INDUSTRIAL AND ENGINEERING CHEMISTRY Searles, S., J . Ant. Chem. SOC.,73, 124-5 (1951). Semonskp, M., Collection Czechoslov. Chem. C o m m u n s . , 15, 1024-36 (1951).
Shacklett, C. D., and Smith, H. A , , J . Am. Chem. SOC.,73, 7 6 6 8 (1951).
Shafer, P. W., and Wagner, G. H. (to Linde Air Products Co.), Brit. Patent 662,916 (Dee. 12, 1951). Sheohter, H., and Kaplan, R. B., J . Am. Chem. SOC.,73, 1883 (1951).
Shikanova, I. A., J . Appl. Chem. (U.S.S.R.), 23, 703-9 (1950). Shimizu, IM., and Ohta, G., J . Pharm. Soc. Japan, 71, 879-82 (1951).
Shirley, D. A., and Reedy, W.H., J . Am. Chem. SOC., 73, 458-9 (1951). Ibid., pp. 4885-6.
Shishido, K., and Furuya, S.,J . Chem. I n d . (Japan),46, 151B (1943).
Sidorova, N. G., Zhur. ObshcheZ Khim., 21, 869-74 (1951). Smith, F. B., and Kraus, C . d.,J . Am. Chem. Soc., 74, 1418-20 (1952).
Smith, G. E. P. (to Firestone Tire and Rubber Co.), U. S. Patent 2,581,906 (Jan. 8, 1952). Societ&Robert Zapp., Ital. Patent 459,251 (Sept. 1 , 1950). Sommer, L. H. (to Don. Corning Co.), Brit. Patent 657,442 (Sept. 19, 1951). Spindt, R. S.,Stevens, D. R., and Baldwin, W.E., J . An?. Chem. Soc., 73, 3693-7 (1951).
Stahly, E. E, (to Koppers Co., Inc.), U. S. Patent 2,539,493 (Jan. 30, 1951). Stempel, G. H., Jr. (to General Tire and Rubber Co.), Brit, Patent 652,618 (April 26, 1951). Stevens, D. R., and Bowman, R. S. (to Gulf Research and Development Co.), U. S. Patent 2,560,666 (July 17, 1951). Swiss, J., and Arnteen, C. E. (to Westinghouse Electric Corp.), I b i d . , 2,595,729 (May 6 , 1952). Tatsuoka, S.,Kinoshita, T., and Nakamori, R., J . Pharm. SOC.Japan, 71, 702-4 (1951).
Temnikova, T. I., and Petrova, L. il., Zhur. Obshchei Iihim., 21, 1877-83 (1951).
Tiefenthal, H. E., Univ. Microfilms P u b . N o . 2086; ,Wicrofilrn Abstr., 11, S o . 2, 259-61 (1951).
(225) Tiganik, L. (to Uddeholms Aktiebolag), Swed. Patent 132,873 (Sept. 11, 1951). (226) Tomita, &I., Uyeo, S., Otaya, H., Maekawa, H., Fukuda, M., Echigo, S., Mieukami, S., and Matsui, T., J. Pharm. SOC. J a p a n , 71, 829-34 (1951). (227) Topchiev, 4.V., and Nametkin, N. S.,Dokludy A k a d . Naulc S.S.S.R., 80, 897-8 (1951). (228) Ibid.. 78. 295-7 11951). (229) Topehie;, A. Y., Kametkin, K. S., and Zhmykhova, N. RI., Ibid., 78, 497-500 (1951). (230) Topchiev, A. I-., and Paushkin, Ya. hI., Ibid., 58, 1057-60 (1947). (231) Topchiev, A. V., Paushkin, Ya. >I., Vishnyakova, T. P., and Kurashov, 31. V., Ibid., 80, 381-4 (1951). (232) Ibid., pp. 611-13. (233) Trave, R., Gam. chim. itnl., 81, 773-81 (1951). (234) Truffault, R . , and Nonteils, Y., Bull. soc. chim. France, 1951, 230-3. (235) Tsuruta, M., Kuroki, N., and Nishio, M,, Chem. H i g h Polymers ( J a p a n ) , 7 , 129-31 (1950). (236) Ungnade, H. E., and Hopkins, T. R., J . Am. Chem. SOC.,73, 3091-3 (1951). (237) Gniversal Oil Products Co., Brit. Patent 655,395 (July 13, 1961). (238) Ibid., 669,657 (April 9, 1952). (239) Upham, J. D. (to Phillips Petroleum Co.), U. S. Patent 2,570,407 (Oct. 9, 1951). (240) Vesely, J. A. (to Universal Oil Products Co.), Ibid., 2,563,087 (Aug. 7, 1951). (241) Wagner, C. R. (to Phillips Petroleum Co.), I b i d . , 2,560,010 (July 17, 1951). (242) Wagner, G . H . , and Strother, C. 0. (to Linde Air Products Co.), Brit. Patent 670,617 (April 23, 1952). (243) Weisburger, E. K., Weisburger, J . H., and Ray, F. E., J . Org. C ~ ~ W Z16. . . 1697-1700 (1951). (244) Wichterle, O., and Esterka, F., Collection Czechoslov. Chem. Communs., 15, 1021-3 (1951). (245) Wilson, W., J. Chem. SOC.,1952, 6-9. (246) Yukawa, Y., J . Chem. SOC.Japan, P u r e Chem. Sect., 71, 547-9 (1950). (247) Yushchenko, Yu. I., Zhur. Obshchei Khim., 21, 1244-7 (1951). (248) Zubarovskii, V.AI.,and Fidel, 9. N., Ibid., 21, 2064-8 (1951).
Amination
mx
JESSE WERNER,
Vol. 45, No. 9
b y Reduction
GENERAL ANILINE
AND FILM CORPORATION, GRASSELLI, N. J .
A method has been developed for the very rapid reduction of steam-volatile nitro compounds by the Bhchamp (iron and acid) method, thus avoiding by-products. Various studies have been carried out on the effect of conditions on yields by catalytic hydrogenation. The reduction of various nitroheterocycles to the corresponding amines by catalytic hydrogenation has been described. A method has been developed for the preparation of relatively pure primary amines by catalytic reduction of oximes. A patent has been issued on the preparation of monoaminopolystyrene from the corresponding nitro compound by reaction with sodium disulfide under pressure. Studies have been carried out on the electrolytic reduction of various nitro compounds and nitriles to amines. Miscellaneous reductions were reported during the year relating to the use of zinc and acid, ferrous sulfate and potassium carbonate, stannous chloride and hydrochloric acid, sodium dithionate, and tetrahydronaphthalene. A patent has been issued on the use of aluminum instead of zinc for the preparation of hydrazobenzenes, intermediates in the manufacture of benzidines. A general method was also developed for the reduction of organic azides to primary amines by means of lithium aluminum hydride.
D
URIKG the 12-month period since the last review (@), a
limited amount of work relating to the unit process amination by reduction has been published in the patent and other technical literature. iis has been customary in the past, this paper will be divided into sections dealing with Bdchamp (iron and dilute acid), catalytic, sulfide, electrolytic, and miscellaneous reductions. As usual, most of the published work is
devoted to catalytic methods: in spite of the fact that other methods are used to a far greater extent in carrying out this unit process on a commercial scale a t the present time. Preparation of amines by catalytic reduction, however, provides a very versatile laboratory and plant tool for obtaining the widest variety of amines, most often in high yield and purity.
BECHAMP REDUCTION A very meager amount of chemical and chemical engineering work has been reported on this method during the past year in spite of the fact that i t is used to a greater extent than any other for the reduction of nitro compounds in industry. Von Bramer et al. (39) have been granted a patent for a very interesting method of reducing steam-volatile, aromatic nitro compounds re-
September 1953
INDUSTRIAL AND ENGINEERING CHEMISTRY
1913
COURTESY OF AMEplCAN CYANAMID CO.
J
Kettles for the Reduction of Nitrobenzene to Aniline at Bound Brook,
ducible to substantially nonvolatile amines. A mixture of nitro compounds and superheated steam is passed into a mixture of iron and acid, resulting in very rapid reduction and, therefore, a minimum of by-products. A yield of 96y0 of p-phenylenediamine from p-nitroaniline is claimed. Rozina (31) has described a method of obtaining o-aminobenzenearsonic acid in a yield of over SOY0 by reducing the corresponding nitro compound with 80 mesh cast iron filings a t a pH of 7 to 8. The use of coarser iron results in some by-product azo compound. A Japanese patent has been issued to Kimura (11)for the purification of aromatic amines produced by reduction of nitro compounds with iron and nzineral acid, whereby the resulting reduction mixture is neutralized, phosphate and casein solution are added, and then sulfuric acid is added to a pH of 4.6 to precipitate everything but the amine.
CATALYTIC REDUCTION A good deal of work has been reported on the preparation of amines by catalytic hydrogenation, both in patents granted and in published journal articles. Flamme ( I S ) has attempted to develop optimum conditions for the hydrogenation of nitrobenzene with Raney nickel by varying the hydrogen pressure, temperature, quantity of catalyst, batch size, and storage conditions for the catalyst. He reports a yield of a t least 97% on carrying out the reduction a t 200" to 220' C. (after prior initiation a t 150" C.) and 20 to 25 atmospheres. Tsutsumi et al. (37') have studied the effect of water on the catalytic hydrogenation of nitrobenzene and benzyl nitrile with Raney nickel and nickel oxide. In the latter case, the presence of water more or less promotes the hydrogenation. Tutumi and Nagao (38) report that nitrobenzene can be hydrogenated easily with nickel-aluminum (1: 1) alloy and copper-aluminum (1: 1) alloy as catalysts, even in the absence of water, and that o-nitrotoluene can be hydrogenated with the former catalyst in the presence of water. A German patent has issued to Noeske (16)for the partial catalytic reduction of nitroparaffins to give predominantly primary aminoparaffins without undesired secondary amine byproducts. The reduction is carried out in the absence (or presence of but very small quantities) of solvents. Tryon (36) has obtained a patent on the batchwise catalytic reduction of 2nitro-2-methylolpropane t o the corresponding amine in high yield by introducing the nitro compound into the agitated reaction zone a t 70" C. to get very rapid reduction. Advantages claimed are higher yields and longer catalyst life. Gregory and Malkin (16) have described the synthesis of 2-amino-3-oxooctadecanoic acid by reducing 3-oxo-2-isonitrosooctadecanoic acid with hydrogen in the presence of a palladium catalyst in hydrochloric acid.
N. J., Plant of Calco Chemical Division of American Cyanamid Co.
The hydrogenation of 1,2-dichloro-4,5-dinitrobenxene over Raney nickel to give 4,5-dichloro-o-phenylenediamine was described by Davis and Ross (11). The synthesis of a powerful surface anesthetic, the diethylamino-ethanol ester of 4-amino-3-butoxybenzoic acid by hydrogenation of the corresponding nitro compound over Raney nickel is given in a British patent assigned to A. Wander, A.-G. (40). Clinton et al. (10) have described the reduction of similar esters of 4-amino-2-hydroxybenzoic acid and 4-amino-2-alkoxybenzoic acids by hydrogenation over platinum oxide and palladium on carbon and also by the BBchamp method. Berezovskii et al. (6) have reported the reduction of 2-chloromethyl-4-nitrotoluene over pyrophoric nickel in methanol and caustic soda to give 3,4-xylidine and the reduction of 2,6-bis(chloromethyl)-4-nitrotoluene over platinum in acetic acid to give 3,4,5-trimethylaniline. Biekart et al. (6) have done a great deal of work on the reduction of the tert-butylnitrobenzenes, the tert-butylacetamidonitrobenzenes, and the tert-butyldinitrobenzenes. Catalytic hydrogenation over Raney nickel always yields the corresponding amines. Reaction of 2,4-dinitrotert-butylbenzene with sodium polysulfide a t reflux gives 4-amino2-nitro-tert-butylbenzene. Ross et al. ($9) have reported the reduction of 2,2'-dinitrodiphenyl to the diamine over platinum oxide in 96y0 yield. Archer et al. (5)have used Raney nickel and platinum oxide for the reduction of 2-substituted m-nitrocinnamic acids to the corresponding amines. T h e preparation of 4,4'-diaminodiphenyl ether by hydrogenation of the corresponding dinitro compound over Raney nickel was given by Reynolds (28). Fel'dman and Gurevich (11)found that bis(nitropheny1thio)acetals and bis(nitropheny1thio)-phthalides could be reduced over Raney nickel to give the corresponding diamines. Ochiai and Satake ($6) reported t h a t the catalytic reduction of 4-chloro-2-methyl-8-nitroquinaldine-l-oxide over palladium on carbon gives 8-amino-2-methylquinaldine. Nakayama (14) similarly reported that such a reduction of 4-nitroquinoline-loxide gives 4-aminoquinoline. Parham and Bleasdale ( 1 7 ) have described the low pressure hydrogenation of 3-nitro4-phenylpyrazole over platinum oxide t o the amine. The reduction of 2-methyl-4-nitrobenzoxazole to the amine in 92 % yield over Raney nickel was reported by Sannie and Lapin ( S I ) . Hultquist et al. (19) have described the preparation of N-(2thiazolyl)-2-aminophenol-4-sulfonamideby reduction of the nitro compound using palladium on carbon a t low pressures. Manske and Ashford ( 2 2 ) have reported the catalytic reduction of 3-methoxy-4-ethoxyphenylacetonitrile t o the corresponding amine by hydrogenation over Raney nickel a t low pressures in the presenoe of ethyl alcohol and sodium hydroxide.
1914
INDUSTRIAL AND ENGINEERING CHEMISTRY
Beregi (4)has studied the reduction of oximes by the Paul method, whereby hydrogenation is carried out over Raney nickel in dioxane solution a t room temperature. H e found that no secondary amines are obtained when the primary amines, which ape found first, are continuously removed from the zone of reaction.
SULFIDE REDUCTION
Very little n-ork has been reported on this method during the past year. Ward and Day ( 4 1 ) studied the reaction of 3,4dinitrotoluene and 2,5-dinitrotoluene with various sulfides. They found t h a t 3,4-dinitrotoluene gives a mixture of the two nitroamines with alkaline sodium tetrasulfide and that 2,5dinitrotoluene gives a mixture of the two nitroamines with sodium hydrosulfide or sodium polysulfide. A patent has been issued to Skogseid (34) on the reduction of mononitropolystyrene to the amine by means of sodium disulfide in an autoclave a t 150" C. The product is claimed to be useful as an anion exchange resin.
ELECTROLYTIC REDUCTION Published ~ o r relating k to electrolytic reduction for the preparation of amines has been quite meager during the past year, as was also true during the preceding 12 months. Brintzinger and Eggers (8) have described the preparation of tris(hydroxymethy1)methglamine by reduction of the nitro precursor with a lead cathode and a carbon or platinum anode. using an electrolyte containing oxalic acid to prevent oxidation a t the anode. Antropov and Vagramyan ( 2 ) published a study of the electrolytic reduction of nitrobenzene, nitrosobcnxene, and phenylhydroxylamine in alcoholic sulfuric acid using a platinum cathode, Eroni a theoretical point of view. Harmon and Cason (16) have described the electrolytic reduction of a series of aromatic nitro compounds t o p-aminophenols as intermediates in the preparation of p-benzoquinones. Honda et al. (17) have published a process for the preparation of p-aminosalicylic acid in 74% yield by electrolytic reduction of p-nitrosalicylic acid using a tin cathode in alcoholic hydrochloric acid solution. An Indian patent was issucd to Janardhan (20)on the reduction of long-chain fatty acid nitriles to amines using a graphite anode, a copper cathode, and a promoter such as Raney nickel.
MISCELLANEOUS REDUCTION Miscellaneous reductions reported on during the past year include the use of zinc and acid, feirous sulfate and potassium carbonate, stannous chloride and hydrochloric acid, aluminum and alkali, lithium aluminum hydride, sodium dithionate, and tetrahydronaphthalene. Airan and Kulkarni (1) have reported the reduction of bis(2-hydroxy-6-nitro-1-naphthy1)sulfide and bis(2-hydroxy-6-nitroI-naphthyl) sulfide to bis( 2-hydroxy-6-amino-1-naphthy1)sulfide by means of zinc and ammonium chloride in ethyl alcohol solution. Patents have been issued to Rottschaefer ( 1 4 , YO) on the and their reducpreparation of 4-alkoxy-2-chloro-5-nitrotoluenes tion to the corresponding amines with zinc and acetic acid. The resulting amines are useful as azo dye intermediates. Smith ( 3 5 )has described the reduction of potassium 2-hydroxy5-nitrophenyl sulfate to the corresponding amine using ferrous sulfate and potassium carbonate a t the boil. Allcaline conditions weFe necessary t o avoid hydrolysis of the sulfate ester. Huckel and Janecka (18)prepared the methyl ether of p-aminosalicylic acid b y reducing the corresponding nitro compound with stannous chloride and hydrochloric acid. A patent has been issued to Sargent and Pedlow (33)on the preparation of benzidine and its derivatives by the reduction of the corresponding precursor nitroaryl compound t o the hydrazo intermediate with aluminum in the presence of a small amount of a zinc compound, followed by rearrangement to the benzidine with acid.
VOl. 45, No. 9
Boyer ( 7 ) has published a general procedure for the reduction oi organic azides t o primary amines by means of lithium aluminum hydride in ether. Examples of compounds prepared are 1naphthylamine, 0-phenylethylamine, l-phenyl-2-aminoethanol, and 1-methyl-2-aminoethanol.A patent was issued to British Resin Products, Ltd. ( 9 ) on the preparation of 4-aminocardanol, whereby theazo compound resulting from the coupling of benzenediazonium chloride with cardanol is reduced with sodium dithionate. The amine is claimed to be a useful antioxidant for petroleum products. Mashio and Yoshida ( 2 3 ) have studied the partial reduction of dinitroaryl compounds with Tetralin (1,2,3,& tetrahydronaphthalene) with and without sulfur. A mixture of nitroamines results in the presence of sulfur, but it is claimed that the o-nitro groups are reduced first when Tetralin is uaed alone.
LITERATURE CITED Airan, J. W., and Kulkarni, D. ll.,J . Indzan Chem. Soc., 28, 33940 (1951). Antropov, L. I., and Vagramyan, S . T., Zhur. Fiz. Khim... 25.. 409-18 (1951). Archer, S.,Hoppe, J . O., and Lewis, T . R., J . Am. Pliarin. A ~ s o c .S, C ~ Ed., . 40, 617-19 (1951). Beregi, L., iMayyar Kbm. Folydirat, 56, 257-4 (1950). Berexovskii, V. M., Kurdynkova, V. A., and Preobraxhenskii, N. A, Zhur. Obshchei Khim., 21, 1163-6 (1951). Biekart, H. J. B., Dessens, H. B., Verkade, P. E., and Wepstor, B.M., Rec. trav. chim.,71, 321-39 (1952). Boyer, J. H., J . Am. Chem. SOC.,73, 5865-6 (1961). Brint>zinger,H., and Eggers, U., Z. Electrochem., 56, 168 (1952), British Resin Products, Ltd., Brit. Patent 662,509 (Dee. 5, 1951). Clinton, I. R. O., Laskowski, S. C., Salvador, U. J., and Wilson, AI., J . Am. Chem. SOC.,73,3674-81 (1951). Davis, W., and Ross, W.C. J., J . Chem. Soc., 1951, 3258. Fel'dman, I. K., and Gurevich, T. I., Zhur. Obshchex Khim., 21, 1540-4 (1951). Flamme, bI. L. R., Chimie & inohstrie, 63, No. 3 bis, 489-91 (1950). General Aniline & Film Corp., Brit. Patent 660,082 (Oct. 31, 1951). Gregory, G. I., and hlalkin, T., J . Chem. SOC.,1951, 2453-6. Harmon, R. E., and C,ason, J., J . Org. Chem., 17, 1047--57 (1952). Honda, K., Yokouchi, R., and Kikuchi, S., J . Electrochern. Soc. Japan, 20,15-17 (1952). Huckel, W., and Janecka, K., Arch. Pharm., 284, 341-51 (1961). Hultquist, M. E., et al., J . Am. Chem. Soc., 73, 2558-66 (1951). Janardhan, P. B., Indian Patent 44,230 (May 24, 1952). Kimura, PI., Japan. Patent 180,804 (Nov. 7 , 1949). RIanske, R. H. F., and Ashford, W.R., J . Am. Chem. SOC.,73, 5144-6 (1951). WIashio, F., and Yoshida, Z., J . Chem. Soc. Japan, Ind. Chem. Sect., 53,211-15 (1950). Sakayama, I., J . P h a r m . SOC.Japan, 71, 1088-91 (1951). Soeske, H. (to Ruhrchemie d.-G.), Ger. Patent 831,996 (Feb. 18, 1952). Ochiai, E., and Gatalte, K., J . Pharnz. SOC.J a p a n , 71, 1078-82 (1951). Parham, IT. E., and Bleasdale, J. L., J . Am. Chem. SOC.,73, 4664-6 (1951). Reynolds, G. L4.,I b i d . , p. 4996. Rosa, S. D., Kahan, G. J., and Leach, W.A , , Ibid., 74, 4122-6 (1952). Rottschaefer, B. IT'. (to General Aniline & Film Corp.), U. S. Patent 2,681,971 (Jan. 8, 1952). Rozina. D. Sh..Z h u r . Priklad. Khim..23. 1110-12 (1950). (32) Sannie,' C., and Lapin, H., Bull. SOC. chim,' France, 1952, 369-72. (33) Sargent, D. E., and Pedlow, G. W.,Jr. (to General Aniline Br Film Corp.), C. S.Patent 2,570,866 (Oct. 9, 1951). (34) Skogseid, A. (to Sorsk Hydro-Elektrisk Kvaelstofaktieselskab), I b i d . , 2,592,349 (April 8, 1952). (35) Smith, J. h-.,J . Cheri. SOC.,1951, 2861-3. (36) Tryon, P. F. (to Commercial Solvents Corp.), U. S. Patent 2,587,572 (I'e'o. 26, 1952). (37) Tsutsurni, S., Kayamori, H., and Kawamura, T., J . Chem. Soc. Japan, I n d . Chem. Sect., 54, 25-7 (1951). (38) Tutumi, S.,and Nagao, S.,Ibid., p. 165-7. (39) Yon Bramer, H., Magoffin, J. E., and Clemens, RI. (to Eastman KodakCo.), U. S.Patent2,578,328 (Dee. 11, 1951). (40) Wander, A , A,-G., Brit. Patent 654,484 (June 20, 1951). (41) Ward, E. R., and Dag, L. A., J . Chem. Soc., 1952, 398-400. (42) Werner, J., IND. EKG.CHmI., 44, 1980-2 (1952).
