Benzyltrimethylammonium cyanide

A simple synthesis of cyanides that can be effected in an aqueous medium consists of treating the alkyl halides with benzyltrimethylammonium cyanide (prepared in situ from benzyltrimethylammonium chloride and sodium cyanide) 442... 

Phase-transfer catalysis. Nucleophilic cyanide ion is transferred from the aqueous to the organic phase as benzyltrimethylammonium cyanide. 

Reaction of alkyl halides with benzyltrimethylammonium cyanide in water proceeds rapidly furnishing an improved method for the prepn. of nitriles. In place of benzyltrimethylammonium cyanide the chloride and alkali cyanide can be used. With the thiocyanate in place of the cyanide good yields of alkyl thiocyanates can be obtained.—E ... 

The benzyltrimethylammonium ion migrates to the butyl bromide phase, carrying a cyanide ion along with it. 

N,N,o-trimethyl-, 34, 61 N-Benzylaniline, 36, 22 Benzyl chloride, 34, 65 Benzyl cyanide, 31, 53 32, 64, 65, 92 N-Benzylidenemethylamine, 34, 65 Benzyl isocyanide, 31, 54 Benzylmagnesium chloride, 34, 65 3-Benzyl-3-methylpentanenitkile, 35, 8 3-BENZYL-3-METHYLPENTANOIC ACID, 35, 6 /S-Benzyl-/ -methylvaleric acid, 35, 6 Benzylthiosulfuric acid, 32, 103 Benzyltrimethylammonium hydroxide,... 

The % ring substitution of the polymer is a critical factor in catalytic activity. Its importance was demonstrated clearly in Regen s first full paper on triphase catalysis 89). Catalysts 2 and 13 (2% CL) were active for cyanide displacement on 1-bromooctane (Eq. (3)) only at 21 % or lower RS (Table 3). Commerical anion exchange resins, polystyrenes highly substituted as benzyltrimethylammonium ions 2 or benzyldimethyl-(2-hydroxyethyl)ammonium ions 14, were inactive. 

Color reactions Boric acid (hydroxyquinones). Dimethylaminobenzaldehyde (pyrroles). Ferric chloride (enols, phenols). Haloform test. Phenylhydrazine (Porter-Silber reaction). Sulfoacetic acid (Liebermann-Burchard test). Tetranitromethane (unsaturation). Condensation catalysts /3-Alanine. Ammonium acetate (formate). Ammonium nitrate. Benzyltrimethylammonium chloride. Boric acid. Boron trilluoride. Calcium hydride. Cesium fluoride. Glycine. Ion-exchange resins. Lead oxide. Lithium amide. Mercuric cyanide. 3-Methyl-l-ethyl-2-phosphoiene-l-oxlde. 3-Methyl-1-phenyi-3-phoipholene-1-oxide. Oxalic acid. Perchloric acid. Piperidine. Potaiaium r-butoxIde. Potassium fluoride. Potassium... 

An aqueous solution of the reagent is prepared by dissolving 0.12 mole each of benzyltrimethylammonium chloride and sodium cyanide in 40-50 ml. of water. An alkyl halide added with stirring and cooling is soon converted in part into the nitrile and a benzyltrimethylammonium halide which acts as an emulsifying agent. After the emulsion has been heated on the steam bath for 1-6 hrs., the nitrile is obtained, usually in good yield. 

Sodium cyanide does not dissolve in butyl bromide. The two reactants contact each other only at the surface of the solid sodium cyanide, and the rate of reaction under these conditions is too slow to be of synthetic value. Dissolving the sodium cyanide in water is of little help because butyl bromide is not soluble in water and reaction can occur only at the interface between the two phases. Adding a small amount of benzyltrimethylammonium chloride, however, causes pentanenitrile to form rapidly even at room temperature. The quaternary ammonium salt is acting as a catalyst it increases the reaction rate. How ... 

The benzyltrimethylammonium ion migrates to the butyl bromide phase, carrying a cyanide ion along with it. Once in the organic phase, cyanide ion is only weakly solvated and is far more reactive than it is in water or ethanol, where it is strongly solvated by hydrogen bonding. Nucleophilic substitution takes place rapidly. The benzyltrimethylammonium bromide formed in the substitution step returns to the aqueous phase, where it can repeat the cycle. 

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