ESTERIFICATION

Oxley, H. F., Thomas, E. B., and Nichols, F. S. (to Celanese. Corp. of iimerioa), U. S. Patent ... Rieveschl, G., Jr. (to Parke, Davis & Co.), Ibid., ...
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INDUSTRIAL AND ENGINEERING CHEMISTRY

1988

(47) hlartin, H., Margot, A., Neracher, O., Schindler, W., and Hodel, E. (to J. R. Geigy, A.G.), U. S. Patent 2,551,891 (May 8, 1951). Mastagli, P., Metayer, hI., and Bricard, A,, Bull. SOC. chim. France, 1950, 1045. Myers, G. S. (to United States Rubber Co.), U. S. Patent 2,571,053 (Oct. 9, 1951). N. V. de Bataafsche Petroleum Maatschappij, Brit. Patent 663,294 (Dec. 19, 1951). O'Gee, R. C., and Woodburn, H. M., J . A m . Chem. Soc., 73, 1370 (1951). Oppenauer, R., U. S. Patent 2,560,240 (July 10, 1951). Oxley, H. F., Thomas, E. B., aiid Hindley, F. (to British Celanese, Ltd.), Brit. Patent 656,154 (hug. 15, 1951).

Oxley, H. F., Thomas, E. B., and Nichols, F. S. (to Celanese Corp. of iimerioa), U. S. Patent 2,550,020 (April 24, 1951). Parke, Davis & Co., Brit. Patent 663,903 (Dec. 27, 1951). Pearson, F. 0. (to American Viscose Corp.), U. S.Patent 2,558,875 (July 3, 1951). Pedlow, G. W., and Miner, C. S. (to Minnesota Mining & hlanufacturing Co.), Ihid., 2,566,363 (Sept. 4, 1951). Phillips, A. P., J . A m . Chem. Soc., 73,5557 (1951). Potts, R. H. (to Armour & Co.), U. S. Patent 2,546,521 (May 27, 1951). Ihid., 2,555,606 (June 5, 1951).

Reynolds, D. D., and Kenyon, W. 0. (to Eastman Kodak Go.), Ibid., 2,581,443 (Jan. 8 , 1952). Rieveschl, G., Jr. (to Parke, Davis & Co.), Ibid., 2,573,607 (Oct. 30, 1951).

Vol. 44, No. 9

(63) Rieveschl, G., Jr., and Coleman, K.R. (to Parke, Davis & Co.), Ibid., 2,573,606. (64) Roe, E. T., Stutzman, J. M.,and Swern, D., 6.A m . C'hwna. Soc., 73, 3642 (1951). (65) Rooseboom, A., Chem. Eng., 58, N o . 3, 111 (1951). (66) Runge, F., and IXummel, H., Chem. Tech., 3, 163 (1951). (67) Slocombe, R. J., and Hardy, E. E. (to Alonsaiito Chemical Co.), Brit. Patent 656,726 (Aug. 29, 1951). (68) Smith, N. L., U. S. Patent. 2,572,066 (Oct. 23, 1951). (69) Societe Carbochimique, Brit. Patent 655,580 (July 25, 1951). (70) Spillane, L. J., and Kayser, W. G., Jr. (to Allied Chemical 6: Dye Corp.), C. S.Patent 2,557,703 (June 19, 1951). (71) Teter, J. W. (to Sinclair Refining Co.), Ibid., 2,567,254 (Sept. 1 1 , 1951). (72) Teter, J. IT.,and Mostek, J. L. (to Sinclair Refining Go.), U. S. Patent 2,552,072 (May 8 , 1951). (73) The B. F. Goodrich Co., Brit. Patent 648,886 (Jan. 17, 1951). (74) Tyerman, W. (to Imperial Chemical Industries, Ltd.), U. 6. Patent 2,547,064 (April 3, 1951). (75) Ihid., 2,570,291 (Oct. 9, 1951). (76) m7eickmann, A. (to Badische Anilin- und Soda-fabrik), Ger. Patent 803,903 (April 12, 1951). (77) Whitehead, W. (to Imperial Chemical Industries, Ltd.), Brit. Patent 649,980 (Feb. 7, 1951). (78) Wood, T. F. (to Burton T. Bush, Inc.), U. S.Patent 2,540,155 (Feb. 6, 1951). RECEIVED for review J u n e 21, 1952.

.&CCBPTED

July 9, 1952.

ESTERIFICATION E

E. EMMET REID

PO3 EAST 33RD ST., BALTIMORE 18, MD.

T h e making of esters goes on apace. In writing this review the problem has been one of selection. M o r e references have been put in than in past years but only one third of those available have been used. M o r e than usual attention has been given to the kinetics of esterification. Transesterification holds its place. In the wake of the silicones, silicic esters have come into prominence. Esters of the various acids of phosphorus are receiving considerable attention. The success of Dacron, ethylene terephthalate, has led to studies of other polymeric esters.

I

N ACID-catalyzed esterification it is assumed that the ion ROH2+ from the alcohol combines with the acid to form a complex from which the water ion, HOH?+, is eliminated. The structure of the acid determines the rate of esterification. A substituent in the alpha position in an aliphatic acid has marked retarding influence, much less in the beta position, and little when further off. Methanol solutions of the acids were heated under specified conditions and the unesterified acid was determined. For butyric this was 1%, for the a-methyl, 4570, and for the @-methyl, 13%. The influence of the methyl group diminishes as the acid chain gets longer. Thus for a-methylcaprylic acid the figure is 19% and for a-methylpalmitic acid, 12%. The ethyl group has a much greater effect than methyl but from then on the size makes little difference. Of stearic acid with groups in the alpha position, the per cent unesterified acid was for methyl, 13; for ethyl, propyl, and butyl, 88; and for hexyl, nonyl, decyl, and hendecyl, 93 (194). The retarding influence of substituents in different positions in aliphatic acids has been compared t o t h a t in aromatic acids (8$). An empirical rule of six relating to this steric influence has been worked out (166). A detailed study has been made of the steps in the reaction of phthalic anhydride with glycerol (199). I n combining with phthalic anhydride an alcohol is supposed to add across the double bond of one carbonyl. The complex so formed rearranges t o the mono ester (101). With 8-propiolactone, acetyl chloride gives (3-acetoxypropionyl

chloride n-hile acetic anhydride gives B-acetoxypropionic anhydride (03). The attack by acetic acid is kinetically of the first order relative t o the acetate ion, since this is similar in reactivity to the acetoxypropionic ion, AcOCH&H&OO-, which is formed (17). The esterification of benzoic acid by diazodiphenylmethane, PhBCN?, is of the first order in respect t o each of the reactants

(i79). A series of reactions has been devised for preparing ethyl acctate tagged with CI4and for converting this to the malonate (181). The average molecular weights of the polymers and the relative amounts of linear polymers and rings formed in the esterification of adipic acid by decamethylene glycol have been calculated for different proportions of the acid and glycol (108). The conclusions have been verified experimentally. The viscosity of the polymer decreases when it is heated for a long time in chlorobenzene, because of establishment of the equilibrium between the linear and cyclic structures (107). When carbon dioxide is passcd into an aqueous jolution of a n alcohol and sodium hydroxide a t 0" C. the ROCOz-ion is formed. With 0 . 3 11.1' benzyl alcohol the percentage of this is 0.65. The rate of formation with benzyl alcohol is 34 times that vith cyclohexanol ($06). The rate of reaction between acetic anhydride and ethyl alcohol in carbon tetrachloride solution v a s followed by measurements of the change in the dielectric constant of the solution ('7). The saponification of ethyl acetate n as studied by means of highfrequency titrimetry (111). The acid hydrolysis of ethyl acetate in acetone-water and in dioxane-a ater solutions has been studird. The rate passes through

September 1952

INDUSTRIAL AND ENGINEERING CHEMISTRY

a minimum when the concentration of the organic part of the solvent is around 80% and a maximum when it is 10% (140). The simple collision theory and the thermodynamic treatment of LaMer are not in agreement in the kinetics of the hydrolysis of potassium ethyl malonate in water-dioxane and in water-tert-butanol solutions (212). I n aqueous solution the hydrolysis of ethyl acetate by an ion exchange resin is more rapid than by an equivalent amount of hydrochloric acid (134) but, for some unknown reason, the reaction stops far short of completion (136). In the hydrolysis of an ester the alkyl-oxygen bond remains intact. However, with esters of alkyl tertiary or aryl secondary alcohols this bond may be broken, causing racemization. The solvenolysie of the monophthalates of several active alcohols has been investigated. In acetic acid racemization takes place while in ethyl alcohol .it does not, With a low concentration of alkali unimolecular racemization goes on but with a higher concentration the optical activity is retained (10-12). In the acid-catalysed, unimolecular hydrolysis of esters of active tertiary alcohols racemization takes place (37). In the nitration of cellulose by nitric acid containing tagged oxygen the oxygen of the cellulose is found in the ester as i t would be in esterification with an organic acid (119). I n the hydrolysis of thioacetates, RCOSR', a sulfur-free acid, and a mercaptan are normally produced but triphenylmethyl acetate splits the other way (145). I n 95% acetone, the hydvolysis of benzoyl chloride and of several of its substitution products is unimolecular (31). A study has been made of the simultaneous hydrolysis and alcoholysis of acetyl, propionyl, and butyryl bromides and chlorides with mixtures of water and seven saturated alcohols. The reactions involve complex formation. The energy of activation depends chiefly on the reacting functional groups. The ratio of alcoholysis t o hydrolysis does not change with the temperature (183). The influence of various groups in the meta and para positions on the rates of hydrolysis of ethyl benzoate has been studied. The tert-butyl group has an anomalous effect (172). The MeSO and MeSOz groups accelerate the hydrolysis (171). Steric hindrance has great influence on the rates of hydrolysis of the anilides of substituted benzoic acids (228). The acetates of several fluorinated alcohols are saponified much more slowly than the corresponding nonfluorinated (08). The relative amounts of normal and of pseudoesters formed in the esterification of a-benzoylbenzoic acid depends on the number and positions of its substituents (167). The esterification and hydrogenation rates of furanacetic acid are both many, many times as high as those of furoic acid (203). A comparison of the ultraviolet absorption spectra of butyl nitrate and nitrite and of nitrobutane points to an alkyl hydroperoxide as an intermediate in the hydrolysis of butyl nitrate (140).

SPEEDING U P AND COMPLETING ESTERIFICATION Comparisons have been made of the activities of lipases from different oil seeds in the synthesis of esters from several alcohols (174). 8-Benzoylacrylic acid requires no catalyst for its esterification by alcohols if the water is taken off azeotropically (62). lLIethallyl lactate is obtained by heating the alcohol with lactic acid. If an acid catalyst is added t o this mixture, rearrangement takes place with the formation of a cyclic ether (86). The efficiency of trifluoroacetic anhydride in the acetylation of polyvinyl alcohol has been traced to the formation of the mixed anhydride, F8CCOOAc. The resulting ester contains no fluorine, The acid itself is an active catalyst (144). The addition of phosphorous pentoxide or oxychloride t o a mixture of a n alcohol with the acid t o be esterified is recommended (178, 107). Acetyl bromide and hydrobromic acid are efficient catalysts,

1989

COURTESY HERCULES POWDER 0 0 .

lower-Type Reactor for Synthesis of the Methyl Ester of Rosin from Rosin and F t h a n o l even for tertiary alcohols (198). Hydrogen chloride, generated in situ, is especially efficient (182). A combination of sulfuric acid with two molar quantities of an organic acid anhydride is recommended as an esterification catalyst (65). An excess of a mineral acid and anhydrous alcohol are desirable for the esterification of 4-amino acids (142, 226). Stirring 147 grams of glutamic acid, 113 grams of 100% sulfuric acid, and 1400 ml. of absolute ethyl alcohol a t 45" C. gives the y-ethyl ester. Other alcohols react similarly (22.4). Chlorosulfonic acid is recommended as a catalyst (71). I n making allyl esters, allyl ether is used to remove the water azeotropically (63). Polyethylene glycol is esterified with rosin a t 500"F. with lime as a catalyst (28).

ESTERIFICATION PROCEDURES V A P O R PHASE

The vapor phase esterification of acetic acid and ethyl alcohol over silica gel has been investigated between 200" and 260" C. and from 1 to 2.33 atmospheres pressure. The rate is limited by the rate of activated adsorption of the acetic acid. The apparent over-all reaction velocity is approximately a linear function of the reciprocal of the absolute temperature (36). Chlorosulfonic acid is recommended for producing ethyl acetate (72). NITRILE TO ESTER

Hydroxyacetaldehyde is combined with hydrocyanic acid containing ' C14 and the resulting nitrile is esterified by ethyl alcohol and sulfuric acid, using toluene t o take off the water, t o make labeled ethyl glycerate (64). Improvements have been made in preparing alkyl malonates from cyanoacetic acid (45,807) and ethyl succinate from ethylene cyanide (112). Esters of thiophene acids have been prepared from the nitriles (f35).

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INDUSTRIAL AND ENGINEERING CHEMISTRY

Vol. 44, No. 9

An ester (166) or a lactone ( 8 9 ) is converted t o an N-substituted amide by ammonolysis. Glycol, as a solvent, favors alcoholysis but hinders ammonolysis ( 6 ) . ACID ANHYDRIDES

Many examples of the use of acetic anhydride are passed over as offering little novelty. Secondary alcohols react slowly unless a base is added. The esterification of cyclohexylphenylcarbinol in acetic anhydride is speeded up 300 times by the addition of pyridine ( 1 0 ) . Some diarylcarbinols react with phthalic anhydride in the presence of trimethylamine but not of pyridine. With tertiary alcohols, a metal derivative such as MeEtPhCOK must be used ( I S ) . ACID CHLORIDE

COURTEOY MONSANTO

Equipment for Making Esters for Plasticizers

ALCOHOLYSIS

The transeskrification of fats has been revien-ed (129). A study has been made of the kinetics of the sodium methylatecatalyzed alcoholysis of the methyl esters of substituted benzoic acids. The rates were measured polarimetrically (214). In the saponification of mono- and tri-acid glycerides in alcohol solution, rapid alcoholysis precedes saponification and the rates measured are those of the saponification of the ethyl esters (109, 159). The rates o f alcoholysis of ethyl stearate by cetyl alcohol and of interchange between ethyl stearate and cetyl acetate have been measured, with the object of throwing light on what goes on in the making of polymeric esters (laoj. The alcoholysis of an acetoacetic ester is rapid at 100" C., even without the aid of a catalyst,. The rate is higher TT-ith a secondary than with a tertiary alcohol and still higher with a primary, but i t is relatively high with the tertiary. Wit'h primary and secondary alcohols the reaction is of the first order with reference t o the ester but of the second order with tertiary ( 8 ,

40). An alkali metal hydride, such as sodium hydride (NaH), is recommended as a catalyst ( 6 9 ) . There is much interest in the transesterification of glycerides (15, 19, 106, 152, 163, 170, 173, 180, 204, 211). Glycol esters ( 2 2 ) and allylic esters are conveniently prepared by alcoholysis (58, 80). Methyl and ethyl acrylates are converted into esters of higher alcohols (175). -4dialkylaminoethyl alcohol, such as HOCHGH2NEt2, replaces ethyl alcohol in an ethyl ester (73): Cyanurates of glycols and of higher alcohols can be prepared from methyl cyanurate (67). An ester of an hydroxycarboxylic acid is converted into a polyester by self-alcoholysis (74, 76). P-Propiolactone reacts as a n ester with an alcohol (16, 91) or with a phenol (30). The products are esters of hydracrylic acid. The alcoholysis of several substituted benzamides was inadvertently studied instead of their hydrolysis (141). Vinyl esters of higher acids are prepared by the acidolysis of vinyl acetate (97, 163, 213). Mercuric acetate with sulfuric acid catalyzes this reaction (213). D-Mannitol hexanitrate dissolved in acetic anhydride, containing sulfuric acid, is converted into the hexaacetate (216,230).

Dozens of examples of the preparation of esters by the reaction of acid chlorides with alcohols are passed over since their novelty is in the ends rather than in the means. Phosgene, in excess, is caused t o react with CHEMICAL GO. an alcohol in the vaDor phase (189). Peroxvdicarbonates, RO.CO~OO.CO.OR;are formed by the reaction of an alkyl chlorocarbonate with aqueous sodium peroxide (210). Cuprous chloride has been used as a catalyst with an acid chloride and an alcohol (133). An alkyl sulfenate, RSOR', is formed from a sulfene chloride and an alcohol (165). A selenate ester, RSeOR', is made in, analogous manner (50). METAL SALTS

A common method for identifying acids is to prepare the pbromophenacyl ester from the sodium salt and p-bromophenacyl bromide. When this method is used with sodium formate, t h e ester is formed but is hydrolyzed so rapidly that what is isolated is p-bromophenacyl alcohol. This as mistaken for the desired formate ester by the author of this review and by others. It has been shown recently t h a t the formic ester, which melts at 99" C. can be isolated (95, 123). 4-Phenylazophenacyl bromide, which gives colored esters, has been recommended for the identification of acids (158). Epichlorohydrin reacts with sodium salts t o give esters of 2 , s epoxypropanol (68). Dimethyl sulfate can be used for making methyl esters (52, 233). Dialkylaminoethyl chloride, RsNCHr CH2CI, is employed for making esters of medicinal interest (26, 56, 208, 225). Ethyl methanetrisulfonate, HC(SO3Et)8, has been synthesized from the silver salt and ethyl iodide (186). KETENE

Ketene serves for the exhaustive acetylation of glycols (169). ADDITION OF ACID TO A N UNSATURATE

Hydrazoic esters result from the addition of hydrazoic acid t o unsaturates in the presence of phosphoric acid (190). ID the presence of perchloric acid, butadiene telomerizes with an organic acid t o esters, RCCO(CaH&H (110). Many thioacetic esters have been prepared by adding thioacetic acid t o a variety of unsaturates (SS). ESTERS FROM ACETYLENE

The patents on vinyl esters have been reviewed (118) and the heat of the reaction of acetic acid with acetylene has been deter-

September 1952

INDUSTRIAL AND ENGINEERING CHEMISTRY

mined (139). The variables-relative concentrations of acetylene and acetic acid, space velocity, and dimensions of the cata4yst bed-in the gas phase synthesis of vinyl acetate have been discussed (88, 84). Processes have been described in patents ( 1 4 , 228) and cadmium and zinc silicates (SO@, zinc acetate '(21),and mercuric phosphate (186) have been claimed as aatalysts. Vinyl formate has been produced by vapor phase syntheais (221). A mixture of esters is formed when acetylene is passed Into a heated mixture of sodium ethylate and ethyl carbonate (66,67). TETRAHYDROFURAN

Esters of tetramethylene glycol are obtained by heating tetrahydrofuran with an acid or acid anhydride and a catalyst (128, BOO). 4Chlorobutyl acetate is formed when acetic acid, phosphorous trichloride, and zinc chloride are ueed (69). A L K Y L SULFATES AND SULFONATES

A study has been made of the combination of sulfuric acid with propylene under different conditions (193). The reaction af sulfuric acid with the lower alcohols has been investigated extensively. An excess of the acid has a remarkable accelerating effect. With 7 moles of the acid t o 3 of ethyl alcohol the rate Is 500 times what it is when this ratio is reversed (817). Polyfluoroalkyl acid sulfates are prepared from the fluoroalkanols and sulfuric or chlorosulfonic acid (94). The tetrasulfonate of pentaerythritol is formed from benzene sulfone chloride in pyridine (99). U N C O N V E N T I O N A L METHODS

Esters are made from an ammonium salt, an alcohol, and ammonium sulfate (76, 7 7 ) . Formaldehyde, acetic acid, and styrene with boron fluoride as a catalyst give an ester, AcOCHr (CH&HPh),OAc, in which ra may be 1 or a higher number (47). Acetic anhydride, furfural, and nitric acid give 5-n i t r o-2-furanemethaned i o l d i a c e t a t e (187). Butyl alcohol is dehydrogenated t o butyl butyrate when heated with sulfur t o 260" t o 325' C. Other alcohols g a v e a s i m i l a r reaction (10.9). PHOSPHOROUS AND PHOSPHORIC ESTERS

A summary of the extensive work of Arbusov on phosphorous esters has been written (4). Diallyl (201) and dineopentyl (87) phosphites have been prepared. A glycol in which the hydroxyls are adjacent or are separated b y only one methylene group may replace two of the chlorine atoms of phosphorous tric h l o r i d e , Pentaerythritol gives a qGro ester (130). When diethyl phosphite is heated with butanol or a higher a l c o h o l , e t h y l alcohol is eliminated, leaving a mixed ester (129). The reaction of a dialkyl

1991

sodiophosphite with allyl chloride may give a dialkyl allyl phosphonate (192) or addition t o tke double bond may take place leading t o a tetraalkyltrimethylene diphosphonate (196). Yellow phosphorus unites with an alkyl disulfide t o form a trialkyl trithiophosphitc (909). Triisopropyl phosphite and methyl iodide give diisopropyl methyl phosphonate and isopropyl iodide ( 7 9 ) . A review of the transformation of trialkyl phosphates into dialkyl alkyl phosphonates has been published (184). Various mixed aryl alkyl thionophosphates of the parathion type have been prepared ( 3 , 102, 117, 192). Some of these contain amido or alkylamido groups in place of alkoxy groups (146, 147). Hexaethyl tetraphosphate has been prepared from 2 moles of phosphorous oxychloride and 5.2 moles of ethyl alcohol (168). An alkyl phosphate can be made by heating phosphoric anhydride with an ether (104). Claim is made for a polyphosphonic ester from cyclohexylphosphorous chloride and 4,4'-dihydroxybiphenyl (234). Tributyl phosphate containing PI* has been made from silver phosphate and butyl bromide (9). SILICIC ESTERS

A stud) has been made of the reactions of higher alcohols with silicon tetrachloride. Several optically active tetraalkyl silicates are described. With tert-amyl alcohol the products are tert-amyl chloride and silicic acid (88). The acid-catalyzed hydrolysis of ethyl silicate is of the second order a t a rate proportional to the acid concentration. The basecatalyzed reaction is of the first order with reference to the ester and is proportional t o the concentration of base hut independent of the amount of water present ( 1 ) . Sodium hydroxide attacks silicon-silicon bonds more readily than siliconrhydrogen (116). The preparation and reactions of orthosilicoformates, HSi( OR)s,and of the corresponding trithio esters, HSi(SR)3, have been studied (27, 176, 231). Complicated esters are formed when silicon tetrachloride r e a c t s with (:atechol, r e s o r c i n , and hydroquinone (195). Liquid organochlorosilanes are passed down a heated column countercurrent t o alcohol vapors t o produce esters (46). A f u r f u r y l silicate is obtained from furfuryl alcohol and silicon disulfide (59). TITANIC ESTERS

Methods of p r e p a r i n g titanic esters have been described (3'0). The dipole moments and association in benzene of the ethfl, propyl, and butyl esters have been investigated (5, 41, 46). The polymerization of the butyl ester and its use in paints have been discussed (229). BORIC ESTERS

-COURTESY

HERCULES POWDER 00

Acetylation Equipment for Converting Cellulose io Cellulose Acetate, Using Acetic Anhydride

There has been some interest in boric esters (30,49, 105). They can be made from boron trichloride (136'); one from a glycol is polymeric (52).

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INDUSTRIAL AND ENGINEERING CHEMISTRY

Vol. 44, No. 9

INDUSTRIAL AND ENGINEERING CHEMISTRY

September 1952 ESTERIFICATION

OF CELLULOSE

Aoetylation. The acetylation and xanthation of various fibers have been studied (116). Cotton linters and wood pulp have been compared (70). The yarn and fabric, produced by various processes, have been tested as to extent of acetylation and durability (61). Vapor phase acetylation has been studied (215) and cellulose acetate fractionated (191). Coarse particles are present along with molecular units (202). The solubility and degree of polymerization have been determined a t stages of the acetylation and hydrolysis (4.6). The carboxyl group in monocarboxycellulose retards acetylation (218). The acetates from carboxycelluloses with a content of 4.4 to 13% carboxylic groups have been evaluated (231) The formic (158)and methacrylic (23) esters have becn made By the use of acid chlorides in pyridine the triesters from acctates t o palmitates have been prepared (132). Activation by some pretreatment is claimed (1,29, 124, 164) and several ways are proposed foi making cellulose sulfate (56, 81, 125, 131). Xanthation. The methylcellulose, obtained by replacement of the xanthate groups by the action of diazomethane, has been hydrolyzed and the unmethylated glucose removed by fermentation. The methllglucoses which remained were converted to the methylglucosides and distilled. Only a trace of a dimethylglucoside was found. Of the original glucose units 28% were untouched, 24% had bcen methylated in the 6-position, 21% in the 3-position, and 27% in the 2-position ( 4 3 ) . The xanthat:on of cellulose is described with a flow sheet (167). Emulsion xanthation has been tried (86) arid the different types of cellulosr have been compared (226). Viscose has been made from wheat and alfalfa straw (188). Ultrasonic vibrations are said to aid in the penetration of the cellulose by the carbon disulfide (58,SS) Gelatin has been xanthated (114,161). Nitration. The nitration of ramie fiber, of pentosans ( W M ) , and of polysaccharides (223) has been considered. Apparatus for the continuous nitration of cdlulose has been described (156). ALKYDS

Some articles on alkyd resins are listed (14, 90, 96, 118, 127, 148, 160, 164, 177). There are also numerous patents. C A R B O N MONOXIDE

Esters are produccd from carbon monoxide and unsaturates with or without hydrogen and acids or acid anhydrides a t high pressures in presence of a catalyst, usually cobalt (34, 93, 94,160, 151). L I N E A R POLYESTERS

Studies have been made of the structures, viscosities, and niolecular weights of ester polymers (18, 61). Methods of preparing polymeric ethylene terephthalate are reported (100, 166, 219, $go). Linear polymeric esters of hexamethylene (1.81) and decamethylene (108) glycols, 2,3-butanediol (2g7), hydroquinone (53, 54), thiodiglycol (48), and dimercaptans (78, 137) with dicarboxylic acids are reported. Ethylene esters from thiophene dicarboxylic acids are claimed (66).

LITERATURE CITED Aelion, R., Loebel, L4.,and Eirich, F., J . Am. Chem. SOC.,72, 5705-12 (1950).

ilktieselskapet Borregaard, Norw. Patent 78,894 (1951). American Cyanamid Co., Brit. Patent 644,616 (1950). Arbuzov, A. E., Uspekhi K h i m . , 20,521-32 (1951). Arbuzov, B. A., and Shavsha, T. G., Doklady Akad. N a u k S.S.S.R., 79, 599-600 (1951).

Arnett, E. M., Miller, J . G., and Day, A. R., J . Am. Chem. SOC., 7 3 , 5 3 9 3 5 (1951).

Axtmann, R. C., Ibid., 73,5367-9 (1951).

1993

Bader, A. R., Cummings, L. O., and Vogel, H. A , Ibid., 73, 4195-7 (1951).

Baldwin, W. H., and Higgins, C. E., Ibid., 74, 2431 (1952). Balfe, M. P., Beaven, G. H., and Kenyon, J., J . Chem. Soc., 1951,376-80.

Balfe, M. P., Darby, R. E., and Kenyon, J., Ibid., 1951, 382-5. Balfe, M. P., Kenyon, J., and Searle, C. E., Ibid., 1951, 380-1. Balfe, M. P., Kenyon, J., and Thain, E. M., Ibid., 1951,386-8. Ballard, S.A,, and Whetstone, R. R. (to Shell Development Co.), U. S. Patent 2,554,973 (1951). Barker, C., Crawford, R. V., and Hilditch, T. P., J . Chem. SOC.,1951,1194-200.

Bartlett, P. D., and Rylander, P. N., J . Am. Chem.

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