DE166899C - - Google Patents

Description

IMPERIAL

PATENT OFFICE

It has been found that the bezw by the action of the magnesium haloalkyl. -aryl double connections of the known type:

/Halogen
Mg / - ether

\ χ

on salts of carboxylic acids of the general formula: *)

R-C

Magnesium-containing intermediates obtainable by the mere action of water, event, with the addition of an acid, pass into tertiary alcohols, so that one on this Ways, that is, starting from salts of carboxylic acids, smoothly get to tertiary alcohols can. The course of the reaction of the new process is essentially different from that in Chem. Centralblatt 1901, II, p. 623 described method, according to which ketones or esters on organomagnesium compounds come to action.

Example 1.

From 109 parts of bromoethyl, 24 parts of magnesium turnings and 250 parts of absolute Ether becomes the well-known double compound

■ *) Where R is an alkyl or aryl radical and M is a monovalent salt-forming atom or. represents an equivalent group (such as NH ₄ etc.).

- C ₂ H ₆

O C ₂ H ₆

shown. 98 parts of finely powdered material are added to the resulting solution with cooling and stirring Potassium acetate, which has been carefully mixed with 200 parts of absolute ether are entered slowly. When heated, copious quantities of a gray one divorce Precipitation, which is the above-mentioned intermediate. To the transfer the same in the corresponding tertiary alcohol is proceeded as follows:

The mixture is left to stand for about 24 hours and then decomposed with ice and diluted Hydrochloric acid. The salts go into the aqueous solution, the methyl diethyl carbinol formed into the ether. By fractional distillation or otherwise in a suitable manner, the alcohol is rendered colorless Liquid with the known properties isolated.

Example 2.

With an absolutely essential solution of the well-known magnesium iodomethyl ether double compound the formula:

Mg

O - C ₂

CH *

(made up of 48 parts magnesium, 284 parts iodomethyl and 500 parts ether) 196 parts of finely powdered potassium

acetate, suspended in 300 parts of ether, brought into reaction. Here too is the process accompanied by heat development. A salt-like intermediate product is formed. It is after 24 hours of standing, as described in Example ι, decomposed. The resulting Trimethylcarbinol is salted out from the aqueous solution by adding common salt and passes into the ether. After the essential solution has dried over potash is, the ether is distilled off and the remaining oil is fractionated.

Example 3.

In the magnesium iodoethyl ether solution (made from 48 parts of magnesium metal, 312 Parts of ethyl iodide and 400 parts of ether) slowly becomes a suspension with stirring and cooling registered of 288 parts of benzoic acid soda in 300 parts of absolute ether. It separates the intermediate product as Precipitation from. After standing for a day it becomes ice water and dilute sulfuric acid added until everything went into solution. The aqueous saline solution is on top removed and the essential solution by shaking several times with soda solution of unaffected benzoic acid freed. After drying over potash, the ether becomes distilled off from the water bath and the remaining oil from vacuum distillation subject. At iio ° under 12 mm pressure it goes over constantly. The initially color

loose oil soon turns a little yellow-green. It contains the well-known dietary phenylcarbinol before which the following formula applies:

if known
Formula:

Methyldiphenylcarbinol der

C ₂ H ₅ - ^ C (OH).

Example 4.

If you replace the ethyl iodide in Example 3 by 190 parts of bromomethyl, which is Applied in 25 percent ethereal solution, and otherwise proceeded completely analogously, this is how it arises the already described dimethylphenylcarbinol of the formula:

CH ₃ ^) C (OH).

c Hy

Example 5.

In Example 2, the methyl iodine is replaced

by 314 parts of bromobenzene and otherwise works exactly in the same way, this results in the same C H

Example 6.

A bromomethylmagnesium ether solution is prepared from 24 parts of magnesium shavings and 95 parts of bromomethyl, dissolved in 400 parts of absolute ether ) Cyclocitrilideneacetic acid, it is advisable to stir for a long time. After 24 hours a precipitate has deposited. This is decomposed by water and steam is passed through the mixture for a long time. In the receiver, ether, water and an oil condense, which completely changes into the ether when the distillate is shaken. The ether solution is separated in a separating funnel, dried over calcined sodium sulfate and finally fractionated in vacuo. As a colorless oil goes constant boiling at 12 mm and 130 ⁰ carbinol via the following formula:

CH ₃ C

CH ₂ C-CH: CH-C (CHJ ₂ OH.

IC H ₂ C (C HJ ₂

CH ₂

It has an intense violet odor.

Example 7.

If the potassium acetic acid is replaced in Example 1 by 77 parts ammonium acetic acid, a precipitate is likewise obtained. In order to obtain the methyl diethyl carbinol from it, the procedure described in Example I is followed.

An analogous procedure is followed when using the intermediate products from others Haloalkyl - respectively. -arylmagnesium double compounds or when using the intermediates from other salts of carboxylic acids.

Claims (1)

Patent claim: Process for the preparation of tertiary alcohols, consisting in that one Magnesium - haloalkyl - respectively. -aryl double links on salts of carboxylic acids of the formula: R-C O OM (where R is any alkyl or aryl radical and M is a monovalent salt-forming atom or an equivalent group such as ammonium) and the intermediates thus prepared with water or. Treated acids.