DE273219C - - Google Patents

Description

IMPERIAL

PATENT OFFICE.

PATENT LETTERING

- M 273219 CLASS 12 or GROUP

Dr. FELIX HEINEMANN in BERLIN.

Addendum to patent 257641.

Patented in the German Empire on March 26, 1913. Longest duration: November 29, 1926.

The main patent and its additions 268829 ^and 271159 protect processes for the preparation of arsenic and phosphorus-containing fatty acids and their salts, which consist in mixing the acids of the acetylene series with trihalogen derivatives of arsenic or phosphorus or with substances that supply these substances , treated.

It has now been found that the derivatives of these compounds are also valuable therapeutic Have properties that in many cases, e.g. B. before the therapeutically usable Salts of the above bodies, have the advantage that they are directly lipoid soluble, and above the free acids those of the neutral reaction, suggesting their direct use of Advantage is.

The method for their preparation consists in that one of the derivatives of the acids Acetylene series subject to the processes protected by the main patent and its additives or the arsenic or phosphorus-containing fatty acids obtainable by this process converted into their acid derivatives.

Example 1.

700 parts of behenolic acid methyl ester are mixed with 900 parts of arsenic trichloride for 6 hours in one with a reflux condenser to 135 ° heated. After the reaction has ended, the excess arsenic trichloride is distilled off in vacuo and the residue after dissolving

washed in ether with water until the running water reacts neutrally. One dries the ether solution and, after the solvent has been distilled off, wins the methyl chloroarsenobehenolate as a brown, oily liquid. It dissolves easily in ether and benzene, difficult in alcohol.

Example 2.

100 parts according to Example 1 of the main patent obtained chloroarsenostearolic acid with 300 parts of ethyl alcohol and 30 parts Sulfuric acid warmed up on the water bath for a short time; the reaction product will be in plenty Poured water and the separated oil separated and washed several times with Water purified. After drying, the methyl chloroarsenostearolate forms a brown color Oil that easily dissolves in chloroform and benzene is insoluble in water.

Example 3.

70 parts of behenolic acid methyl ester and 50 parts of arsenic anhydride are mixed and gradually in a vessel provided with a condenser with 100 parts of thionyl chloride offset. The mixture is heated to 140 ° for 5 hours. Then in the vacuum the low boiling Fractions distilled off and the residue washed neutral after dissolving in ether. Man dries the ethereal solution and, after distilling off the solvent, wins the chlorine

arsenobehenolniethylester of the properties given in the first example.

■ /, example 4.

754 parts of behenolic anhydride (almost colorless crystals which melt at 48 ° and are obtained by the action of phosgene on behenolic acid in the presence of pyridine) are heated at 140 ° with 900 parts of arsenic trichloride for 6 hours. The reaction mass is dissolved in benzene and washed with water until the reaction is neutral. The benzene solution is then dried over calcium chloride, nitrated and the ben- ; " Dol removed by prolonged heating in a vacuum. The chlorarsenobehenolic anhydride / forms a brown, fairly solid mass that dissolves easily in benzene and chloroform.

Example 5.

100 parts of the bromarsehobehenolic acid obtainable according to Example 4 of the main patent will be dissolved in 300 parts of benzene, mixed with 40 parts of pyridine and stirring and cooling 120 parts of a 25 percent phosgene benzene solution added. After standing for two days, washing is carried out with water containing hydrochloric acid to remove the pyridine. It is then washed neutral, dried over anhydrous sodium sulfate and the solvent evaporates.

The bromoarsenobehenolic anhydride forms a brown mass that dissolves in benzene and chloroform dissolves easily.

Example 6.

100 parts of chlorophosphorus behenolic acid (obtained by heating 100 parts of behenolic acid with 100 parts of PCl ₃ to 140 ° for twelve hours) are dissolved in a mixture of 400 parts of methyl alcohol and 40 parts of concentrated sulfuric acid and heated in a water bath for 15 minutes. After cooling, the cloudy mixture is poured into an ice-cold soda solution, the ester is absorbed with ether and freed from unchanged chlorophosphorus behenolic acid by washing with very dilute ammonia solution. The ether solution is then dried over sodium sulfate and the ether is completely distilled off in vacuo. The methyl chlorophosphorus behenolate remains as a light red, "viscous oil.

Example 7.

100 parts according to Example 2 of the main patent obtained chloroarsenobehenolic acid are gradually mixed with 100 parts of thionyl chloride, Poured over, with stormy reaction occurring, and still to complete the conversion briefly heated in a water bath on the reflux condenser. After distilling off the excess Thionyl chloride in vacuo, the residue is dissolved in ether and while cooling with ice mixed with an ethereal solution of 70 parts of aniline. It will be retired from hydrochloric aniline filtered, the filtrate washed with water and dilute hydrochloric acid, dried over sodium sulfate and the ether was completely distilled off in vacuo. That remaining chlorarsenobehenolic acid anilide forms a thick, dark-colored, ointment-like Dimensions. When its alcoholic solution decomposes with alcoholic potassium hydroxide solution begins after standing for a short time, behenolic anilide is excreted.

Claims (1)

Patent claim: Modification of those protected by the main patent and its additions 268829 and 271159 Process for the preparation of arsenic and phosphorus-containing acids of the acetylene series, consisting in that one here of derivatives of the acids of the acetylene series substituted in the acid group goes out, or obtained according to the procedure of the main patent and its additions Arsenic and phosphoric acids converted into their acid derivatives, with the exception of the salts.