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United States Patent Office Patented June 22, 1971 2 Mixture to Aid in Securing High Yields from the Present 3,586,708 Process

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United States Patent Office Patented June 22, 1971 2 Mixture to Aid in Securing High Yields from the Present 3,586,708 Process 3,586,708 United States Patent Office Patented June 22, 1971 2 mixture to aid in Securing high yields from the present 3,586,708 proceSS. ARSANLIC ACTED PRODUCTION PROCESS Joseph W. Nemec, Rydal, and Harry R. Raterink, Drexel The invention consists in the novel methods, processes Hill, Pa., and Stanley W. Wise, Audubon, N.J., as and improvements shown and described. It is to be under signors to Rohm and Haas Company, Philadelphia, Pa. 5 stood that both the foregoing general description and the No Drawing. Filed May 1, 1969, Ser. No. 821,142 following detailed description are exemplary and ex Int. C. C07f 9/76, 9/78 planatory, but are not restrictive of the invention. U.S. C. 260-442 12 Clains In the present process, as in many prior art processes, arsenic acid is caused to react with an excess of aniline to O produce the desired arsanilic acid product. However, un ABSTRACT OF THE DISCLOSURE like prior art processes, the reaction conditions of the present process do not minimize the side reaction which A process is provided for preparing arsanilic acid in produces di-(-aminophenyl) arsenic acid. Instead, this yields of about 45% or higher, based on the weight of compound is also produced during the first reaction, along arsenic acid reactant, by reacting arsenic acid and aniline with arsanilic acid. In a subsequent step of the present at a temperature of about 130 to 180° C. in the presence process, di-(p-aminophenyl) arsenic acid is converted into of a chelating agent and a solvent which forms an azeo arsanilic acid, thereby maximizing the yield of the desired tropic distillate with water formed in the reaction. This product. reaction produces a mixture of arsanilic acid and di-(p- The mol ratios of aniline to arsenic acid used in ac aminophenyl) arsenic acid, and the latter is converted cordance with the present process can be varied rather to arsanilic acid by hydrolysis at an acid pH of about widely while still achieving satisfactory results. Thus, 2 to 3. product yields vary little with variations of aniline/arsenic acid molar ratios between 2 to 1 and 5.5 to 1. As the This invention relates to the production of arsanilic proportion of aniline to arsenic acid is lowered within this acid. More particularly, it relates to a process that achieves 25 range, however, difficulties may be encountered in separa high yields of arsanilic acid by the reaction of arsenic acid tion of the excess aniline phase from the product phase with aniline in the presence of a solvent. of the reaction mixture, and moreover, the reaction mass Para-aminophenyl arsenic acid, commonly known as tends to become rather viscous and difficult to agitate. For 'arsanilic acid,” is a well-known and widely used organic these reasons, ratios of aniline to arsenic acid between 3 arsenic compound. Arsanilic acid and related compounds 30 to 1 and 5 to 1 are preferred, with a ratio of about 4 to 1 prepared from it are used, for example, in the veterinary being considered optimum. field to stimulate growth, control parasites in fowl and In accordance with the invention, the aniline-arsenic SWine, and to increase egg production from fowl. For ex acid reaction is carried out in the presence of a solvent ample, arsanilic acid reacts with potassium cyanate to which forms an azeotropic distillate with water present in yield N-carbamoyl-arSanilic acid, or carbarsome, which the reaction. The reaction mixture contains water from is used, e.g., as an intestinal amebicide and to treat histo two sources. Water is present in the reactants initially moniasis in turkeys. added to the reaction vessel, and water is also formed as It has been difficult in the past, however, to achieve a by-product of the reaction. Since the reaction is carried efficient and economical production of arsanilic acid be out at highly elevated temperatures, the water present cause of the relatively low efficiency of the reactions used 40 from both sources is distilled or boiled off during the in its preparation, in terms of the percentage of the re reaction. actants converted to the desired arsanilic acid product. Al The inclusion in the reaction mixture of a solvent that though claims of higher yields have been made, it has gen form an azeotropic distillate with water in accordance erally been possible to achieve only about 25% con with the present process achieves a number of important version of arsenic acid to arsanilic acid by commercially advantages. If offers a means for controlling the reaction useful prior art processes. temperature by the refluxing system, and a means for It is accordingly an object of the present invention to more readily following and terminating the reaction on provide an improved, and more efficient and economical the basis of measurement of the water eliminated. The process for the production of arsanilic acid. 50 inclusion of the solvent provides an inert operating atmos It is another object of the present invention to provide a phere and prevents aniline removal during the reaction. new and improved process for the production of arsanilic Thus, in accordance with this invention there is no need acid which can be carried out with relatively minor modi for concern that the ratio of aniline to arsenic acid ratio fication of the equipment used in present-day commercial in the reaction mixture may be unduly lowered; and the arsanilic acid production processes, but which achieves present process can be successfully operated at aniline to much greater process efficiency, and greater product yields arsenic acid mol ratios which are lower than those hereto than Such present-day commercial processes. fore employed. These objects are achieved in the present invention. The presence of the solvent causes a better and cleaner through the use of a novel, solvent process for the produc separation of the aniline layer from the aqueous solution tion of arsanilic acid. This process comprises reacting 60 of reaction product present in the reaction mixture, and arsenic acid with an excess of aniline at a reaction tem generally achieves better color in both layers. The presence perature of about 130 to 180° C. in the presence of a of the solvent in the aniline phase of the reaction product solvent which forms an azeotropic distillate with water also affords a means of drying the recovered aniline prior formed in the reaction, to produce a mixture of arsanilic to its recycle. acid and di-(p-aminophenyl) arsenic acid. The mixture is Most important, the presence of the solvent in the then preferably diluted with water and the pH is desirably aniline-arsenic acid reaction mixture has been found to adjusted to about 8.5 to 10. After the aniline layer is re result in unexpectedly improved yields of arsanilic acid moved, the aqueous layer is adjusted to a pH not greater product. The present process realizes yields in the range than about 3.0 and then refluxed to hydrolyze the di-(p- of 45 to 50% conversion of arsenic acid reactant to aminophenyl) arsenic acid and convert it to arsanilic acid. 70 arsanilic acid. It is believed that these improved yields In accordance with a preferred aspect of the present inven are, at least in part, a result of the more efficient tion, a chelating agent is also incorporated in the reaction water removal achieved by the azeotropic distillation of 3,586,708 3. 4. reaction witer in the process of this invention, which invention minimizes the catalytic effect of heavy metal allows the reaction to proceed at a fast than normal rate. impurities, such as copper, on the oxidation of the aniline Any solvent which forms an azeotropic distillate with in the reaction mixture, thereby allowing the effective use water can be used as the solvent or azeotroping agent in of higher temperatures in the reaction without undesir cluded in the reaction mixture in accordance With the able levels of aniline oxidation. The use of higher reac present process. Toluene, benzene, Xylene, and octane, for tion temperatures accelerates the speed of the reaction example, can be satisfactorily used. It is preferred, how and the speed of water removal, and thereby contributes ever, to use less flammable solvents such as perchloro to the achievement of the high yields of the present ethylene, perfluoroethylene, chlorobenzene, and ethylene proceSS. dichloride. Perchloroethylene is presently considered an O The aniline-arsenic acid reaction of the present process optimum azeotroping solvent for use in this process. produces a reaction product which comprises a mixture The amount of solvent or azeotroping agent included of arsanilic acid and di-(p-aminophenyl) arsenic acid. In in the reaction mixture is small-only about 5 to 15 fact, the use of the process of this invention causes greatly weight percent based on the arsenic acid charged to the increased conversion of the arsenic acid reactant to di reaction. The azeotroping solvent preferably is present (p-aminophenyl) arsenic acid, rather than arsanilic acid. in the reaction mixture in amounts between about 8 and The present process, however, provides for the conver 9% by weight of the arsenic acid reactant. Sion of this di(p-aminophenyl) arsenic acid to arsanilic The present process is carried out at a reaction temper acid, and thereby uses this mechanism to achieve higher ature between about 130 and 180° C. The process pref overall conversion of arsenic acid reactant to ultimate erably includes a high temperature reaction in which the product, reaction mixture is heated at a temperature of about 173 The mechanism by which arsanilic acid is produced in to 175° C.
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