Amination by Reduction
m
C1>CH2CI>H>CHa>OC2H6>
OCH,>NHz>OH. Vaubel (46) has published a method for analyzing small quantities of nitrobenzene. The nitrobenzene is reduced t o aniline by means of zinc and hydrochloric acid, the aniline is converted t o the tribromo derivative, and the latter is diazotized and coupled with @-naphthol. Macovski and Riidulescu ( 1 9 ) have reported the reduction of a few aromatic m-nitro amides to m-amino amides by means of zinc powder, alcoholic calcium chloride, and hydrochloric acid. Complex zinc chloride compounds are formed during the reduction and they can be deromposed to the free amines by means of sodium carbonate. Ciba ( 5 ) has patented thc reduction of various amides to amines by means of lithium aluminum hydride in an inert anhydrous organic solvent. Murakami and Yukawa ($1, 48) have described the synthesis of p-phenetidine by treatment of nitrobenzene with zinc or magnesium, absolute alcohol, and 96% sulfuric acid, whereby reduction, rearrangement, and ethoxylation take place without isolation of the intermediate steps. Feitelson and Petrow (9) have published processes from the the synthesis of 4’-arninobiphenylyl-2-arsonic acid by reduction of the corresponding nitro compound with either ferrous sulfate and ammonia or c a t a l ~ ~ i c a lwith l y Raney nickel. A review on nitroparaffins, including their reduction by various methods, has been published b y Carriere ( 4 ) .
(31) Rij, J. H. van, Verkade, P. E., and Wepster, B. M., Rec. trau. chim., 70,236-40 (1951). (32) Rohrer, C . S., Rooley, J., and Brown, 0. W., J . Phys. & Colloid Chem., 55, No. 2, 211-14 (1951). (33) Ruzhentseva, A. K., and Goryacheva, N. S., Dokladg Akad. N a u k S.S.S.R., 81, 849-52 (1981). (34) Samdahl, B., and Berg, B., Bull. soc. chim. France, 1951, 94-7, (35) Sekiya, AT., J . Pharm. SOC. J a p a n , 70,520-9 (1950).
(36) Ibid.,pp. 545-52. (37) Ibid.,pp. 55g-7. (38) Senkus, bl. (to Commercial Solvents Corp.), U. S. Patent 2,543,473 (Feb. 27, 1951). (39) Ibid.,2,550,646 (April 24, 1951). (40) Shingu, H., and Matsushita, H., R e p t s . Inst. Chem. Research, Kgoto Univ., 19, 54-6 (1949). (41) Smith, H. A., and Bedoit, W.C., Jr., J . Phys. & Colloid Chem., 55, 1085-104 (1951). (42) Sokol’skii, D. V., and Shmonina, I-.P., Dokladg Akad. Nauk S.S.S.R.,78,721-4 (1951). (43) Spieler, I., and Prijs, B., Helv. chin^. Acta, 33, 1429-33 (1950). (44) Sugino, K., and Yamashita, M..J . Chem. Soc. Japan, Pure Chem. Sect., 70,71-3 (1949). (45) Vaubel, W., Chem.-Ztg., 75,432-3 (1951). (46) Weisblat, D. I., and Lyttle, D. A. (to Upjohn Co.), U. S.Patent 2,528,928 (Nov. 7, 1950). (47) Yamashita, M., J . Chem. Soc. J a p a n , Pure Chem. Sect., 70, 71-3 (1949). (48) Yukawa, Y., Ibid., 71,547-9 (1950). RZCEIT-ED for review J u n e 23, 1962.
LITERATURE CITED Allisson, F., Conite, J. L., and Fierz-David, €I. E., Helv. Chim. Acta, 34,818-22 (1951). Bhattacharyya, S . C., and Seymour, D. E., J . Chem. Soc., 1950, 1139-40. Campaigne, E. E., Budde, Ti-. hI., and Schaefer, G. F., Org. Synthesis, 31,6-8 (1951). Carribre, G., Chem. en Pharm. Tech. (Dordrecht), 7, 49-51 (1951). Ciba, Ltd., Swiss Patent 273, 953 (June 1, 1951). Condit, P. C. (to California Research Corp.), U. S. Patent 2,560,555 (July 17, 1951). D’Escamard, L. P., Boll. chim. farm., 90, 90-6 (1951). Dornow, A,, and Boberg, F., Chem. Ber., 83,261-4 (1950). Feitelson, B. N., and Petrow, V.,J . Chem. Soc., 1951, 2279-83. Gruber, W., and Renner, H., Monatsh., 81, 751-9 (1950). Haworth, R. D., and Jefferies, P. R., J . Chem. SOC.,1951,206771. Heinzelmann, R. V. (to Upjohn Co.), U. S. Patent 2,549,683 (April 17, 1951). Ibid.. 2.549.684 (Ami117. 1951) Ibid.; 2,549,685’(ipril 17, 1951). Ishifuku, X., Sakurai, H., and Okamoto, H. (to Ohki Drug Mfg. Co.), Japan. Patent 180,563 (Oct. 10, 1949). Iagaryshev, N. A., and Petrova, A. A, J . Phys. Chem. (U;S.S.R.), 24,745-59 (1950). Kornfeld, E. C., J. Org. Chem., 16, 131-8 (1951). Lappin, G. R., and Slezak, F. B., J . Am. Chem. Soc., 72, 2506-7 (1950). Macovski, E., and Rhdulescu, T., Acad. Rep. Populare Romdne, Bul. Stiint., A l , 253-65 (1949). hlerck & Co., Inc., Brit. Patent 648,904 (Jan. 17, 1951). Murakami, M., and Yukawa, Y . , Mem. Inst. Sci. Ind. Research Osaka Ut&., 7, 116-20 (1950). Nozoe, T., Seto, S., Ebine, S.,and Ita, S., J . Am. Chem. SOC., 73,1595 (1951). Ochiai, E., and Katada, M., J . Pharm. Soc. Japan, 63, 156-91 (1943). Ochiai, E., and Naito, T., Ibid., 64,206-10 (1944). Oohiai, E., Teshigawara, T., and Naito, T., Ibid., 65B, 429-30 (1945). Ogata, Y., and Sugiyama, I., Science ( J a p a n ) , 19, 232 (1949). Pandit, P. N., Tilak, B. D., and Venkataraman, K., PTOC. Indian Acad. Sci., 32A, 29-38 (1950). Profft, E., Deut. Chem.-Ztg., 2, 194-7 (1950). Raab, H. (to Farbenfabriken Bayer), Ger. Patent 806,667 (June 18,1951). Reeve, W., and Eareckson, W. A,, J . Am. Chem. Soc., 72, 3299300 (1950).
Vol. 44, No. 9
Houston, Tex.
ACCEPTBDJ u n e 27. 1952,
