DE127855C - - Google Patents

Description

IMPERIAL

PATENT OFFICE.

It has been found that the cis ^ Terpene glycols when heated with dilute acids or other dehydrating agents Agents, partly even when heated, split off a molecule of water and convert it into monovalent cyclic alcohols (terpene carbinols) of the type

pass over while the trans-glycols at same treatment do not change. The unsaturated terpene carbinols obtainable in this way in the case of reduction with sodium in boiling alcoholic solution, they become saturated Terpene carbinols of the type

CH-CH ₉ -OH

above.

So the cis-camphyl glycol supplies the unsaturated one Carbinol:

CH

CH,

CH ₉ .

C-CH ₉ -OH

CH

from which by treatment with sodium in alcoholic solution the corresponding saturated Camphylcarbinol is represented.

The terpene carbinols are colorless or oily crystallizing bodies, easily volatile with water vapors, which, when completely pure, are pleasant smell and, in the case of oxidation, the associated, which can also be represented in other ways Terpene aldehydes provide (see patent 121975).

Example I.

Conversion of menthyl glycol into the carbinols:

CH ₃ CH,
\ /
CH

CH

CH,

CH,

CH

C-CH ₂ -OH

CH

CH ₃

Dehydromenthylcarbinol

CH ₃ CH _S

\ κ

CH

CH

CH ₂ / \

chJ

CH-

OH

CH

CH ₃

Menthyl carbinol.

For the purpose of converting cis-menthyl glycol in dehydromenthylcarbinol the former is expediently given with 20 per cent. Sulfuric acid in one The distillation apparatus is heated to the boil by simultaneously adding dropwise Water ensures that the level of the boiling liquid does not change. That cis-Menthylglycol splits into water and dehydromenthylcarbinol, which with the Distilled water vapors

Dehydromenthylcarbinol is a thin, highly light-refracting oil that smells of aniseed. Boiling point 99 to 10 ° at 18 mm pressure.

For the purpose of preparing menthyl carbinol (see above), the hot solution of ι Th. Dehydromenthylcarbinol in 10 Th. Absolute Alcohol ι Th. Sodium act. After the sodium has disappeared, water is added diluted, the solution neutralized with dilute sulfuric acid, and the alcohol and that Menthyl carbinol exaggerated with water vapors. The distillate is carbonated with Potash saturated and by repeated fractional distillation of the dry alcoholic solution the menthyl carbinol is isolated in a vacuum. Menthylcarbinol is a colorless, weakly after Anise smelling oil which boils below 20 mm at 85 to 90 °.

Example II.

Conversion of camphyl glycol into:
CH

C-CH ₂ -OH

CH

CEL

CH ₃

Dehydrocamphylcarbinol

CH

CH ₉

CH ₂

CH-CH ₂ -OH

CH ₉

CH _S

Camphyl carbinol.

To prepare the dehydrocamphylcarbinol, the molten mixture of cis- and trans-camphylglycol or better still in its hot benzene solution introduced dry hydrogen chloride gas to saturation and the melt respectively. the benzene solution then with excess soda solution distilled in a stream of steam. The dehydrocamphylcarbinol is a colorless crystal mass with the water vapors over while the trans - camphylene glycol is in the distillation flask remain.

Dehydrocamphylcarbinol is a colorless, if completely pure, vanilla-like smelling crystal mass consisting of long needles, which boils ^{at 128 to 129 0 under 19 mm pressure.}

This compound can also be obtained by boiling camphylene glycol with 20 proc. Sulfuric acid, and also by heating the camphylglycol itself to a higher temperature be won.

The conversion of the dehydrocamphylcarbinol into camphylcarbinol is carried out in the same Way, as described above for menthyl carbinol. After careful distillation from the distillate through pot

As soon as the alcoholic solution is deposited, the camphylcarbinol remains rapidly crystalline solidifying oil back.

Camphylcarbinol crystallizes in colorless needles, it is not volatile with steam and melts at 62 to 64 ^0th

The terpene carbinols obtainable by the present process are intended to be used as fragrances and precursors find use for the representation of fragrances.

Claims (1)

Patent claim: Process for the preparation of monohydric cyclic alcohols (terpene carbinols) of the type: V.
C. > C CH-CHv-OH CH, consisting in using the terpene glycols obtainable by the process of patent 123909 mit.wasserentziehenden agents and the resulting unsaturated terpene carbinols for the production of saturated carbinols in alcoholic solution with sodium treated.