SU565910A1 - Method of obtaining tetralone-1 - Google Patents

Description

(54) METHOD OF OBTAINING TETRALON-1

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This invention relates to a process for the preparation of tetralone, a technically important intermediate for the synthesis of naphthol-1, which is obtained by catalytic dehydrogenation of tetralone.

One of the most common methods for producing tetralone-1 is the liquid-phase oxidation of tetralin in the presence of homogeneous catalysts - salts of organic acids of transition metals, mainly cobalt and manganese, 27. Significant disadvantages of this method are the low selectivity (32%). reaction products and low conversion (37%) of the feedstock. All this significantly complicates the method for producing tetralone-i by liquid-phase oxidation of tetralin in the presence of homogeneous catalysts.

There is also known a method for producing tetralone-1, which consists in the liquid-phase oxidation of tetralin with an oxygen-containing gas in the presence of heterogenous zeolite catalysts containing cations.

metals of variable valence at 1OO160 С ЗЗ. The disadvantages of this method are the low yield of tetralone-1 to reacted tetralin (44.1%) and the formation of a significant amount of by-product and tar-like products (up to 23.5%

The aim of the invention is to develop a process for the solid phase oxidation of tetralin, which would increase the yield of the target product and reduce the formation of resinous reaction products.

For this, polyurethane containing cobalt (11) is used as a catalyst, and the process is preferably carried out at 80-100 ° C.

The catalyst is prepared as follows.

Polyurethane formupy

ABOUT

(СН2) and-КН-С-о

placed in chloroform, anhydrous Co C 2 salt added. and the mixture is mixed

within 8 hours After that, the cobalt-containing polymer is separated. The mouth of the unreacted salt is Cocj. In the prepared catalyst, the cobalt content is 20-30 wt.%. % The catalyst is introduced into the oxidizable tetralin in the amount of 0, 15, 0 g per 1 liter of the oxidizable hydrocarbon. The process of tetralin oxidation is carried out in the liquid phase with oxygen-containing gas at 80-140 ° C. Analysis of the reaction products is carried out by the method of quantitative chromium | The chromatographic was analyzed by Tsvet-1O1 chromatograph according to a known method.

Analysis of the products of tetralin oxidation using a new catalyst showed that the process is selectively proceeding over the entire period to form the desired reaction product, tetralone-1. The percent process proceeds with a minimum yield of by-products and resinous products. The initial rate of formation of tetralone-1 using a new catalyst exceeds that of oxidizing tetralin in the presence of other heterogeneous and homogeneous catalysts. The process of oxidation of tetralin in the presence of the proposed catalyst can be stopped in the early stages, achieving a high yield of the desired reaction product tetralone-1 (83%), while no mixed and resinous products are formed in the mixture. The ratio of tetralone-1 to tetralulo-1, which is one of the main indicators of the process, is 10-30, which is more than 1O times higher than that for the oxidation of tetralin in the presence of the best homogeneous catalyst - cobalt stearate. All this facilitates the isolation of the main reaction product, tetralone-1, which, when oxidizing tetralin in the presence of known homogeneous and heterogeneous catalysts, is a difficult problem.

Another advantage of the proposed method of producing tetralone-1 using a new catalyst is the possibility of regenerating this heterogen. catalyst and its subsequent use in the process .. Analysis of the original

catalyst and catalyst regenerated after carrying out the tetralin oxidation process at various temperatures, is given in that. one

The high catalytic activity of the proposed catalyst, the possibility of its regeneration, as well as the indicated advantages of the proposed method for producing tetralone-1 by liquid-phase oxidation of tetralin in the presence of a cobalt-containing polymer catalyst enable the most efficient way to produce this important intermediate.

Example 1. In a bubbling apparatus with a stirrer load 100 ml of tetralin and 0.5 g of catalyst. The process is conducted at 80 C, the air supply rate of 2.7 l / min. After 240 min. since the start of the oxidation, the yield of tetralone-1 is 17.5 wt. % tetralol-1 2, 2 weight. %

Example 2. In a bubbling apparatus with a stirrer, 1OO ml of tetralin and 0.5 g of catalyst are loaded. The process is carried out at 90 ° C, an air supply rate of 2.7 l / min. The results of the analysis on the yield of tetralone-1 and tetralol-1 are given in table. 2

Vacuum distillation of the oxidate at a pressure of 1 mm Hg. after 240 min from the moment of the start of the reaction, it showed that during the oxidation 29.19 weight was formed. % tetralone-1 and 5.78 wt.% by-products of the reaction. The amount of unreacted tetralin is 65.01 wt.%.

Note 3. A 100 ml tetralin and 0.5 g of catalyst are loaded into a bubbling apparatus with a stirrer. A temperature of 100 ° C, an air supply rate of 2.7 l / mol. The results of the analysis on the yield of tetralone-1 and tetralol-1 are given in table. 3

Example 4. In a bubbling apparatus with a stirrer load 100 ml of tetralin and 0.01 g of catalyst. Temperature 14 ° C, air flow rate 2.7 l / min. After 160 minutes from the start of the oxidation, the yield of tetralone-1 was 5.88 wt. %, tetralol-1 - 0.17 weight. %

Catalyst

Original

After oxidation at 80 ° C

(example 1)

After oxidation, at 90 ° C (Example 2)

Table;

The content of cobalt in the catalyst, wt. %

29.3 26.7

23.6

Claims (3)

Invention Formula 2. The method according to claim 1, about tl and h ak; one . The method of producing tetrapone-8O-iOO C. cophazic oxidation of tetra in kiadorod-Sources of information taken in with a gas at elevation TieMne 5, viimai during examination: treatment in the presence of heterosexuals about kata-1, French Patent No. 1O95348, lysator containing transition cations, C 07 C, 1964 g, metals, characterized by that, in order to increase the speed accumulated2, USSR Author's Certificate No target product and selectivityto 340649, ki. C 07 C 49/36, n / a, process, as a catalyst used 3. USSR author's certificate polyurethane containing cobalt (P) .№ 425896, cl. C 07 S 49/76, 1973 565910g w and and with the fact that the process is conducted at