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INDUSTRIAL AND ENGINEERING CHEMISTRY
(44)Rosenblatt, E. F. (to Baker and Co., Inc.), V. S. Patent 2,475,155(July 5,1949). (45)Sahashi, K., et al. (to Rikagaku Kenkyojo), Japan. Patent 172,795(May31.1946). (46) Scharmann, W. G., and Nelson, J. J. (to Standard Oil Development Co.), U.S. Patent 2,451,245(Sept. 6, 1949). (47)Schofield, K., J. C h m . SOC.,1949,2393-9. (48) Sharples Chemicals, Inc., Brit. Patent 615,715(Jan. 11, 1949). (49)Shirley, D.A, Goreau, T. N., and Eiseman, F. S.,Jr., J . Am. Chem. Soc., 71,3173-5 (1949). (50)Sillar S. 8. r. l., Italian Patent 431,671(March 2,1948). (51) Soci6t6 des usines chimiques RhBne-Poulenc, French Patent 866,545(Aug. 18,1941). (52)Tomkuljak, D., Chenb. Zvesti, 2, 114-19 (1948).
Vol. 42, No. 9
(53) Ullyot, G . E. (to Smith, Kline and French Laboratories), W. S. Patent 2,450,105(Aug. 30, 1949). (54)Vainshtetn, Yu, I., Zavodslzaya Lab., 14,517-19 (1948). (55) Weisblat, D. I., and Lyttle, D. A., J. Am. Chem. SOC.,71,3097-
81 (1949). (56)Weiemann, A., Ibid., 71,4154-5 (1949). (57)Werner, J., IND.ENQ.CREM.,41, 1841-6 (1949). (55)Williamson, T. A., Brit. Patent 623,789 (May 23,1949). (59)Yoshida, S., Imaki, K., and dkagi, S., J . Pharm. Soc. Jopan. 69,457-8 (1949). (60)Zimmerman, B. G. (to General Aniline and Film Gorp.), C S. Patent 2,464,194(March 8,1949). RECEIVED June 19, 1950.
AM M0N 0LYSlS DE NEMOURS 8 COMPANY, WILMINGTON, DEL.
R
ECENT development w involving the unit process ammonolysis have heen concerned with: (1) modification and broadening of the application of the reaction of ammonia and hydrocarbons Iwding to nitriles; (2) the use of high pressures in the manufacture of amines through a modified oxo process; (3) numerous applications of the reaction of ammonia and various functionally substituted organic molecules. Mechanism and kinetic studies have been concerned with the catalytic effect of Bodium in the ammonolysia of styrene and the reaction of ammonia with aldehydes and ketones. The problems of separating reaction products and devising continuous procedures for carrying out the reaction continue to receive the attention of investigators. This review has not been limited to ammonolysis in the narrowest sense but has been extended to include amination and reactions involving ammonia and amines in general.
supported on alundum, 6ti% of the methylcyctohexane was attacked, with 44 mole % being converted to benzonitrile. The reaction mixture consisted of 2 moles of ammonia, 1 mole of methylcyclohexane, and 150 moles of air. The reaction was carried out a t 440" C.with a space velocity of 2400 per hour. The catalyst contained 11 .4y0 vanadium, 3.9% molybdenum, and .034% phosphorus. This procedure is applicable to the preparation of aromatic nitriles from aromatic and substituted aromatic hydrocarbons. Examples appear in Table I. Aliphatic nitriles are prepared from olefins by a similar procedure (IO). The reaction of 2-methylpropene with ammonia and air in the ratios of 1 mole of hydrocarbon to 3 moles of ammonia and 110 moles of air results in a yield, based on the hydrocarbon introduced, of 28 mole yo acrylonitrile and 26 mole % acetonitrile. The reaction was carried out a t 485" C . with a space velocity of 3000 per hour. Teter (39)reports that sodium is effective in promoting reduced cobalt and nickel oxide catalysts in the preparation of nitriles by reacting olefins and :mimonia. The yield, based on the olefin feed, of nitrogen-containing products was increased from 11.2% with a catalyst wntaining 0.77% sodium to 36.3% when the sodium content was increased to 2.96%. The sodium is supplied to the catalyst ronipoqition in the form of the acetate or hydroxide. Isobutyronitrile has been prepared by the reaction of amiiioiiis and isobutylene oxide over a catalyst consisting of copper on alumina or silver supported on a combination of silica and alumina (98). The yield based on the olefin oxide charged is 46 mole yo with the latter catalyst. The reaction is effected at approximately 800' F. at atmospheric prewure. The contact time is 1.5 seconds. n-Butyrolnitrile results from the reaction of n-butyl alcohol and ammonia over a molybdenum oxide-alumina catalyst. A contact time of 0.5 second is used with a temperature of 820" F. Two moles of ammonia are used with each mole of alcohol (6).
NITRILES The procedures for the manufacture of nitriles by the direct ammonolysis of olefins and alkyl aromatic hydrocarbons previously reported by Denton, Bishop, and Marisic have been extended to include additional hydrocarbon materials as well as alkyl thiophenes and primary alcohols (13). Originally catalysts for this reaction were limited to the oxides of molybdenum, tungsten, phosphorus, and vanadium preferably supported on activated alumina; now metal salts of these materials have been proposed-for example, iron tungstate, ferric molybdate (Id), nickel and cobalt phosphate (IS, I 4 ) , and uranyl molybdate (16). The preparation of nitriles through the vapor phase ammonolysis of mono-, di-, and trimethylcyclohexenes with catalysts consisting of the oxides of molybdenum, tungsten, and vanadium supported on activated alumina is reported (30). Denton (12) emphasizes the importance of carrying out this reaction of ammonia and alkyl hydrocarbons at temperatures in the range of 975' to 1025 O F. in order to obtain maximum conversions to nitriles and to avoid Ion7 yields based on ammonia, due to decomposition of ammonia in contact with the catalyst. Decomposition ww found to he appreciable at 1075 " F. Table 1. Nitriles via Ammonolysis of Alkyl Aromatic Hydrocarbons in Presence of Oxygen (7 7) By adding air to the reaction mixture, Mole c7. ..___ YieldErchak (16) and Cosby (10) have Moles Mole8 (Based on effected an appreciable improvement in NHs/Mole Air/Mole Space Starting Startinr: Starting Starting TQIII~,., Velocity Msterial yield in this type reaction over previous Material Material Materisl a C. per Hour Product Attacked) investigators. In the vapor phase amToluene 2.0 75 450 2150 Benzonitrile 75 200 465 2260 Chlorobenzortitrile 47 monolysis of methylcyclohexane (18) r?g?$zFluene 3 . 06 BO 440 2700 Terephthdonitrile 26 over a catalyst comprising the oxides of p-Toluonitrile 22 vanadium, molybdenum, and phosphorus
INDUSTRIAL AND ENGINEERING CHEMISTRY
September 1950
Henzyl alcohol is converted to benzonitrile under essentially the same conditions. The yields per pass, based on the amount of alcohol fed to the reactor, are 10% benzonitrile and 45% butyronitiile. A quantitative yield of oleonitrile of high purity is obtained (32) by reading oleic acid and ammonia in the liquid phase at 260" to 290" C. in the presence of catalytic amounts of cobalt oleate. Merrill and Perry (81) obtain an 85 to 90% yield of hydrogen cyanide by reacting ammonia, methane, and oxygen over a platinum gauze catalyst at 1025" to 1150' C. Methane of 91% purity, obtainable from natural gas, is satisfactory for this use. Thomas (40)has made an extensive study of the catalyst for this reaction. A study of the problem of seprtratirig mixtures of nitriles has led to procedures (2, 4 ) for separating aromatic mono- and dinit riles from mixtures containing hydrocarbons. The mixed nitriles are extracted from the crude by treatment with hot 95% ethanol. On cooling the mononitrile and hydrocarbon remain soluble permitting separation of the insoluble dinitrile. The mononitrile may be extracted from the hydrocarbon by diluting the alcohol solution with water to 80 to 85% concentration. Under this condition, the hydrocarbon is insoluble whereas the nitrile remains in solution. Further dilution of the alcohol renders the mononitrile insoluble. The mononitrile is recovered from the alcohol solution through distillation.
AMINES Modifled Oxo Process. The preparation of amines by a modified oxo process has been reported. Larson (26) synthesized di,I-propylamine from ethylene, ammonia, carbon monoxide, and hydrogen. The reaction is carried out with a cobalt catalyst in ether or cyclohexane solution a t 250' C. under 560 to 850 atmospheres pressure. The product, which is somewhat impure, represents a yield of approximately 50% of the theoretical based on .the ethylene charged. Gresham (19) shows that ammonia or mono- and dialkyl ainines react with carbon monoxide and an ethylenic double bond to form amides. Reaction conditions involve temperatures of 230' to 265" C. and pressures of 500 to 850 atmospheres. The reaction indicated is carried out in solvents-fsr example, cyclohexane-in the presence of catalytic amounts of cobalt carbonyl. The catalyst may be made in situ by charging cobalt metal and exposing it to carbon monoxide under high pressure. The yield of propionamide based on ethylene is 68% of tho theoretical. Buckley and Ray (7) have condensed a primary aromatic amine (aniline), and carbon monoxide under approximately 3000 atmospheres pressure at temperatures in the range of 150' to 300' C. in the presence of an acid catalyst. An N-formyl derivative is believed to be an intermediate which polymerizes in a chainlike structure. The produrt is largely soluble in dilute mineral acid.
0
Ola5ns. The reaction of olefina with ammonia or primary or secondary amines in the presence of alkali metal catalysts has been reported by Whitman (46), and Gresham et al. (90). N-Butylamine reacts (46) with ethylene, in the presence of approximately 0.1 part of sodium, based on the N-butylamine, under 800 to lo00 atmospheres pressure at 200" C. Separation of the reaction products resulted in a 48% yield, based on the starting amine, of N,N-diet hylbutylrmine. By a similar pro-
168s
cedure (go), a mixture of N-alkylated hexamethylenediamines is obtained by reacting hexamethylenediamine and butadiene a t 70" to 84" C. in the presence of metdlic sodium. Two moles of amine were used for each mole of butadiene. The product is a mixture of the following compounds which are obtained in the indicated percentage conversions:
N-butenylhexamethylenediamine N, N-dibutenylhexamethylenediamine N,N,N'-tributenylhexamethylenediamine N,N,N'N'-tetrabutenylhexamethylenediamine
21.4% 29.4% 26.1% 3.4%
Wegler and Pieper (46)propose the following iriechariivms for the catalytic effect of alkali metals on the reaction of styrene and ammonia. Sodium is used in amounts equivalent to 1 to 2%of thestyrene. 1. C'6H6-CH=CHz
+ 2Na +C&€s-CHNa-CHzNa
+ CsHb-CHNrt-CH2Na + CsHsCH2CHa+ 3. &NNa + CeH8-CH=CH2 +C6H6-CHNa-CH2NR 4. CeH6-CHNa--CHgN& + R2NH --+ CeHs-CH2CHgNR2 + R2NNa 2. 2%" 2hNNa
Aldehydes and Ketones. The reaction of aldehydes and k e tones with ammonia is a familiar route to amines. A reducing agent is required for converting the intermediate imino compound to the corresponding amine. Although this reduction is ugually effected with hydrogen in the presence of a suitable catalyst, other reducing agents are effective also. The Wallach reaction employs formic acid as the reducing agent. Staple and Wagner (57) have studied the reactions of benraldohyde and cyclohexanone with piperidine, using the Wallach technique-that is, formic acid as the reducing agent. The reaction is represented as follows: >N
-
€I
+ O=. -
CH
