Patent GB-357061-A (GB)
Title: Manufacture of bismuth compounds of benzenearsinic-acid-stibinic-acids
IPC: C07F9/92
Filed: 1931-02-13
Abstract: Bismuth compounds of benzenearsinic-acid-stibinic-acids are obtained by reacting a benzenearsinic-acid-stibinic-acid with a bismuth salt, preferably the nitrate or chloride.  The organic acid is preferably dissolved in an alkaline solvent, for example, caustic soda, and the bismuth salt added, if desired, in the presence of an organic diluent, as glycerin.  The product obtained may be precipitated by alchohol.  The free acid is obtainable by treatment with an acid, for example, acetic acid.  The compounds suspended in oil, for example, olive oil or dissolved in water as alkali salts are used for therapeutic purposes.  In examples salts are used for therapeutic purposes.  In examples:--(1) 4-hydroxybenzene-3-stibinic-acid - 1 - arsinic-acid is dissolved in caustic soda solution and a solution of bismuth nitrate and glycerin is added.  Caustic soda is added subsequently, the solution then made feebly alkaline with acetic acid, and the product precipitated with alcohol.  (2) The alkaline solution obtained as above is feebly acidified with acetic acid and dialysed whereby a solution suitable for sterilization is obtained. (3) 3-acetylamino-4-hydroxy-benzene-5-stibinic-acid-1-arsinic-acid (prepared by diazotizing 3-acetylamino-4-hydroxy-5-aminobenzene-arsinic acid and substituting the stibinic acid residue for the diazo-group) is acted upon by bismuth nitrate and glycerin with caustic soda, and further treated as in (1) or (2) above.  (4) A solution of bismuth nitrate in glycerin and water is reacted with 3-hydroxybenzene-4-stibinic-acid-1-arsinic-acid, and the product worked up as above.  (5) A solution of bismuth nitrate in glycerin and water is reacted with parabenzene-stibinic-acid-arsinic-acid. The jelly obtained is introduced into alcohol, and the mixture filtered and dried.  (6) 4-hydroxybenzene-3-stibinic-acid-1-arsinic-acid is reacted with bismuth nitrate in glycerin and water and the product worked up as above.  (7) 1-phenoxy-acetic-acid-2-stibinic-acid-4-arsinic-acid (prepared from 2-amino-1-phenoxy-acetic-acid-4-arsinic-acid by the diazo process) is dissolved in caustic soda.  Bismuth nitrate, glycerin and water are added, and the precipitate filtered. Reference is made to Berichte der deutschen chemischen Gesellschaft, Vol. 57, page 1143.ALSO:Bismuth compounds of benzenearsinic-acid-stibinic-acids are obtained by reacting a benzenearsinic-acid-stibinic-acid with a bismuth salt, preferably the nitrate or chloride.  The organic acid is preferably dissolved in an alkaline solvent, for example, caustic soda, and the bismuth salt added, if desired, in the presence of an organic diluent, as glycerin.  The product obtained may be precipitated by alcohol.  The free acid is obtainable by treatment with an acid, for example, acetic acid.  In examples:-(1) 4-hydroxybenzene-3-stibinic-acid-1-arsinic-acid is dissolved in caustic soda solution and a solution of bismuth nitrate and glycerin is added.  Caustic soda is added subsequently, the solution then made feebly alkaline with acetic acid, and the product precipitated with alcohol.  (2) The alkaline solution obtained as above is feebly acidified with acetic acid and dialysed whereby a solution suitable for sterilization is obtained.  (3) 3-Acetylamino-4-hydroxy-benzene-5-stibinic-acid-1-arsinic-acid (prepared by diazotizing 3-acetylamino-4-hydroxy-4-aminobenzene-arsinic-acid and substituting the stibinic acid residue for the diazo group) is acted upon by bismuth nitrate and glycerin with caustic soda, and further treated as in (1) or (2) above.  (4) A solution of bismuth nitrate in glycerin and water is reacted with 3-hydroxy-benzene-4-stibinic-acid-1-arsinic-acid, and the product worked up as above.  (5) A solution of bismuth nitrate in glycerin and water is reacted with p-benzenestibinic-acid-arsinic-acid. The jelly obtained is introduced into alcohol, and the mixture filtered and dried.  (6) 4-Hydroxy-benzene-3-stibinic-acid-1-arsinic-acid is reacted with bismuth nitrate in glycerin and water and the product worked up as above.  (7) 1-Phenoxy-acetic-acid-2-stibinic-acid-4-arsinic-acid (prepared from 2-amino-1-phenoxy-acetic-acid-4 arsinic-acid by the diazo process) is dissolved in caustic soda.  Bismuth nitrate, glycerin and water are added, and the precipitate filtered.ALSO:Bismuth compounds of benzenearsinic-acid-stibinic-acids for prophylactic and therapeutic purposes are obtained by reacting a benzenearsinic-acid-stibinic-acid with a bismuth salt, if desired, in the presence of glycerin.  For the above use, the products may be suspended in oil, such as olive oil, or dissolved in water as their alkali salts.  Examples relate to the production of the compounds from 4-hydroxybenzene-3-stibinic-acid-1-arsinic-acid, 3-acetylamino-4-hydroxybenzene-5-stibinic-acid-1-arsinic-acid, 3-hydroxybenzene-4-stibinic-acid-1-arsinic-acid, parabenzenestibinic-acid-arsinic-acid, 4-hydroxybenzene-3-stibinic-acid-1-arsinic-acid, 1-phenoxy-acetic-acid-2-stibinic-acid-4-arsinic-acid.  The solutions obtained may be dialysed to render them suitable for sterilization.