Ryan & Cullinane — Action of Oxideu, Sfc, on Ethyl-o-Tolylurethane. 123 



T).— SYNTHESES AND CONSTITUTIONS OF SOME NITRO-O-TOLYLVRETHANES. 

 I. — Q-Nitro-2-Methyl-Phenylicret1iane. 



A mixture of 4-nitro- and 6-nitro-methyl-acetaiiilides was obtained by the 

 action of nitric acid on o-aceto-toluidide. On steam distilling the mixed nitro- 

 methyl-anilines obtained by the hydrolysis of the acetanilides with hydrochloric 

 acid, 6-nitro-methyl-aniline, which is volatile in steam, was separated (Lellmann 

 and Wiirthner, Liebig's Annal. d. Chem., ccxxviii (1884), p. 240). The latter 

 compound was condensed with ethyl chloroformate as follows : — 



A concentrated benzene solution of 6-nitro-methyl-phenylamine was heated on 

 the water-bath under a reflux condenser with one molecular proportion of chloro- 

 formic ester, which was added in small quantities. When the action had proceeded 

 for an hour, two grams of powdered calcium carbonate were added to decompose the 

 amine hydrochloride. After an hour's further heating, one molecular proportion of 

 the ester was again added as before. The heating was continued for another hour, 

 after which the solution was filtered while hot, and the benzene was removed by 

 distillation. On cooling, almost colourless prismatic crystals were deposited, which, 

 after washing with petroleum and recrystallising from alcohol, melted at 131° C. 

 On analysis the following results were obtained : — 



0-1020 g. of the substance gave 11-22 c.c. of moist nitrogen at 20° C. and 768 mm., 



corresponding to N 12-7. 

 C,oHi,04N2 requires N 12-5. 



Q-Nitro-2-methi/l-pheni/hirethaiie is readily soluble in benzene, alcohol, or chloro- 

 form, somewhat soluble in ether, and slightly soluble in petroleum ether. 



II. — b-Nitro-2-Methyl-PIieiiyltiretliane. 



This compound has been obtained by Vittenet [Bull. Soc. Chim. (3), xxi (1889), 

 p. 592] from alcohol and the corresponding nitro-methyl-phenyl- car bimide ; and by 

 Schiff and Vanni [Liebig's Annal. d. Chem., cclxviii (1891), p. 32b] by the condensa- 

 tion of 5-nitro-2-methyl-phenylamine with ethyl chloroformate. We obtained an 

 almost quantitative yield of it by employing a method similar to that used in the 

 preparation of the 6-nitro compound (above). On recrystallisation of the product 

 from 50 p.c. alcohol, fine white needles were obtained. The melting point 

 (137° C.) was somewhat higher than that obtained by Vittenet (129° (J.), but agreed 

 with that got by Schiff and Vanni. 



III. — A-Nitro-2-Methyl-Phenylurethane. 



This compound, which had previously been obtained by Vittenet (Bull. Soc. 

 Chim. (3), xxi (1889), p. 591), from alcohol and nitro-methyl-phenyl-carbimide, 

 was prepared by us by the combination of 4-nitro-2-methyl-phenylamine and 

 ethyl-chloroforraate, the method employed being similar to that used in the case of 

 the 6-nitro compound. After removal of the benzene by distillation, the re- 

 crystallisation of the resulting solid from alcohol, large, almost colourless, prisms, 

 melting at 135° C. (Vittenet's product melted at 127° C), were obtained in good 

 yield. This compound was found to be identical with the substance of similar 

 melting point described in A — 1(a). 



SOIENT. PKOC. R.D.S., VOL. XVII, NO. 15. Z 



