- CH STRETCHING FREQUENCES AND BOND STRENGTHS, AND METHYL GROUP GEOMETRY IN CH3CXO COMPOUNDS ( X = H, Me, F, Cl, Br, I, CN, OMe) AND CH3CH2CN
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Infrared spectra in the CH stretching region are reported for CHD2CXO and CH3CXO compounds, where X = F, Cl, Br, I, CN, OMe, and for CHD2CD2CN and CD3CHDCN.In all the carbonyl compounds except the iodide the two out-of-plane CH bonds in the methyl group are significantly weaker than the in-plane one.Differences in CH bond length of up to 0.006 Angstroem are predicted, which are considered to be more reliable than the available microwave data.The separations of νasCH3 and νCHD2 frequencies are compatible with a strong angular asymmetry (HsCHa HaCHa) in the acetyl compounds.The gauche and trans effects of halogen on νisCH are similar, but larger, than those in alkyl halides.In ethyl cyanide, the methyl CH bonds are identical in strength.The α and β substituent effects from the CN group fall into no simple pattern.
- McKean, D. C.,Torto, I.
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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; 0050; 0053
(2020/07/21)
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- N-Heterocyclic Carbene-Catalysed Direct Synthesis of Cyano Esters via Cyanation-Esterification Reaction of α-Keto Esters
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The cyanation-esterification reaction of α-keto esters catalysed by N-heterocyclic carbenes (NHCs) is developed. Under the catalysis of 10 mol% 1,3-bis(2,6-diisopropylphenyl)imidazol-2-ylidene, aromatic and aliphatic α-keto esters reacted with ethyl cyanoformate or acetyl cyanide to produce the corresponding cyano esters with a tetrasubstituted carbon center in high yields.
- Zhang, Jie,Wang, Ying,Du, Guangfen,Gu, Cheng-Zhi,Dai, Bin
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p. 1211 - 1215
(2015/11/02)
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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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p. 637 - 641
(2010/06/15)
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- Method for synthesizing sucrose-6-acetic ester
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The present invention discloses a method of synthesizing sucrose-6-acetic ester, comprising the following steps: adding sucrose into a polar aprotic solvent, and stirring the solvent to dissolve it, then generate a suspension solution of sucrose; adding a acetylation agent acetylnitrile into said suspension solution and stirring the solution; adding water into the aforesaid reaction solution, and then concentrating it to generate a concentrated product; adding a crystalline solvent into the concentrated product, stirring to dissolve it, and depositing for crystallization, then filtering and drying it to get a product of sucrose-6-acetic ester. The benefit of the present invention is that the method of synthesizing sucrose-6-acetic ester has simple operation, mild reaction condition, high selectivity, high yield, and is suitable for industrial production.
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Page/Page column 1; 2
(2008/12/04)
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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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- 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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- Unsaturated ozonides from the ozonolysis of cyclodienes in the presence of carbonyl compounds
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Treatment of the conjugated C5- to C8-cyclodienes (5a-5b) with one molar equivalent of ozone in dichloromethane in the presence of added carbonyl compounds (3) resulted almost exclusively in monoozonolysis reactions to give the corre
- Park, Shin Hee,Lee, Joo Yeon,Huh, Tae Sung
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p. 3083 - 3087
(2007/10/03)
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- Reaction of stabilised phosphorus ylides with nitrogen dioxide
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The reaction of the stabilised ylides 14-23 with an excess of NO2 in CH2Cl2 at room temperature gives different results depending on the structure of the starting ylide. The monacyl ylides 14-16 give the corresponding α-oxo nitriles 4 together with Ph3PO · HNO3 (24) which has been fully characterised for the first time. Under the same conditions, the ylide 18 gives 2,4-dinitrobenzonitrile (26), Ph3PO, and benzoic acid. The other ylides examined all give 24 together with a variety of other products.
- Aitken, R. Alan,Karodia, Nazira
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p. 251 - 254
(2007/10/03)
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- NEW HETEROCYCLIC SYNTHESES FROM α-HALOHYDRAZONES. REARRANGEMENTS OF α-ARYLAMINO- AND α-ARYLTHIOACYLHYDRAZONES IN ACID MEDIUM
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α-(Arylamino)-acylhydrazones 1d-f react with polyphosphoric acid to give 2-arylazoindoles 3a-d through a cyclodehydration process involving the arylamino moiety.A deviation from the expected course is observed with the aldehydic substrates 1a-c which give the isatine derivatives 2a-c. α-(Arylthio)-acylhydrazones 1g-i give the 3-(arylthio)cinnolines 4b-d and 4-aminophenyl phenylsulphide 5, the latter being formed through an unprecedented rearrangement.A similar rearrangement is shown by α-phenylthio-α-phenylhydrazonobenzaldehyde, 6, which give 2-aminophenyl phenyl sulphide, 7.
- Benincori, Tiziana,Fusco, Raffaello,Sannicolo, Franco
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p. 635 - 639
(2007/10/02)
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- Ortho Amides, XLVI. - Contributions to the Chemistry of Bis(dialkylamino)malononitriles
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The reaction of chloroformamidinium chlorides 2 with sodium cyanide in the two-phase system ether/water affords bis(dialkylamino)malononitriles 3 with good yields.From 3a and morpholine or aniline the guanidines 5 and 6 can be obtained, respectively.Alcohol-free sodium ethoxide transforms 3a into the urea acetal 10b, whereas in the reaction of 3a with alkoxides in alcohol ortho carbamic esters 11a, b are produced.The malonic esters and acetoacetic esters 12 react with 3a in the presence of two equivalents of sodium hydride to give the ketene aminals 13.The reactionof 3a with malononitrile furnishes the guanidinium salt 14, which cyclized by hydrogen chloride to the pyridinetricarbonitrile 15.In the presence of sodium hydride, 3a and malononitrile or cyanoacetic esters 17 from the ketene aminal 16 and the 1,2,3-tricyanopropenides 18a-c, respectively.The analogous salts 20 and 21 result from the reaction of 3a with the barbituric acid derivatives 19a, and b, respectively.Hydrogen chloride reacts in ether with 3a to afford the piperazinetetracarbonitrile 22.Reaction of carboxylic acid chlorides yields the cyanoformamidinium salt 28a; byproducts are acyl cyanides 29 and dimeric acyl cyanides 30.Triethyloxonium tetrafluoroborate transforms 3a into the salt 28b.Bromine and iodine react with 3a to produce the salts 28c, d and 28e, f, respectively, depending on the stoichiometric ratios of the starting materials.The thiocyanate 28g is prepared from sulfur and 3a.
- Kantlehner, Willi,Greiner, Ulrich
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p. 965 - 973
(2007/10/02)
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- CYANO SUBSTITUTED OZONIDES: PREPARATION, PROPERTIES AND UNUSUAL BEHAVIOR TOWARDS REDUCING AGENTS
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Ozonolyses of 2-cyanopropene (1a) and of 2,4-dicyano-1-butene (1b) gave the corresponding ozonides 3-cyano-3-methyl- (2a) and 3-cyano-3-(2-cyanoethyl)-1,2,4-trioxolane (2b) as the first examples of their kind.Reduction with DMS yielded the expected fragments acetyl cyanide (4a) and β-cyanopropionyl cyanide (4b), along with formaldehyde.Reduction with triphenylphosphine, however, gave cyanomethyl acetate (6a) and cyanomethyl-β-cyanopropionate (6b), respectively.
- Griesbaum, Karl,Huh, Tae-Seong,Gutsche, Sven-Hendrik
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p. 3299 - 3300
(2007/10/02)
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- SYNTHESIS AND THERMAL DECOMPOSITION OF 4-AZIDOISOXAZOLES
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The diazonium salts derived from 1a,b decompose at 0 deg C to give α-cyanodiazoketones 3a,b and, in the case of 1b, also the N-hydroxytriazole 4.The azides 2a,b were prepared from the diazonium salts at -15 deg C.The diazonium salt from 1c is more stable and can be converted into the azide 2c at 0 deg C, along with formation of 5 as a side product.Kinetic measurements have been carried out for the thermal fragmentation of 2a - c which indicated that the reactions occur by a concerted mechanism.
- L'abbe, Gerrit,Godts, Francoise
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p. 229 - 236
(2007/10/02)
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- Volumes of Reaction for the Formation of Some Analogues of Tetrahedral Intermediates
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Two reactions which comprise equilibrium addition of a protic species to a carbonyl group, the hydroxyketone-hemiacetal interconversion (1a) = (1b), and the thiol addition of acetyl cyanide (2a) = (2b), have been studied by n.m.r. and their spectra thoroughly analysed.Equilibrium constants have been measured as a function of pressure to obtain volumes of reaction which relate to the formation of the 'tetrahedral intermediate' of ester hydrolysis.The intramolecular reaction is shown to have a much less negative volume change than the intermolecular analogue, pointing to the important contribution to ΔV and to ΔV(excit.) of molecular bond formation.
- Isaacs, Neil S.,Rzepa, Henry S.,Sheppard, Richard N.,Lobo, Ana M.,Prabhakar, Sundaresan,Merbach, A. E.
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p. 1477 - 1482
(2007/10/02)
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- REACTION OF OXIRANECARBONITRILE WITH L-CYSTEINE METHYL ESTER
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The title reaction yields (3R,5R) and (3R,5S) isomers of methyl 5-cyanotetrahydro-1,4-2H-thiazine-3-carboxylate, together with methyl 2-acetylthiazole-4-carboxylate as a minor by-product.The stereochemistry of the tetrahydrothiazine derivatives is discussed.
- Kopecky, Jan,Smejkal, Jaroslav,Linhart, Igor,Hanus, Vladimir,Turecek, Frantisek
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p. 4295 - 4298
(2007/10/02)
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- Process for the production of caboxylic acid cyanides
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There are produced carboxylic acid cyanides, e.g., acyl cyanides by reacting a carboxylic acid halide with an alkali cyanide or hydrogen cyanide in the presence of a copper (I) salt and a carboxylic acid nitrile. Especially advantageous are glutaric acid dinitrile and 2-methyl glutaric acid dinitrile.
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- Cation-Anion Combination Reactions. 21. Reactions of Thiolate Ions, Cyanide Ion, and Amines with Cations and Carbonyl Compounds in Me2SO Solution
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The pKa's of three alkanethiols and of two ammonium ions, and the rates of reactions of the thiolates, amines, and of cyanide ion with Malachite Green, Crystal Violet, 2,4-dinitrophenyl acetate, and 9-acetyl-9-cyanofluorene, all in Me2SO solution, have been measured.The pKa's of the thiols in Me2SO, compared with those in water, indicate important hydrogen bonding of water to the thiolates.The reactions of nucleophiles with both the triarylmethyl cations and 2,4-dinitrophenyl acetate have rate constants that are greater in Me2SO than in water.The solvent effects on rates are compared with solvent effects on equilibrium constants to arrive at measures of the progress of the transition states toward products as "seen" by solvent.These measures are not in accord with other measures, such as Broensted slopes, possibly indicating that transition states are not solvated in a manner suggested by stable molecule analogues.The pattern of nucleophilic reactivities toward 9-acetyl-9-cyanofluorene is different from that toward 2,4-dinitrophenyl acetate.A possible rationalization involving concerted reactions of 2,4-dinitrophenyl acetate, but stepwise reactions of the ketone, is discussed.
- Ritchie, Calvin D.,Verth, J.E. Van,Virtanen, P.O.I.
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p. 3491 - 3497
(2007/10/02)
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- Trimethylsilyl Cyanide - A Reagent for Umpolung, VIII. Derivatives of 2-(Trimethylsilyloxy)-2-propenenitrile. Syntheses and General Properties
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Rather different derivatives of the new title compuond 7 were synthesized by routes A - H (Table 2 and 3).The effects of substituents and reaction routes on the E/Z ratios (NMR) is discussed.Replacement of SiMe3 in 7 by RCO- and MeSO2- yields other alkenes with donor (O - X) and acceptor groups (CN) at the same C-atom.Their opposite effects on the β-C-atom is estimated from the corresponding 1H- and 13C-NMR signals.
- Hertenstein, Ulrich,Huenig, Siegfried,Reichelt, Helmut,Schaller, Rainer
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p. 261 - 287
(2007/10/02)
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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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- Process for the preparation of certain acyl cyanide compounds
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Acyl cyanide compounds of the formula STR1 are prepared by reacting an acid halide of the formula STR2 with anhydrous hydrocyanic acid in the presence of a tertiary amine at a temperature between -70° and +100° C. R can be hydrocarbyl or substituted hydrocarbyl and X is halogen.
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