-octene claim 10 , 2-octene claim 10 , di-n-butene claim 10 , and mixtures thereof.12. Process according to claim 10 ,wherein the compound comprising Pd in process step b) is selected from palladium dichloride, palladium(II) acetylacetonate, palladium(II) acetate, dichloro(1,5-cycloocta-diene)palladium(II), bis(dibenzylideneacetone)palladium, bis(acetonitrile)dichloro-palladium(II), palladium(cinnamyl) dichloride.13. Process according to claim 10 ,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, and mixtures thereof.14. Process according to claim 10 , ...

Catalysts for (e)-selective olefin metathesis

This invention relates generally to olefin metathesis catalyst compounds, to the preparation of such compounds, and the use of such catalysts in the metathesis of olefins and olefin compounds, more particularly, in the use of such catalysts in (E)-selective olefin metathesis reactions. The invention has utility in the fields of catalysis, organic synthesis, polymer chemistry, and industrial and fine chemicals chemistry.

METHOD FOR IN-SITU FORMATION OF METATHESIS CATALYSTS

Synthetic methods for the in-situ formation of olefin metathesis catalysts are disclosed, as well as the use of such catalysts in metathesis reactions of olefins and olefin compounds. In one aspect, a method is provided for synthesizing an organometallic compound of the formula 2. The compound of claim 1 , wherein M is Ru or Os.3. The compound of claim 1 , wherein L claim 1 , L claim 1 , and Lare independently selected from phosphine claim 1 , sulfonated phosphine claim 1 , phosphite claim 1 , phosphinite claim 1 , phosphonite claim 1 , arsine claim 1 , stibine claim 1 , ether claim 1 , amine claim 1 , amide claim 1 , imine claim 1 , sulfoxide claim 1 , carboxyl claim 1 , nitrosyl claim 1 , pyridine claim 1 , substituted pyridine claim 1 , imidazole claim 1 , substituted imidazole claim 1 , pyrazine claim 1 , thioether claim 1 , and thiocarbonyl.4. The compound of claim 3 , wherein the phosphine is of the formula PRRR claim 3 , wherein R claim 3 , R claim 3 , and Rare each independently selected from aryl claim 3 , substituted aryl claim 3 , alkyl claim 3 , substituted alkyl claim 3 , cycloalkyl claim 3 , substituted cycloalkyl claim 3 , heterocycles claim 3 , and substituted heterocycles.5. The compound of claim 1 , wherein Xand Xare independently selected from hydrogen claim 1 , halide claim 1 , C-Calkyl claim 1 , C-Caryl claim 1 , C-Calkoxy claim 1 , C-Caryloxy claim 1 , C-Calkoxycarbonyl claim 1 , C-Caryloxycarbonyl claim 1 , C-Cacyl claim 1 , C-Cacyloxy claim 1 , C-Calkylsulfonato claim 1 , C-Carylsulfonato claim 1 , C-Calkylsulfanyl claim 1 , C-Carylsulfanyl claim 1 , C-Calkylsulfinyl claim 1 , or C-Carylsulfinyl claim 1 , any of which claim 1 , with the exception of hydrogen and halide claim 1 , are optionally further substituted with one or more groups selected from halide claim 1 , C-Calkyl claim 1 , C-Calkoxy claim 1 , and C-Caryl.9. A method of performing an olefin metathesis reaction claim 1 , comprising contacting the compound of with an olefin.10. The ...

PHOSPHINE LIGAND AND PALLADIUM CATALYSTS BASED THEREON FOR THE ALKOXYCARBONYLATION OF ETHYLENICALLY UNSATURATED COMPOUNDS

The invention relates to a compound of formula (1) 2. Complex comprising Pd and a compound according to .4. Process according to claim 3 , wherein the ethylenically unsaturated compound is selected from ethene claim 3 , propene claim 3 , 1-butene claim 3 , cis- and/or trans-2-butene claim 3 , isobutene claim 3 , 1 claim 3 ,3-butadiene claim 3 , 1-pentene claim 3 , cis- and/or trans-2-pentene claim 3 , 2-methyl-1-butene claim 3 , 3-methyl-1-butene claim 3 , 2-methyl-2-butene claim 3 , hexene claim 3 , tetramethylethylene claim 3 , heptene claim 3 , 1-octene claim 3 , 2-octene claim 3 , di-n-butene claim 3 , or mixtures thereof.5. Process according to claim 3 , wherein the ethylenically unsaturated compound comprises 8 to 22 carbon atoms.6. Process according to claim 3 , wherein the compound comprising Pd in process step b) is selected from palladium dichloride claim 3 , palladium(II) acetylacetonate claim 3 , palladium(II) acetate claim 3 , dichloro(1 claim 3 ,5-cyclooctadiene)palladium(II) claim 3 , bis(dibenzylideneacetone)palladium claim 3 , bis(acetonitrile)dichloropalladium(II) claim 3 , palladium(cinnamyl) dichloride.7. Process according to claim 3 , wherein the alcohol in process step c) is selected from methanol claim 3 , ethanol claim 3 , 1-propanol claim 3 , 1-butanol claim 3 , 1-pentanol claim 3 , 1-hexanol claim 3 , 2-propanol claim 3 , tert-butanol claim 3 , 3-pentanol claim 3 , cyclohexanol claim 3 , phenol claim 3 , or mixtures thereof. The present invention relates to an improved phosphine ligand and to the use thereof in alkoxycarbonylation.The alkoxycarbonylation of ethylenically unsaturated compounds is a process of increasing significance. An alkoxycarbonylation is understood to mean the reaction of ethylenically unsaturated compounds such as olefins with carbon monoxide and alcohols in the presence of a metal or a metal complex and a ligand to give the corresponding esters:Among the alkoxycarbonylation reactions, ethene methoxycarbonylation to ...

FERROCENE-BASED COMPOUNDS AND PALLADIUM CATALYSTS BASED THEREON FOR THE ALKOXYCARBONYLATION OF ETHYLENICALLY UNSATURATED COMPOUNDS

The invention relates to a compound of formula (I) 2. Compound according to claim 1 ,{'sup': 1', '3, 'where Rand Rare each independently selected from furyl, thienyl, 2-pyrrolyl, 4-imidazolyl, oxazolyl, isoxazolyl, thiazolyl, isothiazolyl, pyrazolyl, furazanyl, tetrazolyl.'}3. Compound according to claim 1 ,{'sup': 1', '3, 'where Rand Rare each independently selected from furyl and thienyl.'}4. Compound according to claim 1 ,{'sup': 2', '4, 'sub': 1', '12', '3', '12', '6', '20, 'where Rand Rare each independently selected from —(C-C)-alkyl, —(C-C)-cycloalkyl and —(C-C)-aryl.'}5. Compound according to claim 1 ,{'sup': 2', '4, 'sub': 1', '12, 'where Rand Rare each —(C-C)-alkyl.'}6. Compound according to claim 1 ,{'sup': 1', '3, 'where Rand Rmay each independently be substituted by one or more substituents selected from'}{'sub': 1', '12', '3', '12', '1', '12', '1', '12', '6', '20', '3', '12', '6', '20', '6', '20', '1', '12', '6', '20', '1', '12, '—(C-C)-alkyl, —(C-C)-cycloalkyl, —O—(C-C)-alkyl, —O—(C-C)-alkyl-(C-C)-aryl, —O—(C-C)-cycloalkyl, —(C-C)-aryl, —(C-C)-aryl-(C-C)-alkyl, —(C-C)-aryl-O—(C-C)-alkyl.'}7. Compound according to claim 1 ,{'sup': 3', '4, 'sub': 1', '12', '3', '12', '3', '12', '6', '20, 'where Rand R, if they are —(C-C)-alkyl, —(C-C)-cycloalkyl, —(C-C)-heterocycloalkyl or —(C-C)-aryl,'}{'sub': 1', '12', '3', '12', '1', '12', '1', '12', '6', '20', '3', '12', '6', '20', '6', '20', '1', '12', '6', '20', '1', '12, 'may each independently be substituted by one or more substituents selected from —(C-C)-alkyl, —(C-C)-cycloalkyl, —O—(C-C)-alkyl, —O—(C-C)-alkyl-(C-C)-aryl, —O—(C-C)-cycloalkyl, —(C-C)-aryl, —(C-C)-aryl-(C-C)-alkyl, —(C-C)-aryl-O—(C-C)-alkyl.'}10. Complex comprising Pd and a compound according to .12. Process according to claim 11 ,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- ...

Process for the preparation of esters by means of carbonylation of ethers

The invention relates to a process comprising the process steps of: a) initially charging an ether having from 3 to 30 carbon atoms; b) adding a phosphine ligand and a compound comprising Pd, or adding a comprising Pd and a phosphine ligand; c) feeding in CO; d) heating the reaction mixture, with conversion of the ether; wherein the phosphine ligand is a compound of formula (I) where m and n are each independently 0 or 1; R 1 , R 2 , R 3 , R 4 are each independently selected from —(C 1 -C 12 )-alkyl, —(C 3 -C 12 )-cycloalkyl, —(C 3 -C 12 )-heterocycloalkyl, —(C 6 -C 20 )-aryl, —(C 3 -C 20 )-heteroaryl; at least one of the R 1 , R 2 , R 3 , R 4 radicals is a —(C 3 -C 20 )-heteroaryl radical; and R 1 , R 2 , R 3 , R 4 , if they are —(C 1 -C 12 )-alkyl, —(C 3 -C 12 )-cycloalkyl, —(C 3 -C 12 )-heterocycloalkyl, —(C 6 -C 20 )-aryl or —(C 3 -C 20 )-heteroaryl, may each independently be substituted by one or more substituents selected from —(C 1 -C 12 )-alkyl, —(C 3 -C 12 )-cycloalkyl, —(C 3 -C 12 )-heterocycloalkyl, —O—(C 1 -C 12 )-alkyl, —O—(C 1 -C 12 )-alkyl-(C 6 -C 20 )-aryl, —O—(C 3 -C 12 )-cycloalkyl, —S—(C 1 -C 12 )-alkyl, —S—(C 3 -C 12 )-cycloalkyl, —COO—(C 1 -C 12 )-alkyl, —COO—(C 3 -C 12 )-cycloalkyl, —CONH—(C 1 -C 12 )-alkyl, —CONH—(C 3 -C 12 )-cycloalkyl, —CO—(C 1 -C 12 )-alkyl, —CO—(C 3 -C 12 )-cycloalkyl, —N—[(C 1 -C 12 )-alkyl] 2 , —(C 6 -C 20 )-aryl, —(C 6 -C 20 )-aryl-(C 1 -C 12 )-alkyl, —(C 6 -C 20 )-aryl-O—(C 1 -C 12 )-alkyl, —(C 3 -C 20 )-heteroaryl, —(C 3 -C 20 )heteroaryl-(C 1 -C 12 )-alkyl, —(C 3 -C 20 )-heteroaryl-O—(C 1 -C 12 )-alkyl, —COOH, —SO 3 H, —NH 2 , halogen; and wherein no alcohol is added to the reaction mixture.

Process for the alkoxycarbonylation of ethers

The invention relates to a process comprising the following process steps: a) introducing an ether having 3 to 30 carbon atoms; b) adding a phosphine ligand and a compound which comprises Pd, or adding a complex comprising Pd and a phosphine ligand; c) adding an alcohol; d) supplying CO; e) heating the reaction mixture, the ether being reacted for form an ester; where the phosphine ligand is a compound of formula (I) where m and n are each independently 0 or 1; R 1 , R 2 , R 3 , R 4 are each independently selected from —(C 1 -C 12 )-alkyl, —(C 3 -C 12 )-cycloalkyl, —(C 3 -C 12 )-heterocycloalkyl, —(C 6 -C 20 )-aryl, —(C 3 -C 20 )-heteroaryl; at least one of the R 1 , R 2 , R 3 , R 4 radicals is a —(C 3 -C 20 )-heteroaryl radical; and R 1 , R 2 , R 3 , R 4 , if they are —(C 1 -C 12 )-alkyl, —(C 3 -C 12 )-cycloalkyl, —(C 3 -C 12 )-heterocycloalkyl, —(C 6 -C 20 )-aryl or —(C 3 -C 20 )-heteroaryl, may each independently be substituted by one or more substituents selected from —(C 1 -C 12 )-alkyl, —(C 3 -C 12 )-cycloalkyl, —(C 3 -C 12 )-heterocycloalkyl, —O—(C 1 -C 12 )-alkyl, —O—(C 1 -C 12 )-alkyl-(C 6 -C 20 )-aryl, —O—(C 3 -C 12 )-cycloalkyl, —S—(C 1 -C 12 )-alkyl, —S—(C 3 -C 12 )-cycloalkyl, —COO—(C 1 -C 12 )-alkyl, —COO—(C 3 -C 12 )-cycloalkyl, —CONH—(C 1 -C 12 )-alkyl, —CONH—(C 3 -C 12 )-cycloalkyl, —CO—(C 1 -C 12 )-alkyl, —CO—(C 3 -C 12 )-cycloalkyl, —N—[(C 1 -C 12 )-alkyl] 2 , —(C 6 -C 20 )-aryl, —(C 6 -C 20 )-aryl-(C 1 -C 12 )-alkyl, —(C 6 -C 20 )-aryl-O—(C 1 -C 12 )-alkyl, —(C 3 -C 20 )-heteroaryl, —(C 3 -C 20 )-heteroaryl-(C 1 -C 12 )-alkyl, —(C 3 -C 20 )-heteroaryl-O—(C 1 -C 12 )-alkyl, —COOH, —OH, —SO 3 H, —NH 2 , halogen.

Process for the alkoxycarbonylation of olefins in a medium having a low brønsted acid concentration

Process comprising the following process steps: a) introducing an ethylenically unsaturated compound; b) adding a ligand-metal complex comprising Pd and a bidentate phosphine ligand, or adding a bidentate phosphine ligand and a compound which comprises Pd; c) adding an alcohol; d) supplying CO; e) heating the reaction mixture, the ethylenically unsaturated compound being reacted to form an ester, where the reaction mixture is admixed with less than 0.1 mol %, based on the amount of substance of the ethylenically unsaturated compound, of Brønsted acids having an acid strength of pKa ≦3, characterized in that the phosphine ligand is substituted on at least one phosphorus atom by at least one heteroaryl radical.

Process for the alkoxycarbonylation of alcohols

The invention relates to a process comprising the following process steps: a) introducing a first alcohol, the first alcohol having 2 to 30 carbon atoms; b) adding a phosphine ligand and a compound which comprises Pd, or adding a complex comprising Pd and a phosphine ligand; c) adding a second alcohol; d) supplying CO; e) heating the reaction mixture, the first alcohol reacting with CO and the second alcohol to form an ester; where the phosphine ligand is a compound of formula (I) where m and n are each independently 0 or 1; R 1 , R 2 , R 3 , R 4 are each independently selected from —(C 1 -C 12 )-alkyl, —(C 3 -C 12 )-cycloalkyl, —(C 3 -C 12 )-heterocycloalkyl, —(C 6 -C 20 )-aryl, —(C 3 -C 20 )-heteroaryl; at least one of the R 1 , R 2 , R 3 , R 4 radicals is a —(C 3 -C 20 )-heteroaryl radical; and R 1 , R 2 , R 3 , R 4 , if they are —(C 1 -C 12 )-alkyl, —(C 3 -C 12 )-cycloalkyl, —(C 3 -C 12 )-heterocycloalkyl, —(C 6 -C 20 )-aryl or —(C 3 -C 20 )-heteroaryl, may each independently be substituted by one or more substituents selected from —(C 1 -C 12 )-alkyl, —(C 3 -C 12 )-cycloalkyl, —(C 3 -C 12 )-heterocycloalkyl, —O—(C 1 -C 12 )-alkyl, —O—(C 1 -C 12 )-alkyl-(C 6 -C 20 )-aryl, —O—(C 3 -C 12 )-alkyl, —S—(C 1 -C 12 )-alkyl, —S—(C 3 -C 12 )-cycloalkyl, —COO—(C 1 -C 12 )-alkyl, —COO—(C 3 -C 12 )-cycloalkyl, —CONH—(C 1 -C 12 )-alkyl, —CONH—(C 3 -C 12 )-cycloalkyl, —CO—(C 1 -C 12 )-alkyl, —CO—(C 3 -C 12 )-cycloalkyl, —N—[(C 1 -C 12 )-alkyl] 2 , —(C 6 -C 20 )-aryl, —(C 6 -C 20 )-aryl-(C 1 -C 12 )-alkyl, —(C 6 -C 20 )-aryl-O—(C 1 -C 12 )-alkyl, —(C 3 -C 20 )-heteroaryl, —(C 3 -C 20 )-heteroaryl-(C 1 -C 12 )-alkyl, —(C 3 -C 20 )-heteroaryl-O—(C 1 -C 12 )-alkyl, —COON, —OH, —SO 3 H, —NH 2 , halogen.

1, 1' -bis(phosphino)ferrocene ligands for alkoxycarbonylation

Diastereomer mixture comprising diastereomers of the formulae (I.1) and (I.2) where R 2 , R 4 are each independently selected from —(C 1 -C 12 )-alkyl, —(C 3 -C 12 )-cycloalkyl, —(C 3 -C 12 )-heterocycloalkyl, —(C 6 -C 20 )-aryl; the R 1 , R 3 radicals are each a —(C 3 -C 20 )-heteroaryl radical; R 1 , R 3 may each independently be substituted by one or more substituents selected from —(C 1 -C 12 )-alkyl, —(C 3 -C 12 )-cycloalkyl, —(C 3 -C 12 )-heterocycloalkyl, —O—(C 1 -C 12 )-alkyl, —O—(C 1 -C 12 )-alkyl-(C 6 -C 20 )-aryl, —O—(C 3 -C 12 )-cycloalkyl, —S—(C 1 -C 12 )-alkyl, —S—(C 3 -C 12 )-cycloalkyl, —COO—(C 1 -C 12 )-alkyl, —COO—(C 3 -C 12 )-cycloalkyl, —CONH—(C 1 -C 12 )-alkyl, —CONH—(C 3 -C 12 )-cycloalkyl, —CO—(C 1 -C 12 )-alkyl, —CO—(C 3 -C 12 )-cycloalkyl, —N—[(C 1 -C 12 )-alkyl] 2 , —(C 6 -C 20 )-aryl, —(C 6 -C 20 )-aryl-(C 1 -C 12 )-alkyl, —(C 6 -C 20 )-aryl-O—(C 1 -C 12 )-alkyl, —(C 3 -C 20 )-heteroaryl, —(C 3 -C 20 )-heteroaryl-(C 1 -C 12 )-alkyl, —(C 3 -C 20 )-heteroaryl-O—(C 1 -C 12 )-alkyl, —COOH, —OH, —SO 3 H, —NH 2 , halogen; and R 2 , R 4 , if they are —(C 1 -C 12 )-alkyl, —(C 3 -C 12 )-cycloalkyl, —(C 3 -C 12 )-heterocycloalkyl or —(C 6 -C 20 )-aryl, may each independently be substituted by one or more substituents selected from —(C 1 -C 12 )-alkyl, —(C 3 -C 12 )-cycloalkyl, —(C 3 -C 12 )-heterocycloalkyl, —O—(C 1 -C 12 )-alkyl, —O—(C 1 -C 12 )-alkyl-(C 6 -C 20 )-aryl, —O—(C 3 -C 12 )-cycloalkyl, —S—(C 1 -C 12 )-alkyl, —S—(C 3 -C 12 )-cycloalkyl, —COO—(C 1 -C 12 )-alkyl, —COO—(C 3 -C 12 )-cycloalkyl, —CONH—(C 1 -C 12 )-alkyl, —CONH—(C 3 -C 12 )-cycloalkyl, —CO—(C 1 -C 12 )-alkyl, —CO—(C 3 -C 12 )-cycloalkyl, —N—[(C 1 -C 12 )-alkyl] 2 , —(C 6 -C 20 )-aryl, —(C 6 -C 20 )-aryl-(C 1 -C 12 )-alkyl, —(C 6 -C 20 )-aryl-O—(C 1 -C 12 )-alkyl, —(C 3 -C 20 )-heteroaryl, —(C 3 -C 20 )-heteroaryl-(C 1 -C 12 )-alkyl, —(C 3 -C 20 )-heteroaryl-O—(C 1 -C 12 )-alkyl, —COOH, —OH, —SO 3 H, —NH 2 , halogen. The invention further relates to Pd complex mixtures ...

Method for Preparation of Fluoro Alkylated Compounds by Homogeneous NI Catalysis

The invention discloses a method for the preparation of fluoro alkylated compounds by homogeneous Ni catalyzed fluoro alkylation with fluoro alkyl halides in the presence of a base. 2. The method according to claim 1 , wherein{'sub': '3', 'LIG is compound of formula (DPEPhos) or PhP.'}3. The method according to claim 1 , wherein{'sub': 2', '3', '3', '4, 'BAS is selected from the group consisting of CsCO, KPO, NaH and NaOtBu.'}5. The method according to claim 1 , wherein by 1, 2 or 3 in case of COMPSUBST-I being a monocyclic compound with 5 endocyclic atoms,', 'by 1, 2, 3, 4 or 5 in case of COMPSUBST-I being a monocyclic compound with 6 endocyclic atoms,', 'by 1, 2, 3 or 4 in case of COMPSUBST-I being a bicyclic compound wherein a 5-membered and a 6-membered ring are ortho-fused,', 'by 1, 2, 3, 4 or 5 in case of COMPSUBST-I being a bicyclic compound wherein two 6-membered rings are ortho-fused,, 'COMPSUBST-I is unsubstituted or substituted'}{'sub': 1-4', '3', '2', 'm', '2, 'identical or different substituents independently from each other selected from the group consisting of Calkyl, CM alkoxy, OH, C(H)═O, N(R10)R11, CN, F, Cl, Br, CF, (CH)—C(O)Y1, and S(O)R50;'}{'sub': '1-4', 'said Calkyl substituent of COMPSUBST-I is unsubstituted or substituted with 1, 2 or 3 identical or different substituents selected from the group consisting of halogen;'}{'claim-ref': {'@idref': 'CLM-00001', 'claim 1'}, 'with R10, R11, m, Y1, R50 and halogen as defined in .'}7. The method according to claim 1 , wherein{'sub': 1-20', '2', 'n3', '2, 'FAHALIDE is selected from the group consisting of perfluoro Calkyl-X1, Br—(CF)—Br, and FHC—X1;'}with n3 being an integer of 2 to 10.8. The method according to claim 1 , whereinn3 is 2, 3, 4, 5, 6.9. The method according to claim 1 , wherein{'sub': 21', '10', '21', '10', '17', '8', '17', '8', '13', '6', '13', '6', '9', '4', '9', '4', '7', '3', '7', '3', '3', '3', '2', '4', '2', '2, 'FAHALIDE is selected from the group consisting of FC—I, FC—Br, FC—I, ...

Method for Preparation of Fluoro Alkylated 1,4-Dioxene by Homogeneous NI Catallysis

The invention discloses a method for the preparation of fluoro alkylated 1,4-dioxene by homogeneous Ni catalyzed fluoro alkylation with fluoro alkyl halides of -dioxane in the presence of a base. 2. The method according to claim 1 , wherein NISALT is NiCland LIG is compound of formula (dppb).3. The method according to claim 1 , wherein BAS is selected from the group consisting of CsCO claim 1 , NaCO claim 1 , KPO claim 1 , NaH and NaOtBu.4. The method according to claim 1 , wherein FAHALIDE is selected from the group consisting of perfluoro Calkyl-X1 claim 1 , Br—(CF)—Br claim 1 , and FHC—X1;with n3 being an integer of 2 to 10.5. The method according to claim 1 , wherein n3 is 2 claim 1 , 3 claim 1 , 4 claim 1 , 5 claim 1 , 6.6. The method according to claim 1 , wherein FAHALIDE is selected from the group consisting of FC—I claim 1 , FC—Br claim 1 , FC—I claim 1 , FC—Br claim 1 , FC—I claim 1 , FC—Br claim 1 , FC—I claim 1 , FC—Br claim 1 , FC—I claim 1 , FC—Br claim 1 , FC—I claim 1 , FC—Br claim 1 , Br—(CF)—Br claim 1 , FHC—I claim 1 , and FHC—Br.7. The method according to claim 1 , wherein FAHALIDE is selected from the group consisting of FC—I claim 1 , FC—I claim 1 , FC—I claim 1 , FC—I claim 1 , FC—I claim 1 , and FC—I.8. The method according to claim 7 , wherein the reaction is done neat or in a solvent SOL.9. The method according to claim 8 , wherein SOL is selected from the group consisting of alkanes claim 8 , chlorinated alkanes claim 8 , ketones claim 8 , ethers claim 8 , esters claim 8 , aliphatic nitrils claim 8 , aliphatic amides claim 8 , sulfoxides claim 8 , CFand mixtures thereof The invention discloses a method for the preparation of fluoro alkylated 1,4-dioxene by homogeneous Ni catalyzed fluoro alkylation with fluoro alkyl halides of 1,4-dioxane in the presence of a base.I. Hanna in Tetrahedron Letters, 1999, 40, 2521-2524 discloses that furans are important functional groups that can be found in many natural products and have frequently been ...

Chiral synthesis of fused bicyclic raf inhibitors

The present disclosure generally relates to improved synthesis of fused bicyclic Raf inhibitor enantiomers of formula (I), (Ia), (Ib), (II), (IIa), or (IIb), or a pharmaceutically acceptable salt, tautomer, or stereoisomer thereof, with high enantiomeric excess (% ee). The disclosure also relates to method of using the compound of formula (I), (Ia), (Ib), (II), (IIa), or (IIb), or a pharmaceutically acceptable salt, tautomer, or stereoisomer thereof, for treating diseases such as cancer, including colorectal cancer.

GOLD-CATALYSED PROCESS FOR MANUFACTURING CHROMENES INTENDED FOR THE PREPARATION OF THERMOSETTING RESINS

A process for manufacturing chromenes intended for the preparation of thermosetting resins, includes transforming an aromatic propargyl ether of general formula (I) into a chromene by homogeneous gold(I) catalysis with the catalyst (acetonitrile)[(2-biphenyl)di-tert-butylphosphine]gold(I) hexafluoroantimonate in an organic solvent under an inert or non-inert atmosphere. Moreover, a process for preparing a material made of thermoset resin, includes successively a) implementation of the above process; polymerization of the reaction product obtained in step a) so as to obtain the material made of thermoset resin; c) recovery of the material made of thermoset resin obtained in step b). 2. The process according to claim 1 , wherein the aromatic propargyl ether of general formula (I) is chosen from the group consisting of propargylated resorcinol claim 1 , propargylated eugenol claim 1 , propargylated coupled eugenol claim 1 , propargylated coupled isoeugenol claim 1 , propargylated isoeugenol and mixtures thereof and the cis/trans isomers thereof and the optical isomers thereof and the racemic mixtures thereof.3. The process according to claim 2 , wherein the molar percentage of residual propargyl functions in the chromene is less than 11% when the aromatic propargyl ether of general formula (I) is propargylated resorcinol claim 2 , the molar percentage of residual propargyl functions in the chromene is less than 39% when the aromatic propargyl ether of general formula (I) is propargylated coupled eugenol and the molar percentage of residual propargyl functions in the chromene is less than 35% when the aromatic propargyl ether of general formula (I) is propargylated coupled isoeugenol.4. The process according to claim 1 , wherein the organic solvent is chosen from tetrahydrofuran and 2-methyltetrahydrofuran.5. The process according to claim 1 , wherein the content of catalyst in the reaction medium is between 0.1 mol % and 2 mol %.7. The process according to claim 1 , ...

LIGANDS AND CATALYST SYSTEMS FOR HYDROFORMYLATION PROCESSES

The present invention relates to ligands and catalyst systems for the hydroformylation of short and long chain olefins, preferably for the hydroformylation of ally alcohol producing 4-hydroxybutyraldehyde. The ligands disclosed herein are all-trans phosphinomethyl-cyclobutane ligands, such as, for example, all-trans-1,2,3, 4-tetra[bis-(3,5-xylyl)phosphinomethyl]-cyclobutane. The catalyst systems comprise these all-trans phosphinomethyl-cyclobutane ligands in combination with an organometallic rhodium complex such as, e.g., (acctylacetonato)-dicarbonyl-rhodium (I). The ligands and catalyst systems of the present invention may be employed in the hydroformylation of olefins, in particular in the hydroformylation of allylalcohol, and provide improved selectivity and high reaction yields. wherein Ris alkyl, preferably methyl, ethyl or propyl, Ris H or an alkoxy group, Rand R, independently of one another, CHOR, CHO-aralkyl, CHOH,CH-[P(3,5-R,R-4-R-phenyl)] or CHO-(CH-CH-O)-H (with m being an integer between 1 and 1,000). 2. The phosphinomethyl-cyclobutane ligand according to claim 1 , wherein Ris methyl claim 1 , ethyl or propyl claim 1 , Ris H claim 1 , Rand Rare CH-[P(3 claim 1 ,5-R claim 1 ,R-4-R-phenyl)].3. The phosphinomethyl-cyclobutane ligand according to claim 1 , selected from the group consisting of all-trans-1 claim 1 ,2 claim 1 ,3 claim 1 ,4-tetra[bis-(3 claim 1 ,5-xylyl)phosphinomethyl]-cyclobutane claim 1 , all-trans-1 claim 1 ,23-tris[his-(3 claim 1 ,5 xylyl)phosphlnomethyl]-4-(methoxymethyl)-cyclobutane claim 1 , all-trans-1 claim 1 ,2 claim 1 ,3-tris[bis-(35-xylyl)phosphinomethyl]-4-(hydroxymethyl)-cyclobutane claim 1 , all trans 1 claim 1 ,2bis [bis-(3 claim 1 ,5-xylyl)phosphinomethyl]-3 claim 1 ,4-bis(trityloxymethyl)-cyclobutane and all-trans-1 claim 1 ,2 claim 1 ,3-tris[bis-(3 claim 1 ,5-xylyl)phosphinomethyl]-4-[CH—(O—CH—CH—O) claim 1 ,H]-cyclobutane (with m being an integer between 1 and 1 claim 1 ,000) and mixtures and combinations thereof.5. The ...

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- ...

LIGAND COMPOUND, ORGANIC CHROMIUM COMPOUND, CATALYST SYSTEM FOR OLIGOMERIZATION OF OLEFINS, AND METHOD FOR OLIGOMERIZATION OF OLEFINS USING THE CATALYST SYSTEM (AS AMENDED)

The present invention relates to a ligand compound, a catalyst system for oligomerization of olefins, and a method for oligomerization of olefins using the catalyst system. The catalyst system for oligomerization of olefins according to the present invention not only has excellent catalytic activity, but also exhibits high selectivity to 1-hexene or 1-octene, thus enabling more efficient preparation of alpha-olefin. 2. The ligand compound according to claim 1 , wherein each of Rto Ris independently a substituted or unsubstituted C1-10 alkyl group claim 1 , a substituted or unsubstituted C4-10 cycloalkyl group claim 1 , a substituted or unsubstituted C6-15 aryl group claim 1 , a substituted or unsubstituted C7-15 arylalkyl group claim 1 , or a substituted or unsubstituted C1-10 alkoxy group.4. The ligand compound according to claim 3 , wherein each of Rto Ris independently a substituted or unsubstituted C1-10 alkyl group claim 3 , a substituted or unsubstituted C4-10 cycloalkyl group claim 3 , a substituted or unsubstituted C6-15 aryl group claim 3 , a substituted or unsubstituted C7-15 arylalkyl group claim 3 , or a substituted or unsubstituted C1-10 al koxy group.6. The organic chromium compound according to claim 5 , wherein each of Rto Ris independently a substituted or unsubstituted C1-10 alkyl group claim 5 , a substituted or unsubstituted C4-10 cycloalkyl group claim 5 , a substituted or unsubstituted C6-15 aryl group claim 5 , a substituted or unsubstituted C7-15 arylalkyl group claim 5 , or a substituted or unsubstituted C1-10 alkoxy group.7. A catalyst system for oligomerization of olefins claim 5 , comprising:{'claim-ref': {'@idref': 'CLM-00001', 'claim 1'}, 'i) a chromium source, the ligand compound according to , and a cocatalyst; or'}{'claim-ref': {'@idref': 'CLM-00005', 'claim 5'}, 'ii) the organic chromium compound according to and a cocatalyst.'}8. The catalyst system according to claim 7 , wherein the chromium source is one or more compounds ...

TRANSFER HYDROGENATION OF CYCLOPAMINE ANALOGS

Provided herein is a process for the transfer-hydrogenation of ketone analogs of members of the jervine type of alkaloids, such as cyclopamine. Also provided herein are novel ruthenium transfer-hydrogenation catalysts. 3. The process of wherein the ring carbon atom that is directly attached to the hydroxyl group on the compound of formula (II-AA) has an (S) stereochemical configuration and Ris hydrogen in the β-position.4. The process of claim 1 , wherein the ruthenium transfer-hydrogenation catalyst comprises an amino alcohol ligand.5. The process of claim 4 , wherein the amino alcohol ligand is achiral.7. The process of claim 6 , wherein Rand Rare both —CHand Ris —CHCH.8. The process of claim 1 , wherein the ruthenium transfer-hydrogenation catalyst comprises an optionally substituted benzene ligand.9. The process according to claim 8 , wherein the optionally substituted benzene ligand is selected from benzene claim 8 , mesitylene claim 8 , p-cymene claim 8 , and hexamethylbenzene.10. The process according to claim 9 , wherein the ruthenium transfer-hydrogenation catalyst is generated from (hexamethylbenzene)ruthenium chloride dimer and an achiral amino alcohol.14. The process according to claim 13 , wherein Xis chloro.17. The process of claim 16 , wherein Rand Rare each methyl claim 16 , Ris ethyl claim 16 , each of R claim 16 , R claim 16 , R claim 16 , R claim 16 , R claim 16 , and Ris methyl claim 16 , and Xis Cl.18. The process of claim 1 , wherein the hydrogen donor is an organic alcohol.19. The process of claim 18 , wherein the reducing is carried out in an ether solvent.20. The process of claim 19 , wherein the reducing is carried out at a temperature of about 10° C. to about 40° C.21. The process of claim 19 , wherein the reducing is carried out in the presence of base. This application is a continuation of U.S. patent application Ser. No. 13/232,851, filed Sep. 14, 2011, now allowed, which claims the benefit of U.S. Provisional Patent Application No. 61/ ...

BIS(PHOSPHINE)-CARBODICARBENE CATALYST COMPLEXES AND METHODS OF USING THE SAME

An organometallic complex of a tridentate bis(phosphine)-carbodicarbene ligand and a transition metal, is described. In some embodiments the ligand has the structure of Formula (I): The complexes are useful in methods of making an allylic amine carried out by reacting a 1,3-diene with a substituted amine in the presence of such an organometallic complex to produce by intermolecular hydroamination the allylic amine. 1. An organometallic complex , comprising:(a) a tridentate bis(phosphine)-carbodicarbene ligand, and(b) a transition metal.4. The complex of claim 1 , wherein said transition metal is selected from the group consisting of ruthenium claim 1 , nickel claim 1 , palladium claim 1 , platinum claim 1 , rhodium claim 1 , iridium claim 1 , cobalt claim 1 , iron claim 1 , silver claim 1 , gold claim 1 , and molybdenum.5. The complex of claim 2 , wherein R claim 2 , R claim 2 , R claim 2 , and Rare each independently selected alkyl or aryl.6. The complex of claim 2 , wherein at least one R′ is S-L- claim 2 , where S is a solid support and L is a linking group.7. The complex of claim 2 , wherein each R′ is independently hydrogen claim 2 , halo claim 2 , loweralkyl claim 2 , loweralkoxy claim 2 , or hydroxyl.8. A reaction mixture comprising an organometallic complex of claim 1 , a solvent claim 1 , a 1-3 claim 1 , diene substrate claim 1 , and a substituted amine substrate.11. A method of making an allylic amine claim 1 , comprising:{'claim-ref': {'@idref': 'CLM-00001', 'claim 1'}, 'reacting a 1,3-diene with a substituted amine in the presence of an organometallic complex of in a catalytic amount to produce by intermolecular hydroamination said allylic amine.'}14. A tridentate bis(phosphine)-carbodicarbene pincer ligand. This application claims the benefit of U.S. Provisional Patent Application Ser. No. 61/979,749, filed Apr. 15, 2014, the disclosure of which is incorporated by reference herein in its entirety.The present invention concerns carbodicarbene ligands, ...

IN-SITU GENERATION OF RUTHENIUM CATALYSTS FOR OLEFIN METATHESIS

The present invention relates to a process for preparing olefins by means of metathesis, which comprises the following steps 2. The process according to claim 1 , wherein the anionic ligands X are identical and are each chlorine and Lis selected from the group consisting of nitrogen bases claim 1 , phosphanes claim 1 , phosphinites claim 1 , phosphonites claim 1 , phosphites and arsanes.3. The process according to claim 2 , wherein Lis selected from the group consisting of benzene claim 2 , toluene claim 2 , xylene claim 2 , cymene claim 2 , trimethylbenzene claim 2 , tetramethylbenzene claim 2 , hexamethylbenzene claim 2 , tetrahydronaphthalene and naphthalene claim 2 , and Lis selected from the group consisting of N-heterocyclic carbenes and phosphanes.4. The process according to claim 3 , wherein Lis selected from the group consisting of P(phenyl) claim 3 , P(cyclohexyl)and N-heterocyclic carbenes of the formula VI claim 3 , VII claim 3 , VIII claim 3 , IX claim 3 , X and XI.6. The process according to claim 5 , wherein the ruthenium compound is a compound of the general formula RuXLL(II) claim 5 , wherein the anionic ligands X are identical and are each chlorine and Lis selected from the group consisting of N-heterocyclic carbenes and phosphanes.7. The process according to claim 6 , wherein Lis selected from the group consisting of benzene claim 6 , toluene claim 6 , xylene claim 6 , cymene claim 6 , trimethylbenzene claim 6 , tetramethylbenzene claim 6 , hexamethylbenzene claim 6 , tetrahydronaphthalene and naphthalene claim 6 , and Lis selected from the group consisting of P(cyclohexyl)and the N-heterocyclic carbenes of the formulae VI claim 6 , VII claim 6 , VIII claim 6 , IX claim 6 , X and XI.8. The process according to claim 7 , wherein the ruthenium compound is selected from the group consisting of compounds of the formulae A claim 7 , B and C.9. The process according to claim 5 , wherein the ruthenium compound is a compound of the general formula RuXL( ...

METHOD FOR PREPARING FORMAMIDE COMPOUND

Disclosed is a method for preparing a formamide compound, the method uses carbon dioxide, hydrogen and an amine compound as raw materials and a transition metal complex as a catalyst, and the reaction is carried out in an organic solvent or in the absence of a solvent to form a formamide compound. The method of the present invention is an effective method of chemical utilization of carbon dioxide, which has the advantages of high reaction efficiency, a good selectivity, mild conditions, economic and environmental protection, being simple and convenient to operate and the like, and has a good popularization and application prospect. 114-. (canceled)17. The method of claim 15 , wherein the molar ratio of the organoamine compound to the catalyst is 1000-5600000:1.18. The method of claim 15 , wherein the molar ratio of the organoamine compound to the catalyst is 10000-4000000:1.19. The method of claim 15 , wherein claim 15 , in step a) claim 15 , a base additive is further used claim 15 , wherein the base additive is selected from a group consisting of alkali metal salts of alcohols claim 15 , alkali metal carbonates claim 15 , alkali metal hydroxides claim 15 , or combinations thereof.20. The method of claim 17 , wherein the molar ratio of the base additive to the catalyst is 1-100:1.21. The method of claim 17 , wherein the molar ratio of the base additive to the catalyst is 1-20:122. The method of claim 17 , wherein the molar ratio of the base additive to the catalyst is 1-5:1.23. The method of claim 15 , wherein the reaction time of the method is 0.1-1000 hours.24. The method of claim 15 , wherein claim 15 , in the method claim 15 , the pressure of hydrogen is 1-100 atmosphere claim 15 , and/or the pressure of carbon dioxide is 1-100 atmospheres.25. The method of claim 15 , wherein the reaction is carried out at 60-200° C.26. The method of claim 15 , wherein the reaction is carried out in an organic solvent; wherein the organic solvent is selected from a group ...

METHODS FOR RECOVERING AND REUSING SELECTIVE HOMOGENEOUS HYDROGENATION CATALYST

The present invention pertains to a method for recovering a selective homogeneous hydrogenation catalyst and a method for reusing the recovered selective homogeneous hydrogenation catalyst. The method for recovering a selective homogeneous hydrogenation catalyst comprises: a step for synthesizing cyclododecene by selectively hydrogenating a first reaction solution containing cyclododecatriene, triphenylphosphine, formaldehyde, and ruthenium chloride, wherein a selective homogeneous hydrogenation catalyst is prepared during the selective hydrogenation reaction from the triphenylphosphine, formaldehyde, and ruthenium chloride to synthesize the cyclododecene; and a step for distilling and separating unreacted cyclododecatriene and cyclododecadiene, as well as the product cyclododecene, from a second reaction solution in which the cyclododecene synthesis has been completed, and recovering the selective homogeneous hydrogenation catalyst. 1. A method for recovering a selective homogeneous hydrogenation catalyst , comprising:a step of synthesizing cyclododecene by selectively hydrogenating a first reaction solution containing cyclododecatriene, triphenylphosphine, formaldehyde, and ruthenium chloride, the cyclododecene being synthesized by preparation of a selective homogeneous hydrogenation catalyst from the triphenylphosphine, the formaldehyde, and the ruthenium chloride during the selective hydrogenation; anda step of distilling and separating unreacted cyclododecatriene and cyclododecadiene, and the cyclododecene that is a product from a second reaction solution in which the cyclododecene synthesis is completed, and recovering the selective homogeneous hydrogenation catalyst.2. The method of claim 1 , wherein the distillation and separation is performed at a temperature of 100 to 200° C. and a pressure of 0.5 bar or less.3. The method of claim 1 , wherein the recovering of the selective homogeneous hydrogenation catalyst is performed at a temperature of 10 to 30° C. ...

MONOCARBONYL RUTHENIUM AND OSMIUM CATALYSTS

The invention relates to monocarbonyl complexes of ruthenium and osmium with bi- and tridentate nitrogen and phosphine ligands. The invention relates to methods for preparing these complexes and the use of these complexes, isolated or prepared in situ, as catalysts for reduction reactions of ketones and aldehydes both via transfer hydrogenation or hydrogenation with hydrogen. 3. The complex of claim 1 , of formula (VII):{'br': None, '[MX(CO)(NN)(PP)]W \u2003\u2003(VII)'}{'sub': 2', '2', '2', '2', '2, 'provided that when X is Cl or H, (NN) is not ethylenediamine or 2-(aminomethyl)pyridine and the diphosphine (PP) is not PhP(CHCHCH)PPh.'}4. The complex of claim 1 , of formula (VIII):{'br': None, 'MXY(CO)(HCNN)(P) \u2003\u2003(VIII).'}5. The complex of claim 1 , of formula (IX):{'br': None, 'MX(CO)(CNN)(P) \u2003\u2003(IX).'}7. The complex of claim 1 , of formula (XI):{'br': None, 'MX(CO)(CP)(HCP) \u2003\u2003(XI)'}{'sup': 23', '21', '22, 'sub': '3', 'provided that when X is Cl and Ris —CH, R-Rare not phenyl.'}8. The complex of claim 1 , of formula (XII):{'br': None, 'MXY(CO)(PP)(P) \u2003\u2003(XII).'}9. The complex of claim 1 , of formula (XIII):{'br': None, 'MXY(CO)(HCN)(PP) \u2003\u2003(XIII).'}10. The complex of claim 1 , of formula (XIV):{'br': None, 'MXY(CO)(PNN) \u2003\u2003(XIV).'}11. The complex of claim 1 , wherein X and Y are the same and are Cl claim 1 , H claim 1 , a C1-C20 alkoxide claim 1 , or a C1-C20 carboxylate.18. A process for preparing a complex of formula (XII) of claim 8 , comprising reacting a compound of formula MXY(CO)(PPh) claim 8 , or formula MXY(CO)(PPh)(dmf) claim 8 , wherein (dmf) is dimethylformamide claim 8 , with a phosphine (P) that is:{'sup': 16', '17', '18', '16', '18, 'a phosphine of formula PRRR, wherein R-Rare each, independently, H, a C1-C20 aliphatic group, or a C5-C20 aromatic group; or'}an optically active phosphine that is (S)-neomenthyldiphenylphosphine or (R)-(+)-2-(diphenylphosphino)-2′-methoxy-1,1′-binaphthyl;or a ...

HIGHLY EFFICIENT PROCESS FOR THE PREPARATION OF SITAGLIPTIN VIA RHODIUM CATALYZED ASYMMETRIC HYDROGENATION

The present invention provides highly efficient process for the preparation of enantiomerically enriched Sitagliptin of Formula (Ia). More particularly, a direct rhodium catalyzed asymmetric hydrogenation in the presence of bis-phosphine chiral ligand has been developed to yield enantiopure Sitagliptin product with the highest enantiomeric excess of 85-99.9%. 14-. (canceled)6. The process of claim 5 , wherein the rhodium catalyst is [Rh(COD)OTf].7. The process of claim 6 , wherein the additive is selected from the group consisting of salicylic acid claim 6 , acetic acid claim 6 , ammonium chloride claim 6 , phosphoric acid claim 6 , ammonium salicylate claim 6 , tetramethyl ammonium iodide claim 6 , tetraethyl ammonium iodide claim 6 , tetra butyl ammonium bromide claim 6 , butyl phosphoric acid claim 6 , dibutyl phosphate claim 6 , and tributyl phosphate.8. The process of claim 6 , wherein the solvent is selected from the group consisting of methanol claim 6 , dichloromethane claim 6 , tetrahydrofuran claim 6 , trifluoroethanol claim 6 , toluene claim 6 , 1 claim 6 ,4-dioxane claim 6 , and ethyl acetate. This application is a national-stage application under 35 U.S.C. § 371 of International Application No. PCT/IN2019/050896, filed Dec. 9, 2019, which International Application claims benefit of priority to Indian Application No. 201811046767, filed Dec. 11, 2018.The present disclosure provides highly efficient process for the preparation of enantiomerically enriched Sitagliptin. More particularly, a direct rhodium catalyzed asymmetric hydrogenation in the presence of bis-phosphine chiral ligand has been developed to yield enantiopure Sitagliptin product with the highest enantiomeric excess of 85-99.9%.Beta amino acids and its derivatives have lot of medicinal significance. Beta amino acids are also present in peptides and different heterocycles. In beta amino acids, the amino group is linked to the beta carbon. Different free forms and derivatives of beta amino acid ...

COLORIMETRIC DETERMINATION OF AQUEOUS NITRATE CONCENTRATION

A method of measuring nitrate concentration in an aqueous sample include mixing the aqueous sample with a water-soluble thioether compound including a chromophore group in the presence of a water soluble catalyst; measuring a color change, and correlating the color change to nitrate concentration. 1. A method of measuring nitrate concentration in an aqueous sample , comprising:a. mixing the aqueous sample with a water-soluble thioether compound including a chromophore group in the presence of a water soluble catalyst,b. measuring a color change, andc. correlating the color change to nitrate concentration.2. The method of wherein the water-soluble thioether compound is chosen to oxidize in the presence of nitrate.3. The method of wherein the water-soluble thioether compound has the formula:{'br': None, 'sup': 3', '2, 'R—S—R,'}{'sup': 3', '2, 'sub': 1', '6, 'wherein Ris a hydrophilic chromophore group and Ris a C-Calkyl group or a polyalkyleneoxide group.'}4. The method of wherein the hydrophilic chromophore group comprises a residue of a water-soluble conjugated chromophore.5. The method of wherein the hydrophilic chromophore group comprises a residue of a water-soluble claim 3 , substituted aromatic chromophore.6. The method of wherein the hydrophilic chromophore is selected from the group consisting of a hydrophilic diarylmethane chromophore claim 3 , a hydrophilic triarylmethane chromophore claim 3 , a hydrophilic xanthene chromophore claim 3 , a hydrophilic boron-dipyrromethene chromophore and a hydrophilic pyrene chromophore.7. The method of wherein the polyalkyleneoxide comprises 4 to 5000 carbon atoms.8. The method of wherein the water soluble catalyst comprises MoOCl(L)wherein L is a hydrophilic group.9. The method of wherein L comprises a water soluble phosphine.10. The method of wherein L is trisulfonated-triphenylphosphineoxide.11. The method of wherein the water soluble catalyst further comprises a Cu co-catalyst.12. The method of wherein the color change ...

Process for oligomerization

The invention relates to oligomerization of olefins, such as ethylene, to higher olefins, such as a mixture of 1-hexene and 1-octene, using a catalyst system that comprises a) a source of chromium b) one or more activators and c) a phosphacycle-containing ligating compound. Additionally, the invention relates to a phosphacycle-containing ligating compound and a process for making said compound.

Method for Producing Alpha, Alpha-Difluoroacetaldehyde

Disclosed is an industrial method for efficient production of an α,α-difluoroaldehyde compound, which includes reaction of an α,α-difluoroacetate with hydrogen gas (H2) in the presence of a ruthenium catalyst and a base. By the adoption of specific reaction conditions (catalyst, base, pressure etc.), it is possible to produce the target α,α-difluoroaldehyde compound with a high conversion rate and high selectivity.

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 ...

Process for the separation and purification of a mixed diol stream

Disclosed is a process for the purification of a mixed diol stream. The mixed diol stream comprising two-, three-, and four-carbon diols is separated into component diols by extraction with a hydrophobic solvent mixture. The diols recovered in the extractant may be removed from the extractant stream by back extraction with water or by distillation with an azeotrope-forming agent present, preferably an azeotroping agent already present in the extractant mixture.

PHARMACEUTICAL PROCESS AND INTERMEDIATES

The present disclosure concerns the large-scale manufacture of pharmaceutical compounds, and novel intermediates for use in the manufacture. International Patent Application WO2011154737 discloses morpholine pyrimidines useful for treating cancer, processes for their preparation and pharmaceutical compositions thereof. In particular, WO2011154737 discloses, as experimental Example 2.02 on page 60, the compound 4-{4-[(3R)-3-methylmorpholin-4-yl]-6-[1-((R)—S-methylsulfonimidoyl)cyclopropyl]pyrimidin-2-yl}-1H-pyrrolo[2,3-b]pyridine (hereafter referred to as the compound of Formula (I)). The structure of the compound of Formula (I) is shown below. A synthetic route to the compound of Formula (I) is described at pages 51 to 57, 66 and 67 of WO2011154737, and is summarised below in Scheme 1. 9. The process according to claim 8 , wherein the compound of Formula (XIII) is prepared by reacting a compound of Formula (VIII) with OH—Rwherein Ris a phthalimide or tetrachlorophthalimide group.17. The compound according to any or claim 8 , wherein LGis chlorine and LG claim 8 , if present claim 8 , is chlorine.18. Use of a compound of any one of to claim 8 , or a salt thereof claim 8 , as a pharmaceutical intermediate.21. A process for preparing a compound of Formula (I) as claimed in claim 20 , wherein step (i) further comprises the addition of diethanolamine after reaction with a boron reagent in the presence of a palladium catalyst.24. The process for preparing a compound of Formula (I) as claimed in any of to claim 20 , further comprising the steps:(a) cyclopropanating a compound of Formula (IX) followed by hydrolysis to form a compound of Formula (VIII);(b) reacting a compound of Formula (VIII) with an acylating agent to form a compound of Formula (VII);(c) reacting a compound of Formula (VII) with urea or thiourea to form a compound of Formula (VI);(d) reacting a compound of Formula (VI) with a suitable reagent to form a compound of Formula (V);(e) reacting a compound of ...

6,6'-([1,1'-BIPHENYL]-2,3'-DIYLBIS(OXY))DIDIBENZO[D,F][1,3,2]DIOXAPHOSPHEPINES

6,6′-([1,1′-Biphenyl]-2,3′,-diylbis)oxy))didibenzo[d,f][1,3,2]dioxaphosphepines and the use thereof in hydroformylation. 2. Compound according to claim 1 , where R claim 1 , R claim 1 , R claim 1 , Rare selected from: —H claim 1 , —(C-C) alkyl.3. Compound according to claim 1 , where at least one of the radicals R claim 1 , R claim 1 , R claim 1 , Ris —H.4. Compound according to claim 1 , where R claim 1 , R claim 1 , R claim 1 , Rare —H.5. Compound according to claim 1 , where R claim 1 , R claim 1 , R claim 1 , Rare selected from: —H claim 1 , —O—(C-C) alkyl.6. Compound according to claim 1 , where at least one of the radicals R claim 1 , R claim 1 , R claim 1 , Ris —H.7. Compound according to claim 1 , where R claim 1 , R claim 1 , R claim 1 , Rare —H.9. Use of a compound according to in a ligand-metal complex for catalysis of a hydroformylation reaction.10. Process comprising the process steps of:a) initially charging an olefin,{'claim-ref': {'@idref': 'CLM-00001', 'claim 1'}, 'b) adding a compound according to and a substance containing a metal selected from: Rh, Ru, Co, Ir,'}{'sub': '2', 'c) feeding in Hand CO,'}d) heating the reaction mixture from steps a) to c), with conversion of the olefin to an aldehyde. The invention relates to 6,6′-([1,1′-biphenyl]-2,3′-diylbis(oxy))didibenzo[d,f][1,3,2]dioxaphosphepines and to the use thereof in hydroformylation.Phosphorus-containing compounds play a crucial role as ligands in a multitude of reactions, e.g. in hydrogenation, in hydrocyanation and also in hydroformylation.The reactions between olefin compounds, carbon monoxide and hydrogen in the presence of a catalyst to give the aldehydes with one carbon atom more are known as hydroformylation or the oxo process. Catalysts used in these reactions are frequently compounds of the transition metals of group VIII of the periodic table of the elements. Known ligands are, for example, compounds from the phosphine, phosphite and phosphonite classes, each containing trivalent ...

BIOFUEL AND METHOD FOR PREPARATION BY ISOMERIZING METATHESIS

Subject of the invention is a process for producing a biofuel from fatty acid methyl esters (FAMEs) obtained by transesterification of vegetable oils, comprising the steps of 124.-. (canceled)25. A process for producing a biofuel from fatty acid methyl esters (FAMEs) obtained by transesterification of vegetable oils , comprising the steps of(a) ethenolysis of the fatty acid methyl esters in the presence of ethylene and an ethenolysis catalyst, and(b) isomerizing metathesis in the presence of an isomerization catalyst and a metathesis catalyst, wherein ethenolysis (a) and isomerizing metathesis (b) are carried out simultaneously and wherein the process is carried out without an additional solvent.26. The process according to claim 25 , wherein the vegetable oil and/or fatty acid methyl esters comprise more than 80 mol-% unsaturated fatty acids claim 25 , based on the total amount of fatty acids in esterified and free form claim 25 , wherein the vegetable oil is preferably rapeseed oil claim 25 , soy bean oil claim 25 , jatropha oil or tall oil.27. The process according to at least claim 25 , wherein the isomerization catalyst is an organometallic palladium catalyst.28. The process according to at least claim 25 , wherein the isomerization catalyst is an organometallic palladium containing palladium in oxidation states selected from the group consisting of Pd(0) claim 25 , Pd(I) claim 25 , Pd(II) and combinations thereof.29. The process according to at least claim 25 , wherein the isomerization catalyst is an organometallic palladium catalyst containing at least one structural element Pd—P(RRR) claim 25 , wherein the Rto Rradicals each independently have 2 to 10 carbon atoms claim 25 , each of which may be aliphatic claim 25 , alicyclic claim 25 , aromatic or heterocyclic claim 25 , with the proviso that at least one of the Rto Rradicals contains a beta-hydrogen.31. The process according to claim 30 , wherein groups Yand Yare the same.32. The process according to ...

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, ...

Iron-catalyzed transfer hydrogenation of esters to alcohols

Iron-based homogeneous catalysts, supported by pincer ligands, are employed in the transfer hydrogenation of esters using C2-C12 alcohols as sacrificial hydrogen donors to produce corresponding alcohols from the esters. No external H2 pressure is required. The reaction can be carried out under ambient pressure.

SYNTHESIS OF GLYCOLS VIA TRANSFER HYDROGENATION OF ALPHA-FUNCTIONAL ESTERS WITH ALCOHOLS

A transfer hydrogenation process for forming vicinal diols by hydrogenating 1,2-dioxygenated organic compounds using alcohols as the reducing agent instead of the traditional Hgas. The transfer hydrogenation is carried out under milder conditions of temperature and pressure than is typical for ester hydrogenation with H. The milder conditions of operation provide benefits, such as lower operating and capital costs for industrial scale production as well as savings in product purification due to the avoidance of by-products from exposure of reaction mixtures and products to high temperatures. 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 and amides.5. The process according 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 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 50 to 180° C.13. The process according to claim 1 , wherein the contacting step is conducted at a temperature of 75 to 100° C.14. The process ...

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 ...

HOMOGENEOUS IRON CATALYSTS FOR THE CONVERSION OF ETHANOL TO ETHYL ACETATE AND HYDROGEN

Iron-based homogeneous catalysts, supported by pincer ligands, are employed in the catalytic dehydrocoupling of ethanol to produce ethyl acetate and hydrogen. As both ethanol and ethyl acetate 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 according 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 , ...

IRON-CATALYZED CROSS-COUPLING OF METHANOL WITH SECONDARY OR TERTIARY ALCOHOLS TO PRODUCE FORMATE ESTERS

A process for preparing a variety of secondary and tertiary alkyl formate esters via the coupling of methanol and secondary (or tertiary) alcohols. Iron-based catalysts, supported by pincer ligands, are employed to produce these formate esters in high yields and unprecedentedly high selectivities (>99%). Remarkably, the coupling strategy is also applicable to bulkier tertiary alcohols, which afford corresponding tertiary formate esters in moderately high yields and high selectivities. 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 according 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 ...