at the life of the catalyst may be
HE: unit process amina siderable attention
t poisons. The Mitsui Chemical s pressure or
*
ir
by the more modern and more elegant catalytic method. Love ( 4 A ) , in describing German production of inorganic pigments, has given detailed processes for the production of aniline by the BBchamp method in the I. G. Farbenindustrie A. G. Iron oxide pigments were an important by-product of this manufacture. In the United States it is not generally deemed worth while t o recover the iron oxide. Buckley and Elliot ( 1 A ) have reported the reduction of 3 4 troalkyl cyanides with iron and dilute acid t o give aminopyrrolines. Zinc and ammonium chloride or hydrogen in the presence of Raney nickel a t low temperature and pressure have also been successfully used in this reaction. Hodgson and Dodgson ( 8 A ) have found t h a t N-benzoyl-3,B'dinitrodiphenylamine readily gives the corresponding diamino compound on treatment with iron in the presence of dilute ferrous sulfate. J. R. Geigy A. G . ( 2 A ) has patented the BBchamp reduction of 4-nitrophenylsulfonylurea as a simple approach t o the synthesis of the Pamino derivative, which is claimed t o be therapeutically valuable as a sulfa drug. Winnek ( 6 A ) has described the eame reaction t o make similar aminoguanidino sulfonamides. Ciba ( 6 A )has protected the same reaction in the manuby means of a patent. acture of 2-sulfanilamido-l,3,4thiadia~ole
C A T A L Y T I C REDUCTIONS Considerable work on catalytic reduction has been reported in the past 12 months, covering both laboratory and plant scale aspects of this method. This is undoubtedly due t o the basic economy and versatility of this method and its ready adaptability to continuous processing. Sakuyama (B8B) has studied the continuous liquid phase reduction of nitrobenzene with hydrogen a t ordinary pressures using
Dolgov and Panina (8B) have reported t h a t the reduction of triethylsilylnitrolienzene with hydrogen in the presence of Raney nickel results in the corresponding amino derivative. Dohrn and Laubereau (7B)have described the preparation of 4-aminophenyl5-amino-2-pyridylsulfone, which is claimed t o have extraordinary bactericidal effect and low toxicity, b y the catalytic reduction of the corresponding dinitro compound with hydrogen in the presence of a nickel catalyst in methanol solution. Senkus (BN?) has patented the reduction of nitro diamino paraffins with hydrogen in the presence of Raney nickel at 30" t o 50 ' C. and 500 pounds per square inch gage t o give the triamines. Johnson ( I 7 B ) has described the liquid phase catalytic reduction under pressure of 2-nitro-%alkyl-N,N'-diaryl-l,3-propanediamines to the corresponding %amino derivative. Mosingo and Fonken (24B) have worked out the catalytic reduction of 2,4 diamino-5-nitroso-6-hydroxypyrimidine t o 2,4,5-triamino-6-hydroxypyrimidine using palladium, platinum oxide, or Raney ion a t about room temperature. Markees e reported the catalytic reduction of 142amino-4-thiazolyl)-2-(p-nitrophenyl)cyclopropanet o the amino compound using hydrogen and Raney nickel in acetone solution at 40" C. The resulting product gives promise as an antitubercular agent. Patents related t o the wartime manufacture of xylidines by catalytic reduction by the Standard Oil Company of New Jersey are still iesuing t o this company and its subsidiaries. Standard Oil Development Company (31B) has patented the process for continuous reduction of aryl nitro compounds to amines in the vapor phase using fluidized finely divided hydrogenation catalysts, preferably sulfur-activated catalysts. I n a patent assigned t o the same company, Voorhies (33B) has described the preparation of molybdenum sulfide and mixtures of this sulfide with nickel or tungsten sulfides, supported on suitable carriers such as alumina 1841
INDUSTRIAL A N D E N G I N E E R I N G CHEMISTRY
Vol. 41, No.
E)
C O U R T E S Y S H E L L C H E M I C A L CORPORATIOh
Cactus Ordnance Works Plant Where Xylidines Were Produced at Rate of 1,000,OOQ Pounds per Day b y Catalytic Hydrogenation of Nitroxylenes
or clay, for the catalytic reduction of nitroxylenes. I n another patent issued to this company (32%) there is described the process for the continuous reduction of aromatic nitro compounds t o amines by passing the nitro body concurrently with water and hydrogen through a reaction zone containing molybdenum, tungsten, or chromium sulfides. Controlling the temperature within narrow limits is claimed to be a decided improvement. The inlet temperature is held below 360" F., the reaction zone held between 330 and 470"F., and the recycle water and hydrogen, separated from effluent, below 390' F. A small stream of carbon disulfide may be added to the recycle stream to activate the catalyst. Probably the most spectacular story concerning this unit process which has been published to date is the disclosure of Shell's production of xylidines during the latter part of 1943 and the early part of 1944 b y a continuous catalytic process at the astounding rate of over 1,000,000 pounds per day. This is more than three times the normal daily production of aniline in the United States. This process has been described by DeLargey et al. (6B)and by Nelson et al. (86B), and covered by a patent issued to Souders (SOB) and assigned to the Shell Development Company. I n 1943,Shell Chemical Corporation undertook to convert an ammonia plant located a t Cactus Ordnance Works for the production of xylidines by continuous catalytic reduction for use as a n antiknock blending agent in aviation fuels for the purpose of enhancing engine performance under rich mixture conditions required for take-off and combat operations. Production was started about 9 months after conception of the program in spite of the fact that development took place under the stress of wartime conditions. The nominal design capacity of the plant was 960,000 pounds per day.
The crude nitroxylenes were purified with 20% soda ash solution a t 175' F. and then water washed. Unnitrated hydrocarbons were removed in B tray column and the nitroxylenes vacuum distilled in a second two-tray column, which actually was two 9foot columns in parallel in the plant. Because of possible explosion hazard a t this stage, design conditions provided for a maximum temperature of 310' F. and a maximum dinitroxylene CQUtent in the bottoms stream of 30%. Direct contact condensing sections in the distillation columns were used t o minimize pressure drop as well as t o accommodate the use of existing tubular equipment. Once-through vertical vapor lift type reboilers WPPB used to reduce peak temperatures to a minimum. The hydrogenation reactor unit consisted of four parallel reactors 8 feet in diameter b y 72 feet high. Each reactor contained ten catalyst beds and ten bubble trays below the beds. Temperature was controlled by water injection with the nitroxylene feed. The catalyst was copper-nickel on an inert support in the form of pel. lets which were about 0.25 inch in diameter by 0.375 to 0.5 inch in length. The catalyst was regenerated in place by burning ob accumulated carbonaceous residues with steam-air and again re. ducing with hydrogen. The unit was designed to provide f o ~ one reactor down for regeneration with three reactors on-stream. The dbtilled nitroxylene feed was supplied as ten separate streams, one t o the space between each bed and tray. After adding the requisite amount of water to maintain proper temperature the mixtures flowed on to the bubble trays beneath where heat was transferred from the recycling vapor which simultaneously cooled the reactants and vaporized the feed. The hydrogen wae preheated to 390' F. and entered a t the bottom of the reactor. The reactor was operated at about 400' t o 525' F. and 110 t o 140
September 1949
c
R
3
c
INDUSTRIAL AND ENGINEERING CHEMISTRY
pounds per square inch gage. The vaporized product was removed overhead. cooled to about 150' F., and the condensed xylidine and water mixture separated from recycle gas withdrawn to surge for further purification. Due t o the fact that separation of the xylidine and water presents difficulties because of the small specific gravity difference, a heptane diluent stream was injected to lower the density of the oil phase and allow rapid settling of the water phase. This was then extracted with diluent to prevent any losses due to solubility of the xylidine in water. The organic phase was then distilled in a column operating at atmospheric pressure to remove the diluent heptane. The bottoms from the Grst column went to the second column, operating a t slight vacuum, t o remove light by-products such as dimethylcyclohexylamine and dimethylcyclohexane. The bottoms from the second column were then sent to the last xylidine purification column, operating at 500-mm. reboiler pressure and about 9 feet in diameter with 24 trays. Specification xylidine was withdrawn overhead, The bottoms contained small amounts of nitroxylenes and high boiling by-products. I n a typical run, the hydrogen to nitroxylene mole ratio was 21, the water t o nitroxylene ratio was 6.3,the average inlet temperature to the catalyst bed wm 350" F., and the average outlet temperature was 480' F. The conversion of nitroxylene per pass was 94% and the yield was 95.8%. The average production was 17,000 pounds per hour per reactor or a total of over 1,000,000 pounds per day. A major problem was the distribution of liquid on the obtaining of uniform vapor composition in the BE the mixture was carried upward through the beds. This was solved successfully by installing disk-and-doughnut type vapor mixing baffle%between the trays and the catalyst beds. The overlapping part of the disk and doughnut was provided with vanes placed at a n angle to impart a swirling motion to the gas. The doughnut was above the disk in the reactor and wm secured to the wall by angle supports. These baffles had a beneficial effec the temperature distribution in the catalyst, and as a rem greatly enhanced ease of control and increased reactor capacity more than 5Q%. I n the short time that this plant was running i t produced over 200,000 barrels of xylidine. When the demand for xylidine diminished toward the end of the war, this plant was reconverted to ammonia production. I n addition to the publication of material concerning hydrogenation of nitro compounds t o amines, a number of publications have appeared with reference t o the catalytic reduction of cyano groups t o aminomethyl residues. Weber and Bell (b4B) have patented the continuous catalytic reduction of amboacetonitrile to ethylenediamine in the presence of ammonia, Imperial Chemical Industries, Ltd. (16B),has also covered the hydrogenation of the same compound by means of a patent in which the reduction is carried out under pressure in the presence of a catalyst and at least 15 moles of an inert diluent or a t least 4 moles of a saturated aliphatic ester. Hoffmann-LaRoche and Company, A.G. (14B)has patented a similar redu Grunfeld (11B)has d
tion of the benzene ,patented the hydrog
1843
ylic diesters of 1,l-diglycols in the presence of ammonia, primary, or secondary amines using hydrogen and a catalyst such as Raney nickel to give the corresponding primary, secondary, or tertiary amines, Some work has appeared on the preparation and utilization of vrtrious reduction catalysts. Adkina and Billica (1B)have described the preparation of two very active Raney nickel catalysts. Marisic and Rutledge (I1B) have patented the method of producing a porous, catalytically active nickel body, prepared by electrolytically depositing alternate layers of dense and porous nickel plates. Hernandez and Nord (I3B) have described the preparation of a catalytically active stable Colloidal dispersion of rhodium and have successfully used it for the catalytic reduction of a number of organic nitro compounds. They have found t h a t the rates are similar t o those obtained with a colloidal dispersion of palladium. E. I. du Pont de Nemours & Company (9B)has obtained another patent on catalytic hydrogenation in the presence of titanium hydride using organic solvents a t 100" t o 125' C. and 1000 t o 2000 pounds per square inch gage. It is claimed nitrobenzene gives aniline under neutral conditions and azobenzene in the presence of potassium hydroxide, and adiponitrile gives both the corresponding aminonitrile and diamine. Komarewsky and Riesz @OB) have written a rather thorough review of catalytic reactions and catalysts.
SULFIDE REACTIONS Comparatively little has appeared during the past year concerning this phase of a d n a t i o n by reduction. Borodkin et al. (IC)have reported the reduction of various chloronitrodiphenylamines to the corresponding amines using sodium sulfide in aqueous alcohol at the boil. Morley et al. (SC) have described the partial reduction of the oxime of 2,Pdinitrophenylacetone t o the corresponding 2-aminc-4-nitro compound using sodium hydrosulfide in aqueous ethanol. It is interesting to note that the free 2,4dinitrophenylacetone gives the same type of reduction on treatment with stannous chloride and hydrochloric acid in aqueous ethanol. Price and Stacy (8C)have published a procedure for mation of p-aminophenyl disulfide by treating Pchloronitrobenzene with boiling aqueous sodium sulfide and then with hydrogen peroxide.
INDUSTRIAL AND ENGINEERING CHEMISTRY
1844
Vol. 41, No. 9
benzene on reaction with zinc and alcoholic caustic. The hydrazo compound can be oxidized to 3,3'-divinylazobenzene with ferric chloride in aqueous ethanol. Dolgov and Panina (8B) have reported that treatment of triethylsilylnitrobenzene with zinc and alkali in alcoholic solution gives the expected azo and hydrazo compounds.
SULFITE REDUCTIONS Although the reaction of aromatic nitro compounds with sulfites t o form amines and aminosulfonic acids (Piria reaction) presents a fascinating field for study from the aspects of both theoretical organic chemistry and practical process development, little new work has been published during the past year. Goldblum and hlontonna ( I F ) have studied the Piria reaction on l-nitronaphthalene, whereby sodium naphthionate is obtained as major product together with smaller amounts of 1-naphthylamine and l-naphthylamine-2,4-disulfonic acid. From the experimentally determined values of the sulfate found in the reaction and the sulfate in the disulfonic acid fraction, they have concluded thc~ mechanism proposed by Sprung and co-workers is correct.
COURTESY E560 STANDARD OIL COMPANY
Compressor and Pumphouse of Hydrogenation Pilot Plant Catalytic Reduction of Nitroxylenes
for
ELECTROLYTIC REDUCTIONS The only published new electrolytic woik concerning this unit process during the past year has been reported by Dey and his eo-workers in India. Dey, Maller, and Pai ( I D ) have published a review of the chemical and elect1ochemical reductions of 2,4-dinitrophenol t o 2,4-diarninophenol and a dixcussion of some of the aspects of the electrolytic reduction of polynitro compounds. They describe a reduction a t 90" C. in the presence of 307, SUIfuric acid using a copper or Monel cathode and a current. density of 2.0 t o 2.3 amperes per square decimeter. A yield of 8170 of pure sulfate is claimed. The same investigators ( 2 0 , 3D) have studied the elcctrolytic reduction of 0-, m-, and p-nitrotoluene in sulfuric acid to give the corresponding toluidines and amino cresols. They have found the best conditions for the 0- and m- compounds to include a copper or Monel cathode with additives such as copper or mercuric sulfate and the optirnuin temperature to be 70" to 75" C. The para derivative results in p-aminobenzyl alcohol. Dey and Udupa ( 4 0 ) have found a 4595 yield of 2,1diaminophenol can be oblained by the electrolytic reduction of rn-dinitrobenzene which is mechanically dispersed in 40% sulfuric acid a t 90 t o 95 C. using a Monel or copper cathode with mrrcuric sulfate as catalyst,. Swann (5D) has written a comprehensive review of electrolvtic reactions, including a detailed discussion of electrolytic reductions.
MISCELLANEOUS REDUCTIONS Ghielmetti (4G) has published the claim that reduction 01 pnitrosalicylic acid with tin or zinc and hydrochloric acid or with stannous chloride always leads to m-aminophenol, and that prtininosalicyclic acid cannot be prepared in this way. Dewing and Dyke (3G) have described the I. G. Farbenindustrie process for the reduction of 4-amino-5isonitrosouracil with zinc and sulfuric acid to give 4,5-diaminouracil, an important intermediate i n the production of caffeine. Weizmann et ul. (19G) have worked out the rcduction of l,l,l-trichlor0-2,2-bis(4-nitrophenyl)ethane i o the corresponding diamine by using stannous chloride and hydrochloric acid in acetic acid a t lorn temperaturrs. Under these conditions dehytlrohalogeriatioii is avoidcd. Hodgson and Dixon (6G) have reported the reduction of 4,4'-dinitro-2,2'binaphthyl with zinc and hydrochloric acid in boiling acetic has acid to give the diamino compound. Krueger (I&) patented the process for preparing sgm-triaminobenzene andltriaininotoluene from the trinitro derivatives using mossy tin and wncentrated hydrochloric acid a t 60" to 70" C. The triamines are precipitated as hydrochlorides by inearis of gaseous hydrogen chloridc. Ward, Blenkinsop and Company, Ltd., and Goldberg ( I 8 G ) have ybtained a pateiif covering the reduction of 2,7-dinitro(3( 10H)acridone to the corre~poliding2,7-diamino-9(IOH)acridone
O
M E T A L AND A L K A L I REDUCTIONS Very little work has appeared in the literature with reference to the reduction of aromatic nitro compounds by means o€ metals in the presence of alkali to give azo and hydrazo derivatives, nor has anything been reported on the acid rearrangement of hydrazo compounds to benzidines. Wiley and Smith ( I E ) have described the reduction products of rn-nitrostyrene using various reducing agents. With zinc and hydrochloric acid, an 84y0yield of a polyincr of m-adnostyrene is obtained. On treatment with sodium methylate in methanol or zinc and ammonium chloride in aqueous ethanol, there is formed 3,3'-divinylazoxybenzene in a 78% yield. The azoxy derivhtive gives a 74.5 % yield of 3,3'-divinylhydrazo-
COURTESY ESSO STANDARD OIL COMPANY
High Pressure Reactor Stall a t Hydrogenation Pilot Plant. Unit Catalytic Reduction of Nitroxylener
For
INDUSTRIAL AND ENGINEERING CHEMISTRY
September 1949
c
by means of stannous chlori-.! an trated hydrochloric acid at 80” t o 90” C. This reag case. since the use of sodium amal line ’solution gives 2,7-diaminoacrildine. Lockemann a& Kiigler (11G) have described the reduction of nitrobenzoyl derivatives of tolylhydrazines, toluidines, benzylidenephenylhydrazines, and naphthylamines with zinc and acetic acid. Sulfuric acid was used in place of acetic acid where the compounds were not sensitive t o acid hydrolysis. Bean (IC)has patented the preparation of aminophenols by treatment of aromatic nitro compounds with aluminum and aqueous acids, preferably sulfuric acid, at 80” t o 100” c. Smith and Opie (I5G)have described the reduction of o-nitrobenzaldehyde t o o-aminobenzaldehyde by means of ferrous sulfate and ammonium hydroxide. Romeo (14G) has reported the preparation of 2-amino-4-acetylaminobenzoic acid from the corresponding nitro acid by reaction with ferrous hydroxide and ammonia at low temperatures.
acid t o 3-(2-furp1)propylamine by treatment with sodium in butanol, followed by neutralization. Ino and Oda (7#,8G) have studied the reduction of nitrobenzene to azo- and azoxybenzene and found that good yields of azobenzene may be obtained by treatment with methanolio caustic at high temperatures and pressures. Where the methanol is replaced by benzyl or allyl alcohol and the reaction carried out at 120O to 130”C., azoxybenzene is the major product. Bredereck and von Schuh (dG) have reported that the reduction of nitro derivatives of peptidelike compounds, such as Q~N(CaH&ONH).CeH4COOR proceeds well by treatment with phenyl hydrazine. The advantages of using phenyl hydrazine are its good solvent power and volatile oxidation products. When x = 1, the reduction may be carried out with zincdust and ammonium chloride. Pascual (1SG)has patented the reduction of 4hydroxy-3-nitrophenylarsonic acid to sodium 4,4’-dihydroxy3,3’-diaminoarsenobenzenemethanesulfoxylate(Neosalvarsan) by means of sodium hydroxymethanesulfonic ac sulf oxylate) Nystrom and Brown (12G)have described the use of lithium aluminum hydride in reducing aromatic and aliphatic ni aminoethyl derivatives, and Uffer and Schlittler (Ira)have employed the same reagent for a similar reduction of substituted and unsubstituted amides. Gluck (6G), in reporting on the I. G. Farbenindustrie manufacture of Agfacolor material, has described processes for producing color components, sensitizers, and stabilizers, including several procedures involving amination by reduction using BBchamp, catalytic, and other methods,
.
t
LITERATURE CITED B~CHAMP REDUCTIONS
(1A) Buckley, G. D., and Elliot, T. J., J . Chem. Soc., 1947, 1508-11. (2A) Geigy A. G., J. R., Swiss Patent 224,070 (Feb. 1,1943). (3A) Hodgson, H. H., and Dodgson, D. P., J. Chem. SOC.,1948, 10046. (4A) Love, C. H., U. 9. Dept. of Commerce, Waghington, D. C. O T S , FIAT Final Rept. 814 (1946). (5A) SOC.pour l’ind. chim. B Bhle, Swiss Patent 230,859 (April 17, 1944). (644) Winnek, P. 8.(to American Cyanamid Co.),U. 5. Patent 2,436,062 (Feb. 17, 1948). CATALYTIC REDUCTIONS
(1B) Adkins, H., and Billica, H.. J. Am. Chem. SOC.,70, 695-8 (1948). (2B) Alexander, E. R., and Misegades, A. L.. Ibid., pp. 131 (3B) Arbuzov and Poahil’tsova, Bull. acad. ai. U.R.S. sci. chim., 1946, pp. 65-70.
1845
(4B) Bruson, H. A., and Niederhauser, W. D. (t Rohm & Haas Co.), U. S. Patent 2,460,733 (Feb. 1, 1949). (5B) DeLaTgey, R. J., Okie, J. P., and Roberts, L. M., Chem. Eng., 55, NO. 10, 124-6 (1948). (6B) Direnga, 0. G., and Leaper, P. J., Office of Technical Services, U. S. Dept. of Commerce, Washington, D. C., OTS, F I A T FinaZ Rept. 1081 (1947). (7B) Dohrn, M., and Laubereau, 0. (vested in the Attorney Gens. Patent 2,456,258 (Dec. 14, eral of the United States), 1948). nina, 0. K., Zhur. Obshchet Khim. [J. .)I, 18, 1129-32 (1948). & Go., E. I., British Patent 603,825
u.
(10B) Emerson, W. S., Org. Reactions, 4, 174-255 (1948). (11B) Grunfeld, M. (to the Attorney General of the United States), U.S. Patent 2,449,036 (Sept. 7, 1948). (12B) Haskelberg, L., J. Am. Chem. Soc., 70,2811-12 (1948). (13B) Hernandez, L., and Nord, F. F., J . Colloid Sci., 3, 363-75 (1948). (14B) Hoffmann-LaRoche and Co., A. G., F., Swiss Patent 226,014 (June 1, 1943). (15B) Imperial Chemical Industries, Ltd., British Patent 595,384 (Dec. 3, 1947). (16B) Institute of Physical and Chemical Research, Japanese Patent 162,726 (March 12, 1944). (17B) Johnson, H. G. (to Commercial Solvents Gorp.), U. S. Patent 2, 1948). sci. e tec. (Pa&a),3, 183-5 (1948). man, B., and SchOrfe, E., Ann., 560, 215-21
.
I., and Riesz, C. II., “Technique of Organic Chemistry,” Vol. IT, pp. 1-78 of Weissberger, A., “Catalytic, Photochemical, and Electrolytic Reactions,” New Pork, Interscience Publishers, 1948. (21B) Marisic, M. M., and Rutledge, T. F. (to Socony-Vacuum Oil Co., Inc.), U. 8.Patent 2,453,668 (Nov. 9, 1948). (22B) Markees, D. G., and Burger, A., J. Am. Chem. Soc., 70, 3329-
32 (1948). (23B) Mitsui Chemical Industry Co., Japanese Patent 161,969 (Feb. 22, 1944). (24B) Mozingo, R., and Fonken, G. S. (to Merck & Co., Inc.) U. S. Patent 2,447,623 (Aug. 24, 1948). (25B) Nelson, C. R., Wilson, J. G., and Raymond, C. L., presented before the Regional Meeting, American Institute of Chemical Engipeers, Los Angeles, Calif., March 8, 1949. (26B) Prichard, W. W. (to E. I. du Pont de Nemours & Go., Inc.), U. 5. Patent 2,456,315 (Dec. 14, 1948). and Olin, J. F. (to Sharples Chemicals, ,452,602 (Nov. 2, 1948). c. Chem. Ind. Japan, 47,266-71 (1944).
mercial Solvents Gorp.), U. S. Patent 1948).
Shell Development Go.), U. S. Patent
2,458,214 (Jan. 4, 1949).
(31B) Standard Qil Development Go., British Patent 599,252 (March 9. 1948). (32B) Ibid., 602;bSO (June 4, 1948). (33B) Voorhies, A., Jr. (to Standard Oil Development Go.), U. 9. Patent 2,445,713 (Dec. 17, 1948). (34B) Weber, A. G., and Bell, C. D. (to E. I. du f o n t de Nemours & Go., Inc.), U. S.Patent 2,436,368 (Feb. 17, 1948). SULFIDE REDUCTIONS
(1C) Borodkin, V. F., Mal’kova. T. V., and Nikol’skaya, N , N., Zhur. Prihlad. Khirn. J . Applied Chem. (U.S.S.R.)I 20, 283-6 (1947). (2C) M o & i J. S., Simpson, J. C. E., and Stephenson, O., J . Chem. SOO.,1948, 1717-19. (3C) Price, C . C., and Stacy, G. W., OTg. Synthesis, 28, 14-15 (1948). ELECTROLYTIC REDUCTIONS
(1D) Dey, B. B., Maller, R. K., and Pai, B. R., J. Sci. Ind. Revearch (2D) (3D) (4D) (5D)
(India), 7B, 71-6 (1948). Ibid., pp. 107-113. Ibid., pp. 113-116. Dey, B. B., and Udupa, H. V., Ibid., 6B,83-92 (1947). Swann, S., Js., “Technique of Organio Chemistry,” Vol. 11, pp. 143-208 of Weissberger, A., “Catalytic, Photochemical, and Electrolytic Reactions,” New York, Interscience Publishers, 1948.
M E T A L AND A L K A L I REDUCTIONS
(1E) Wiley, R. IT., and Smith, N. R..,.J. Am. Chem. SOC.,70, 2295-6 (1948).
INDUSTRIAL AND ENGINEERING CHEMISTRY
1846 SULFITE REDUCTIONS
(1F) Goldblum. K. B., and Montonna, R.E., J . Org. Chem., 13, 17985 (1948). MISCELLANEOUS REDUCTIONS
Bean, F. R. (to Eastman Kodak Co.), U. S. Patent 2.446.519 (Aug. 10, 1948). Bredereck, H., and von Schuh, H., Chem. Ber., 81, 215-21 (1948).
Dewing, T., and Dyke, W. J. C., British Intelligence Objectives Sub-committee, London, BIOS Final Rept. 306 (1946). Ghielmetti, G., Farm. sci. e tec. (Pavia),3,51-2 (1948). Gluck, B., U. S. Dept. of Commerce, Washington, D. C., OT6, FIAT Final Rept. 943 (1947).
Hodgson, H. H., and Dixon, S., J. Chem. SOC.,1948,1714-15. Ino, K., and Oda, R., J. SOC.Chem. Ind. Japan, 46, 552-3 (1943) Ibid., pp. 1182-3. I
Vol. 41, No. 9
(9G) Jain, B. C., Mirohandani. P., Iyer. B. H., and Guha, P o e.. J . Indian Chena.SOC.,24,191-2 (1947). OOG) Krueger, J. (to Edwal Laboratories, Inc.), U. S. Patent 2,461,498 (Feb. 8, 1949). (11G) Lockemann, G., and Kegler, H., Chem. Ber., 80,479-84 (1947). (12G) Nystrom, R. F.,and Brown. W. G.. J . A m . Chem. SOC..70 3738-40 (1948). (13G)Pascual, J. A., British Patent 607,490 (Aug. 31, 1948). (14G) Romeo, A., Ricercu sci. e ricostruz., 18, 1057-8 (1948). (15G) Smith, L. I., and Opie, J. W., Org. Syntheses, 28, 11-13 ( 1 9 4 8 ~ ~ (16G) Sorm, F., and Brandejs, J., Collection Czech. Chem. Communs., 12, 444-54 (1947). (17G) Uffer, A., and Schlittler, E., Helu. Chim. Acta, 31, 1397-14001 (1848). (18G) Ward, Blenkinsop and Go., Ltd., and Goldberg, A. A., Britie'b Patent 602,231 (May 25, 1948). (19G) Weizmann, M.. Israelashvili, S., and Papo, R., J . Am. C R m SOC.,70, 4263-4 (%94S),
RECEIVED June 16, 1949.
Bs ARTHUR C.STEVENSON, DE N E M O U R S
AM MON OLYSI E. I. DU PONT
C O M P A N Y , INC., W I L M I N G T O N , DEL.
T
HERE have been numerous applications of the unit proc-
ess ammonolysis during the past year. Much of the work has been concerned with expanding and improving well established applications-for example, reactions of ammonia with acids, aldehydes, alcohols, esters, olefins, and substituted unsaturated compounds. Improvements have been made in controlling the nature of the reaction leading to specific products. Some attention has been given to development of new catalysts, ammonia recovery, and isolation of the products of the reaction. A new development is found in the manufacture of nitriles directly from paraffinic and aromatic hydrocarbons. This novel etdvance has been contributed by Denton, Bishop, Marisic, Caldwell, and Chapman of the Socony-Vacuum Oil Company, with their procedure for manufacture of nitriles by the direct combination of hydrocarbons and ammonia. The reaction is effected in the vapor phase a t approximately 1000 I?. in the presence of a catalyst composed of one or more of the oxides of tungsten, molybdenum, or vanadium, preferably supported on alumina. For tlue purpose of discussion this unit process has been divided into a number of sections according to starting materials. O
Ammoniaandhydrocarbonin the molar ratio of 2 to 1pass through the catalyst chamber with an average contact time of 4 seconds. The products are condensed from the unreacted material and are fractionally distilled. While a number of cycloparaffinic matepi. a1s have been used as feed stocks, those containing methyl groupr are preferred-for example, methyl and dimethyl cyclohexane. In most cases, there is some cleavage of carbon t o carbon bonds during the reaction. This cleavage leads to nitriles containing fewer carbon atoms than the starting materials. The products resulting from the ammonolysis of several different starting paraffinic materials are shown in Table I.
A R O M A T I C HYDROCARBONS Application of this technique to the direct reaction of alkyl aromatics with ammonia has led to practical processes for the manufacture of benzonitrile, tolunitrile, and xylonitrile according to the following equation:
0 CN
CH,
-'
825' to 1075' F.
HI IiHr MoOa.P2Oa.A1~Oa * PARAFFINS " " Past practice in the manufacture of aliphatic nitriles has involved reactions of ammonia with olefins, aldehydes, or aliphatic This simple one-step procedure is in marked contrast t o the acids in the presence of appropriate catalysts frequently consistformer methods of preparation of aromatic nitriles-namely, the reaction of aromatic halides or sulfates with alkali cyanides; the ing of various forms of cobalt, manganese, or chromium supported on silica or alumina. The reaction of ketones with hydrodecomposition of diazonium halides with potassium cuprow gen cyanide in the presence of a dehydration catalyst likewise cyanide; or the decomposition of isothiocyanates with copper OK zinc dust. leads to nitriles. Marisic et al. (344)have, devised a new procedure involving a direct vapor phase reaction of paraffinic or cycloparaffinic hydrocarbons with Table 1. Products of Ammonolysis of Paraffinic Hydrocarbons Product Wt. % Conversion per ammonia in the presence of a PASS Based on HC NHs/HC, Contaot catalyst made up of one or Molar Time, ScetoBenaoToluPropioCatalyst Ratio Sec. nitrile nitrile nitrile nibrile more of the oxides of molybdenum or tungsten. The reacCycloparaffin Stocks Methylcyclohexane (20) 20% Moos, 80% AlzOs 2 : 1 2.5 1.6 1.5 ... .. tion is effected a t a temperaDimethylcyclohexane 20% M O O S ,SO% Altos 2:1 5.0 0.5 ... 1.8 (10) ture of approximately 1000° F. 0 . 5 (mixed aromatic nit,riled Methylcyclopentane (14) 20% VzOs, SO% Ala03 2:1 2.5 1 .O in a reactor consisting of a shell containing a catalyst chamber Propane (16) 20% VzOa 80'7 AI& 2:l 4.0 3.6 ... ... ... ... Butane (16) 20% Vzos: Sod AlzOs 2:1 4.0 3.0 heated with a heat transfer Heptane (fa) Moos, WOs, AlzOs 2.7:1 0.9 0.5 3:O ... i:4 medium from outside the shell. "
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