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Efficient nickel-catalyzed hydrocyanation of alkenes using acetone cyanohydrin as a safer cyano source
An active nickel catalyst prepared in situ from a Ni(II) compound, phosphine ligand, and zinc powder was found to be an efficient catalyst system for the hydrocyanation of various alkenes using acetone cyanohydrin as a safer cyano source. The combination of NiCl2·6H2O and 1,3-bis(diphenylphosphino)propane was the most efficient catalyst precursor in DMF. Under the optimized conditions, various styrenes, heterocyclic alkenes, and aliphatic alkenes were converted to their corresponding nitriles in excellent yields.
Nemoto, Koji,Nagafuchi, Tsuyoshi,Tominaga, Ken-ichi,Sato, Kazuhiko
p. 3199 - 3203
(2016/07/06)

Photoinduced, Copper-Catalyzed Carbon-Carbon Bond Formation with Alkyl Electrophiles: Cyanation of Unactivated Secondary Alkyl Chlorides at Room Temperature
We have recently reported that, in the presence of light and a copper catalyst, nitrogen nucleophiles such as carbazoles and primary amides undergo C-N coupling with alkyl halides under mild conditions. In the present study, we establish that photoinduced, copper-catalyzed alkylation can also be applied to C-C bond formation, specifically, that the cyanation of unactivated secondary alkyl chlorides can be achieved at room temperature to afford nitriles, an important class of target molecules. Thus, in the presence of an inexpensive copper catalyst (CuI; no ligand coadditive) and a readily available light source (UVC compact fluorescent light bulb), a wide array of alkyl halides undergo cyanation in good yield. Our initial mechanistic studies are consistent with the hypothesis that an excited state of [Cu(CN)2]- may play a role, via single electron transfer, in this process. This investigation provides a rare example of a transition metal-catalyzed cyanation of an alkyl halide, as well as the first illustrations of photoinduced, copper-catalyzed alkylation with either a carbon nucleophile or a secondary alkyl chloride.
Ratani, Tanvi S.,Bachman, Shoshana,Fu, Gregory C.,Peters, Jonas C.
supporting information
p. 13902 - 13907
(2016/01/15)

METHOD FOR PRODUCING NITRILE COMPOUNDS FROM ETHYLENICALLY UNSATURATED COMPOUNDS
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)

PROCESS FOR THE PRODUCTION OF NITRILE COMPOUNDS FROM ETHYLENICALLY UNSATURATED COMPOUNDS
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)

ORGANOPHOSPHORUS COMPOUNDS, CATALYTIC SYSTEMS COMPRISING SAID COMPOUNDS AND METHOD OF HYDROCYANATION USING SAID CATALYTIC SYSTEMS
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)

Stable fluorophosphines: Predicted and realized ligands for catalysis
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.
supporting information; experimental part
p. 118 - 122
(2012/03/26)

PROCESS FOR PRODUCING COMPOUNDS COMPRISING NITRILE FUNCTIONS
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)

NICKEL METAL COMPOSITIONS AND NICKEL COMPLEXES DERIVED FROM BASIC NICKEL CARBONATES
Nickel-metal-containing solids for use in manufacturing nickel metal complexes are disclosed. The nickel-metal-containing solids are made by reducing basic nickel carbonates. By varying the molar ratios of carbonates and bicarbonates to nickel salts, the methods provide basic nickel carbonates that produce superior nickel metal-containing solids that react more effectively with phosphorous-containing ligands. The phosphorous containing ligands can be both monodentate and bidentate phosphorous-containing ligands.
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Page/Page column 9

(2011/08/22)

Cage phosphinites: Ligands for efficient nickel-catalyzed hydrocyanation of 3-pentenenitrile
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.
experimental part
p. 974 - 985
(2011/05/04)

PREPARATION OF NITRILES FROM ETHYLENICALLY UNSATURATED COMPOUNDS
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)

HYDROCYANATION OF PENTENENITRILES
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)

Reactions in water: Alkyl nitrile coupling reactions using Fenton's reagent
(Chemical Equation Presented) The coupling reaction of water-soluble alkyl nitriles using Fenton's reagent (Fe(II) and H2O2) is described. The best metal for the reaction is iron(II), and the greatest yields are obtained when the concentration of the metal is kept low. Hydrogen-atom abstraction is selective, preferentially producing the radical α to the nitrile. In order to increase the production of dinitrile, in situ reduction of iron(III) to iron(II), using a variety of reducing agents, was investigated.
Keller, Christopher L.,Dalessandro, James D.,Hotz, Richard P.,Pinhas, Allan R.
p. 3616 - 3618
(2008/09/20)

HYDROCYANATION OF 2-PENTENENITRILE
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)

Process for preparing nitrile compounds from ethylenically unsaturated compounds
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)

STERICALLY HINDERED CHELATE PHOSPHINITE-PHOSPHITE LIGAND, CATALYST, COMPRISING AT LEAST ONE NICKEL(0) COMPLEX STABILIZED BY SAID LIGAND AND METHOD FOR PRODUCTION OF NITRILES
The invention relates to phosphinite phosphites I of formula 1, 2, 3, 4, 5 or 6 and mixtures thereof, wherein R1, R2, R4 independently represent an alkyl or alkylene group with 1 to 8 carbon atoms, provided that at least one of the groups R1, R2, R4 is different from H; R5 to R22 independently represent H, an alkyl or alkylene group with 1 to 8 carbon atoms; R3 is H, methyl or ethyl; X is F, Cl or CF3, if n = 1 or 2 and X is H, if n = 0.
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Page/Page column 22

(2008/06/13)

METHOD FOR PRODUCING 3-PENTENENITRILE
The invention relates to a method for producing 3-pentenenitrile, said method being characterised by the following steps: (a) 1,3-butadiene is reacted with hydrogen cyanide on at least one catalyst to obtain a flow (1) containing 3-pentenenitrile, 2-methyl-3-butenenitrile, the at least one catalyst, and 1,3-butadiene; (b) the flow (1) is distilled in a column to obtain a top product flow (2) rich in 1,3-butadiene, and a bottom product flow (3) that is poor in 1,3-butadiene and contains 3-pentenenitrile, the at least one catalyst, and 2-methyl-3-butenenitrile; (c) the flow (3) is distilled in a column to obtain a top product flow (4) containing 1,3-butadiene, a flow (5) in a side-tap of the column, containing 3-pentenenitrile and 2-methyl-3-butenenitrile, and a bottom product flow (6) containing the at least one catalyst; and (d) the flow (5) is distilled to obtain a top product flow (7) containing 2-methyl-3-butenenitrile, and a bottom product flow (8) containing 3-pentenenitrile.
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Page/Page column 32-35; sheet 4

(2008/06/13)

PRODUCTION OF 3-PENTENENITRILE FROM 1,3-BUTADIENE
The invention relates to a method for producing 3-pentenenitrile by means of the hydrocyanation of 1,3-butadiene, whereby 1,3-butadiene is reacted with hydrogen cyanide in the presence of at least one catalyst, and the resulting flow is purified by distillation, the bottom temperature not exceeding 140 °C during the distillation.
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Page/Page column 25-29; sheet 2

(2008/06/13)

METHOD FOR PRODUCING LINEAR PENTENENITRILE
The invention relates to a method for producing 3-pentenenitrile, characterised by the following steps: (a) isomerisation of an educt stream containing 2-methyl-3-butenenitrile on at least one dissolved or dispersed isomerisation catalyst to form a stream (1), which contains the isomerisation catalyst(s), 2-methyl-3-butenenitrile, 3-pentenenitrile and (Z)-2-methyl-2-butenenitrile; (b) distillation of the stream (1) to obtain a stream (2) as the overhead product, which contains 2-methyl-3-butenenitrile, 3-pentenenitrile and (Z)-2-methyl-2-butenenitrile and a stream (3) as the bottom product, which contains the isomerisation catalyst(s); (c) distillation of the stream (2) to obtain a stream (4) as the overhead product, which is enriched with (Z)-2-methyl-2-butenenitrile in comparison to stream (2), (in relation to the sum of all pentenenitriles in stream (2)) and a stream (5) as the bottom product, which is enriched with 3-pentenenitrile and 2-methyl-3-butenenitrile in comparison to stream (2), (in relation to the sum of all pentenenitriles in stream (2); (d) distillation of stream (5) to obtain a stream (6) as the bottom product, which contains 3-pentenenitrile and a stream (7) as the head product, which contains 2-methyl-3-butenenitrile.
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Page/Page column 72-76; sheet 2

(2008/06/13)

METHOD FOR PRODUCING DINITRILES
The invention relates to a method for producing adipodinitrile and methylglutar nitrile, said method being characterised by the following steps: (a) an educt flow containing pentenenitriles is reacted with hydrogen cyanide in the presence of at least one
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Page/Page column title page; 33-36; sheet 1

(2008/06/13)

Design of ionic phosphites for catalytic hydrocyanation reaction of 3-pentenenitrile in ionic liquids
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
p. 1835 - 1847
(2007/10/03)

Ligand descriptor analysis in nickel-catalysed hydrocyanation: A combined experimental and theoretical study
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
p. 803 - 810
(2007/10/03)

Detection of the electrohydrodimerization intermediate acrylonitrile radical anion by scanning electrochemical microscopy
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Zhou, Feimeng,Bard, Allen J.
p. 393 - 394
(2007/10/02)

Cobalt Carbonyl Mediated Michael Addition: Direct Synthesis of Esters Containing Other Functional Groups from Activated Olefins
Hydrocarbalkoxylation of acrylonitrile with stoichiometric amounts of alcohols in the presence of catalytic amounts of Co2(CO)8 and pyridine bases leads to 2,4-dicyano-2-methylbutanoic acid esters.The yield of these Michael adducts shows a maximum as a function of the pyridine/cobalt ratio.Analogues reactions using equimolar amounts of alcohol, acrylonitrile, and an other activated olefin result in products with at least three different functional groups.Acrylonitrile with pyH gives (1-cyanoethyl)cobalt tetracarbonyl, which is proposed to be the key intermediate of the hydrocarbalkoxylation.This complex may be deprotonated to a "Michael donor" anion, i.e. the Michael adducts are most probably formed in a cobalt-mediated way.The above catalytic system promoted also the Michael addition of some C-H acids to activated olefins under atmospheric conditions.
Sisak, Attila,Ungvary, Ferenc,Marko, Laszlo
p. 2508 - 2513
(2007/10/02)

Oxidative cyclization of 2-methylglutaronitrile to 3-cyanopyridine
A process for making 3-cyanopyridine by the vapor phase catalytic reaction of 2-methylglutaronitrile with molecular oxygen.
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(2008/06/13)

LIGAND EFFECTS IN THE HYDROFORMYLATION OF ACRYLONITRILE BY COBALT CARBONYL
The hydroformylation of acrylonitrile (VCN) using Co2(CO)8/L (L = HN(CH2CN)2, , Me2N(CH2)2NMeH, PPh3, and PCy3) has been examined in methanol solvent.Four reaction pathways are observed which are dependent on L.With no L or with L = HN(CH2CN)2, the reaction produces the desired acetal (MeO)2CHCH2CH2CN.For the more basic amines the reactin produces ca. 50percent yields of hydrodimerization products NCCHMe(CH2)2CN/NC(CH2)4CN in a 10/1 ratio and an ca. 30percent yield of the hydrogenation product CH3CH2CN.These reactions are shown to be metal catalyzed.The main reactionfor Co2(CO)8/PR3 catalyzed systems appears to be a classical Michael addition reaction of the solvent, methanol, with acrylonitrile to give MeOCH2CH2CN.Evidence is given to show that this reaction is catalyzed by phosphine which has dissociated under reaction conditions and not by a ligated cobalt complex.
Dubois, R. A.,Garrou, P. E.
p. 69 - 76
(2007/10/02)