Tolu-nitrile

NAPHTHALENETHIOL, 51, 759 o-Tolualdehyde, by reduction of o-tolu-nitrile with Raney nickel alloy in formic acid, 51,25 p-Toluenesulfonyl azide, with 2-(hy-... 

The details of this preparation are practically the same as those given for p-tolu-nitrile (Preparation 82). A cuprous-potassium cyanide solution, prepared as therein described, is warmed to about 70°, and added in small portions to a solution of benzene-diazonium chloride prepared from 18-6 gms. (1 mol.) of aniline as described in Preparation 379. When the addition is complete, the liquid is warmed on a water bath for 15 minutes and distilled in steam the distillate is extracted with ether. The ethereal solution is washed repeatedly with dilute caustic soda and with dilute sulphuric acid, dried over anhydrous potassium carbonate, filtered, and the oil which remains on driving off the ether fractionated. Owing to the evolution of cyanogen and hydrocyanic acid, this preparation must be carried out in a good fume cupboard. 

Toluic acid (m.p. 178°) may be obtained from -tolu-nitrile by the same process and in the same yields. This acid is less soluble in benzene and about 9 I. is needed for recrystallization. 

The available studies indicate that diimide has been used as a reducing agent for the preparation of HNBR. It has been used mainly as an alternative for hydrogenation of nitrile rubber latex. The use of diimide to hydrogenate low-molecular weight olefines is well known in the organic literature [93]. Diimide can be conveniently generated in situ by thermal treatment of solutions of p-tolu-enesulfonyl hydrazide or oxidation of hydrazine. 

The hydrogenation in a liquid-liquid system with ionic liquids as the catalyst phase was also applied to the hydrogenation of polymers. The first studies were presented by the group of Rosso et al. [91], who investigated the rhodium-catalyzed hydrogenation of polybutadiene (PBD), nitrile-butadiene rubber (NBR) and styrene-butadiene rubber (SBR) in a [BMIM][BF4]/toluene and a [BMIM][BF4]/tolu-ene/water system. The activity of the catalyst followed the trend PBD>NBR> SBR, which is the same order as the solubility of the polymers in the ionic liquid. The values in percentage total hydrogenation after 4 h reaction time were 94% for PBD and 43% for NBR, and after a reaction time of 3 h was 19% for SBR. 

A soln. of p-tolu-syn-aldoxime and methylketene diethyl acetal in dry ether refluxed 4 hrs. ->adduct (Y 95%) refluxed 3 hrs. in dry ether in the presence of 2 drops of 40% BF3-etherate and a little HgO p-toluisonitrile (Y 73%).— Ar. anfi-aldoximes and aliphatic aldoximes give nitriles under the same conditions. F. e., also nitriles, s. T. Mukaiyama, K. Tonooka, and K. Inoue, J. Org. Ghem. 26, 2202 (1961) isonitriles from aldoximes s. a. E. Muller and B. Narr, Z. Naturf. 16b, 845 (1961). 

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