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UNITED STATES PATENT OFFICE 2,539,238 PROCESS for the PRODUCTION of MONOCLOROACET CACD Charles M

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UNITED STATES PATENT OFFICE 2,539,238 PROCESS for the PRODUCTION of MONOCLOROACET CACD Charles M Patented Jan. 23, 1951 2,539,238 UNITED STATES PATENT OFFICE 2,539,238 PROCESS FOR THE PRODUCTION OF MONOCLOROACET CACD Charles M. Eaker, Affton, Mo., assignor to Mon santo Chemical Company, St. Louis, Mo., a cor poration of Delaware No Drawing. Application August 20, 1949, Serial No. 111,582 6 Claims. (C. 260-539) 1. This invention relates to monochloroacetic monochloroacetic acid. Therefore, in order that acid; more specifically this invention relates to this process as heretofore used be practical com an improved process for the production of mercially, it is necessary that the process be car monochloroacetic acid, which comprises the ried out on a continuous basis, constantly sep chlorination of a mixture containing certain def arating a monochloroacetic acid fraction and re inite proportions of acetic acid and acetic anhy cycling the unchlorinated acetic acid to prevent dride whereby said mixture is converted to Sub the formation of excessive quantities of poly stantially pure monochloroacetic acid. chlorinated acetic acid. Furthermore, in the Monochloroacetic acid is a valuable organic above described continuous process as hereto intermediate, being utilized as a basic reactant 0. fore utilized, the monochloroacetic acid fraction in many organic reactions. Pure monochloro Separated from the reaction mixture has a crys acetic acid (alpha modification) crystallizes at tallizing point significantly less than 59° C. due about 63° C. In most industrial organic Syn to the presence of acetic acid and polychlorin theses wherein monochloroacetic acid is utilized ated acetic acids. It is, therefore, necessary to as one of the basic reactants, it is preferred that 5 remove the acetic acid by fractionation and then monochloroacetic acid be of such a degree of statically crystallize the remaining fraction in purity so as to have a crystallizing point greater Order to separate the monochloroacetic acid from than about 59 C. Various procedures for the the polychloroacetic acids contained therein in preparation of monochloroacetic acid have been order to obtain monochloroacetic acid having a disclosed in the prior art that are capable of crystallizing point greater than 59 C. Obvious producing monochloroacetic acid having the re ly, this is a costly unit operation requiring exten quired degree of purity. Typical of these various sive process equipment. procedures are the hydrolysis of trichloroethyl It is an object of this invention to provide an ene in the presence of sulfuric acid, chlorination improved batch process for the production of of ketene followed by hydrolysis, the reaction of monochloroacetic acid. formaldehyde, carbon monoxide and anhydrous It is a further object of this invention to provide HCI under pressure and at elevated temperature, an improved batch process for the production of and the direct chlorination of acetic acid in the monochloroacetic acid by the chlorination of a presence of catalytic quantities of a suitable cat mixture containing glacial acetic acid and acetic alyst, such as phosphorus, sulfur, iodine, the ox 30 anhydride, in which process the mixture may be ides and chlorides of phosphors and Sulfur, chlorinated until conversion to the monochloro chloroacetaldehyde or acetic anhydride. stage has been substantially complete without Of the above-mentioned procedures for the the formation of significant quantities of poly preparation of monochloroacetic acid, only one chloroacetic acids. has become of interest from a commercial stand It is another object of this invention to pro point. The most widely used commercial proc vide an improved batch process for the produc ess for the production of monochloroacetic acid tion of monochloroacetic acid by the chlorina is the chlorination of acetic acid in the presence tion of a mixture containing glacial acetic acid of catalytic quantities, of the order of 5% or less and acetic anhydride, whereby the mixture is by weight, of acetic anhydride. In this process, 40 converted to a reaction product having a crystal however, there exists two serious deficiencies, lizing point greater than 59° C. consisting of sub viz., exceedingly low conversion to monochloro stantially pure monochloroacetic acid. acetic acid is obtained and extensive recovery It is a still further object of this invention to and purification procedures are necessary in provide an improved batch process for the pro order to obtain monochloroacetic acid having a duction of monochloroacetic acid wherein the crystallizing point greater than 59 C. reaction mixture obtained from the reaction of In the chlorination of a mixture containing 1 molecular proportion of chlorine and approxi glacial acetic acid and catalytic quantities of mately a 1 molecular proportion of a mixture of acetic anhydride, of the order of 5% by weight or glacial acetic acid and acetic anhydride, calcu less, chlorination temperatures in excess of about 50 lated as acetic acid, be used without further 110° C. are required in order that the reaction purification in various organic syntheses. proceed. Under such conditions significant Other objects will become apparent from the quantities of polychloroacetic acids are formed discussion of the novel process of this invention unless chlorination is stopped when about and the claims. 30-40% of the acetic acid has been converted to As previously stated, when a mixture of gla 2,539,288 3 4. cial acetic acid and catalytic quantities of acetic the crystallizing point of the reaction product anhydride, of the order of 5% by weight, is chlo reaches a maximum of above about 59 C., after rinated with gaseous chlorine at the elevated l'em Oval of the hydrogen chloride formed, at temperatures required when chlorinating such a which point the reaction product is then sub mixture, significant quantities of polychloro Stantially pure monochloroacetic acid. acetic acids are formed if the chlorination is Due to the fact that the reaction product ob carried much beyond the stage where 30-40% of tained in the novel process of this invention con the acetic acid in the mixture has been chlorin tains, prior to hydrolysis, an impurity content ated to the mono derivative. In such a process comprised of chloroacetyl chloride and/or chlo if substantially molecular quantities of chlorine 0. roacetic anhydride, both of which hydrolyze to are introduced for each molecular quantity of monochloroacetic acid, and a quantity of poly acetic acid in the mixture, the resultant reac chloroacetic acids So insignificantly Small that tion product would contain monochloroacetic it need not be removed in order to obtain a mono acid and exceedingly large quantities of polv chloroacetic acid of a degree of purity suitable chloroacetic acids which would have to be puri 15 for use in subsequent industrial organic syn fied by distillation and static crystallization in theses, the reaction product, prior to hydrolysis, Order to obtain Substantially pure monochloro may be used directly in various organic syn acetic acid. It has now been discovered, how theses wherein substantially pure monochloro ever, that if a mixture comprised of 15-75% gla acetic acid is used as a reactant. Thus, in those cial acetic acid and 85-25% acetic anhydride, 20 organic syntheses which are carried out in an i. e., a mixture containing at least about 25%, a dueous medium, the reaction product obtained acetic anhydride and not more than about 85% in the novel process of this invention, may be acetic anhydride, is chlorinated with gaseous used directly without first hydrolvzing the im chlorine at a temperature in the range of from purities to monochloroacetic acid, since such hy about 70° C. to about 110° C., chlorination pro 25 drolysis will take place in the aqueous medium in ceeds quite differently. It has been discovered which the particular organic synthesis is car that under such temnerat11re conditions such a rjed out. Typical examples of Such utility are mixture of acetic anhvdride and glacial acetic the preparation of halogenated phenoxy acetic acid may be chlorinated directly and completely acids and cyanoacetic acids. In preparing halo to the monochloroacetic acid stage without the 30 genated phenoxy acetic acids, monochloroacetic formation of appreciable quantities of poly acid is reacted with a halogenated phenol in an chloroacetic acids. In Such a process it has been aqueous alkaline medium. In the preparation of folind that the significant impurities that are cyanoacetic acid, an alkali metal cyanide is re formed during the chlorination procedure are 'acted with an alkali metal chloroacetate which not polvochloroacetic acids but ch'oroacetvl chlo had been formed by the neutralization of chloro ride and/or chloroacetic anhydride. Both of acetic acid in an aqueous medium. Therefore, these impurities formed in the novel chlorina in both of these described syntheses, the reaction tion procedure of this invention, when hydro product obtained in the novel process of this in lyzed, yield monochloroacetic acid and hydrogen vention, prior to hydrolysis, may be utilized since chloride. Therefore, chlorinating a mixture 40 the significant impurities in the reaction prod containing from 15-75% glacial acetic acid and uct will hydrolyze to monochloroacetic acid dur 85-25% acetic anhydride with an approximately ing the described syntheses, which are carried 1 molecular protoortion of chlorine for each 1 olt in an aqueous medium. molecular proportion of the mixture calculated In addition to having utility in those organic as acetic acid, yields a reaction
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