DE1070627B - - Google Patents

Description

CO 7 C ^ 9/38

0 °

FEDERAL REPUBLIC OF GERMANY

GERMAN mmm, PATENT OFFICE

kl. 12 ο 25

INTERNAT. KL. C 07 C

EXPLAINING PUBLICATION 1070 627

B 47891 IVb / 12 ο

AN M E LDE DAY: 18 FE B RU 4 R 1958

NOTICE
THE REGISTRATION
AND ISSUE OF THE
EDITORIAL: DECEMB 10, 1959

It is known that by treating compounds with alcoholic or phenolic Hydroxyl groups can produce ketones with catalysts. It is also known that in such treatments water is split off from compounds with two hydroxyl groups. So z. B. from cyclooctanediol- (1,2) cyclooctanone.

Surprisingly, it has now been found that in the treatment of cyclooctanediol- (1,4) with 100 to 200 ° C with dehydrogenating catalysts a hydroxyl group into the ketone group can convert, but the second hydroxyl group is retained. This unexpected course of the reaction makes it possible to produce the new substance cyclooctanolone- (l, 4) to come up with a new base for the manufacture of valuable plastics and pharmaceuticals Products.

Method of manufacture
of cyclooctanolone- (1,4)

OH

OH

OH

Serving as starting material cyclooctanediol (1,4) can be z. B. by treating cyclooctene with performic acid (Cope, J. Am. Chem. Soc. Vol. 74, 1952, p. 5884). You can do it Cyclooctanediol- (1,4), which is obtained here as a mixture with cyclooctanediol- (1,2), either by Extraction with absolute ether or the cyclooctane diol (1,2) as an isopropylidene derivative from the mixture take from the diols. But you can also dehydrate the mixture of the two diols directly. From the The proportion of cyclooctanediol- (1,4) (about 60%) is obtained cyclooctanolone- (1,4), while the cyclooctanediol- (1,2) is converted into cyclooctanone by elimination of water via its enol form. The Cyclooctanolone- (1.4) can be separated from the cyclooctanone by simple fractionation.

The known dehydrogenation catalysts, such as copper, silver, magnesium, zinc, tin, lead, chromium, cobalt, nickel and iron or oxides, Use hydroxides or mixtures thereof. If you use oxide catalysts or mixed catalysts, it is advantageous to use the same before Use with hydrogen, expediently at 150 to 300 ° C, to reduce. As particularly beneficial the use of copper-chromium-zinc and magnesium-iron-copper catalysts has proven its worth. The catalysts, as such or in finely divided form, can be applied to the customary support applicants:

Aniline & Soda Factory in Baden

Corporation,

Ludwigshafen / Rhine

Dr. Hans Moell, Ludwigshafen / Rhine,

Dr. Otto Schlichting, Esslingen / Neckar-Hegensberg,

and Dr. Nicholas v. Kutepow, Karlsruhe-Rüpurr,

have been named as inventors

substances applied, are used. As carrier substances are, for. B. pumice stone or activated carbon suitable. The catalysts can also be used in

^a 5 pure form, e.g. B. pressed into lozenges, use.

The dehydrogenation is carried out at 100 to 200 ° C, preferably at 150 to 200 ° C, conveniently below normal or slightly increased pressure. But you can also use slightly reduced pressure,

z. B. at 300 to 400 mm Hg, work.

The dehydrogenation is preferably carried out in the gas phase. You can z. B. the cyclooctanediol- (l, 4) melted and drop into an evaporator and the vaporous cyclooctane

Pass diol (l, 4) together with inert carrier gases over the catalyst. Suitable as an inert carrier gas yourself, e.g. B. when using air-sensitive catalysts, especially hydrogen. The usage of Hydrogen as a carrier or protective gas is special

advantageous when working under reduced pressure. The carrier or protective gas can after leaving of the reaction chamber can be used again. A small part of it becomes useful Replace with constant addition of fresh gas. The Ver-

But you can also drive as a so-called trickle process, in which the cyclooctanediol- (1,4) over a preheater is run and then trickles over the catalyst in a tower-like reaction furnace, carry out. Furthermore, dehydration can also

be made in the sump phase. Appropriate the catalyst is suspended in cyclooctanediol- (l, 4) and while heating kept in constant motion by a suitable stirring device.

The hydrogen formed and the reaction product are continuously removed and replaced by appropriate Amounts of fresh cyclooctanediol supplemented. The new keto alcohol produced by this process Cyclooctane can be used as an intermediate for the manufacture of plastics and pharmaceuticals Products are used.

example 1

A continuously operating reaction furnace of 1.21 capacity is equipped with a catalyst made of copper, Chromium and zinc oxide, which is applied to pumice stone, filled. Before the dehydrogenation, the catalyst is used Treated with hydrogen at 220 ° C. for 40 hours. In a heated burette, pure cyclooctanediol (1.4) (M.p. 85 to 86 ° C) melted and at a rate of 50 g / hour into a Evaporator dripped. The vaporous cyclooctanediol- (1,4) is passed over the catalyst at 200 ° C. The dehydrogenation product obtained is thin. In the case of distillation under reduced pressure the 1200 g of cyclooctanediol- (1,4) 850 parts of pure cyclooctanediol reacted in total in 24 hours are obtained Cyclooctanolone- (1,4) with a melting point of 58 to 59 ° C, that is a yield of 72% of theory.

Example 2

A reaction furnace of 1.2 1 content is equipped with a catalyst made of magnesium, iron and Copper oxide, pressed in pellet form, filled. The catalyst is used at 250 ° C for 24 hours Hydrogen treated. A liquid mixture of cyclooctanediol- (1,4) and cyclooctanediol- (1,2), in where the two components are present in a ratio of about 3: 2, in proportions of 30g / hour evaporated at 200 ° C in an evaporator and the vaporous mixture of the cyclooctanediols with the help a stream of nitrogen at 180 ° C. passed over the catalyst. That for a total of 48 hours The resulting dehydrogenation mixture is distilled under reduced pressure. This gives 342 g Cyclooctanone and 620 g cyclooctanolone- (1,4) (m.p. 58 to 59 ° C). The yield of cyclooctanolone- (1,4) corresponds to 44% of theory.

Claims (2)

Claims. 1. A process for the preparation of Cyclooctanolon- (l, 4), characterized in that one Cyclooctanediol- (1,4) passes over dehydrogenation catalysts at 100 to 200 ° C. 2. The method according to claim 1, characterized in that a mixture is used as the starting material of cyclooctanediol (1,4) used with cyclooctanediol (1,2) and that from the cyclooctanediol (l, 2) Cyclooctanone formed is separated from the cyclooctanolone- (1,4) by distillation.