CS268571B1 - Process for the preparation of verbonine - Google Patents

Abstract

Verbena, ^,6,6-triÍJaethylbiocyclo— -(3,1,1)-hopt—3-4n—2-one, is prepared from alpha-pinone by oxidation with oxygen in the presence of a catalyst and a cocatalyst at a temperature of $0 to 80 ° C for 4 to |2 hours in the presence of 0.005 to 0.1 mol of a cobalt complex of the type dlpyridylcobo.lt - dlbromld or cobalt carboxylic acid oil · number of carbons in the molecule 1^1 to 18 as a catalyst'* and 0.001 to 0.005 mol of a large carboxylic acid oil with a number of carbons in the molecule 1^ to 18 as a cocatalyst per 1 kg of alpha-pinene when the composition of the cobalt complex C o ? Ώτ- ■ pyridine 1; 1 to 2 ; 2 to 3 .

Description

EN 268 571 B1 1

The invention relates to epoeobic preparation of verbenaine.

Vorbonine, 4,6,6-trimethylbioyclo [3,1,1] -hept-3-en-2-one, constitutes a detergent component and is used as a perfume component for the preparation of a rosin-aromatic aromatic compound, Recently it was gold that the active S -ol-v-benzene and the (R) -oia-verbenol are important compounds useful as components of the ferromagnetic corona and, moreover, affect the behavior of insect pests.

This is the compound and prepares for reductions of the verbena, which thus remains an important intermediate in production.

Verbena e is prepared by the oxidation of alpha-pinene by various eposobrales, by the oxidation of ootanomic acid in the ootic acid and the advantage of high extracts but also by the disadvantage of its toxioltyco and the problems of waste treatment - Sea K. · Agr. Biol, Chem, 40, 415-8 / 1976 /, CA 84135842, Possibly There is Oxidation in Benzene and Environmental Impairer and Obtained by Trone-Verbenolpo Reoxide and Chromium Oxide in Pyridine Provided by Verbene - Mitsubishi Cham, Ind.

Co., Ltd ,: Jap, vykl. 81 30, 940, CA 95, 15, 956. Oxidation by the use of lead oxide, chromium trioxide or even manganese dioxide It is possible in pyridine, aethane, benzene or else in the art. It is known from Iglesias D., Dora I. A, Retamar J, A, Fssenze Deriv. Agrum. 42, 41-7 (1972), CA 77, 164860, Oxidation of the acid at up to 100 ° C without catalyst gave the products alpha-pinoxide, trans-verbenol and verbene - Moore R, N., Goluro-bio C. , Fischer G, S.1 J, Amer. Chem. Soo. 8, 1173-6 (1956). Similar to air oxidation at 60 DEG-9 DEG C., Bain J.P., Booth A.B., Klein E.A. / Glidden Co, (U.S. Pat. No. 2,863,882 / 1958 /, CA 53, 8194. At temperatures above about 5 ° C, a relatively large amount of mainly resinous products is already formed, at 50 ° C, the desired products are obtained as pre-feeds, in a better extract (Bain J). P, Gary VY / Glidden Co: US Pat., 2,911,442 / 1959 /, CA 55,607. Oxidation with 40 ° C Oxide in the presence of an oleate or cobalt or mongonate oleate as a catalyst has been obtained in up to 40 Suzuki TO.:

Bull, Inst. Phys, Chem. Rea, (Tokyo): 14, 179-81 (1935), CA 0223058, by oxidizing the acid at temperatures of from about 10 ° C to about 40 ° C, in the presence of benzaldehyde and a cobalt acetylene catalyst, verbene is obtained. and recruited in excess of 40% - Romanlohin A.M., Pp.N.I., Prudničhko E.K., Chim, Teohnol. 20, 177-9 (1977) · Oxidation of acid at a temperature of 60 to 65 ° C in the presence of pyridine and cobalt palmitate as catalyst and after reoxidation by carbon monoxide yielded a yield of 33% - Kalvoda L., Vr-J J: Pat , CSSR AO 215,485 (1982), by modifying the process and using dibenzoyl peroxide as an initiator and peroxyacid acid, respectively, was obtained in yields of up to 40%, and the reaction time was reduced from 24 to 18 hours - Collective; Feromans, research report, VCR CR Bratislava 1983 · A mixture of verbenol and verbene - Bohe R, L, Essonze Doriv, Agrum 22 »148-56 / 1983 /, CA 101 also obtained by autoxidation of oxygen at 25 ° C in the presence of naphthenobutobalt catalysts 21.48, Oxidation with oxygen or air at 20 ° C for 20 hours in the presence of a dipyridyldijadazine complex as a catalyst gave a good yield of Hhaduri S., Mahandru. M, / Indian Explosion Co, (Brit, Pat, 2,078,223 (1982), CA 96, 218066, Oxidium Oxygen in the presence of palladium (II) chloride and copper (I) chloride as catalysts with adducts such as lithium chlorides, sodium, potassium and barium) they got a verbale and verbena nvo extract 57 - Strakova V., Dimitrov D, Angolov V, · Dokl, Bolg. Akad, Nauk 37, 767-9 (984), CA 10 1, 2, 1,484. Oxidation at temperatures of 68 to 80 ° C There is perhaps even a thickened konvorzie will increase the extract of products as mentioned in - Dimitrov D., Sirekova V ,, Angelov V ,, Stefan R,: Chim. Ind, (Sofia, 56, 54-56 (1984), CA 101, 38676, Oxidioacetate at 80 ° C using azodiisobutyronitrile / AIBN / as saliskal initiator as well as verbene for products for cosmetic purposes - Pritzkow V, VanTrien V Schmidt-Renner V, Miltitzter Berichte 1982, 17-25. By oxidizing the acid at a temperature of 70 to 80 ° C, using the Νátoraátora as the initiator, in addition to the other products, recruitment is obtained, the main purpose being kinetic measurements and the design of probabilities. mooha-nizmu roakoie - Martinez de la Cuesta P, J., Martinez Martinez Rus,, Garoia Herruzo F.: Ann,

I 2 EN 268 571 D1

Qulm, Ser, A 80, 262-6 (198). Oxidation of oxygen at 50 to 80 ° C for up to 12 hours in the presence of dipyridyl dibromide cobalt as catalyst and A1BN or inorganic oxides in the form of zwitterionic extractants of 10-vortonin and 10-carbonol, with the reoxidation of these oxidizing products at up to 90 ° C. % verbonol springs to verbonone - Kizlink J., Uroneo M, Cvengroi Z ,, Kuruo £., Kriz H., Obladinski A, Ilavnky J. ·. CSSR PV 9112-86.

The alpha-pinene oxidation of the eight-salt lead or triple-salt salts of Jo is disadvantageous in view of the high toxicity of the reagents and thus the waste disposal problems. Oxidation in alkali alkali with cobalt or manganese salts is called. the soaps of the metal are well sucked and yields a good extract of the products, but a considerable amount of harmful organo-alkali bases such as pyridine, ohinoline, tero is present. aminyata. In addition to the friendly work, they also make it difficult for health care workers, In some procedures, there is a considerable economic intensity caused mainly by the liquidation of waste and the operation of technological equipment.

The above drawbacks are partly obstructed by the preparation of the verbonone from alpha-pinene oxide by oxygen in the presence of a catalyst at 50 to 80 ° C for b to 12 hours according to the invention, the reaction being carried out in the presence of 0.005 to 0.01 mole of cobalt dipyridyl co-dibromide complex or a cobalt salt of a carboxylic acid having a carbon number of from 1 to 18 as catalyst and from 0.001 to 0.005 mol of a carboxylic acid salt having a carbon number of from 1 to 18 as cocatalyst per kg of alpha-pinene in the composition of the cobalt complex Co: Brtpyridine 1: 1 and 2: 2 to 3. The reaction catalyst may be in the presence of a solvent of cobalt complex catalyst such as carboxylic acids, e.g. The carboxylic acids can be present in the presence of azonitriles of carboxylic acids with a carbon number in the molecule b or an organometallic peroxide compound, e.g. Thus, a plurality of iiaoxidated pinone is obtained as the so-called frakoia U., which contains verbenone and traium-verenol. The reaction mixture obtained is separated into the fracoi, containing mainly the nonsecrated pinone, which can be re-cycled, and contains mainly oxygen-containing monoterpenes on the fraction of the oxidation products, which can be obtained by distillation under vacuum to give a relatively warm purity of 7%. to 85 for other purposes, e.g., reoxidation and the like.

The fraction of the oxidation products can be reoxidated in an acidic medium with a homogeneous medium in a homogeneous medium at a temperature of 0 to 10 ° C. In this process, the carbon monoxide is converted to verbenone and this can then be recovered from the rectification mixture under a very high purity of 87 to 97%. sufficient for its handling by rodukoia to the desired oisverbenol.

The range of temperatures used is 30 to 90 ° C, preferably about 55 to 65 ° C. In the case of lower temperatures, less product is produced, but the reaction time is too long, when the temperature rises, the proportion of the product components mainly of bituminous character is high and above 80 ° C. The removal of the reactants by a suitable device will favor the course of the reactors. Also, there was a considerable spare space in the reactor for the substantial oxidation of the oxidized pinone, that is to say 5 to 5 times the pinon pinon in the feed. The cobalt complex catalyst used can be prepared by the simple method of J. Chem, Soo. 1963, 5bb9 and cobalt and chromium, respectively, by scavenging the high sodium salt solutions of carboxylic acids with a solution of an inorganic cobalt salt or a cobalt or cobalt, respectively. ohrom. EN 268 571 B1 3 Example 1

Alpha-Pinone Oxidation

Into the oxide reactor in the scanner shape by 800 [mu] m length, at 95 mm / s with an eletrically cut coating, thermometer, cooling coil and possibly with an azeotropic attachment to the water section, and 500 g of filament after the flowing of the rotameter. alpha-pinene / Purity 97 " by GLC. After withdrawing the obsolete reactor at 90-100 [deg.] C. and maintaining the oxygen flow at 20-3 [deg.] 1.h-1a, 2.0 g / 0.005 moles were added sequentially to the reactor bed. Only the long-term cobalt-cobalt-dlbroiumide / PygCoBrg catalyst is known and 1.6 g (0.002 mol) of palmitate compromised 4b o (PoCr) and 50 g ootic acid for better solubility. the majority of the catalyst was dissolved and the temperature was adjusted to 60 ° C and the flow rate of 20 µl of silica was added and 0.9 g (0.0025 mol) of azobisisobutyronitrile (AIBN) was added as an initiator. , allowed to cool to about 30 ° C, poured over and thereafter either the filling of the packed collar (length 1,000 mm, the diameter of 25 mm, the glass or the porcelain Rasohig rings / heated to 110 to 115 ° C or the carbon black in the cone was maintained at 30 minutes) was disrupted present peroxides. After cooling, the reaction mixture was distilled under vacuum (20 torr) for two fractions, fraction I, up to 70 ° C, which contained predominantly unreacted pinene, which was recycled (and fracoium II) to the flask temperature. 180 ° C (containing oxidation products, mainly verbene and trans-verbenol) The distilled residue contains bituminous bituminous substances and catalyst habits. Frakoia II. was then filtered under vacuum using a puncture column and 8 TP. In total, 159 g of unreacted pinone (frakia I.) and 182 g (36.9%) of oxidation products (frakia II./) were obtained, with 58.9 g / 32.1 verbene and 37.1 g / 20 being obtained, 9% / verbenol. Conversion was 68% and selectivity 0.25. Example 2

As in Example 1, a pinene feed was used and at 60 ° C, a catalyst of 5.7 S / 0.0 mol / cobalt / palladium palmitate / PaCo / and a cocaialyser of 1.6 g / 0.002 mol / ohromite / PaCr was used. 5 K triethylamine and 1 ml peroxytoic acid (90%) and 1 ml cumene hydroperoxide (90%) after 10 minutes. After 12 hours of oxidation, the reaction mixture was worked up as in Example 1 to obtain 136 g of unreacted pinene (frakia I) and 227 g (95.9%) of oxalate products (frakia II) from which 63 was obtained, 1 g / 27.8 µg / verbene and 97.0g / 20.7 ° / verbenol. The conversion was 73 and selectivity was 0.27. Example 3

As in Example 1, a pinene feed was used, and at 60 ° C, a catalyst of 5.7 g (0.01 mol / PaCo, 1.6 g / 0.002 mol / PaCr, 6 g triethylamine and initiator was used as the starting material). in Example 2. After 6 hours of oxidation, the temperature was raised to 80 ° C and the oxidase was treated for 2 hours. Thereafter, the reaction mixture was worked up in a manner similar to that of the preceding examples to obtain 109 g of unreacted pinene (frakia I.) and 223 g (99.6) of oxidation products (frakia II) from which 59.0 g / 29 was obtained, 2/2 / verbenone and 99.8 g / 20.1% / verbenol, conversion was 78% and selectivity 0.23. Example 9

Similarly, in Example 1, a pinene feed was used and at 60 ° C, a catalyst of 5.7 g (0.01 mol / PaCo), 1.6 g (0.002 mol) stearate stearate, 5 g trl-phthylmerminine was used at 60 ° C. as in Example 2. After 6 hours of oxidation, the reaction mixture was treated similarly to the previous example and 180 g of unreacted pinene / fractions were obtained.

Claims (3)

4 CS 268 571 B, oia I. / a 190 g / 38 her / oxidation products / fraction II./, of which 55.7 K / 29.3% / verbenone and 48.8 g / 25.7 i were obtained vorbenol, Conversion was 66% and selectivity 0.29. EXAMPLE 5 Reoxidation of Oxidizing Products To a conical flask of 1000 ml volume and a baffle and a heat transfer vessel, 100 g fracoie II, (32.8%) verbenone and 3.7 ml verbenol were weighed. 230 ml of hexane and 180 ml of water were added and the reaction mixture was cooled to 0-5 ° C. Aromatic mixture (38.5 with Cr 2 O 4, 142 ml of water, 58 g of 98% Na 2 SO 4) was added sequentially and thereto, so that the temperature was at a maximum of 10 ° C, then 1 point was added. and separated in a separator, the upper and upper layers were separated and the aqueous layer was extracted with 3 x 100 ml of hexane, the organic layers were combined and washed with 50 ml of 10% aqueous solution and 200 ml of water and dried. filtering off the drying agent and separating the hexane and the deactivating residue and fractionating under vacuum at 20 torr (20 torr) using a small column. Frnkoia to 105 ° C is full, which can be re-cycled. 70 g of crude product (35.4 g of verbenone and 0.4 g of verbenol) were obtained and 24.8 g of verbenone and 0.3 g of verbene were obtained, representing a yield of 68.8 g of verbenone and a variation of 89 of verbenol. The oxidation product analysis was performed by gas chromatography (GLC), using glass columns of 2,000 mm in length, 3 in diameter and 10 in 10 OV-17 / Chromaton N-AV-DHCS at 110 to 250 ° C and a gradient of 10 ° C, min -1. The temperature of the 250 ° C dispenser, the FID detector was 270 ° C and the nitrogen flow rate was 30 µm, min. The dipropyl phthalate (t, 305 ° C) was the standard. i Physics .1 non constants of compounds compound molecular weight 1.1, t.al. rf20 -3 kg.ro 20 / - / - alpha-pinene 136,2 156 874 1,4660 verbenone 150,2 - 253 973,, 496 1 oia-verbenol 152,2 70 215 - - trans-verbeno1 152,2 14 250 965 1.6916 SUBJECT OF THE INVENTION 1, the preparation of verbenone from alpha-pinene by oxygen oxidation in the presence of catalyst and cocatalyst at 50 to 80 ° C starting from 4 to 12 hours, characterized in that the reaction takes place in the presence of 0.005 to 0.1 mole of cobalt dipyridine complex dylcobalt-dibromide alobo cobaltic acid salts of carboxylic acid and carbon atoms in the molecules 14 to 18 as catalysts and 0.001 to 0.005 moles of chromium (II) carboxylic acid and the number of carbons in the molecule of 14 to 18 cocatalyst per kilogram of alpha-pinene for cobalt composition complex Co: Br: pyridine 1: 1 to 2; 2 to 3 » 2, wherein the reaction is carried out in the presence of a solvent of a cobalt complex catalyst, such as carboxylic acids, e.g. 3, the preparation of the stage 2, characterized in that it reacts and activates the ozonitrile carboxylic acid and the number of carbons in the molecule 4 or the organic peroxidio compounds, preferably cumene hydroperoxide, ethylbenzone hydroperoxide, dibenzoyl peroxide.