CS270180B1 - A method of preparing the burner and verbenone by oxidation of α-pinene - Google Patents

Abstract

The solution relates to a method for preparing verbenol and verbenone by oxidizing α-pinene with oxygen or an oxygen-containing gas at a temperature of 60 to 120 °C and a pressure of 0.01 to 1 KPa in the presence of a water-insoluble cobalt catalyst, which is deposited on the surface of activated carbon in combination with chromium salts soluble in the reaction system. The amount of catalyst used with respect to α-pinene is 0.005 to 0.03 wt. % Co in combination and 0.005 to 0.02 wt. % Cr. The solution can be used in the cosmetic industry and in forestry in the preparation of biological traps used for the destruction of spruce bark beetle.

Description

CS 270 180 B1

AND

BACKGROUND OF THE INVENTION The present invention relates to a process for oxidizing oxygen (or oxygen-containing oxygen).

Both verbenol and verbenone, formed by the oxidation of β-pinene, ed by the raw materials in the cosmetic industry and verbenol, or its isomer S-cis-verbenol, are the active ingredient of the ferro-ammonium mixture used to control ammonium nitrate. S-cis-verbenol is prepared by step-wise synthesis, and in the first step "by oxidation of" (- pinene, a mixture of oxidation products is obtained which is oxidized by chromosulphurate in the second stage), or by oxidation-inorganic oxidizing agents. Eectification yields a verbenone fraction with a content of greater than 90%, from which Sr-cis-verbenol is obtained by stereoselective reduction.

Oxidation of (- foamed with air or oxygen produces, besides verbenol and verbenone, «(- pinene oxide, verbenyl, myrtenyl, and pinocarvyl hydroperoxide, myrtenal, myrtenol, pino-carveol, pinocarvone and cis- and trans-3-pinene-2 Their proportion in the reaction mixture can be influenced to a certain extent by the lightness of the various solvents and the catalyst system used, and at 20 to 24% conversion of n -pinene is formed by oxidation of (-pinene with air at 30 to 40 ° C in the presence of cobalt acetate) and benzaldehyde as a catalyst, o (-pinene oxide in 36-40% yield, trans-verbenol in 20-25% yield, and verbenone in 14-19% yield) (U.S. Pat. No. 2,911,441). (-Ppinene at 25 ° C predominantly trans-verbenol and verbenone at an optimum cobalt concentration of 0.4 to 0.5% by weight (Essenze Deriv. Agrum. 1983, 53 (2), 148).

Oxidation of <RTIgt; (-ppinene </RTI> in pyridine cobalt-catalysed palmitate) gives a temperature of 60-65 [deg.] C. and a reaction time of 24 hours after subsequent oxidation of the primary reaction product with chromosulphate verbenone in 33% yield (British Pat. No. 2,078,223). The reaction time is reduced by about one third under similar reaction conditions (Os. Pat. No. 215 485) in the presence of a catalyst, and in the presence of a catalytic system consisting of palladium (II) chloride PdCl2, CuCl2 chloride and hydrochloric acid B31. or perchloric acid, is obtained by oxidation of (-ppinene at 80 ° C, predominantly verbenol and verbenone lead to mixtures of anionic carbonic alcohols and ketones. The ratio of verbenol to verbenone can be influenced by an organic solvent. nu verbenon (God. Vissh. Khim.-Technol. Inst. Sofia 1983, 29 (3), 106) In the environment of chlorobenzene with palladium chloride PdOIg or copper chloride CuCl2 in combination with lithium chloride, the oxidation of the. trans-verbenol and verbenone with a total selectivity of 57% at 24% conversion! (4-pinene (Oxid. Commun. 7, 3-4, 399, 1984) In testing the catalytic activity of the monohydric salts of various monocarboxylic acids, e.g., acetic acid, chloroacetic acid and trichloroacetic acid, it has been found that substituents with acceptable effects increase the catalytic activity. activity (Essenze Deriv. Agrum. 1983, 53 (4), 492).

The method of preparing verbenol and verbenone by oxidizing oxygen (or oxygen-containing oxygen) in the presence of a catalyst according to the invention is that the reaction is carried out at a temperature of 60 to 120 ° C, a pressure of 0.01 to 1 UPa in the presence of a catalyst. based on the water-insoluble cobalt salt deposited on the surface of the activated carbon 8 with a cobalt content of 1 to 20% by weight based on the weight of the carrier in an amount of 0.005 to 0.03% by weight of cobalt based on the weight of the (-pinene).

The acceleration of the disintegration of the hydroperoxides is added to the reaction mixture from 0.005 to 0.02% by weight. of chromium based on the weight of the (-ppinene, in the form of chromium salts soluble in the reaction medium).

To prepare the cobalt catalyst, a solution of cobalt salt (e.g., cobalt nitrate, sulfate, or chloride) in dilute acetic acid is gradually added to the activated carbon / aqueous sodium carbonate solution. An aqueous solution of HaOH is gradually added dropwise to the above-mentioned mixture at 70 DEG -90 DEG C. to pH 12. The cobalt catalyst and the cobalt content of Co are from 1 to 20% by weight. after washing with distilled water and drying it is used for reactors. . The presence of chromium salts accelerates the pronounced decomposition of hydroperoxides in the reaction mixture by simultaneously increasing the content of verbenone. The advantage of the process according to the invention is that the reaction is carried out only in the X-pinane medium without the use of a solvent at relatively low concentrations of catalyst and cobalt catalyst. the insoluble cobalt compound, deposited on the surface of activated charcoal and retains its original activity after multiple use. The oxidation of the X-pinene according to the invention is carried out at a temperature of 40 to 120 ° C, preferably 80 to 100 ° C and oxygen pressure or oxygen-containing gas. 0.01 to 1 UPa, preferably 0.05 to 0.3 UPa at a relatively short reaction time of 5 to 6 hours.

To the 50 cm 3 stainless steel reactor was weighed 9 g (-pinin, 0.0606 g cobalt catalyst, precipitated on Colorex K activated carbon, with Co 2.2 wt% <0.015% Co for X-pinane) ) and 0.0216 g of an ethanolic solution of chromium stearate (0.01% by weight of Cr H 2 O-pinane) containing 4.15 wt. The Cr. The entire system was purged with oxygen, pressurized with 0.3 UPa, and the reactor was placed in an oil bath where the temperature was heated to 100 ° C over 5 min. The reaction was counted from the moment the reactor was agitated to intensively mix the reaction mixture. the pressure pressure due to oxygen consumption was automatically compensated for by the pumping of an inert liquid whose volume, corresponding to the oxygen consumption, was recorded at certain time intervals after conversion to the reactor pressure. After the oxygen uptake was complete, the reaction was terminated after 45 minutes and after the catalyst had settled in the reaction mixture, it was determined by gas-liquid chromatography, internal standard method, verbenol, verbenone and unreacted pinane content. At 48.3% conversion of β-pinane, 40.1% of the selectivity was obtained and the verbenol of 38.4% of the selectivity was obtained. After subsequent oxidation of the reaction product with a chromosulphide mixture, verbenone was obtained in 37.8 µmol. Example 2

To the bubbled 550 cm 3 stainless steel tower reactor was weighed 220 µl-pinene and 0.50 g of cobalt catalyst precipitated on the surface of DB-1 activated carbon containing 10% by weight. Co (0.023 wt% Co vs. X-pinene). The reactor was heated to 65 ° by circulating water from the thermostat to the reactor jacket. Oxygen was injected into the lower part of the reactor through a glass frit at a pressure of 0.2 UPa. The reactor pressure was maintained at the desired value with a membrane manometer and a flow rate of 300 cm 3 min -1 was controlled by a rotameter. Samples Λ of the reaction mixture of 1 to 2 cm 3 were taken at certain time intervals by means of a sampling valve. Before sampling, the capillary was purged with nitrogen from a pressure bottle. After 6 h, the reaction was complete. After the catalyst had settled, the reaction product was aspirated from the reactor and the catalyst was used for further oxidation, and at 12.8% conversion of n -pyrane, verbenone was obtained with 29.6% selectivity and verbenol with 58.8% selectivity. 3

220 g of X-pinane and 0.53 g of ethanolic chromium stearate solution containing Cr 4.15% by weight were weighed into the bubbled tower reactor described in Example 2. (0.01 wt% Cr to o-pinane). At a temperature of 80 ° C, an oxygen pressure of 0.1 MPa and a flow rate of 300 cm 3 min -1, it was obtained at 28.6% conversion after 6 h! o (-pinane verbenone with 35.6% selectivity and verbene and 3 ', 4% selectivity).

To the bubbled tower reactor described in Example 2, 220 g of fresh o (-pinene and 0.2115 g of cyclohexane solution) were weighed into the catalyst used in Example 2 above.

Claims (2)

P R E D Μ E T OF THE INVENTION Process for the preparation of verbenol and verbenone by oxidation of eipenene with molecular oxygen * at a temperature of 60 to 120 ° C and a pressure of 0.01 to 1 MPa in the presence of a catalyst, characterized in that a water-insoluble cobalt salt applied on the surface is used as catalyst. activated carbon and a cobalt content of t to 20% by weight, where% are based on the weight of the support, in an amount of 0.05 to 0.03% by weight of cobalt, the% being based on the weight of X-pinene. 2. The process according to claim 1, characterized in that the catalyst is activated by chromium eols soluble in the reaction medium in an amount of 0.005 to 0.2% by weight of chromium, based on the weight of .alpha.-pinene.