- Liquid-Phase Hydration of Acrylonitrile to Acetamide over the Copper-Nickel Alloy Catalysts
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The liquid-phase hydration of acrylonitrile to acrylamide has been examined over various metal catalysts at 75 deg C.Five metal elements - Cu, Ag, Fe, Co, and Ni - showed the catalytic conversion of acrylonitrile.The Cu and Ag catalysts gave the acrylamide with a 100 percent selectivity, while the other metals, Fe, Co, and Ni, yielded three products: acrylamide, ehylene cyanohydrin, and bis(2-cyanoethyl) ether.The alloying of Cu and Ni led to an increse in the formation of acrylamide with keeping the high selectivity to acrylamide.Especially, Cu-Ni alloys, with a range of 20-70 percent Cu in their bulk composition, were much more active catalysts than Cu.The maximum yield of acrylamide was obtained on the Cu-Ni alloy catalysts was observed, although such a retardation occurred on the Cu catalyst surface.The maximum synergistic effect was observed over the alloy with the surface component ratio of Cu to Ni of 4; this effect was discussed.
- Sugiyama, Kazuo,Miura, Hiroshi,Watanabe, Yoshichika,Ukai, Yasunori
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- Kinetics and Mechanism of Nitrile Hydration Catalized by Unhindered Hydridobis(phosphine)platinum(II) Complexes. Regioselective Hydration of Acrylonitrile
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The reaction between trans-PtHCl(PR3)2 (R = Me and Et) and 1 equiv of NaOH in 50-50 water/acetonitrile solutions yields a species that catalyzes the hydrolysis of acetonitrile to acetamide at rates of 178 and 70 mol/(mol of catalyst h) for the R = Me and Et derivatives, respectively, at 80 deg C.These catalysts remain active for days and give as many as 6000 turnovers.The PMe3 derivate catalyzes hydrolysis of acrylonitrile but exhibits low regioselectivity between the olefin and nitrile functionalities at 80 deg C; at 25 deg C, it hydrates 21 mol of acetonitrile/(mol of catalyst h) and regioselectively (97percent) hydrates 6.1 mol of acrylonitrile/(mol of catalyst h) to acrylamide.The catalytic intermediates, +, +, and PtH(NHC(O)Me)(PEt3)2, have been intercepted and stereoscopically characterized and their interconversions demonstrated.Execpt at low hydroxide concentrations, the rates of catalysis were independent of hydroxide concentration, and proton transfer from solvating water to coordinated N-carboxamido, rather than nucleophilic attack of hydroxide on coordinated nitrile, limits the rate.Rate constants of ca. 8 and ca. 20 s-1 were determined for the proton-transfer process for the PEt3 and PMe3 systems, respectively.A kinetic isotope effect of 3.4 was observed in reactions using D2O.Adjusting the catalytic solutions to pH 8.5 resulted in a linear hydroxide dependence, and rate constants of 4.9 +/ -0.3 and 7.0 +/- 0.4E3 M-1s-1 were measured for nucleophilic attack of hydroxide on coordinated acetonitrile for the PEt3 and PMe3 systems, respectively.Deuterium labeling experiments using trans-PtDCl(PMe3)2 to catalyze acrylonitrile hydration showed that olefin hydration proceeds through a coordinated olefin intermediate and, unlike nitrile hydration, involves a reductive elimination step in the catalytic cycle.
- Jensen, Craig M.,Trogler, William C.
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- SELECTIVE HYDRATION OF ACRYLONITRILE ON METAL OXIDE CATALYSTS
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The selective hydration of acrylonitrile to form acrylamide has been studied on several metal oxide catalysts.MnO2, CuO and Co3O4 catalysts were found to be active and selective.Catalytic activities were strongly affected by the method of preparation.Hydration activity of MnO2 was related to the amount of phenol adsorption.
- Miura, Hiroshi,Sugiyama, Kazuo,Kawakami, Soichiro,Aoyama, Toshiyuki,Matsuda, Tsuneo
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- Development of 3-methoxy-4-benzyloxybenzyl alcohol (MBBA) resin as polymer-supported synthesis support: Preparation and benzyl ether cleavage by DDQ oxidation
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3-Methoxy-4-benzyloxybenzyl alcohol (MBBA) resin was synthesized by a two-step sequence under microwave irradiation involving the reaction of commercially available Merrifield resin with vanillin, followed by reduction with sodium borohydride. MBBA resin was treated with bromides in the presence of sodium hydride to afford the corresponding resin-bound benzyl ethers. Cleavage of the resin-bound benzyl ethers from the MBBA resin was carried out using 2,3-dichloro-5,6-dicyanobenzoqunone (DDQ) to give the corresponding alcohols in good yields. Moreover, the recovery, regeneration, and reuse of this polymer support could be achieved easily. MBBA resin can be developed as a kind of solid-phase synthesis bead of alcohols. Indian Academy of Sciences.
- Huang, Qiang,Zheng, Bao-Zhong,Long, Quan
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- Preparation method of 3-aminopropanol
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The invention relates to a preparation method of 3-aminopropanol, wherein the preparation method comprises the following steps: (1) carrying out a reaction on acrylonitrile with benzyl alcohol under the catalysis of a base catalyst, and separating the obtained reaction solution to obtain 3-benzyloxypropionitrile; and (2) in a liquid-phase reaction system in the presence of a hydrogenation catalyst, carrying out a hydrogenation reaction on the 3-benzyloxypropionitrile, separating the obtained reaction liquid to obtain 3-aminopropanol, and recycling the obtained by-product toluene as an extractant in the step (1).
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Paragraph 0064; 0065
(2020/05/05)
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- Method used for producing 3-hydroxypropionic acid
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The invention belongs to the technical field of chemistry, and more specifically provides a method used for producing 3-hydroxypropionic acid. The method comprises following steps: 1, under catalyst effect, hydrogen cyanide and ethylene oxide are reacted to generated 3-hydroxypropionitrile; 2, an acid is added into the 3-hydroxypropionitrile prepared using step 1 for hydrolysis, and 3-hydroxypropionic acid and an inorganic slat are generated through reaction; 3, a reaction solution obtained in step 2 is subjected to continuous chromatography separation to obtain 3-hydroxypropionic acid and aninorganic salt solution, and the inorganic salt solution is subjected to concentration to obtain a by-product. According to the method, continuous chromatography method is adopted to process the 3-hydroxypropionitrile hydrolysis reaction solution, so that the amounts of waste water, waste gas, and waste residue can be reduced effectively, high content of the target product is obtained at high yield, and production cost is reduced.
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Paragraph 0037; 0045-0047
(2019/12/08)
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- Method for catalytically synthesizing 3-hydroxylpropionitrile from hydrocyanic acid and epoxyethane
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The invention relates to a method for catalytically synthesizing 3-hydroxylpropionitrile from hydrocyanic acid and epoxyethane. An activated alumina immobilized boron trifluoride and 1,2-pentanediol complex is used for catalyzing a reaction between hydrocyanic acid and epoxyethane so as to synthesize 3-hydroxylpropionitrile. By the method, during the reaction, a reaction mixture is not required to be neutralized with a large volume of acid, and the generation of a large amount of inorganic salts is absent, so that the reaction has the atom economy of 100%; the reaction route is short, the number of operating steps is small, and the product separation is easy, so that the reaction is simple and convenient in operation; and hydrocyanic acid in a system is free of risk of numerous overflowing under the condition of low-temperature reaction, so that the reaction is safe in operation.
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Paragraph 0030; 0031; 0032; 0033; 0034; 0035; 0036-0048
(2017/07/20)
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- Efficient and rapid synthesis of phenolic analogs of 4-phenylbutanoic acid using microwave-assisted Michael addition as a key reaction
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ABSTRACT: The addition of phenols to acrylonitrile in the presence of aqueous benzyltrimethylammonium hydroxide or tetramethylammonium hydroxide under microwave irradiation yielded the corresponding Michael adducts. The obtained adducts were easily transformed to phenolic analogs of 4-phenylbutanoic acids via the hydrolysis of nitrile groups.
- Iida, Hirokazu,Akatsu, Yusuke,Mizukami, Kazushi,Natori, Sho,Matsukawa, Minako,Takahashi, Kie
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supporting information
p. 581 - 585
(2016/07/06)
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- Bio-based nitriles from the heterogeneously catalyzed oxidative decarboxylation of amino acids
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The oxidative decarboxylation of amino acids to nitriles was achieved in aqueous solution by in situ halide oxidation using catalytic amounts of tungstate exchanged on a [Ni,Al] layered double hydroxide (LDH), NH4Br, and H2O2 as the terminal oxidant. Both halide oxidation and oxidative decarboxylation were facilitated by proximity effects between the reactants and the LDH catalyst. A wide range of amino acids was converted with high yields, often > 90%. The nitrile selectivity was excellent, and the system is compatible with amide, alcohol, and in particular carboxylic acid, amine, and guanidine functional groups after appropriate neutralization. This heterogeneous catalytic system was applied successfully to convert a pro-tein-rich byproduct from the starch industry into useful biobased N-containing chemicals.
- Claes, Laurens,Matthessen, Roman,Rombouts, Ine,Stassen, Ivo,De Baerdemaeker, Trees,Depla, Diederik,Delcour, Jan A.,Lagrain, Bert,De Vos, Dirk E.
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p. 345 - 352
(2015/01/30)
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- Ruthenium-catalyzed aerobic oxidative decarboxylation of amino acids: A green, zero-waste route to biobased nitriles
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Oxidative decarboxylation of amino acids into nitriles was performed using molecular oxygen as terminal oxidant and a heterogeneous ruthenium hydroxide-based catalyst. A range of amino acids was oxidized in very good yield, using water as the solvent. This journal is
- Claes, Laurens,Verduyckt, Jasper,Stassen, Ivo,Lagrain, Bert,De Vos, Dirk E.
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supporting information
p. 6528 - 6531
(2015/04/14)
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- Sustainable, mild and efficient p-methoxybenzyl ether deprotections utilizing catalytic DDQ
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A procedure for the selective deprotection of p-methoxybenzyl ethers using catalytic amounts of DDQ and of sodium nitrite, with oxygen as the terminal oxidant, is reported.
- Walsh, Katie,Sneddon, Helen F.,Moody, Christopher J.
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p. 7380 - 7387
(2017/09/13)
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- METHOD FOR SYNTHESISING BIS[3-(N,N-DIALKYLAMINO)PROPYL]ETHERS
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The invention relates to an improved method for synthesizing bis[3-(N,N-dialkylamino)propyl]ethers from acrylonitrile, comprising the following reactions: first addition reaction of a water molecule and an acrylonitrile molecule to produce 3-hydroxypropionitrile (reaction 1),second addition reaction of a 3-hydroxypropionitrile molecule obtained by reaction 1 and an acrylonitrile molecule to produce bis(2-cyanoethyl)ether (reaction 2),hydrogenation reaction of the bis(2-cyanoethyl)ether to conduct a reduction of the nitrile functions to primary amine functions in order to produce bis(3-aminopropyl)ether (reaction 3),aminoalkylation reaction of the bis(3-aminopropyl)ether to produce bis[3-(N,N-dialkylamino)propyl]ether (reaction 4).
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Paragraph 0036; 0037; 0038; 0039
(2014/11/27)
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- Zinc triflate: A mild and efficient catalyst for deprotection of tetrahydropyranyl ethers
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Treatment of tetrahydropyranyl (THP) ethers with zinc triflate in methanol provides a simple and efficient process for deprotection of these ethers and the parent alcohols are obtained in excellent yields.
- Srinivasulu,Satyanarayana,Ravi Kumar
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p. 2419 - 2422
(2014/03/21)
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- Simple and efficient method for deprotection of tetrahydropyranyl ethers by using Silica supported sodium hydrogen sulphate
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Tetrahydropyranyl (THP) ethers have been efficiently and simply deprotected by using Silica supported sodium hydrogen sulphate (NaHSO4-SiO 2) in methanol at room temperature to regenerate the parent alcohols in high yields. Tetrahydropyranyl (THP) ethers have been efficiently and simply deprotected by using silica supported sodium hydrogen sulphate (NaHSO 4-SiO2) in methanol at room temperature to regenerate the parent alcohols in high yields.
- Kumar, K. Ravi,Satyanarayana,Reddy, B. Srinivasa
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experimental part
p. 1189 - 1191
(2012/07/27)
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- APPARATUS AND PROCESS FOR CONTINUOUSLY PREPARING ETHYLENE CYANOHYDRIN
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The invention relates to an apparatus and to a process for continuously preparing ethylene cyanohydrin.
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Page/Page column 1
(2009/07/10)
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- CONTINUOUS PROCESS FOR THE MANUFACTURE OF 3-HYDROXY PROPIONITRILE
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A fully continuous process for the manufacture of 3-hydroxypropionitrile, which process comprises (a) an addition reaction where acrylonitrile and water are reacted in the presence of a weak base to form a reaction mixture of 3-hydroxypropionitrile, bis(cyanoethyl)ether and unreacted acrylonitrile, which mixture is continuously neutralised during the transfer to the second process step; and (b) a reactive distillation where the bis(cyanoethyl)ether contained in the reaction mixture is fragmented into 3-hydroxypropionitrile and acrylonitrile and the 3-hydroxypropionitrile is subsequently separated and isolated.
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Page/Page column 5-6
(2008/06/13)
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- Cyanidation of halogen compounds and esters catalyzed by PEG400 without solvent
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Primary aliphatic and aromatic nitriles were synthesized in excellent yields (84-96%) and purity by the cyanidation of halogen compounds and esters with dry powdered sodium cyanide catalysed by phase transfer catalyst PEG400 under solvent-free conditions.
- Cao,Chen,Pei
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p. 2203 - 2207
(2007/10/03)
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- Synthesis of 13C-dilabeled 4-coumaroylspermidines
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Five 13C-dilabeled constitution isomers of 4-coumaroylspermidines were prepared in nine to eleven steps: N1,4-di[(E)-4-coumaroyl]-(5,8- 13C2)spermidine (13b), N1-[(E)-4-coumaroyl]-(5,8-13C2)spermidine (17b), N1,8-di[(E)-4-coumaroyl]-(1,4-13C2)spermidine (20b), N4-[(E)-4- coumaroyl]-(1,4-13C2)spermidine (24b) and N1,4,8-tri[(E)-4-coumaroyl]- (5,8-13C2)spermidine (26). The two 13C-atoms were subsequently introduced using labeled potassium cyanide. The synthesis proceeds through stepwise construction of the polyamine backbone including protection and deprotection steps of the amino functions. Based on 1H-1H NOE interactions, the preliminary study of their binding reveals that 20b binds to tRNA in the same way as spermidine does, whereas 24b and 26 do not show any NOE effects with the tRNA protons.
- Geneste, Herve,Hesse, Manfred
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p. 15199 - 15214
(2007/10/03)
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- The decomposition of aliphatic N-nitro amines in aqueous sulfuric acid. Bisulfate as a nucleophile
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In aqueous sulfuric acid, aliphatic N-nitro amines decompose to N2O and alcohols. An excess acidity analysis of the observed rate constants for the reaction shows that free carbocations are not formed. The reaction is an acid-catalyzed SN2 displacement from the protonated aci-nitro tautomer, the nucleophile being a water molecule at acidities below 82-85% H2SO4, and a bisulfate ion at higher acidities. Bisulfate is the poorer nucleophile by a factor of about 1000. Twelve compounds were studied, of which results obtained for nine at several different temperatures enabled calculation of activation parameters for both nucleophiles. The reaction appears to be mainly enthalpy controlled. The intercept standard-state rate constants are well correlated by the σ* values for the alkyl groups; the slopes are negative, with a more negative value for the slower bisulfate reaction. Interestingly the m?m* slopes also correlate with σ*, although the scatter is bad.
- Cox, Robin A.
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p. 1774 - 1778
(2007/10/03)
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- (Me3Si)3SiH: An Efficient Hydrosilylating Agent of Alkenes and Alkynes
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Tris(trimethylsilyl)silane adds across the double bond of a variety of mono-, di-, and trisubstituted olefins under free-radical conditions in good yields.The reaction, which proceeds via a free-radical chain mechanism, is highly regioselective (anti-Markovnikov).Addition to prochiral olefins bearing an ester group is highly stereoselective.The factors that control the sterochemistry have been discussed in terms of preferred conformations of the intermediate carbon-centered radicals and are thought to be of steric origin.
- Kopping, B.,Chatgilialoglu, C.,Zehnder, M.,Giese, B.
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p. 3994 - 4000
(2007/10/02)
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- Synthesis and chemistry of 2-pyridyl(phosphine) complexes of platinum(0)
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The complexes tetrakisplatinum(0), 1, and trisplatinum(0), 2, are synthesized, and characterized by 31P and 195Pt NMR spectroscopy.The reactions of 1 and 2 with olefins (ethylene, maleic anhydride, diethyl maleate, and olefinic nitriles) are studied and some square-planar Pt(PR3)2(η2-olefin) species isolated (PR3 = the pyridylphosphine).No olefin hydration products are observed on heating the olefin complexes in aqueous solution.Oxidative addition of MeI to 1 and 2 gives the trans-PtI(Me)(PR3)2 species.However, the trans-Pt(H)Cl(PR3)2 species is isolated only from reaction of 2 with gaseous HCl; the hydride reacts with acrylonitrile to form cis-PtCl(CH2CH2CN)(PR3)2.
- Xie, Yun,James, Brian R.
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p. 277 - 288
(2007/10/02)
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- Joint preparation of 3-dialkylaminopropionitriles, bis-(2-cyanoethyl) ether and, if desired, ethylene-cyanohydrin
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3-Dialkylaminopropionitriles STR1 where R1 and R2 are each C1 -C4 -alkyl which may furthermore be bonded to form a 5-membered or 6-membered ring, bis-(2-cyanoethyl) ether II and, if desired, ethylenecyanohydrin III are prepared jointly by a process in which (a) acrylonitrile and water are reacted in the presence of a base at from 60° to 150° C. to give a mixture of acrylonitrile, water and bis-(2-cyanoethyl) ether II, the base being a mineral base, a quaternary nitrogen base or a mixture of these, (b) this mixture is reacted at about 0°-50° C. with a dialkylamine of the general formula IV STR2 to give a mixture of water, a dialkylaminopropionitrile I and bis-(2-cyanoethyl) ether II, and this mixture is separated into its components and (c) if desired, the ether II obtained in proces stage (b) or an aqueous solution of this ether and/or the reacted mixtures containing this ether and obtained from process stage (a) or (b) is allowed to react at from 50° to 150° C. with the dialkylamine IV to give a mixture of a 3-dialkylaminopropionitrile I and ethylenecyanohydrin III, and, if desired, the said mixture is separated into its components.
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- Reaction of Cyclopropanamines with Hypochlorite
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Ethylene was formed in 65percent yield when 1-(1-piperidino)cyclopropanol 6, was treated with hypochlorite.This observation raised the possibility that 1-aminocyclopropanecarboxylic acids (ACCs) could yield ethylene by a mechanism that involves (1) decarboxylation to a 1-aminocyclopropanol, followed by (2) a fragmentation of the carbinolamine to ethylene induced by a hypochlorite equivalent.Although this mechanism could be ruled out only for 1e, no evidence could be found for it in the reactions of other ACCs, 1a-f, with hypochlorite.The fact that 1b-cis-2,3-d2 yieldedonly ethylene-cis-1,2-d2 is consistent with either the mechanism described above or a nitrenium ion mechanism.In the reaction of cyclopropanamines with neutral hypochlorite, ethylene is not the major product.From the primary and secondary amino acids 1a-c, a 3-hydroxypropanenitrile or propanamide, 2a-c, probably the product of a nucleophilic ring-opening step followed by decarboxylation, is formed.Similar products are formed from other cyclopropanamines: 2a from 1g, 2d from 1h, 2e and 2f from 1i, and lactone 5 from 1j.
- Vaidyanathan, Ganesan,Wilson, Joseph W.
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p. 1815 - 1820
(2007/10/02)
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- REDUCTION SELECTIVE PAR LE BOROHYDRURE DE SODIUM D'UN GROUPE ESTER OU NITRILE DANS LES EPOXYDES GEM DISUBSTITUES PAR DEUX GROUPES ATTRACTEURS D'ELECTRONS.
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Sodium borohydride reduced the ester group of the epoxides 1 or one cyano group of 2 selectively within 5 minutes to give new hydroxy - or amino - functionalized epoxides.This unusual reduction of a cyano group has been extended to other α,α-dicyano derivatives.
- Mauger, J.,Robert, A.
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p. 2493 - 2502
(2007/10/02)
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- Organic Chemistry in water (part II). NUCLEOPHILIC ADDITION OF WATER-SOLUBLE PHOSPHINES ON ACTIVATED OLEFINS
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Triphenylphosphine m-trisulfonate P(PhSO3Na)3 = TPPTS and triphenylphosphine m-monosulfonate Ph2PPhSO3Na = TPPMS react in water with α,β unsaturated acids affording hydrosoluble phosphonium salts.The conversion is quantitative because water readily protonates the carbanionic intermediate thus displacing the equilibrum towards the right.This nucleophilic addition of hydrosoluble phosphines has been extended to non water miscible activated olefins in biphasic media; depending on the pH, phosphine oxides or phosphonium salts are obtained.When the reactions are carried out in D2O, the addition products are specifically deuterated.
- Larpent, Chantal,Patin, Henri
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p. 6107 - 6118
(2007/10/02)
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- A NEW METHOD FOR THE PREPARATION OF 2-CYANOETHANOL
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A method is proposed for the preparation of 2-cyanoethanol by the hydrolysis of acrylonitrile in 1.7 N aq.NaOH at 50 deg C with subsequent neutralization with cooling and isolation of the product by evaporation and vacuum distillation in 92percent yield.
- Konstantinov, V. V.,Misharin, A. Yu.
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p. 1087 - 1088
(2007/10/02)
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- KINETIC STUDY OF HYDRATION OF ACRYLONITRILE IN AQUEOUS PHASE.
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An investigation was conducted of kinetic relationships in the catalytic hydration of ACN and the development of a kinetic model for use in calculating an AA synthesis reactor by mathematical modeling. A hypothesis is advanced as to the process mechanism, according to which a complex of acrylonitrile with copper is attacked by water that is not adsorbed on the catalyst; the interaction with water is the rate-determining stage.
- Grigoryan,Andreeva,Danov,Savel'zon,Gudkov
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p. 339 - 343
(2007/10/02)
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- LITHIUM ALUMINIUM HYDRIDE ON SILICA GEL - SELECTIVE REDUCTION OF KETONES AND CARBOXY ESTERS IN THE PRESENCE OF NITRO AND CYANO GROUPS
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Cyano and nitro groups were found not to be reduced by lithium aluminium hydride on silica gel and with the use of this reagent ketones and carboxy esters bearing cyano and nitro groups were successfully converted into the corresponding cyano and nitro alcohols.
- Kamitori, Yasuhiro,Hojo, Masaru,Masuda, Ryoichi,Inoue, Tatsuro,Izumi, Tatsuo
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p. 2575 - 2576
(2007/10/02)
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- Process for preparing acid amides
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A process for preparing acid amides by hydration of the corresponding nitrile compounds with water in the presence of a catalyst, characterized in that the catalyst is the one prepared by treating a vanadate with a cuprous salt or with at least two of metallic copper, a cuprous salt and a cupric salt.
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