- HETEROGENEOUS HYDROCYANATION
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The present invention relates to an improved process for addition of hydrogen cyanide across olefins and, in particular, to the use of a specific aluminum oxide to catalyze the reaction. The aluminum oxide catalyst must have total alkali metal and/or alkaline earth metal content, measured in the form of alkali metal oxide and/or alkaline earth metal oxide, of less than 3,000 ppm by weight.
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Paragraph 00031; 00032
(2015/07/07)
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- METHOD FOR PRODUCING NITRILE COMPOUNDS FROM ETHYLENICALLY UNSATURATED COMPOUNDS
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The present invention relates to a method for the hydrocyanation of organic ethylenically unsaturated compounds including at least one nitrile function. The invention specifically relates to a method for the hydrocyanation of a hydrocarbon compound including at least one ethylenic unsaturation by a reaction with hydrogen cyanide in a liquid medium and in the presence of a catalyst including a metal element selected from the transition metals and an organophosphorous ligand, the organophosphorous gaud including a compound of general formula (I), where R1 and R2, which are identical or different, are a linear or branched alkyl radical having 1-12 carbon atoms, which can include heteroatoms, or an optionally substituted aromatic or cycloaliphatic radical that can include heteroatoms, wherein the covalent bond between P and R1, and that between P and R2, are P—C bonds.
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Paragraph 0081-0088
(2014/09/16)
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- PROCESS FOR THE PRODUCTION OF NITRILE COMPOUNDS FROM ETHYLENICALLY UNSATURATED COMPOUNDS
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A method is described for the hydrocyanation of organic ethylene-unsaturated compounds into compounds including at least one nitrile function. Also described, is a method for the hydrocyanation of a hydrocarbon compound including at least one ethylenic unsaturation by reaction in a liquid medium with hydrogen cyanide in the presence of a catalyst including a metal element selected from among the transition metals and an organophosphorous ligand including, in one embodiment of the invention, an organophosphorous compound. The described method can be used in particular for the synthesis of adiponitrile from butadiene.
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Paragraph 0117-0124
(2013/03/26)
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- ORGANOPHOSPHORUS COMPOUNDS, CATALYTIC SYSTEMS COMPRISING SAID COMPOUNDS AND METHOD OF HYDROCYANATION USING SAID CATALYTIC SYSTEMS
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The present invention relates to organophosphorus compounds belonging to the phosphinite-phosphite family, catalytic systems comprising a metallic element forming a complex with said phosphinite-phosphite compounds and methods of hydrocyanation employed in the presence of said catalytic systems.
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Paragraph 0104-0110
(2013/03/26)
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- PROCESS FOR PRODUCING COMPOUNDS COMPRISING NITRILE FUNCTIONS
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The present invention relates to a process for producing compounds comprising at least one nitrile function by hydrocyanation of a compound comprising at least one non-conjugated unsaturation. The invention proposes a process for producing compounds comprising at least one nitrile function by hydrocyanation of an organic compound comprising at least one non-conjugated unsaturation, comprising from 2 to 20 carbon atoms, by reaction with hydrogen cyanide in the presence of a catalytic system comprising a complex of nickel having the oxidation state of zero with at least one organophosphorus ligand chosen from the group comprising organophosphites, organophosphonites, organophosphinites and organosphosphines and a cocatalyst of the Lewis acid type.
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Page/Page column 3
(2012/01/14)
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- Stable fluorophosphines: Predicted and realized ligands for catalysis
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Ligand maps lead to treasure! The activity of complexes of fluorophosphines (R2PF) in catalytic hydroformylation and hydrocyanation is predicted from a ligand map. However, the instability of R2PF to disproportionation is well-documented. Examples of R2PF ligands (see scheme) are described that are stabilized to such an extent that they can be used in catalysis and are shown to be highly effective.
- Fey, Natalie,Garland, Michael,Hopewell, Jonathan P.,McMullin, Claire L.,Mastroianni, Sergio,Orpen, A. Guy,Pringle, Paul G.
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supporting information; experimental part
p. 118 - 122
(2012/03/26)
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- Cage phosphinites: Ligands for efficient nickel-catalyzed hydrocyanation of 3-pentenenitrile
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The cage monophosphinites CgPOR {where CgP = 6-phospha-2,4,8-trioxa- adamantane and R = C6H5 (La); 2-C 6H4CH3 (Lb); 2,4,6-C 6H2(CH3)3 (Lc); 2,4-C6H3tBu2 (Ld); CH3 (Le); CH2CF3 (Lf)} and diphosphinites CgPZPCg {where ZH2 = 2,2′-biphenol (L g) or 1,2-benzenedimethanol (Lh)} have been made from CgPBr and the corresponding alcohol or phenol. The cage phosphinites are remarkably stable to water. All the ligands La-h have been tested for nickel(0)-catalyzed hydrocyanation of 3-pentenenitrile in the presence of Lewis acids (ZnCl2, Ph2BOBPh2, or iBu2AlOAliBu2), and tentative structure-activity relationships are suggested. The hydrocyanation activities obtained with catalysts derived from monophosphinite Lf (with iBu2AlOAliBu2) and diphosphinite Lh (with ZnCl2) are comparable with the commercial catalyst based on P(OTol)3. The complexes trans-[PtCl 2(L)2] where L = La (1a), Le (1e), and Lf (1f) and the chelate cis-[PtCl2(Lh)] (1h) are reported. From the νCO values for the complexes trans-[RhCl(CO)(La-f)2] (2a-f), it is concluded that ligand Lf is the most phosphite-like of the monophosphinites. Treatment of [Ni(cod)2] (cod = 1,5-cyclo-octadiene) with L h leads to a mixture of products, one of which was characterized as the binuclear [Ni2(Lh)2(μ-cod)] (3h). The crystal structures of Lh, 1a, 1e, 1f, 1h?2CH2Cl 2, and 3h?3C6H5CH3 are reported.
- Mikhel, Igor S.,Garland, Michael,Hopewell, Jonathan,Mastroianni, Sergio,McMullin, Claire L.,Orpen, A. Guy,Pringle, Paul G.
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experimental part
p. 974 - 985
(2011/05/04)
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- PREPARATION OF NITRILES FROM ETHYLENICALLY UNSATURATED COMPOUNDS
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A process for the hydrocyanation of a hydrocarbon-based compound having at least one site of ethylenic unsaturation into a nitrile compound includes reaction thereof, in a liquid medium, with hydrogen cyanide in the presence of a catalyst containing a metal element selected from among the transition metals and an organophosphorus ligand, wherein the organophosphorus ligand is a mixture of at least one monodentate organophosphite compound and at least one monodentate organophosphine compound; the subject process is especially useful for the synthesis of adiponitrile from butadiene.
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Page/Page column 4-5
(2011/07/29)
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- HYDROCYANATION OF PENTENENITRILES
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The invention provides a hydrocyanation process to produce adiponitrile and other dinitriles having six carbon atoms, in the presence of catalyst composition comprising a zero-valent nickel and at least one bidentate phosphorus-containing ligand wherein the bidentate phosphorus-containing ligand gives acceptable results according to at least one protocol of the 2-Pentenenitrile Hydrocyanation Test Method.
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Page/Page column 32-33
(2009/07/25)
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- HYDROCYANATION OF 2-PENTENENITRILE
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The invention provides a process for hydrocyanation, comprising: contacting 2-pentenenitrile with hydrogen cyamide at a temperature in the range of about 0° C. to about 150° C. in the presence of at least one Lewis acid promoter and a catalyst precursor composition, wherein the catalyst precursor composition comprises a zero-valent nickel and at least one bidentate phosphite ligand selected from a member of the group represented by Formula I and Formula II, in which all like reference characters have the same meaning, except as further explicitly limited: wherein R1 and R5 are independently selected from the group consisting of C1 to C5 hydrocarbyl; and R2, R3, R4, R6, R7 and R8 are independently selected from the group consisting of H and C1 to C4 hydrocarbyl.
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Page/Page column 7
(2008/06/13)
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- Process for the Preparation of Dinitriles
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The present invention relates to a process for the preparation of dinitriles by hydrocyanation of unsaturated nitrile compounds in the presence of a catalyst based on a metal element in the zero oxidation state and on organophosphorus ligands;the invention relates more particularly to a process for the recovery from the hydrocyanation medium of a catalyst for the hydrocyanation of unsaturated nitrites to dinitriles. It consists in controlling the concentration of unsaturated nitrites in the reaction medium resulting from the hydrocyanation reaction in order to obtain a concentration by weight of unsaturated nitrites of less than 20% in the said medium, and in then feeding the said medium to a stage of settling into two upper and lower phases. The lower phase comprises most of the catalytic system, while the upper phase is composed essentially of the dinitriles.
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Page/Page column 4-5
(2008/06/13)
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- Process for preparing nitrile compounds from ethylenically unsaturated compounds
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The present invention concerns a process for hydrocyanating ethylenically unsaturated organic compounds to compounds containing at least one nitrile function. It relates more particularly to the hydrocyanation of diolefins such as butadiene or of substituted olefins such as alkenenitriles, for instance pentenenitriles. According to the process of the invention the reaction is implemented in the presence of a metal complex catalyst comprising a transition metal such as nickel and an organic ligand.
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Page/Page column 37
(2008/06/13)
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- Design of ionic phosphites for catalytic hydrocyanation reaction of 3-pentenenitrile in ionic liquids
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The synthesis and characterization of a novel class of ionic phosphites bearing either a single cationic group obtained by quaternization of aminophosphites or three cationic groups prepared by reaction of phosphorus trichloride with imidazolium phenols are reported. The catalytic hydrocyanation reaction of 3-pentenenitrile (3PN) into adiponitrile has been performed in the presence of Ni(0) with ionic phosphite ligands, and a Lewis acid in biphasic ionic liquid/organic solvent system. The screening of several original cationic phosphites was performed and the experimental conditions were optimized for the tricationic phosphite tris-4-[(2,3-dimethylimidazol-1-yl) methyl]phenyl phosphite tris[bis(trifluoromethylsulfonyl)amide]. It is possible to obtain performance similar to molecular systems and the catalyst and the Lewis acid were immobilized in the ionic phase.
- Vallee, Christophe,Chauvin, Yves,Basset, Jean-Marie,Santini, Catherine C.,Galland, Jean-Christophe
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p. 1835 - 1847
(2007/10/03)
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- Ligand descriptor analysis in nickel-catalysed hydrocyanation: A combined experimental and theoretical study
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The problem of choosing the 'right chelating ligand' for a homogeneously catalysed reaction is outlined. A model is introduced that combines mechanistic information and ligand descriptors. This model is used together with automated synthesis tools to study the structure-activity relationship in a diverse set of forty-two ligands, and extract information on active regions in the catalyst space. The concept is demonstrated on nickel-catalysed hydrocyanation, using bidentate phosphine and phosphite ligands. The charge at the ligating atoms, the rigidity of the molecules, the steric crowding around the Ni atom, and the bite angle are found to be the most important descriptors. A comparison is made with literature hydrocyanation data and approaches for designing new homogeneous catalysts are discussed.
- Burello, Enrico,Marion, Philippe,Galland, Jean-Christophe,Chamard, Alex,Rothenberg, Gadi
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p. 803 - 810
(2007/10/03)
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- Hydrocyanation method for ethylenically unsaturated organic compounds
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The invention concerns a method for hydrocyanation of ethylenically unsaturated organic compounds into compounds comprising at least a nitrile function. More particularly, it concerns a method for hydrocyanation of organic compounds comprising at least a ethylenical bond by reacting hydrogen cyanide, in the presence of a catalytic system comprising a transition metal and an organophosphorus ligand. The organophosphorus ligand is a compound with monophosphanorbornadiene structure. The invention concerns in particular hydrocyanation of butadiene into adiponitrile.
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