Method for preparing 2,10-epoxypinane

FIELD: organic chemistry, chemistry of terpene compounds.

SUBSTANCE: invention relates to a method for synthesis of 2,10-epoxypinane (β-pinene epoxide). Method involves epoxidation of β-pinene double bond with diluted hydrogen peroxide in an aqueous solution of polar solvents (methanol, N,N-dimethylformamide or acetonitrile) under condition of catalytic effect of manganese sulfate in the presence of sodium hydrocarbonate and salicylic acid. Then epoxide and β-pinene are extracted with aliphatic solvent from the reaction mixture. Polar and aliphatic solvents can be used repeatedly. At final step 2,10-epoxypinane is isolated from crude epoxide by distillation under vacuum with purity degree 95% and the yield 60-70%. Invention provides the development of technological method for synthesis of intermediate compound used in preparing some medicinal, technical and perfume preparations.

EFFECT: improved method of synthesis.

7 ex

 

The invention relates to the field of chemistry terpene compounds, namely to obtain 2,10-emoksipina General formula I:

Compound I can be used to obtain products used as intermediate in the synthesis of various aromatic (fragrant), pharmaceutical and perfumery preparations [Aida L., Villa de P., Dirk E. De Vos et al. Tetrahedron Letters, 1998, 39 8521; Naima Fdil, Abderrahmane Romane, Smail Allaoud et al. J. Molec. Catal. A: Chemical, 1996 108 15], as well as compounds with a sweet taste and low calorie [Li Qian-he, Yin Du-lin, Xiao Yi et al. Ying yong Huaxue 2000, 17, 536].

Another promising use of 2,10-emoksipina is its isomerization in perilly alcohol [DE 3541939A1, 1985; US 5994598A, 1998]. At last discovered the ability to suppress the development of tumors [De Oliveira Bras Heleno, Strapasson H. E. Rogerio Antonio. Braz. Arch. Biol. Technol. 2000, 43 11; Rajesh Deepika, Stenzel On Rachelle A., Howard Steven P. J. Biological Chemistry 2003, 278 35968].

2,10-Emoxypine get epoxydecane β-pinene, which is difficult to epoxidase the olefins [Camile Century Woitiski, Yuriy Kozlov, Dalma Mandelli et al. J. Molec. Catal. A: Chemical, 2004 222 103].

There are several ways of turning β-pinene in epoxide:

1. Oxidation of the double bond with oxygen, catalyzed by a mixture of 15 oxides of rare earth elements in the presence of propionic aldehyde in the solution of ethyl acetate [EP 127911, 1984]. The disadvantages of this method are the low yield of the selectivity (48%), the high cost of the catalyst, the need for the use of some auxiliary reagents phase transfer catalyst and an acid acceptor;

2. The effect of nakilat, such as peracetic [Zhong Xu-dong, Cheng Zhi. Linchan Huaxue Yu Gongye 1993 13 177] and nedosypanija [Laicity, Sagawa, Web and other GOH. 2001. 71. 1233]. The disadvantage of these methods is the use of expensive and hazardous oxidant is peracetic or nodocibozamoo acids. It should also be noted as a disadvantage of the use of equimolar β-pinene amount of acetonitrile, absolute methanol and potassium bicarbonate;

3. The action of hydrogen peroxide in the presence of a twofold excess of dicyclohexylcarbodiimide in an inert atmosphere for 24 hours [George Majetich, Rodger Hicks, Guang-ri sun et al. J. Org. Chem. 1998, 63 2564]. This method of ethnological because dicyclohexylcarbodiimide is laboratory and unsafe reagent is used in large excess, the reaction is carried out in an inert atmosphere; treating the reaction mixture complicated.

As a prototype of the selected epoxidation β-pinene by the action of hydrogen peroxide in the presence of methyltrioxorhenium (MTO) [Aida L., Villa de P., Dirk E. De Vos et al. Tetrahedron Letters, 1998, 39 8521]. The process of epoxidation is carried out at 0°C. the Mixture β-pinene and pyridine (pyridine 42 mol%. from β-pinene) chloride IU Elena is added to the solution MTO 35%hydrogen peroxide. The molar ratio of β-pinene:MTO:N2About2is 1:0.005:1.7.

The disadvantages of this method include the fact that the catalyst methyltrioxorhenium remote and roads, and pyridine - toxic reagent with a sharp odor.

The present invention is to develop a simple, economical, suitable for industrial application of the method of obtaining 2,10-emoksipina. The chemical structure of the solution of the task is the gradual interaction β-pinene with aqueous hydrogen peroxide in an aqueous solution of polar solvent (N,N-dimethylformamide, acetonitrile or methanol) in the presence of a catalytic system consisting of manganese sulfate, sodium bicarbonate and salicylic acid. Next, the reaction mixture is extracted non-polar solvent (petroleum ether, neprasam or hexane) 2,10-Emoxypine together with unreacted β-pinene. The resulting solution is concentrated by evaporation of the solvent. 2,10-emoxypine stands out from concentrate (epoxide raw) vacuum distillation. The outputs of 2.10-emoksipina reach 60-70%. Polar and aliphatic solvents can be reused.

Applying the above catalytic system containing manganese sulfate, sodium bicarbonate and salicylic acid, for epoxidation β-is Innov not described. The novelty of the proposed method to obtain 2,10-emoksipina is that education oxiranes rings in hard epoxidization connection, which is β-pinene, is achieved by the action of a simple, industrially available and non-toxic reagents. Instead of exotic methyltrioxorhenium synthesized on the basis of hard-to-reach rhenium complex technology, it is proposed to use low-cost manganese sulfate and salicylic acid, and instead of toxic and environmentally unfriendly pyridine and methylene chloride - soda solution cheap chlorine-free solvents.

The invention is illustrated by the following examples.

Example 1. Getting epoxide raw in aqueous solution of N,N-dimethylformamide (DMF)

In a glass reactor with mechanical, rapidly rotating stirrer, thermometer and fitting for the fluid fill 3.03 g (21.8 mmol) of β-pinene, 38.5 ml of DMF containing 0.3% water, poured 0.066 g (0.44 mmol) of anhydrous manganese sulfate and 0.12 g (0.87 mmol) of salicylic acid. Within 2.5 hours evenly fed into the reactor cooled mixture of 28.5 ml of a 0.4 molar sodium bicarbonate solution and 17.0 ml of 38% aqueous hydrogen peroxide. The temperature in the reactor is maintained within 18-22°C. Stir the mixture at this temperature for another 15 minutes. The reaction mixture was treated several times with hexane, extras the CT washed with water, dried, the solvent is distilled off in vacuum at temperatures up to 25°C. Obtain 2.52 g of epoxide raw, containing according to a joint analysis methods1H NMR and GC 80% 2,10-emoksipina. The signals in the spectrum of1H NMR: 0.90 (From8H3), 1.24 (9H3), 2.61 AB-system (10H2). Yield 66%. Distilled solvent containing 0.2% β-pinene and 2.10-emoksipina, is used for the extraction of the reaction mixture in the next cycle get epoxide β-pinene.

Example 2. Getting epoxide raw in an aqueous solution of acetonitrile

In the reactor described in example 1 is poured 3.04 g (21.9 mmol) of β-pinene, 39 ml of distilled acetonitrile, fall asleep 0.067 g (0.44 mmol) of anhydrous manganese sulfate and 0.12 g (0.88 mmol) of salicylic acid. Within 3 hours evenly fed into the reactor cooled mixture of 29 ml of a 0.4 molar sodium bicarbonate solution and 19 ml of 35%aqueous hydrogen peroxide, maintaining the temperature in the reactor within 18-22°C. Stir the mixture at this temperature for another 15 minutes. Two-phase reaction mixture is separated, each phase is treated separately. From the upper phase is extracted distilled hexane dissolved substances. The extract is washed with water and dried. The solvent is distilled off in vacuum at temperatures up to 25°C. Obtain 2.11 g of epoxide raw, containing according to the joint is these analysis methods 1H NMR and GC 95% 2,10-emoksipina. The signals in the spectrum of1H NMR: 0.90 (From8H3), 1.23 (9H3), 2.63 AB-system (10H2). The output of 2.10-emoksipina taken on β-pinene was 66%, spent (including return on epoxidation clubbed together with solvent β-pinene) - 74%. Removing the source and target connections from the lower phase of the reaction mixture according to the described scheme allows you to allocate an additional 0.17 g of epoxide raw, contain 59% of the target compounds. The output of 2.10-emoksipina rises to 76% taken up to 87% spent β-pinene.

Example 3. Regeneration of the DMF from the reaction mixture after the extraction from it of epoxide and β-pinene and getting epoxide raw using regenerated DMF

76 g of the Residue after separation of the extract from the reaction mixture of experience described in example 1 was processed for recycling waste DMF. This residue (raffinate) clarify by centrifugation. From the supernatant evaporated in vacuum the water. The remainder lighten again by centrifugation, receiving 31 g of the supernatant liquid, which is used as a solvent in epoxydecane β-pinene.

In the reactor described in example 1, carry out epoxidation with downloads and in the conditions of example 1 using as the organic process is Italia a mixture of 20 ml of fresh and 20 ml of the regenerated DMF. As extractant used nefras with a boiling point 60-80°C. Obtain 2.44 g of a slightly coloured epoxide raw, containing according to the analytical methods of example 1 40% 2,10-emoksipina, yield 35%.

Example 4. Regeneration of acetonitrile from the reaction mixture after the extraction from it of epoxide and β-pinene and getting epoxide raw using regenerated acetonitrile

68 g of the Residue after separation of the extract from the lower phase of the reaction mixture of experience described in example 2 is subjected to bleaching. The resulting solution (65 g) dispersing under atmospheric pressure. The first fraction, autohausaz at a temperature in pairs 75-77° (19 g), is an azeotropic mixture of acetonitrile with water. The second fraction (36 g) is water. Cube (6 g) as a viscous brown liquid.

Repeat the experience described in example 2, using as the organic solvent a mixture of 19.5 ml of acetonitrile and 19.5 ml of azeotropic mixtures obtained. After treatment of the reaction mixture from the upper phase was isolated 1.59 g, from the bottom 0.56 g of epoxide raw. According to the results of a comprehensive analysis by NMR and GC content of the epoxy product from the upper phase 94%, from the bottom of 59%. The total yield of 2.10-emoksipina - 59%.

Example 5. Getting epoxide raw in an aqueous solution of methanol

In the conditions of example 1 at boot β-pinene 1.88 g (13.7 mmol) of the floor is with 1.37 g of epoxide raw containing the results of a comprehensive analysis by NMR and GC-30% 2,10-emoksipina. The signals in the spectrum of1H NMR: 0.90 (C8H3), 1.24 (C9H3), 2.60 AB-system (C10H2). Yield 22%.

Example 6. Vacuum distillation of resin raw

The mixture of epoxides-raw synthesized in examples 1-5, is subjected to distillation at a residual pressure of 5 mm Hg from a flask with a reflux condenser. In the scheme of acceleration establish a cooled trap. The initial mixture contains 12% β-pinene and 83% of the epoxide. Faction β-pinene (fraction 1) is distilled at a temperature in pairs to 45°S, the fraction of epoxide - at temperatures up to 118°With (cube) and 60-40°With (pair). Of 8.8 g of the mixture to obtain 0.7 g of fraction 1 (mainly in the trap), 6.3 g of the desired product containing 96% 2,10-emoksipina, 2% β-pinene and unidentified compounds, and 0.5 g of VAT residue.1H NMR spectrum of the target product corresponds to the range of 2.10-emoksipina. The output of the specified epoxide with rectification of 86%. The total yield per β-pinene was 57%.

Example 7. Vacuum distillation of resin raw

The mixture of epoxides-raw (9.5 g)synthesized in experiments similar to those described in examples 1-5, is subjected to rectification, using the schema of example 6. The residual pressure of 4-5 mm Hg Initial mixture contains 7% β-pinene and 65% of the epoxide. Fraction Argonaut at a temperature of 78° With the cube and up to 45°in pairs. Then, when the temperature in the cube to 117°and in pairs within 50-35°With selected fraction of the epoxide. Fraction 1 and the cube is subjected to re-distilled in the same conditions. The result is 0.9 g pianoboy faction, 6.4 g of epoxy containing 95% 2,10-emoksipina, 3% β-pinene and unidentified components, and 0.5 g of a mixture containing not less than 50% of resin and 0.2 g of the cubic residue.1H NMR spectrum of epoxy fraction corresponds to the range of epoxide β-pinene. The output of the technical product in the distillation of 100%, 100% - 95%. The output is taken in the process β-pinene - 56%, consumed 73%.

The method of obtaining 2,10-emoksipina General formula I

by interacting β-pinene with aqueous hydrogen peroxide in the environment of a solvent and in the presence of a catalyst, wherein the catalyst used manganese sulfate in the presence of sodium bicarbonate and salicylic acid, and the solvent used polar solvent (methanol, N,N-dimethylformamide or acetonitrile).



 

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