- Regioselective biocatalytic hydrolysis of (E,Z)-2-methyl-2-butenenitrile for production of (E)-2-methyl-2-butenoic acid
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Acidovorax facilis 72W nitrilase catalyzed the regioselective hydrolysis of (E,Z)-2-methyl-2-butenenitrile, producing only (E)-2-methyl-2-butenoic acid with no detectable conversion of (Z)-2-methyl-2-butenenitrile. (E)-2-Methyl-2-butenoic acid, produced in aqueous solution as the ammonium salt, was readily separated from (Z)-2-methyl-2-butenenitrile, and isolated in high yield and purity. The combination of nitrile hydratase and amidase activities of several Comamonas testosteroni strains were also highly regioselective for the production of (E)-2-methyl-2-butenoic acid from (E,Z)-2-methyl-2- butenenitrile.
- Hann, Eugenia C.,Sigmund, Amy E.,Fager, Susan K.,Cooling, Frederick B.,Gavagan, John E.,Bramucci, Michael G.,Chauhan, Sarita,Payne, Mark S.,DiCosimo, Robert
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Read Online
- Process for producing pentenenitriles
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The invention provides methods useful in the industrial scale process for hydrocyanation of butadiene to adiponitrile for recycle of unwanted byproduct 2-methyl-3-butenenitrile (2M3BN) by conversion to process intermediate pentenenitrile. The invention provides a process for generating catalysts useful for carrying out the hydrocyanation of butadiene to adiponitrile, the process comprising contacting the 2M3BN and a solution of a nickel-ligand catalyst in cis-2-pentenenitrile (cis-2PN), trans-2-pentenenitrile (trans-2PN), or a mixture thereof. The improved methods of the invention can provide improved catalyst solubility for bidentate ligands without a requirement for a Lewis acid catalyst promoter such as zinc chloride to be present.
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Page/Page column 26
(2018/04/20)
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- A metal-ligand cooperative pathway for intermolecular oxa-michael additions to unsaturated nitriles
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An unprecedented catalytic pathway for oxa-Michael addition reactions of alcohols to unsaturated nitriles has been revealed using a PNN pincer ruthenium catalyst with a dearomatized pyridine backbone. The isolation of a catalytically competent Ru-dieneamido complex from the reaction between the Ru catalyst and pentenenitrile in combination with DFT calculations supports a mechanism in which activation of the nitrile through metal-ligand cooperativity is a key step. The nitrile-derived Ru-N moiety is sufficiently Br?nsted basic to activate the alcohol and initiate conjugate addition of the alkoxide to the α,β-unsaturated fragment. This reaction proceeds in a concerted manner and involves a six-membered transition state. These features allow the reaction to proceed at ambient temperature in the absence of external base.
- Perdriau, Sébastien,Zijlstra, Douwe S.,Heeres, Hero J.,De Vries, Johannes G.,Otten, Edwin
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supporting information
p. 4236 - 4240
(2015/04/14)
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- Process for Isomerization of CIS-2-Pentenenitrile to 3-Pentenenitriles
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The present invention relates to an improved process for batchwise or continuous isomerization of cis-2-pentenenitrile to 3-pentenenitriles in the presence of 1,4-diazabicyclo[2.2.2]octane as catalyst.
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Paragraph 0059; 0060; 0061
(2013/11/06)
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- ORGANOPHOSPHORUS COMPOUNDS BASED ON TETRAPHENOL (TP)-SUBSTITUTED STRUCTURES
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The invention relates to the synthesis of tetraphenol-substituted structures, in particular meta-substituted xylenes. Said tetraphenol-type structures are reacted to obtain organic phosphorus compounds, in particular organophosphites. The invention further relates to the production of catalytically active compositions which contain transition metals in addition to the aforementioned organic phosphorus compounds. According to another subject matter of the invention, said catalytically active compositions are used in chemical reactions with small molecules, e.g. HCN, CO, hydrogen, and amines.
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- PROCESS FOR MAKING AND REFINING 3-PENTENENITRILE, AND FOR REFINING 2-METHYL-3-BUTENENITRILE
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The invention provides an integrated, continuous process for the production of 3-pentenenitrile, the refining of 3-pentenenitrile, and the refining of 2-methyl-3-butenenitrile, the process comprising: (a) contacting, in a reaction zone, a hydrogen cyanide-containing feed, a butadiene-containing feed, and a catalyst composition, wherein the catalyst composition comprises a zero-valent nickel and at least one bidentate phosphorus-containing ligand selected from the group consisting of a phosphite, a phosphonite, a phosphinite, a phosphine, a mixed phosphorus-containing ligand, and combination thereof; (b) maintaining a residence time in the reaction zone sufficient to convert about 95% or more of the hydrogen cyanide and to produce a reaction mixture comprising 3-pentenenitrile and 2-methyl-3-butenenitrile, wherein the 2-methyl-3-butenenitrile concentration is maintained below about 15 weight percent of the total mass of the reaction mixture; (c) distilling the reaction mixture to obtain a first stream comprising 1,3-butadiene, a second stream comprising 3-pentenenitrile, 2-methyl-3-butenenitrile, (Z)-2-methyl-2-butenenitrile, and optionally 1,3-butadiene, and a third stream comprising the catalyst composition; (d) distilling the second stream to obtain a fourth stream comprising 1,3-butadiene, a fifth stream comprising 2-methyl-3-butenenitrile, (Z)-2-methyl-2-butenenitrile, and optionally 1,3-butadiene, and a sixth stream comprising 3-pentenenitrile; and (e) distilling the fifth stream to obtain a seventh stream comprising 1,3-butadiene, an eighth stream comprising (Z)-2-methyl-2-butenenitrile, and a ninth stream comprising 2-methyl-3-butenenitrile.
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Page/Page column 23-24
(2009/07/25)
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- PROCESS FOR MAKING 3-PENTENENITRILE BY HYDROCYANATION OF BUTADIENE
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The invention provides a continuous process for the production of 3-pentenenitrile, comprising: (a) contacting, in a reaction zone, a hydrogen cyanide-containing feed, a 1,3-butadiene-containing feed, and a catalyst precursor composition, wherein the cata
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Page/Page column 9; 9-10; 10
(2008/06/13)
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- PROCESS FOR MAKING 3-PENTENENITRILE BY HYDROCYANATION OF BUTADIENE
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The invention provides a continuous process for the production of 3-pentenenitrile comprising: (a) contacting, in a reaction zone, a hydrogen cyanide-containing feed, a butadiene-containing feed, and a catalyst precursor composition, wherein the catalyst
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Page/Page column 6; 6-7; 7
(2008/06/13)
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- PREPARATION OF (E)- AND (Z)-2-METHYL-2-BUTENOIC ACIDS
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A method has been developed to prepare (E)- and (Z)-2-methyl-2-butenoic acids (2M2BA) from a mixture of (E,Z)-2-methyl-2-butenenitriles (2M2BN) by the regioselective hydrolysis of (E)-2M2BN to (E)-2-methyl-2-butenoic acid (2M2BA) using enzyme catalysts having either a nitrilase activity or a combination of nitrile hydratase and amidase activities. The method provides high yields without significant conversion of (Z)-2M2BN to (Z)-2M2BA. The regioselective hydrolysis of (E)-2M2BN to (E)-2M2BA makes possible the facile separation of (E)-2M2BA from (Z)-2M2BN or (Z)-2-methyl-2-butenamide (2M2BAm), and the subsequent conversion of (Z)-2M2BN or (Z)-2M2BAm to (Z)-2M2BA.
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