DE1196646B - Process for the production of cyclododecanol - Google Patents

Description

Process for the production of Cyclododecanol It is from the German Auslegeschrift 1 058 987 known that cyclododecatriene (l, 5.9) can be obtained by action of organic peracids or other organic per compounds 1,2-epoxycyclododecadiene- (5,9) obtained, which can be hydrogenated to cyclododecanol. While hydrogenation in general The use and handling is more organic Peracids prevent the reaction from being carried out on a larger scale.

It has now been found that cyclododecanol can be obtained from cyclododecatriene- (l, 5.9) in a simple manner, which can also be easily carried out on an industrial scale, if the Epoxidation stage carried out in such a way that one by optionally in one Solvent dissolved cyclododecatriene- (1,5,9) at a temperature of 20 to 200 "C in the presence of heavy metal catalysts known as oxidation catalysts Oxygen or gases containing such conducts and the reaction product obtained distilled.

Cyclododecatriene- (1,5,9) serves as the starting material, although there is none It plays an important role whether one or the other geometric isomer is used will.

One can use both the transtranscis connection and the transtranstrans connection use.

Pure oxygen can be used as the oxygen-containing gas, however, it is usually preferred, with air or with an oxygen-inert gas mixture to oxidize, in which the oxygen makes up about 3 to 30 percent by volume. As an inert gas In addition to nitrogen, carbon dioxide is particularly suitable.

The execution is within the specified temperature range at 100 to 150 "C preferred.

The process is usually carried out under normal pressure. Man but it can also perform at increased pressure, e.g. B. at 2 to 20 at or at even higher pressure.

Execution under pressure has, especially when used, relatively volatile Solvents matter. The solvent can be, for. B. low molecular weight Use fatty acids or benzene.

Compounds and salts of the can be used as oxidation catalysts heavy metals commonly used in oxidation processes such as silver, copper, barium, Vanadium, molybdenum, chromium, tungsten, manganese, iron, nickel and especially cobalt, such as the platinum group metals can also be used. They are particularly suitable salts soluble in cyclododecatriene (1,5,9), such as naphthenates, stearates and in general Salts of higher mono- and dicarboxylic acids.

The various catalysts are generally used in amounts of 0.001 to 10 / ,, based on the Cyclododecatriene- (1,5,9). You can However, carry out oxidation also at higher concentrations.

When using soluble metal catalysts, the process is described in homogeneous liquid phase carried out. When using insoluble catalysts, z. B. the oxides or the chlorides of heavy metals, you can also use the catalyst fixed, e.g. B. on supports, and arrange the reactants in cocurrent or countercurrent lead over this catalyst.

The catalytic effect of the heavy metal compounds listed can by adding nitrogen bases, such as di-n-butylammonium bromide, piperidinium bromide in amounts of 0.001 to 1.00 / ,, based on cyclododecatriene (1,5,9) increased will.

The process of catalytic oxidation of cyclododecatriene- (l, 5,9) is generally only with conversions of 2 to 20 0 / ,, but preferably from 3 to 100 / whether carried out. Yields of cyclododecadiene epoxide are based on the converted cyclododecatriene- (1,5,9), achieved from about 50 to 6501o.

The reaction mixture is expediently with the addition of customary polymerization inhibitors, such as thiodiphenylamine, distilled in amounts of 0.001 to 0.01 0 / o. Receives a fraction that consists of unreacted cyclododecatriene (l, 5.9), optionally a fraction of solvent as well as a fraction consisting essentially of cyclododecadiene epoxide Fraction. The cyclododecadiene epoxide can then be obtained in pure form by fine distillation Isolate form and then hydrate.

However, it has proven advantageous to use the cyclododecadiene epoxide not just to isolate, but to use the relatively broad fraction that is used in simple distillation as cyclododecadiene epoxide works, but there are still a number of them Contains unspecified other oxidation products, immediately below the usual ones Conditions to hydrogenate, e.g. B. at temperatures of 100 to 140 "C and pressures of 100 to 200 at using catalysts such as Raney nickel.

Compared to what is known from German Auslegeschrift 1, 177 will Process in which cyclododecatriene is first hydrogenated to cyclododecane and then hydrogenated is oxidized to a mixture of cyclododecanone and cyclododecanol, the following must be separated, the new process can be with fewer process steps and run with a more favorable hydrogen yield.

Example 1 In a 700 mm long, electrically heated glass tube, which has a diameter of 35 mm, is replaced by 500 g of cyclododecatriene (l, 5.9), in which 0.05 g of silver stearate is dissolved, at 130 "C for 1/2 hour an air flow of 35 1 / hour headed. Then the reaction mixture is distilled at a pressure of 0.5 torr.

456 g of unreacted cyclododecatriene (l 5.9) and with are obtained 100 to 120 "C a fraction which consists essentially of cyclododecadiene epoxide.

This fraction is dissolved in 80 ml of ethanol and placed under hydrogen pressure hydrogenated from 200 atmospheres in an autoclave at 120 "C in the presence of 5 g of Raney nickel. 25 g of cyclododecanol are obtained from the hydrogenation mixture in the distillation, corresponding to 50.1% of theory, based on the cyclododecatriene (1,5,9) used.

Example 2 In a 2 l three-necked flask equipped with a stirrer and Reflux condenser, is under constant flow Mixture with 1500 g of cyclododecatriene (l , 5.9), in which 0.05 g of cobalt ethyl hexanate is dissolved, is a stream of air at 130 "C for 1/2 hour of 30 1 / hour finely divided. The reaction mixture thus obtained is distilled. At 85 ° to 110 ° C. and 0.3 Torr, 25 g of a fraction are obtained which essentially consists of cyclododecadiene epoxide. It is then hydrogenated as in Example 1. 23 g of cyclododecanol are obtained. The yield, based on converted cyclododecatriene, is 620 / o of theory.

Claims (1)

Claim: Process for the production of cyclododecanol by Epoxidation of cyclododecatriene (l, 5.9) and hydrogenation of the 1,2-epoxycyclododecadiene (5.9) obtained at 100 to 140 "C and 100 to 200at in the presence of conventional hydrogenation catalysts, like Raney-Nickel, denoted by k e n n nz e i c h n e t that epoxidation carried out in such a way that one by optionally dissolved in a solvent Cyclododecatriene- (1,5,9) at a temperature of 20 to 200 "C in the presence of Oxygen or heavy metal catalysts known as oxidation catalysts such containing gases passes and the reaction product obtained is distilled. Publications considered: German Auslegeschriften No. 1 058 987, 1111177.