- Selective Monohydrocyanation of Diimine using Potassium Hexacyanoferrate(II)-Benzoyl Chloride Reagent System as a Cyanide Source
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The selective monohydrocyanation of diimines using potassium hexacyanoferrate(II)-benzoyl chloride reagent system as a cyanide source under catalyst-free condition is described. The advantages of this protocol are the non-toxic, non-volatile and inexpensive cyanide source, high yield, and simple work-up procedure. [Figure not available: see fulltext.]
- Li, Zheng,Wen, Fei,Yang, Jingya
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Read Online
- CONVERSION OF 3-AZIDO-5-PHENYL-1,2,4-OXADIAZOLE INTO BENZOYL CYANIDE; A NEW THERMAL FRAGMENTATION
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Flash vacuum pyrolysis of 3-azido-5-phenyl-1,2,4-oxadiazole gives benzoyl cyanide for which a mechanism involving the formation and fragmentation of N-benzoylpentaazafulvene is proposed.
- Choi, P.,Rees, C.W.,Smith, E.H.
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Read Online
- Metal-Free Transformation of Sulfonyl Oxime Ethers with Amines to Oxime Ethers
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Sulfonyl oxime ethers undergo facile radical substitutions with various amines to yield the corresponding oxime ethers. An efficient arylation of sulfonyl oxime ethers was accomplished under ambient temperature and metal-free conditions, with a wide range of functional group tolerance. Mechanistic investigations indicate that a phenyl radical is involved in the catalytic cycle.
- Zhang, Jia-Yuan,Hu, Jinglin,Li, Xiao-Xuan,Tang, Wei-Ke,Feng, Yi-Si
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p. 12676 - 12682
(2021/09/18)
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- Copper-mediated simple and direct aerobic oxidative esterification of arylacetonitriles with alcohols/phenols
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A simple and direct aerobic oxidative esterification reaction of arylacetonitriles with alcohols/phenols is achieved in the presence of a copper salt and molecular oxygen, which produces a broad range of aryl carboxylic acid esters in good to high yields. Copper salt plays multiple roles in the transformation, which allows the oxygenation of C-H bond, cleavage of inert C-C bond, and formation of C-O bond in one pot without the assistance of any of the acids, bases, ligands, and so on. The reaction provides a simple, direct, and efficient protocol towards functionalized esters, especially aryl benzoates, from readily available starting materials.
- Dong, Jianyu,Chen, Xiuling,Ji, Fangyan,Liu, Lixin,Su, Lebin,Mo, Min,Tang, Jian-Sheng,Zhou, Yongbo
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- Thiocyanate radical mediated dehydration of aldoximes with visible light and air
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We developed a new means of activating aldoximes by an in situ generated thiocyanate radical from ammonium thiocyanate and molecular oxygen at room temperature. With a catalytic amount of organic dye aizenuranine as the photocatalyst, the dehydration of aldoximes proceeds smoothly under visible light irradiation, providing a simple to handle, excellent functional group tolerance, and metal-free protocol for a wide range of nitriles.
- Ban, Yong-Liang,Dai, Jian-Ling,Jin, Xiao-Ling,Zhang, Qing-Bao,Liu, Qiang
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supporting information
p. 9701 - 9704
(2019/08/15)
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- Palladium-Catalyzed One-Pot Four-Component Synthesis of β-Cyano-α,β-unsaturated Ketones Using Calcium Carbide as an Acetylene Source and Potassium Hexacyanoferrate(II) as an Eco-Friendly Cyanide Source
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Palladium-catalyzed one-pot four-component synthesis of β-cyano-α,β-unsaturated ketones by the reactions of aryl halides, calcium carbide, potassium hexacyanoferrate(II) and aroyl chlorides is described. The salient features of this protocol are the direct use of easy-to-handle acetylene source and eco-friendly cyanide source, wide scope of substrates with good functional group tolerance, and simple work-up procedure. (Figure presented.).
- Lu, Hao,Li, Zheng
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supporting information
p. 4474 - 4482
(2019/08/20)
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- Reactions of 3-(Polyfluoroalkyl)propane-1,2,3-trione-2-oximes with Diaminoarenes
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Novel quinoxaline derivatives have been synthesized via the reaction of 3-trifhioromethyl-1,2,3-propanetrione-2-oximes with 1,2-diaminobenzene or 2,3-diaminonaphthalene: 2-trifluoromethyl-3-aroylquinoxaline and 2-trifluoromethyl-3-aroylbenzo[g]quinoxaline. Under similar conditions, 3-RF-1,2,3-propanetrione-2-oximes [RF = C3F7, H(CF2)4, C4F9, and C6F13] with the same diaminoarenes have given a mixture of the condensation and fragmentation products in different ratios. The structure of (4-methylphenyl)[3-(tri-fluoromethyl)benzo[g]quinoxalin-2-yl]methanone has been elucidated by means of X-ray diffraction analysis.
- Boltacheva,Slepukhin,Pervova,Filyakova,Charushin
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p. 416 - 423
(2019/05/06)
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- Aerobic oxidation of alcohols with air catalyzed by decacarbonyldimanganese
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The oxidation of alcohols to carbonyl compounds using air as the terminal oxidant is highly desirable. As described in previous reports, the abstraction of α-H of the alcohol is the most important step, and it typically requires not only a metal catalyst but also complex ligands, co-catalysts and bases. Herein, we report a practical and efficient method for the oxidation of primary alcohols, secondary alcohols, 1,2-diols, 1,2-amino alcohols, and other α-functionalized alcohols using a commercially available catalyst, Mn2(CO)10, and no additives. Preliminary mechanistic studies indicated that an alkoxyl radical intermediate existed in our system, and a plausible mechanism consistent with the experimental results and literature was proposed.
- Meng, Shan-Shui,Lin, Li-Rong,Luo, Xiang,Lv, Hao-Jun,Zhao, Jun-Ling,Chan, Albert S. C.
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supporting information
p. 6187 - 6193
(2019/11/20)
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- A Cyanide-Free Synthesis of Acylcyanides through Ru-Catalyzed C(sp3)-H-Oxidation of Benzylic Nitriles
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A practical method for generation of acylcyanides devoid of any external cyanide sources is presented that relies on a mild Ru-catalyzed selective C?H-oxidation of benzylic nitriles. The starting materials are smoothly generated through condensation of the corresponding carboxylic acid amides using silanes. The obtained acylcyanides can be employed in a plethora of transformation as exemplified to some larger extend in the sequence of C?H-oxidation-Tischenko-rearrangement for the generation of structurally diverse benzoyloxycyanohydrines.
- Eisele, Pascal,Bauder, Michael,Hsu, Shih-Fan,Plietker, Bernd
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p. 689 - 691
(2019/05/07)
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- Synthesis method of benzoyl cyanide
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The invention discloses a synthesis method of benzoyl cyanide. The method is characterized in that sodium cyanide and benzoyl chloride are taken as raw materials, the mixture of polyethylene glycol 600 and trioctylmethylammonium chloride is taken as a phase transferring catalyst, water or glycerol is taken as an auxiliary catalyst, the reaction with the benzoyl chloride is conducted at the temperature of 60 DEG C-110 DEG C, a benzoyl cyanide coarse product and a reaction bi-product are prepared after the reaction is conducted for 3-5 hours, and the coarse product is washed and separated to prepare a benzoyl cyanide fine product under the action of a solvent. The method has the advantages that the benzoyl cyanide is synthesized through a simple method, an alkaline chlorination method is adopted to perform treatment in order to reduce pollution and turn harm into benefit, and therefore cyanide is oxidized and destructed by active chlorine under strong alkaline conditions to generate atoxic sodium chloride; the solvent can be recycled, so that the synthesis method has the advantages of low pollution, high conversion, simple operation and the like.
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Paragraph 0011; 0017; 0018; 0021
(2019/04/29)
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- Benzoyl cyanogen new synthetic process (by machine translation)
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The invention relates to a pesticide formulation preparation method, and in particular relates to benzoyl cyanogen new synthetic process. Including the following steps: adding sodium cyanide to the reaction kettle, reaction catalyst, a phase transfer catalyst and organic solvent, heating to reflux water diversion, dropping benzoyl chloride, dropping time is 1 - 3 the H, to obtain [...]; wherein the reaction catalyst is cuprous cyanide, cuprous chloride or cuprous iodide in one or several kinds of combined; the phase transfer catalyst is polyethylene glycol, tetrabutyl ammonium bromide, triethyl benzyl ammonium chloride or three butyl myristylpyridinium chloride in one or several kinds of combined; organic solvent is toluene, in the xylene or a-pipe. With the introduction of the new catalyst and a phase transfer catalyst, improves the reaction rate, reduces the occurrence of side reactions, thus increasing the yield. (by machine translation)
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Paragraph 0013-0022
(2019/05/08)
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- A preparation method of benzoyl cyanogen
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The invention provides a preparation method of benzoyl cyanogen, to xylene as solvent, by benzoyl chloride with sodium cyanide in the presence of catalyst the reaction, the reaction is finished after the after filter pressing, the xylene distilled under reduced pressure first, and then to continue to reduced pressure distillation to obtain high-quality benzoyl cyanogen product; the benzoyl chloride with sodium cyanide in a molar ratio of 1: 1.03; and the catalyst is zinc and tetrabutyl ammonium chloride; said catalyst consumption is benzoyl chloride by weight of 0.5 - 5%; and the catalyst zinc and tetrabutyl ammonium chloride in the weight ratio of 1:3; the xylene with benzoyl chloride in a weight ratio of 1:1 - 8:1. In the invention of the iodination zinc tetrabutyl ammonium chloride composite catalyst can avoid reaction in the production of the impurity of the dimers, benzoyl cyanogen content by 97% increased to 99% or more, the product yield is 89.5% increased to 95% or more, at the same time also has accelerated the reaction speed, reaction time from 6 hr shortened to 3 hr; at the same time the process of the invention is simple, safe and reliable in operation, easy to industrial production.
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Paragraph 0019-0036
(2019/03/29)
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- Novel synthesis method for oxophenylacetate
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The invention discloses a novel synthesis method for oxophenylacetate and belongs to the technical field of synthesis. The novel synthesis method comprises the steps: firstly, reacting benzonitrile and a halogenation reagent at 20-35 DEG C to obtain dihalogenated phenylacetonitrile; then, adding a mixed solution of acid and water into dihalogenated phenylacetonitrile at 35-55 DEG C, and carrying out a reaction at 50-60 DEG C for 2-8 h, wherein the molar ratio of a product I to the water to the acid is 1:(1-10):(1-10); and finally, adding alcohol into the reaction solution in the former step at50-60 DEG C, then, carrying out stirring, controlling the temperature at 60-70 DEG C, carrying out a constant-temperature reaction for 1-4 h, and carrying out cooling and extraction to obtain a target product. The reaction raw materials adopted in the method are wide in source and low in price, the operation process is simple, and the yield of the product is high.
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Paragraph 0026; 0028; 0031; 0033; 0036; 0038; 0041; 0043
(2019/04/06)
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- Oxidation of aromatic alkenes and alkynes catalyzed by a hexa-acetonitrile iron(ii) ionic complex [Fe(CH3CN)6][BF4]2
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Oxidative cleavage of aromatic alkenes and oxidation of alkynes have been catalyzed by a simple Fe(ii) complex [Fe(CH3CN)6][BF4]2 using H2O2 as an oxidant at room temperature. A free radical mechanism has been proposed involving the peroxy (OOH) radical to account for our experimental findings.
- Yap, Chew Pheng,Ng, Jing Kuang,Madrahimov, Sherzod,Bengali, Ashfaq A.,Chwee, Tsz Sian,Fan, Wai Yip
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p. 11131 - 11136
(2018/07/05)
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- Preparation method for D, L-phenylglycine and analogue thereof
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The invention provides a preparation method for D, L-phenylglycine and an analogue thereof. According to the method, benzaldehyde, an analogue thereof and hydrocyanic acid are adopted as raw materials and subjected to cyanidation reaction, and then 2-hydroxy-benzyl cyanide or 2-hydroxy-benzyl cyanide analogue (cyanohydrin for short) is generated. Cyanohydrin reacts with carbon dioxide and the aqueous solution of ammonia, and then 5-phenyl-hydantoin and an analogue thereof (hydantoin for short) are generated. hydantoin is successively subjected to steam stripping, alkaline hydrolysis, steam stripping, decolorization, neutralization, crystallization, washing, centrifuging, drying and the like to obtain D, L-phenylglycine and the analogue thereof. Compared with the prior art, the preparation method for D, L-phenylglycine and the analogue thereof can significantly and effectively reduce the pollution, and fewer inorganic salt by-products are generated. Meanwhile, the prepared D, L-phenylglycine and the analogue thereof are high in product yield and high in purity. Counted in benzaldehyde and the analogue thereof, the yield of D, L-phenylglycine and the analogue thereof is larger than or equal to 96%, and the product purity is larger than or equal to 99%. Meanwhile, the process flow is simple and feasible, so that the method is worthy of market popularization and application.
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Paragraph 0019; 0023; 0027
(2017/03/17)
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- Acceptorless and Base-free Dehydrogenation of Cyanohydrin with (η6-Arene)halide(Bidentate Phosphine)ruthenium(II) Complex
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Ruthenium-catalyzed dehydrogenation of cyanohydrins under acceptorless and base-free conditions was demonstrated for the first time in the synthesis of acyl cyanide. As opposed to the thermodynamically preferred elimination of hydrogen cyanide, the dehydrogenation of cyanohydrins could be kinetically controlled with ruthenium (II) bidentate phosphine complexes. The effects of the arene, phosphine ligands and counter anions were investigated in regard to catalytic activity and selectivity. Selective dehydrogenation can occur via β-hydride elimination with the experimentally observed [(alkoxide)Ru] complex. (Figure presented.).
- Kim, Kicheol,Moeljadi, Adhitya Mangala Putra,Hirao, Hajime,Hong, Soon Hyeok
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supporting information
p. 3292 - 3298
(2017/09/06)
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- Rh-Catalyzed Asymmetric Hydrogenation of 1,2-Dicyanoalkenes
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A highly efficient enantioselective hydrogenation of 1,2-dicyanoalkenes catalyzed by the complex of rhodium and f-spiroPhos has been developed. A series of 1,2-dicyanoalkenes were successfully hydrogenated to the corresponding chiral 1,2-dicyanoalkanes under mild conditions with excellent enantioselectivities (up to 98% ee). This methodology provides efficient access to the asymmetric synthesis of chiral diamines.
- Li, Meina,Kong, Duanyang,Zi, Guofu,Hou, Guohua
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p. 680 - 687
(2017/04/26)
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- Synthesis method of glycopyrronium bromide drug intermediate benzoyl nitrile
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The invention relates to a synthesis method of a glycopyrronium bromide drug intermediate benzoyl nitrile, which comprises the following steps: adding 1.31-1.33 mol of cyanamide and 1.1 mol of benzoyl bromide into a reaction vessel, adding 0.3 mol of stannous chloride and 300ml of nitromethane, controlling the stirring rate at 130-160 rpm, heating the solution to 240-245 DEG C, reacting for 3-4 hours, collecting a 230-240-DEG C fraction in a condenser, cooling, curing, adding the obtained solid into 500ml of sodium sulfite solution to wash 5-6 times, washing with a salt solution 2-3 times, adding into an ethylenediamine solution for washing, stratifying, dehydrating the organic layer with a dehydrating agent, carrying out low-pressure distillation, collecting a 180-185-DEG C fraction, cooling, and curing to obtain the colorless crystal benzoyl nitrile, wherein the mass percent of the sodium sulfite solution in the step (i) is 30-35%, and the salt solution is any one of sodium sulfate and potassium nitrate.
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Paragraph 0014; 0015
(2016/10/17)
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- Dual Lewis Acid/Lewis Base Catalyzed Acylcyanation of Aldehydes: A Mechanistic Study
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A mechanistic investigation, which included a Hammett correlation analysis, evaluation of the effect of variation of catalyst composition, and low-temperature NMR spectroscopy studies, of the Lewis acid-Lewis base catalyzed addition of acetyl cyanide to prochiral aldehydes provides support for a reaction route that involves Lewis base activation of the acyl cyanide with formation of a potent acylating agent and cyanide ion. The cyanide ion adds to the carbonyl group of the Lewis acid activated aldehyde. O-Acylation by the acylated Lewis base to form the final cyanohydrin ester occurs prior to decomplexation from titanium. For less reactive aldehydes, the addition of cyanide is the rate-determining step, whereas, for more reactive, electron-deficient aldehydes, cyanide addition is rapid and reversible and is followed by rate-limiting acylation. The resting state of the catalyst lies outside the catalytic cycle and is believed to be a monomeric titanium complex with two alcoholate ligands, which only slowly converts into the product.
- Laurell Nash, Anna,Hertzberg, Robin,Wen, Ye-Qian,Dahlgren, Bj?rn,Brinck, Tore,Moberg, Christina
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p. 3821 - 3829
(2016/03/08)
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- A Ruthenium Complex-Catalyzed Cyclotrimerization of Halodiynes with Nitriles. Synthesis of 2- and 3-Halopyridines
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Monohalo- and dihalodiynes efficiently undergo [2+2+2] cyclotrimerization with nitriles in the presence of a catalytic amount of the ruthenium complex Cp*RuCl(cod) (10 mol%) to afford the corresponding halopyridines under ambient conditions in good isolated yields (up to 90%). The halopyridines are formed as two separable regioisomers. This is the first example of a direct synthesis of halopyridines from haloalkynes and nitriles. (Figure presented.) .
- Bedná?ová, Eva,Colacino, Evelina,Lamaty, Frédéric,Kotora, Martin
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supporting information
p. 1916 - 1923
(2016/07/06)
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- Detrifluoroacetylation of 4,4,4-trifluoro-3,3-dihydroxy-2-(hydroxyimino)butan-1-ones as a convenient synthetic strategy for acyl cyanides Dedicated to Academician Valery N. Charushin on his 65th birthday.
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A reaction reinvestigation of fluorinated 1,3-dicarbonyl compounds with NaNO2 in acidic conditions revealed the formation of corresponding 1,1,1-trifluoro-3-hydroxyimino-butan-2,4-diones which predominantly isolated as hydrates. A novel synthesis of ethoxy-, alkyl-, (het)aryl substituted carbonylcyanides via acid-catalyzed detrifluoroacetylation of obtained 2-hydroxyimino derivatives of 1,3-dicarbonyl compounds was described.
- Bazhin, Denis N.,Kudyakova, Yulia S.,Nemytova, Natalia A.,Burgart, Yanina V.,Saloutin, Victor I.
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- An outstanding catalyst for the oxygen-mediated oxidation of arylcarbinols, arylmethylene and arylacetylene compounds
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A convenient and sustainable protocol for the aerobic oxidation of benzyl alcohols to carbonyl compounds, based on the use of 1,2,4-triazole-type ligands and nickel(ii) bromide, is described. This combination leads to the formation of an exceedingly active, enzyme-like system that allows for other oxidative processes, such as benzylic C-H oxidation and oxygen-mediated cleavage of C-C triple bond, a pioneering procedure for transformation of alkynes into carboxylic acids.
- Urgoitia,Sanmartin,Herrero,Domínguez
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supporting information
p. 4799 - 4802
(2015/03/18)
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- Synthesis of benzoyl cyanide through aerobic photooxidation of benzyl cyanide using carbon tetrabromide as a catalyst
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We developed a synthetic method toward benzoyl cyanide through aerobic photooxidation of benzyl cyanide in the presence of carbon tetrabromide under visible light irradiation with fluorescent lamps.
- Sugiura,Tachikawa,Nagasawa,Tada,Itoh
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p. 70883 - 70886
(2015/09/08)
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- Aerobic oxidation at benzylic positions catalyzed by a simple Pd(OAc)2/bis-triazole system
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An efficient catalyst system for the Pd-catalyzed aerobic oxidation of benzylic positions has been developed. The combination of palladium(ii) acetate and 3,5-bis((1H-1,2,4-triazol-1-yl)methyl)benzoate ligand allows the selective oxidation at carbon adjacent to arene rings (primary and secondary benzylic alcohols, and other benzyl compounds) to provide the corresponding carbonyl and carboxy derivatives, employing molecular oxygen as oxidizing agent and a very low metal loading (10-5 mol%).
- Urgoitia, Garazi,Maiztegi, Ainhoa,Sanmartin, Raul,Herrero, María Teresa,Domínguez, Esther
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p. 103210 - 103217
(2015/12/23)
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- Copper-catalyzed aerobic oxidative inert C-C and C-N bond cleavage: A new strategy for the synthesis of tertiary amides
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A copper-catalyzed aerobic oxidative amidation reaction of inert C-C bonds with tertiary amines has been developed for the synthesis of tertiary amides, which are significant units in many natural products, pharmaceuticals, and fine chemicals. This method combines C-C bond activation, C-N bond cleavage, and C-H bond oxygenation in a one-pot protocol, using molecular oxygen as the sole oxidant without any additional ligands.
- Chen, Xiuling,Chen, Tieqiao,Li, Qiang,Zhou, Yongbo,Han, Li-Biao,Yin, Shuang-Feng
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supporting information
p. 12234 - 12238
(2015/03/31)
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- Conversion of N-benzyloxycarbonylamino- and N-Tosylamino-benzyl phenylsulfones by green Strecker reactions to α-aminobenzyl nitriles using potassium hexacyanoferrate(II)
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The cyanation of aldimines, generated in situ from N- benzyloxycarbonylamino- and N-tosylamino-benzyl phenylsulfones, to the corresponding N-protected a-aminobenzyl nitriles has been achieved by eco-friendly Strecker reactions using potassium hexacyanofer
- Hu, Xiaochun,Li, Rongzhi,Li, Zheng
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p. 432 - 436
(2014/08/05)
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- Monohydrocyanation of symmetrical azines using potassium hexacyanoferrate(II) as an environmentally friendly cyanide source
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The monohydrocyanation of symmetrical azines to synthesize α-hydrazinonitriles using potassium hexacyanoferrate(II) as cyanide source and benzoyl chloride as a promoter under catalyst-free conditions is described. The advantages of this protocol are the environmentally friendly cyanide source, high yield, and simple work-up procedure. Georg Thieme Verlag Stuttgart New York.
- Hu, Xiaochun,Li, Hongbo,Yang, Jingya,Li, Zheng
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supporting information
p. 1786 - 1790
(2014/08/05)
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- Hydrocyanation of sulfonylimines using potassium hexacyanoferrate(II) as an eco-friendly cyanide source
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An efficient and eco-friendly method for hydrocyanation of sulfonylimines via one-pot two-step procedure using potassium hexacyanoferrate(II) as a cyanide source, benzoyl chloride as a promoter, and potassium carbonate as a base is described. This protocol has the features of using nontoxic, nonvolatile and inexpensive cyanide source, high yield, and simple work-up procedure.
- Li, Zheng,Li, Rongzhi,Zheng, Huanhuan,Wen, Fei,Li, Hongbo,Yin, Junjun,Yang, Jingya
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p. 1739 - 1743
(2014/01/06)
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- Phosphonium salt-catalysed synthesis of nitriles from in situ activated oximes
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A metal-free catalytic method for the conversion of aromatic and aliphatic aldoximes to nitriles at room temperature using oxalyl chloride (1.2 equiv) in combination with 5 mol % of triphenylphosphine oxide is reported. Of the many potential pathways leading from oxime to nitrile a manifold involving chlorophosphonium salt-catalysed decomposition of oxime chlorooxalates formed in situ is shown to be operative.
- Denton, Ross M.,An, Jie,Lindovska, Petra,Lewis, William
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supporting information; experimental part
p. 2899 - 2905
(2012/05/05)
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- Conjugate hydrocyanation of aromatic enones using potassium hexacyanoferrate(II) as an eco-friendly cyanide source
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A selective conjugate hydrocyanation of aromatic enones by a one-pot, two-step procedure using potassium hexacyanoferrate(II) as an original eco-friendly cyanide source, potassium hydroxide as a base, and benzoyl chloride as a promoter was described. This protocol has the advantages of a nontoxic cyanide source, high yield, and simple workup procedure. Georg Thieme Verlag Stuttgart · New York.
- Li, Zheng,Liu, Chenhui,Zhang, Yupeng,Li, Rongzhi,Ma, Ben,Yang, Jingya
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supporting information
p. 2567 - 2571
(2012/11/13)
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- Palladium NCN and CNC pincer complexes as exceptionally active catalysts for aerobic oxidation in sustainable media
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The oxidation of secondary benzyl alcohols is catalyzed by two palladacycles at atmospheric pressure in PEG-400, a sustainable reaction media. Recycling of the active catalytic species is performed up to the 5th run, and catalyst loadings decreased down to 10-8 mol%, thus achieving unprecedented TON and TOF values. In addition, the same conditions proved to be effective for the aerobic oxidation of benzyl methylene compounds, a scarcely explored process by palladium catalysts.
- Urgoitia, Garazi,Sanmartin, Raul,Herrero, Maria Teresa,Dominguez, Esther
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experimental part
p. 2161 - 2166
(2011/10/03)
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- One-Pot Three-Component Solvent-Free Cyanoaroylation of Aldehydes Using Potassium Hexacyanoferrate(II) as an Environmentally Benign Cyanide Source
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An efficient method for one-pot three-component solvent-free cyanoaroylation of aldehydes using potassium hexacyanoferrate(II) as an environmentally benign cyanide source and triethylamine as a catalyst has been described. This method has advantages of not using strongly toxic cyanating agents and volatile organic solvents. In addition, the product was obtained in high yield using a simple workup procedure.
- Li, Zheng,Tian, Guoqiang,Ma, Yuanhong
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supporting information; experimental part
p. 2164 - 2168
(2010/10/21)
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- Kinetics and mechanism of nucleophilic displacement reactions of Y-substituted phenyl benzoates with cyanide Ion
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Second-order rate constants (kCN-) have been measured for nucleophilic substitution reactions of Y-substituted phenyl benzoates (1a-r) with CN- ion in 80 mol % H2O/20 mol % DMSO at 25.0 ± 0.1 °C. The Bronsted-type plot is linear with βlg = -0.49, a typical βlg value for reactions reported to proceed through a concerted mechanism. Hammett plots correlated with σo and σ-constants exhibit many scattered points. In contrast, the Yukawa-Tsuno plot for the same reaction exhibits excellent linearity with pY = 1.37 and r = 0.34, indicating that a negative charge develops partially on the oxygen atom of the leaving aryloxide in the rate-determining step (RDS). Although two different mechanisms are plausible (i.e., a concerted mechanism and a stepwise pathway in which expulsion of the leaving group occurs at the RDS), the reaction has been concluded to proceed through a concerted mechanism on the basis of the magnitude of βlg and pY values.
- Kim, Song-I,Kim, Eun-Hee,Um, Ik-Hwan
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experimental part
p. 689 - 693
(2010/08/19)
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- ZnI2-catalyzed cyanation of acyl chlorides with TMS-CN: An interesting role of iodine
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Both aliphatic and aromatic acyl cyanides have been synthesized with TMSCN and acyl chloride with ZnI2 (0.5 mol%). However the in situ generated I2 is proposed accounting for the formation of by-product O-TMS enolate at high catalyst loading rather than 0.5 mol%. Asymmetric reduction of benzoyl cyanide with borane has been explored in 82% yield and 24% ee.
- Zeng, Wei,Yang, Jingya,Meng, Bo,Zhang, Bo,Jiang, Mingzhe,Chen, Fu-Xue
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experimental part
p. 637 - 641
(2010/06/15)
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- A new convenient synthesis of aroyl cyanides via the formation of cyanohydrin nitrate intermediates
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The treatment of α-bromoarylacetonitriles with AgNO3 generates cyanohydrin nitrate intermediates, which easily eliminate nitrous acid with the formation of carbonyl bond to afford aroyl cyanides in good to high yields.
- Sueda, Takuya,Shoji, Masashi,Nishide, Kiyoharu
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p. 5070 - 5072
(2008/12/21)
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- o-iodoxybenzoic acid- and tetraethylammonium bromide-mediated oxidative transformation of primary carboxamides to one-carbon dehomologated nitriles
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A clean and efficient method for the oxidative transformations of primary carboxamides to one-carbon dehomologated nitriles using the combination of o-iodoxybenzoic acid and tetraethylammonium bromide has been developed. This method exhibits a broad scope and is expected to be of great utility in organic synthesis.
- Bhalerao, Dinesh S.,Mahajan, Ulhas S.,Chaudhari, Kiran H.,Akamanchi, Krishnacharya G.
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p. 662 - 665
(2007/10/03)
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- Quantitative evaluation of the mechanism of electroreduction of benzoyl cyanides
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The mechanism of reduction of benzoyl cyanide, 6, p-methoxybenzoyl cyanide, 7, and p-chlorobenzoyl cyanide, 8, has been studied in acetonitrile (6 and 7), N,N-dimethylformamide (6), and acetonitrile containing water (all three compounds). The reaction proceeds by initial reduction to form the anion radical followed by dimerization to produce an intermediate dianion, the dianion of the dicyanohydrin of benzil. The latter loses cyanide to give the anion of the monocyanohydrin of benzil, which undergoes two parallel reactions: expulsion of cyanide to give the corresponding benzil and rearrangement to the monoanion of mandelonitrile benzoate. The addition of water brings about an increase in the dimerization rate constant and an associated increase in the amount of benzil that is produced. The standard potentials for the initial reduction step have been evaluated, and their dependence on the substituent is discussed. The dimerization rate constants have also been evaluated.
- Macias-Ruvalcaba, Norma A.,Evans, Dennis H.
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p. 589 - 594
(2007/10/03)
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- AgI-PEG400-KI catalyzed environmentally benign synthesis of aroyl cyanides using potassium hexacyanoferrate(II) as the cyanating agent
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A practical cyanation of aroyl chlorides with 0.2 equivalent of non-toxic cyanide source, K4[Fe(CN)6], 3 mol% AgI, 4 mol% PEG-400, and 3 mol% KI as the catalyst system is described. The reactions were performed in DMF at room temperature and provided the corresponding aroyl cyanides in 64-89% yield, typically in less than ten hours. Georg Thieme Verlag Stuttgart.
- Li, Zheng,Shi, Shengyi,Yang, Jingya
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p. 2495 - 2497
(2008/02/11)
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- Structure-reactivity correlations in nucleophilic substitution reactions of Y-substituted phenyl X-substituted benzoates with anionic and neutral nucleophiles
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A kinetic study is reported for the reactions of 4-nitrophenyl X-substituted benzoates (1a-l) and Y-substituted phenyl benzoates (2a-l) with two anionic nucleophiles (OH- and CN-) and three amines (piperidine, hydrazine, and glycylglycine) in 80 mol% H2O-20 mol% dimethyl sulfoxide (DMSO) at 25.0 ± 0.1 °C. Each Hammett plot exhibits two intersecting straight lines for the reactions of 1a-l with the anionic nucleophiles and piperidine, while the Yukawa-Tsuno plots for the same reactions are linear. The Hammett plots for the reactions of 2a-l with hydrazine and glycylglycine demonstrate much better linear correlations with σ- constants than with σ° or σ constants, indicating that the leaving group departure occurs at the rate determining step (RDS). On the contrary, σ- constants result in poorer Hammett correlation than σ° constants for the corresponding reactions with OH- and CN-, indicating that the leaving group departure occurs after the RDS for the reactions with the anionic nucleophiles. The large ρX value (1.7 ± 0.1) obtained for the reactions of 1a-l with the anionic nucleophiles supports the proposal that the reactions proceed through an addition intermediate with its formation being the RDS. The Royal Society of Chemistry 2006.
- Um, Ik-Hwan,Lee, Ji-Youn,Fujio, Mizue,Tsuno, Yuho
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p. 2979 - 2985
(2008/02/11)
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- The behaviors of metal acetylides with dinitrogen tetroxide
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Lithium phenylacetylide (1a) and N2O4 (2) at - 78° yield diphenylbutadiyne (6a) by oxidative coupling, phenylacetylene (7a) by oxidation and then solvent H-abstraction, and benzoyl cyanide (8) by dimerizative-rearrangement of nitroso(phenyl)acetylene (23). Nitro(phenyl)acetylene (3, R = Ph) is not obtained. Benzonitrile (9), a further product, possibly results from hydrolytic decomposition of nitroso(phenyl)ketene (27) generated from phenylacetylenyl nitrite (26). Phenylacetylene (7a) and 2 give, along with (E)- and (Z)-1,2-dinitrostyrenes (34 and 35, resp.), 3-benzoyl-5-phenylisoxazole (10), presumably as formed by cycloaddition of benzoyl nitrile oxide (40) to 7a. Further, 2 reacts with other lithium acetylides (1b-1e), and with sodium, magnesium, zinc, copper, and copper lithium phenylacetylides, 1f-1l, to yield diacetylenes 6a-6c and monoacetylenes 7a-7c. Conversions of metallo acetylide aggregates to diacetylenes are proposed to involve generation and addition reactions of metallo acetylide radical cationic intermediates in cage, further oxidation, and total loss of metal ion. Loss of metal ions from metallo acetylide radical cations and H-abstraction by non-caged acetylenyl radicals will give terminal acetylenes. The principal reactions (75-100%) of heavy metal acetylides phenyl(trimethylstannyl)acetylene (44) and bis(phenylacetylenyl)mercury (47) with 2 are directed nitrosative additions (NO+) and loss of metal ions to give nitroso(phenyl)ketene (27), which converts to benzoyl cyanide (8).
- Woltermann, Christopher J.,Shechter, Harold
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p. 354 - 369
(2007/10/03)
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- A novel heterogeneous synthesis of acyl cyanides catalyzed by PEG400 and zinc iodide
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Aroyl cyanides were readily synthesized in moderate yields by the cyanation of aroyl chlorides with dry powdered potassium cyanide under the catalysis of PEG400 and zinc iodide in dichloromethane at room temperature. A preliminary study on the one-pot preparation of acetyl cyanide was also reported.
- Cao, Yu-Qing,Du, Yun-Fei,Chen, Bao-Hua,Li, Ji-Tai
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p. 2951 - 2957
(2007/10/03)
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- An efficient synthesis of diaryl ketones by iron-catalyzed arylation of aroyl cyanides
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An alternative to acyl chlorides: Iron(III)-catalyzed arylation of aroyl and heteroaroyl cyanides with aryl magnesium reagents (see example in scheme) provides an easy and mild approach to polyfunctionalized diaryl ketones in yields up to 98%.
- Duplais, Christophe,Bures, Filip,Sapountzis, Ioannis,Korn, Tobias J.,Cahiez, Gerard,Knochel, Paul
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p. 2968 - 2970
(2007/10/03)
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- Conversion of pollutants in dilute aqueous waste streams to useful products: A potential method based on phase-transfer catalysis
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Many waste streams contain anions at low concentration in water. This paper describes results obtained when aqueous solutions of various anions at 1 wt% were subjected to reactions with alkyl and acyl halides without solvent. High yields of valuable products such as phenylacetonitrile, alkyl phenyl ethers, alkyl acrylate, and benzoyl cyanide were obtained at moderate temperatures and reaction times. The formation of byproducts deriving from reactions with large amounts of water was easily controlled. The method was successfully applied to selectively react and extract a target anion out of a mixture of anions.
- Bielski, Roman,Joyce, Peter J.
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p. 551 - 552
(2013/09/05)
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- PROCESS FOR MAKING ORGANIC PRODUCTS FROM NON-PRODUCT STREAMS USING A CATALYST
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A method for preparing a product from non-product streams, such as waste or byproduct liquid streams, uses a phase transfer catalyst to enhance the reaction between two or more constituents each from a separate non-product stream. Since the non-product streams have different phases, a phase transfer catalyst may be used to transfer a chemical species from the aqueous phase to the organic phase where it will react. In one embodiment, the aqueous solution is contacted with an electrophile and a phase transfer catalyst and, optionally, a pH adjusting agent in the event that the chemical species in the aqueous solution needs to be ionized. A method for continuously preparing a product involves carrying out two processes providing two non-product streams, then contacting the two non-product streams in the presence of a phase transfer catalyst, then separating the aqueous phase from the organic phase, and then dividing the organic phase into the product and the phase transfer catalyst, which is then recycled or discarded. The catalyst can also remain in the aqueous phase and be discarded from there.
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Page/Page column 16
(2008/06/13)
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- Process for making organic products and improving the quality of non-product streams using phase transfer catalysis
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A method for preparing organic products from aqueous solutions, such as waste or byproduct liquid streams and waste or byproduct gas or vapor streams, uses phase transfer catalysis to transfer a chemical species in low concentration from the aqueous solution to the organic phase or the aqueous-organic interface. The system has little or no organic solvent, and the organic phase contains an electrophile which participates in the reaction. In one embodiment, the aqueous solution is contacted with the electrophile and a phase transfer catalyst and, optionally, a pH adjusting agent in the event that the chemical species in the aqueous solution is not sufficiently ionized to react with the electrophile, and optionally an organic solvent. A method for continuously converting a chemical species involves this contacting step, separating the phases, then dividing the organic phase into the product, the phase transfer catalyst, and the optional organic solvent.
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- Reinterpretation of curved hammett plots in reaction of nucleophiles with aryl benzoates: Change in rate-determining step or mechanism versus ground-state stabilization
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A kinetic study is reported for the reaction of the anionic nucleophiles OH-, CN-, and N3- with aryl benzoates containing substituents on the benzoyl as well as the aryloxy moiety, in 80 mol % H2O-20 mol % dimethyl sulfoxide at 25.0 °C. Hammett log k vs σ plots for these systems are consistently nonlinear. However, a possible traditional explanation in terms of a mechanism involving a tetrahedral intermediate with curvature resulting from a change in rate-determining step is considered but rejected. The proposed explanation involves ground-state stabilization through resonance interaction between the benzoyl substituent and the electrophilic carbonyl center in the two-stage mechanism. Accordingly, the data are nicely accommodated on the basis of the Yukawa-Tsuno equation, which gives linear plots for all three nuceophiles. Literature reports of the mechanism of acyl transfer processes are reconsidered in this light.
- Um, Ik-Hwan,Han, Hyun-Joo,Ahn, Jung-Ae,Kang, Swan,Buncel, Erwin
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p. 8475 - 8480
(2007/10/03)
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- Photosensitized regeneration of carbonyl compounds from oximes
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(Matrix Presented) Deprotection of oximes to their corresponding carbonyl compounds through the use of photosensitized electron-transfer reactions proceeds in reasonable to good yields. Better yields are obtained in nonpolar solvents and when triplet sensitizers are used. Preliminary mechanistic studies suggest the involvement of an iminoxyl radical.
- De Lijser, H. J. Peter,Fardoun, Fadia H.,Sawyer, Jody R.,Quant, Michelle
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p. 2325 - 2328
(2007/10/03)
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- Flash vacuum pyrolysis of 3-oxo-2-arylhydrazonopropanals and related derivatives
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Flash vacuum pyrolysis (FVP) of 3-oxo-2-arylhydrazonopropanals at 500°C and 0.02 Torr yielded the corresponding derivatives of anilines, N-formylanilines, N-benzoylanilines and benzoylnitriles. Similar FVP of phenylhydrazonomalononitrile, phenylhydrazonoa
- Ibrahim, Yehia A,Kaul, Kamini,Al-Awadi, Nouria A
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p. 10171 - 10176
(2007/10/03)
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- An Efficient Synthesis of Dinitrile Derivatives by the Reaction of Oxime Esters or Acid Anhydrides with Cyanotrimethylsilane Catalyzed by La(OiPr)3
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The reaction of oxime esters with cyanotrimethylsilane (Me3SiCN) under the influence of a catalytic amount of lanthanide compounds produced α-trimethylsilyloxydinitrile derivatives in excellent yields accompanied with the formation of trimethylsilyl oxime ethers. Among the lanthanoid catalysts examined, La(OiPr)3 was found to be the best catalyst. The reaction seems to proceed through the formation of acyl cyanides as intermediates, followed by the addition of Me3SiCN to them. Additionally, the reaction of acetic anhydride with Me3SiCN catalyzed by La(OiPr)3 gave 1-trimethylsilyloxyethane dinitrile. Thus, various α-trimethylsilyloxydinitriles were synthesized in good yields by allowing oxime esters or acid anhydrides to react with Me3SiCN in the presence of a catalytic amount of La(OiPr)3.
- Fujii, Akiko,Sakaguchi, Satoshi,Ishii, Yasutaka
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p. 6209 - 6212
(2007/10/03)
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