INDUSTRIAL AND ENGINEERING CHEMISTRY voii Elbe, G., and Lelria, B., J . Chem. Phys., 10, 366 (1942) von Elbe, G., and LMentser,M., J . Chem. Phys., 13, 89 (1945) von Stein, M., U. 8. Dept. Commerce, QTS, PB 27738, Ma:'
Voll. 40, No. 9
I
1946.
Vulis, L. X.,J . Tech. P h y s , (U.S.S.R.), 16, 83, 89, 98 (1946; Walsh, A. D., Trans. Faraday Soc., 4 2 , 2 6 9 (1946). Watson, E. A., and Clarlre, J. S ~Flight, 9 51, 552 (1947); J . Tn.,si Fuel, 21, (116)' i (1947). Wear. J. D., Held, L. F., and Slough, J. W., Natl. Advisory Corn. Aeronautic* (TVnshington) Wai.tim,e Rept. E 2 4 (1944). Wheeler, W. PI., Whittaker, IT.* and Pike, FI. H. M., J IWI Fuet, 20, 137 (1947). 120.'299 (1946), Wicker, W. S., Ru' iMsch,
RE making of esters is big business: approximate figuIe~ for current production in the United States, i n millions of pounds per yem, are: Ethyl acetate Butyl aoetate Dibutyl phthalate Cellulose acetate
125 (1845) BOO
Alkyd resina
190
Rosin esters
45 (1945) 280
Cellulose xanthate Plasticizers
88 700
170
Alkyd resins are mixed esters from phthalic and other acid:: with pentaerythritol, glycerol, and glycols. Plasticizers are largely phthalates and include dibutyl phthalate. Cellulosc nitrate, glyceryl trinitrste, vinyl acetate, and ethylidene dincetate are in the same class as regzrds amounts produced. EiTcient processes for these established products have been in operation for considerable periods and have beoonie st'andardieed. Changes arc, of course, being made from time to t h e , but t h e j are minor improvements and seldom get into the news. Cellulose acetate and xanthate are not taken up In this brief review. The basic chemistry involved in making them is cornparatively simple, but the details of their manufacture a.re multitudinous.
GENERAL In esterification and in the sapoaificatioii of asters, the alkyloxygen bond usually remains intact but is broken in specia,! caees. Partial racemization in the acidolysis of monophthahtrs oE active alcohols indicates the fission of this bond (I@* The hydrolysis of triphenyl-mothy1 thiobenzoate gives Lriphenj ' _ carbinol instead of the mercaptan (th-bi) : PhCBSCPh,
-+ K20
-+
PhCOGfI
+ PhsCOEP
I
l3r)
! '40) (l4t) ,142) (
143)
(144) Si
154, 157, 158 (1946). L. 8 , Fuel Eoon ~ o i i f World ~, Power Conf., Thb Hague, Sect 6 2 ,Payer 1, Piepiint (1947). Wilkinson, P. H., "Aircraft Engines of the World," London, Pitman and Sons,1947. Willich, N.,A i r Tech. Berv. Command, W r i g h t Field, D a y t o n , Ohio, A A F T ~ a n s l 513 . (1946). Yellott, J. I.,Power Plant E f i ~ .51, , 84, 132 (1947). Yellott, J. I., and Hot,tcarng, 6. F a , Ry. Age, 121, 551, 66(r (1946). Zhorowski, H., TSatl. Advisory Corn. Aeronautics (Washington), Tech. Memo. 1145 (1947). %eldovioh,I.lO.,J. Tech.Phy8. (U.B.S.R.), 17, 3 (1947). \~I~COXSOII,
( 1%)
-':TVEU
.Tunc 2 4 , 1948.
secund at a lower velocity. The heats of activation are 12,3M1: and 10,800 calories (47). Glycerol (8.8), pentaery'h-itol, and other polyhydric cornpounds (%@ have been esterified under various conditions and the rates and lixits determined. The esterification of 2,3-butylen0 glycol by acetic acid, catalyzed by sulfuric acid, goes in pairr;. of consecutive reactions which do not follow first, second, or third wder equations (187'). I n the esterification of higher fatty acids in the preseuce of catalysts, methanol gives higher velocities and better yields tha;; ethanol (99). The formation of oxonium salts when alcohols are mixed d f u r i c acid is indicated by the sharp rise in viscosities ($8)" This may have to do with the catalytic effect of'the acid in esterification. h number of' kinetic studiee have been made of the hydrolyeis of esters (70, 83, 88, 159). The rates for the ethyl eeters of uubstit,uat,adbenzoic acids have been compared (29). The t e d butyl esters of oxalic, malonic, and succinic acids are hydrolyzed more rapidly in water-dioxane mixture, 1 to 2, than in pure water, t the reverse is true for the glutaric and adipic esters (rej. e temperat,ure coefficient for methyl and ethyl formates is out 1.7 for 10" between 5' and 35' C. (80). The addition of methanol Ion-em the rat,e of hydrolysis i n aqueous mlUtkJn. Ethanol, propanol, and acetone have the samc offect hut t o a, Iwx drgree (150, 161). The use of high boiling uoivents, such as glycerol (130) dielhylene glycol (102),for the potassium hydroxide in the saponlfication of esters is recommended. In tlie presence of hydrochloric acid at 25' C., the esterification cf galacturonic acid is 25 tirnss as fast as glucoside formatioil $17
(83) ~
This niay be attributed to tlie exceptional tendency of tliphenylnicthyl to dissociate (81). In a study of the kinetics of the esterlfication QE butyl alcohol by acetic acid surprieingly low values oE R were found, ranging froni 2.25 to 1.66 according to the raiio of the reactants. The rate was proportional t u the square of the acetic acid concentration (95). For p-iodopropiouic acid amd methanol the valce of K was 4.57 a t 25' C. and 4.42 a.t 35" C. (116). The est,erification velocities of the sulfide acids, RSCH,CO,H, are higher than those for RSCH2CH2C02H,b u t all are loffer than those of the corresponding acids without the sulfur link (117'). The uncatalyxed esterification of glycerol by peanut oil acids has been found to be bimolecular in two successive states, the
Surprisingly cnough, good y+elds QE esters can be obtained by heating animorr,ium salts of organic acids with alcohols. Ammonia and water are given off (.@).
SPEEBlNG UP ESTERlFKATllON The well known, long-used esterification cataiysts, sulfuric. acid, hpdrogcii chloride, and p-toluenesulfonic acid, are still the staid-bgs but oxides and salts of metals are mentioned, particularly in patents. Zinc and tin chlorides are said to be outatandingly activa catalysts, while the chlorides of other heavy metals are relatively inactive (47). Zinc chloride (75, 110), oxide (104, 147), hydroxide (104), and salts (110, 147), as well as Lead (55, 138, 147) and manganese (147) oxides are reconimcndfd.
September 1948
INDUSTRIAL A N D ENGINEESING CHEMISTRY
1.592
Plant for Manufacture of Rosin Esters This is an exterior view ofthe Hercules Powder Company building containing the reactors. To the far left are storage tanks for rosin glycol, glycerol, etc. At the left center is a low building housing pumps for handling raw materials, Eome of which are oarried in the pipe lines in the foreiround. T o the rear of the main buildin is the drumming houae in which the resins are discharged into 50-gallon galvanized iron drums. Some of the drums of finished product are standing on palets in front of the drumming house. The two wooden tanks in the center are for preliminary treatment of by-product washes.
These oxides can be used at temperatures as high as 250" C. a t which charring would take place with sulfuric acid. They are probably converted to salts of the acids that are being mterified. Calcium oxide (17, 1.47) and calcium and barium acetates (22) are used in making pentaerythritol ( 1 7 ) and sorbitol (22) esters. The esterification rate is doubled by the addition of 0.5% of a mixture of 3 parts of calcium acetate and 1 part of barium acetate (22). Mannitol is esterified by palmitic acid in the presence of 0.05% of sodium hydroxide a t 240' C. in an inert gas (60). Siliceous compounds, such as fuller's earth, bentonite, kieselguhr, and silica gel (104) and a dry intumesced silicate such as ignited water glass (loo),are said to aid esterification. Esterification is said to be speeded up by shaping the reaction vessel so that circulation of the liquid is facilitated ( 1 1 5 ) . Sodium bisulfate is recommended for the esterification of a&unsaturated carboxylic acids (8). Hydrogen chloride or bromide may be generated in situ by adding sulfuric acid to a magnesium, calcium, or strontium chloride or bromide dissolved in the esterification mixture. The sulfate that is formed should be insoluble and precipitate (163). Chlorosulfonic acid is recommended as a catalyst (45). An interesting novelty is the use of an acid ion-exchange resin as a catalyst (94, 146, 169). This has several advantages; the catalyst does not contaminate the reactants and can be removed by filtering and reused. The rate seems to be proportional to the surface area of the catalyst (94). In the hydrolysis of methyl,
ethyl, and butyl esters Amberlite IR-100 calculated on an equivalent weight of 500, was found to be several times as efficient as hydrogen chloride (169). It is reported that German chemists discovered the usefulness of these catalysts during the war and were on the point of large scale continuous operation (94). A single portion of catalyst has been used five times without deterioration (146).
COMPLETING ESTERIFICATION 'The removal of one of the products of the reaction is still relied upon to effect the completion of an esterification. When the reactants are relatively nonvolatile, as is the case with glvcols, polyglycols, and pentaerythritol and the higher fatty acids, the water can be driven off by heating to 200' C. and above (6, 64, 56, 76). Polypentaerythrit$olis esterified by rosin acids a t 270' C. ( 7 ) . Monoesters of pentaerythritol are said t o be obtained by simple heating (1%). The elimination of the water may be facilitated by passing carbon dioxide (20, 21, 144, 160) or some other inert gas (33,96) through the heated mixture. Azeotropic distillation is much used. For lower alcohols benzene (48, 126) or carbon tetrachloride ( 19) may be the entraining agent; for higher o-dichlorobenzene, anisol, or nitrobenzene may serve (9). A9 is well known, butyl alcohol is its own entraining agent (18,51). A careful study has been made of the esterification of acetic acid by an excess of butanol boiling under a five-plate
1598
INDUSTRIAL AND E N G I N E E R I N G C H E M I S T R Y
column (95). A column is used in a continuous process for esterifying glycols with volatile acids (65). The vapors from a refluxing esterification mixture may be freed from water by contact with a drying agent (59,98). The ester may be continuously extracted from the esterification mixture (40). In a continuous process for use where both the acid and alcohol are relatively nonvolatile, the mixture of these with the catalyst is passed downyard through a bubble cap column, countercurrent to an inert gas which is passed upward to carry off the water. VYth a 40-plate column and 20 minutes' passage time the yield of ester is 97% (%5).
VAPOR-PHASE ESTERIFICATION The vapor-phase esterification of acetic acid by six primary alcohols,. one of them unsaturated, by two secondary, and by three tertiary has been studied over twelve catalysts. The best, yields were: 59Oj, with ethyl alcohol over silver vanadate con~ propanol over titania, and taining 7% of free silver, 9 5 ~ 7TTith 94y0 with amyl alcohol over thoria. The secondary alcohols, isopropanol and s-butanol, gave 40 and 35%, respectively, over titania. The tertiary alcohols, tert-butyl and tcrt-amyl, gave 16 and 24yc, respectively, over the same catalyst (141). With ethanol and acetic acid, containing hydrochloric acid, the rate was found to be proportional to the area of the glass vessel. There was 92y0 of ester in the adsorbed layer (58). The experimental vapor liquid equilibrium data agree with the calculated (108). The equilibrium constant for acetic acid, ethanol, ethyl acetate, and water in the liquid phase can be calculated from that, in the vapor phase and the vapor pressures of t,he constituents. The vapor phase K is 305 a t 45" and 196 a t 7 5 " C. (56, 6 7 ) . The rate seems to be controlled by diffusion through a condensed phase (74).
ALCOHOLYSIS Alcoholysis, or transest,erification, is receiving more and morr attention. The alcoholysis of 2-naphthyl aceta.t,ein a number of alcohols a t 25" C. with hydrogen chloride catalyst has been studied. The activa.tion energy is 12,700 calories. It is most rapid in methanol, less so in ethanol and propanol, and much slower in isopropanol ( 6 7 ) . The rates of alcoholysis of methyl formate by dimethyl carbinol, cyclohexanol, and dipropyl and diisopropyl carbinols have been compared. The number of hours required to reach 25y0 alcoholysis were 7.5, 6.5, 13, and 30, respectively (43). Acrylic est,ers of higher alcohols and of unsaturated alcoholj have been prepared from methyl acrylate by alcoholysis with aluminum isopropoxide as a catalyst (126, 127). Lactatm of complicated alcohols are made f r o m methyl lactate using the same catalyst (46). Glycol esters of glycolic (97) and fuma.ric acids (143) have been obtained from .the methyl and ethyl esters. A glycol and an ethyl ester of a dibasic acid give a polymeric ester. Lithium methylate is the catalyst (39). Tristearin and triolein heated together with sodium methylate gradually exchange their acid radicals and tend to equilibrium (111). Sodium methylate is tho best catalyst (38). Mixtures of triglycerides arc interesterified and approach the compositions expected from random distribution. Stannous hydroxide on diatomaceous earth is a suitable catalyst (114). When a natural triglyceride such as linseed oil is mixed with ethanol and a catalyst, the glycerol separates out and leaves the ethyl esters of the acids present (31, 162). This method may be used for the production of glycerol (36, 87) from esters of t>helower alcohols (42, 154). Sodium hydroxide, carbonate, or methylate, calcium and barium oxides, tet,ramethylammonium hydroxide, boron fluoride, aluminum chloride, and hydrochloric, trichloroacetic, and phosphoric acids (3) as well as calcium naphthenate and salts of a large number of organic acids are said to
Vol. 40, No. 9
be catalysts (27'). The processes may be made continuous by passing the mixturc of glyceride, alcohol, and catalyst through a heatki coil (3,8, 122, 154). To makc an est,er of a higher acid and a lower alcohol, glycerol may be combined with the acid and then displaced by the alcohol (93). I t has been proposed that lower acid radicals be removed froni glycerides by exchange with esters of higher acids and low alcohols, effected by heating to 250' C. or above in a vacuum (109). Esters of alkylamine alcohols, such as EteNCH2CH20H,arc' readily prepared from the corresponding ethyl esters b!. alcoholysis (124, 132, 138). To estimate its acetyl contcnt a compound is boiled with ethanol and hydrochloric acid arid the ethyl acetate is distilled into standard alkali (106, 145). Even silicate esters undergo alcohol- ; methanol can be partially or completcly driven out of tetramethyl silicate by heating it, with higher alcohols axid an acid catalyst (7f,121).
ESTERS F R O M A M I D E S Heating ail IT-hydroxyethyl amide with hydrochloric acid isninerises it to the hydrochloride of thti aminoet,hylester ( I d $ ) : RCONHCHzCHnOH
+ HCl
+
RCOaCHgCHzNHgHCl
A diamide heated with a n alcohol to 190' C. or above is changed to an ester. Sodium bisulfate may be used to absorb the ammonia (101). An amide heated Tvith an alkyl chloride in the presencecrf hydrogen chloride is changed t,o t,he ester (85):
RCOh-Hg
+ R'Cl-+
RCOaR'
+ NHdCl
ESTERS F R O M ACID ANHYDRIDES AND CHLORIDES Thousands of tons of cellulosr esters art' made by the action 01 the. mhydrides of acetic and other acids in the presence of sulfuric: or sume other acid catalyst. Enormous quantities of xanthates are produced by the action of carbon disulfide, a thioanhydridr, on alkali cellulose. Thesc are both big stories, too big to be told in this brief review. 1,actic esters are readily acetylated; the addition of one drop of sulfuric acid to a mixture of 156 grams of methyl lactato. 169 g,rams of acetanhydride, and -50 grams of diphenyl ethcr causes the temperature to rise to 100" C. The yield of the acetate is Wjyc(50). The reaction of an acid anhydride with an alcohol mag be aided by a catalytic amount (28) or an equivalent amount of pyridine (11, 165) or by pyridine as a solvent (89). Starch can be acetylated in an anhydrous medium of a m monium acetate and acetamide (62). Maleic anhydride combines quickly and quantitatively with one equivalent of an alcohol to form a monoester (139). Tetrachlorophthalic anhydride reacts more slowly (113). Esters of nicotinic acid are made from the acid chloride and the alcohols (10). Acid chlorides react well with alcohols in pyridine solution (14, 143). Glycol dibenzoate has becn made in this way (68). Acid chlorides react particularly well with alcohols, even tertiary, in ethcr solution in the presence of rnagnesiwn (118, 119, 142). Silicon tetrackiloiide may react partially with ethanol to give the intermediate ester-chlorides, EtOSiClo, (EtO)&Clg, and (Et0)3SiC1 (185). Hexyl and octyl alcohols give similar products (169). From these and the sodium salts of carboxy acids mixed esters can be obtained ( I S ) . Phosphorus oxychloride, POCl,, and tliiochloride, PSCII, react stepwise or completely with alcohols or mercaptans. The presence of alkali favors the end products. Some of the products are: SP(OEt),, OP(OEt)&l, SP(OEt)El, OP(SEt)&l, and SP(SEt)&l (105). A variety of products is obtained with
INDUSTRIAL AND E N G I N E E R I N G CHEMISTRY
September 1948
1599
ESTERS FROM KETENE There are few recent references to acetylation by ketene. Aliphatic cyanohydrins are acetylated a t room temperature (6). Salicylic acid can be acetylated (140). Butyraldehyde containing a trace of sulfuric acid is converted by ketene to I-butenyl acetate. Other aldehydes react siinilarly (76).
ADDITION OF ACIDS TO ETHYLENE DERIVATIVES
Addition of acids to ethylene derivatives is a n important method of making esters, but little information on recent practice is available. The mechanism of the addition of benzoic acid t o isobutene (Smethylpropene) and to trimethylethylene in the presence of sulfuric acid has been studied. It takes place according to Markownikow's rule (4). Boron fluoride (16, $4, 107) and hydrofluoric acid (16) are recommended as ratalysts. The acid resulting from the hydrolysis of a nitrile can be added to a n unsaturate without isolation. Thus a mixture of propionitrile, a dodecene, and 65% sulfuric acid stirred at around 50" C. givw dodecyl propionate (108). T O ACETYLENE
glycols (129). Phenylphosphonyl chloride, PhPOCl2, and allyl alcohol react well i n pyridine (153). In the presence of dimethylaniline, arsenic trichloride gives slkyl arsenites with ethyl, isopropyl, and allyl alcohols (86).
Many millions of pounds of vinyl acetate and ethylidene diacetate are made by the addition of acetylene and acetic acid but little has been published recently on this subject. There are a few patents. Zinc and cadmium compounds are recommended as catalysts in the addition of acetylene to organic acids (41). Oxonium compounds (&), dimethylaniline (&), and cacodyl compounds (84) are said to be useful additions to the usual catalysts. Complexes containing fluorine (6.2) or boron fluoride are claimed (78). Vinyl trimethyl acetate (37) and vinyl acrylate (16) w e made by combining acetylene with the proper acids. The addition of acetylene to an acid may be effected in the vapor phase over various catalysts (36,63, 78, 79, 80).
ESTERS F R O M SALTS AND A L K Y L HALIDES
OTHER METHODS
Ethyl iodide and silver propionate give ethyl propionate (115). The ester is formed when triphenvlmethyl chloride and silver benzoate are refluxed in benzene (68). Allyl lactate results from the interaction of a salt of lactic acid and allyl chloride (197). The free fatty acids of low grade fats are converted into esters by dimethyl sulfate and a mild alkali (21). A monoester of glycol is obtained by reacting ethylene chlorohydrin and the sodium salt o l a n acid (69, 133'). Acetamide may be used as a reaction medium for the salt and alkyl halide (156). Thioacetic acid reacts with a n a-chloro ester in pyridine (1.20).An old Radischer patent (1912) claims t h a t the addition of a small amount of an amine to a mixture of a sodium salt and a halide improves the yield of ester. This has been verified recentlyin the preparation of benzyl benzoate from sodium benzoate and benzyl chloride. only tertiary amines have this effect (181,148). A novel variation of this method has appeared recently. A dry sodium salt is added t o butyl chlorosulfite:
Xitrilcs may be converted directly into esters by heating with a n alcohol containing a n acid catalyst (161). This may be a continuous process (8.4). Acetaldehyde can be converted into 3-hydroxybutyl acetate using magnesium aluminum ethyl, Mg (AIEt&, as the catalyst (158):
Three Reactors for Manufacture of Rosin Esters
RCOaNa
+ CISOSBU
-+
RCOzBu
+ NaCl + Soz
Sulfur dioxide escapes, leaving the butyl wter (119).
3CHaCHO
-.+
CHaCH(0H)CHzCHzOAc
Butanol and acetaldehyde over a catalyst a t 300" C. givr butyl acetate (90). Ethylene and carbon monoxide a t high pressures, with boron fluoride hydrate as a catalyst, unite to form ethyl methyldiethyl acetate (66). Ethyl dimethylethyl acetate is made from a mixture of ethylene and propylene under the same conditions (5.2). Kickel carbonyl added to a mixture of ethanol and concentrated hydrochloric acid saturated with acetylene gives a quantitative yield of ethyl acrylate (128). The Russians are still interwted i n converting an alcohol direetly into a n ester by passing its vapor over a catalyst (90, 91, 92).
INDUSTRIAL AND ENGINEERING CHEMISTRY
b 600
Vol. 40, No. 9
Cockerille, F. 0. (to E. I. du Pont de Yemours & Co.), U. B P n-. t e- . n.t- -, 2 361 .- -,994 - - - (1844). Colgate-Falmolive-Peet Co., British Patents 578,751,587,523 587,524, 587,530, 587,532, 587.533(1946) Coppock, P. D., and Hadley, D. J. (to Distillers Co.), U. 8. Patent 2.398.820(1946). (37) Cornthwaite, R.,-aIid Scott, N. D., U. 9. Patent 2,381,338 (1945). (38) Desnuelle, P., and Naudet, M., Bull. soc. chim., 1946,90-4. British Pa,tent 579,462(1946). (39) Dickson, J. T., (40) Dieta, A. A., Degering, C. F., and Schopmeyer, R. H., IND. ENG.CHEM.,39,82-5 (1947). (41) Distillers Co., Staudinger, J. J. P., Coppock, P. D., and Hadley, D. J.,British Patent 578,405(1946). (42) Dreger, E. E., (to Colgate-Palmolive-Pcet Co.), U. S. Patent 2,383.596 (1945) (43) Ducasse, J . , BulE. SOC. chim., 12,918-20 (1945) lNDUSTRlAL I N S T A L L A T I O N S (44) du Font de Nemours and Co., E. I., British Patents 567,914 (1945); 579,715;581,627(1946). The manufacture of ethyl acetate from pyroligneous acid i n (45) Erdos, Jos6, Anales escuela nacl. cienc., bioL ( M e x . ) , 4,387-90 France has been described (64). The Hercules Powder Company (1947). (46) Fein, M. L., and Fish.er, C . H., J . Am. Chem. $or., 68.2631-2 pilot plant for the production of rosin esters was written up in this I1 846) ,---, journal three years ago (30). Now through the courtesy of (47) Feuge, R . O . , Kraemer, E. A., and Bailey, A. E., QiZ & Soap, Finar West, views are shown of the resin plant of the Synthetics 22,202-7 (1945). Department of that company at Burlington, \T2T. .J. (48) Filachione, E. M. (to [J~ 8. A.)9 U. S.Patents2,402,129,2,402,130 (1946). (49) Fisher, C. H., Ea,stern Regional Laboratory, privat,e oomLITERATURE CITED munication. (50) Fisher, C . IT., and Fein, IM.L. (to Secretary of Agriculture TJ. (1) Adarns, C. E., and Shoemaker, B. H. (to Standard Oil Go., S.A . ) U. ~ S. Patent 2,374,428 (1945). Ind.), U. S.Patent 2,372,244 (1945) (51) Flood, D. T., PTOC. Roy. Irish Acad., 51B,197-210 (1947). ( 2 ) Agre, C. L., (to E. I. du Pont de Nemours & C o . ) , U.8 . Patent (52) Ford, T. A. (to E. I, du Pont de Nemours & Go.) U. S,Patont 2,381,888 (1945). 2,424,653 (1947). (3) Allen, H. D., and Klein, W. A. (to Colgate-Palmolive-Peet C’o.), (53)Freed, W. V. (to E. I. du Pont de Nemours & C o . ) , U. 9. PatU. S.Patent 2,383,579 (1945). ent 2,411,962 (1946). Altschul, Rolf, J. Am. Chem. SOC.,68,2605 (1946). (54)Gayer, F. E., and Fawkes, C. E . , (io Continental Research American Cyanamid Co., British Patent 556,829(1943). Corp.), U.S. Patent 2,411,536 (1946). American Cynamid Co. (to H. 6. C. Fairweather), B r i h h (56) Gidvani, B. S., and Kamath, N. R., London Shellac Research Patent 569,470(1945). Bureau, Tech. Paper 28 (1948). (7) Anderson, G . R. (to Hercules Powder Co.), C . 8.Patenb 2,420.( 5 6 ) Gol’danskii, V. I., J . Phw/s. Chem. (U.S.S.R.), 21, 431--S (1947). 926 (1947). (57) Gol’danskii; V. I.,and Chirkov, N. M., 15id., 20, 1333-45 (8)Arrowsmith,‘ C. J., and Ross, John, U. S. Patent 2,383,581 (1946); Acta. Physicochirn. U.E.S.S., 22,363-80(1947). (1945) (58) Gol’danskii, V. I., Semenov, N. N.,and Chirkov, N. M.” 9.C . , J . (9)Ault, W.C.,Weil, J. K., Nutting, G . C., and COTWCR, Compt. rend. acad. sci. U.R.S.S., 52,777-9 (1946)(Eng.) Am. Chem. Soc., 69,2003-5(1947). (58) Gord.on, P.L., and Aronowitz, Ruth, IND.ENG.CHEM.,37, (10) Badgett, C. O., Provost, R. C., Jr., Ogg, C. L., and Woodward, 780-2 (1945). C . F., Ibid., 67,1135-8 (1946). (60) Griffin, W.C . (to Atlas Powder Go.), U. 5. Patent, 2,380,168 (11) Badgett, C . O., and Woodward, C. F., Ibid., 69,2907 (1947) (1945). (12)Balfe, M.P.,Downer, E. A. Tv., Evans, A. A., Kenyon, J . , (61) Groen, M. G. (to Mien Property Custodian), U. 9. Pa,tent Poplett, R., Searle, C. E., and Tarnoky, A. L., J. Chem, 2,4 12,2 13 (1946) SOC.,1946,797-803. (62) Groth, B. S., and Johanaon, B. H. S., U. 8. Patont 2,376,964 (13) Barry, A. J. (to Dow Chemical Co.), U. 8.Patent 2,405,986 (1945); Swedish Patent 106,961(1943). (1946). (63) Grubb, H. W., Q’Hara, L. M., and Atwood. Kenton (to Joseph (14) Bartlett,P. D., andRoss,S.D.,9.A7n.C~1cm.S0~.,69,460(1947), Seagram and Sons, I R ~ .U. ) ,S. Patent 2,426,968 (1947). (15) Bauer, Walter, and Kautter, C . T. (to Rohm. & Ham Co.) (64) Guinot, H., and Aug6, M., Chimie & industrie, 55, 167--73 U. 5 . Patent 2,363,286 (1944). (1946). (16) Bearse, A. E., and Morin, R. D. (to Standard Oil CO., In$.) (65) Hanford, W, E., and Roland, J. R.,U. 8, Patent 2,378,009 U. S.Patents 2,414,999,2,415,000 (1947) (1945). (17) Bernardi, D. J., and Florence, R. T. (to Interchemical Gorp.), , 953-6 (66) Harher. W. I.,and Poran, C. 8., IND.ENO.C H E W .37, U. S. Patent 2,406,795 (1946). (1945). (18) Bersworth, F.C., U.S . Patent 2,428,353 (1947). (67) Harfenist, Morton, and Baitsly, Richard, J. Am. Chem. Soc., (19) Blumenfeld, Joseph, U. S. Patent 2,405,873 (1946j. 69,362-5 (1947). (20) Bradley, T. F. (to American Cyanamid Co.), U.S. Patent 2,398,(68) Hauser, 6. R., Saperstein, P. O.,and Shivers, Y. C., W d . , 90, 827 (1945). 606-8 (1948) (21) Bradshaw, G. B., and Meuly, W. C. (to E. I. du Pont d.e Ne(69) Heim, H. C., and Poe, C . F., J.Org. Chem., 9,299-301(1944) mours & Co.) * U. 8.Patent 2,398,492 (1946) (70) Hoinanen, Pekka, Ann. Acad. Fannicae, Ber. A. II? Chem., (22) Brandner, J. D., Hunter, R. H., Brewster, M. D., and Bonner, N O .9, 3-13 (1943). R.E., IXD. E s a . CHEM.,37,809-12(1945). (71)HeIferich, Burckhsrdt, and Rcimann, WoKgang, Chem. Ber., 80, ( 2 3 ) Brehmer, Laina and Elo, Helli, Ann. Acad. Sci. Pennkcae, S e r ~ 1634(1947). A , II,Chem., N o . 16 (1945)(German). (72) Hoerig, E. F., Hanson, D., and Kowalbo, 0. L., IND.FNG. (24) Bruson, H . A. (to Resinous Products Co.), U. 8.Patent 2.410,CHEU., 35, 575 (1943). 425 (1946). (73) Roffmarin-La Roche, Inc., British Patent, 579,333(1946) (25) Bruun, J. H., and Perrine, J. N., U. S . Patent 2,384,793 (1945) (74) Homan, J. D. €I., Rec. trav. chim., 63,181-8 (1944). ( 2 6 ) Burrell, Harry, IND. ENG. CHEX.,37,86-9(1945) (75) Howard, J. B. (to Bell Telephone Laboratories), U. 8. Patent (27) Burrell, Harry ( t o Heyden Chemical Corp.), U. S. Pa.tenL 2,410,073 (1946). 2,360,393, 2,360,394 (1944). (76) Hull, D. @., and Agell, A. E. (to Enstman ICadak G.),T J ~8. (28) Byer, A. J., and Dull, M .F,, J. Am. Chem. Soc., 69,973-4 Patent 2,422,679 (1947) (1947). (77) Iler, R.K.*and Pinkney, P. S.,IND. E N G@ . H E M . , 39,1379-84 (29) Carson, J. F., Jr., and Maclay, W. D., I b i d . , 67,787-9 (1.945) (1947). (30) Carter, R.P., IKD. ENG.CHEM, 37,448-50(1945). (78) I. G. Farbenindustrie (to Heinrich Lange and 0 t h Dorrer), (31) Champetier, G., and Petit, J., BtdZ. SOC. chim. 12,680-8,689--9L German Patent 637,257(1936). (1948). (79) I. G . Farbenindustrie, Belgian Pa,t,ents444,559, 444,560(1942) (32) Chelintsev, V. V., Compt. rend. a,cad. sei. U.R.S.S., 55, 323-6 (SO) Imperial, Chemical Industries, British Patent 581,501(1946) (1947). (81) Xskander, Yousset, Nature, 165, 14.1 (1948). (33) Clocker, E.T., and Cox, R. P., Oil d S o a p , 22, 57-60 (1945).
To analre a lauric ester of ascorbic acid 8.8 granis of asoorbic acid and 8.0 grams of lauric acid are dissolved in 100 ml. of 95% sulfuric acid. After 16 hours at room temperature the mixture Es poured onto ice (73). Ethylene oxide and carbon dioxide are caused to combine, at above 150” C. under pressure in the presence of catalysts, t o form ethylene carbonate (157) Phosphoric esters can he made from phosphoric acid arid ethylene oxide ( 1 ) . The preparation of boric esters has been described (13.6). Means have been found for the direct esterification of silicic. scid (7’7).
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September 1948
INDUSTRIAL AND ENGINEERING CHEMISTRY
(82) Ivanoff, Nina, Bull. met. grasscs inst. colonial Marsdlle, 29, 13-9 (1945). (83) Jansen, E.F., and Jang, Rosie, J. Am. Chem. SOC.,68,1475-7 f 1946). (84) Jillk L. T.(to E. I. du Pont de Nemours & Co.), U. 5. Patent 2,416,756(1947). (85) Joyce, R. M., (to E. I. du Pont de Nemours & Co.), U. 8. Patent 2,375,301(1945). (86) Kamai, G.,J.Gen. Chem. (U.S.S.R.), 17,553-5(1947). (87) Keim, G. I.,and ROSS,John (to Colgate-Palmolive-Peet Co.), U. S. Patent 2,383,602(1945). (88) Korte, E. R., and Salmi, E. J., Suomen Kemistilehti,20B,8-12 (1947). (89) Leimu, R., Korte, R., Laaksonen, Eevi, and Lehmuskoski, Ulla, Ibid., 19B,93-7 (1946). 49,652-4 (90) Lel’chuk, 9. L., Compt. rend. acad. sci. U.R.S.S., (1946)(Eng.) : K h i m . Prom., 1946,No.9,16-7. (91) Lel’chuk, S.L., Balandin, A. A., Vaskevich, D. N., and Groer, I.I., J.Applied Chem. (U.S.S.R.), 17,604(1944). (92) Lel’chuk, S. L.,and Vaskevich, D. N., U.S.S.R. Patent 64,836 ( 1945) (93) Lever Bros. and Unilever, N. V., Dutch Patent 60,567(1948). (94) Levesque, 6. L., and Craig, A. M., IND. ENG.CHEM.,40,96-9 (1948). (95) Leyes, C. E., and Othmer, D. F., Trans. Am. Inst. Chem. Engrs., 41,157-96 (1945); IND.ENG.CKEM.,37,968-77 (1945). (96) Lindner, Kurt, Fette u.Seifen, 50, 396-8 (1943). (97) Loder, D. J. (to E. I. du Pont de Nemours & Co.), U. Se Patent 2,388,164 (1945). (98) Long, J. R. (to Wingfoot Corp.), U. S. Patent 2,370,055(1945) (99) Loury, and Mellier, M. T., Bull. soc. chim., 1947,349-51. (100) Luce, 6 . B. (to Monsanto Chemical Co.). _ .U. S. Patent 2. .411..138 (1946). MacGregor, J. H. (to Courtaulds, Ltd.), British Patent 592,106 (1947). Maglio, M. M., Chemist Analyst, 35,39-41(1946). Mahan. J. E. (to Phillips Petroleum Co.), U. S. Patent 2,408,940 (1946). Martin, F. C., U. 8. Patent 2,421,842 (1947). Martin, T. W., Norman, G. R., and Weilmuenster, E. A., J . Am. Chem. Soc., 67,1662-4(1945). Matchett, J. R., and Levine, Joseph, IND. ENG.CHEM.,ANAL. ED., 13,98-9 (1941). May, R. L. (to Sinclair Refining Ca.), U. S. Patent 2,397,498 (1943). Monick, J. A., Allen, H. D., and Marlies, C. J., OiZ & 8oap,*23, 177-82(1946). Murphy, J. F., and Holt. E. K. (to Lever Bros.), U. S. Patent 2,418,898 (1947). Nakaya, Shinkichi, and Hori, Tomoo, Sumitomo Denki Iho (Sumitomo Elec. Bull.), No. 30,26-36 (1943). Naudet, M., and Desnuelie, P., Bull. SOC. chim., 1946,595-8. Newman, M. S., and Fones, W. S., J . Am. Chem. Soc., 69,1046 7 (1947). Nordlander, B. W., and Cass, W. E., Ibid., 69,2679-82 (1947). Norris, F. A., and Mattil, K. F., Oil & Soup, 23,289-91 (1946), J . Am. Oil Chemists’ Soc., 24,274-5(1947). N. V. Vereenigde Stearine Kaarsenfabrieken “Gouda-Apollo,” Dutch Patent 54,344(1943). Palomaa, M. H., Soumen Kemistilehti, 19B,53-6 (1946) Palomaa, M. H., and Kaski, T., Ibid., 19B,85-8 (1946). Paquot, C., Bull. SOC. chim., France, 1947,926-7. Paquot, C., and Bouquet, F., Ibid., 1947,321-2. Pavlic, A. A., (to E. I. du Pont do Nemours & Co.), U.S. Patent 2,408,094 (1946). Peppard, D. F., Brown, W. G., and Johnson, W. C., J . Am. Chem., Sac., 68,73-5,76-7 (1946). Percy, J. H. (to Colgate-Palmolive-Peet Co.), U. 8. Patent 2,383,614 (1945). Phillips, A. P., and Baltsly, Richard, J . Am. Chem. SOC.,69, 200-4 (1947). Pleger, K. G., and Hill, A. J., U. S. Patent 2,410,791(1946). Rambaud, Ren6, and Dondon, 34. L., Compt. rend., 223,381-3, (1946). Reiberg; C. E., Org.Syntheses, 26, 2-6,18-21 (1946). Rehberg, C. E., and Fisher, C. H., J. Org. Chem., 12,226-31 (1947); U. S.Patent 2,367,798 (1945). Reppe, W., NodernPlastics, 23,No. 3,162-5,210(1945). Eossiiskaya, P.A,, and Kabachnik, M. I., Bull. acad. sci. U.B.S.S. Classe sci. chim., 1947,509-14. Rovira, Sanuago, Ann. chim., 20,660-700 (1945). Rueggeberg, W. H.C., Ginsberg, Abram, and Frants, R. C . , IND. ENG.CHEM.,38,207-11(1946). Sargent, D. E. (to American Cyanamid Co.), Canadian Patents 439,626,439,861,439,630,439,860 (1947).
1601
(133) Savary, Paul, Bull. soc. chim. France, 30,84-7 (1946); 1947, 258-60;Compt. rend., 226,89-90 (1948). (134) Scattergood, Allen, J.Am. Chem. Soc., 67,2160-2(1945). (135) Schumb, W. C., and &,evens, A. J., Ibid., 69,726(1947). (136) Schwarcman, Alexander (to Spencer Kellogg and Sons), U. S. Patent 2,412,176(1946). (137) Shlechter, Nathan, Othmer, D. F., and Marshak, Seymour, IND. ENG.CHEM.,37,900-5(1945). (138) Sickels, J. P., and Schols, T. F. (to American Cyanamid Co.). Canadian Patent 439,631(1947). (139) Siegel, E. F., and Moran, M . K., J. Am. Chem. Soc., 69,14579 (1947). (140) Skoldinov, A. P., Smirnova, N. V., and Smolin, D. D., U.S.S.R Patent 66,328(1946). (141) Spangenberg, J. F., Industria y qubmica (Buenos A i r e s ) , 7, 393-401 (1945); C.A. 41,4028 (1947). (142) Spasov, Aleksand’r. Annuaire univ. Sofia, Facult6 phys.-math., 38,Livre 2,63-80 (1941-2). (143) Strain, Franklin (to Pittsburgh Plate Glass Co.), U.S. Patents 2,379,252,2,379,261 (1945); 2,392,621 (1946). 1144) Straus, F. A. (to Wecoline Products Co.), U. S. Patent 2,372,522 (1945). (145) Stuart, R. G., Analyst, 72,235-41(1947). (146) Sussman, Sidney, IND.ENG.CHEM.,38,1228-30 (1946). (147) Svensson, O., Swedish Patent, 104,969(1942). (148) Tharp, I. D., Nottorf, H. A., Herr, C. H., Hoover, T. B., Wagner, R. B., Weisgerber, C. AnpWillcins, J. P., and Whitmore, F. C., IND.ENQ.CHEM.,39,1301r-2 (1947). (149) Thomas, G . G., and Davis, C. W., Nature, 159,372 (1947). (150) Tommila, Eero, Suomen Kemistilehti, 15B,9-10,10-11 (1942) (151) Tommila, Eero, and Kstonen, Liisa, Ibid.. 18B,24-8 (1945). (152) Tommila, Eero, and Sternberg, Helger, Ibid., 19B,19-23 (1946) (153) Toy,A. D. F., J. Am. Chem. Soc., 70,186-8(1948). (154) Trent, W. R. (to Colgate-Palmolive-Peet Co.), U. S. Patents 2,383,632, 2,383,633 (1945); Reissue, 22,751(1946). (155) Tyron, P. F., J . Am. Chem. SOC.,69,972-3(1947). (156) Tucker, N. B., (to Procter and Gamble Co.) Ti. S. Patent 2,399,959(1946). (157) Vierling, Karl (to I. G . Farbenindustrie), German Patent 740,366 (1943). (158) Villani, F. J., and Nard, F. F., J . Am. Chem. Soc., 68, 167445 (1946). (159) Val’nov, Yu. N., J . Gen. Chem. (U.S.S.R.), 17,231-4(1947). (160) Widegren, Benkt, Tek. Tid., 74,153-8(1944). (161) Wingfoot Corp., British Patent 569,846(1945). (162) Victor Wolf, Ltd., and Rosenbusch, Richard, British Patent 563,481(1944). (163) Victor Wolf, Ltd.; and Rowe, Richard, British Patent 591,421 (1947). ~
R ~ C E I V EJune D 14, 1948.
Reactor for Manufacture of Rosin Esters This Bhows the operating level of a 2000-gallon reactor used for preparation of rosin esters. In the background is the condenser used when esters of glycols and glycerol are produced. In the center is the agitator drive. The reactor is heated by Dowtherm supplied by 8, boiler located some distance from the operating building.
