DE168941C - - Google Patents

Description

,1

KAISERXrCHES

It has been found that if you can on symmetrical dihaloacetones, the known magnesium haloalkyl or aryl derivatives can act, new halogen magnesium compounds arise from the formula:

CH ₂ • halogen

RC - 0'Mg halogen
CH,

i ₂ - halogen,

which when decomposed with water or with dilute acids replaced new β-substituted Dihalohydrins type of the formula:

CH ₂ • halogen

I.
R - C- (OH)

I.
CH ₂ - halogen

(where R is any alkyl or aryl radical). For example, symmetrical dichloroacetone and magnesium bromoethyl are normally converted into β-ethyl dichlorohydrin, despite the presence of two halogen atoms in the molecule

CH ₂ -Cl

I.
C ₂ H, -C- (OH)

I.
C H ₂ Cl,

a colorless, aromatic smelling oil, which boils undecomposed at J7 ° under 15 mm pressure. The new β-substituted dihalohydrins form valuable starting materials for physiologically valuable derivatives.

Example 1.

48 parts of magnesium shavings are placed in a reflux condenser and stirrer Apparatus, which can be cooled by ice, brought and enough Pour over a lot of anhydrous and alcohol-free ether. Then let out of a separating funnel slowly and with constant stirring 218 parts of bromoethyl, which with diluted with the same volume of ether, add dropwise. This dissolves when heated Metal, being the well-known double compound

Br

C ₂ H ₅

forms. The solution of bromoethylmagnesium thus obtained is gradually added with careful cooling and with stirring, 254 parts of symmetrical dichloroacetone, dissolved in the appropriate amount of dry ether added; the mixture remains Stand at night, then ice and water are carefully added. One gives now a lot of dilute sulfuric acid is added until the precipitated magnesium compound is in solution has gone. The ether solution is then drawn off, dried and distilled off of the ether concentrated. By distillation

Se
the

s oil in a vacuum becomes the ^ heue ß-ethyl- F

diehlorhydfin of the formula:
^r ' ^{: r} ■■ ■ CH ₂

Cl

C ₂ H ₅ -C- (OH) ' : ^Vi % V],

I.
CH ₂ -Cl

Obtained as a colorless, aromatic smelling oil, which boils undecomposed at yy ° and 15 mm pressure.

Example 2.

If the bromoethyl in Example 1 is replaced by 312 parts of iodoethyl, one gets to the same result.

Example 3.

It is prepared according to the method described in Example I from 24 parts of magnesium shavings, 156 parts of iodoethyl and 150 parts of absolute ether are a solution of the known Magnesium iodoethyl ether - double compound. Gradually, 310 symmetrical parts are allowed into this Diiodoacetone, dissolved in 400 parts of absolute ether, run in, being careful cools and stirs. The reaction mass is then worked up as described in Example 1. A self is obtained by distilling the oil obtained in this way in vacuo In the air, slightly reddish coloring oil with an aromatic odor of the formula:

CH ₂ -J

35

C ₂ H ₅ -C (OH)

CH ₂ - J ,
the new ß-ethyldiiodobydrin, which boils at 10-3 to 1 (54 ° and 12 mm pressure without decomposition.

^/ Example 4.

In Example 1, bromoethyl is used

31 ^ 'parts bromobenzene and works otherwise exactly as stated there, the resulting is obtained by fractional distillation The new ß-phenyldichlorohydrin of the formula:

CH ₂ -Cl

C ₆ H ₅ -C- (OH) ■ I

C H ₂ - Cl,

which boils at 162 ⁰ under a pressure of 22 mm.

Other symmetrical dihaloacetones can be used as well other magnesium haloalkyls for the organomagnesium compounds used in the examples or -aryles are used without affecting the essence of the process something is changed.

Claims (1)

65 patent claim: Process for the preparation of symmetrical dihalogen derivatives of tertiary Alcohols of the formula: RC (OH) (CH ₂ - halogen, consisting in the fact that the by the action of symmetrical dihaloacetones on the known magnesium halogen radical double compounds available with water or Treated acids.