Acetyl cyanide preparation

In the case of pyrene, there are two sextets and two fixed double bonds similar to the phenanthrenic double bond. In agreement with this argument and with the result for phenanthrene, co-ozonolysis of pyrene with formaldehyde or acetyl cyanide afforded the expected normal ozonide 114 and the cross-ozonide 115 with an aldehydic group. In a separate co-ozonolysis of 115 with vinyl acetate, diozonides 116 were prepared. No cross-ozonide was obtained in the presence of benzoyl cyanide, which afforded only the normal mono-ozonide 114 (Scheme 36 and Table 15). 

Chloromycetin has been prepared analogously,1189 starting from dichloro-acetyl cyanide, which may be produced in situ from chloral and sodium cyanide.1190... 

Acetyl cyanide 455 Copper cyanide is prepared by adding potassium cyanide in portions to copper(n) sulfate with cooling and vigorous shaking. The copper cyanide is filtered off, washed thoroughly, and dried in a thermostat at 60-70°. Acetyl bromide (1 mole) is added to copper cyanide (1 mole), which causes ebullition no solvent is used. The mixture is heated under reflux for 1.5-2 h, then the nitrile formed is separated from the copper bromide formed by distillation from an oil-bath the nitrile boils at 93° the yield is 85-87%. 

The nitrile group is very sensitive to alkalis and the elimination of it by the action of potassium hydroxide on acetaldehyde cyanohydrin was described by Simpson and Gauthier as one of the reactions of the acetaldehyde cyanohydrin, a substance that they prepared for the first time. That the nitriles of the aldonic acids yield cyanides under the action of alkali, is described by Wohl as one of the properties of penta-acetyl-D-glucononitrile. 

A Japanese group have been investigating the use of readily accessible dihydrocinnoline derivatives of the type 1 (R = alkyl, aryl, styryl, ethoxy X = H or methoxy) as novel precursors for the synthesis of other types of heterocycles. The following synthesis of 2-acetyl-3-cyanoindole is representative of a new general method (22-88% for 10 examples) for the preparation of 2-acyl- and 2-ethoxycarbonyl-3-cyanoindoles from 1 a mixture of 1 (R = Me, X = H 1 eq.) and powdered potassium cyanide (2 eq.) was stirred overnight in aqueous DMF at room temperature. Addition of water to the reaction mixture precipitated 2-acetyl-3-cyanoindoIe, which was obtained in 54% yield after recrystallisation. 

Stacey and Turton61 showed that 2,3,4,6-tetra-O-acetyl-D-glucosone hydrate can be used in two of the established methods for the production of analogs of ascorbic acid. Methods of preparation, reactions, and importance of this class of compound have been reviewed previously.62 Addition of hydrogen cyanide to 2,3,4,6-tetra-O-acetyl-D-glucosone hydrate, and hydrolysis by the usual methods, led to a keto-acid (not isolated) which was converted by enolization and lactonization to D-gluco-ascorbic acid monohydrate, isolated in 50% yield. The product was identified by its (52) F. Smith, Advances in Carbohydrate Chem., 2, 79 (1946). 

Aryl-6-cyanopurines, prepared from the 6-chloro derivatives and potassium cyanide, were converted into 9-aryl-6-acetyl-, 6-propionyl- and 6-benzylpurines by reaction with Grignard reagents <90H(30)435>. 

The conversion of aliphatic and aromatic acyl halides to a keto nitriles has been effected by heating the halides with dry metallic cyanides, of which cuprous cyanide has given the most satisfactory results (60-87%). The acyl bromides rather than the chlorides ate preferred, at least in the formation of aliphatic compounds. Thus, pyruvonitrile is prepared in 77% yield from acetyl bromide and cuprous cyanide whereas no product is obtained if acetyl chloride is employed. Benzoyl cyanide is made in 65% yield by heating the corresponding acyl chloride with cuprous cyanide. "... 

The cyanide ion, which is strongly nucleophilic, reacts, even in alkaline solution, with 17. The reaction proceeds stereospecifically, affording crystalline 2-amino-2,6-anhydro-2-deoxy-D-idononitrile (38), which gives an N-nitroso derivative (37). The configuration at C-2 was proved by hydrogenation of the nitrile, with subsequent acetylation. The l,2-bis(acetamido)-3,4,5-tri-0-acetyl-2,6-anhydro-l,2-di-deoxy-D-iditol (39) had a rotation numerically the same as, but of opposite sign to, that of the enantiomorph prepared in another wav (see Section 11, 2 p. 137). 

In the preparation of N-methyl-L-glucosaminic acid nitrile by treatment of an ethanol solution of N-methyl-L-arabinosylamine with hydrogen cyanide, it was to be expected that the epimeric N-methyl-L-man-nosaminic acid nitrile Avould also be formed. Wolfrom and Thompson" were able to isolate in crystalline condition the acetylated nitrile of N-methyl-L-mannosaminic acid from this reaction mixture. This compound was converted to crystalline N-methyl-L-mannosaminic acid. 

Somsak, L, Batta, G, Farkas, I, Preparation of 1,2-cis-glycosyl cyanides by the stereoselective reduction of acetylated 1-bromo-D-glycosyl cyanides. Tetrahedron Lett., 27, 5877-5880, 1986. 

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