- Anomalous Reaction of Arylmalononitriles with Nitric Acid. Para-Directing Nature of Dicyanomethyl Group and a Through-Ring Nitro/aci-Nitro Tautomerism of 4-Nitrophenylmalononitrile
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Phenylmalononitrile reacts with nitric acid in dichloromethane at room temperature to afford 1,2-bis(4-nitrophenyl)-1,1,2,2-tetracyanoethane as an initial product, which readily suffers oxidative cleavage to give 4-nitrobenzoyl cyanide.Contrary to common
- Suzuki, Hitomi,Koide, Hideki,Ogawa, Takuji
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Read Online
- 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; 0056; 0059
(2020/07/21)
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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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- 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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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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- 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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- 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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supporting information
p. 5597 - 5601
(2015/12/23)
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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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- 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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- 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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- Oxime amides and hydrazone amides having fungicidal activity
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The invention relates to compounds having usefulness in the control of Take-All disease in plants, particularly cereals, a method for the control of Take-All disease, and fungicidal compositions for carrying out the method. Compounds of the invention are oximes or hydrazones of arylgloxamides or heteroarylglyoxamides or cycloalkenylglyoxamides.
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Page column 9
(2008/06/13)
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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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- Oxime amides and hydrazone amides having fungicidal activity
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The invention relates to compounds having usefulness in the control of Take-All disease in plants, particularly cereals, a method for the control of Take-All disease, and fungicidal compositions for carrying out the method. Compounds of the invention are oximes or hydrazones of arylgloxamides or heteroarylglyoxamides or cycloalkenylglyoxamides.
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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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- 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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- Oxidation of alcohols by silica gelsupported bis(trimethylsilyl) chromate
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Bis(trimethylsilyl) chromate generated from chromic anhydride and hexamethyldisiloxane in dichloromethane was supported onto silica gel surface. This supported chromium (VI) reagent was excellent for oxidizing alcohols of various types of the corresponding carbonyl compounds.
- Lee, Jong Gun,Lee, Jung A.,Sohn, Soo Yun
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p. 543 - 549
(2007/10/03)
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- Reactions of β-Dicarbonyl Compounds with Acyl Cyanides Catalyzed or Promoted by Metal Centres in the Homogeneous Phase
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The C-C bond-forming reaction between β-dicarbonyl compouds and acyl cyanides is catalyzed by nickel acetylacetonate or promoted by tin tetrachloride.Thus, β-diketones react with acyl cyanides in the presence of catalytic amounts of to give β-
- Veronese, Augusto C.,Callegari, Rosella,Basato, Marino,Valle, Giovanni
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p. 1779 - 1786
(2007/10/02)
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- Ruthenium-catalyzed oxidations for selective syntheses of ketones and acyl cyanides. Selective acylation of amino compounds with acyl cyanides
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Oxidation of alcohols to the corresponding carbonyl compounds with tert-butyl hydroperoxide in the presence of dichlorotris(triphenylphosphine)ruthenium catalyst gives the corresponding carbonyl compounds with high efficiency. This method can be applied to the oxidation of cyanohydrins to give acyl cyanides which are versatile synthetic intermediates. Acylation of amino compounds with acyl cyanides thus obtained proceeds chemoselectively. Thus, the reaction of amino alcohols with acyl cynides gives N-acylated products exclusively. In the similar N-acylation of polyamines primary amines are selectively acylated in the presence of secondary amines. These reactions are highly useful for the synthesis of spermidine and spermine alkaloids such as spermidine alkaloids such as spermidine siderophores. Dimeric cyclocoupling reaction of diacyl cyanides such as iso- and terephthaloyl cyanides with polyamines can be performed under the similar reaction conditions to give the corresponding polyazamacrocycles with high efficiency.
- Murahashi,Naota
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p. 433 - 440
(2007/10/02)
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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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p. 1085 - 1090
(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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- Palladium Catalyzed Cyanocarbonylation of Organic Iodides
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Palladium complex catalyzed carbonylation of aromatic and heteroaromatic iodides in the presence of potassium cyanide gave aroyl cyanides in fair to excellent yields, offering the first example of cyanocarbonylation.
- Tanaka, Masato
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p. 637 - 638
(2007/10/02)
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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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- TRIBUTYLTIN CYANIDE: A FACILE CYANATING AGENT OF ACYL CHLORIDES
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Tributyltin cyanide was prepared from tributyltin chloride and potassium cyanide, and was found to be an efficient cyanation reagent for acyl chlorides to give acyl cyanides in excellent yields.
- Tanaka, Masato
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p. 2959 - 2962
(2007/10/02)
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- Process for the production of acyl cyanides (A)
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There are prepared acyl cyanides of the formula STR1 where R is a straight or branched chain alkyl group having 1 to 18 carbon atoms, preferably 1 to 10 carbon atoms, and which also can be substituted by one or more phenyl groups or halogen atoms, preferably chlorine, or R is preferably a cycloalkyl group having 3 to 8 carbon atoms, preferably cyclopropyl, which can have one or more 1 to 3 carbon atom alkyl or halogen, preferably chlorine, substituents wherein in all of the above set forth substitutions the halogen atoms and the phenyl groups are not on the carbon atom adjacent to the carbonyl group or R is a substituted phenyl group, a naphthyl group, a substituted naphthyl group or a five membered heterocyclic group, e.g., furyl, thienyl or alkyl substituted thienyl, wherein the substituents on the phenyl or naphthyl are halogen atoms, nitro groups or alkyl or alkoxy groups having 1 to 5 carbon atoms. The process comprises reacting an acyl halide of the formula in which R is as defined above and Hal is a chlorine or bromine atom, with CuCN at a temperature of about 50° to 180° C in the presence of a carboxylic acid nitrile inert under the reaction conditions, there being employed about 1 to 10 parts by weight of the carboxylic acid nitrile and about 0.5 to 20 parts by weight of at least one organic solvent which is inert under the reaction conditions. Certain of the compounds are novel per se.
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- Substituted cyclopropyl glyoxylnitriles
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There are prepared acyl cyanides of the formula STR1 where R is a straight or branched chain alkyl group having 1 to 18 carbon atoms, preferably 1 to 10 carbon atoms, and which also can be substituted by one or more phenyl groups or halogen atoms, preferably chlorine, or R is preferably a cycloalkyl group having 3 to 8 carbon atoms, preferably cyclopropyl, which can have one or more 1 to 3 carbon atoms alkyl or halogen, preferably chlorine, substituents wherein in all of the above set forth substitutions the halogen atoms and the phenyl groups are not on the carbon atom adjacent to the carbonyl group or R is a substituted phenyl group, a naphthyl group, a substituted naphthyl group or a five membered heterocyclic group, e.g., furyl, thienyl or alkyl substituted thienyl wherein the substituents on the phenyl or naphthyl are halogen atoms, nitro groups or alkyl or alkoxy groups having 1 to 5 carbon atoms. The process comprises reacting and acyl halide of the formula in which R is as defined above and Hal is a chlorine or bromine atoms, with CuCN at a temperature of about 50° to 180° C in the presence of a carboxylic acid nitrile inert under the reaction conditions, there being employed about 1 to 10 parts by weight of the carboxylic acid nitrile and about 0.5 to 20 parts by weight of at least one organic solvent which is inert under the reaction conditions. Certain of the compounds are novel per se.
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