Halogenation - Industrial & Engineering Chemistry (ACS Publications)

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HALOGENATI mg EARL T. McBEE and OGREN R, PIERCE PURDUE UNIVERSITY, LAFAYETTE, IND.

T

H E continued high production of chlorine and chlorinated organic compounds is again evidenced in a review of the field for the past year. I n March 1950, 167,091short tons of chlorine were produced as contrasted to 148,693 short tons in March 1949 (94, 96). This trend is a reflection of the generally higher production levels of important inorganic chemicals in the United States. Some production figures for February 1950 are of interest: carbon tetrachloride, 14,688,762 pounds; chlorobenzene, 24,776,675 pounds; dichlorodiphenyltrichloroethane (DDT), 2,868,075pounds; and hexachlorocyclohexane, 3,181,834 pounds.

CHLORINATION PARAFFINS

An excellent discussion (100) of the chlorination of methane was presented by Wilson and Howland describing the effects of temperature, methane flow rate, ratio of methane to chlorine, and size of jets on the reaction. Steiner and Watson (86) found a correlation between relative reaction rates and decreasing carbonhydrogen bond strength in the chlorination of hydrocarbons having primary, secondary, and tertiary hydrogen atoms, and that the activation energy was dependent on the length of the carbon chain. Hirschkind (42) presented a comprehensive review of the chlorination of saturated hydrocarbons with emphasis on the compounds of lower molecular weight. Kilgren and Gorin (47) chlorinated hydrocarbons, such as methane and ethane, a t 325 O to 500 a C. in the presence of cupric oxychloride. The cupric oxychloride was reported to be transformed into cupric chloride by reaction with hydrogen chloride produced in the chlorination reaction. The resultant mixture of chlorine and cupric chloride comprised a more efficient chlorinating agent than chlorine alone. A modification of the reaction (39)employed cupric oxychloride and hydrogen chloride in equimolar ratio as the chlorinating agent. Flett (99) chlorinated petroleum distillates, such as the kerosene fraction, by first employing liquid phase chlorination to obtain a chlorine content of 15% and then circulating the partially chlorinated mixture at 60"to 175" C. through the reaction zone while introducing chlorine. I n this way, a highly chlorinated mixture with a low aniline point was obtained. A process (64) for the continuous liquid phase photochemical chlorination of hydrocarbons of low molecular weight was described, in which the reaction medium was a polychlorinated hydrocarbon having the same number of carbon atoms as the starting material. Chlorine and the hydrocarbon were introduced a t separate points in the reaction zone maintained at 25" to 150" C. and the reaction mixture was circulated. In particular, a highly chlorinated propane (63)WEM obtained by this procedure, employing l,%dichloropropane as the initial reaction medium. Thurman and Downing(98)chlorinated l,%dichloroethane,containing 2 to 3% of phosphorus pentachloride by weight, at 80" to 105" C. to produce l,l,%trichloroethane in good yield. Polychloropropanes (81) comprising mostly penta- to heptachloropropanes were first treated with an alkaline earth hydroxide (1 to 2% by weight of the starting material) and then photochemically with chlorine at 90"to 150' C. and 10 to 100 pounds per square inch pressure to produce octachloropropane in 94.2% yield. Plump (76) chlorinated l,l,l,%tetrachloropropane a t 60' to 100' C. in the presence of ferric chloride to give the solid isomer of pentachloropropane in good yield. Photochemical chlorina-

tion (68)of chloroform as compared to deuterochloroform showed that the former reacted faster and that the rates fitted the following expression:

L~llc.l = 1.4 * 0.2exp. (710

F

90/RT

OLEFINS

Chlorination (31 ) of vinyl chloride in l,l,%trichloroethane at low temperatures and in the absence of light produced 1,1,2trichloroethane in nearly quantitative conversion. Pudovik (77) chlorinated butadiene at -5' to -15" C. in chloroform solution to produre l,%dichloro-3-butene in 60% yield. The isomer, 1,4dichloro-%butene, as well as 1,2,3,4-tetrachlorobutane was also obtained. A procedure (61) was developed for the vapor phase chlorination of butadiene which comprised introducing chlorine and butadiene in a ratio of 1 to 1.24 into the reaction zone a t temperatures in the range of 25" to 100" C. and then passing the reaction mixture into water to separate the chlorinated products. At a reaction temperature of 78.8" C., the yield of dichlorobutenes was 84% and the ratio of 1,4-dichloro%butene to l,%dichloro-bbutene was 1.22 to 1. Buntin (9) chlorinated iso-octene in carbon tetrachloride solution in the presence of ultraviolet light to yield polychlorinated products containing 60 to 80% chlorine. These materials were found to possess insecticidal properties. Chlorination (27) of a polyethylene polymer in carbon tetrachloride solution at 77" C. in the dark was found to proceed rapidly in the presence of a small amount of a,a-azobis(cu,ydimethylvaleronitrile). The product contained 53.9% chlorine and formed pliable films. Babayan (2)photochemically chlorinated a solution of 3% polyethylene in carbon tetrachloride to obtain a product containing 73% chlorine. This material was characterized by a softening point above 200" C . and a decomposition point above 230" C, Hydrochlorination of Olefins. Jones and Barker (46) prepared vinyl chloride in high yield by the reaction of acetylene with aqueous hydrogen chloride in the presence of cuprous chloride and a monoethanolamine salt. I n the absence of the acid, vinylacetylene was obtained. Vapor phase reaction (6) of hydrogen chloride and acetylene in the presence of Zchlorovinylmercuric chloride at relatively low reaction temperatures produced vinyl chloride in good yield. Patat and Weidlich (74) studied the effect of metal salts on the formation, of vinyl chloride from the reaction of acetylene and hydrogen chloride. Mercuric chloride was found to incresse the reaction velocity 100 to 1000 times as compared to the following salts: platinic chloride, mercurous chloride, calcium chloride, ferric chloride, and barium chloride. Walker (97) prepared chlorine-containing materials by the reaction of acetylene, aqueous hydrogen chloride, and formaldehyde in the presence of zinc chloride at 45' to 75' C. Two compounds, CsH&llO~and CeH,sCls08, were the principal products. The monohydrochloride of vinylcyclohexene (46) was obtained by the reaction of aqueous hydrogen chloride with vinylcyclohexene at 55" to 75" C. At higher temperatures, the dihydrochloride wm obtained. Aromatics. The preparation of benzene hexachloride has been the principal research interest in the chlorination of aromatic compounds. An excellent discussion of the chlorination of benzene is presented by Schwabe et al. (80). Chlorination of benzene (88) in aqueous 1% sodium hydroxide at 50" C. gave a

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*

COURTESY E. I. DU PONT

oe N E M O U R ~k

GO., INC.

Reactor in Which Chlorine Is Combined with Acetylene to Form Tetrachloroethane, e Step in the Manufacture of Trichloroethylene and Perchloroethylene for Dry Cleaning, Extraction of Vegetable Oilr, and Degrearing of Metals

64% yield of benzene hexachloride composed of the following mixture of isomers: 70% alpha, 5% beta, 12% gamma, 13% omega. Stormon (87)chlorinated benzene photochemically by p m i n g a mixture of 4.27 moles of benzene to 1 mole of chlorine through a reaction zone maintained at 57' to 60" C. The conversion to benzene hexachloride was 7.1% and the product contained 14.7% of the gamma isomer. Chlorination of benzene (16)at 60" C. in the presence of anhydrous ferric chloride produced chlorobenzene in 55% yield. Webb (98) chlorinated a mixture of benzene and Chlorobenzene at 30" to 110' C. in the presence of ferric chloride to obtain a high yield of the isomeric dichlorobenzenes having the follow ing composition: 33.7y0ortho, 2.8% meta, 61.4y0para, and 2.1% polychlorobenzenes. The chlorination of benaene (93) in the presence of a clay catalyst at 25' to 30" C.was found to be more efficient in chlorine utilization than chlorination in the presence of a ferric chloride catalyst, The former favored the formation of chlorobenzene, while the latter produced larger amounta of polychlorobenzenes. Kress (48) chlorinated diethylbenzenes in the dark to produce bis(chloroethy1)benzenes in 36 to 60% yields. In the presence of light and phosphorus pentachloride at 60" C., higher yields of the bis(chloroethy1)benzenes were obtained. Nitrogen-Containing Compounds. Nagy and Kaiier (67) chlorinated substituted isomelamines in water solution containing sodium acetate to produce a product containing 31.3% available chlorine. The material was found to be unstable, decomposing violently after heating for 3 minutes at 160' C. Chlorination (1) of pyrazine at 200' to 250" C. in the presence of activated carbon impregnated with calcium chloride gave 2-chloropyrazine

in 23 t o 44% yield. A noncatalytic chlorination at 600" C. gave a 46% conversion to Zchloropyrazine. Oxygen-Containing Compounds. Billitzer (6) treated ethyl alcohol with calcium chloride and aqueous hydrogen chloride to produce ethyl chloride in nearly 100% conversion. Chlorination of 95% ethyl alcohol (13)in light at 30" to 60" C. gave the following products:

The proceea can be adapted to continuous operation. Reaction of polyvinyl alcohol (33)suspended in propionitrile with anhydrous hydrogen chloride at 50 " C. produced a polymer containing 7.1% chlorine, which formed a clear, flexible film. Cavelti (14)chlorinated resorcinol with sulfuryl chloride in the presence of a small amount of acetic acid to give 2,4,6-trichlororesorcinol. By slowly adding the resorcinol to the mixture of sulfuryl chloride and acetic acid, a smooth reaction was obtained. Phenol (30)was chlorinated at 80' to 90 " C. to produce a product melting at 37" C. which could be converted to 2,4dichlorophenoxyacetic acid in 80% yield calculated on the phenol. Acetic acid ($6,36) w&s chlorinated a t 105" C. in the presence of acetic anhydride or acetyl chloride to give chloroacetic acid in 82% conversion. The product could be obtained in a purity of 97.5y0 on crystallization by cooling. Price and Sprules (76) chlorinated long-chain keto acids in carbon tetrachloride solution a t 20' to 60' C.to obtain substitution in the two positions alpha to the keto group. Chlorination (89) of alpha, beta unsaturated aldehydes a t

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temperatures in the ranges 200" to 600" C. produced unsaturated acyl halides in good yields. Acrolein in a molar ratio to chlorine of 1.91 to 1 a t 225' C. gave a high yield of acrylyl chloride. Furfural (72) was chlorinated in carbon tetrachloride solution a t 27 C. to produce tetrachlorofurfural in excellent conversion. Di-tert-butyl peroxide (78) was chlorinated photochemically a t 30" to 40" C. to produce the monochlorinated derivative in 42 to 43% yield. Polychlorinated peroxides were obtained on further chlorination. Carlson (12) treated diallyl ether with hydrogen chloride at 30" C. in the presence of cuprous chloride to obtain allyl chloride in a conversion of 85.4%. Chlorination of coumarin (84) in pentachloroethane solution a t 100" to 110" C. gave 3-chlorocoumarin in yields ranging from 89 to 93%. Sulfur-Containing Compounds. Chlorination of thiophene or 2-chlorothiophene (44) at 50" C. followed by treatment with alkali gave 2,5dichlorothiophene in high yield. Coonradt and Hartough (19) chlorinated thiophene at an initial temperature of40' C. followed by a temperature increase to 190" C. to produce mixture of polychlorothiophenes of the followingcomposition: O

Dichlorothiophene Trichlorothiophene Tetrachlorothiophene Hesachlorodit hienyl High boilers

Loss

22.4% 46.3% 27.9% 1.1% 0.7 1.6%

A t a final reaction temperature of 123" C. and by treatment

of the products with aqueous sodium carbonate, the amount of tetrachlorothiophene in the products was increased to 79.2% (20). Chlorination (71) of thiophene in the presence of iodine a t 70" to 75" C. followed by treatment with aqueous potassium carbonate gave hexachlorothiolene in 80% yield. Norris and McCracken (70) prepared hexachlorothiolane in 21.7% yield by the chlorination of thiophene a t 84" to 153" C. This material was found to be a useful extreme-pressure additive to motor oils (69). Hartough (37) chlorinated thiophene a t 15' to 47" C. followed by treatment with aqueous sodium carbonate to produce Zchlorothiophene in 43% yield and 2,5-dichlorothiophene in 14% yield. When the chlorination reaction time waa increased, 2,3,5-trichlorothiophene was also obtained. A continuous procedure (18) was developed, similar to the preceding reaction, which produced monochlorothiophene in 47% yield and dichlorothiophene in 11%yield. Another modification (88) employed zinc instead of aqueous alkali to produce chlorothiophene from the chlorination mixture. Octachlorothiolane (21) was prepared in 37% yield by chlorination of thiophene in chloroform solution in the presence of iodine a t 10" C. followed by treatment with aqueous alkali. Chlorination (28) of dimethyl sulfide at 0" C. gave bis(ch1oromethyl) sulfide in 75% yield. The latter compound, when chlorinated at 0" C., produced bis(dichloromethy1) sulfide in 83% yield. Further chlorination of bis(dichloromethy1) sulfide a t 20 " to 25 C. yielded chloroform, carbon tetrachloride, and perchloromethanethiol. Wood (101)chlorinated trithiane a t ice-bath temperatures to obtain dichloromethyl sulfenyl chloride in 94% yield.

FLUORINATION An excellent survey ( 8 ) of the production of fluorine and fluorinated compounds in Germany during World War I1 has been released by the British Intelligence Objectives Sub-committee. Continuing interest in the field of fluorine chemistry in Great Britain is evidenced by a symposium (96)held in late 1949 in London. Particular interest was shown in the reactions of chlorine trifluoride, bromine trifluoride, and iodine pentafluoride. FLUORINE AND METAL FLUORIDES

Whitaker (99) has developed a modified electrolytic cell for the generation of fluorine, which employs a steel cathode and a carbon anode containing 35 to 47% copper in the form of a network.

Vol. 42, No. 9

The electrolyte is a mixture of potamium fluoride, hydrogen fluoride, and lithium fluoride and the operating temperature is in the range 95" to 115" C. A process (40)for the recovery of fluorine from stack gases formed during the processing of phosphate rocks was described by Hignett and Siegel. Sharpe (82) prepared AuBrFg by reaction of gold with bromine trifluoride. The auric bromofluoride reacted violently with carbon tetrachloride and benzene, and exploded on contact with alcohol. Various fluorides of molybdenum and vanadium (94) were prepared and their properties studied. The compound, MoF3, was found to be relatively stable and unaffected by alcohol and carbon tetrachloride. Trimethylamine (91) was fluorinated in the vapor phase at 130' to 220" C. with cobalt trifluoride to produce perfluorodimethylamine in good yield. McBee et al. (68, 69) fluorinated both unsaturated and saturated halocarbons with cerium tetrafluoride at temperatures in the range 100" to 500" C. and obtained both addition of fluorine to the unsaturated linkages and halogen replacement with retention of the same carbon skeletal structure as the starting material. Fluorination (62) of o-dichlorobenzene with silver difluoride and manganese trifluoride a t 300" to 400" C. produced both chloroundecafluorocyclohexane and dichlorodecafluorocyclohexane. Hexachlorobenzene (62) on reaction with lead tetrafluoride a t 300 " C. yielded trichlorononofluorocyclohexane. Sarsfield (79) prepared perfluoroheptane in 24% yield by fluorination of heptane a t 300" to 400" C. with cobalt trifluoride. A vapor phase fluorination process ( 8 ) was described in which the organic compound and fluorine were introduced separately into a permeable catalyst comprising copper coated with silver fluoride and having a diminishing ratio of mass to area in the direction of the gas flow. Musgrave and Smith (66,66) studied the vapor phase fluorination of hydrocarbons with fluorine and metal catalysts. In the fluorination of benzene, copper turnings coated with gold were the most effective catalyst, with the following coatings listed in order of decreaeing activity: cobalt, silver, nickel, copper, brass, mercury, chromium, rhodium, and iron. Fluorine (49),diluted with nitrogen, was used to fluorinate polymeric chlorotrifuoroethylene a t 20" to 30' C. The resultant product possessed increased stability to heat and 'chemical mtion, and good electrical properties. A process (10) was developed for the stabilization of fluorinated oils containing less than 1% residual hydrogen, which comprised reaction of the oil with fluorine initially a t 60" to 150" C. with a final temperature of 250" to 315" C. Simons (83) prepared tridecafluorocyclohexylarnine by electrolyzing aniline or cyclohexylamine dissolved in liquid hydrogen fluoride. Dodecafluorocyclohexane was also obtained from the reaction. An extension (84) of the reaction to the fluorination of dialkyl ethers produced perfluorinated ethers. Ethylene glycol monobutyl ether, however, gave nonofluorobutyl trifluorornethyl ether. HALOGEN EXCHANOE

The reaction of benzotrichloride with the fluorides of bismuth, cadmium, copper, lead, sodium, and zinc wm studied by Tewksbury and Haendler (90) and a qualitative relationship was found between remtivity and the oxidation-reduction potential of the metal-metal-ion couple. Ligett et al. (60) treated pentachlorobenzotrifluoride with bromine trifluoride at 0" to 150" C.; the product from this reaction was then treated with antimony pentafluoride at 60" to 140" C. to produce a mixture of the average composition CoClrF&F3. Dehalogenation of this mixture with zinc dust in ethyl alcohol gave dichloroheptafluoro(trifluoromethyl) cyclohexene and trichlorohexafluoro(trifluoromethy1) cyclohexene. The reaction(66,67)of brominetrifluoridewith hexachlorobenzene a t 0" to 100" C. produced a mixture of CeBrCllFt and CsBr2ClaFp. Treatment of this reaation product with antimony pentafluoride a t 120" C. followed by reaction with zinc

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INDUSTRIAL AND ENGINEERING CHFMISTRY

dust in ethyl alcohol produced chloroheptafluorocyclohexadiene, dichlorohexafluorocyclohexadiene,and trichloropentafluorocyclohexadiene (61). Decachlorobiphenyl (83)on reaction with bromine trifluoride at 50' to 160' C. yielded a mixture of the average composition, C I S B ~ C ~ ~Perfluorotoluene F~~. (66) was prepared by, fist, reaction of bromine trifluoride with pentachlorobenzotrifluoride a t 10' to 150" C., then treatment of this reaction product with antimony pentafluoride at 90' to 140" C. to produce a mixture of the average composition, C&l+FrCFa, followed by dehalogenation with ninc to give the desired perfluorotoluene. The reaction can be extended to the preparation of other perfluorinated aromatic compounds. Benning and Park ( 4 ) fluorinated compounds of the type C1(CFa),,CI and H(CF&Cl with antimony pentafluoride at 150" to 350" C. to obtain materials of the type CI(CFB)nCFa, CFa(CFg)nCFa, and H(CF2),CFa. Fluorination (IS, 1 7 ) of vinyl chloride with hydrogen fluoride in the presence of stannic chloride a t 0' to 38" C. gave 1-chloro-1-fluoroethane in 51% yield. Crawford and Wallsgrove (22) fluorinated hexachloropropene with hydrogen fluoride and antimony pentachloride at 147' C. and BO pounds per square inch pressure fo obtain l,l,%trichlorotrifluoropropene in 69% yield. Reaction (98)of l,%dibromo-1,ldichloroethane with a mixture of antimony trifluoride, antimony pentachloride, and hydrogen fluoride at 169' C. gave %bromol,l,l-trifluoroethane in 85% yield. MISCELLANEOUS REACTIONS

c

Iodotrifluoromethane and iodopentafluoroethane (96) when irradiated and heated with mercury formed the corresponding mercuric iodide. Bis(trifluoromethy1)mercury (26) wa8 prepared by the reaction of trifluoromethylmercuric iodide with silver, copper, or cadmium amalgams a t 120" to 160" C. in good yields ranging from 80 to 90%. Haszeldine (39)treated iodotrifluoromethane with ethylene in the presence of ultraviolet light or heat to produce compounds of the type CFa(CH*CH&,I, where n = 1, 2, and 3. Short-chain polymers of the general formula, CFa(CF*.CF,)nI ( n = 1 to 10) were obtained from the reaction of tetrafluoroethylene and iodotrifluoromethane. Simons et al. (48, 86) treated fluorocarbons with hydrogen at temperatures ranging from 700" to 900" C. to obtain cleavage products containing hydrogen, such as fluoroform. Similarly, reaction (7) with chlorine or bromine at 700" to 900" C. gave cleavage products composed of chbro- or bromofluorocarbons. Miller, Fager, and Griswald (64)found that chlorofluorocarbons would rearrange to form compounds containing the maximum possible fluorine substitution per carbon atom .when treated with aluminum chloride. Dichloro difluoromethane (62) was passed oi'er aluminum fluoride at 820' C to form, principally, chlorotrifluoromethane and smaller amounts of carbon tetrafluoride, trichlorofluoromethane, carbon tetrachloride, tetrachloroethylene, and hexachloroethane. Extension (68) of the reaction to l,l,ltrichlorodifluoroethane at 325' C. gave a product composed principally of 1,1,l-trifluoroethane and l-chloro-1-fluoroethylene. Park, Sharrah, and Lacher (7'3)prepared 1,2-diaIkoxy-3,3,4,4tetrafluorocyclobutane by reaction of hexafluorocyclobutene with alcohols in the presence of base. McBee et a2. (80) described the bromination of (trifluoromethy1)-substituted benzenes with a mixture of bromine, chlorine, and antimony pentachloride. Almost quantitative utilization of the bromine was obtained in this way. Chlorination of ethylidene fluoride (11) in the presence of light at 300" C. produced l-chloro-1,l-difluoroethanein yields up to 67%. Hillyer (41) prepared a mixture of vinyl chloride and vinyl fluoride from the reaction of acetylene, hydrogen chloride, and hydrogen fluoride at 175" to 180" C., using a catalyst composed of activated carbon impregnated with mercuric chloride and calcium chloride. By increasing the concentrations of either of the hydrogen halides, the yield of the corresponding vinyl halide

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increased. Esters (102)of chlorofluoroacetic acid were prepared in 50 to 80% yield by hydrolysis of the corresponding 1-alkoxy-schloro-1, lJ2-trifluoroethane with sulfuric acid. Hydrolysie (108) of l-alkoxy-l,1,2,%tetrafluoroethanewith sulfuric acid gave the correspondingester of difluoroacetic acid in 40% yield. ACKNOWLEDGMENT WW

The authors gratefully acknowledge the assistance of hIrs. Thomas Riethof and Z. D. Welch in the preparation of this paper,

LITERATURE CITED (1) American Cyanamid Co.,Brit. Patent 613,109(Nov. 23,1948). (2) Babayan, V. K.,U.8. Patent 2,481,188(Sept. 6,1949). (3) Benning,A.F.,Ibid., 2,505,877(May 2,1950). (4) Benning, A. F., and Park, J. D., Ibid., 2,490,764 (Dec. 13, 1949). (5) Billitzer, A. W., Azlatralkn Chem.Inst. J . and Proc.,15,261-7 (1948). (6) Bralley, J. A., Brit. Patent 617,335(Feb. 4,1949). (7) Brice, T.J., Pearlson, W. H., and Simons, J. H., J . Am. Chem. rSao., 71,2499-501 (1949). (8) British Intelligence Objeatives Sub-committee, B.I.O.S. F i n d Rept.1595,Item 22 (1949). (9) Buntin, G.A., U. S. Patent2,490,202(Dec. 6,1949). (10) Burford, W. B., 111,and Weber, C. E., Ilrid., 2,496,115(Jan. 31, 1960). (11) Calfee, J. D.,and Smith, L. B., Ibid., 2,499,629(March 7,1950). (12) Carlson, G.J., Ibid., 2,494,034(Jan. 10,1950). (13) Cass, 0.Pi.,Ibid., 2,478,152(Aug. 2, 1949). (14) Cavelti, J. E., Ibid., 2,485,562(Oct. 25,1949). (15) Chakravarti, D. P., Dutta, A. P., and Sen Gupta, S. B., J. Proc.Inst. Chemists (India), 19,111-16 (1947). (16) Chapman, J.. and Roberts, R.,Brit. Patent 627,773 (Aug. 16, 1949). (17) Chapman, J., and Roberta, R., U.9. Patent 2,495,407(Jan. 24, 1950). (18) Coonradt, H. L.,Ibid., 2,492,622(Dee. 27,1949). (19)Coonradt, H.Lo,and Hartough, H. D., Ibid., 2,492,623(Dec. 27, 1949). (20)Ibid., 2,492,624(Dec. 27,1949). (21)Ibid., 2,504,068(April 11,1950). (22) Crawford, J. W. C., and Wallsgrove, E. R., Brit. Patent 623,227 (May 13,1949). (23) Darragh, J. L.,U. S. Patent 2,473,990(June 21,1949). 1949,2979-82. (24) Emeleus, H.J., and Gutman, V., J . Chem. SOC., (25) Emeleus, H. J., and Haazeldine, R. N., Ibid., 1949,2948-52. (26)Ibid., pp. 2953-6. (27) Ernsberger, M. L.,U.S. Patent 2,503,252(April 11, 1950). (28) Feiohtinger, H.,and Moos, J., Chem. Bw., 81,371-5 (1948). (29) Flett, C. H., U.8.Patent 2,499,578(March 7,1950). (30) Foster, R. T.,and Bennett, N., Ibdd., 2,493,126(Jan. 3, 1990). (31) Goodrich Co., B.F., Brit. Patent 627,263(Aup. 4,1949). (32) Gorin, E., U.S. Patent 2,498,646(Feb. 21,1950). (33) Hagemeyer, H.J., Jr., Ibid., 2,484,502(Oct. 11,1949). (34) Halbedel, H. S., Ibid., 2,478,824(Aug. 9,1949). (35) Hammond, A. R.,John, J. A,, and Page, R.,Brit. Patent 621,531 (April 11, 1949).. (36) Hammond, A. R.,John, J. A., and Page, R., U. S. Patent 2,503,334(April 11, 1950). (37) Hartough, H. D., Ibid., 2,492,633(Dec. 27,1949). (38)Ibid., 2,492,634(Dec. 27,1949). (39) Hasreldine, R.N.,J. Chem. Sac., 1949,2856-61. ENQ.CHEM.,41,2493-8 (40)Hignett, T.P., and Siegel, M. R., IND. (1949). (41) Hillyer, J. C.,U. S. Patent 2,480,021(Aug. 23,1949). 41,2749-52 (1950). (42) Hirschkind, W.,IND.ENQ.CHEM., (43) James, W. R., Pearlson, W. H., and Simons, J. H., J . Ant. C h t . Sac., 72, 1761-4 (1950). (44) Johnson, G. C.,U.5. Patent 2,492,644(Dec. 27,1949). (45) Johnson, H.L.,and Stuart, A. P., Ibid., 2,499,505 (Maich 7, 1950). (46) Jones, W.E.,and Barker, R. L., Brit. Patent 628,731 (Sept. 2, 1949). (47) Kilgren, E. W., and Gorin, E., U. S. Patent 2,498,552(Feb. 21, 1950). (48) Kress, B. H., Brit. Patent 627,509(Aug. 10,1949). (49) F o p s , E. L.,U. 5. Patent 2,497,046(Feb. 7,1950). (50) Ligett, W. B.,McBee, E. T., and Lindgren, V. V., Ibid., 2,480,080 (Aug. 23, 1949). (51)Ibid., 2,498,891(Feb. 28,1950). (52) Lindgren, V. V.,and McBee, E. T., Ibid., 2,480,081 (.4ug. 23, 1949).

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1698

(53) McBee, E. T., and Devany, L. W., Ibid., 2,473,161(June 14, 1949). (54)Ibid., 2,473,162(June 14,1949). (55) McBee, E.T.,Lindgren, V. V., and Ligett, W. B., Ibid., 2,488,216 (Nov. 15,1949). (56) Ibid., 2,489,969(Nov. 29,1949). (57)Ibid., 2,489,970(Nov. 29,1949). (58) hlcBee, E.T., Robb, R. M., and Ligett, W. B., Ibid., 2,493,007 (Jan. 3, 1950). (59)Ibid., 2,493,008(Jan. 3,1950). (60) McBee, E.T.,Sanford, R. A., and Graham, P. J., J . Am. Chem. SOC.,72,1651-2 (1950). (61) Mahler, P., U.S.Patent 2,484,042(Oct. 11, 1949). (62) Miller, C. B., and Bratton, F. H., Ibid., 2,478,201 (Aug. 9, 19491. (63)Ibid., 2,k78,932(Aug. 16,1949). (64) Miller, W.T.,Jr., Fager, E. W., and Griswald, P. H., J . Am. Chetn. SOC., 72,705-7(1950). (65) Musgrave, W.K.R., and Smith, F., J . Chem. Soc., 1949,30216. (66)Ibid.. 1949,3026-8. (67) Nagy, D. E.,and Kaiser, D. W., U. S. Patent 2,498,217(Feb. ii, 1950). (68) Newton, T. W., and Rollefson, G. K., J . Chem. Phys., 17,71825 (1949). (69) Norris, M. D., and MoCrecken, J. H., U. S. Patent 2,503,290 (April 11, 1950). (70) Ibid., 2,504,083(April 11, 1950). (71)Ibid., 2,504,084(April 11,1950). (72) Novotny, E.E.,and Vogelsang, G. K., Ibid., 2,490,462(Dec. 6, 1949).

(73) Park, J. D., Sharrah, M. L., and Lacher, J. R., J . Am. Chem. SOC.,71,2337-9 (1949). (74) Patat, F., and Weidlich, P., H e h . Chim. Acta, 32, 783-94 (1949). (75) Plump, R. E., U. S. Patent 2,478,008(Aug. 2,1949). (76) Price, D., and Sgrules, F. J., Ibid., 2,481,036(Sept. 6,1949). (77) Pudovik, A. N., Zhur. Obschel Khim., 19,1174-92 (1949). (78) Rust, F. F.,Vaughan, W. E., and Wheatcroft, R. W., U. S. Patent 2,501,966(March 28,19.50).

WILLIAM J. TAPP,

Vol. 42, No. 9

(79) Sarsfield, N. F.,Ibid., 2,473,911(June 21,1949). (80) Schwabe, K., Schmidt, H., and Kuhneman, R., Angew. Chem., 61,48-6 (1949). (81) Sconce, J. S.,Rosenberg, D. S., and Johnson, A. W., U. S. Patent 2,492,941(Dec. 27,1949). (82)Sharpe, A. G., J . Chem. SOC.,1949,2901-2. (83) Simons, J. H.,U. 5. Patent 2,490,099(Dec. 6,1949). (84)Ibid., 2,500,388(March 14,1950). (85) Simons, J. H., Pearlson, W. H., and James, W. R., Ibid., 2,494,064 (Jan. 10,1950). (86) Steiner, H., and Watson, H. R., Discussions Faraduy SOC.,1947, NO.2,88-97. (87) Stormon, D. B., U. S. Patent2,499,120(Feb. 28,1950). y biopufm., Univ. nacl. mayor (88) Suarez, D. V., Rev. facultad fm. S a n Marc08 ( L i m a , Peru), 10, 323-32 (1948). (89) Tess, R. W.,Kearne, G. W., and Yale, H. L., U. 9. Patent 2.490.386 [Dec. 6. 1949). (90) Tew’ksbury,d. I., and Hae’ndler,H. M., J . Am. Chem. Soc., 71, 23357 (1949). (91) Thompson, J., and Emeleus, H. J., J. Chem. Soc., 1949,3080. (92) Thurman, P. J., and Downing, J., U. S. Patent 2,480,982(Sept. 6, 1949). (93) Tome, E. B.,and Dickey, J. B., Ibid., 2,500,218(March 14, 1950). (94) U. S. Bur. Census, Inorgpic Chemicals, U. S. Production Series M19A-30. (95)U. S. Office of Naval Research, London Branch, Tech. Rept. OANAB-52-49 (1949). (96) U.S.Tariff Commission, Chemical Division, Series 62-67. (97) Walker, J. F.,U. S.Patent 2,463,227(March 1, 1949). (98) Webb, 0.A,, Brit. Patent 625,940(July 6,1949). (99)Whitaker, G. C.,U.S. Patent 2,506,438(May 2,1950). (100) Wilson, M. J. G., and Howland, A. H., Fuel, 28,No. 6,127-35 (1949). (101)Wood, 8. R., U. S. Patent 2,484,061(Oct. 11, 1949). (102)Young, J. A., and Tarrant, P., J . Am. Chem. SOC.,71,2432-3 (1949). (103)Ibid., 72,1860-1 (1950). RECEIVED June 21,1950

CARBIDE AND CARBON CHEMICALS DIVISION,

UNION CARBIDE AND CARBON CORPORATION, SOUTH CHARLESTON, W. VA.

OST of the reactions of water with other molecules can be divided into two classes: hydration and hydrolysis. The scope of each of these, although defined in an earlier review (116),may be redescribed here. Hydration involves the reaction of water with a given compound in which the reaction product contains both reactants in a single compound. Hydrolysis, by contrast, is the reaction of water with a compound to yield two or more products, no one of which contains all of the components of both reactants. These definitions have been used as a basis for classifying the reactions that are described below. The following discussion covers developments during the past two years; in some instances, however, earlier developments whose general availability has been delayed and which were deemed to be of some importance have also been included. Although both fields are older industrially than most of organic chemistry, publication of new discoveries in these fields is extremely unusual. For that reason it is believed that only biennial review is justified. HYDRATION In the industrial aspects of hydration the manufacture of alcohols reprepents by far the major commercial application. The

number of bulk and fine chemicals which may be obtained from alcohols by substitution, oxidation, and dehydrogenation reactions followed by subsequent reactions of the products obtained has been described in a number of publications. Until the recent development of the carbonylation of olefins with carbon monoxide, essentially all of the commercially available alcohols of two to ten carbon atoms were derived by hydration of the corresponding olefins. Even with the introduction of the Oxo synthesis on a manufacturing scale, the major production of alcohols is achieved by a hydration process. Developments in the field of olefin hydration have been concerned with improvements in catalysts, processing conditions, and reaction equipment. By contrast, the hydration of acetylene and substituted acetylenes has received little attention; many of the new developments of products from acetylene, such as the enormous developments by Reppe and his coworkers, have involved the addition of water as only one of several reactants. OLEFINS

Judging from the number of patents relating to the hydration of olefins, particularly ethylene and propl,lene, the majority of