- Reactions of Zirconocene-1-Aza-1,3-diene Complexes with Acyl Cyanides: Substrate-Dependent Synthesis of Acyl- or Non-Acyl-Substituted Pyrroles
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Insertion of acyl cyanides into azazirconacyclopentenes derived from 1,3-azadienes has been described, which affords acyl- or non-acyl-substituted pyrroles upon acidic quenching. These reactions are initialized through C=O insertion into the azazirconacycle to afford seven-membered oxaazazirconacycles. In the cases of 1,4- or 1,2,4-substituted azadienes, addition of a second molecule of acyl cyanide followed by cyclization upon acidic quenching leads to acyl-substituted pyrroles. In the cases of 1,3,4-substituted azadienes, the addition of a second molecule of acyl cyanide cannot proceed due to the steric hindrance caused by the R3 group on the zirconium intermediate. Acidic quenching of the resulting zirconium intermediate affords non-acyl-substituted pyrroles.
- Xiong, Meijun,Yu, Shasha,Xie, Xin,Li, Shi,Liu, Yuanhong
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- Reaction of Aromatic Acyl Chlorides with Potassium or Sodium Cyanide Impregnated onto Amberlite XAD Resins. Efficient Synthesis of Aromatic Acyl Cyanides
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The effects of alkali metal cyanide impregnated on Amberlite XAD resins (KCN/XAD, NaCN/XAD) have been examined using the cyanation of benzoyl chloride.In benzene, benzoyl cyanide was obtained in a very high yield with high selectivity under mild conditions.It is proposed that the reaction occurs on the surface of the resin.On the basis of the result obtained in the absence of any solvent, the reactivity of KCN/XAD toward dimerization of benzoyl cyanide has been found to be much poorer than that of KCN in solution.Although the reaction of acyl chlorides with KCN/XADor NaCN/XAD in benzene gave various acyl cyanides in good to excellent yields, no aliphatic acyl cyanide could be obtained.
- Sukata, Kazuaki
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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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- 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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- 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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- Novel synthesis method of alpha-carbonyl acid ester
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The invention discloses a novel synthesis method of alpha-carbonyl acid ester. The method comprises the following steps: carrying out chlorination reaction on an alpha-methylene-containing nitrile compound and chlorine to obtain dichloronitrile, reacting the dichloronitrile product in a sulfuric acid and water system to obtain formyl cyanide, then acquiring an imino sulfate compound in the same reaction system, and finally performing esterification to obtain the target product. The adopted reaction raw materials are wide in sources and low in price, highly toxic solid sodium cyanide can be prevented from being used in the prior art, the method is environmentally friendly, and the method is easy to operate, mild in condition and easy to industrialize.
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Paragraph 0016; 0068; 0071
(2020/07/21)
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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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- 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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- 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 0035
(2017/03/17)
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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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supporting information
p. 3821 - 3829
(2016/03/08)
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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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- 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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- 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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- Glyt1 Transporter Inhibitors and Uses Thereof in Treatment of Neurological and Neuropsychiatric Disorders
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The invention provides a compound of formula (I) or a solvate thereof: wherein R1, R2, R3, R4, R5, R6, and n are as defined in the specification, and uses of such compounds. The compounds i
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Page/Page column 24
(2008/12/08)
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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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- 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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- 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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- Herbicidal methods and compositions comprising epoxy compounds
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A method of combating undesired plant growth at a locus is disclosed, the method comprising applying to the locus a compound of general formula: STR1 where R1 and R2 independently represent a hydrogen atom or an optionally substituted alkyl or alkenyl group or R1 and R2 together represent an optionally substituted alkyl or alkenyl chain; R3 represents an optionally substituted saturated or unsaturated homocyclic or heterocyclic group; and Z represents a group --COOR4 where R4 represents a hydrogen atom, a cation or an optionally substituted alkyl, alkenyl, alkynyl or aryl group, or Z represents a group --CHO. The use of a compound of general formula I as a herbicide and a herbicidal composition are also disclosed.
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- Ruthenium-Catalyzed Oxidations of Alcohols
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A combination of low-valent ruthenium complexes and peroxides such as t-BuOOH and peracids serves as efficient catalytic systems for the oxidation of aromatic and aliphatic hydroxy compounds. The utility of these methods was demonstrated by the synthesis of acyl cyanides which are versatile synthetic intermediates. The principle of the catalytic oxidations with peracids lead to the novel and efficient method for aerobic oxidation of alcohols in the presence of aldehydes. This reaction is of importance in synthetic and large scale industrial processes and from environmental points of view. The present principle will provide new chemistry of oxidative transformations of various industrially important functional materials.
- Murahashi,Naota
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p. 203 - 213
(2007/10/03)
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- On the Preparation of Acyl Cyanides from Aldehydes
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The O-silylated cyanohydrins 3 prepared from the aldehydes 1 with trimethylsilyl cyanide are oxidized photochemically or thermally with N-bromosuccinimide to afford the acyl cyanides 4a-n.Scope and limitations of the procedure are discussed.
- Haerle, Helmut,Jochims, Johannes C.
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p. 1400 - 1412
(2007/10/02)
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- RUTHENIUM CATALYZED OXIDATION OF CYANOHYDRINS TO ACYL CYANIDES USEFUL REAGENTS FOR SELECTIVE N-BENZOYLATION OF AMINOALCOHOLS
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Ruthenium catalyzed oxidation of cyanohydrins with tert-butyl hydroperoxide gives the corresponding acyl cyanides in good to excellent yields.Acyl cyanides thus obtained are useful reagents for selective N-benzoylation of aminoalcohols.
- Murahashi, Shun-ichi,Naota, Takeshi,Nakajima, Nobuyuki
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p. 925 - 928
(2007/10/02)
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- Process for the preparation of acyl cyanides
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A novel process for the preparation of acyl cyanides of the general formula wherein R represents an optionally substituted alkyl radical with 1 to 8 carbon atoms, an optionally substituted cycloalkyl radical with 3 to 12 carbon atoms, an optionally substituted aryl radical or an optionally substituted 5-membered or 6-membered heterocyclic radical, which can additionally be fused to a benzene ring, in which a carboxylic acid fluoride or the general formula in which R has the abovementioned meaning is reacted with an alkali metal cyanide, optionally in the presence of a diluent, at a temperature between 10° and 200° C. The acylcyanides (I) can be used as intermediates in the synthesis of known herbicides.
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- Process for the preparation of acyl cyanides
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Acyl cyanides of the general formula STR1 in which R represents alkyl or substituted alkyl of from 1 to 8 carbon atoms; cycloalkyl or substituted cycloalkyl with 3 to 12 carbon atoms; aryl or substituted aryl; or an optionally substituted 5-membered or 6-membered heterocyclic radical which can additionally also be fused with a benzene ring, are prepared by reacting the corresponding carboxylic acid anhydride with an alkali metal cyanide or anhydrous hydrocyanic acid, at a temperature of between 50° and 250° C. and the resulting acyl cyanide is removed from the reaction medium by distillation, immediately after it has been formed.
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- Process for the preparation of acyl cyanide compounds
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Acyl cyanides of the formula STR1 wherein R is alkyl or substituted alkyl with 1 to 8 carbon atoms, or cyano-carbonyl substituted alkyl, i.e., containing another STR2 group, cycloalkyl or substituted cycloalkyl with 3 to 12 carbon atoms or aryl or substituted aryl or represents an optionally substituted 5-membered or 6-membered heterocyclic radical which can additionally also be fused with a benzene ring, Are made by reacting the corresponding acid halide with an alkali metal cyanide or anhydrous hydrocyanic acid in the presence of a heavy metal cyanide and optionally in the presence of a diluent, at a temperature of between 100° C. and 300° C.
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