Hydration and Hydrolysis

(123) Van Cleave, A. B., and Blake, R. I., Can. J. Chem., 29, 785-9. (1951). (124) Van Vleck, R. T. (to Texas Co.), U. 5. Patent 2,562,994 (Aug. (125)...
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(117) Tarrant, P., and Brown, H. C., J. Am. Chem. SOC.,73, 5831-3 (1951). (118) Terakawa, T. (to Fujisawa. Drug Manufacturing Co.), Japan. Patent 178,797 (May 18, 1949). (119) Union chimique belge, Soc. anon., Brit. Patent 652,740 (May 2,1951). (120) U. S. Dept. of Commerce, Bur. of Census, National Production Authority, "Facts for Industry," Ser. Ml9A-131 (April 4 , 1952). (121) U. S. Tariff Comm., Chem. Division, "Facts for Industry," Ser. 6-2-86 (1961). (122) Ibid., 6-2-96 (1952). (123) Van Cleave, A. B., and Blake, R. I., Can. J. Chem., 2 9 , 785-9 (1951).

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(124) Van Vleck, R. T. (to Texas Co.), U.5. Patent 2,562,994 (Aug. 7, 1951). (125) Wakefield, L. B., 1 r m . E ~CHXM., ~. 43,2363-6 (1951). (126) Warren, G. W. (to The Dow Chemical Co.), U. 8. Patent 2,677,388 (Dec. 4,1951). (127) Whitman, G. M. (to E. I. du Pont de Nemours & Co., Jnc.), Ibid., 2,578,913 (Dec. 18, 1951). (128) Wibaut, J. P., and Haak, F. A., Rec. trae. chim., 69, 1 3 8 7 4 2 (1950). (129) Wiegandt, H. F., and Lantm, P. R., IND. ENG. CHEM., 43, 2167-72 (1951). (130) Young, It. B. (to General Electric Co.), U. 8. Patent 2,590,SlO (March 25,1952). RECEIVED for review June 16. 1952. ACCEPTBD June 17, 1962.

Hydration and Hydrolysis ea

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DIVISION OF UNION CARBIDE AND CARBON CORPORATION, SOUTH CHARLESTON, W. VA. I n the field of industrial chemistry, hydration and hydrolysis are relatively old processes. In fact, when one considers the ancient arts of soapmaking and fermentation, commercial hydrolysis antedates industrial processes as we visualize them today. Hydration, which i s limited primarily to the aliphatic chemical industry, i s one of the early commercial processes in this field. The manufacture of ethyl alcohol followed closely the commercial development of ethylene chlorohydrin and ethylene dichloride only some 30 years ago. It is not surprising then that new and noteworthy advances in these two fields have been somewhat sparse. The developments discussed here cover data published during the past two years and earlier information which had not been available previously. As discussed in earlier reviews (67),no attempts will be made to evaluate such subjects as enzymatic hydrolyses, inversion of disaccharides, soap manufacture, or wood pulp processes.


YDRATION, the reaction of water with a compound to yield a reaction product containing both reactants in a single substance, is essentially a process of industrial aliphatic chemistry. Two general classes of compounds are hydrated on a large commercial scale-olefins and acetylenes. From the aspect of tonnage of product, capital investment, and number of manufacturers, the production of alcohols from olefins far surpasses the products made from acetylene. Two very interesting surveys (IO,34) have been published concerning ethylene and derived products. The manufacture of ethyl alcohol from ethylene has increased steadily during the past years, and during the past four years, half or more of the nation's production has been from this source. During this time annual production of ethyl alcohol has been of the order of 200,000,000 gallons and if by no other standards, hydration of ethylene has become big business,


Developments in the field of ethylene hydration with sulfuric acid have been primarily along lines of process improvement. Two patents (69, 60) have been issued t o the Standard Oil Development Co. for a continuous process in which ethylene is absorbed in concentrated sulfuric acid a t an olefin to acid mole ratio of 1.4 t o 1, followed by a two-step hydrolysis of the mixed diethyl and ethyl hydrogen sulfates a t 80' t o 90" C. and subsequent removal of the ethyl alcohol with steam. Hunter ( 2 7 ) has claimed an improved manufacturing procedure through the hydrolysis of ethyl hydrogen sulfate with the minimum amount of water, followed by vacuum distillation t o remove ethyl alcohol and simultaneously concentrate the dilute sulfuric acid in a single operation. Because most ethylene hydration processes depend upon utilization of relatively pure olefin, two related patents (6, 70) as-

signed to Phillips Petroleum Co. R ~ C of interest. Cracking gases containing ethylene and higher olefins m e mixed with isobutane, and after removal of methane and hydrogen, are treated with concentrated sulfuric acid a t 80' to 130' C. and pressurc'.i in the range of 250 t o 2000 pounds per square inch gage. Under these conditions alkylation of isobutane w i t h o l e f i n s c o n t a i n i n g three or more carbons occurs, and paraffins are formed which may be separated readily from the ethyl sulfates. Anhydrous hydrogcn fluoride, a t somewhat higher reaction temperatureq is claimed to be satisfactory in the same process. The undesirable aspects of acid-catalyzed hydration, particularly with sulfuric acid, such as corrosion, air and stream pollution in acid recovery, and the current shortages of sulfur, have given added impetus t o the development of other catalysts. Such endeavor is not new but its continuation reflects efforts to improve existing processes. Improved formation of ethyl alcohol has been claimed (44) by the reaction of ethylene and steam a t 200" t o 300' C. over a catalyst prepared by adsorbing phosphoric acid at about 60% concentration on diatomaceous earth, followed by drying t o raise the concentration of the acid t o 75 t o 85%. Powdered, activated montmorillonite impregnated with 8% hydrogen fluoride and dried, powdered, pelleted, and then calcined for 10 hours a t 550" C. is claimed in a patent ( 4 ) t o be effective as a catalyst for the preparation of ethyl alcohol from ethylene at 300' C. and 4000 pounds per square inch gage. Studies have been published (@) concerning the use of zinc oxide as a hydration catalyst, but the data are not sufficient t o indicate specific process application. Two potentially interesting processes have been patented for the simultaneous hydration, dehydrogenation, cracking, and condensation of a n olefin using ethylene and steam. In one, Nozu (49) has reported the formation of acetaldehyde, propionaldehyde, and acetone by the reaction of ethylene and steam in a weight ratio of 1 to 2 t o 5 at 25O'to 350 O 6. over a supported catalyst. The catalyst wm reported t o be composed of cadmium chromate, molybdate, tungstate, or vanadate, singly or mixed on bentonite or acid clay. The catalyst was prepared for use after forming by drying at 150" C. The equivalent zinc salts were claimed to be equally effective. The second process (63) utilized

September 1952


cadmium or zinc phosphates plus activated silver or copper compounds; quartz powder was added t o the mixture as a diluent. Acetaldehyde, acetone, or a mixture of these two were reported aa being formed from ethytene and steam utilizing this catalyst in a fluid catalysis reactor system. PROPYLENE

Developmental work in isopropyl alcohol manufacture, using sulfuric acid, has been along the lines of processes in which acid of approximately 70% concentration is used. Two patents granted t o Howlett and Wood (96,96) describe the absorption of a mixture of propylene and propane, containing at least 40% olefin, in 75% sulfuric acid at 340 t o 350 pounds per square inch and 80" C. in a countercurrent system. In 4 hours 95.2% absorption occurred ,with 40% propylene. Hydrolysis, by dilution t o 42% acid concentration at 90" t o 100" C., gave yields of 89.5% alcohol, 7.3% ether, and 0.870polymer. Smith (66) has described an analogous process for the continuous manufacture of isopropyl alcohol by the reaction of propylene and 70% acid at 80" C. and 250 pounds per square inch, followed by dilution t o 45% acid and hydrolysis at 95 " C. Interesting data have been published by Schrage and Amick (64) on the effect of temperature and composition on the total propylene present as isopropyl hydrogen sulfate in propylenesulfuric acid solutions. Optimum hydrolysis conditions t o provide maximum yields of alcohol were obtained by distillation from solutions at 45 t o 46% sulfuric acid concentration under moderately reduced pressures. Absorption of olefin from a mixture of propane, butanes, and 16% propylene by means of 98% sulfuric acid at temperatures of below 30" C. has been reported ( 4 6 )t o give 92% conversion t o diisopropyl and isopropyl hydrogen sulfate. Two other hydration catalysts for propylene have been reported. A catalyst containing 40% phosphoric acid, prepared by preheating silica gel or kieselguhr, impregnating with acid, and drying, was claimed (14) t o produce isopropyl alcohol by the reaction of propylene and steam at 180" C. and 250 pounds per square inch gage. The yield of 4% alcohol was reported to be 90% of the equilibrium value. A tungsten oxide catalyst (approximate composition WtOa) in the form of pellets, prepared from hydrated tungstic oxide reduced with propylene at 250" C. for 3 hours, has been reported (36) t o yield 92.5% isopropyl alcohol a t 17.3% propylene conversion per pass. The hydration wa8 conducted at 250' t o 290" C. and 250 atmospheres pressure; no other products except polymers were obtained. Engel (17') has devised an interesting one-step hydration and dehydrogenation proceas for the production of acetone from propylene. I n the proce89, which is claimed t o be satisfactory for any o l e h containing three or more carbons, the hydrocarbon and an excess of water are reacted at 300" t o 425" C. and at 10 to 50 atmospheres pressure. The catalyst is reported t o be a mixture of one or more oxides of the metals of the 11, 111, IV, or VI groups and one or more metals from the I, VII, or VI11 groups of the periodic table. Optimum conversion t o acetone waa obtained at a propylene t o water mole ratio of 20 t o 1 at 400" C. and 21 atmospheres over a catalyst containing copper, aluminum, thorium, and chromium in an atomic ratio of 50 to 50 t o 5 t o 15 By recycling the unreacted gas, yields of 80% have been obtained. HIGHER OLEFINS

As in the manufacture of ethyl and isopropyl alcohols, sulfuric acid continues t o play a major role in the synthesis of alcohols from four-carbon and higher oleha. Katsuno (99) has published data on the absorption of 1-butene in sulfuric acid and subsequent hydrolysis of the di(%butyl) sulfate. The effect of acid concentration and reaction temperature upon the extent of polymer formation and yield of 2-butanol has been shown. Optimum yields (70 t o 75%) of the alcohol were obtained by absorp-

202 1

tion in 87% acid at 15 O C. An improved prosees for the manufacture of %butanol (or 2- or 3-pentanol) from the corrmponding straight-chain olefin containing undesired tertiary olefins (such as isobutylene) has been claimed by Archibald and Mottern (3). The process involves treatment of the mixture with sulfuric acid a t 62 t o 70% concentration t o polymerize the tertiary olefins, followed by subsequent reaction with 83 t o 92% acid t o hydrate the straight-chain olefins. Patterson (50) has received a patent which is related to some degree to (a) for preparing %butanol from a mixture of butene and butanea. Separation of the paraffinic hydrocarbon is achieved by an extractive distillation using water and acetone; butane is removed as distillate and the olefinketone-water mixture as a still residue. After separation of the olefin, hydration was accomplished with 70 t o 93% sulfuric acid. Hydration of isobutylene t o tertiary butanol from a mixture of iso-olefin, butanes, and n-butenes was reported (la)t o be achieved readily using 40% sulfuric acid at 50" C. Part of the tertiary butanol produced in the hydrolysis step waa returned t o the acid absorption stage t o increaae the rate of olefin absorption. Tungsten oxide, described in the hydration of propylene, has been claimed (36') to be satisfactory for the conversion of isobutylene and %butene t o the corresponding alcohols. Isobutylene at 201 " C. and %butene at 230"t o 270" C. at 250 atmospheres were reported t o give 14.3 and 8.4% conversion t o alcohol per pass, respectively. The catalyst was WOa and graphite reduced at 250" C. with ethyl alcohol. Still another hydration catalyst for tertiary olefins has been devised by Serniuk and Vanderbilt (55). Boron trifluoride polyalkylene glycol complexes, prepared by adding 6 to 40 moles of ethylene or propylene oxide t o alcohols, phenols, or fatty acids and treating with boron trifluoride, have been reported t o be effective. Over such a oatalyst from olelyl alcohol reacted with 16 t o 20 moles of ethylene oxide and then boron trifluoride, an 86% yield of tertiary butanol was prepared a t 26" C. after 40 hours by the reaction of isobutylene and water. High yields of six- and seven-carbon alcohols from the oorresponding olefins have been claimed in a British patent (6). The principal claim t o novelty appears t o be the stepwise hydrolysis of the absorption product. Mottern (48) has described a method for the reduction of polymer formation in the manufacture of aliphatic alcohols from n-olefins, The procedure involves addition of corresponding dialkyl sulfates of the olefins and a trace of sulfuric acid t o the gas stream before it is introduced into the absorption zone. Greene (91) has received a patent on the manufacture of cyclohexanol from cyclohexene. The olefin was reacted with 65 t o 75% sulfuric acid at 50" C., and on hydrolysis a 75.2% yield of the alcohol and 19.3% recovery of the olefin were obtained.

HYDRATION OF ACETYLENES The industrial synthesis of acetaldehyde is achieved by either the hydration of acetylene or the dehydrogenation of ethyl alcohol. Choice of process is dependent on the economic aspects of the raw materials. Thus, in areas with low-cost ethylene, ethyl alcohol is the preferred source, but in areas where natural gas is not readily available or where electric costs (for the manufacture of calcium carbide) are low, acetylene is the starting material. Thus it is understandable that many of the developments in acetylene hydration have been made abroad rather than in this country where the aliphatic chemical industry has been based on readily available natural gas supplies. Many of the processes reviewed here are Japanese developments of the war and postwar period. Kawasaki (3l)has reviewed industrial methods, including his own, for the manufacture of acetaldehyde, which involve the reaction of acetylene and methanol, followed by hydrolysis of the methyl vinyl ether t o yield acetaldehyde and methanol. Considerable development of phosphate catalysts has been reported. Mollerstedt (41) claims excellent yields of aldehyde by reaction of acetylene and water a t 250" C. over a zinc phosphate



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catalyst. The gas mixture was passed through a preheater con&butene-l-yne, and 2% 2-methyl-1-butene-3-one. The catalgfit taining phosphoric acid. Data have been reported (78) on vapor for this process was zinc phosphate on Celite V. In Winslow's phase hydrolysis over a copper phosphate catalyst. A Japanese second patent ( 7 6 )phosphoric acid on Celite V was effective in patent (47) cites the use of a liquid phase catalyst composed of producing 98% conversion of the acetylenic alcohol t o a mixture cuprous chloride, ammonium chloride, phosphoric acid, and similar to that described above; by increasing the amount of ter. Conversions of 6% at 100" C. were reported but no effiwater introduced into the reartion, an 85% yield of butenone ciency data were listed. Low conversion to mono- and divinyl and a 15% yicld of dimer were obtained. .4Britishpatent (61) acetylenes was claimed. In has been issued on t h e a vapor phase process (65) manufacture of keto alcoa 97% yield of acetaldehyde hols from acetylenic alcowas reported by a reaction hols as a liquid phase proca t 280" to 300" C. over a ess a t temperatures below catalyst prepared byimpreg35" C. in the presence of nating activated carbon m e r c u r i c sulfate-sulfuric with cupric acetate, phosacid-iron catalyst. Yields phoric acid, and a small of keto alcohols in excess of amount of potassium iodide. 80% were reported for a Cadmium has been renumber of aliphatic and ported to be an effective aromatic substituted acetylacetylene hydration cataenic alcohols. lyst. I n a Swedish patent ( 6 4 )hydration with yields of HYDROLYSIS 95% aldehyde a t 350" C. over a catalyst of cadmium Application of hydrolysis phosphate precipitated on on an industrial scale is inglass wool has been claimed. volved in most major chemiIn still another process (45) cal m a n u f a c t u r i n g i n stallations in one or more a 95% yield of aldehyde was reported from hydration a t processes. I n s o m e i n 300" C. over a mixed stances, as in soap manuc a d m i u m - c a 1c i u m oxide facture and wood pulp pro* catalyst. Zinc oxide on cssing, hydrolysis is the ferric oxide (62) has been principal process: in others, found highly effective as a rmch as the manufacture of catalyst for aldehyde propharmaceutical chemicals, duction, with 95% yields it is only one of a series of C O U R T E S Y U N I O N C A R B I D E AND C A R B O N CORP. claimed, and Sakaki (55) interdependent processes. Thus the diversity of chemihas studied the use of zinc Alcohol Refining Still ea1 compounds subjected to oxide alone as a catalyst. h y d r o l y s i s i s far greater I n these studies, acetaldethan those vihich are subjected to hydration on an industrial hyde, acetic acid, and acetone were recovered as products acscale. It is not feasible t o attenipl t o present developments in companied by the formation of hydrogen, carbon dioxide, and every hydrolvsis operation that has been described during the methane. Antimonic oxide mixed with phosphoric acid (33) period covered by this review. An attempt, however, has been has been used as a catalyst for the hydration of acetylene a t made t o discuss significant developments that have been reportcd 350' C. Under the conditions used acetaldehyde was formed in 4470yield a t 95% efficiency to acetylene. PHENOLS Kawahra and coworkers (SO)have reported on the formation of The classical synthesis of phenol is by sulfonation of benzene, acetaldehyde by the action of supersonic waves on inixtures of followed by hydrolysis of the benzenesulfonic acid formed. Dcacetylene and water. Although no industrial process was prospite the development of alternative routes to the desired end posed the data are sufficiently interesting to warrant some furproduct, the sulfonation process has continued to survive s a t i s ther investigation. Improvement in aldehyde yields by hydratfactorily. An excellent review of this synthesis has been preing acetylene in the presence of a mercuric sulfate-sulfuric acidsented by Kenyon and Boehmer (53)in a diseussion of the ecoiron catalyst has been claimed by Randall (65') by using a connomics, alternate production methods, design, and materials of tinuous process in which hexane is introduced a t just below the construction. A British patent (77) has been granted which dereaction temperature. Aldehyde and water &-ere removed by scribes means for conservation and re-use of the sodium hydroxide distillation and the resinous by-products were removed in the hexneeded in the fusion stage of the hydrolysis by reaction of the soane layer. dium sulfate with slaked lime. In a patent Yura (Y9)has claimed Winslow has been issued two patents on the hydration of acetya similar achievement by recycling the sodium sulfite to the proclenic compounds, I n one (75)hydration of acetylenic olefins such ess. He has also published data (80) concerning the effect of difas 2-methyl-3-butene-1-yne is carried out a t 250' C. with 30% ferent catalysts of varying basicity on the degree of hydrolysb conversion per pass and an average yield of 86'% methyl isoproand the nature of the products. Hydrolysis of sodium benzenepenyl ketone. Some of the butenone dimer is formed. The catsulfonate in the presence of barium hydroxide, calcium hydroxide, alyst was Celite V impregnated with a solution of chromic oxide, or sodium aluminate gave high yields of phenol. With trisodium phosphoric acid, ammonium hydroxide, and tungstic oxide and phosphate or sodium molybdate the principal products were diignited at 500" C. Also describ9d in the same patent is the hyphenyl ether and diphenyl sulfide; optimum yields of phenol dration of acetylenic carbinols to a mixture of olefinic aldehyde, were obtained with sodium hydroxide. olefinic ketone, and ene-yne compounds. Thus 2-methyl-3-buOne of the most important developments in the manufacture of tyn-2-01 and water gave 87,5y0 conversion of the carbinol a t 200' phenols has occurred during this review period. This process is C , t o give yields of 36% 3-methyl-2-butene-l-a1, 44% 3-methyl.


September 1952


t h e oxidation of isopropyl benzene t o the corresponding hydroperoxide, followed by hydrolysis t o acetone and phenol using sulfuric acid as a catalyst. The process has been outlined in several British patents assigned t o Distillers, Ltd. ( 1 , 16, 16). I n addition t o sulfuric acid as catalyst, acetic, ptoluenesulfonic acid, and Zeokarb HIT ( a sulfonated phenol-formaldehyde resin) are claimed as hydrolysis catalysts (16). Hydrolysis of the sodium hydroperoxide with sulfuric acid at different concentrations has been described ( 1 ) . Sixty per cent acid a t 60' C. for 20 minutes gave quantitative yields of phenol, and 10% acid for 21/2 hours gave a 72% yield. The corresponding yields of acetone were 71 and 58%, respectively. I n the same patent a continuous hydrolysis wm described in which yields of 91% phenol and 88% acetone were obtained. Applicability of the process t o 0- , m- , or p-diisopropyl benzene has been claimed (16). With 10% SUIfuric acid, pisopropyl phenol was obtained from the corresponding dihydroperoxide, and with 20% acid, o-dihydroxybenzene was obtained from the o-dihydroperoxide. Reports in the chemical news magazines indicate interest in the process in this country, and at least one major chemical manufacturer has been reported t o have been licensed t o use the process. Another new development in the manufacture of phenols is a process said t o involve a boron catalyst. Hydrocarbon Chemicals, Inc., has been reported ( 1 1 ) t o have developed a process in which toluene vapor is passed through a mixture of sulfuric acid and an unnamed boron compound. The boron-toluene complex which is formed is hydrolyzed in good yields t o form p-cresol. The process has been claimed t o be effective for the manufacture of phenol and resorcinol. Friedlin and Fridman (18)have phblished data on the effect of cupric chloride on silica gel as catalyst for the vapor phase hydrolysis of 0- and p-chlorophenol, and o- and pdichlorobeneene. Information was given on yields and efficiencies at various reaction temperatures. ETHERS

The hydrolysis of ethers can with cyclic ethers be called a hydration and the term ether hydration is used frequently in industrial practice. Because the reaction of acyclic ethers yields two or more products containing portions of the added water, these reactions have been classed here as hydrolyses. Mason (39) has received a patent for the hydrolysis of aliphatic ethers t o the corresponding alcohols. The details refer t o the reaction of diethyl ether and water over an alumina catalyst at 320' t o 330" C. and at 200 pounds per square inch gage pressure. Ethylene was introduced t o minimize dehydration of the ethyl alcohol formed in the process, and alcohol yields of 55 t o 66% were obtained. Data have been obtained by Valentin (69) for the equilibrium between ethyl alcohol and diethyl ether-water mixtures a t various temperatures and 3 atmospheres pressure over an alum catalyst and over a catalyst of sulfuric acid on silica gel promoted with calcium sulfate. Much of the ethylene glycol produced in this country is obtained by the hydrolysis of ethylene oxide, and in a general survey of the subject, McClellan (37)has described the reaction and the extent of by-product formation. Kuhn and Hutcheson (34) have estimated that the production of ethylene glycol from ethylene oxide represents the major source of t h e 510,000,000 pounds of ethylene glycol made in 1950. Another hydrolysis of cyclic ethers is one described by Smith and Ballard (67) in a recent patent. I n the presence of acetic acid catalyst, 2-alkoxy3,4dihydro-2H-pyrans were hydrolyzed t o glutaraldehyde. Yields of 84% aldehyde as a distilled product or of 97% as an aqueous solution were reported. ESTERS

Historically, the hydrolysis of esters is one of the oldest chemi-

cfal processes. Developments in this particular field, as a result, are not revolutianary or fundamental in general. Nachod (43)


has reviewed the application of ion exchange resins as catalysts for the hydrolysis of esters. A British patent (68) has been issued for a countercurrent process for the hydi.olysis of esters; the use of heat exchangers is claimed t o achieve great economy in operation although little novelty appears t o be illustrated. A vapor phase hydrolysis of alkyl acetates with steam over acetates of cadmium, silver, or zinc on silica gel has been described (68). Using methyl acetate quantitative yields were claimed over zinc acetate on silica gel at elevated temperatures. The hydrolysis of polymeric compounds containing ester groups has provided a means of obtaining otherwise difficultly prepared polymers. Hydrolysis in alkaline medium of a copolymer of allylidene diacetate and vinyl acetate has been used (28) t o obtain a product containing recurring aldehyde and alcohol groups. Production of polyvinyl esters by hydrolysis with 0.1 t o 5 weight yo guanidine carbonate has been described by Bryant (8). Weak acids such as acetic acid were effective in terminating the hydrolysis. Glavis and coworkers (20) discussed the use of quaternary ammonium hydroxides in the hydrolysis of polyacrylic eaters t o obtain quaternary ammonium polyacrylates. Hydrolysis of a mixture of 3-acetoxy- and 1-acetoxy-1-propene with dilute sulfuric acid gave allyl alcohol, propionaldehyde, and acetic acid, thereby providing an improved method of separating a reaction mixture t o give usable products (9). ORGANIC HALIDES

Upon suitable hydrolysis organic halogen compounds offer a source of oxygenated molecules. A process for the production of alcohols has been described in a recent patent (7). Halides of aliphatic hydrocarbons containing eight or more carbon atoms were reacted under pressure at 200' t o 210 O C. with alkaline materials, such as calcium or barium hydroxides or sodium or potassium carbonates, in the presence of hydrocarbon solvents, which are necessary in order t o repress the formation of ethers, Yields of the desired alcohols were reported t o be 87% and minimum ether formation was observed. Hatch ( 2 4 )and his coworkers investigated the hydrolysis of several allylic chlorides in the presence of cuprous chloride catalyst and attributed the catalytic activity of the copper salt to the formation of a coordination complex at the olefinic bond. Hydrolysis of a mixture of 4-chloro-lmethyl-I-butene and 3-chloro-4methyl-I-butene with aqueous sodium carbonate has been shown (67) t o yield only 3-hydroxy-4methyl-1-butene. Weizmann (79) has received a patent for the production of 2-alkoxyisobutyric acid by the hydrolysis of 1,l,Itrichloro-2-methyl-2-butanol with potassium hydroxide in the presence of the appropriate alcohol. AMIDES AND NITRILES

Two processes have been described for the manufacture of acrylamide. I n the fimt of these. ( 7 1 ) treatment of acrylonitrile with anhydrous hydrogen chloride at approximately 50 O C. was followed by dehydrohalogenation of 8-chloropropionamide hydrochloride with aqueous sodium hydroxide t o give a 60% yield of acrylamide. In the second process ( 8 )hydrolysis of acrylonitrile with 84.5% sulfuric acid in the presence of powdered copper was reported t o give a 95% yield of acrylamide. Wenner (73, 74) has described the stepwise hydrolysis of arylacetonitriles t o the corresponding amides and acids. Data have been cited t o show the effect of various aryl substituents on the rates and yields. A German patent (48) has been issued describing the continuous hydrolysis of phenylacetonitrile t o phenylacetic acid with a reported yield of 83% highly refined product. Hydrolysis of a variety of amides and nitriles with sulfuric acid in the presence of mercuric sulfate has been investigated and reported in detail (66). The alkaline hydrolysis of polyhexamethyleneadipamide wastes has been used as a means (la)of recovering both the diamine and adipic acid. Tungstic oxide on alumina, with only traces of sodium ion being tolerated, has been reported (19, 88)t o be effective a catalyst for the hydrolysis of vinyl



ethers in a vapor phase process. Essentially quantitative yields of carbonyl compound and alcohol with minimum by-product formation were obtained. Hager (25) has received a patent on a process for the simultaneous hydrogenation and hydrolysis of nitrobenzene t o yield cyclohexanol. The process waa carried out in the vapor phase over a nickel copper chroniite catalyst, and amine by-products w’ere obtained. Hydrolysis of p-chlorosulfonic acid, a by-product in the manufacture of DDT, has been used (68)t o recover chlorobenzene.


Vol. 44, No. 9

Levy, N.,and Greenhalgh, R. K. (to Imperial Chemical Iiidiistries, Ltd.), Brit. Patent 646,284 (Nov. 22, 1950). Levy, N., and Greenhalgh, R. K. (to Imperial Chemicals, Ltd.), U. S. Patent 2,531,284 (Nov. 21, 1950); Brit. Patent 646,407 (Nov. 22, 1950). (37) McClellan, P. P., I K D . E N G . CHEErf., 42,2402-7 (1950). (38) McKinley, C. (to General ttniline and Film Corp.), U. 8.Patent 2,533,172 (Dec. 5, 1950). (39) iMason, R. B. (to Standard Oil Development Co.), E d . , 2,519,061 (Aug. 15, 1950). (40) Miyahara, Y., and Sano, I., J . Chem. Soc. Japan, Pure (;heoi. Sec., 69,90-1 (1948). (41) Mollerstedt, B. 0. P. (to Stockholm Superfosfat Fabriks .\ticbolag), Swed. Patent 124,669 (April 19, 1949). (42) Mottern, H. 0. (to Standard Oil Development Co.), U. 8. T ’ s t ent 2,496,251 (Jan. 31, 1950). \ (43) Sachod, F. C., “Ion Exchange,” pp. 268-73. New York, :\eademic Press, Inc., 1949. (44) Nelson, C. R., Taylor, M. A , Davidson, D. D., and Peters, L. N. (to N. V. de Bataafsche Petroleum Maatschappij), J31,it. Patent 651,275 (March 14,1951). (45) Nippon Chemical Industries Co., Japan. Patent 155,433 ( h w c h 12,1943). (46) Ibid., 156,639 (May 24, 1943). (47) Nippon Nitrogenous Fertilizers a,, Ibid., 155,852 (Apiil 6, 1943). (48) Nordmark-Werke, G.m.b.H., Oor. Patent 802,818 (Feb. 28, 1951). (49) Nozu, R , Japan. Patent 156,174 (April 23,1943). (50) Patterson, J. A. (to Standard Oil Development Co.), U. S. I’atent 2,514,291 (July4, 1950). (61) Polymeriznble Products, Ltd., Brit. Patent 640,477 (July 19, 1950). (52) Randall, M., U. S. Patent 2,511,787 (June 13, 1950). 153) Sakaki, T., J. Chem. Soc. J a p a n , 67,117-9 (1946). (54) Schrage, R. W., and Amick, E. H., Jr., IND.ENG C H U V ,42, 2550-3 (1950). (55) Serniuk, G. E., and Vanderbilt, B. M. (to Standard Oil Development Co.), U. S. Patent 2,534,304 (Dec. 19, 1950). (56) Smith, B. I. ( t o Standard Oil Development Co.), Ibid., 2,511,873 (Feb. 13, 1951). (57) Smith, C. W., and Ballard, 8. A. (to Shell Development e o . ) , Ibid., 2,546,018 (March 20, 1951). (58) Soci6ti5 Normande de products chimique, Brit. Patent 628,656 (Sept. 1,1949). (59) Standard Oil Development Co., I b d , 628,003 (hug. 19, 1949). (60) Ibid., 628,003 (Aug. 19, 1949). (61) Tapp. W. J.. IND.ENG.CHEM.,40, 1619-23 (1948); 42, 16981704 (1950). (62) Tekko Society, Inc., Japan. Patent 155,905 (April 7, 1943). (63) Topsp’e, H. F. A. (to Stockholm8 Superfosfat Fabrika Aktielolag), Swed. Patent 127,558 (March 14, 1950). (64) Topspe, H. F. A., and Nielsen, A., Ibid., 124,737 (April 26, 194‘31. (65) Toyo Textile Mills Co., Japan. Patent 158,604 (Aug. 30, 1943). (66) Travagli, G., Ann. univ. Perrara, 8, Pt. 1,23pp. (194849). (87) Ut&, A. J., Rec. Irar. chim.,68,483-4 (1949). (68) United States Rubber Go., Brit. Patent 640,213 (July 12, 1950). (69) Valentin, F. H. H., J . Chem. Soc., 1950,498-500. (70) Weinrich, W. W. (to Phillips Petroleum CO.), U. S. Patent 2,511,758 (June 13, 1950). (71) Weisgerber, C. A, (to Hercules Powder CO.),Zbid., 2,535,245 (Dec. 26,1950). (72) Weizmann, C. (to Polymerizohle Products, Ltd.),Z b X , 1,400,109 (Dec. 6,1949). (73) Wenner, W., J . Org. Chenz., 15, 548-61 (1950). (74) Wenner, W. (to Hoffman-LaRoche, Inc.), U. S. Potent 2,489 :iU, (Nov. 29, 1949). (75) Winslow, E. V. (to Publicker Industrias, Ino.), Zbid., 2,524,h05 (Oct. 10,1950). (76) Ihid., 2,524,866 (Oct. 10, 1950). 177) Yorkshire Tar Distillers. Ltd., iMilner, D. W., and Holdsworth. E. C., Brit. Patent 645,144 (Oct. 25, 1950). (78) Yoshino, K., Chem. High Polgmers (Japan), 1,29-37 (1944). (79) Yura, S., Japan. Patent 174,470 (Feb. 3,1947). (80) Yura, S., et al., J . Soc. C h m . I d . Japan, 50, 136-7, 137-8 (1947).

(1) Aller, B. V., Hall, R. H., and Lace>*,R. N. (to Distiller6 Co., Ltd.), Brit. Patent 620,429 (Sept. 20,1949). (2) American Cyanamid Co., Ibid., 631,592 (Nov. 7, 1949). (3) Archibald, F. M., and Mottern, H. 0. (to Standard Oil Development Co.). U. s. Patent 2.543.820 (March 6. 1951). (4) kchibald, R. C., and Trinible; R. ’A. (to Shell Development Co.), Ibid., 2,504,618 (April 18, 1950). (5) Arnold, P. M. (to Phillips Petroleum Co.), Ibid.,2,511,810 (June 13,1950). (6) N. V. Bataafsche Petroleum Maatschappij and Dammers, 13 F’., Brit. Patent 643,136 (Sept. 15, 1950). (7) Renedictis, A. D., Ballard, S. A., and Hearne, G. W. (to Shell Development Co.), U. S. Patent 2,572,251 (Oct. 23, 1951). (8) Bryant, H. W. (to E. I. du Pont de Nemours & Co., Inc.), Ibid., 2,481,388 (Sept. 9, 1949). (9) Burchfield, P. E. (to Wyandotte Chemicals Corp.), Ibid., 2,485,694 (Oct. 25,1949). (10) Chem. Eng. News, 29,4932-8 (1951). (11) Chem. Week, 68, No. 20, 16 (1951). (12) Compagnie d mngeis de raffinage, French Patent 932,838 (March 28, 1948). (13) D’Ali, P., Ital. Patent 443,260 (Dec. 15, 1948). (14) Deering, R. F. (to Union Oil Co. of California), U. S. Patent 2,496,621 (Feb. 7, 1951). (15) Distillers Co., Ltd., Aller, B. V., Hall, R. H., Quin, D. C., and Tuerck, K. H. W., Brit. Patent 626,095 (July8, 1949). (16) Distillers Co., LM.,Hawkins, E. G. E., Quin, D. C., and Salt, F. E., Ibid., 641,250 (Aug. 9, 1950). (17) Engel, W. F. (to Shell Development Co.), U. S. Patent 2,523,686 (Sept. 26, 1950). (18) Friedlin, L. Kh., and Fridman, G. A., Bull. acad. sci. U.R.S.S.. Classe sci. chim.,1949, 317-25. (19) General Aniline and Film Corp. and McKinley, C., Brit. Patent 630,926 (Oct. 24, 1949). (20) Glavis, F. J., Park, E., and Neher, H. T. (to Rohm and €Ta:is Co.). U. 8.Patent 2,435,777 (Feb. 10, 1948). (21) Greene, R. B. (to Allied Chemical and Dye Corp.), IbU., 2,504,517 (Aoril 18.1950). Greshim: W. E”. (to E. I. du Pont de Nemours & Co.. Tnc.), Ibid., 2,511,476 (June 13, 1950). Hager, G . F. (to E. I. du Pont de Nemours & Co., Inc.), Ibid., 2,481,922 (Segt. 13, 1949). Hatch, L. F., Brown, A. N., and Bailey, H. P., J . Am. Chern. SOC.,72,3198-200 (1950). Howlett, J., and Wood, W. L. (to Distillers Co., Ltd.), Brit. Patent 642,905 (Sept. 13, 1950). (26) Howlett, J., and Wood, W. L. (to Distillers Co., Ltd.), U. S. Patent 2,533,808 (Dec. 12, 1950). (27) Hunter, W. (to Celanese Corp. of America), Ibid., 2,529,553 (Nov. 14, 1950). (28) Izard, E. F. (to E. I. du Pont de Nemours & Co., Inc.), Ibid., 2,485,239 (Oct. 18, 1949). (29: Katsuno, M., J . 8oc. Chenz. Ind., J a p a n , 44, Suppl. binding, 275-82 (1941). (30) Kawahra, H., O h , R., and Karino, I., d . Electrochem. Assoe. J a p a n , 14,172-5 (1946). (31) Kawasrtki, K., J. 8oc. O T ~Sunthetic . Chem. J a p a n , 7, 77-83 (1949). (32) Kenyon, R. L., and Boehmer, N., IND. ENQ.CHEM.,42, 144655 (1950). (33) Kubota, B., and Takeshima, T., Rept. Sci. Research Ins!. (Japan),24,195-8 (1948). (34) Kuhn. W. E., and Hutcheson, J. W., Chem. W e e k , 69, No. 13, 19-34 (1951). RECEIVED for review May 28,


AccePrED June 4 , 195”.