INDUSTRIAL AND ENGINEERING CHEMISTRY
September 1954
(83H) Tarrant, P., Warner, D. A, and Taylor, R. E., Ibid., 75,4360-2 (1953). (84H) Thomas, C. L., U. S. Patent 2,673,884 (March 30, 1954). (85H) Thomas, W. M., and O'Shaughnessy, ill. T., J . Polymer Sci., 11, 445-70 (1953). (8613) Tycakowski, E. A,, and Bigelow, L. A., J . A m . Chem. Soc., 75. 3523-6 (1953). (87H) Wagner, G. H. (to'Union Carbide and Carbon Corp.), U. S. Patent 2,637,738 (May 5, 1953). (88R) Wiseman, P. A. (to The Firestone Tire and Rubber Co.), Ibid., 2,647,110 (July 28, 1953). (8911) Wrightson, J. M . , and Uittman, A. L. (to The AI. W. Keliogg Co.), Ibid., 2,667,518 (.Jan. 26, 1954). BROMINATION
Cason, J., Kalm, M. J . , and Mills, R. H., J . Org. Chern., 18, 1670-3 (1953).
Carey, E. J., J . A m . Cherrr. SOL.,75, 3297-9 (1953). Eckstein, B. H., Scheraga, H. A , and Van Artsdalen, E. K., J . Chem. Phys., 22, 28 35 (1954). Ferguson, L. N., Garner, A . Y., and Mack, J. L., J . Ani. Chem. SOC.,76, 1250-1 (1954).
Frevel, L. K., and Hedelund, .J. W. (to The Daw Chemical Co.), U. S. Patent 2,659,760 (Nov. 17, 1953). Golmov, V. P., J . Gen. Chem., U.S.S.R., 22, 2187-9 (1952) (English Translation).
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1841
(7C) Greenwood, F. L., and Kellert, hl. D., b. Am. C"hem. Soc., 75, 4842-3 (1953). Hatch, L. F., and Kidwell, L. E., Jr., Ihid., 76, 289-90 (1954). Rertog, H. J. den, and Bruin, P. (to Shell Development Co.), U. 9. Patent 2,672,439 (March 16, 1954). Hurd, C. D., and Anderson, H. J., J . Am. Chem: Soc., 75, 3517-20 (1953). Kosolapoff, G. M., Ibid., pp. 3596-7. Lamneck, 6. H., Jr., I b i d . , 76, 1106-7 (1954). Ruh, R. P., and Davis, R. A. (to The Dow Chemical Co.), U. S. Patent 2,639,301 M a y 19, 1953). Ibid., 2,658,086 (Nov. 3, 1953). Sharpe, A. G., J . Chem. Soc., 1953, 3713-4. Speier, J. L., Jr. (to Daw Corning Corp.), U. S. Patent 2,640,064 (May 26, 1953). Stevens, C. L., and Holland, W., J . Ora. Cheni., 18, 1112-6 (1953). Tsuruta, T., Sasaki, K., and Furukawa, J., J . A m . Chem. SOC., 76, 994-8 (1954). IODINATION
(ID) Djerassi, C., and Lenk, C. T., ,/. Sin. Chem. So(. 75, 3493 5 (1953). (2D) Forsman, J. P., and Lipkin, D., Ibzd., pp. 3145-8. (3D) Forsyth, P. F., Weber, E. N., and Schuler, 1i H., , J , Chmni. Phus., 22, 86-70 (1954). (4D) Potts, K. T., J . Chem. Soc., 1953, 3711-12.
Hydrution and Hydrolysis MONSANTO CHEMICAL CO., TEXAS CITY, TEX.
It i s beyond the scope of this review to cover completely the literature on hydration and hydrolysis; however, selected references are discussed to show trends and illustrate the variety of interests. Enzymatic processes are not included, and treatment of hydrolysis of fats and carbohydrates is limited. The patent literature continues to be the major source of inFormation about developments in this field. The majority of work has been concerned with process improvements and synthesis of new compounds. Highlights of this review period are emphasis on the direct hydration of olefins, improvements in the sulfonation process For phenols, syntheses of cresol, preparation of polyelectrolyte soil conditioners, continued interest in silicones. and hydrolysis of wood to dextrose.
YDRATION and hydrolysis are processes involving thc reaction of water with other compounds. These processes are well establishedindustriallyand few outstanding changes have been made. Developments reported during this review period, late 1951 to early 1954, arc classified in a manner similar to that used by Tapp in previous reviews (86).
HYDRATION The largest commercial application of hydration is in the production of alcohols by the hydration of olefins. Hatch (SI)has recrntly summarized the chemistry of this operation. The main emphasis of current work has been placed on improvement of pi oduct quality, yields, and catalysts, and a trend toward direct, hydration processes is evident. ETHYLENE
Several improvements in the process for the preparation of ethyl alcohol by the direct hydration of ethylene have been rep o r t d Thomson and Reynolds (88) claim greatly increased yields in a process comprising contacting a t 290' to 300' C. and 300 atmospheres pressure a mixture of gaseous ethylene and partly gaseous water in the presence of a titania-promoted tung5 t N l ovide catalyst. I n one Case a 95% conversion to ethyl
alcohol was obtained, and the pass yield, defined as the molar percentage of ethyl alcohol produced over ethylene fed, was 74.6%. Schrader, Young, and Berntsen ( 7 6 ) have Datented a cvclic Drocess that involves the Feaction of ethylene and steam Kith a supported phosphoric acid catalyst a t elevated temperature and pressure. Prolonged catalyst life and increased yield and conversion are claimed when free oxygen content of the reactants is kept a t a very low level (less than 0.2% and usually less than 0.05%). Removal of oxygen also allows operation a t high (.40'%) levels of impurities in the recycle stream. An improved process (60) for continuous manufacture of ethyl alcohol consists of passing a heated mixture of ethylene and water vapor a t 280' to 300' C. and pressures of 700 to 1200 pounds per squaro inch through a catalyst bed. The catalyst is prepared b y impreynating Celite VI11 (a calcined diatomaceous earth) with aqueous phosphoric acid of less than 70% strength and increasing the acid strength to 70% or above by heating to reaction temperature. Temperature, pressure, and ratio of feed gases are controlled to maintain an acid concentration of a t least 70%. ibIrtycock (@) claims a high quality ethyl alcohol of low permanganate time and unadulterated odor. The effluent stream from the hydration of ethylene is sprayed with an alkali metal hydroxide t o give a p H of 6.5 t o 7.5 in the condensate, and the condensate is distilled to give an enriched ethyl alcohol fraction that is hydrogenated in the presence of a nickel catalyst. The preparation of ethyl alcohol from low grade hydrocarbon gases containing from 30 to 40% by volume of ethylene and containing propylene as an impurity presents a favorable economic "
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1842
INDUSTRIAL AND ENGINEERING CHEMISTRY
picture. Such a process is reported ( 8 4 ) whereby the low grade gas is contacted with 95 to 100% sulfuric acid a t 60"to 100" C. and 300 to 500 pounds per pquare inch gage to give an extract containing 1 to 1.3 mols of ethylene per mol of sulfuric acid. Further cont,acting the extract with a higher purity ethylene (free of propylene) for 1 to 3 hours a t the same conditions eliminates the propylene impurity and increases the ethylene absorbed. The extract is hydrolyzed to the alcohol. Fuqua (24) has developed a process for removal of carbonaceous material from the spent acid of the sulfonation process. PROPYLENE
For t,he direct hydration of propylene to isopropyl alcohol a process is reported ( 4 2 ) using blue oxide of tungsten as catalyst a t 250 atmospheres and 270" C. Ucing a don-nmard flow a S6% conversion was obtained while an upward flow gave only 8% conversion. The economic operation of such a process depends on the recycle of unreacted olefin. Levy and associates (43) have described a process for recovery of isopropyl alcohol from the propylene prior to recycle. After rcact'ion the pressure is reduced to about 20 atmospheres, and the reaction mixture is fed to the bottom of a distilling column where the alcohol is separated, and the propylene is obtained for rccycle. Amick (2) has patented a proccss for the product,ion of isopropyl alcohol by an indirect hydrat,ion employing 65 to iOyo sulfuric acid in which reconcentration of the acid is avoided by stripping the extract a t subatmospheric pressures. Improved quality of isopropyl alcohol is claimed ( 2 6 ) for the sulfuric acid process by pretreating the propylene feed t o remove impurities consisting of Cr hydrocarbons, methyl acetylene, and propadicne. Wilson (93) describes a process for the removal of both high boiling and low boiling impurities present in the crude isopropyl alcohol from t,he sulfonation process. Improved odor qualities are claimed as the result of the tvio step fractionation under alkali conditions where high boilers are removed as bottoms of the first step distillation and the refined isopropyl alcohol as bottoms of the jecond st'ep, HIGHER AND MIXED OLEFINS
.A process is claimed (10) for t,he production of ether-free alcohols by the direct hydration of an olefin a t elevated t,emperature and pressure in the presence of an acid catalyst and subsequent extractive distillation of the gaseous product. Akpplication to ethyl alcohol and isopropyl alcohol processes is claimed. A continuous process (18) for the hydration of olefins with aqueous eulfuric acid comprises feeding the olefins to a hydration bath containing a predetermined initial acid and free alcohol content. Isobutylene in a mixture of 65% butane and isobutane, 20% butylene, and 15% isobutylene is selectively hydrated to isobutyl alcohol with a hydration solution consisting of 40 to 50% sulfuric acid and 30 to 30% free isohutyl alcohol. LIonoand dialbyl sulfates having from 5 to 12 carbon atoms in each radical and yielding steam-volatile alcohols are hydrolyzed in a two step process ( 2 8 ) . The mixture of mono- and dialkyl sulfate and dilute sulfuric acid are heated in the first reactor to hydrolyze the mono- hut not the dialkyl sulfate; in a second reactor the mixt,ure is steam stripped to hydrolyze the dialkyl sulfate and obtain the alcohol. The alkyl sulfates are obtained by sulfation of olefins obtained from cracked wax distillates. A superior catalyst (47) for the hydration of COto C6 olefins consists of porous alumina on the surface of which silica has been uniformly precipitated to provide a predominately silica surface. The catalyst contains from 10 to 25% silicon dioxide. With catalysts composed of alumina, silica, zirconia, or thoria, high selectivity and increased yields are obtained if the catalyst, is pretreated with m t e r a t the hydration conditions ( 4 6 ) . Deering ( 1 4 ) has developed a method for preparing a hydration catalyst of improved mechanical strength by precalcining the siliceous support a t 800"to 1400" C., impregnating with phosphoric acid
Vol. 46, No. 9
and a transitional metal phosphate, and drying beloiv 300" C. hpplication to hydration of gaseous olefins and acetylenes is claimed. I n another patent ( 1 5 ) he reports that an efficient catalyst for vapor phase hydration of olefins is prepared by impregnating silicon carbide, or other carbides of group I V with phosphoric acid and drying a t 105" to 240' C. -4nother pioceqs for hydrating normally gaseous olefins has been described by Linn (44).The olefin is contacted with 60 to 90% aqueous hydrofluoric acid in a continuous or batch process operating a t 0' to 50" C. and up to 100 atmospheres pressure. I n the hydration of 1-butene large amounts of 2-fluorobutane and polymer mere formed in addition to the product 2-butanol. Carnell describes (9) a process for converting a mixture of aliphatic olefins having different numbers of carbon atoms per molecule to the corresponding alcohols by selectively hydrating the olefins in successive steps. A mixture of ethylene, propylene, and butene. was brought in contact with an excess of 10 to 20% hydrofluoric acid a t 60" to 90' C and superatmospheric pressure where moTt of the butene was hydrated; propylene was reacted in the next step with 20 to 30% hydrofluoric acid a t 90" to 120" C ; and ethylene, in the third step with a hydrofluoric acid concentintion of 40% and temperature of 180' to 280" C. Hydration of straight chain and cyclic olefins containing 2 to 20 carbon atoms is accomplished by contacting the olefin with an aqueous boron trifluoride solution (specific gravity 1.65 to 1.75 a t 25" C., arid liquified sulfur dioxide a t a reaction temperature of 25 O to - 50 C. and a mol ratio of sulfur diovide to olefin of 0.05 to 5 to 1 (8$). A novel process has been developed (59) for converting olcfins of not more than 5 carbon atoms into primary alcohols containing a larger number of carbon atoms than the olefin from vvhich thcy are derived. The reaction is carried out a t substantially atmospheric pressure a t 50" to 150' C. with a mol ratio of n-atf.r t O olefin of 4 t o 10 and exposed to the silent electric discharges of 10,000 to 20,000 volts and 50 to 500 cycles per second. In one case propylene gave a 13.5% yield of 2,3-dimethyl-S-but~nol Finch and Furman (21) have patented a process for converting olefins of a t least 3 carbon atoms into the corresponding ketone by treating with xater a t 200" to 500' C. and 150 to 2000 pounds per square inch pressure in the presence of a catalyst contiining a sulfide of molybdenum, tungsten, tellui ium, OP selenium together with 0 t o 40 mol % sulfide of iron, nickel, or cobalt 1-Octene with nickel sulfide-tungsten sulfide catalyst a t 300" C and 1600 pounds per square inch gave a 38% yield of ketone Isoprene is converted to isovaleraldehyde in a process patented by Pines and Ipatieff (70). The diolefin is contacted with mater in the presence of an acid acting solid catalyst.
HYDROLYSIS Because of the diversity of materials that undergo hydrolysis the industrial application of this process is widespread. For a process as old as hydrolysis, new advancements appear rather infrequently, and the major portion of work in this field is concerned with improvements or modifications of old procedures and application of established techniques to new materials. Only those processes using hydrolysis as a major step are dipcussed in this section. ETHERS
On a commercial scale, the hydrolysis of cthcrs finds only limited application. The largest single application is the hydrolysis of ethylene oxide to ethylene glycol. Davis ( 1 3 ) ha.+ rcceived a pat'ent for a method of making ethylene glycol from dilute ethylene oxide streams. The dilute stream, contairiing about 2% et'hylene oxide, is passed into a dilute aqueous solution of hydrochloric acid until a neutral solution of ethylcne chlorohydrin and ethylene glycol is formed. The chlorohydrin is removed overhead as an azeotrope by distillation, and ethylene glycol is recovered from the bottom. The ethylene chloro-
September 1954
INDUSTRIAL AND ENGINEERING CHEMISTRY
hydrin is reacted with milk of lime to form ethylene oxide which is cycled to the system or recovered as such. Robeson and Webb (73) claim high yields and minimum side reaction in a process for the production of lJ2-propylene glycol by the hydrolysis of 1,2propylene oxide. The process comprises heating the oxide with from 3 to 5 parts by weight of water a t elevated temperatures and pressure while maintaining the pH a t from 6 to 6.5. 1,2Propylene oxide was reacted with 4 parts by weight of water at p H of 6.2, temperature of 150' C. and a pressure of 170 pounds per square inch; 89% of the oxide is hydrolyzed to glycols, of which 87.3% is 1,2-propylene glycol. Young (95) describes a process for the conversion of epoxides of the general formula
1843
Mercier ( 5 1 )claim a process for treating methyl acetate solutions and recovering the methanol and acetic acid after hydrolysis, The hydrolysis of polymeric esters is of interest. Several patents have been granted for the production of polyvinyl alcohol by hydrolysis of polyvinyl acetate in the absence of organic solvents. Catalysts for this heterogeneous process include organic sulfonic acids ( d 7 , 6O), esters of orthophosphoric acid (7), and quaternary ammonium bases (6). ORGANIC HALIDES
The hydrolysis of organic halides provides a means of proa wide variety of oxygenated compounds. Kulka and ducing R' Manske (41) claim the production of terephthalic acid by a I CEI~-C-R~ process in which p-xylene dichloride is heated in a 70% nitric \ / acid solution where it is hydrolyzed to the p-bis (hydroxymethyl) '0' benzene which is oxidized immediately to the acid. a-Alkylideneinto the corresponding glycols by heating in intimate contact 6-hydroxypropionitriles are prepared from the a-alkylidenewith an aqueous alkaline solution to temperatures of 150' to halopropionitriles by selective hydrolysis under controlled con200' C. in the presence of a mutual solvent for the epoxide and ditions such that the hydrolysis of the nitrile does not take place alkali. Hydrolysis of 2,3-dihydro-1,4-pyran-2-carboxaldehyde (38). Schmerling ( 7 5 ) has formed ketones from certain unin water a t 90" C. gives a 90% yield of 2-hydroxy-l,6-hexanedial saturated halides by hydrolysis. Reaction of l-chloro-3,3dimethyl-1-butene and water containing 2% sodium bicarbonate (91 ). Hoaglin and Hirsh (36) have described a process for making a t 250" C. produced a 40% yield of 3,3-dimethyl-2-butanone. unsaturated aldehydes by reacting a saturated aliphatic aldehyde A continuous process (90)for the hydrolysis of 1,2-dichlorowith a vinyl alkyl ether in the presence of boron trifluoride to form ethane consists of passing the reaction mixture, composed of the an intermediate that is hydrolyzed to an unsaturated aldehyde organic chloride and aqueous sodium carbonate, through tubes of more carbon atoms than the original. A method for the vapor in series a t a temperature of 150" to 155' C. and controlled p H of phase hydrolysis of alkenyl alkyl ethers has been patented by 8.4 to 8.7; 44% conversion to ethylene glycol is obtained. Hagemeyer and Anderson (SO). A mixture of the ether and Glycerol dichlorohydrins, from chlorination of allyl chloride in steam is passed over silver oxide deposited on a carrier a t a dilute aqueous solution, are hydrolyzed to glycerol by a process temperature of 150' t o 400' C. Ethyl isopropenyl ether gave in which part of the dichlorohydrins are converted to epichloroa 63% conversion to ethyl alcohol and acetone with a 97% rehydrins before carrying out the final hydrolysis (89). Morris covery of unreacted ether. and Van Winkle (56) have described a process for preparing 2Methylal, a by-product from oxidation of hydrocarbons, is monoethers of glycerol from the corresponding dichlorohydrin converted into more valuable methanol and formaldehyde by a by selective hydrolysis. Allyl 1,3-dichloro-2-propyl ether was vapor phase hydrolytic process using phosphoric acid-treated converted to 2-monoallyl ether of glycerol by heating 3.5 hours actirated charcoal as a catalyst (61). Reaction products of a t 175" C. and 170 pounds per square inch in the presence of aldehydes and alcohols (such as acetals, hemiacetals, and unsodium acetate and excess yater. saturated ethers) are separated into their components by a combination acid hydrolysis and extractive distillation (55). NITROGEN COMPOUNDS ESTERS
The most important process involving hydrolysis of esters is that of saponification of fats and oils to yield glycerol and fatty acids or soap, A recent practice consists of continuous hydrolysis of fats by water alone, or with small amounts of catalyst, employing high temperature and pressure in a countercurrent system. Darkening of the resulting products from this type of operation is retarded by the use of 0.01 to 5.0% stabilizer consisting of a hydroxy aromatic compound having a t least one alkyl group on the benzene nucleus ( 7 4 ) . Other improvements in splitting operations include a method for preventing discoloration of the fatty acid by oxidizing the latent color formers to nonvolatile materials (67); recovery of fatty acids from fat-containing substances by heating with water a t temperatures and pressure sufficient to dissolve the fatty acid ( 7 2 ) ; and a method of preparing fatty acid concentrates by restricting the conversion and employing a countercurrent solvent fractionation (68). Auster-' weil ( 4 ) uses anion exchange resins to catalyze the hydrolysis of oils, fats, and waxes, and to isolate the alcohol part. Esters of acetic acid are hydrolyzed with sulfuric acid catalyst in the presence of hydrocarbons such as pentane that form azeotropes with the alcohols. This aids separation from the acetic acid upon distillation (67). Products from the conversion of carbon monoxide and hydrogen into fuel are heated in the vapor phase a t 500' to 1000" F. with an alkaline earth catalyst to hydrolyze esters to alcohols and acids, and thereby facilitate recovery of valuable organic compounds (S5). Mention and
A novel and inexpensive method of preparing p-alanine from acrylamide is described by Matlack (48). The amide is contacted with strong base to give a polymeric intermediate which is hydrolyzed to 6-alanine. Polson reports ( 7 1 ) a process for the hydrolysis of nitrile groups in polyacrylonitrile to amide groups. Polyacrylonitrile is diesolved a t 0" to 30" C. in an aqueous solution of nitric acid (55 t o 70%) and the temperature maintained until 25 to 65% of the nitrile groups are converted into amide groups. The resulting material is useful in preparing fibers. The hydrolysis of a number of polymers and copolymers containing nitrile groups has been described by Mowry and Hedrick (58). The nitrile groups are hydrolyzed to amide and carboxylic acid groups to produce watersoluble polyelectrolytes suitable as soil conditioners. Amino acids such as a-methylglutamic acid (69); alanine, isoleucine, and or-amino-butyric acids (SW), and a-amino-a, adiphenyl acetic acid (19) have been prepared by the hydrolysis of hydantoins. PRODUCTION OF PHENOLS
Several modifications and improvements have been reported for the manufacture of phenols by the classical sulfonation process. Molinari and Affholter ( 5 4 ) claim a more economical process by replacing the sodium hydroxide fusion step with one which comprises directing the sulfonate into molten sodium phenate, passing steam through the mixture to hydrolyze the components and carry off the phenol, condensing the vapors, and
1844
1N
DU S Tn I A L A N D EN G I N E ER I N G CH E M I STR Y
recovering the free phenol layer. T h e water-phenol layer is reacted with lime and sodium sulfite to give make-up sodium phenate. This in effect substitutes linx for the more expensive soda. ddams, Bauer, and Taj-lor ( 1 ) describe a proces? iii which phenol is manufactured continuously from the sulionic acid by passing the feed reactants (an aqueous solution of sodiuni hydroxide and benzene sulfonic acid in cquiinolecular proportions) into a h i o n mixture containing sodium beltzene siilfonate, *odium phenate, sodium hydroxide, and steam. The reaction bkes place in a vertical tube which rges to an upper zone, from which part of the mixture is r t ~ and part is withdrawn to remove the sodium sulfite. T nol-eteam vapors are removed overhead from the upper zone and passed into an :ihsorption column \There phenol is absorbed with tricresyl phosphate and subsequent,ly recoveiwl by distillation. A 97 % conversion of sodium bciizene sulforitr ttr with 96% yield of phenol is obtained. Sn-elling and froth forniatiori ociated with the fusion step i p climirittted by heating a dry mi ire of potassium sulfonic acid : i i ; d calcium hydroxidc at 400" t o 420" C.in a nitrogen atmosphere until half the sulfonate is converted to phenate, after which steam is paL;scJ thi,ough io Corin t,hc phenol and carry it overhead (16,29). Milner and I-Ioldsworth ( 6 2 ) claim that the live of an alkali metal aluminate d l o v v ~the phenol to be easily removed from the d i d products or hydrolysis by steani distillation. They also report (53) that the ndditioii of potmsium hydroxide to sodium hydroxido results in a lower melt temperatuw and lower viscosity of the sulfonate. Yura and Cr:o (06)report that the hydrolysis of sodium benzene sulfonate by steani in zn autoclave begins a t 200" C. with maximum yield at 450" C . and have concluded that phenol ip formed directly, without the intermediate sodium phenate. Englund, Aries, and Othiiier (90)have published an excellent discussion on the synthesis of cresol Irom toluene. Addition of 96% sulfuricacid to toluene in thc shortest timc possiblcwith rapid removal of water and a t a temperature below 150" C. gave 92 to 95% toluene sulfonic acid (84% para isomer). F'usion witli sodium hydroxide alone is possi'ole, with a yield of cresol coniparable to that obt,ainc:d !with potassium hydroxide. No isomer rearrangement talres place during the fuclioii step. Swisher ( 8 5 )has described the preparation oi' resorcinol by the c:tustic fusion of benzene disulfonic x i d . Another process for iiiaking resorcinol involves heating the sodium benzenc clisulfonate arid sodium hydroxide i n theoretical amounta at 350" to 400" C. in a stream of nitrogrii ( 1 7 ) . Various procedures have been reportcd for the SJ-n phenols by the hydrolysis of aromatic olilorides. The pilica gel-cupric chloride catalyst for the vnpor pha,sn hydrolysis of chlorobenzene to phenol has been studied (63, 6.5,66). Tezuk:~ ( 8 7 ) ha8 received a patent for the produclioii of phenol I)y thp hydrolysis of chlorobenzene in a process comprising passing chlorobenzene, r a t e r and aininonia vapors through a silicate or phosphate catalyst at 475" to 600" C. Chlorophenols have been prepared by Ohta and Kaganii ( 6 4 ) ; 0-: 772-, and p-dichlorobenzenes hcnted \vit,h methanol and sodiuni hydroxide: a t 180" to 200' C. v e r e hydrolyzed to the corresponding rhlorophenols. Henrich ( 5 3 ) describes a method for the preparation of sodium phenates b y hydrolysis of a polychlorobenzene with excess sodium hydroxide in 90% methanol a t 230 pounds per square inch pressure. Isomers (except the gamma) of C6EIaC16heated a t 175" to 185" C. in an autoclave with sodium hydroxide, Tmter, and niethanol yield 66.7% 2,5-dichlorophenol (3). for the production of pentaT w o improvemerits in the pro( chlorophenol are of interest. Bruce (8)has modified the pmification step by adding sufficient xater to dissolve the water soluble portion of the hydrolysis product and then precipitating the sodium pentachlorophenate by addition of a salt such as sodium chloride. Rartlett ( 5 ) r.lainis R piirrr product, by carrying out
Vol. 46,No. 9
the react,ion in the presence of a liquid aliphatic tertiary alcohol c,ontaining up to 10 carbon at,om. Iislc (45) reports the r e d i o n of I-amino-6-hydroxy m p l i t hilene \Tiih aqueouc; sodium bisulfite a t 95" to 105' C., follo~vodl>y all~ilinehydrolysis a t 60" t,o 95" C. and acidification to yic.It1 1ii-iial~hthalenediol. Xymnietricxl trihydroxybenzenes linvc. \ w i i plcparc?tl l-)y reducing the eoriwponding trinitrobenzr:nc 1 o t h~ :imine tint1 hydrolyzing (40). ORGANIC SILICON COMPOUNDS
IH~-thlysisplays an iinpor1.aiit role in the synthesis of ni;i 11)'
givcn by Jeffes ( 3 7 ) . silanes which on hydrolysis arid (midensation yieid polysilosii I u * s iu which the stability of tlicl !or~-hiitj~l group is compfri.:iblc i o thiit of phenyl or methyl. The linkages Si-H and Si-Olj, tend to k)realc in the present.(> or ivater and the preparation of silo:s hy hydrolysis and decarboxylation of the corresponding ketoastcra (81) and prepsration of krtoiiloxanes from these ketones by reaction with concentrated wlfuric : i d folloved by hydinlj.si~ (80). Other reactions of inlercst iuclude production 01 silolactones (78),triorgarlosil.ylbcn~aldeh).dej( U ) trialkylail , ncid ( 8 2 ) ) aminosiloxanes ( 7 0 ) ) and fluorohydroc:irl-)oii-~iii)s:titut,ed silanols (58,39). WOOD
Current work on saccharifica tion of wood is iliustratrtl bj(iilbert, Hobbs, and Levine (25) nho presented the data from the TVA pilot plant for hydrolysis of ~voodusing dilute sulfuric acid. This process comprise3 covering wood chips with a solutioii containing 0.5% sulfuric: acid Find 1 .O% reducing sugar a,t 200" to 275" F., digesting, theii percolating n i t h 0.5'% acid rind gradually increasing the temperature of the entering aciti to 375" F. About 75% of the potential reducing sugar content is obtxined. The final product is suitable as feed material. Anotlier report (11) describes the modified Rheinau pro1 production of dextrose from wood xvaete with a yield of 85% of the theoretical. The process consists of "prehydrolyzing" wood waste? to obtain cellulose and lignin, converting the cellulose to sugar by counter-current uonlacting with 41 cghydrochloric acid a t 70" F., and recovering the polysaccharides for conversion to dextrose in a third hydrolysis step. This process is claimed to be economically coinparable with the hydrolyeis of corn.
LITERATURE CITED (1) hdama, J. F., Bauer, R. L., and Taylor. G . E. (to AIoiinrint,o Chemical Co.), U.S. Patent 2,632,028 (March 17, 1953). ( 2 ) Amick, E. H. (to Standard Oil Development Go.),I b j d , , 2,609,400 (Sept. 2, 1954). (3) hoyagi, A. (to Nissen Chemical Industries Co.), Japan. I'iLceiic 2672 ('51) (May 26, 1961). (4) Austerwcil, G. V . (to Pechiney-Compagnie de produits rhiniiqucs et electrom&tallurziques), U. S. Patent 2,604,432 (.Tidy 2 2 , 1962).
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INDUSTRIAL A N D E N G l N E E A I N G CHEMISTRY
( 5 ) Bartlett, P. D. (to Columbia-Southern Chemical Corp.), Ibid., 2,644,015 (June 30, 1953). (6) Blume, K. C. (to E. I. du Pont de Nemours .& Co.), Ibid., 2,581,832 (Jan. 8, 1952). (7) I b i d . , 2,583,991 (Jan. 29, 1952). (8) Bruco, E. A. (to The Pennsylvania Salt Manufacturing (20.1,
I h i d . , 2,563,815 (Aug. 14, 1951). (9) Carnell, P. H. (to Phillips Petroleum Co.), Ibid., 2,583,413 (Jan. 22, 1952). (10) Carrier, E. W. (to Standard Oil Development Co.), Ibid., 2,648,711 (Aug. 11, 1953). (11) Chem. Eng., 61, NO. 2, 138-42 (1964). (12) Coinpagnie franqaise de raffiiiage, Brit. Patent 676,353 [July 23, 1 RR2I. (13) Dai-ia. H. S. (to American Cyanamid Co.), U S.Patent 2,636,906 (April 28, 1953) (14) Dcering. R. F. (to Union Oil Co of California), I h d , 2,569,092 (Sept. 25, 1951). (15) Ibid., 2,583,359 (Jan. 22, 1952). (16) Directie van de Staatsmijnen in Limburg, Brit. Patents 666,589 (Feb. 13, 1952), 672,512 (May 21, 1952); Dutch Patent 69,367 (Jan. 15, 1952). (17) Ibid., Brit. Patent 672,511 (May 21, 1952), Dutch Patent 69,752 (March 15, 1952). (18) Duane, J. J. (to Union Carbide and Carbon Corp.). U. S. Patent, 2,646,441 (July 21, 1953). (19) Duschinsky, R. (to Hoffmann-La Roche, Inc.), Ibid., 2,593,860 (April 22, 1952). (20) Englund, S. W.,and associatee, Ixu. ENG. CHEM.,45, 189-97 (1953). (21) Finch, H. D., and F’urman, K. E. (to Shell ‘Development Co.), U. S.PaLent 2,635,119 (April 14, 1953). (22) Frisch, K. C., and Shroff, P. D. (to General Electric Co.), Ibid., 2,641,605 (June 9, 1953). (23) Frisch, K. C., and Young, R. 13. (to General Electric Co.), I b i d . , 2,671,100 and 2,671,101 (March 2, 1954). (24) Fuqua, M. C. (to Standard Oil Development Co.), Ibid., 2,629,747 (E’eb. 24, 1953). (25) Gilbert. N., Hobbs, J. A,, and Levine, ,J. D., IND.ENG.CIIEM., 44.1712-20 (19521. (26) Giraitis, A. P.,and Fuqua, AI. C. (to Standard Oil Development Co.), U. S. Patent 2,657,243 (Oct. 27, 1953). (27) Goebel, AI. T. (to E. I. du Pont de Nemours & Co.), I b i d . , 2,629,713 (Feb. 24, 1953). (28) . . Goldsbrounh, L. N. (to Shell Develooment Co.). Ibid., 2,640,085 (May 26, 1953); Brit. Patent 668i538 (March 19, 1952). (29) Goris, 3. It. H., U. S.Patent 2,677,709 (RiIay4, 1954). (30) Hagemeyer, H . J., and Anderson, D. C. (to Eastman Xodak Co.), Ibid., 2,662,919 (Dec. 15, 1953). (31) Hatch, L. F., Petroleum Refinel, 33, No. 2, 1 4 1 4 (1954). (32) Hearne, G. TV., and La France, D. S.(to ShellDevelopment Co.), U. S.Patent 2,601,659 (June 24, 1952). (33) Henrich, G. J . (to Mathieson Chemical Corp.), Ibid., 2,616,923 (Oct. 28, 1952). (34) Hersh, J. A i . (to Continental Oil Co.), Ibid., 2,615,033 (Oct. 21, 1952). (35) Hess, H. V.,Arnold, G. B., and Drabkin, M . L. (to The Texas Co.), Ibid., 2,591,699 (April 8 , 1952); Brit. Patent 676,710 (July 30, 1952). (36) Hoaglin, 11. I., and Hirsh, D. H. (to Union Carbide and Carbon Corp.), U. S.Patent 2,628,257 (Feb. 10, 1953). (37) Jeffes, J. H. E., Chemistry & Industru 1954, No. 18, pp. 498.-501. (38) Kohl, C. F. (to Corning Glass Works), U.8. Patent 2,640,063 (May 26, 1953). (39) Ibid., 2,640,066 (May 26, 1953). (40) Krueger, J. (to Edwal Laboratories, Inc.), U. S. Patent 2,614,126 (Oct. 14, 1952). (41) Kulka, hi., and Manske, R. H. F. (to United States Rubber Co.), Ihid., 2,666,786 (Jan. 19, 1954). (42) Levy, N., and Imperial Chemical Industries, Ltd., Brit. Patent, 671,971 ( N a y 14, 1952). (43) Levy, N., Thomson, R. C., and Imperial Chemical Industries, Ltd., I b i d . , 667,391 (Feb. 27, 1952). (44) Linn, C. B. (to Universal Oil Products Co.), U. 5 . Patent 2,616,933 (Sov. 4, 1952). (45) Lisk, G. F. (to Allied Chemical and Dye Corp.), Ibid., 2,665,313 (Jan. 5, 1954). (46) Lukasiewicz, S. J., and Denton, W. I. (to Socony-Vacuum Oil Co.), Ihid., 2,633,744 (Dec. 22, 1953); Brit. Patent 692,800 (June 17, 1953). (47) Lukasiewica, S.J., Denton, W. I., and Plank, C. J. (to SoconyVacuum Oil Co.), U.S.Patent 2,658,924 (Nov. 10, 1953). (48) Matlack, -4.S.(to Hercules Powder Co.), U. S. Patent 2,672,480 (March 16, 1954). (49) Maycook, R. L. (to Shell Development Co.), lbid., 2,575,556 (Nov. 20, 1951).
1845
(50) Mayne, J . E. O., and Warson, €1. ,to Vinyl Products, Ltd.), Brit. Patent 655,734 (Aug. 1, 1951).
(51) Mention, M., and hZercier, J. (to Les Usines de Melle Societe Anonyme), U. S.Patent 2,650,249 (-4ug. 25, 1953). (52) Ililner, D. W., and Holdsworth, E. G. (to Vulcan Chemical Co,, Ltd.), Brit. Patent 67b,109 (,July 23, 1952). (53) Ibid., 680,939 (Oct. 15, 1952). (54) Molinari, V., and Affholter, 13. G. (to Union Carbide and Carbon Corp.), U.S. Patent 2,578,823 (Dee. 18, 1951). (55) Morrell, C . E., Stewart, J., and Carlson. C. S. (to Standard Oil Development Co.), I b i d . , 2,614,970 Oct. 21, 1952). (56) Morris, R. C., and Van Winkle, J. L. (to Shell Derclopmc.iiC Co.), Ibid., 2,634,296 (April 7 , 1953). (57) Mortenson, E. N. (to Swift B- Co.). Ibid., 2,645,651 (July 14, 1953). (58) BIowry, D. T., and IIedriek, I < . AI. (to Monsianto Cliaiiicnl Co.), Ibid., 2,625,471 (Jan. 13, 1953). (59) Naamlooae Vennootschap De Bataafsche Petroleum hl:int+ chappij, Brit. Patent 695,076 (Aug. 5, 1953). (60) Selson, C. R., and associates (to Shell Development Co.), U. S. Patent 2,579,601 (Dec. 25, 1951). ( G I ) Newcombe, J. (to Cities Service Oil Co.), Ibid., 2,605,287 (July 29, 1952). (62) Kitasche, S., and Pirson, E. (to Wacher-Chemie G. m. b. E€,), Ibid., 2,647,911 (hug. 4, 1953). (63) Ohta, N., Repts. Gort. Chem. I v d . Research Znst., T o k y o , 46, 163-72 (1951). . Chem., J u J m n , (64) Ohta, N., and Kagami, K. J . Suc. O T ~Synthet. 10.295-7 (19521. (65) Ohta; N., and Tezuka, T.. J . Chcm. SOC.Japan, I n d . (‘hem. Sect., 54, 328-30 (1951). (66) Ohta, N., Teauka. T., Imamura, J., and associates, Ibid., ($81-3 (1951). (67) Okado, T., and Sato, 13. (to Woguchi Research Inztitiite), Japan. Patent 4009 (’51) (July 25, 1951). (68) Palmer, G. H. (to AI. W.Kellog Co.), U. S. Patent 2,654,768 (Oct. 6 . 19531. (69) Pfister 111, K., and Leanaa, W. J. (to Merck and Co , h e . ) , Ibid., 2,658,912 (Nov. 10, 1953). (70) Pines, H., and Ipatieff, V 3.(to Universal Oil Produc+ c‘o.), Ibid., 2,623,905 (Dec. 30, 1952). (71) Polson, A. E. (to E. 1. du Pont de Kemours & Co.1, Ihul.. 2,579,451 (Dec. 18, 1951). (72) Reinish, ill. D., and Caldarera, J . 1’. (to Colgate-Palmolivr-Peet Co.), Ibid., 2,664,430 (Dec. 29, 1953). (73) Robeson, M . O., and Webb, T. P. (to Celanese Corp. of i\inerica) Ibid.. 2.623.909 inec. 30. 18521. (74) Ross, J., ’and Trent, W. R. (to Colgate-Palmolive-Peet Co.), Ihid., 2,619,494 (Kov. 25, 1952). (75) Schmerling, L. (to Uriiveisal Oil Products Co.), I b i d . , 2,658,919 (Nov. 10, 1963). (76) Schrader, R. J., Young, 13. S., and Berntsen, H . I. (to Eactnian Kodak Co.), Ibid., 2,673,221 Warch 23. 1954). (77) Rommer, I,. H. (to Dow Corning Corp.), Ibid., 2,626,270 (Jan. 20. 1953). (78) Ihid.; 2,635,109 (April 14, 1953). (79) Ibid., 2,662,909 (Dec. 15, 1953). (80) Ibid., 2,662,910 (Dee. 15, 1953). (81) Ibid., 2,672,474 (March 16, 1954). (82) Speier, J. L. (to Dow Corning Corp.). U. S. Patent 2,628,245 (Feb. 10, 1953). (83) Ibid., 2,629,727 (Feb. 24, 1953). (84) Standard Oil Development Co., Brit. Pat. 660,652 ( N o r . 7 , 1051). (851 Swisher. R. D.. I b i d . 679.827 (Sent. 24. 19521. Tapp, I$. J., IND.ENG.CHBM.,‘40, 1619-23 (1948); 42, 16981704 (1950); 44,2020-4 (1952). Tezuka, T. (to Bureau of Industrial Technics), Japan. Patent 886 (’51) (Feb. 23, 1951). Thomson, R. C., Reynolds, P. W.. and Imperial Chcniicals, Ltd., Brit. Patent 665,214 (Jan. 16, 1952). (89) Tymstra, F. T. (to Shell Development Co.), IJ. R. Patent 2,605,293 (July 29, 1952). (90) United Kingdom Chemicals, Ltd., and Schafer, G., Brit. Patent 684,763 (Dec. 24, 1952). (91) Whetstone, R. R.,and Ballard, S.A . (to Shell Developinent Co.), U.S.Patent 2,639,297 (May 19, 1953). (92) White, H. C . (to Dow Chemical Co.), Ibid., 2,642,459 (June 16, 19531. (93) Wilson: S. W. (to Standard Oil Development Co.), Ibid., 2,588,446 (March 11, 1952). (94) Woodbridge, J. E. (to Atlantic Refining Co.), Ibid.. 2,617,834 (Nov. 11, 1952). (95) Young, D. P. (to Distillers Co. Ltd.), Ibid., 2,650,940 (Sept. 13, 1953). (96) Yura, S., and Uno, K., J . Chem. SOC.Japan. Ind. Cheui. Sect. 54,119-20 (1951). I~
