CS268571B1 - Method of verbenone preparation - Google Patents

Abstract

Verbene, ^, 6,6-triazetylbioyclo- - (3,1,1) -hopt-3-4n-2-one, βλ prepares from alpha-pinone to axldaol by cysteine for the second Catalyst and Cocatalyst at a temperature of from 0 to 80 ° C, ranging from 4 to 2 hours with the presence of 0.005 to 0.1 mol of the cobalt complex type dlpyridylkobo.lt - dlbromld or cobalt eol carboxylic acid number of carbons v molecule 1 ^ 1 to 18 eye catalysts * and 0.001 to 0.005 nol of stunning carboxylic acid acid with the number of carbons per molecule 1 to 18 as a cocatalyst per kg of alpha-solid in the cobalt composition complex C o? ■τ- ■ pyri 1; 1 to 2; 2 to 3.

Description

The invention relates to a process for the preparation of verbenane.

Verbenane, h, 6,6-trimethylbioyclo- [3,1,1] -hept-3-en-2-one, is a component of some βΐΐίο and uses e «as a component of jMUfunov a, j nko nmtz 1 product for the preparation of various other It has recently been found that the optioc active (S) -ols-verbenol and (R) -ol 3 -verbenol are important compounds useful as components of pheromans for beetles and, in addition, affect the behavior of some species of harmful insects. These compounds are prepared by reducing verbenane, which thus becomes an important intermediate for the production.

Verbena is prepared by oxidation of alpha-pinene with various epitobes, oxidation with lead ootane in ootic acid with the advantage of high yields but the disadvantage of its toxicity as well as the problems of waste treatment - Mori K. · Agr. Biol, Chem. 40, 415-8 (1976), CA 84 135842. It is possible to oxidize in benzene and alkaline media and the tranververbonol obtained after reoxidation with chromium oxide in pyridine provided verbenan - Mitsubishi Chem, Ind., Co., Ltd., Jap, vykl. , file 81 30, 9 ^ θ, CA 95, 15θ956. Oxidation with the aid of lead dioxide, chromium oxide or even manganese dioxide. It is possible in pyridine, acetane, benzene or even ligroin. Agrum. 42> 41-7 (1972), CA 22 «16 ^ 860, Oxidation of oxygen at a temperature of up to 100 ° C without a catalyst gave the products alpha-pinene oxide, trans-verbenol and verbenane - Moore R, N., Golumbio C., Fischer G, S.: J, Amer, Chem. Soo. £ 8, 1173-6 (1956). Similarly, they oxidized with air at a temperature of 60 to 9 ° C and obtained, in addition to products for cosmetic purposes, also verbene - Bain JP, Booth AB, Klein EA (Glidden Co., U.S. Pat. No. 2,863,882 (1,958), CA 53, 8194. above 5θ ° C, a potting lot is already formed in addition to the live products, at the temperature of 50 ° C the desired products were obtained as before, in better extract / Bain J, P ,, Gary V. Y, / Glidden Co /: USA pat. U.S. Pat. Phys. Chem. Res. (Tokyo): 14, 179-81 (1935), CA 2, 5830, Oxidizing with oxygen at temperatures of 3θ to 40 ° C in the presence of benzaldehyde and cobalt ootane as catalyst gave verbenol and verbenane in a yield of over 40 - Romanlohln A, M ., Popova N. I ,, Prudnichenko E, K .: Chirn, Toohnol, 20, 177-9 (1977). Oxidizing with oxygen at a temperature of 60-65 ° C in the presence of pyridine and cobalt palmitate as catalyst, after reoxidation with temple oxide, verbene was obtained in extract 33 - Kalvoda L., Vrkoč J, Pat, Czechoslovakia A0 215,485 (1982). of perbenzoyl peroxide as the initiator or peroxyacetic acid and verbenane was obtained in a yield of up to 40 .mu.m, while the rocass time was also reduced from 24 to 18 hours - Collective; Ferromany, research report, VÍCHT Bratislava 1983. By a mixture of verbonol and verbenane - Boho R, L ,: Essenze Deriv, Agrum 22 «148-56 / 19θ3 / , CA 101, 211481, Oxidizing with oxygen or air at 50 ° C for 20 hours in the presence of a dipyridyl diiodium-copper complex as a catalyst was obtained verbene in good yield - Hhaduri S., Mahandru, M. / Indian Explosives Co., British U.S. Pat. - Strakova V., Dimitrov D ,, Angelov V. · Dokl, Bolg, Akad, Nauk 37, 767-9 / 1984 /, CA 10 1, 2 1 1484. Oxidation at temperatures of 68 to 80 ° C increase in conversion will also increase the yield of products as stated in - Dimitrov D., Strakova V ,, A ngelov V ,, Stefanova R ,: Chim. IND, / Sofia / 56, 5 ^R * -56 / 1984 / CA 101, 38676, Oxidáoiou with oxygen at 80 ° C using azodiisobutyronitrile 3 / AIBN / e and initiator addition to the products obtained for the purpose of well and kozmetiokó verbenán - Pritzkow in ,, Van Trion V ,, Schmidt-Renner V ,; Miltitzter Berichte 1982, 17-25. Oxidation of oxygen at a temperature of 70-80 ° C using AIBN as an inlotter has yielded verbenane in addition to other products, the main purpose of which is bell kinetic measurements and design. mechanism roakoio - Martinez de la Cuesta P. J ,, Rus Martinez E ,, Garoia Herruzo F .: Ann.

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CS 268 571 B1

Quim ,, Ser. A 80, 262-6 (1984). Oxidation of the alkali at a temperature of 50 DEG to 80 DEG C. begins for 4 to 12 hours with the use of dipyridyl dibromo discobalt as catalyst and AXHN or organic alcohols as zinc thioniters with a yield of 36 g of carbon dioxide and 10% of carbon monoxide. up to 90 verbenol converted to verbenon - Klzlink J., Uroneo M,, Cvengrošová Z ,, Kuruo 1., Křiž H., Obložinaký A., Ilnvaký J. · ČSSR PV 9112-86.

Oxidation of alpha-pinene by means of tetravalent lead salts or even trivalent monosalium salts is disadvantageous from the point of view of the high toxicity of the agents and thus of the problems of waste disposal. Oxidation in alkaline atmospheres of cobalt or manganese salts, so-called metal soaps are very good and the products are obtained in goodness of the extract, but a considerable amount of harmful organic bases present, such as pyridine, olein, tero. amines and so on. In addition to unpleasant work, they also cause more demanding health protection for workers. In some processes, the considerable economic complexity is caused mainly by the disposal of waste and the operation of technological equipment.

These shortcomings are partially eliminated by the process for the preparation of verbonone from alpha-pinene by oxidizing oxygen in the presence of a catalyst at a temperature of 50 to 80 ° C for 4 to 12 hours according to the invention. dipyridylcobalt dibromide or a cobalt salt of a carboxylic acid and the number of carbons in the molecule 14 to 18 as a catalyst and 0.001 to 0.005 small chromium salts of a carboxylic acid with the number of carbons in the molecule 14 to 18 as a cocatalyst per 1 kg of alpha-pinene with a cobalt complex composition Co: Br : pyridine 1: 1 to 2: 2 to 3. The reaction was also carried out in the presence of a solvent of a cobalt complex such as carboxylic acids, e.g. in the presence of azonitriles carboxylic acids with a carbon number in the molecule of 4 or organic peroxides compounds e.g., cumene hydroperoxide, ethylbenzone hydroperoxide, dibezoyl peroxide as initiators. Thus, a larger amount of oxidized pinon is obtained than the so-called fracol U., which contains verbenon and trans-verbenol.

The reaction mixture obtained is partitioned into a fraction containing mainly reacted solid which can be recycled and into a fraction of oxidation products containing mainly oxygenated monoterpenes, from which verbene and tranaverbenol can be obtained in relatively good purity by distillation under vacuum, 7θ to 85. other · machining », eg rooxldáoiou, etc.

By fractionation of oxidation products It is possible to subject the reoxidal in an acidic environment to the salts of hexammonium chromium in a homogeneous environment at temperatures of 0 to 10 ° C. In this process, the oxidized transverbenol verbenone and this is readily obtained from a mixture rektifikáoiou in vacuum at very high purity of 87-97 the J ^e sufficient for His JLalšie spraoovanle redukoiou to žladaný oisverbenol.

The temperature range used is 30 to 90 ° C and preferably around 55 to 65 ° C. At lower temperatures fewer by-products are formed, but the reaction time is too long, at higher temperatures the proportion of by-products, mainly bituminous, is already considerably high and above 80 ° C. The formation is practically unbearable. and working up the reaction mixture. The abrasion yes varies about the water of reaction with a suitable solution without favoring the effect on the course of the reaction. There must also be a considerable spare space in the reactor for a considerable amount of oxidized pinon, namely up to 5θ of the height of the etipo-pinon in the charge. The cobalt complex catalyst used can be prepared relatively simply by J, Chem, Soo. 1963, 5449 and cobalt and chromium soaps, respectively, by heating hot solutions of sodium salts of carboxylic acids and a solution of inorganic salts of cobalt reap, heated.

CS 268 571 B1

Example 1

Alpha-pinene oxidation

Into the oxidation reactor in the form of a sloping wall / length 800 nuu, breakthrough 45 n * n / s with an oloctrically heated plate, a thermometer, a cooling coil and possibly an azeotropic attachment to the water compartment g of alpha-pinene (purity $ 97 according to GLC). After heating the reactor vessel to a temperature of 90-100 ° C and maintaining the oxygen flow in the range of 20 to 30 1.h ^-1 , the process was added 2.0 g (0.005 mol) to a finely divided mixture of dlpyridyl-cobalt-dibroaldehyde catalyst (PygCoBrg). 1.6 g (0.002 mol) of palmitate amaze the same (PaCr) and, for better solubility, also 50 g of ootic acid. After 10 minutes, most of the catalyst dissolved and the temperature was adjusted to 60 DEG C. and the oxygen flow to 20 DEG C. and 0.4 g (0.0025 mol) of azobiaisobutyronitrile (AIBN) was added as initiator. The mixture was oxidized for 6 hours, allowed to cool to about 30 ° C, filtered and then passed through a packed column (length 1,000 mm, diameter 25 mm, glass or porcelain Rasohig rings) with a temperature to 110-115 ° C or mln <nn1n in a conical flask was kept at a temperature for 30 minutes, thereby disrupting the peroxides present. After cooling, the reaction mixture was distilled under vacuum at about 2.66 kPa (20 torr) into two fractions, fraction I, up to 70 ° C (which contains predominantly unreacted feed, which can be recycled) and fraction II, to a temperature of 180 ° C flask (which contains oxidation products, mainly verbene and trans-verbenol). The distillation residue contains various bituminous substances and catalyst residues. Frakoiu II. and then rectified using a vacuum using a puncture column and 8 TP. A total of 159 g of unreacted pinene (fraction I) and 182 g (36.4%) of oxidation products (fraction II) were obtained, from which 58.4 g (32.1%) of verbonone were obtained at 37.1%. (20.4%) of verbenol. The conversion was 68% and the selectivity was 0.25.

Example 2

As in Example 1, a pinene charge was used and a catalyst of 5.7 8 (0.01 mol) cobalt palmitate (PaCo) and a cocatalyst 1.6 g (0.002 mol / bromine palmitate / PaCr) was added at 60 ° C. 0.5 g of triethylamine and 1 ml of peroxyacetic acid (40%) and after 10 minutes of 1 ml of cumene hydroperoxide (90%). After 12 hours of oxidation, the reaction mixture was treated similarly to Example 1 to give 136% of unreacted feed fraction I, (and 227 g) of 45.4% oxidation products (fraction II), from which 63.1 e (27.8 .mu.m) of verbene and 47.0 g (20.7%) of verbenol were obtained. The conversion was 73% and the selectivity was 0.27.

Example 3

As in Example 1, a pinene charge was used and a catalyst was added at 60 ° C at 5.7 8 / 0.01 mol / PaCo, 1.6 g / 0.002 mol / PaCr, 6 g of triethylamine and an eye initiator in Example 2. After 6 hours of oxidation, the temperature was raised to 80 ° C and the oxidation was continued for 2 hours. Then, the reaction mixture was treated similarly to the previous examples to obtain 109 g of unreacted pinene (fraction I) and 223 8 (44.6%) of oxidation products (fraction II), from which 54.0 g (24.2) were obtained. j) of verbena and 44.8 g (20.1%) of verbenol. The conversion was 78% and the selectivity 0.23.

Example k

Also the eye in Example 1, ea used a pinene charge, and at 60 ° C a catalyst was added, namely 5.7 g (0.01 mol / PaCo, 1.6 g - (0.002 mol) of stearate stearate, 58 g of triethylamine and an initiator as in Example 2. After 6 hours of oxidation, the reaction mixture was treated similarly to the previous example to give 180 g of unreacted pinene (fraction 268 571 B1 of duty I) and 190 g (38 of oxidation products (fraction II)), from which aa 55% (29.3%) of verbenone and 48.8 g (25.7%) of verbenol were obtained. The conversion was 64% and the selectivity 0.2%.

Example 5

Reoxidation of oxidation products

100 g of fraction II, (32.8%) of verbenone and 3.7 .mu.l of verbenol were weighed into a 1000 ml conical flask with stirrer and thermometer. 230 ml of hexane and 180 ml of water were added, and the reaction mixture was cooled to 0 to 5 ° C. A chromosulfur residue (38.5 B CrO 2, 142 ml of water, 58 g of 90% N 2 SO 4) was gradually added thereto so that the temperature was max. 10 ° C, The mixture was stirred for 1 hour, the mixture was partitioned, the upper organic layer was separated and the lower aqueous layer was extracted with 3 x 100 ml of harane. The organic layers were combined, washed with 5θ ml of a 10% solution of soda and 200 ml of water and dried over Ka 2 SO 4. small box. Fractures up to 105 ° C It is full, which can be recycled. 70 g of crude product (35.4 g of verbenone and 0.4 .mu.l of verbenol) were obtained, of which 24.8 g of verbenone and 0.3 g of vorbenol were obtained, which represents a yield of 68.8 .mu.g of verbenone and a conversion of 89 .mu.l of verbenol.

Analysis of the oxidation products was performed using 2,000 mm long glass columns, the ton of N-AV-DMCS at 110-250 ° C was 250 ° C, the FID detector was 270 ° C. The standard was dipropyl phthalate / t, v.

by the method of gas chromatography (GLC), diameter 3 π “ ^{11 e with a} charge of 10 .mu.-OV-17 / Chromagradient 10 ° C, min ^- '. The metering temperature and nitrogen flow were 30 rpm, min. 305 ° C.

Physics, 1 not compound constants

compound molecular weight 1.1, t.v. - '° -3 kg.m ^J 20 ⁿ o / - / - alpha-pinane 136.2 - 156 874 1,466c verbone 150.2 - 253 973 1,496 1 oie-verbenol 152.2 70 215 - - trans-verbeno1 152.2 i4 250 965 1.4914

BEFORE THE METHOD OF THE INVENTION

Claims (3)

BEFORE THE METHOD OF THE INVENTION A process for the preparation of verbenone from alpha-pinene by oxidation with a catalyst in the presence of a catalyst and a cocatalyst at a temperature of 5θ to 80 ° C for 4 to 12 hours, characterized in that the reaction takes place in the presence of 0.005 to 0.1 mol of a cobalt complex cobalt salts of a carboxylic acid having 14 to 18 carbons as a catalyst and 0.001 to 0.005 moles of a chromium carboxylic acid having 14 to 18 carbons as a cocatalyst per 1 leg of alpha-pinene in the composition of the cobalt complex Co: Br; pyridine 1 : 1 to 2, 2 to 3. 2, The process is prepared according to claim 1, characterized in that the reaction takes place in the presence of a solvent of a cobalt complex catalyst, such as carboxylic acids, e.g. acetic acid or ioh anhydrides. 3. The process for the preparation of step 2 is characterized in that the reaction is initiated with ozonitriles of carboxylic acids having a carbon number in the molecule of 4 or organic peroxide compounds, preferably cumane hydroperoxide, ethylbenzone hydroperoxide, dibenzoyl peroxide. .