НЕОРГАНИЧЕСКИЕ/ПОЛИМЕРНЫЕ КАТАЛИТИЧЕСКИЕ ГИБРИДНЫЕ МАТЕРИАЛЫ С ВЫСОКОЙ АКТИВНОСТЬЮ В РАЗЛИЧНЫХ РАСТВОРИТЕЛЯХ

Настоящее изобретение относится к каталитическому материалу, проявляющему каталитическую активность в химических реакциях. Материал содержит гибридное соединение, состоящее из оксидов металла и поливинилового спирта или их производных. Оксиды металла включают по меньшей мере одно вещество, выбранное из соединений кремниевой кислоты, соединений вольфрамовой кислоты и соединений циркониевой кислоты, при этом металлическая частица катализатора внедрена в гибридное соединение. Гибридное соединение содержит полимерные добавки, которые имеют звено -СН-СН-O- и имеют разветвленную структуру, и/или содержит полимерные добавки, которые имеют звено -Si(CH)-O- с карбоксильными группами, добавленными к части атомов кремния. Также предложены способы получения каталитического материала. Изобретение позволяет получить каталитические материалы с высокой активностью, которые могут использоваться в каталитических процессах в сочетании с различными типами растворителей. 3 н. и 1 з.п. ф-лы, 8 табл., 9 пр.

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

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

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 ...

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 ...

СИНТЕЗ 6-АРИЛ-4-АМИНОПИКОЛИНАТОВ И 2-АРИЛ-6-АМИНОПИРИМИДИН-4-КАРБОКСИЛАТОВ ПРЯМЫМ СОЧЕТАНИЕМ СУЗУКИ

СПОСОБ ПОЛУЧЕНИЯ СОЕДИНЕНИЯ ПИРАЗОЛАМИДА

КОМПЛЕКСЫ

СПОСОБ ПОЛУЧЕНИЯ ДИЕНОВ ГИДРОДИМЕРИЗАЦИЕЙ

... 1. Способ получения замещенных или незамещенных 1,7-диолефинов гидродимеризацией нециклических олефинов, по меньшей мере, с двумя сопряженными двойными связями в присутствии восстановителя и катализатора, отличающийся тем, что в качестве катализатора используют карбеновый комплекс металла, который содержит металл от 8-й до 10-й групп Периодической системы элементов и, по меньшей мере, один карбеновый лиганд формулы (1), (2), (3) или (4): ! , , ! , , ! в которой R1, R2 означают -(CH2)n-B, ! B означает моноциклическую или полициклическую арильную группу с 6-14 атомами углерода или моноциклический или полициклический гетероцикл с 5-14 атомами углерода и гетероатомами, который содержит от 1 до 3 гетероатомов, выбранных из группы, включающей азот, кислород и серу, ! n означает число от 0 до 4, ! R3, R4, R5 и R6 означают водород, алкил, гетероарил, арил, -CN, -COOH, -COO-алкил, -COO-арил, -OCO-алкил, -OCO-арил, -OCOO-алкил, -OCOO-арил, -CHO, -CO-алкил, -CO-арил, -NH2, -NH(алкил), -N(алкил)2, ...

ПОВЕРХНОСТНО-МОДИФИЦИРОВАННЫЙ КАРБОНАТ КАЛЬЦИЯ В КАЧЕСТВЕ НОСИТЕЛЯ ДЛЯ КАТАЛИЗАТОРОВ НА ОСНОВЕ ПЕРЕХОДНЫХ МЕТАЛЛОВ

СПОСОБ ПОЛУЧЕНИЯ СОЕДИНЕНИЯ, СОЕДИНЕНИЯ, КОМПЛЕКСНЫЙ МЕТАЛЛООРГАНИЧЕСКИЙ КАТАЛИЗАТОР

... 1. Способ получения соединения формулы (I)в которой R1 и R2 могут быть одинаковыми или различными и по отдельности представляют собой замещенную или незамещенную группу, выбранную из алкильной, циклоалкильной, арильной, алкилокси-, циклоалкилокси-, арилокси, алкиламино-, циклоалкиламино, ариламино, металлоценильной группы;R3, R4, R5, R6 могут быть одинаковыми или различными и по отдельности представляют собой атом водорода либо замещенную или незамещенную группу, выбранную из алкильной, циклоалкильной, арильной, алкилокси-, циклоалкилокси-, арилокси-, алкиламино-, циклоалкиламино-, ариламиногруппы;Е представляет собой замещенную или незамещенную группу, выбранную из PR7R8, P(BH)R7R8, -CH-PR7R8, -CH-P(BH)R7R8, -BR9R10, -CR11R12OH, -COR11, -SiR11R12R13; -SiR11R12-CH-PR7R8;где R7 и R8 могут быть одинаковыми или различными и по отдельности представляют собой водород, замещенную или незамещенную группу, выбранную из алкильной, циклоалкильной, арильной, алкилокси-, циклоалкилокси-, арилокси, ...

СПОСОБ ИЗОМЕРИЗАЦИИ АЛЬФА-ОЛЕФИНОВ ДО ОЛЕФИНОЫ С ВНУТРЕННИМИ ДВОЙНЫМИ СВЯЗЯМИ

... 1. Способ изомеризации 1-алкена до внутреннего алкена, включающий а) совмещение по меньшей мере одного 1-алкена в жидкой фазе при температуре от примерно 50 до примерно 200°С с катализатором, где катализатор готовят введением в контакт (I) по меньшей мере одной соли переходного металла группы VIII и (II) по меньшей мере одного алюмоалкильного соединения, в результате чего образуется первая смесь; б) совмещение первой смеси стадии (а) с по меньшей мере одной промытой кислотой глиной при температуре от примерно 100 до примерно 300°С с получением конечной смеси. 2. Способ по п.1, в котором по меньшей мере один 1-алкен содержит по меньшей мере 4 углеродных атома. 3. Способ по п.2, в котором по меньшей мере один 1-алкен содержит от примерно 5 до примерно 40 углеродных атомов. 4. Способ по п.3, в котором по меньшей мере один 1-алкен содержит от примерно 6 до примерно 30 углеродных атомов. 5. Способ по п.4, в котором по меньшей мере один 1-алкен содержит от примерно 10 до примерно 20 углеродных ...

Способ получения ненасыщенных эфиров карбоновых кислот

Heterocyclische Carbene enthaltende Metallkomplexe als Katalysatoren für C-C-Verknüpfungen

VERFAHREN ZUR HERSTELLUNG VON GERADKETTIGEN FETTSAEUREN ODER IHRER ESTER

VERFAHREN ZUR HERSTELLUNG VON N-OCTADIENOL

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).

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

Polymere phosphorhaltige Zusammensetzungen und deren Verwendung in Hydrocyanierungs-, Isomerisierungs- und Hydroformylierungs-Reaktionen

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

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

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

Aminosäurekomplexe und ihre Verwendung zur Herstellung von Olefinpolymerisaten

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

Verfahren zur Herstellung von aromatischen Acetylenen mit Palladazyklen als Katalysatoren

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

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 ...

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

VERFAHREN ZUM CARBONYLIEREN VON PENTENNITRIL

Verfahren zur Durchfuehrung einer durch einen heterogenen Metallkatalysator katalysierten Reaktion

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

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

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

Vinyl acetate - from acetic acid and ethylene,using palladium and cupric catalysts,free from halogens

A catalytic compsn. for the synthesis of vinyl acetate pour acetic acid and ethylene in a medium free from halogen ions, consists of a combination of a cupric salt, pref. the acetate, and a Pd chelate in which the chelating agent is an amino acid or a peptide. The ratio of Cu to Pd is pref. 1/10 - 10,000, esp. 2-300. Compsn. pref. also includes an alkali metal salt, pref. the acetate. The process may be carried out continuously. Freedom from halogen ions minimises corrosion.

Metallacarboranes

The invention provides a polynuclear compound comprising two or more metal-hapto-3-capped nidocarborane groups. Also provided is the use of such a compound as a catalyst in a chemical reaction such as a hydrogenation or oxidation reaction.

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.

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.

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

Nanoparticles and preparation method

DIMERIZATION OF ALIPHATIC MONO-OLEFINS

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.

ORGANOMETALLIC COMPLEXES AND CHEMICAL PROCESS USING SAME

... 1,217,417. Organometallic complexes. NATIONAL DISTILLERS & CHEMICAL CORP. 5 July, 1968 [14 July, 1967; 17 July, 1967], No. 32314/68. Headings C2C and C2J. [Also in Division C5E] The invention comprises organometallic complexes of the formula where n is zero or an integer from 1 to 4; each R is selected from lower alkyl (C 1 -C 4 ) group, aryl group having from 6 to 16 carbon atoms, hydroxy group, nitro group, halide, dialkyl. amino, diarylamino and alkarylamino groups having 2 to 12 carbon atoms, or alkoxy or aryloxy group having 1 to 6 carbon atoms; M is Ru, Pt, Os, Pd, Ir, or Rh; Y is chloride bromide, nitrate, acetate, thiocyanate or cyanide group; A is -CR1 =N- (where R1 is hydrogen or an alkyl or aryl group having 1 to 10 carbon atoms), and Z is an alkyl group having 1 to 10 carbon atoms, aryl group or alkaryl, an alkoxy or aryloxy group having 1 to 10 carbon atoms, a hydroxy group, or an alkylamino, dialkylamino, arylamino or diarylamino group having 1 to 12 carbon ...

AROMATIC CARBONATES

Improvements in and relating to catalysis

The invention relates to a process for the production of a straight chain aldehyde from an olefin comprising reacting said olefin in a liquid reaction medium with hydrogen and carbon monoxide in the presence of a complex of Rh(I) in solution in the said medium as catalyst and a heterogeneous co- catalyst comprising a catalytic metal (e.g. Ru, Rh, Pd, It, Pt or alloys thereof) deposited upon a solid particulate support.

Complexes

Metal chelate complexes for foming oxidation catalyst.

A robust chelate complex is provided having formula (I) wherein M is a metal, preferably a transition metal; Z is an anionic donor atom, at least three of which are nitrogen, and the other is preferably nitrogen or oxygen; LI is a labile ligand; Ch,, Ch and Ch3, are oxidation resistant chelate groups which are the same or different and which form 5- or 6-membered rings -with the metal, and Ch^ is a chelate group having structure (a) wherein R, and R2_are the same or different and are preferably selected from the group consisting of hydrogen, halogen, methyl, and CF or when linked, a 5- or 6-membered ring cyclo substituent. The complex provides a stable, long-lived oxidation catalyst or catalyst activator.

Long-lived homogenous oxidation catalyst

Long-lived homogenous oxidation catalysts

Asymmetric syntheses.

Long-lived homogenous oxidation catalyst

PHOSPHINVERBINDUNGEN, ÜBERGANGSMETALLKOMLEXE WITH THE CONNECTIONS, WHICH WHEN LIGAND IN IT CONTAINING ARE, AND ASYMMETRICAL SYNTHESIS CATALYSTS WITH THESE COMPLEXES

CATALYSTS AND PROCEDURES FOR THE CATALYTIC OXIDATION

PLASTIC GETRÄGERTE PHOSPHORUS LIGAND USABLE IN THE CATALYSIS

PROCEDURE FOR THE ASYMMETRICAL SYNTHESIS

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

CHIRALE PHOSPHINE, THEIR COMPLEXES WITH TRANSITION METALS AND THEIR USE IN ASYMMETRICAL SYNTHESIS REACTIONS

PROCEDURE FOR HYDROFORMYLIERUNG OF ETHYLENISCH INSATIATED CONNECTIONS OF MEANS OF A ZWEIZÄHNIGEN DIPHOSPHIN COMPOSITION WITH A VERB-MOVING GROUP CONTAINING SP2-HYBRIDISIERTE AND TO THE PHOSPHORUS ATOMS BOUND CARBON ATOMS

CATALYST COMPOSITIONS.

AMIDIERUNG OF PYRIDINEN.

PROCEDURE FOR TELOMERISATION OF ACYCLI CONJUGATED DIOLEFINEN

PROCEDURE FOR THE CLEANING AND RUECKGEWINNUNG WITH OF THE CARBONYLIERUNG POLLUTED ONE BY METHYL ACETATE AND/OR DIMETHYLETHER RESULTING, KATALYSATORLOESUNG.

PROCEDURE FOR THE PRODUCTION OF AROMATIC OLEFINE

PROCEDURE FOR THE PRODUCTION OF POLYKETONEN

CATALYSTS

CHIRALE LIGANDS, ITS TRANSITION METAL COMPLEXES AND THE APPLICATION OF THESE IN ASYMMETRICAL REACTIONS

VEFAHREN AND CATALYST SYSTEM FOR THE PRODUCTION OF AROMATIC CARBONATES

P-FUNKTIONALISIERTE OF AMINES OF N-HALTIGER ONES AROMATICS, THEIR PRODUCTION AND YOUR USE IN CATALYTIC REACTIONS

PROCEDURE FOR THE PRODUCTION OF AMINES CATALYZED REDUCTIVE ONES THROUGH HOMOGENEOUS AMINIERUNG FROM CARBONYLVERBINDUNGEN

DIPHOSPHIN

PROCEDURE FOR THE ASYMMETRICAL HYDROGENATION OF KETOCARBONSÄUREESTERN

STABILIZATION OF PHOSPHITELIGANDEN INTO THE HYDROFORMYLIERUNGSVERFAHREN

CHIRALE FERROCENE

HETERO ARYL ARYL DIPHOSPHINE AS CHIRALE LIGAND

ASSEMBLY-METRIC LIGANDS FOR USE IN TRANSITION METAL-CATALYZED SYNTHESES AND EQUIVALENT EPOXY REACTIONS

CHIRALER FIRM CATALYST, ITS PRODUCTION AND ITS USE TO HESRTELLUNG OF PRACTICAL ENANTIOMERENREINEN PRODUCTS

NEW ASYMMETRICAL PHOSPHIN LIGAND

BY A UNTIL PHOSPHORINAN DERIVATIVE AND CONNECTION SUITABLE FOR THE PRODUCTION OF A CARBONYLIERUNGS OF CATALYST SYSTEM

PROCEDURE FOR THE CARBONYLIEREN OF AETHYLENISCH INSATIATED CONNECTIONS

BY TRANSITION METAL COMPLEXES WITH CYCLIC CHIRALEN ASYMMETRICAL SYNTHESIS CATALYZED LIGANDS

Catalyst preparation and epoxidation process

Method for defining an experimental space and method and system for conducting combinatorial high throughput screening of mixtures

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.

CATALYST COMPOSITIONS FOR THE PREPARATION OF COPOLYMERS OF CARBON MONOXIDE

CATALYTIC COMPOSITION FOR ALKENE-CARBON MONOXIDE POLYMERISATION

Diphosphines, preparation and uses thereof

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

Organo-metallic frameworks derived from carbenophilic metals and method of making same

The disclosure provides organic frameworks comprising increased stability.

Carbonylation catalyst system

CATALYST FOR OLEFIN/CO POLYMERIZATION

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.

Supported metal catalysts

The present invention relates to supported metal catalysts, wherein the catalysts are modified by at least one amine, a method for the preparation thereof and hydrogenation processes utilising the supported metal catalysts.

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.

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.

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 ...

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.

ORGANOMETALLIC COMPLEX CATALYST

An organometallic complex catalyst that makes it possible to obtain a higher yield of a desired product than conventional catalysts in a cross-coupling reaction. The organometallic complex catalyst has a structure represented by formula (1) and is for use in a cross-coupling reaction. In formula (1), M is the coordination center and represents a metal atom such as Pd or an ion thereof. R1, R2, and R3 may be the same or different and are a substituent such as a hydrogen atom. R4, R5, R6, and R7 may be the same or different and are a substituent such as a hydrogen atom. X represents a halogen atom. R8 represents a substituent that has a π bond and 3-20 carbon atoms. With regard to the electron-donating properties of R1-R7 with respect to the coordination center M of the ligand containing R1-R7 that is indicated in formula (2), R1-R7 are arranged in combination such that the TEP value obtained from infrared spectroscopy shifts toward the low frequency side compared to the TEP value of the ligand of formula (2-1). 3. The ligand according to claim 1 , wherein the organometallic complex catalyst represented by the formula (1) is used in a C—N cross-coupling reaction. This application is a divisional of U.S. application Ser. No. 16/466,413, filed on Jun. 4, 2019, which is a 371 of International Application No. PCT/JP2017/043890, filed on Dec. 6, 2017, which is based upon and claims the benefit of priority from the prior Japanese Patent Application No. 2016-237942, filed on Dec. 7, 2016 and Japanese Patent Application No. 2016-237941, filed on Dec. 7, 2016, the entire contents of which are incorporated herein by reference.The present invention relates to an organometallic complex catalyst for use in a cross-coupling reaction. More specifically, the present invention relates to an organometallic complex catalyst for use in a cross-coupling reaction which has a ligand having a nitrogen-containing heterocyclic carbene structure.Aromatic amines are widely used in medicines, ...

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- ...

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 ...

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 , ...

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- ...

LIGHT UPCONVERSION MICROCAPSULES

A composition, method, and article of manufacture are disclosed. The composition is a microcapsule that includes a transparent shell encapsulating a mixture comprising light upconversion molecules. The method is a method of forming a microcapsule, which includes obtaining light upconversion molecules, forming an emulsion of the light upconversion molecules and a shell formation solution, and encapsulating the light upconversion molecules in a transparent shell. The article of manufacture comprises the microcapsule. 1. A microcapsule , comprising:a transparent shell encapsulating a mixture, the mixture comprising light upconversion molecules.2. The microcapsule of claim 1 , wherein the light upconversion molecules comprise a molecular sensitizer and a molecular annihilator.3. The microcapsule of claim 1 , wherein the mixture further comprises a non-polar solvent.4. The microcapsule of claim 1 , wherein the transparent shell is a urea-formaldehyde shell.5. The microcapsule of claim 1 , wherein the light upconversion molecules comprise a molecular sensitizer selected from the group consisting of a transition metal complex of a porphyrin and a transition metal complex of a phthalocyanine.6. The microcapsule of claim 1 , wherein the light upconversion molecules comprise a molecular annihilator selected from the group consisting of a furanyldiketopyrrolopyrrole and a perylene.7. A method of forming a microcapsule claim 1 , comprising:obtaining light upconversion molecules;forming an emulsion that includes the light upconversion molecules and a shell formation solution; andencapsulating the light upconversion molecules in a transparent shell.8. The method of claim 7 , wherein the light upconversion molecules comprise a molecular sensitizer and a molecular annihilator.9. The method of claim 8 , further comprising:forming a reaction system that includes the microcapsule, a photocatalyst, and a substrate; andexposing the reaction system to light having sufficient energy to ...

SURFACE-MODIFIED LIGHT UPCONVERSION SILICA PARTICLES

A composition, method, and article of manufacture are disclosed. The composition includes a silica particle with light upconversion molecules bound to its surface. The method includes obtaining silica particles and light upconversion molecules having sidechains with reactive functional groups. The method further includes binding the light upconversion molecules to surfaces of the silica particles. The article of manufacture includes the composition. 1. A composition , comprising:a silica particle; andlight upconversion molecules bound to a surface of the silica particle.2. The composition of claim 1 , wherein the light upconversion molecules comprise molecular sensitizers.3. The composition of claim 1 , wherein the light upconversion molecules comprise molecular annihilators.4. The composition of claim 1 , wherein the light upconversion molecules comprise molecular annihilators and molecular sensitizers.5. The composition of claim 1 , wherein the surface of the silica particle includes a first face and a second face.6. The composition of claim 5 , wherein the light upconversion molecules comprise molecular sensitizers bound to the first face of the silica particle.7. The composition of claim 6 , wherein the light upconversion molecules comprise molecular annihilators bound to the second face of the silica particle.8. A method of forming surface-modified particles claim 6 , comprising:obtaining silica particles;obtaining light upconversion molecules having sidechains with reactive functional groups; andbinding the light upconversion molecules to surfaces of the silica particles.9. The method of claim 8 , wherein the reactive functional groups are silyl groups.10. The method of claim 8 , further comprising forming a reaction environment claim 8 , the reaction environment comprising:the surface-modified particles;a photocatalyst; anda substrate.11. The method of claim 8 , wherein the silica particles are Janus particles.12. The method of claim 8 , wherein the light ...

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 ...

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- ...

PHOSPHINE SUBSTITUTED FERROCENYL COMPLEX

A functionalized magnetic nanoparticle including an organometallic sandwich compound and a magnetic metal oxide. The functionalized magnetic nanoparticle may be reacted with a metal precursor to fol in a catalyst for various C—C bond forming reactions. The catalyst may be recovered with ease by attracting the catalyst with a magnet. 2. (canceled)3. The complex of claim 1 , wherein Ris an optionally substituted alkyl.4. The complex of claim 1 , wherein Ris an optionally substituted aryl.5. The complex of claim 1 , wherein X is NH.620-. (canceled) This application claims the priority of the filing date of the U.S. Provisional Patent Application No. 62/406,449 filed Oct. 11, 2016, the disclosure of which is hereby incorporated herein by reference in its entirety.This project was funded by the National Plan for Science, Technology and Innovation (MAARIFAH)-King Abdulaziz City for Science and Technology through the Science and Technology Unit at King Fahd University of Petroleum and Minerals (KFUPM), the Kingdom of Saudi Arabia, award number 15-NAN4650-04.Aspects of this technology are described in an article “Magnetic nanoparticle-supported ferrocenylphosphine: a reusable catalyst for hydroformylation of alkene and Mizoroki-Heck olefination” by M. Nasiruzzaman Shaikh, Md. Abdul Aziz, Aasif Helal, Mohamed Bououdina, Zain H. Yamania, and Tae-Jeong Kim, in RSC Advances, 2016, pages 41687-41695, which is incorporated herein by reference in its entirety.The present disclosure relates to a functionalized magnetic nanoparticle including an organometallic sandwich compound and a functional group which can bind to a nanoparticle. The disclosure also relates to a magnetic catalyst which catalyzes C—C bond forming reactions such as hydroformylation and the Mizoroki-Heck coupling reaction.Carbon-carbon bond formation reactions mediated by various transition metals have emerged as increasingly important methodologies for the preparation of numerous organic building blocks for drugs, ...

CATALYSTS FOR ELECTROLESS METALLIZATION CONTAINING FIVE-MEMBERED HETEROCYCLIC NITROGEN COMPOUNDS

Catalysts include five-membered nitrogen containing heterocyclic compounds as ligands for metal ions which have catalytic activity. The catalysts are used to electrolessly plate metal on metal clad and un-clad substrates. 16-. (canceled)8: The catalyst of claim 7 , wherein the one or more compounds are chosen from hydantoin claim 7 , 1-methylhydantoin claim 7 , 1 claim 7 ,3-dimethylhydantoin claim 7 , 5 claim 7 ,5-dimethylhydantoin claim 7 , allantoin claim 7 , 1 claim 7 ,3-dihydroxymethyl-5 claim 7 ,5-dimethylhydantoin and succinimide.9: The catalyst of claim 7 , wherein a molar ratio of the one or more compounds to metal ions is from 1:1 to 4:1.10: The catalyst of claim 7 , wherein the one or more compounds are in amounts of 25 ppm to 1000 ppm. The present invention is directed to catalysts for electroless metallization containing five-membered heterocyclic nitrogen compounds. More specifically, the present invention is directed to catalysts for electroless metallization containing five-membered heterocyclic nitrogen compounds which are stable during storage and electroless metallization.Conventional printed circuit boards (PCBs) consist of laminated non-conductive dielectric substrates that rely on drilled and plated through holes (PTHs) to form a connection between the opposite sides and/or inner layers of a board. Electroless plating is a well-known process for preparing metallic coatings on surfaces. Electroless plating of a dielectric surface requires the prior deposition of a catalyst. The most commonly used method to catalyze or activate laminated non-conductive dielectric substrate regions, prior to electroless plating, is to treat the board with an aqueous tin-palladium colloid in an acidic chloride medium. The colloid consists of a metallic palladium core surrounded by a stabilizing layer of tin(II) ions. A shell of [SnCl] complexes act as surface stabilizing groups to avoid agglomeration of colloids in suspension.In the activation process, the palladium ...

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 ...

METAL CATALYST, METHOD OF C-N COUPLING USING THE SAME AND APPLICATIONS OF THE SAME

The present disclosure relates to a metal catalyst for C—H bond activation and/or C—N coupling reaction, and a method using the same and application thereof. Specifically, a metal catalyst represented by the following formula: 4. The metal catalyst according to claim 1 , wherein W claim 1 , X claim 1 , and Y are the same.5. The metal catalyst according to claim 1 , wherein M is Ni claim 1 , Pd claim 1 , Fe claim 1 , Co claim 1 , Cr claim 1 , Mn claim 1 , Cu claim 1 , or Pt.6. A method for C—H bond activation and/or C—N coupling reaction comprising using the metal catalyst according to .7. The method according to claim 6 , wherein the C—N coupling reaction forms C—N bonds between a spcarbon and a primary or secondary amine to form substituted or an alkylated amine.8. The method according to claim 7 , wherein the primary or secondary amine is an aliphatic or aromatic amine.9. The method according to claim 7 , wherein spcarbon is an aliphatic and aromatic hydrocarbon.10. The method according to claim 6 , wherein the C—H bond activation and/or C—N coupling reaction is performed under ambient and mild conditions.11. The method according to claim 6 , wherein the C—H bond activation and/or C—N coupling reaction is performed without the presence of an oxidant or a base.12. The method according to claim 6 , wherein the C—N coupling reaction forms C—N bonds between aliphatic amines claim 6 , to form a cyclic amine.13. The method according to claim 6 , wherein the C—N coupling reaction forms C—N bonds between primary amines claim 6 , to obtain an oligomeric compound.14. The method according to claim 6 , wherein the C—H bond activation and/or C—N coupling reaction is performed in presence of an oxidant or a base.15. The method according to claim 14 , the C—H bond activation and/or C—N coupling reaction is performed in presence of an oxidant that is selected from a group consisting of oxygen claim 14 , hydrogen peroxide claim 14 , t-butylhydroperoxide claim 14 , peracetic acid ...

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 ...

ELECTROLESS METALLIZATION OF DIELECTRICS WITH ALKALINE STABLE PYRAZINE DERIVATIVE CONTAINING CATALYSTS

Pyrazine derivatives which contain one or more electron donating groups on the ring are used as catalytic metal complexing agents in aqueous alkaline environments to catalyze electroless metal plating on metal clad and un-clad substrates. The catalysts are monomers and free of tin and antioxidants. 2. The method of claim 1 , wherein the one or more pyrazine derivatives are chosen from 2 claim 1 ,6-dimethylpyrazine claim 1 , 2 claim 1 ,3-dimethylpyrazine claim 1 , 2 claim 1 ,5-dimethylpyrazine claim 1 , 2 claim 1 ,3 claim 1 ,5-trimethylpyraizine claim 1 , 2-acetylpyrazine claim 1 , aminopyrazine claim 1 , ethylpyrazine claim 1 , methoxypyrazine claim 1 , 3 claim 1 ,4-dimethylpyrazine and 2-(2′-hydroxyethyl)pyrazine.3. The method of claim 1 , wherein a molar ratio of the one or more pyrazine derivatives to the metal ions is 1:1 to 4:1.4. The method of claim 1 , wherein the metal ions are chosen from palladium claim 1 , silver claim 1 , gold claim 1 , platinum claim 1 , copper claim 1 , nickel and cobalt.5. The method of claim 1 , wherein the metal on the substrate is copper claim 1 , copper alloy claim 1 , nickel or nickel alloy.6. The method of claim 1 , wherein the aqueous alkaline catalyst solution has a pH of 8.5 or greater.7. The method of claim 6 , wherein the aqueous alkaline catalyst solution has pH of 9 or greater.8. The method of claim 1 , wherein the substrate comprising the dielectric further comprises a plurality of through-holes.9. The method of claim 8 , wherein the substrate comprising the dielectric further comprises metal cladding. The present invention is directed to electroless metallization of dielectrics with alkaline stable pyrazine derivative containing catalysts. More specifically, the present invention is directed to metallization of dielectrics with alkaline stable pyrazine derivative containing catalysts as a replacement for palladium/tin colloidal catalysts.Conventional printed circuit boards (PCBs) consist of laminated non-conductive ...

Method for Aerobic Oxidative Coupling of Thiophenes with a Ligand-Supported Palladium Catalyst

An oxidative homocoupling method of synthesizing certain 2,2′-bithiophenes from thiophenes using oxygen as the terminal oxidant is disclosed. In non-limiting examples, the method uses oxygen along with a catalytic system that includes palladium, an assistive ligand, and a non-palladium metal additive to catalyze one of the following reactions: 1. A catalytic system for catalyzing the synthesis of a 2 ,2′-bithiophene or analog thereof from two thiophenes or analogs thereof , comprising:oxygen gas;palladium;a transition metal, alkali metal, alkaline earth metal, bismuth salt, or aluminum salt; anda ligand.2. The catalytic system of claim 1 , wherein the palladium is in the form of dipalladium(0) tris(dibenzylideneacetylacetone).3. The catalytic system claim 1 , wherein the palladium is in the form of a palladium salt.4. The catalytic system of claim 3 , wherein the palladium salt is selected from the group consisting of palladium(II) acetate claim 3 , palladium(II) propionate claim 3 , palladium(II) pivalate claim 3 , palladium(II) benzoate claim 3 , palladium(II) acetylacetonate claim 3 , palladium(II) trifluoroacetate claim 3 , palladium(II) nitrate dihydrate claim 3 , and palladium(II) iodide.5. The catalytic system of claim 1 , wherein the ligand is selected from the group consisting of a 1 claim 1 ,10-phenanthroline-5 claim 1 ,6-dione; a 2 claim 1 ,2′-bipyridine claim 1 , a 2 claim 1 ,2′-bipyrimidine; a 4 claim 1 ,5-diazafluoren-9-one; a quinoline; a 1 claim 1 ,10-phenanthroline; a bis(arylimino)acenaphthene; and a 2 claim 1 ,2′-biquinoline.7. The catalytic system of claim 6 , wherein 1 claim 6 , 2 claim 6 , 3 claim 6 , 4 claim 6 , 5 or all 6 of R claim 6 , R claim 6 , R claim 6 , R claim 6 , Rand Rare hydrogen.8. The catalytic system of claim 7 , wherein all 6 of R claim 7 , R claim 7 , R claim 7 , R claim 7 , Rand Rare hydrogen (the ligand is 1 claim 7 ,10-phenanthroline-5 claim 7 ,6-dione (phd)).10. The catalytic system of claim 9 , wherein one or more of R ...

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

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

PD-CATALYZED DECOMPOSITION OF FORMIC ACID

Process for Pd-catalyzed decomposition of formic acid 2. Process according to claim 1 ,wherein the compound in process step b) is selected from:{'sub': 2', '2', '3', '3', '2', '2', '3', '2, 'Pd(acac), PdCl, Pd(dba)*CHCl (dba=dibenzylideneacetone), Pd(OAc), Pd(TFA), Pd(CHCN)Cl.'}3. Process according to claim 1 ,{'sub': '2', 'wherein the compound in process step b) is Pd(OAc).'}4. Process according to claim 1 ,wherein the process comprises additional process step f):f) addition of an acid.5. Process according to claim 4 ,{'sub': 2', '4', '3', '3', '3', '3, 'wherein the acid in process step f) is selected from: HSO, CHSOH, CFSOH, PTSA.'}6. Process according to claim 4 ,wherein the acid in process step f) is PTSA.7. Process according to claim 1 ,{'sup': 1', '2', '3', '4, 'sub': 1', '12', '1', '12', '4', '14', '4', '14', '1', '12', '1', '12', '3', '14', '3', '14', '2, 'wherein R, R, R, Rare each independently selected from: —(C-C)-alkyl, —O—(C-C)-alkyl, —(C-C)-aryl, —O—(C-C)-aryl, cycloalkyl, —(C-C)-heteroalkyl, —O—(C-C)-heteroalkyl, —(C-C)-heteroaryl, —O—(C-C)-heteroaryl, —COO-alkyl, —COO-aryl, —C—O-alkyl, —C—O-aryl, NH, halogen and the residues are also capable of forming a larger condensed ring;'}wherein the recited alkyl groups, aryl groups, cycloalkyl, heteroalkyl groups, heteroaryl groups may be substituted as follows:{'sub': 1', '12', '1', '12, '—(C-C)-alkyl, —O—(C-C)-alkyl, halogen;'}{'sup': 1', '2', '3', '4, 'and at least one of the radicals R, R, R, Rdoes not represent phenyl.'}8. Process according to claim 1 ,{'sup': 1', '2', '3', '4, 'sub': 1', '12', '4', '14', '1', '12', '3', '14, 'wherein R, R, R, Rare each independently selected from: —(C-C)-alkyl, —(C-C)-aryl, cycloalkyl, —(C-C)-heteroalkyl, —(C-C)-heteroaryl, halogen and the residues are also capable of forming a larger condensed ring;'}wherein the recited alkyl groups, aryl groups, cycloalkyl, heteroalkyl groups, heteroaryl groups may be substituted as follows:{'sub': 1', '12', '1', '12, '—(C-C)-alkyl, ...

STRONGLY LEWIS ACIDIC METAL-ORGANIC FRAMEWORKS FOR CONTINUOUS FLOW CATALYSIS

Lewis acidic metal-organic framework (MOF) materials comprising triflate-coordinated metal nodes are described. The materials can be used as heterogenous catalysts in a wide range of organic group transformations, including Diels-Alder reactions, epoxide-ring opening reactions, Friedel-Crafts acylation reactions and alkene hydroalkoxylation reactions. The MOFs can also be prepared with metallated organic bridging ligands to provide heterogenous catalysts for tandem reactions and/or prepared as composites with support particles for use in columns of continuous flow reactor systems. Methods of preparing and using the MOF materials and their composites are also described. 1. A method for preparing a catalyst , said method comprising:{'sub': '2', '(a) providing a parent metal-organic framework (MOF), wherein the parent MOF comprises periodic repeats of a coordination complex comprising (i) an organic bridging ligand and (ii) a metal-containing secondary building unit (SBU), wherein said metal-containing SBU comprises a metal oxo cluster comprising a metal ion M and one or more terminal or bridging OH or OHligands; and'}{'sub': '2', '(b) reacting the parent MOF with a silyl triflate to replace one or more of the one or more terminal or bridging OH or OHligands with a triflate ligand.'}2. The method of claim 1 , wherein the SBU is selected from the group consisting of Zr-oxo cluster claim 1 , a Fe-oxo cluster claim 1 , a Cr-oxo cluster claim 1 , and an A-oxo cluster.3. The method of claim 1 , wherein the organic bridging ligand is substituted with one or more carboxylate claim 1 , pyridine claim 1 , and/or phosphonate moieties.4. The method of claim 3 , wherein the organic bridging ligand is trimesic acid (BTC).5. The method of claim 1 , wherein the parent MOF is provided by contacting a parent precursor MOF with a strong acid claim 1 , wherein the parent precursor MOF comprises periodic repeats of a coordination complex comprising: (i) the organic bridging ligand and (ii ...

METHOXYCARBONYLATION WITH FORMIC ACID AS CO SOURCE

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

METHOXYCARBONYLATION WITH FORMIC ACID AND METHANOL

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

METAL-CATALYZED COUPLING OF ARYL AND VINYL HALIDES WITH ALPHA, ALPHA-DIFLUOROCARBONYL COMPOUNDS

The coupling of aryl, heteroaryl, and vinyl halides with α,α-difluoroketones or silyl ethers or siylenol ethers of α,α-difluoroketones and α,α-difluoroamides and esters are described. Further derivatization of the coupling products (such as ketone cleavage and Baeyer-Villiger oxidation) is also described. 2. The composition according to claim 1 , wherein said complex is present in said composition in an amount of less than 10 mol % relative to said α claim 1 ,α-difluoromethyl carbonyl compound.3. The composition according to claim 2 , wherein said complex is present in said composition in an amount of about 2 mol % to about 5 mol % relative to said α claim 2 ,α-difluoromethyl carbonyl compound.5. The composition according to claim 4 , wherein said complex is present in said composition in an amount of less than 10 mol % relative to said silyl enol ether.6. The composition according to claim 5 , wherein said complex is present in said composition in an amount of about 2 mol % to about 5 mol % relative to said silyl enol ether.76. The composition according to any one of - claims 4 , wherein said composition does not contain BuSnF.87. The composition according to any one of - claims 4 , wherein said composition does not contain an organotin reagent.98. The composition according to any one of - claims 4 , wherein R claims 4 , R claims 4 , and Rare independently selected from unsubstituted C claims 4 , C claims 4 , C claims 4 , C claims 4 , Cand Calkyl.10. The composition according to claim 9 , wherein one or more of R claim 9 , R claim 9 , and Rare methyl.11. The composition according to any preceding claim claim 9 , further comprising a solvent.12. The composition according to claim 11 , wherein said solvent is a non-polar claim 11 , organic solvent.13. The composition according to claim 12 , wherein said solvent is toluene.14. The composition according to any preceding claim claim 12 , wherein said base is a member selected from CsCOand KPO.17. The composition ...

Catalytic system for preparation of high branched alkane from olefins

The present invention discloses a catalytic system for preparing highly branched alkane from olefin, which contains novel nickel or palladium complexes. In the presence of the catalytic system, highly branched oily alkane mixture can be efficiently obtained from olefins (such as ethylene) under mild conditions. The alkane mixture has a low bromine number, and can be used as a processing aid(s) and lubricant base oil with high-performance. Provides also was a method for preparing the catalyst and a method for preparing an oily olefin polymer.

N-HETEROCYCLIC CARBENE (NHC) BASED LIGANDS AND RELATED METHODS

Polydentate macrocyclic NHCs (NHC ligands) and related methods are disclosed. Such ligands advantageously facilitate a variety of ligand coordination modes and stabilize oxidation states of metal complexes with a number of coordination environments and shapes. The NHC ligands described herein comprise pendant groups configured to facilitate a variety of reactions including: cis-trans isomerization, proton shuttling and facilitating changes in coordination environments as a result of redox reactions. 4. The ligand of claim 1 , wherein Rand Rare both methyl benzene.5. The ligand of claim 1 , wherein the composition comprises a salt and the salt is a halide salt.6. The ligand of claim 1 , wherein the composition comprises a cis isomer.7. The ligand of claim 1 , wherein the composition comprises a trans isomer.9. The catalyst of claim 8 , wherein M is Ag claim 8 , Pd claim 8 , Ni claim 8 , Pt claim 8 , Ru claim 8 , Re claim 8 , or Ir.12. The catalyst of claim 8 , wherein Rand Rare both methyl benzene.13. The catalyst of claim 8 , wherein the catalyst comprises C2 symmetric cis metal complex.14. The catalyst of claim 8 , wherein the catalyst comprises a C2 symmetric trans metal complex. The present application claims priority pursuant to 35 U.S.C. § 119(e) to U.S. Provisional Patent Application Ser. No. 62/547,253 filed Aug. 18, 2017 which is incorporated herein by reference in its entirety.N-heterocyclic carbenes (NHCs) are ubiquitous ligands often used to support a variety of metal environments for catalysis. However, existing NHCs have limited scopes and lifetimes. It is challenging to obtain catalysts that can be reliably employed in industrial processes.Accordingly, a need exists for improved NHC ligands (macrocycles) and related methods.Polydentate macrocyclic NHCs (NHC ligands) and related methods are disclosed. Such ligands advantageously facilitate a variety of ligand coordination modes and stabilize oxidation states of metal complexes with a number of ...

O-AMINOHETEROARYL ALKYNYL-CONTAINING COMPOUND, PREPARATION METHOD THEREFOR, AND USE THEREOF

An o-aminoheteroaryl alkynyl-containing compound has a structure represented by formula (I), and the compound of formula (I) has advantages of a high FGFR and RET double target inhibitory activity and a relatively low KDR activity, and the compound of formula (I) exhibits a strong inhibitory activity in a human lung cancer cell line NCI-H1581 and a gastric cancer cell line SNU16 as well as an RET-dependent sensitive cell line BaF3-CCDC6-Ret and a mutant thereof. Pharmacokinetic data shows that the o-aminoheteroaryl alkynyl-containing compound has druggability, and exhibits significant relevant inhibition of the growth of related tumors in a long-term animal model of drug efficacy and results in favorable animal condition at effective doses. 2. The compound claim 1 , or the deuterated compound claim 1 , or the pharmaceutically acceptable salt or the prodrug thereof of claim 1 , wherein:the alkyl is a saturated aliphatic straight or branched alkyl having 1 to 6 carbon atoms, preferably having 1 to 4 carbon atoms, more preferably 1 to 3 carbon atoms, and still more preferably is methyl, ethyl, propyl, isopropyl or tert-butyl;the modified alkyl is an alkyl having one or more substituents selected from the group consisting of —O—, —COO—, —CONH—, —CH═CH—, —C≡C—, halogen, hydroxyl, carboxyl, primary amino, secondary amino, tertiary amino, cycloalkyl, heterocyclyl, and heterocyclylene;the aryl is a 6-10 membered and preferably 6-8 membered monocyclic or fused bicyclic ring;the heteroaryl or heteroaryl ring is a 6-10 membered and preferably 6-8 membered monocyclic or fused bicyclic ring containing 1-3 heteroatoms selected from N, O and S;the cycloalkyl is a saturated or unsaturated 3-6 membered monocyclic or polycyclic ring;the cycloalkylene is a saturated or unsaturated 3-6 membered monocyclic or polycyclic ring;the heterocyclyl is a 4-7 membered and preferably 4-6 membered monocyclic or polycyclic heterocycle containing 1-3 heteroatoms selected from N, O, and S;the ...

Fused thiophene ditin monomers

The disclosure relates to thiophene-based ditin compounds and methods of making and using such compounds. The disclosed compounds are novel structures having organotin groups on a conjugated aryl group spaced from and adjacent to a fused thiophene moiety. The formation of trialkyl tin groups spaced away from the fused thiophene moieties is advantageous in that it allows for novel polymerization via Stille coupling.

SOLID-SUPPORTED PALLADIUM(II) COMPLEX FOR CATALYZING MIZOROKI-HECK COUPLING REACTIONS AND A METHOD THEREOF

A solid-supported palladium(II) complex which catalyzes the Mizoroki-Heck coupling reaction efficiently and a method of employing the solid-supported palladium(II) complex to synthesize cinnamic acid and derivatives thereof. The solid-supported palladium(II) complex is also stable and can be recycled without significantly losing catalytic activity. 2: The solid-supported ligand of claim 1 , wherein{'sub': 1', '2', '3, 'Rand Rare CH;'}{'sub': 3', '4', '5', '6, 'R, R, R, and R, are H;'}n is 1;X is O; andthe solid support is silica gel.3: The solid-supported ligand of claim 1 , wherein the solid support is in the form of a particle with an average diameter of 1-100 μm.4: A solid-supported catalyst claim 1 , comprising a reaction product of:{'claim-ref': {'@idref': 'CLM-00001', 'claim 1'}, 'the solid-supported ligand of ; and'}{'sub': '2', 'a palladium(II) salt of the formula PdZ;'}wherein the reaction product comprises a palladium(II) ion bound to a nitrogen atom in each oxazoline heterocycle; andZ is selected from the group consisting of Cl, I, Br, OAc, and OTf.5: The solid-supported catalyst of claim 4 , wherein{'sub': 1', '2', '3, 'Rand Rare CH;'}{'sub': 3', '4', '5', '6, 'R, R, R, and Rare H;'}n is 1;X is O;the solid support is silica gel; andZ is Cl.6: The solid-supported catalyst of claim 4 , wherein the solid support is in the form of a particle with an average diameter of 1-100 μm.7: The solid-supported catalyst of claim 4 , which comprises 0.1-1 mmol of palladium per gram of the solid-supported catalyst.8: The solid-supported catalyst of claim 4 , which has a turnover number in a range of 1 claim 4 ,500-2 claim 4 ,500 and a turnover frequency in a range of 200-1 claim 4 ,500 per hour.9: A method for synthesizing cinnamic acid or derivatives thereof claim 4 , the method comprising:{'claim-ref': {'@idref': 'CLM-00004', 'claim 4'}, 'reacting an aryl halide with an acrylic acid or derivatives thereof in the presence of a solvent, a base, and the solid-supported ...

PROCESS FOR PREPARING BTK INHIBITORS

Methods for preparing the Bruton's Tyrosine Kinase (“BTK”) inhibitor compound 2-{3′-hydroxymethyl-1-methyl-5-[5-((S)-2-methyl-4-oxetan-3-yl-piperazin-1-yl)-pyridin-2-ylamino]-6-oxo-1,6-dihydro-[3,4′]bipyridinyl-2′-yl}-7,7-dimethyl-3,4,7,8-tetrahydro-2H,6H-cyclopenta[4,5]pyrrolo[1,2-a]pyrazin-1-one are provided. Methods for preparing tricyclic lactam compounds are also provided. 2. The method of claim 1 , wherein the volume to weight ratio of the solvent system to compound 170 in the reaction mixture is from about 5:1 to about 20:1 liters per kg.3. The method of claim 1 , wherein:{'sub': 3', '4, 'the base in the first reaction mixture is KPO, and the solvent system in the first reaction mixture comprises water and a polar aprotic solvent, wherein the volume ratio of water to polar aprotic solvent is from about 0.1:1 to about 0.4:1.'}4. The method of claim 1 , wherein:the yield of compound 190 is at least 80%, and the purity of compound 190 is at least 99 area %.6. The method of claim 5 , wherein the ratio of the solvent volume to compound 160 weight in the reaction mixture is from about 5:1 to about 15:1 liters per kg claim 5 , and wherein the equivalent ratio of catalyst to compound 160 is from about 0.01:1 to about 0.03:1.7. The method of claim 6 , wherein the catalyst is Pd(OAc) claim 6 , the ligand is DPPF claim 6 , the base is potassium carbonate claim 6 , and the polar aprotic solvent is tetrahydrofuran.89-. (canceled)11. The method of claim 10 , wherein the reaction mixture comprises: a ratio of solvent volume to compound 180 weight of from about 5:1 to about 20:1 liters to kg; an equivalent ratio of borylation reagent to compound 180 of between 1 and 2; an equivalent ratio of palladium catalyst to compound 180 of from 0.001:1 to about 0.005:1; an equivalent ratio of catalyst ligand to catalyst of from about 1.5:1 to about 3; and an equivalent ratio of potassium acetate to compound 180 of greater than 1:1.13. The method of wherein the catalyst ligand is XPhos. ...

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 (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) claim 1 , and a second step of deprotecting the 3-benzyl-5-(4-methoxyphenyl)pyrazin-2-amine (5) to provide the 4-(5-amino-6-benzylpyrazin-2-yl)phenol (7).3. The method of claim 1 , wherein the silyl protected 1 claim 1 ,1-diethoxy-3-(4-hydroxyphenyl)propan-2-one is 3-(4-((tert-butyldimethylsilyl)oxy)phenyl)-1 claim 1 ,1-diethoxypropan-2-one (23) and wherein the 3-(4-((tert-butyldimethylsilyl)oxy)phenyl)-1 claim 1 ,1-diethoxypropan-2-one (23) is synthesized by:i. reacting 4-hydroxybenzaldehyde (8) with tert-butyldimethylsilyl chloride to provide 4-((tert-butyldimethylsilyl)oxy)benzaldehyde;ii. reacting the 4-((tert-butyldimethylsilyl)oxy)benzaldehyde with sodium borohydride to provide (4-((tert-butyldimethylsilyl)oxy)phenyl)methanol;iii. reacting the (4-((tert-butyldimethylsilyl)oxy)phenyl)methanol with methanesulfonyl chloride to provide tert-butyl(4-(chloromethyl)phenoxy)dimethylsilane(21);iv. reacting the tert-butyl(4-(chloromethyl)phenoxy)dimethylsilane (21) with magnesium to provide (4-((tert- ...

BUTADIENE TELOMERIZATION CATALYST AND PREPARATION THEREOF

Catalyst compositions are prepared by contacting a palladium source and 1,3,5,7-tetramethyl-6-(2,4-dimethoxyphenyl)-2,4,8-trioxa-6-phosphaadamantane and a methoxyocta-diene compound, in a primary aliphatic alcohol, under suitable conditions including a ratio of equivalents of palladium to equivalents of 1,3,5,7-tetramethyl-6-(2,4-dimethoxyphenyl)-2,4,8-trioxa-6-phosphaadamantane ranging from greater than 1:1 to 1:1.3. The result is a complex of palladium, a 1,3,5,7-tetramethyl-6-(2,4-dimethoxyphenyl)-2,4,8-trioxa-6-phosphaada-mantane ligand, and a ligand selected from a methoxyoctadiene ligand, an octadienyl ligand, or a protonated octadienyl. Such complexes may, in solution, exhibit surprising solubility and storage stability and are useful in the telomerization of butadiene, which is a step in the production of 1-octene. 1. A catalyst composition useful for catalyzing the telomerization of butadiene comprising a complex comprising palladium , a 1 ,3 ,5 ,7-tetramethyl-6-(2 ,4-dimethoxyphenyl)-2 ,4 ,8-trioxa-6-phosphaada-mantane ligand , and a ligand selected from a methoxyoctadiene ligand , an octadienyl ligand , and a protonated octadienyl ligand.2. The composition of wherein the methoxyoctadiene ligand is selected from 1-methoxy-2 claim 1 ,7-octadiene and 3-methoxy-1 claim 1 ,7-octadiene.3. The composition of wherein the complex is dissolved in a primary aliphatic alcohol.4. The composition of wherein the primary aliphatic alcohol is selected from methanol claim 3 , ethanol claim 3 , propanol claim 3 , butanol claim 3 , ethylene glycol claim 3 , propylene glycol claim 3 , glycerol claim 3 , and combinations thereof.5. The composition of wherein the composition further comprises at least one of: (a) the counteranion of a carboxylic acid; (2) a promoter selected from alkoxides claim 1 , enolates claim 1 , phenoxides claim 1 , borohydrides claim 1 , and hydrazides claim 1 , all of alkali metals; alkaline earth metals and quaternary ammoniums; alkali metal salts; and ...

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: (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. The invention also relates to biofuels obtainable by the inventive process and to uses of ethylene for adjusting and optimizing biofuels.

PROCESS FOR PREPARING BTK INHIBITORS

Methods for preparing the Bruton's Tyrosine Kinase (“BTK”) inhibitor compound 2-{3′-hydroxymethyl-1-methyl-5-[5-((S)-2-methyl-4-oxetan-3-yl-piperazin-1-yl)-pyridin-2-ylamino]-6-oxo-1,6-dihydro-[3,4′]bipyridinyl-2′-yl}-7,7-dimethyl-3,4,7,8-tetrahydro-2H,6H-cyclopenta[4,5]pyrrolo[1,2-a]pyrazin-1-one are provided. Methods for preparing tricyclic lactam compounds are also provided. 2. The method of wherein the volume to weight ratio of the solvent system to compound 170 in the reaction mixture is from about 5:1 to about 20:1 liters per kg claim 1 , or about 10:1 liters per kg claim 1 , and the equivalent ratio of compound 181 to compound 170 is greater than 1:1 claim 1 , and the equivalent ratio of the palladium catalyst to compound 170 is from about 0.005:1 to about 0.02:1 claim 1 , or about 0.01:1.4. The method of wherein:the yield of compound 190 is at least 60%, at least 70%, at least 80% or at least 90%, and the purity of compound 190 is at least 99 area % or at least 99.5 area %; andthe yield of compound 200 is at least 60%, at least 70%, at least 80%, or at least 85%, and the purity of compound 200 is at least 99 area % or at least 99.5 area %.6. The method of wherein the ratio of the solvent volume to compound 160 weight in the reaction mixture is from about 5:1 to about 20:1 liters per kg claim 5 , from about 5:1 to about 15:1 liters per kg claim 5 , or about 10:1 liters per kg claim 5 , and wherein the equivalent ratio of catalyst to compound 160 is from about 0.01:1 to about 0.03:1.7. The method of wherein the catalyst is Pd(OAc) claim 6 , the ligand is DPPF claim 6 , the base is potassium carbonate claim 6 , and the solvent is tetrahydrofuran.9. The method of wherein the polar aprotic solvent is THF; the mole ratio of n-butyl lithium to compound 95 is between 1:1 and 2:1 claim 8 , or from about 1.2:1 to about 1.6:1; the first reaction mixture and the second reaction mixture are formed at a temperature of greater than −35° C.; of the solvent volume to ...

PROCESS FOR PRODUCING HETEROCYCLIC COMPOUND

The present invention provides a method of efficiently producing an optically active 6-(3-aminopiperidin-1-yl)-2,4-dioxo-1,2,3,4-tetrahydropyrimidine derivative. The optically active piperidine-3-carboxamide or a derivative thereof, which is obtained by subjecting 1,4,5,6-tetrahydropyridine-3-carboxamide or a derivative thereof to an asymmetric reduction in the presence of a catalyst, is used as an intermediate. 2. The method according to claim 1 , wherein the organic metal complex is a transition metal complex.3. The method according to claim 2 , wherein the transition metal complex is a ruthenium complex.4. The method according to claim 3 , wherein the ruthenium complex is represented by the formula:{'br': None, 'sup': 'a', 'sub': '2', '[Ru(OCOR)L*]\u2003\u2003(VIII)'}wherein{'sup': 'a', 'sub': '1-3', 'Ris an optionally substituted Calkyl group; and'}{'sup': 'a', 'Lis a diphosphine ligand.'} This application is a divisional of U.S. application Ser. No. 15/125,299, which is the U.S. National Stage application of PCT/JP2015/057541, filed Mar. 13, 2015, which claims priority from Japanese application 2014-052809, filed Mar. 14, 2014.The present invention relates to a production method of an optically active 6-(3-aminopiperidin-1-yl)-2,4-dioxo-1,2,3,4-tetrahydropyrimidine derivative which is useful as a dipeptidylpeptidase inhibitor, and various intermediates useful therefor, and production methods thereof.An optically active 6-(3-aminopiperidin-1-yl)-2,4-dioxo-1,2,3,4-tetrahydropyrimidine derivative is known to be useful as a dipeptidylpeptidase inhibitor and an agent for the treatment of diabetes.Patent Document 1 discloses a method of producing a 6-(3-aminopiperidin-1-yl)-2,4-dioxo-1,2,3,4-tetrahydropyrimidine derivative by reacting optically active 3-aminopiperidine with a 6-chloro-2,4-dioxo-1,2,3,4-tetrahydropyrimidine derivative.Patent Document 2 discloses a method of efficiently producing an optically active 8-(3-aminopiperidin-1-yl)xanthine derivative by ...

CATALYST AND BATTERY COMPONENTS DERIVED FROM CONDENSATION REACTIONS WITH CARBA-CLOSO-DODECABORATE AMINES

Described herein is the fusion of two families of unique carbon-containing molecules that readily disregard the tendency of carbon to form four chemical bonds, namely N-heterocyclic carbenes (NHCs) and carborane anions. Deprotonation of an anionic imidazolium salt with lithium diisopropylamide at room temperature leads to a mixture of lithium complexes of C-2 and C-5 dianionic NHC constitutional isomers as well as a trianionic (C-2, C-5) adduct. Judicious choice of the base and reaction conditions allows for the selective formation of all three stable polyanionic carbenes. In solution, the so-called abnormal C-5 NHC lithium complex slowly isomerizes to the normal C-2 NHC, and the process can be proton catalyzed by the addition of the anionic imidazolium salt. These results indicate that the combination of two unusual forms of carbon atoms can lead to unexpected chemical behavior, and that this strategy paves the way for the development of a broad new generation of NHC ligands for catalysis. 2. The carborane compound according to claim 1 , wherein alkyl claim 1 , aryl claim 1 , silyl claim 1 , siloxy claim 1 , alkoxy claim 1 , and aryloxy in Rare optionally substituted with a member independently selected from the group consisting of hydrogen claim 1 , halogen claim 1 , hydroxyl claim 1 , and hydroxide.3. The carborane compound according to claim 1 , wherein Ris selected from alkyl and aryl.5. The carborane compound according to claim 1 , wherein Hetis selected from the group consisting of an N-heterocyclic carbene (NHC) moiety or an NHC precursor moiety.8. The carborane compound according to claim 7 , wherein{'sup': '1', 'each Ris independently selected from H, halogen, alkyl, aryl, silyl, siloxy, alkoxy, and aryloxy, and wherein'}{'sup': '1', 'each alkyl, aryl, silyl, siloxy, alkoxy, and aryloxy in Ris optionally substituted with a member independently selected from the group consisting of halogen, hydroxyl, and hydroxide.'}9. The carborane compound according to ...

Spiroketal-Based C2-Symmetric Scaffold For Asymmetric Catalysis

Provided herein is a compound of formula (I): 4. The compound of claim 1 , wherein at least one X is OH.5. (canceled)6. The compound of claim 1 , wherein at least one X is PAr.7. (canceled)8. The compound of claim 1 , wherein at least one X is OPAr.9. (canceled)10. The compound of claim 1 , wherein at least one X is P(O)Ar.1112.-. (canceled)13. The compound of claim 6 , wherein Ar comprises phenyl.14. The compound of claim 1 , wherein both X together form OPNR′.1518.-. (canceled)19. The compound of claim 14 , wherein R′ is methyl.2022.-. (canceled)23. The compound of claim 1 , wherein R is ethyl.2428.-. (canceled)29. The compound of claim 1 , wherein at least one R is 3-10 membered heterocycloalkyl having 1-4 heteroatoms independently selected from N claim 1 , O claim 1 , and S.3034.-. (canceled)36. A catalyst comprising the compound of formula (I) according to and a transition metal.37. The catalyst of claim 36 , wherein the transition metal comprises iridium claim 36 , palladium claim 36 , rhodium claim 36 , platinum claim 36 , copper claim 36 , nickel claim 36 , cobalt claim 36 , or gold.38. A method of preparing the catalyst of comprising admixing the compound of formula (I) and the transition metal to form the catalyst.39. (canceled)40. The method of claim 38 , wherein the transition metal comprises [Ir(COD)Cl] claim 38 , [Pd(allyl)Cl] claim 38 , or Pd(dba).41. The method of claim 38 , wherein the compound of formula (I) and the transition metal are provided in a molar ratio of about 6:1 to 1:1.42. A method comprising:{'claim-ref': {'@idref': 'CLM-00036', 'claim 36'}, 'admixing a first reactant, a second reactant, and the catalyst of under conditions sufficient to allow reaction of the first reactant and the second reactant to form a reaction product, wherein the reaction product comprises a chiral center and the reaction produces an enantiomeric excess (ee) of the reaction product.'}43. The method of claim 42 , wherein the reaction comprises a hydroarylation ...

Low system memory detection

Methods, systems, and computer readable media may be operable to facilitate an anticipation of an execution of a process termination tool. An allocation stall counter may be queried at a certain frequency, and from the query of the allocation stall counter, a number of allocation stall counter increments occurring over a certain duration of time may be determined. If the number of allocation stall counter increments is greater than a threshold, a determination may be made that system memory is running low and that an execution of a process termination tool is imminent. In response to the determination that system memory is running low, a flag indicating that system memory is running low may be set, and one or more programs, in response to reading the flag, may free memory that is not necessary or required for execution.

Double alkoxycarbonylation of dienes as one-pot synthesis

Process for the double alkoxycarbonylation of dienes as one-pot synthesis.

METHOD FOR PRODUCING ESTER COMPOUND

A method for producing an ester compound including reacting a compound having at least one cyclic structure of a norbornene ring and a norbornadiene ring with an alcohol and carbon monoxide by using a palladium catalyst and an oxidizing agent, to thereby introduce ester groups to carbon atoms forming a double bond in the cyclic structure and obtain the ester compound, wherein the palladium catalyst comprises a palladium complex having a bipyridyl as a ligand. 1. A method for producing an ester compound , comprising:reacting a compound having at least one cyclic structure of a norbornene ring and a norbornadiene ring with an alcohol and carbon monoxide by using a palladium catalyst and an oxidizing agent, to thereby introduce ester groups to carbon atoms forming a double bond in the cyclic structure and obtain the ester compound, whereinthe palladium catalyst comprises a palladium complex having a bipyridyl as a ligand.2. The method for producing an ester compound according to claim 1 , whereinoxygen is used as the oxidizing agent.3. The method for producing an ester compound according to claim 2 , whereina chlorine-containing compound, a copper compound other than a chloride, and a manganese compound other than a chloride are used in combination with the oxidizing agent.4. The method for producing an ester compound according to claim 2 , whereinmanganese chloride, copper acetate, and manganese acetate are used in combination with the oxidizing agent. The present invention relates to a method for producing an ester compound.Conventionally, as a method for obtaining an ester compound, a method (a method utilizing so-called the oxidative alkoxycarbonylation reaction (esterification reaction)) has been known in which a norbornene-based compound having a carbon-carbon double bond is reacted with an alcohol and carbon monoxide by using a palladium catalyst to thereby introduce (add) ester groups to the carbon atoms forming the double bond and obtain an ester compound.For ...

Purified cenicriviroc and purified intermediates for making cenicriviroc

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

Supported Metal Catalysts

The present invention relates to supported metal catalysts, wherein the catalysts are modified by at least one amine, a method for the preparation thereof and hydrogenation processes utilising the supported metal catalysts. 2. The supported metal catalyst of claim 1 , wherein the support is carbon claim 1 , alumina claim 1 , calcium carbonate claim 1 , titania claim 1 , silica claim 1 , zirconia claim 1 , ceria claim 1 , or a combination thereof.3. The supported metal catalyst of claim 2 , wherein the alumina is alpha-AlO claim 2 , beta-AlO claim 2 , gamma-AlO claim 2 , delta-AlO claim 2 , theta-AlOor a combination thereof.4. The supported metal catalyst of claim 2 , wherein the carbon is activated carbon claim 2 , carbon black claim 2 , graphite claim 2 , or a combination thereof.5. (canceled)6. (canceled)7. The supported metal catalyst of claim 1 , wherein the metal is ruthenium claim 1 , rhodium claim 1 , palladium claim 1 , osmium claim 1 , iridium claim 1 , platinum claim 1 , gold claim 1 , silver claim 1 , copper claim 1 , iron claim 1 , cobalt claim 1 , nickel claim 1 , or a combination thereof.8. The supported metal catalyst of claim 1 , wherein the metal is palladium claim 1 , platinum claim 1 , gold claim 1 , or a combination thereof.9. The supported metal catalyst of claim 1 , wherein the Group VIII or IB metal is present in a range of from 0.01 wt % to 20 wt % claim 1 , relative to the total weight of the supported metal catalyst.10. The supported metal catalyst of claim 1 , wherein the amine is a natural amino acid claim 1 , non-natural amino acid claim 1 , peptide claim 1 , alkylamine claim 1 , alkyldiamine claim 1 , alkylpolyamine claim 1 , or combinations thereof.11. The supported metal catalyst of claim 10 , wherein the amine is lysine claim 10 , glycine claim 10 , proline claim 10 , alanine claim 10 , serine claim 10 , phenylalanine claim 10 , asparagine claim 10 , aspartic acid claim 10 , valine claim 10 , butylamine claim 10 , 6-aminocaproic acid ...

FUNCTIONALIZED MAGNETIC NANOPARTICLE, A CATALYST, A METHOD FOR FORMING C-C BONDS

A functionalized magnetic nanoparticle including an organometallic sandwich compound and a magnetic metal oxide. The functionalized magnetic nanoparticle may be reacted with a metal precursor to form a catalyst for various C—C bond forming reactions. The catalyst may be recovered with ease by attracting the catalyst with a magnet. 2: The complex of claim 1 , wherein M is iron.3: The complex of claim 1 , wherein Ris an optionally substituted alkyl.4: The complex of claim 1 , wherein Ris an optionally substituted aryl.5: The complex of claim 1 , wherein X is NH.8: The functionalized magnetic nanoparticle of claim 7 , wherein the nanoparticle comprises iron(II) oxide and iron(III) oxide.9: The functionalized magnetic nanoparticle of claim 7 , wherein the nanoparticle has an average diameter in a range of 1-20 nm.10: The functionalized magnetic nanoparticle of claim 7 , wherein Ris an optionally substituted alkyl.11: The functionalized magnetic nanoparticle of claim 7 , wherein Ris an optionally substituted aryl.12: The functionalized magnetic nanoparticle of claim 7 , wherein the functionalized magnetic nanoparticle has a saturation magnetization in a range of 40-70 emu/g.13: A catalyst claim 7 , comprising:{'claim-ref': {'@idref': 'CLM-00007', 'claim 7'}, 'sup': '8', 'sub': '2', 'a reaction product of the functionalized magnetic nanoparticle of and a palladium complex or a rhodium complex, wherein the catalyst comprises palladium or rhodium bound to a phosphorous atom in at least one —PRgroup.'}14: The catalyst of claim 13 , wherein the catalyst has a saturation magnetization in a range of 30-70 emu/g.15: The catalyst of claim 13 , wherein the catalyst retains at least 90% of an initial catalytic activity when the catalyst is reused.16: A hydroformylation method claim 13 , comprising:{'claim-ref': {'@idref': 'CLM-00013', 'claim 13'}, 'sup': '8', 'sub': '2', 'reacting an optionally substituted alkene with carbon monoxide and hydrogen in the presence of the catalyst of ...

NANO-TO-NANO FE/PPM Pd CATALYSIS OF CROSS-COUPLING REACTIONS IN WATER

In one embodiment, the present application discloses a catalyst composition comprising: a) a reaction solvent or a reaction medium; b) organometallic nanoparticles comprising: i) a nanoparticle (NP) catalyst, prepared by a reduction of an iron salt in an organic solvent, wherein the catalyst comprises at least one other metal selected from the group consisting of Pd, Pt, Au, Ni, Co, Cu, Mn, Rh, Ir, Ru and Os or mixtures thereof; c) a ligand; and d) a surfactant; wherein the metal or mixtures thereof is present in less than or equal to 50,000 ppm relative to the iron salt. 120.-. (canceled)22. The method of claim 21 , wherein the metal claim 21 , other than Pd claim 21 , is selected from the group consisting of Pt claim 21 , Au claim 21 , Ni claim 21 , Co claim 21 , Cu claim 21 , Mn claim 21 , Rh claim 21 , Ir claim 21 , Ru and Os or a mixture thereof.23. The method of further comprising:iii) contacting the product mixture with an organic solvent to form an organic phase and an aqueous phase; andiv) separating the organic phase from the aqueous phase containing the micelle composition as well as the iron/ppm Pd nanoparticles.24. The method of further comprising:v) re-cycling the aqueous phase containing the micelle composition and Fe/ppm Pd nanoparticles for use in a subsequent cross coupling or other reactions.25. The method of claim 21 , wherein the reaction solvent is water claim 21 , and the reaction solvent further comprising an organic solvent claim 21 , wherein the organic co-solvent is present in at least 5% claim 21 , 10% claim 21 , 20% claim 21 , 30% claim 21 , 40% claim 21 , 50% claim 21 , 70% claim 21 , 80% or at least 90% wt/wt.2611. The method of claim claim 21 , wherein the organic co-solvent is present at a wt of organic co-solvent to the wt of water (wt/wt) of 1/10 claim 21 , 2/10 claim 21 , 5/10 claim 21 , 10/10 claim 21 , 20/10 claim 21 , 30/10 claim 21 , 50/10 claim 21 , 70/10 claim 21 , 90/10 claim 21 , 100/10 claim 21 , 200/10 claim 21 , 300/10 ...

DIRECT PALLADIUM-CATALYZED AROMATIC FLUORINATION

Provided herein are palladium complexes comprising a ligand of Formula (A′) and a ligand of Formula (B), wherein R-Rare as defined herein. The palladium complexes are useful in methods of fluorinating aryl and heteroaryl substrates. Further provided are compositions and kits comprising the palladium complexes. 3. The method of claim 1 , wherein the palladium is palladium (II) or palladium (III).4. The method of claim 1 , wherein the palladium complex further comprises a fluoro (F) ligand.5. (canceled)6. The method of claim 1 , wherein each of R claim 1 , R claim 1 , R claim 1 , R claim 1 , R claim 1 , R claim 1 , and Rare H claim 1 , and Ris halogen.7. The method of claim 1 , wherein each of R claim 1 , R claim 1 , R claim 1 , R claim 1 , R claim 1 , R claim 1 , R claim 1 , R claim 1 , R claim 1 , and Ris hydrogen.10. The method of claim 1 , wherein the compound of Formula (D) claim 1 , (E) claim 1 , or (F) is electron neutral.11. The method of claim 1 , wherein the compound of Formula (D) claim 1 , (E) claim 1 , or (F) is electron deficient.12. The method of claim 1 , wherein the compound of Formula (D) claim 1 , (E) claim 1 , or (F) is electron rich.13. The method of claim 1 , wherein the fluorinating agent is an N-fluorinated amine or N-fluorinated quaternary amine salt.1416-. (canceled)17. The method of claim 1 , wherein each of R claim 1 , R claim 1 , R claim 1 , R claim 1 , R3 claim 1 , R claim 1 , R claim 1 , R claim 1 , R claim 1 , and Rof the palladium(II) complex of Formula (A) is hydrogen.18. The method of claim 1 , wherein each of R claim 1 , R claim 1 , R claim 1 , R claim 1 , R claim 1 , R claim 1 , and Rof the phenanthroline ligand of formula (B) is hydrogen and Rof the phenanthroline ligand of formula (B) is halogen.19. (canceled)20. The method of claim 1 , wherein each of R claim 1 , R claim 1 , R claim 1 , R claim 1 , R3 claim 1 , R claim 1 , R claim 1 , R claim 1 , R claim 1 , and Ris hydrogen; R claim 1 , R claim 1 , R claim 1 , R claim 1 , R ...

BILATERALLY-SUBSTITUTED TRICYCLIC COMPOUNDS FOR THE TREATMENT OF HUMAN IMMUNODEFICIENCY VIRUS TYPE-1 (HIV-1) INFECTION AND OTHER DISEASES

The invention relates to novel bilaterally-substituted tricyclic compounds and pharmaceutical compositions containing them, for use as medicaments. 18-. (canceled)10. A compound according to selected from2″,3,5,6″-tetrakis(2-aminoethyl)-4″-methoxy-2′,6′-dimethyl-[1,1′:4′,1″-terphenyl]-4-ol2,2′,2″,2′″-(4″-(benzyloxy)-4-methoxy-3′,5′-dimethyl-[1,1′:4′,1″-terphenyl]-2,3″,5″,6-tetrayl)tetraethanamine2″,3,5,6″-tetrakis(2-aminoethyl)-2′-ethyl-4″-methoxy-[1,1′:4′,1″-terphenyl]-4-ol2,2′,2″,2′″-(4″-(benzyloxy)-3′-ethyl-4-methoxy-[1,1′:4′,1″-terphenyl]-2,3″,5″,6-tetrayl)tetraethanamine2″,3,5,6″-tetrakis(2-aminoethyl)-2′,6′-diethyl-4″-methoxy-[1,1′:4′,1″-terphenyl]-4-ol 'or a pharmaceutical salt, ester, solvate, or hydrate thereof.', '2,2′,2″,2′″-(4″-(benzyloxy)-3′,5′-diethyl-4-methoxy-[1,1′:4′,1″-terphenyl]-2,3″,5″,6-tetrayl)tetraethanamine'}11. (canceled)121. A method for the prevention and/or treatment of HIV-1 infection; infections caused by HIV-2 claim 9 , the virus of severe acute respiratory syndrome claim 9 , hepatitis C virus claim 9 , yellow fever virus claim 9 , dengue virus claim 9 , West Nile virus claim 9 , polio virus claim 9 , influenza viruses claim 9 , the Ebola virus claim 9 , human parainfluenza virus claim 9 , rotavirus claim 9 , or by gram-positive and gram-negative bacteria; neuroblastoma claim 9 , prostate cancer claim 9 , ovarian cancer claim 9 , breast cancer claim 9 , head and neck cancer claim 9 , multiple myeloma claim 9 , renal cell cancer claim 9 , Burkitt lymphoma claim 9 , colon cancer claim 9 , hepatocarcinoma; herpes simplex virus infections claim 9 , hypertension claim 9 , psoriasis claim 9 , asthma claim 9 , lupus claim 9 , multiple sclerosis claim 9 , rheumatoid arthritis claim 9 , fibromyalgia claim 9 , epilepsy claim 9 , Alzheimer's disease and Parkinson disease claim 9 , said method comprising administering a therapeutically effective amount of a compound as defined in claim .13. The method according to for the treatment and/or ...

Process for Reducing the Light Oligomer Content of Polypropylene Oils

Disclosed herein are catalyst systems containing an alpha-diimine nickel halide complex, a chemically-treated solid oxide, and an optional co-catalyst. These catalyst systems can be used to reduce the light oligomer content of propylene oligomer streams, for instance, by oligomerizing olefin feedstocks containing Cto Cpropylene oligomers to produce oligomer compositions having higher molecular weights. 1. A process comprising:{'sub': 6', '27, 'contacting an olefin feedstock comprising Cto Cpropylene oligomers with a catalyst composition comprising (i) an alpha-diimine nickel halide complex, (ii) a chemically-treated solid oxide, and (iii) optionally, a co-catalyst, to produce an oligomer composition, wherein a number-average molecular weight (Mn) of the oligomer composition is greater than that of the olefin feedstock.'}2. The process of claim 1 , wherein the Mn of the oligomer composition is greater than that of the olefin feedstock by from about 5% to about 100%.3. The process of claim 1 , wherein a ratio of a total of Cto Coligomers to a total of Cto Coligomers of the oligomer composition is greater than that of the olefin feedstock by from about 25% to about 2500%.4. The process of claim 1 , wherein:the catalyst composition comprises a co-catalyst; andthe chemically-treated solid oxide comprises a fluorided solid oxide and/or a sulfated solid oxide.5. The process of claim 4 , wherein the co-catalyst comprises an organoaluminum compound.6. The process of claim 1 , wherein the chemically-treated solid oxide comprises fluorided alumina claim 1 , sulfated alumina claim 1 , fluorided silica-alumina claim 1 , sulfated silica-alumina claim 1 , fluorided silica-coated alumina claim 1 , fluorided-chlorided silica-coated alumina claim 1 , sulfated silica-coated alumina claim 1 , or any combination thereof.7. The process of claim 1 , wherein the alpha-diimine nickel halide complex comprises an alpha-diimine nickel chloride complex.8. The process of claim 1 , wherein the ...

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.

ELECTROLESS COPPER PLATING AND COUNTERACTING PASSIVATION

Prior to electroless copper plating on substrates containing copper, an aqueous composition containing select six-membered heterocyclic nitrogen compounds is applied to the substrate. The aqueous composition containing the select six-membered heterocyclic nitrogen compounds counteract passivation of the copper on the substrate to improve the electroless copper plating process. 1. (canceled)2. A method of electroless copper plating comprising:a) providing a substrate comprising passivated copper;b) applying a catalyst to the passivated copper of the substrate;c) treating the catalyzed passivated copper of the substrate with an aqueous composition comprising a reducing agent and a six-membered heterocyclic nitrogen compound selected from the group consisting of 2-(aminomethyl)pyridine, 2-aminopyrazine, cytosine, di-(2-picolyl)amine, 4,4′-dipyridyl, 2-(hydroxymethyl)pyridine, 3-(hydroxymethyl)pyridine and mixtures thereof;d) applying an electroless copper plating bath to the treated anti-passivated copper of the substrate; ande) electroless plating copper on the treated anti-passivated copper of the substrate with the electroless copper plating bath.3. The method of claim 2 , further comprising applying a conditioner to the substrate comprising the passivated copper prior to applying the catalyst.4. The method of claim 2 , further comprising rinsing the substrate with the catalyzed anti-passivated copper after the treatment with the aqueous composition with a water rinse solution.5. The method of claim 4 , wherein the water rinse solution comprises a six-membered heterocyclic nitrogen compound selected from the group consisting of 2-(aminomethyl)pyridine claim 4 , 2-aminopyrazine claim 4 , cytosine claim 4 , di-(2-picolyl)amine claim 4 , 4 claim 4 ,4′-dipyridyl claim 4 , 2-(hydroxymethyl)pyridine claim 4 , 3-(hydroxymethyl)pyridine claim 4 , and mixtures thereof.6. (canceled)7. The method of electroless copper plating of claim 2 , wherein the aqueous composition ...

COMPLEXES

A palladium(II) complex of formula (1) or a palladium(II) complex of formula (3). 2. A palladium(II) complex according to claim 1 , wherein E is P.3. A palladium(II) complex according to claim 1 , wherein Rand Rare independently selected from the group consisting of substituted and unsubstituted straight-chain alkyl claim 1 , substituted and unsubstituted branched-chain alkyl claim 1 , substituted and unsubstituted cycloalkyl claim 1 , substituted and unsubstituted aryl claim 1 , and substituted and unsubstituted heteroaryl wherein the heteroatoms are independently selected from sulfur claim 1 , nitrogen and oxygen.4. A palladium(II) complex according to claim 1 , wherein R claim 1 , R claim 1 , Rand Rare independently selected from the group consisting of —H claim 1 , substituted and unsubstituted straight-chain alkyl claim 1 , substituted and unsubstituted branched-chain alkyl claim 1 , substituted and unsubstituted cycloalkyl claim 1 , substituted and unsubstituted alkoxy claim 1 , substituted and unsubstituted aryl claim 1 , substituted and unsubstituted heteroaryl claim 1 , substituted and unsubstituted —N(alkyl)(wherein the alkyl groups may be the same or different and are independently selected from straight-chain or branched-chain groups) claim 1 , substituted and unsubstituted —N(cycloalkyl)(wherein the cycloalkyl groups may be the same or different) claim 1 , substituted and unsubstituted —N(aryl)(wherein the aryl groups may be the same or different) claim 1 , substituted and unsubstituted —N(heteroaryl)(wherein the heteroaryl groups may be the same or different) and substituted and unsubstituted heterocycloalkyl groups.5. A palladium(II) complex according to claim 4 , wherein each of R claim 4 , R claim 4 , Rand Rare —H.6. A palladium(II) complex according to claim 4 , wherein each of R claim 4 , R claim 4 , Rand Rare independently straight-chain alkyl groups claim 4 , preferably -Me.7. A palladium(II) complex according to claim 1 , wherein two of R claim ...

HETEROBIMETALLIC CATALYSTS AND SITE-DIFFERENTIATED LIGANDS FOR PREPARATION THEREOF

Phosphine phosphonate and phenoxyphosphine ligands bearing polyethylene glycol (PEG) chains are used as described herein to produce heterobimetallic catalysts. The ligands can be metallated selectively with palladium or nickel and secondary metal ions to provide well-defined heterobimetallic compounds. These heterobimetallic complexes exhibit accelerated reaction rates and greater thermal stability in olefin polymerization compared to other catalysts. 2. The method of claim 1 , wherein the metal salt is a salt of Ca claim 1 , Mg claim 1 , Co claim 1 , or Zn.3. A heterobimetallic catalyst prepared by the method of .4. A method for catalyzing homopolymerization of ethylene claim 1 , comprising:{'claim-ref': {'@idref': 'CLM-00003', 'claim 3'}, 'combining ethylene with the heterobimetallic catalyst of , whereby the ethylene undergoes homopolymerization.'}5. A method for catalyzing copolymerization of ethylene and polar olefins claim 1 , comprising:{'claim-ref': {'@idref': 'CLM-00003', 'claim 3'}, 'combining ethylene and polar olefins with the heterobimetallic catalyst of , whereby the ethylene and polar olefins undergo copolymerization.'}7. The method of claim 6 , wherein the metal salt is a salt of Ca claim 6 , Mg claim 6 , Co claim 6 , or Zn.8. A heterobimetallic catalyst prepared by the method of .9. A method for catalyzing homopolymerization of ethylene claim 6 , comprising:{'claim-ref': {'@idref': 'CLM-00007', 'claim 7'}, 'combining ethylene with the heterobimetallic catalyst of , whereby the ethylene undergoes homopolymerization.'}10. A method for catalyzing copolymerization of ethylene and polar olefins claim 6 , comprising:{'claim-ref': {'@idref': 'CLM-00007', 'claim 7'}, 'combining ethylene and polar olefins with the heterobimetallic catalyst of , whereby the ethylene and polar olefins undergo copolymerization.'} This application is a continuation of and claims priority to U.S. patent application Ser. No. 17/255,846, filed Dec. 23, 2020, entitled “ ...

PALLADIUM ACYCLIC DIAMINOCARBENE COMPLEXES AS PRECATALYSTS FOR HIYAMA COUPLING AND THE TANDEM ONE-POT FLUORIDE FREE HIYAMA COUPLING/CYCLIZATION FOR THE SYNTHESIS OF BIOLOGICALLY RELEVANT

The present invention provides Acyclic diaminocarbene complex of formula (I): 3. The Acyclic diaminocarbene complex as claimed in is effective in the Hiyama coupling reaction of Csp3Csp2 type.4. The Acyclic diaminocarbene complex as claimed in is effective in the Hiyama coupling reaction of Csp3Csp type.5. The Acyclic diaminocarbene complex as claimed in is effective in the Hiyama coupling reaction of Csp2-Csp2 type.6. The Acyclic diaminocarbene complex as claimed in is effective in the Hiyama coupling reaction of Csp2-Csp type.7. The Acyclic diaminocarbene complex as claimed in is effective in the Hiyama coupling reaction of Csp-Csp type.8. The acyclic diaminocarbene (ADC) complexes as claimed in is adapted to perform Csp2-Csp Hiyama alkynylation between aryl iodide and various triethoxysilylalkynes.9. The Acyclic diaminocarbene complex as claimed in is effective in catalyzing the Csp2-Csp type Hiyama coupling reaction followed by cyclization reaction to provide benzofuran compounds.10. The palladium acyclic diaminocarbene (ADC) complexes as claimed in is effective in catalyzing Csp2-Csp type Hiyama alkynylation followed by cyclization reaction to provide a time efficient one-pot tandem route to provide benzofuran compounds. The present invention reports a series of palladium acyclic diaminocarbene (ADC) complexes, particularly to the compounds of the formulation cis-[(R1NH)(R2)methylidene]PdCl2(CNR1) [R1=2,4,6-(CH3)3C6H2: R2=NC5H10 (2); NC4H8(3); NC4H8O (4)] and represented by Formula (I) and acts as metal catalyst for the organic synthesis reactions particularly for Hiyama coupling and for Csp2-Csp type Hiyama coupling followed by cyclization of reactions.Singh, C. et al. “One-Pot Tandem Hiyama Alkynylation/Cyclizations by Palladium(II) Acyclic Diaminocarbene (ADC) Complexes Yielding Biologically Relevant Benzofuran Scaffolds” (2018) ACS Omega 3 (2): 1740-1756 was authored by the inventors Prasenjit Ghosh and Chandan Singh and by A. P. Prakasham, Manoj K. Gangwar ...

TRI-(ADAMANTYL)PHOSPHINES AND APPLICATIONS THEREOF

In one aspect, phosphine compounds comprising three adamantyl moieties (PAd) and associated synthetic routes are described herein. Each adamantyl moiety may be the same or different. For example, each adamantyl moiety (Ad) attached to the phosphorus atom can be independently selected from the group consisting of adamantane, diamantane, triamantane and derivatives thereof. Transition metal complexes comprising PAdligands are also provided for catalytic synthesis including catalytic cross-coupling reactions. 1. A method of synthesizing a tri-(adamantyl)phosphine compound , PAd , comprising:{'sub': 2', '2', 'N', '3, 'providing a reaction mixture including di-(adamantyl)phosphine (PAd) and a substituted adamantyl moiety and reacting the PAdand substituted adamantyl moiety via an S1 pathway to provide the PAd.'}2. The method of claim 1 , wherein adamantyl moieties (Ad) of the PAdare independently selected from the group consisting of adamantane claim 1 , diamantane claim 1 , triamantane and derivatives thereof.3. The method of claim 1 , wherein the substituted adamantyl moiety comprises a leaving group.4. The method of claim 3 , wherein the leaving group is selected from the group consisting of acetate claim 3 , triflate claim 3 , tosylate and hydroxyl.5. The method of claim 1 , wherein yield of the PAdis greater than 50 percent.6. The method of claim 1 , wherein yield of the PAdis greater than 60 percent.7. The method of claim 1 , wherein synthesizing the tri-(adamantyl)phosphine is performed at room temperature.8. A method of synthesizing a tri-(adamantyl)phosphine compound claim 1 , PAd claim 1 , comprising:{'sub': 2', 'N', '3, 'providing a reaction mixture including di-(adamantyl)phosphide and a substituted adamantyl moiety and reacting the PAdand substituted adamantyl moiety via an S1 pathway to provide the PAd.'}9. The method of claim 8 , wherein adamantyl moieties (Ad) of the di-(adamantyl)phosphide are independently selected from the group consisting of ...

PHOSPHINE TRIPLY CROSS-LINKED BY ORGANIC POLYMER, TRANSITION METAL COMPLEX USING SAID PHOSPHINE AS A LIGAND, AND CATALYST

Provided are: a polymer-supported phosphane compound exhibiting excellent catalytic reaction activity; a complex including the compound and a transition metal; and a catalyst including the complex. This polymer compound includes: units of threefold styrene cross-linked phosphane; and styrene units having substituent groups (R) in position 4 (provided that R represents hydrogen, a C1-6 lower alkyl group, a C1-6 lower alkoxy group, or a polar functional group). In the formula in which the polymer compound includes structure (1), PS represents a polystyrene unit chain including the styrene units having the substituent groups (R). The complex includes the polymer and a transition metal. The catalyst for an organic compound coupling reaction includes the complex. 19.-. (canceled)10. A complex comprising a polymer compound and a transition metal , wherein the polymer compound comprises a threefold styrene cross-linked phosphane unit and styrene units each having a substituent R at the 4-position wherein R represents a hydrogen atom , a lower alkyl group having 1 to 6 carbon atoms , a lower alkoxy group having 1 to 6 carbon atoms , or a polar functional group , wherein the styrene units have substituents R which are the same or different , and wherein the polymer compound binds to the transition metal through a phosphine group in the threefold styrene cross-linked phosphane unit.11. The complex according to claim 10 , further comprising claim 10 , as a ligand claim 10 , an atom or group selected from halogen claim 10 , carbonyl claim 10 , hydroxy claim 10 , nitro claim 10 , amino claim 10 , sulfonyl claim 10 , and cyano.12. The complex according to claim 11 , wherein when the ligand is carbonyl claim 11 , the carbonyl is present in a group selected from ester claim 11 , aldehyde claim 11 , ketone claim 11 , and amide.13. The complex according to claim 10 , wherein the transition metal is selected from palladium claim 10 , iridium claim 10 , rhodium claim 10 , platinum ...

SPIRO-1,1'-BINDANE-7,7-BISPHOSPHINE OXIDES AS HIGHLY ACTIVE SUPPORTING LIGANDS FOR PALADIUM-CATALYZED ASYMMETRIC HECK REACTION

The present invention relates to catalyst complexes comprising palladium (Pd) and at least one spiro-1,1′-biindane-7,7′-bisphosphine oxide ligand as disclosed herein, and their use. The present invention is further directed to the asymmetric catalyzed covalent carbon-carbon single bond formation from aryl, heteroaryl and alkenyl triflates and halides and olefins utilising the said catalyst complexes.

COMPOUND OF 3,3,3',3'-TETRAMETHYL-1,1'-SPIROBIINDANE-BASED PHOSPHINE LIGAND, AND PREPARATION METHOD THEREOF

The present application discloses a 3,3,3′,3′-tetramethyl-1,1′-spirobiindane-based phosphine ligand, an intermediate, a preparation method and uses thereof. The compound of phosphine ligand is a compound having a structure represented by formula I or formula II, or an enantiomer, a raceme, or diastereomer thereof. The phosphine ligand can be prepared via a preparation scheme in which the cheap and easily available 6,6′-dihydroxyl-3,3,3′,3′-tetramethyl-1,1′-spirobiindane is used as a raw material and the compound represented by formula III serves as the key intermediate. The new phosphine ligand developed by the present application can be used in catalytic organic reaction, in particular as a chiral phosphine ligand that is widely used in many asymmetric catalytic reactions including asymmetric hydrogenation and asymmetric allyl alkylation, and thus it has economic practicability and industrial application prospect. 4. The compound represented by formula I or formula II according to claim 1 , wherein Ris selected from the group consisting of phenyl claim 1 , benzyl claim 1 , pentafluorophenyl claim 1 , 4-methylphenyl claim 1 , 4-methoxyphenyl claim 1 , 4-trifluoromethyl-phenyl claim 1 , 3 claim 1 ,5-dimethylphenyl claim 1 , 3 claim 1 ,5-difluorophenyl claim 1 , 3 claim 1 ,5-dimethoxyphenyl claim 1 , 3 claim 1 ,5-di-tert-butylphenyl claim 1 , 3 claim 1 ,4 claim 1 ,5-trimethoxyphenyl claim 1 , 3 claim 1 ,5-dimethyl-4-methoxy-phenyl claim 1 , 3 claim 1 ,5-di-tert-butyl-4-methoxy-phenyl claim 1 , 3 claim 1 ,5-dimethyl-4-methoxy-phenyl claim 1 , and 3 claim 1 ,5-bis(trifluoromethyl)-phenyl.10. A use of the 3 claim 1 ,3 claim 1 ,3′ claim 1 ,3′-tetramethyl-1 claim 1 ,1′-spirobiindane-based phosphine ligand according to claim 1 , wherein the phosphine ligand is complexed with a metal salt of iron claim 1 , osmium claim 1 , gold claim 1 , silver claim 1 , copper claim 1 , platinum claim 1 , rhodium claim 1 , ruthenium claim 1 , iridium claim 1 , nickel claim 1 , molybdenum ...

Triaryl phosphine ligands, preparation method therefor, and use in catalysing coupling reactionsons

Triaryl phosphine ligands, as shown in general formulae Ia and Ib, or a mixture thereof, and a preparation method therefor. The invention addresses the deficiencies of biaryl phosphine ligands invented by Buchwald et al. Also provided are a triaryl phosphine coordinated palladium complex, a system composed of triaryl phosphine ligand and a palladium salt or complex, and a use of the triaryl phosphine coordinated palladium complex in catalysing organic reactions, in particular a use in catalysis of coupling reactions involving (pseudo)halogenated aromatic hydrocarbon as substrate.

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.

Purified cenicriviroc and purified intermediates for making cenicriviroc

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

Cylinder Resident Hydrolysis of Olefins to Petroleum Gases

An additive has been prepared for blending with gasoline that facilitates a cylinder resident reaction, in high compression internal combustion engines (ICEs), to produce an increase in engine's mechanical energy output. A method of increasing mechanical efficiency of an internal combustion engine (ICE) comprising blending an amount of additive with gasoline to perform hydrolysis of olefin hydrocarbons, represented by octene (C8) into petroleum gas hydrocarbons, represented by butane (C4), wherein the additive facilitates cylinder-resident reaction, aided by a low concentration of organometallic catalyst, to utilize the elements of the water combustion product, to hydrolyze olefin hydrocarbons such as octene, resident in the gasoline, into petroleum gas hydrocarbons such as butane, and to increase the ICE's efficiency of utilization of the energy of the fuel. 1. A method of increasing mechanical efficiency of an internal combustion engine (ICE) comprising blending an amount of additive with gasoline to perform hydrolysis of olefin hydrocarbons , represented by octene (C8) into petroleum gas hydrocarbons , represented by butane (C4) , wherein the additive consists of a plurality of units of chemicals and is evenly dispersed through-out the gasoline , and wherein the units of chemicals consists of a base explosive that detonates , under the requisite pressure and temperature conditions , a chain of reactions that are aided by a low concentration of lead , an organopalladium or an organoplatinum catalyst , that utilize an elemental component of water present as a combustion product to perform hydrolysis of olefin hydrocarbons , represented by octene (C8) into petroleum gas hydrocarbons , represented by butane (C4) , to increase the engine's mechanical efficiency through the mechanisms of: increasing the pressure in the compression stroke , above the engine's 10:1 or higher; contributing components with an octane number (ON) of 102 to the gasoline that enters the ...

A PROCESS FOR PREPARING ALECTINIB OR A PHARMACEUTICALLY ACCEPTABLE SALT THEREOF

The present invention relates to a process for preparing the Alectinib or a pharmaceutically acceptable salt thereof using lesser reaction steps and also eliminating expensive and time-consuming column chromatography. The invention also relates to novel polymorphic forms of Alectinib and Alectinib hydrochloride. 2. The process according to claim 1 , wherein the reaction is carried out in the presence of a catalyst.3. The process according to claim 1 , wherein the reaction is carried out in the presence of a catalyst and a ligand.4. The process according to claim 2 , wherein the catalyst is a palladium (II) catalyst.5. The process according to claim 4 , wherein the palladium (II) catalyst is selected from palladium(II) acetate claim 4 , [1 claim 4 ,2-bis(diphenylphosphino)ethane]dichloropalladium(II) and [1 claim 4 ,1′-bis(diphenylphosphino) ferrocene]palladium(II) dichloride.6. The process according to claim 3 , wherein the ligand is a phosphine ligand.7. The process according to claim 6 , wherein the phosphine ligand is selected from tricyclohexylphosphine claim 6 , tri-tert-butylphosphine claim 6 , triphenylphosphine and 2-dicyclohexylphosphino-2′ claim 6 ,4′ claim 6 ,6′-triisopropylbiphenyl.8. The process according to claim 1 , wherein the reaction is carried out in the presence of a solvent selected from amide solvents claim 1 , sulfoxide solvents claim 1 , ethers and mixtures thereof.9. The process according to claim 8 , wherein the solvent is selected from N-methylpyrrolidone claim 8 , dimethylsulfoxide claim 8 , dimethylacetamide claim 8 , diethylacetamide claim 8 , dimethylformamide claim 8 , dioxane claim 8 , tetrahydrofuran and mixtures thereof.10. A crystalline form of Alectinib or a hydrochloride salt thereof selected from the group consisting of (a) form B of Alectinib characterized by an X-ray powder diffraction (XRPD) pattern comprising peaks at about 10.6 and 12.6±0.2° 2θ claim 8 , (b) form IV of Alectinib hydrochloride characterized by an XRPD ...

Electroless metallization of dielectrics with alkaline stable pyrazine derivative containing catalysts

Pyrazine derivatives which contain one or more electron donating groups on the ring are used as catalytic metal complexing agents in aqueous alkaline environments to catalyze electroless metal plating on metal clad and un-clad substrates. The catalysts are monomers and free of tin and antioxidants.

METAL CATALYST, METHOD OF C-N COUPLING USING THE SAME AND APPLICATIONS OF THE SAME

A method for C—H bond activation and/or C—N coupling reaction comprises adding a hydrocarbon material to a container; adding a metal catalyst to the container; adding a primary or a secondary amine to the container. The metal catalyst is represented by the following formula: 2. The method according to claim 1 , wherein the amount of the metal catalyst is 0.02 to 2 mol %. This application is a divisional application of U.S. patent application Ser. No. 17/148,736, filed Jan. 14, 2021, now allowed, which is a divisional application of U.S. patent application Ser. No. 16/054,181, filed Aug. 3, 2018, abandoned, which claims priority to and the benefit of U.S. Provisional Patent Application Ser. No. 62/540,770, filed Aug. 3, 2017, which are incorporated herein in their entireties by reference.The present disclosure relates to a metal catalyst, a method of C—N coupling using a metal catalyst and applications of the same. In certain embodiments, a metal catalyst with varying substituents is used for direct coupling of primary and secondary amines with hydrocarbons containing activated and non-activated C—H bonds (spcarbon).The background description provided herein is for the purpose of generally presenting the context of the disclosure. Work of the presently named inventor, to the extent it is described in this background section, as well as aspects of the description that may not otherwise qualify as prior art at the time of filing, are neither expressly nor impliedly admitted as prior art against the present disclosure.Nitrogen-based compounds have great value in various fields ranging from fine chemicals to pharmaceuticals. In particular, aromatic nitrogen-based compounds have even more great value, extending to even more fields such as agrochemicals, electronica materials, xerography, pigmentation, and photography. Because of their diverse uses, developing a cheap and easy to use methodology for C—N coupling has become an area of great importance.In the past several ...

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

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

Butadiene telomerization catalyst precursor preparation

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

Phosphinyl Amidine Compounds, Metal Complexes, Catalyst Systems, and Their Use to Oligomerize or Polymerize Olefins

N 2 -phosphinyl amidine compounds, N 2 -phosphinyl amidinates, N 2 -phosphinyl amidine metal salt complexes, N 2 -phosphinyl amidinate metal salt complexes are described. Methods for making N 2 -phosphinyl amidine compounds, N 2 -phosphinyl amidinates, N 2 -phosphinyl amidine metal salt complexes, and N 2 -phosphinyl amidinate metal salt complexes are also disclosed. Catalyst systems utilizing the N 2 -phosphinyl amidine metal salt complexes and N 2 -phosphinyl amidinate metal salt complexes are also disclosed along with the use of the N 2 -phosphinyl amidine compounds, N 2 -phosphinyl amidinates, N 2 -phosphinyl amidine metal salt complexes, and N 2 -phosphinyl amidinate metal salt complexes for the oligomerization and/or polymerization of olefins.

SOLID-SUPPORTED CATALYST FOR CROSS-COUPLING

A solid-supported catalyst ligand which chelates palladium (II) species to form a complex that functions as a heterogeneous catalyst that is stable and can be recycled without significantly losing any catalytic activity in a variety of chemical transformations, a method for producing the solid-supported catalyst ligand and a method for catalyzing a palladium cross-coupling reaction, such as the Suzuki-Miyaura, Mizoroki-Heck, and Sonagashira reactions. 2: The solid-supported catalyst of claim 1 , wherein the solid resin bead is Merrifield resin.4. (canceled)5: The solid-supported catalyst of claim 1 , wherein the solid-supported catalyst is in the form of a particle having an average particle size in terms of an average diameter of 1-100 μm.6: (canceled)7: The solid-supported catalyst of claim 1 , wherein{'sub': 1', '2', '3, 'Rand Ris —CH;'}{'sub': 3', '4', '5', '6, 'R, R, R, and Ris —H;'}X is O;and{'sup': '+2', 'sub': 2', '2, 'the Pdspecies having the formula PdZis PdCl.'}8: The solid-su ported catalyst of claim 1 , which comprises 0.05-1.5 mmol of palladium per gram of the catalyst composition.9: The solid-supported catalyst of claim 1 , which has a turnover number in a range of 1500-2500 and a turnover frequency in a range of 200-1500 per hour.1020-. (canceled) This application claims the benefit of priority from U.S. Provisional Application No. 62/313,849 filed Mar. 25, 2016, the entire contents of which are herein incorporated by reference.The present disclosure relates to a solid-supported catalyst ligand and palladium (II) complexes and catalyst compositions thereof. Additionally, the present disclosure relates to methods for producing the solid-supported catalyst ligand and methods employing its complexes to catalyze chemical transformations including palladium cross-coupling reactions.The “background” description provided herein is for the purpose of generally presenting the context of the disclosure. Work of the presently named inventors, to the extent it ...

ARYL HALIDE CROSS-COUPLING METHOD AND PRODUCT MADE THEREFROM

A solid-supported catalyst ligand which chelates palladium (II) species to form a complex that functions as a heterogeneous catalyst that is stable and can be recycled without significantly losing any catalytic activity in a variety of chemical transformations, a method for producing the solid-supported catalyst ligand and a method for catalyzing a palladium cross-coupling reaction, such as the Suzuki-Miyaura, Mizoroki-Heck, and Sonagashira reactions. 113-. (canceled)15: The method of claim 14 , wherein{'sub': 1', '2', '3, 'each Rand Ris —CH;'}{'sub': 3', '4', '3', '6, 'each R, R, R, and Ris —H;'}X is O;and{'sup': '+2', 'sub': 2', '2, 'the Pdspecies having the formula PdZis PdCl.'}16: The method of claim 14 , further comprising:separating the solid-supported catalyst from the palladium cross-coupling product to recover the solid-supported catalyst; andreusing the solid-supported catalyst in at least 2 reaction cycles with a less than 10% decrease in at least one selected from the group consisting of a turnover number and a turnover frequency.17: The method of claim 14 , wherein a molar yield of the palladium cross-coupling product is at least 75% relative to an initial molar amount of the aryl halide.18. (canceled)19: The method of claim 14 , wherein the palladium cross-coupling product comprises less than 100 ppb palladium claim 14 , based on the total weight of the palladium cross-coupling product or derivatives thereof.20. (canceled) This application claims the benefit of priority from U.S. Provisional Application No. 62/313,849 filed Mar. 25, 2016, the entire contents of which are herein incorporated by reference.The present disclosure relates to a solid-supported catalyst ligand and palladium (II) complexes and catalyst compositions thereof. Additionally, the present disclosure relates to methods for producing the solid-supported catalyst ligand and methods employing its complexes to catalyze chemical transformations including palladium cross-coupling reactions ...

N-heterocyclic carbene type palladium catalyst and its preparation method as well as applications

The present invention relates to an n-heterocyclic carbene (NHC) type palladium catalyst and its preparation method as well as applications. Its preparation process is as below: select glyoxal as the raw material to synthesize glyoxaldiimine in the presence of Lewis acid or Bronsted acid, and then react with paraformaldehyde to get the NHC type ligand. Use palladium (II) to react with the compound containing carbon-nitrogen double bonds to get palladium (II) cyclic dimer; make the palladium cyclic dimer and the NHC type ligand coordinated to get the NHC type palladium catalyst. The palladium catalyst with a brand new structure according to the present invention, boasts high activity and multi-purpose. In addition, it shows excellent reaction activity in a lot of catalytic-coupling reactions including Suzuki-Miyaura, Heck, Buchwald-Hartwig, Kumada-Tamao-Corriu, Sonogashira, Negishi and α-ketone arylation reactions, and some reactions even can be carried out with the presence of an extremely low concentration of catalyst, exhibiting favorable industrialization prospect.

CATALYST SYSTEMS FOR USE IN CONTINUOUS FLOW REACTORS AND METHODS OF MANUFACTURE AND USE THEREOF

The present application provides a composite material and system for use in a heterogeneous flow reactor, which can include: a catalytic polymeric framework comprising catalyst-containing monomeric units each separated by at least one non-catalyst-containing monomeric unit; and a solid support material, wherein the catalytic polymeric framework is covalently or non-covalently immobilized on or in the support material. Each catalyst-containing monomeric subunit in the polymeric framework comprises a transition metal bound to a catalyst ligand. Also provided are methods of manufacture and use of the catalyst system and composite material. 133-. (canceled)35. The system of claim 34 , wherein the catalyst-containing monomer subunits comprise a diphosphine ligand.40. The system of claim 39 , wherein A is a binaphthyl group claim 39 , or a derivative of a binaphthyl group claim 39 , each being unsubstituted or substituted with one or more groups independently selected from Calkyl claim 39 , OCalkyl and halo.42. The system of any one of claim 34 , wherein the transition metal is Cr claim 34 , Mo claim 34 , Fe claim 34 , Ru claim 34 , Os claim 34 , Co claim 34 , Rh claim 34 , Ir claim 34 , Ni claim 34 , Pd claim 34 , Pt claim 34 , Cu claim 34 , Ag claim 34 , and/or Au.44. The system claim 34 , wherein the solid support material comprises BaSO claim 34 , barium (L)- and (D)-tartrates claim 34 , aluminum oxide (AlO) claim 34 , silica (SiO) claim 34 , FeO claim 34 , Teflon™ claim 34 , Celite™ claim 34 , AgCl claim 34 , sand claim 34 , or any combination thereof.45. The system of claim 34 , wherein the flow reactor is a continuous flow reactor claim 34 , such as an H-Cube® reactor.46. The system of claim 34 , which additionally comprises means for generating active catalyst.47. The system of claim 46 , wherein the means for generating active catalyst comprises a silver salt claim 46 , such as AgSbF.48. A method for metal-catalyzed organic synthesis comprising flowing a ...

METHOD FOR SYNTHESIZING INDOMETHACIN AND ANALOGUE THEREOF

The present disclosure belongs to the technical field of indomethacin synthesis, and discloses a method for synthesizing an indomethacin and an analogue thereof. The method for synthesizing an indomethacin and an analogue thereof includes steps of: introducing an alkyl group, an aromatic ring or a heteroaromatic ring directly at the C2 position of indole, a carboxylic acid fragment at the C3 position of the indole, and an aroyl group at the N1 position of the indole through palladium-catalyzed reactions. The present disclosure solves a problem: most of the existing indomethacin synthesis methods are achieved by construction of an indole ring and modification; simple structural changes of an indomethacin molecule based on this synthetic strategy often require de novo synthesis; the late modification and structure-activity relationship study of the indomethacin molecule have lengthy synthetic steps. 1. A method for synthesizing an indomethacin and analogues thereof , wherein the method comprises the steps of:introducing an alkyl group, an aromatic ring or a heteroaromatic ring directly at the C2 position of an indole, introducing a carboxylic acid fragment at the C3 position of the indole, and introducing an aroyl group at the N1 position of the indole through palladium-catalyzed reactions.3. The method for synthesizing an indomethacin and analogues thereof according to claim 2 , wherein in the chemical formulas: R claim 2 , R claim 2 , R claim 2 , R claim 2 , and Rare either identical or different; Ris selected from the group consisting of alkyl group claim 2 , alkoxy group claim 2 , halogen claim 2 , ester group claim 2 , amide claim 2 , amino group claim 2 , a substituted aromatic or heteroaromatic ring at one or more of the C4 claim 2 , C5 claim 2 , C6 and C7 positions of the indole 1 claim 2 , either mono-substituted or poly-substituted; Ris a fragment in a halogenated compound used in reaction (2) and is selected from the group consisting of alkyl group claim 2 ...

Method of preparing metal complexes of formula Z-M, in particular carbene-metal complexes

The present invention relates to an improved method of preparing metal complexes, in particular carbene-metal complexes. The method comprises the step of subjecting a salt of formula Z—X and a non-ionic metal salt of formula MLor subjecting a metallate of formula Z . . . MLX to a mechanical mixing process in the presence of a base. The method allows to formation of heterocyclic carbene metal complexes such as a nitrogen-containing heterocyclic carbene (NHC)-metal complexes. The invention also relates to the use of metal complexes, in particular carbene-metal complexes such as heterocyclic carbene-metal complexes obtainable by the method according to the present invention as catalysts. 1. A method of preparing a metal complex of formula Z-M , the method comprising the steps of{'sup': +', '−, 'sub': 'n', 'i1) providing a salt of formula Z—X and a non-ionic metal salt of formula ML; or'}{'sup': +', '−, 'sub': 'n', 'claim-text': with', 'Z comprising a two-electron donor ligand;', 'X comprising an anion;', 'M comprising a metal;', 'L comprising an anion or an electron donor ligand;', 'and, 'i2) providing a metallate of formula Z. . . MLX,'}{'sup': +', '−', '+', '−, 'sub': 'n', 'ii) subjecting the salt of formula Z—X and the metal salt of formula ML of step i1) or the metallate of formula Z. . . MLX, of step i2) to a mechanical mixing process in the presence of a base to form said metal complex of formula Z-M.'}2. The method according to claim 1 , wherein said method does not require the use of a solvent.3. The method according to claim 1 , wherein said salt of formula Z—X of step i1) has a single two-electron donor ligand Z or wherein said metallate of formula Z. . . MLX of step i2) has a single two-electron donor ligand Z.4. The method according to claim 1 , wherein said non-ionic metal salt of formula ML comprises a single metal M.5. The method according to claim 1 , wherein said metal complex of formula Z-M has a single two-electron donor ligand Z.6. The method ...

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

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

Novel isocyanide compound and hydrosilylation reaction catalyst

A hydrosilylation reaction catalyst prepared from a catalyst precursor comprising a transition metal compound of groups 8, 9, or 10 of the periodic table, excluding platinum, such as an iron carboxylate, cobalt carboxylate, or nickel carboxylate, and a ligand comprising an isocyanide compound having an organosiloxane group.

Ylide-functionalised phosphanes for use in metal complexes and homogeneous catalysis

The invention relates to ylide-functionalized phosphane ligands, the production of same and use in transition metal compounds, as well as the use of same as catalysts in organic reactions.

METAL-ORGANIC FRAMEWORKS CONTAINING NITROGEN-DONOR LIGANDS FOR EFFICIENT CATALYTIC ORGANIC TRANSFORMATIONS

Metal-organic framework (MOFs) compositions based on nitrogen donor-based organic bridging ligands, including ligands based on 1,3-diketimine (NacNac), bipyridines and salicylaldimine, were synthesized and then post-synthetically metalated with metal precursors, such as complexes of first row transition metals. Metal complexes of the organic bridging ligands could also be directly incorporated into the MOFs. The MOFs provide a versatile family of recyclable and reusable single-site solid catalysts for catalyzing a variety of asymmetric organic transformations. The solid catalysts can also be integrated into a flow reactor or a supercritical fluid reactor. 1. A method for preparing a crystalline and porous metal-organic framework (MOF) , wherein said crystalline and porous MOF comprises periodic repeats of a metal-based secondary building unit (SBU) and a nitrogen donor-based bridging ligand , said method comprising:providing a nitrogen donor-based bridging ligand; andcontacting the nitrogen donor-based bridging ligand with a first metal source to obtain the crystalline and porous MOF.2. The method of claim 1 , wherein the nitrogen donor-based bridging ligand is a derivative of one of the nitrogen donor moieties selected from the group comprising bipyridines claim 1 , phenanthrolines claim 1 , terpyridines claim 1 , salicylaldimines claim 1 , pyridylphenols claim 1 , 1 claim 1 ,3-diketimine (NacNac) claim 1 , and bis(oxazolines).3. The method of claim 1 , wherein the nitrogen donor-based bridging ligand is a derivative of a nitrogen donor moiety claim 1 , wherein the nitrogen donor moiety is substituted by one or more substituents selected from a carboxylate claim 1 , pyridine claim 1 , and/or phosphonate moiety.4. The method of claim 3 , wherein the nitrogen donor-based bridging ligand is a dicarboxylate claim 3 , a tricarboxylate claim 3 , a tetracarboxylate claim 3 , a bipyridine claim 3 , a tripyridine claim 3 , a tetrapyridine claim 3 , a diphosphonate claim 3 , ...

METHOD FOR COUPLING A FIRST COMPOUND TO A SECOND COMPOUND

The present disclosure describes a method of coupling a first compound to a second compound, the method comprising: providing the first compound having a fluorosulfonate substituent; providing the second compound comprising an amine; and reacting the first compound and the second compound in a reaction mixture, the reaction mixture including a catalyst having at least one group 10 atom, the reaction mixture under conditions effective to couple the first compound to the second compound. The present disclosure further describes a one-pot method for coupling a first compound to a second compound. 1. A method of coupling a first compound to a second compound , the method comprising:providing the first compound having a fluorosulfonate substituent, the first compound comprising an aryl or a heteroaryl group;providing the second compound comprising an amine; andreacting the first compound and the second compound in a reaction mixture, the reaction mixture including a catalyst having at least one group 10 atom, the reaction mixture under conditions effective to couple the first compound to the second compound.2. The method of claim 1 , wherein the reaction mixture further includes a ligand.3. The method of wherein the catalyst is generated in-situ from a palladium precatalyst.4. The method of wherein the catalyst is generated in-situ from a palladium precatalyst claim 3 , the palladium precatalyst is selected from the group consisting of: Palladium(II) acetate claim 3 , Palladium(II) chloride claim 3 , Dichlorobis(acetonitrile)palladium(II) claim 3 , Dichlorobis(benzonitrile)palladium(II) claim 3 , Allylpalladium chloride dimer claim 3 , Palladium(II) acetylacetonate claim 3 , Palladium(II) bromide claim 3 , Bis(dibenzylideneacetone)palladium(0) claim 3 , Bis(2-methylallyl)palladium chloride dimer claim 3 , Crotylpalladium chloride dimer claim 3 , Dichloro(1 claim 3 ,5-cyclooctadiene)palladium(II) claim 3 , Dichloro(norbornadiene)palladium(II) claim 3 , Palladium(II) ...

Catalytic ester decarbonylation

A process of preparing olefins of the formula (I) is described herein: with R 1 being a substituted or unsubstituted (C 1 -C 30 )hydrocarbyl, and R 2 being a substituted or unsubstituted (C 1 -C 20 )hydrocarbyl. The process includes reacting a compound of formula (II) wherein Ar is chosen from in the presence of a palladium-based catalyst and an organic solvent. A process of preparing olefins of the formula (III) is also described: with R 3 being a substituted or unsubstituted (C 1 -C 30 )hydrocarbyl, R 4 being a substituted or unsubstituted (C 1 -C 20 )hydrocarbyl, and R 5 being a substituted or unsubstituted (C 1 -C 30 ) hydrocarbyl. The process includes reacting a compound of formula (IV) wherein Ar is chosen from with a compound of formula (V) wherein Ar is chosen from in the presence of a palladium-based catalyst and an organic solvent.

Carbon Dioxide as a Directing Group for C-H Functionalization Reactions Involving Lewis Basic Amines, Alcohols, Thiols, and Phosphines for the Synthesis of Compounds

Methods of synthesizing compounds using COas a directing group for C—H functionalization, and compounds made thereby, are described. 1. A method of functionalizing a C—H bond , the method comprising using COas a directing group to convert a C—H bond in a substrate compound into a C—C , C—B , C—N , C—O , C—F , C—Cl , C—Br , C—I , C—P , or C—S bond , wherein the substrate compound comprises an amine , alcohol , thiol , or phosphine functional group.2. The method of claim 1 , wherein the C—H bond is in a γ-position relative to the amine claim 1 , alcohol claim 1 , thiol claim 1 , or phosphine functional group.3. The method of claim 1 , wherein the substrate compound is reacted with a reactant in the presence of COand a transition metal catalyst.4. The method of claim 3 , wherein the transition metal catalyst comprises palladium.5. The method of claim 1 , wherein the amine is a primary amine.6. The method of claim 5 , wherein the primary amine is selected from the group consisting of: 1-ethylcyclopentan-1-amine (S-1) claim 5 , 1-ethylcyclohexan-1-amine (S-2) claim 5 , 1-ethylcycloheptan-1-amine (S-3) claim 5 , 4-(tert-butyl)-1-ethylcyclohexan-1-amine (S-4) claim 5 , 9-ethyl-9H-fluoren-9-amine (S-5) claim 5 , 3-methylheptan-3-amine (S-6) claim 5 , 3-methylnon-3-amine (S-7) claim 5 , 3-methylpentan-3-amine (S-8) claim 5 , 3-ethylpentan-3-amine (S-9) claim 5 , and heptan-3-amine (S-10).7. The method of claim 1 , wherein the amine is a secondary amine.8. The method of claim 7 , wherein the secondary amine is selected from the group consisting of: N-(tert-pentyl)propan-1-amine (S-12) claim 7 , N-(tert-pentyl)butan-1-amine (S-13) claim 7 , N-(tert-pentyl)pentan-1-amine (S-14) claim 7 , 2-methyl-N-phenethylbutan-2-amine (S-15) claim 7 , N-benzyl-2-methylbutan-2-amine (S-16) claim 7 , N-(4-methoxybenzyl)-2-methylbutan-2-amine (S-17) claim 7 , N-(3-methoxybenzyl)-2-methylbutan-2-amine (S-18) claim 7 , N-(4-tolyl)-2-methylbutan-2-amine (S-19) claim 7 , N-(3-tolyl)-2-methylbutan-2 ...

PRODUCTION METHOD OF POLYMER COMPOUND

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

PHOSPHORUS-CONTAINING CATALYSTS

The invention provides compounds of general structure I: (Ar—Ar—Ar-E-P(=D)R-)MXL″. In this structure: •Ar, Arand Arare aromatic groups wherein: —Arand Arare in a 1,3 relationship on Ar, —each of Ar, Arand Aroptionally comprises one or more ring substituents of formula YR′wherein each Y independently is absent or is O, S, B, N or Si and each R′ is independently H, halogen, alkyl, cycloalkyl, aryl or heteroaryl and r is 1, 2 or 3, where r is 1 if Y is absent or is O or S, 2 if Y is B or N and 3 if Y is Si, —Ar, Arand Arare each independently carbocyclic or heterocyclic and each is independently monocyclic, bicyclic or polycyclic and each ring of each of Ar, Arand Arindependently has 5, 6 or 7 ring atoms; •E is absent or is selected from the group consisting of O, S, NR″, SiR″, AsR″and CR″; •M is a complexing metal; •X is selected from the group consisting of H, F, Br, CI, I, OTf, dba (dibenzylidene acetone), OC(═O)CFand OAc; •L is selected from the group consisting of PR″, NR″, OR″, SR″, SiR″, AsR″, alkene, alkyne, aryl and heteroaryl, each of said alkene, alkyne, aryl and heteroaryl being optionally substituted, for example with one or more halogens and/or with one or more R groups as defined herein; •each R is independently alkyl, cycloalkyl, heterocyclyl, heterocycloalkyl, aryl or -, heteroaryl; •D is absent or is ═S or —O or —Z-linker-Z—, where each Z independently is O or NH or N-alkyl and linker is an alkyl chain of 2-5 carbon atoms in length; •each R″ is independently H, alkyl, cycloalkyl, heterocycloalkyl, aryl or heteroaryl, each other than H being optionally substituted, or R″is —Z-linker-Z— as defined above; and •m is 0 or 1 or 2; wherein if m is 0, n is 1, n′ and n″ are 0 and -- is absent; and if m is 1 or 2, n is 1 or 2 and n′ and n″ are integers such that the coordination sphere of M is filled, and D is absent. 2. The compound of wherein m is 1 or 2 and M is bonded to a ring atom of Arortho to E.3. The compound of or wherein E is O or S or NR″.4. The ...

ORGANOMETALLIC COMPLEX CATALYST

An organometallic complex catalyst is disclosed for use in a cross-coupling reaction. In formula (1), M is the coordination center and represents a metal atom such as Pd or an ion thereof. R, R, and Rmay be the same or different and are a substituent such as a hydrogen atom. R, R, R, and Rmay be the same or different and are a substituent such as a hydrogen atom. X represents a halogen atom. Rrepresents a substituent that has a π bond and 3-20 carbon atoms. With regard to the electron-donating properties of R-Rwith respect to the coordination center M of the ligand containing R-Rthat is indicated in formula (2), R-Rare arranged in combination such that the TEP value obtained from infrared spectroscopy shifts toward the low frequency side compared to the TEP value of the ligand of formula (2-1). 3. The organometallic complex catalyst according to claim 1 , which is used in a C—N cross-coupling reaction.7. The ligand according to claim 5 , wherein the organometallic complex catalyst represented by the formula (1) is used in a C—N cross-coupling reaction. The present invention relates to an organometallic complex catalyst for use in a cross-coupling reaction. More specifically, the present invention relates to an organometallic complex catalyst for use in a cross-coupling reaction which has a ligand having a nitrogen-containing heterocyclic carbene structure.Aromatic amines are widely used in medicines, pesticides and electronic materials.As methods for synthesizing the aromatic amines, a method for synthesizing through a C—N coupling reaction by using a palladium complex catalyst has been reported (for example, Non-Patent Documents 1 to 3).Furthermore, in order to proceed the C—N coupling reaction more efficiently, there has been proposed a Pd complex catalyst having a ligand which contains a structure of nitrogen-containing heterocyclic carbene (N-Heterocyclic Carbene, hereinafter referred to as “NHC”, as occasion demand).The ligand containing the structure of the ...

Process for pd-catalyzed hydroxycarbonylation of diisobutene: ratio of 3,5,5-trimethylhexanoic acid/h20

Process for Pd-catalyzed hydroxycarbonylation of diisobutene: ratio of 3,5,5-trimethylhexanoic acid/H2O.

Process for pd-catalyzed hydroxycarbonylation of diisobutene: effect of solvent

Process for Pd-catalyzed hydroxycarbonylation of diisobutene: Effect of solvent

PYRIDINIUM OXAZOLE DYAD SCAFFOLD AND A PROCESS FOR PREPARATION THEREOF

The present invention relates to a pyridinium oxazole dyad scaffold of formula (I) and a process for the preparation thereof. The present invention further discloses a pyridine compound of formula (II) which is used for the preparation of formula (I) and a process for preparation thereof. 13.-. (canceled)58.-. (canceled)9. A process for the preparation of pyridine compound of formula (II) as claimed in claim 4 , wherein said process comprising the steps of:a) degassing the reaction mixture consisting of pyridine derivative, boronic acid in suitable solvent with nitrogen;b) adding sodium carbonate or potassium carbonate, Palladium catalyst to the reaction mixture of step a under continuous flow of nitrogen;c) heating the reaction mixture of step b at the temperature ranging from 70 to 80° C. for 4 to 10 hours to afford desired product of formula (II).10. The process as claimed in claim 9 , wherein said boronic acid of step (a) is 2 allkynyl phenyl boronic acid and said solvent of step (a) is DMF/HO in a ratio of 1:1 and the said catalyst of step (b) is PdCl(PPh). This application is a divisional of U.S. application Ser. No. 16/343,260 filed Apr. 18, 2019, which is a 35 U.S.C. § 371 National Phase of PCT Application No. PCT/IN2017/050480 filed Oct. 17, 2017, which claims priority to Indian Application No. 201611035581 filed Oct. 18, 2016. The disclosures of these applications are incorporated in their entireties herein by reference.The present invention relates to a Pyridinium oxazole dyad scaffold of formula (I) and a process for the preparation thereof.The discovery and development of organic fluorophores is essential for progress in many areas of chemistry, biology and functional materials research. As an emerging subclass, fluorescent organic salts are gaining much attention because of their unique properties. Because of their charged nature, they impart high thermal stabilities, phase tunabilities, water-solubility and chemoselective sensing via electrostatic ...

METHOD FOR PALLADIUM-CATALYZED CINAMMIC ACID FORMATION

A solid-supported palladium(II) complex which catalyzes the Mizoroki-Heck coupling reaction efficiently and a method of employing the solid-supported palladium(II) complex to synthesize cinnamic acid and derivatives thereof. The solid-supported palladium(II) complex is also stable and can be recycled without significantly losing catalytic activity. 18-. (canceled)10. The method of claim 9 , further comprising:separating the solid-supported catalyst from the cinnamic acid; andreusing the solid-supported catalyst in at least two cycles, wherein the solid-supported catalyst loses less than 5 wt % of the palladium after the at least two cycles.11. The method of claim 9 , wherein the aryl halide is a limiting reactant.12. The method of claim 9 , wherein an amount of the solid-supported catalyst is in a range of 0.05-10 mol % relative to a number of moles of the aryl halide.13. The method of claim 9 , wherein the solvent comprises 5-95% by volume of water and 5-95% by volume of an organic solvent claim 9 , based on a total volume of the solvent.1419-. (canceled) This project was funded by the National Plan for Science, Technology and Innovation (MARIFAH)-King Abdulaziz City for Science and Technology—through the Science & Technology Unit at King Fahd University of Petroleum & Minerals (KFUPM), the Kingdom of Saudi Arabia, award number (14-PET2737-04).The present disclosure relates to a solid-supported palladium(II) complex which catalyzes the Mizoroki-Heck coupling reaction and a method of employing the solid-supported palladium(II) complex to synthesize cinnamic acid and derivatives thereof.The “background” description provided herein is for the purpose of generally presenting the context of the disclosure. Work of the presently named inventors, to the extent it is described in this background section, as well as aspects of the description which may not otherwise qualify as prior art at the time of filing, are neither expressly or impliedly admitted as prior art against ...

PALLADIUM(II)-SILICA SUPPORTED CATALYST

A solid-supported palladium(II) complex which catalyzes the Mizoroki-Heck coupling reaction efficiently and a method of employing the solid-supported palladium(II) complex to synthesize cinnamic acid and derivatives thereof. The solid-supported palladium(II) complex is also stable and can be recycled without significantly losing catalytic activity. 13-. (canceled)5. (canceled)6. silica-supported catalyst of claim 4 , wherein the solid silica support is in the form of a particle with an average diameter of 1-100 μm.7. The silica-supported catalyst of claim 4 , which comprises 0.1-1 mmol of palladium per gram of the silica-supported catalyst.8. The silica-supported catalyst of claim 4 , which has a turnover number in a range of 1 claim 4 ,500-2 claim 4 ,500 and a turnover frequency in a range of 200-1 claim 4 ,500 per hour.9. A method for synthesizing cinnamic acid or derivatives thereof claim 4 , the method comprising:{'claim-ref': {'@idref': 'CLM-00004', 'claim 4'}, 'reacting an aryl halide with an acrylic acid or derivatives thereof in the presence of a solvent, a base, and the silica-supported catalyst of at a temperature in a range of 35-110° C., thereby forming the cinnamic acid or derivatives thereof.'}10. The method of claim 9 , further comprising:separating the silica-supported catalyst from the cinnamic acid or derivatives thereof; andreusing the silica-supported catalyst in at least two cycles, wherein the silica-supported catalyst loses less than 5 wt % of the palladium after the at least two cycles.11. The method of claim 9 , wherein the aryl halide is a limiting reactant.12. The method of claim 9 , wherein an amount of the silica-supported catalyst is in a range of 0.05-10 mol % relative to a number of moles of the aryl halide.13. The method of claim 9 , wherein the solvent comprises 5-95% by volume of water and 5-95% by volume of an organic solvent claim 9 , based on a total volume of the solvent.14. (canceled)15. The method of claim 9 , wherein the ...