- Synthetic method of adiponitrile
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The invention provides a synthetic method of adiponitrile. The target product adiponitrile can be obtained by taking 1, 3-butadiene which is relatively easy to obtain as an initial raw material, carrying out a hydroaminocarbonylation reaction on terminal olefin of 1, 3-butadiene and then dehydrating, and the whole preparation process is mild in condition, good in reaction selectivity, high in yield, clean and non-toxic in reaction raw material and catalyst and small in environmental pollution.
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Page/Page column 0030-0032; 0035-0037; 0039-0041; 0043-0045; 0049
(2020/05/30)
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- METHOD FOR PRODUCING ADIPAMIDE AS INTERMEDIATE FOR PRODUCTION OF RAW MATERIAL FOR BIO-BASED NYLON
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Disclosed is a method for producing adipamide, which may include the steps of: (a) reacting glucose, nitric acid (HNO3), sodium nitrite (NaNO2) and potassium hydroxide (KOH) to produce a glucaric acid potassium salt, (b) producing glucamide by reacting the glutaric acid potassium salt, with an acidic solution and removing a potassium ion from the glucaric acid potassium salt, (c) preparing an reaction admixture by adding the glucamide and a catalyst to hydrogen halide and acetic acid, and (d) treating the reaction admixture with hydrogen gas in a reactor thereby producing the adipamide.
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Page/Page column 0061-0065; 0077
(2020/03/23)
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- METHOD FOR PRODUCING ADIPAMIDE AS INTERMEDIATE FOR PRODUCTION OF RAW MATERIAL FOR BIO-BASED NYLON
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Disclosed is a method for producing adipamide, which may include the steps of: (a) reacting glucose, nitric acid (HNO3), sodium nitrite (NaNO2) and potassium hydroxide (KOH) to produce a glucaric acidpotassium salt, (b) producing glucamide by reacting the glutaric acid potassium salt, with an acidic solution and removing a potassium ion from the glucaric acid potassium salt, (c) preparing an reaction admixture by adding the glucamide and a catalyst to hydrogen halide and acetic acid, and (d) treating the reaction admixture with hydrogen gas in a reactor thereby producing the adipamide.
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Paragraph 0064-0084
(2020/03/17)
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- Hydration of nitriles using a metal-ligand cooperative ruthenium pincer catalyst
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Nitrile hydration provides access to amides that are important structural elements in organic chemistry. Here we report catalytic nitrile hydration using ruthenium catalysts based on a pincer scaffold with a dearomatized pyridine backbone. These complexes catalyze the nucleophilic addition of H2O to a wide variety of aliphatic and (hetero)aromatic nitriles in tBuOH as solvent. Reactions occur under mild conditions (room temperature) in the absence of additives. A mechanism for nitrile hydration is proposed that is initiated by metal-ligand cooperative binding of the nitrile.
- Guo, Beibei,Otten, Edwin,De Vries, Johannes G.
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p. 10647 - 10652
(2019/12/02)
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- Transfer Hydration of Dinitriles to Dicarboxamides
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We present a robust method for double transfer hydration of dinitriles to afford diamides. The transfer hydration of 1, n -dinitriles (n = 1-6) proceeds smoothly in the presence of a palladium(II) catalyst with acetamide as a water donor, affording the corresponding diamides in moderate to high yields, without involving significant side reactions such as monohydration or cyclization. The equilibrium was shifted in the forward direction by removing coproduced acetonitrile under reduced pressure.
- Naka, Hiroshi,Naraoka, Asuka
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supporting information
p. 1977 - 1980
(2019/10/22)
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- Synthesis method for organic synthesis of intermediate adipamide
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The invention relates to a synthesis method for organic synthesis of an intermediate adipamide. The method mainly includes the steps of: adding 4mol dimethyl adipate, a 5-6mol p-toluidine solution, and a 6mol aqueous solution into a reaction container, raising the temperature of the solution to 40-45DEG C, controlling the stirring speed at 110-130rpm, performing stirring for 50-70min, conducting standing for 90-120min, lowering the solution temperature to 10-15DEG C, precipitating crystals, conducting filtering, and performing washing with a potassium bromide solution, an acetonitrile solutionand a cyclohexane solution, and conducting dehydration with a dehydrant, thus obtaining the finished product adipamide.
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Paragraph 0111; 0013; 0014; 0015
(2018/07/30)
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- Modulation of Nitrile Hydratase Regioselectivity towards Dinitriles by Tailoring the Substrate Binding Pocket Residues
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The regioselective hydration of dinitriles is one of the most attractive approaches to prepare ω-cyanocarboxamides or diamides and such regioselectivity is often beyond the capability of chemical catalysts. The use of nitrile hydratase to biotransform dinitriles selectively would be highly desirable. Molecular docking of two aliphatic dinitriles and two aromatic dinitriles into the active site of a nitrile hydratase (NHase) from Rhodococcus rhodochrous J1 allowed the identification of proximal NHase substrate binding pocket residues. Four residues (βLeu48, βPhe51, βTyr68, and βTrp72) were selected for single- and double-point mutations to modulate the NHase regioselectivity towards dinitriles. Several NHase mutants with an altered regioselectivity were obtained, and the best one was Y68T/W72Y. Docking experiments further indicated that the poor binding affinity of aliphatic and aromatic ω-cyanocarboxamides to the NHase variants resulted in distinct regioselectivity between wild-type and mutated NHases.
- Cheng, Zhongyi,Cui, Wenjing,Xia, Yuanyuan,Peplowski, Lukasz,Kobayashi, Michihiko,Zhou, Zhemin
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p. 449 - 458
(2017/12/15)
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- Corresponding amine nitrile and method of manufacturing thereof
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The invention relates to a preparation method of nitrile. Compared with the prior art, the preparation method has the characteristics of obvious reduction of the usage amount of ammonia sources, low environmental pressure, low energy consumption, low production cost, high purity and yields of nitrile products, and the like, and can be used for obtaining nitrile with a more complex structure. The invention also relates to a method for preparing corresponding amine with nitrile.
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Paragraph 0124; 0125; 0127
(2018/05/24)
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- Corresponding amine nitrile and method of manufacturing thereof (by machine translation)
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The present invention relates to a nitrile manufacturing method, which has characteristics of significantly-reduced ammonia source consumption, low environmental pressure, low energy consumption, low production cost, high nitrile purity, high nitrile yield and the like compared with the method in the prior art, wherein nitrile having a complicated structure can be obtained through the method. The present invention further relates to a method for producing a corresponding amine from the nitrile.
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Paragraph 0124; 0125; 0126; 0127
(2018/07/15)
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- Corresponding amine nitrile and method of manufacturing thereof
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The invention relates to a preparation method of nitrile. Compared with the prior art, the preparation method has the characteristics of obvious reduction of the usage amount of ammonia sources, low environmental pressure, low energy consumption, low production cost, high purity and yields of nitrile products, and the like, and can be used for obtaining nitrile with a more complex structure. The invention also relates to a method for preparing corresponding amine with nitrile.
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Paragraph 0125; 0126; 0127; 0128
(2018/07/15)
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- METHOD FOR PRODUCING EPSILON-CAPROLACTAM
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A method for selective production of ε-caprolactam, wherein a substance inducible from a biomass resource is used as a material; the reaction process is short; ammonium sulfate is not produced as a by-product; and production of by-products is suppressed; is disclosed. The method for producing ε-caprolactam comprises the step of reacting a particular compound inducible from a biomass resource, such as α-hydromuconic acid, 3-hydroxyadipic acid, or 3-hydroxyadipic acid-3,6-lactone, or a salt thereof with hydrogen or ammonia.
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Paragraph 0071; 0085; 0087
(2017/11/29)
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- Synthesis of and catalytic nitrile hydration by a cationic tris(μ-hydroxo)diruthenium(II) complex having PMe3ligands
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While phenyl vinyl ether does not react with [Ru(η4-1,5-COD)(η6-1,3,5-COT)] (1)/PMe3, the C–O bond cleavage of phenyl vinyl ether occurs by 1/PMe3in the presence of water to give a tris(μ-hydroxo)diruthenium(II) complex [(Me3P)3Ru(μ-OH)3Ru(PMe3)3]+[OPh]?·HOPh (3·HOPh) with evolution of ethylene. The molecular structure of 3·HOPh is unequivocally determined by X-ray analysis. The most likely mechanism for the formation of 3·HOPh is protonation of [Ru(η4-1,5-COD)(PMe3)3] (2c) by water and subsequent insertion of phenyl vinyl ether into the resulting Ru–H bond followed by the β-phenoxide elimination and hydrolysis and dimerization of the phenoxoruthenium(II) species. Complex 3 acts as a catalyst for nitrile hydration. As a typical example, the hydration of benzonitrile was achieved by 3 (1.0 mol%) in 1,4-dioxane at 120 °C for 6 h to give benzamide quantitatively.
- Kiyota, Sayori,Kobori, Takako,Soeta, Hirofumi,Ichikawa, You-ichi,Komine, Nobuyuki,Komiya, Sanshiro,Hirano, Masafumi
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- Bis(allyl)-ruthenium(IV) complexes with phosphinous acid ligands as catalysts for nitrile hydration reactions
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Several mononuclear ruthenium(iv) complexes with phosphinous acid ligands [RuCl2(η3:η3-C10H16)(PR2OH)] have been synthesized (78-86% yield) by treatment of the dimeric precursor [{RuCl(μ-Cl)(η3:η3-C10H16)}2] (C10H16 = 2,7-dimethylocta-2,6-diene-1,8-diyl) with 2 equivalents of different aromatic, heteroaromatic and aliphatic secondary phosphine oxides R2P(O)H. The compounds [RuCl2(η3:η3-C10H16)(PR2OH)] could also be prepared, in similar yields, by hydrolysis of the P-Cl bond in the corresponding chlorophosphine-Ru(iv) derivatives [RuCl2(η3:η3-C10H16)(PR2Cl)]. In addition to NMR and IR data, the X-ray crystal structures of representative examples are discussed. Moreover, the catalytic behaviour of complexes [RuCl2(η3:η3-C10H16)(PR2OH)] has been investigated for the selective hydration of organonitriles in water. The best results were achieved with the complex [RuCl2(η3:η3-C10H16)(PMe2OH)], which proved to be active under mild conditions (60 °C), with low metal loadings (1 mol%), and showing good functional group tolerance.
- Tomás-Mendivil, Eder,Francos, Javier,González-Fernández, Rebeca,González-Liste, Pedro J.,Borge, Javier,Cadierno, Victorio
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p. 13590 - 13603
(2016/09/04)
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- Process for the preparation of caprolactam
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The invention provides a process to produce caprolactam comprising contacting hydrogen, dimethyl adipate, and a source of ammonia in the presence of a soluble catalyst system and a protic component. This process allowes the production of caprolactam from renewable sources, e.g. biomass, and can be advantageously done at mild temperatures, saving energy.
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Paragraph 0027; 0028
(2015/01/18)
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- PRODUCTION OF CAPROLACTAM FROM ADIPIC ACID
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Processes are disclosed for the conversion of adipic acid to caprolactam employing a chemocatalytic reaction in which an adipic acid substrate is reacted with ammonia and hydrogen, in the presence of particular heterogeneous catalysts and employing unique solvents. The present invention also enables the conversion of other adipic acid substrates, such as mono-esters of adipic acid, di-esters of adipic acid, mono-amides of adipic acid, di-amides of adipic acid, and salts thereof to caprolactam. Solvents useful in the process that do not react with ammonia are also disclosed. Catalyst supports are disclosed which catalyze the reaction of the substrate with ammonia in the absence of added metal. Metals on the catalyst supports comprise ruthenium (Ru), rhodium (Rh), palladium (Pd), osmium (Os), iridium (Ir), and/or platinum (Pt). Heterogeneous catalysts comprising ruthenium (Ru) and rhenium (Re) on titania and/or zirconia supports are also disclosed. Further, disclosed are products produced by such processes, as well as products producible from such products.
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Paragraph 0061; 0062
(2013/09/12)
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- PROCESS FOR PREPARING HEXAMETHYLENEDIAMINE AND POLYAMIDES THEREFROM
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Provided herein are processes for preparing hexamethylenediamine from one or more of the cis,cis-, cis,trans- and trans,trans- double-bond isomers of muconate diester. The muconate diester can contain carbon atoms derived from biomass containing detectable 14C content determined according to ASTM D6866 and optionally containing a 14C content up to 0.0000000001%. The process converts one or more of the cis,cis-, cis,trans- and trans,trans- double-bond isomers of muconate diester to the one or more of the cis,cis-, cis,trans- and trans,trans- double-bond isomers of muconamide. The isomer(s) of muconamide is then either: 1) directly converted by reduction to hexamethylenediamine; or 2) dehydrated to one or more of the cis,cis-, cis,trans- and trans,trans- double-bond isomers of mucononitrile which is then reduced to the hexamethylenediamine; or 3) reduced to adipamide, which is dehydrated to adiponitrile, and which is converted to hexamethylenediamine. Hexamethylenediamine so prepared can be used to make various polyamides.
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Page/Page column 41-43
(2012/11/06)
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- A heterogeneous catalytic method for the conversion of nitriles into amides using molecular sieves modified with copper(II)
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A heterogenous catalytic method is developed for the hydration of nitriles into amides with acetaldoxime. Copper(II) supported on 4 molecular sieves is an efficient catalyst for this reaction.
- Kiss, árpád,Hell, Zoltán
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experimental part
p. 6021 - 6023
(2011/11/28)
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- Chemistry by nanocatalysis: First example of a solid-supported RAPTA complex for organic reactions in aqueous medium
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A ruthenium-arene-PTA (RAPTA) complex has been supported for the first time on an inorganic solid, that is, silica-coated ferrite nanoparticles. The resulting magnetic material proved to be a general, very efficient and easily reusable catalyst for three synthetically useful organic transformations; selective nitrile hydration, redox isomerization of allylic alcohols, and heteroannulation of (Z)-enynols. The use of low metal concentration, environmentally friendly water as a reaction medium, with no use at all of organic solvent during or after the reactions, and microwaves as an alternative energy source renders the synthetic processes reported herein "truly" green and sustainable. RAPTA's delight: A nano-RAPTA complex supported on silica-coated ferrite nanoparticles proved to be a general, very efficient and easily reusable catalyst for three synthetically useful organic transformations; selective nitrile hydration, redox isomerization of allylic alcohols, and heteroannulation of (Z)-enynols. The use of low metal concentrations, water as a reaction medium, and microwaves as an energy source renders these processes green and sustainable.
- García-Garrido, Sergio E.,Francos, Javier,Cadierno, Victorio,Basset, Jean-Marie,Polshettiwar, Vivek
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experimental part
p. 104 - 111
(2012/01/06)
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- Optimization of adiponitrile hydrolysis in subcritical water using an orthogonal array design
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A study of the hydrolysis of adiponitrile (ADN) was performed in subcritical water to research the dependence on experimental conditions. An L25(56) orthogonal array design (OAD) with six factors at five levels using statistical analysis was employed to optimize the experimental conditions for each product in which the interactions between the variables were temporarily neglected. The six factors were adiponitrile concentration (ADN c, wt%), temperature (T), time (t h), percentage of additives (reactant/additive, wt/wt%), additives (A), and pressure (p, MPa). The effects of these parameters were investigated using the analysis of variance (ANOVA) to determine the relationship between experimental conditions and yield levels of different products. The results showed that (ADN c) and T had a significant influence on the yields of adipamide, adipamic acid, and adipic acid at p0.05. Time was the statistically significant factor for the yield of 5-cyanovalermic acid at p0.05 and (ADN c) was the significant factor for the yield of 5-cyanovaleramide at p0.1. Finally, five supplementary experiments were conducted under optimized conditions predicted by the Taguchi method; the results showed that the yield obtained of each product was no lower than that of the highest in the 25 experiments. Carbon balance was calculated to demonstrate the validity of the experimental technique and the reliability of the results. Based on the experimental results, a possible reaction mechanism was proposed.
- Duan, Peigao,Wang, Yuanyuan,Yang, Yan,Dai, Liyi
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body text
p. 241 - 258
(2009/10/17)
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- RhI-catalyzed hydration of organonitriles under ambient conditions
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(Chemical Presented) New scoop on scope and selectivity: The hydration of organonitriles catalyzed by a RhI(OMe) species under nearly pH-neutral and ambient conditions (25°C, 1 atm) is chemoselective and high-yielding (93 to 99%), has a broad substrate scope, and may thus be complementary to enzymatic hydration methods for the introduction of a terminal amido group (CONH2) onto a carbon chain.
- Goto, Akihiro,Endo, Kohei,Saito, Susumu
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p. 3607 - 3609
(2008/12/23)
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- Enzymatic nitrile hydrolysis catalyzed by nitrilase ZmNIT2 from maize. An unprecedented β-hydroxy functionality enhanced amide formation
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To explore the synthetic potential of nitrilase ZmNIT2 from maize, the substrate specificity of this nitrilase was studied with a diverse collection of nitriles. The nitrilase ZmNIT2 showed high activity for all the tested nitriles except benzonitrile, producing both acids and amides. For the hydrolysis of aliphatic, aromatic nitriles, phenylacetonitrile derivatives and dinitriles, carboxylic acids were the major products. Unexpectedly, amides were found to be the major products in nitrilase ZmNIT2-catalyzed hydrolysis of β-hydroxy nitriles. The hydrogen bonding between the hydroxyl group and nitrogen in the enzyme-substrate complex intermediates that disfavors the loss of ammonia and formation of acyl-enzyme intermediate, which was further hydrolyzed to acid, was proposed to be responsible for the unprecedented β-hydroxy functionality assisted high yield of amide formation.
- Mukherjee, Chandrani,Zhu, Dunming,Biehl, Edward R.,Parmar, Rajiv R.,Hua, Ling
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p. 6150 - 6154
(2007/10/03)
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- 5-Cyanovaleramide production using immobilized Pseudomonas chlororaphis B23
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A biocatalytic process for the hydration of adiponitrile to 5- cyanovaleramide has been developed which can be run to higher conversion, produces more product per weight of catalyst, and generates significantly less waste products than alternate chemical processes. The biocatalyst consists of Pseudomonas chlororaphis B23 microbial cells immobilized in calcium alginate beads. The cells contain a nitrile hydratase (EC 4.2.1.84) which catalyzes the hydration of adiponitrile to 5-cyanovaleramide with high regioselectivity, and with less than 5% selectivity to byproduct adipamide. Fifty-eight consecutive batch reactions with biocatalyst recycle were run to convert a total of 12.7 metric tons of adiponitrile to 5-cyanovaleramide. At 97% adiponitrile conversion, the yield of 5-cyanovaleramide was 13.6 metric tons (93% yield, 96% selectivity), and the total weight of 5-cyanovaleramide produced per weight of catalyst was 3150 kg/kg (dry cell weight).
- Hann, Eugenia C.,Eisenberg, Amy,Fager, Susan K.,Perkins, Neal E.,Gallagher, F.Glenn,Cooper, Susan M.,Gavagan, John E.,Stieglitz, Barry,Hennessey, Susan M.,Dicosimo, Robert
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p. 2239 - 2245
(2007/10/03)
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- Chemoenzymic Production of Lactams from Aliphatic α,ω-Dinitriles
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Five- and six-membered ring lactams have been prepared by first converting an aliphatic α,ω-dinitrile to an ω-cyanocarboxylic acid ammonium salt, using a microbial cell catalyst having an aliphatic nitrilase activity (Acidovorax facilis 72W, ATCC 55746) or a combination of nitrile hydratase and amidase activities (Comamonas testosteroni 5-MGAM-4D, ATCC 55744). The ω-cyanocarboxylic acid ammonium salt was then directly converted to the corresponding lactam by hydrogenation in aqueous solution, without isolation of the intermediate ω-cyanocarboxylic acid or ω-aminocarboxylic acid. Only one of two possible lactam products was produced from α-alkyl-substituted α,ω-dinitriles, where the nitrilase of A. facilis 72W regioselectively hydrolyzed only the ω-cyano group to produce a single cyanocarboxylic acid ammonium salt in greater than 98% yield.
- Gavagan, John E.,Fager, Susan K.,Fallon, Robert D.,Folsom, Patrick W.,Herkes, Frank E.,Eisenberg, Amy,Hann, Eugenia C.,DiCosimo, Robert
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p. 4792 - 4801
(2007/10/03)
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- Ruthenium-Catalyzed Hydration of Nitriles and Transformation of δ-Ketonitriles to Ene-lactams: Total Synthesis of (-)-Pumiliotoxin C
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Hydration of nitriles with 1-2 equivalents of water can be performed efficiently by using RuH2(PPh3)4 catalyst to give the corresponding amides.Under the similar reaction conditions, δ-ketonitriles can be converted into the corresponding ene-lactams, which are versatile synthetic intermediates.The efficiency of the reaction is demonstrated by the short-step synthesis of (-)-pumiliotoxin C.
- Murahashi, Shun-Ichi,Sasao, Shigehiro,Saito, Eiichiro,Naota, Takeshi
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p. 8805 - 8826
(2007/10/02)
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- MODIFICATION OF LYSINE WITH DIETHYL DIIMINOADIPATE DIHYDROCHLORIDE
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The kinetics of two reactions of diethyl diiminoadipate dihydrochloride in aqueous solutions and in the mixed water-dioxane solvent at pH 7-9, i.e., the hydrolysis and amidination of the ε-amino group of DL-lysine as a protein model, were studied.In the aqueous organic medium the ratio of the rate constants for the parallel amidination and hydrolysis reactions is increased by two to three orders of magnitude, and this makes it possible to recommend that the modification of proteins (enzymes) by diimino esters should be conducted in weakly alkaline media in a mixture water and dioxane.
- Kyaerd, A. Ya.,Kestner, A. I.,Siimer, E. Kh.
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p. 1497 - 1502
(2007/10/02)
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