DE209610C - - Google Patents

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IMPERIAL

PATENT OFFICE.

PATENT LETTERING

- JVi 209610 CLASS Mq. GROUP

Addendum to patent 209609 of October 6, 1907.

Patented in the German Empire on February 16, 1908. Longest duration: October 5, 1922.

The attempts, from the methylene ethers of 3 · 4-Dioxyphenyl-ß-bromo-a-hydroxyethans and of 3 · 4-dioxyphenylhydroxyethylmethylamine splitting off the methylene group did not lead to the desired result (Barger & Jowett, Journ. Chem. Soc. 87 [1905], p. 971). Likewise, this could not be achieved with the methylenedioxyphenylethylene dibromide, on the contrary, when exposed to phosphorus pentachloride, it became a dibromohydrin of unknown constitution (1. c. p. 974) obtained.

In the main patent 209609 is then shown been that it is possible to remove the methylene group from the methylenedioxyphenylethylenedihalides split off and the o-Dioxyphenyläthylenhalogenhydrin by first converting them into the halohydrins by reaction with water, these halohydrins then treated with phosphorus pentahalides and finally decomposed with water. It has now been found that the preparation of o-dioxyphenylethylene chlorohydrin:

Oh

raw

CH (OH) -CH ₂ -Cl

from the . Methylenedioxyphenyläthylendichloriden succeeds without such a detour. If namely 3 · 4-methylenedioxyphenylethylene dichloride Treated immediately with phosphorus pentachloride and then with water, this is the result Dioxyphenyläthylenchlorhydrin, its reaction with primary aliphatic amines or ammonia leads to the compounds of adrenal base character.

The vinyl catechol methylene ether dichloride used as the starting material:

35

40

45

CH (Cl) -CH ₂ -Cl

is obtained by introducing the theoretical amount of chlorine into a cooled solution of 14.8 g vinyl catechol methylene ether in about five times the amount of carbon tetrachloride. After the solvent has been distilled off, the crude product can be used without further purification are processed. The dichloride in the. Vacuum distilled, Kp. 22 Ms 24 mm at about 170 °. It is a colorless one Oil easily discolored in common organic solvents is easily soluble.

Example:

22 parts of vinyl catechol methylene ether dichloride are mixed with 43.78 parts of phosphorus.

phosphorus pentachloride gradually mixed with cooling / then the reaction mass some Heated to about 105 ° for hours until the evolution of hydrogen chloride stops. The chlorophosphorus compounds are then distilled off in vacuo and the oily residue in acetone solved. Water is added to this solution and the mixture is stirred until everything has become soluble in water. By distilling off the acetone in vacuo and extracting the filtered and sodium carbonate almost neutralized solution with ether can o-Dioxyphenyläthylenchlorhydrin:

OH
J ^

y-OH

CH (OH) -CH ₂ -Cl

to be isolated. When the ether evaporates in a vacuum, it remains as soon as it solidifies Oil. If you dissolve it in alcohol and add twice the amount of methylamine, it takes place conversion to o-dioxyphenylethanolmethylamine even at normal temperature when standing for several hours, which can be isolated in a known manner. If one uses ammonia or instead of methylamine other primary aliphatic amines, e.g. B. ethylamine and its homologues, see above

the corresponding ethanolamine derivatives are obtained.

Claims (1)

Patent claim: - Modification of the process for the representation of ο - Dioxyphenylethanolamines of the general formula: OH -OH CH (OH) -CH ₁ -NH-R (R = hydrogen or alkyl), consisting in that here the 3 4-methylenedioxyphenylethylene dichloride: O CH, CH (Cl) -CH ₂ -Cl treated one after the other with phosphorus pentachloride and water and then so obtained o-dioxyphenylethylene chlorohydrin with primary aliphatic amines or with ammonia.