111-69-3Relevant academic research and scientific papers
One-step Synthesis of Adiponitrile by Catalytic Ammoxidation over Antimony-Vanadium Phosphorus Oxide/γ-Alumina Catalyst
Reddy, B. Mahipal,Manohar, B.
, p. 330 - 331 (1993)
The selective synthesis of adiponitrile from cyclohexanol, cyclohexanone,cyclohexane and n-hexane in a single step by vapour-phase ammoxidation over an antimony-promoted vanadium phosphorus oxide catalyst supported on alumina is reported.
Stable fluorophosphines: Predicted and realized ligands for catalysis
Fey, Natalie,Garland, Michael,Hopewell, Jonathan P.,McMullin, Claire L.,Mastroianni, Sergio,Orpen, A. Guy,Pringle, Paul G.
, p. 118 - 122 (2012)
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.
Electrochemical synthesis of adiponitrile from the renewable raw material glutamic acid
Dai, Jian-Jun,Huang, Yao-Bing,Fang, Chi,Guo, Qing-Xiang,Fu, Yao
, p. 617 - 620 (2012)
Current affairs: Adiponitrile, used to produce nylon 6.6, is prepared from the renewable compound glutamic acid by an electrochemical route, involving electro-oxidative decarboxylation and Kolbe coupling reactions. The new route is an example of the use of glutamic acid as a versatile substrate in the transformation of biomass into chemicals. Also, it highlights the use of electrochemical methods in biomass conversion.
A new simple method for the synthesis of cyclobutyl cyanide
Cohen, Shlomo,Rothenberg, Gadi,Sasson, Yoel
, p. 3093 - 3094 (1998)
A clean and efficient intramolecular cyclization of δ- halovaleronitrile to cyclobutyl cyanide was achieved using NaOH and phase- transfer catalysts in a solid-liquid system at 70°C.
Backbone diversity analysis in catalyst design
Maldonado, Ana G.,Hageman, Jos A.,Mastroianni, Sergio,Rothenberg, Gadi
, p. 387 - 396 (2009)
We present a computer-based heuristic framework for designing libraries of homogeneous catalysts. In this approach, a set of given bidentate ligand-metal complexes is disassembled into key substructures ("building blocks"). These include metal atoms, ligating groups, backbone groups, and residue groups. The computer then rearranges these building blocks into a new library of virtual catalysts. We then tackle the practical problem of choosing a diverse subset of catalysts from this library for actual synthesis and testing. This is not trivial, since 'catalyst diversity' itself is a vague concept. Thus, we first define and quantify this diversity as the difference between key structural parameters (descriptors) of the catalysts, for the specific reaction at hand. Subsequently, we propose a method for choosing diverse sets of catalysts based on catalyst backbone selection, using weighted D-optimal design. The computer selects catalysts with different backbones, where the difference is measured as a distance in the descriptors space. We show that choosing such a D-optimal subset of backbones gives more diversity than a simple random sampling. The results are demonstrated experimentally in the nickel-catalysed hydrocyanation of 3-pentenenitrile to adiponitrile. Finally, the connection between backbone diversity and catalyst diversity, and the implications towards in silico catalysis design are discussed.
Linear relationship between activity of a new Ru-catalyst and acidity of substituted benzoic acids in the dimerization of acrylonitrile
Kashiwagi, Kohichi,Sugise, Ryoji,Shimakawa, Toshihiro,Matuura, Tunao,Shirai, Masashi
, p. 186 - 187 (2006)
A new type of catalyst system using ruthenium and carboxylic acid is useful for the tail-to-tail dimerization of acrylonitrile, proceeding without the formation of undesired by-product propionitrile. Carboxylic acids having pK a 3.5-5 are suitable as co-catalysts for the dimerization of acrylonitrile. The relationship between the logarithm of the relative rate in the dimer formation and the pKa of m- and p-substituted benzoic acids (Bronsted plot) was linear (R2 = 0.946) with a slope of -0.199. The role of the carboxylic acids can be considered to be effective protonation in the protonolysis of the carbon-ruthenium bond of an intermediate Ru complex. Copyright
1,4-DICYANOBUTENE-BRIDGED BINUCLEAR RHODIUM(I) COMPLEXES AND THEIR CATALYTIC ACTIVITIES
Park, Hwa-Kun,Kim, In Bum,Chin, Chong Shik
, p. 431 - 436 (1987)
Reactions of Rh(ClO4)(CO)(PPh3)2 with dicyano olefins, cis-NCCH=CHCH2CH2CN (c-DC1B), trans-NCCH=CHCH2CH2CN (t-DC1B), trans-NCCH2CH=CHCH2CN (t-DC2B), and NCCH2CH2CH2CN (DCB) produce the binuclear dicationic rhodium(I) complexes, (ClO4)2 (NC-A-CN=c-DC1B (1), t-DC1B (2), t-DC2B (3), DCB (4)).Complexes 1 and 2 are catalytically active for the hydrogenation of c-DC1B and t-DC1B, respectively, to give DCB, while complex 3 catalyzes the isomerization of t-DC2B to give c-DC1B and t-DC1B, and the hydrogenation of t-DC2B to DCB at 100 deg C.
Improvement of catalyst activity in the Ru-catalyzed dimerization of acrylonitrile by using diphenyl ether as a solvent
Kashiwagi, Kohichi,Sugise, Ryoji,Shimakawa, Toshihiro,Matuura, Tunao
, p. 1384 - 1385 (2007)
For the catalyst system of ruthenium and carboxylic acid, which is useful for the efficient tail-to-tail dimerization of acrylonitrile, the TON increases as the ruthenium catalyst concentration is decreased. Furthermore, the addition of aromatic solvents of equal volume to that of acrylonitrile improves the catalyst activity. Especially, the use of diphenyl ether leads to a 1.7 time improvement of the TON. Copyright
Ligand descriptor analysis in nickel-catalysed hydrocyanation: A combined experimental and theoretical study
Burello, Enrico,Marion, Philippe,Galland, Jean-Christophe,Chamard, Alex,Rothenberg, Gadi
, p. 803 - 810 (2005)
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.
STUDIES OF A COBALT-PROMOTED ACRYLONITRILE COUPLING REACTION
Druliner, J. D.,Blackstone, R. C.
, p. 277 - 284 (1982)
A stoichiometric cobalt-promoted acrylonitrile (AN) coupling reaction leading to adiponitrile (ADN) formation was reinvestigated.The active catalyst appears to involve cobalt(0) species.Cobalt hydride complexes are either inactive or give only low yields of ADN .Intermediate Co(AN)2 species can be reduced to give ADN using H2S or using H2 and Pt on C.Choice of ligand is a factor in determination of ADN yield, such yields decreasing in the order (CH3)2NCHOPPh3>P(OPh)3>P(CH3)3>P(OC2H5)3.Formation of stoichiometric ADN yields from Co(N2)(PPh3)3 and AN indicate that co-promoters, such as ZnCl2 and CoCl2, are not required.Different ADN/c,t-1,4-dicyanobutene-1 product ratios, obtained by H2S treatment of Co(AN)2 species and a known complex, suggest that the intermediate Co(AN)2 species consist mainly of polymeric structures rather than monomeric metallacyclic complexes.
