Method for preparing 2,4a,8,8-tetramethyloctahydrocyclopropa[d]naphthalen-3(1H)-one under catalysis of MTO

Abstract

The invention discloses a method for preparing 2,4a,8,8-tetramethyloctahydrocyclopropa[d]naphthalen-3(1H)-one through catalysis of MTO, and belongs to the technical field of synthesis of fine organic chemicals. According to the method, under the action of an MTO catalyst, 3-methylpyrazole is used as an alkaline ligand, and thujopsene is subjected to an oxidation reaction to obtain 2,4a,8,8-tetramethyloctahydrocyclopropa[d]naphthalen-3(1H)-one. The MTO is used as the catalyst, so that the catalyst has good solubility and thermal stability and is green and environment-friendly; 3-methylpyrazole is used as an alkaline ligand, so that side reactions in the reaction are reduced, the selectivity of alkyl ketone is increased, and the yield of a target product is greatly improved; the prepared 2,4a,8,8-tetramethyloctahydrocyclopropa[d]naphthalen-3(1H)-one has sweet fragrance of costustoot and ambergris, is noble and lasting in fragrance and high in stability, has a very good industrial application prospect, and can be used in daily-use essence such as perfume, soap, cosmetic essence and the like.

Description

technical field

[0001] The invention belongs to the technical field of synthesis of fine organic chemicals, and in particular relates to a method for catalyzing the preparation of cypress ketone by using MTO (methyl rhenium trioxide). Background technique

[0002] Mogrosanone is a sesquiterpene ketone compound. It is a colorless to light yellow oily liquid with a very sweet woody and ambergris aroma. The aroma is valuable and long-lasting. It can be used to prepare woody and ambergris It can also be used in the preparation of perfume, leather and tobacco.

[0003] At present, cedrene-based fragrances are mainly oxidized and synthesized from α, β-cedrene, and the obtained cedrene products contain a pungent smell, the animal aroma is not obvious, and the quality is average; Cedaryl ketone has a strong aroma and has valuable aroma characteristics of musk and ambergris. Both cedrene and α, β-cedrene are derived from cedarwood oil, but α, β-cedrene has been studied more in the ...

Examples

Embodiment 1

[0023] Get 6.12g pagodarene, 0.018g methyl rhenium trioxide, 0.612g 3-methylpyrazole, 15mL ethanol, join in the reactor, and 6.8g 30%H 2 o 2 Slowly drop into the reactor, then stirred at 30°C for 3h. After the reaction was completed, the reaction solution was extracted with ethyl acetate (3*50mL); the organic phase was sequentially washed with 10% Na 2 CO 3 solution (3*50mL), deionized water (3*50mL), saturated sodium chloride solution (3*50mL) for washing; the organic phase was dehydrated with anhydrous sodium sulfate, the solvent was recovered by distillation, and finally obtained by vacuum distillation The yield of pedigrinone was 3.14g, and the purity of pedigrinone by gas chromatography was 94.6%, the yield of pedigree ketone was 57.3%, and the conversion rate of cedarene was 76.8%. GC-MS: m / z=220[M] +

Embodiment 2

[0025] Get 6.12g pagodarene, 0.018g methyl rhenium trioxide, 0.612g 3-methylpyrazole, 15mL dichloromethane, join in the reactor, and 6.8g 30%H 2 o 2 Slowly drop into the reactor, then stirred at 30°C for 3h. After the reaction was completed, the reaction solution was extracted with ethyl acetate (3*50mL); the organic phase was sequentially washed with 10% Na 2 CO 3 solution (3*50mL), deionized water (3*50mL), saturated sodium chloride solution (3*50mL) for washing; the organic phase was dehydrated with anhydrous sodium sulfate, the solvent was recovered by distillation, and finally obtained by vacuum distillation 3.53 g of the pedigrinone product were obtained. According to the gas chromatography analysis, the purity of the pedigree ketone was 93.7%, the yield of the pedigree ketone was 60.4%, and the conversion rate of cedrene was 80.7%. GC-MS: m / z=220[M] +

Embodiment 3

[0027] Get 6.12g pagodarene, 0.018g methyl rhenium trioxide, 0.612g 3-methylpyrazole, 15mL ethyl acetate, join in the reactor, and 6.8g 30%H 2 o 2 Slowly drop into the reactor, then stirred at 30°C for 3h. After the reaction was completed, the reaction solution was extracted with ethyl acetate (3*50mL); the organic phase was sequentially washed with 10% Na 2 CO 3 solution (3*50mL), deionized water (3*50mL), saturated sodium chloride solution (3*50mL) for washing; the organic phase was dehydrated with anhydrous sodium sulfate, the solvent was recovered by distillation, and finally obtained by vacuum distillation 3.84g of pedigrinone product was obtained. According to the gas chromatography analysis, the purity of pedigree ketone was 94.1%, the yield of pedigree ketone was 62.6%, and the conversion rate of cedrene was 81.3%. GC-MS: m / z=220[M] +

technical field

[0001] The invention belongs to the technical field of synthesis of fine organic chemicals, and in particular relates to a method for catalyzing the preparation of cypress ketone by using MTO (methyl rhenium trioxide). Background technique

[0002] Mogrosanone is a sesquiterpene ketone compound. It is a colorless to light yellow oily liquid with a very sweet woody and ambergris aroma. The aroma is valuable and long-lasting. It can be used to prepare woody and ambergris It can also be used in the preparation of perfume, leather and tobacco.

[0003] At present, cedrene-based fragrances are mainly oxidized and synthesized from α, β-cedrene, and the obtained cedrene products contain a pungent smell, the animal aroma is not obvious, and the quality is average; Cedaryl ketone has a strong aroma and has valuable aroma characteristics of musk and ambergris. Both cedrene and α, β-cedrene are derived from cedarwood oil, but α, β-cedrene has been studied more in the ...

Examples

Embodiment 1

[0023] Get 6.12g pagodarene, 0.018g methyl rhenium trioxide, 0.612g 3-methylpyrazole, 15mL ethanol, join in the reactor, and 6.8g 30%H 2 o 2 Slowly drop into the reactor, then stirred at 30°C for 3h. After the reaction was completed, the reaction solution was extracted with ethyl acetate (3*50mL); the organic phase was sequentially washed with 10% Na 2 CO 3 solution (3*50mL), deionized water (3*50mL), saturated sodium chloride solution (3*50mL) for washing; the organic phase was dehydrated with anhydrous sodium sulfate, the solvent was recovered by distillation, and finally obtained by vacuum distillation The yield of pedigrinone was 3.14g, and the purity of pedigrinone by gas chromatography was 94.6%, the yield of pedigree ketone was 57.3%, and the conversion rate of cedarene was 76.8%. GC-MS: m / z=220[M] +

Embodiment 2

[0025] Get 6.12g pagodarene, 0.018g methyl rhenium trioxide, 0.612g 3-methylpyrazole, 15mL dichloromethane, join in the reactor, and 6.8g 30%H 2 o 2 Slowly drop into the reactor, then stirred at 30°C for 3h. After the reaction was completed, the reaction solution was extracted with ethyl acetate (3*50mL); the organic phase was sequentially washed with 10% Na 2 CO 3 solution (3*50mL), deionized water (3*50mL), saturated sodium chloride solution (3*50mL) for washing; the organic phase was dehydrated with anhydrous sodium sulfate, the solvent was recovered by distillation, and finally obtained by vacuum distillation 3.53 g of the pedigrinone product were obtained. According to the gas chromatography analysis, the purity of the pedigree ketone was 93.7%, the yield of the pedigree ketone was 60.4%, and the conversion rate of cedrene was 80.7%. GC-MS: m / z=220[M] +

Embodiment 3

[0027] Get 6.12g pagodarene, 0.018g methyl rhenium trioxide, 0.612g 3-methylpyrazole, 15mL ethyl acetate, join in the reactor, and 6.8g 30%H 2 o 2 Slowly drop into the reactor, then stirred at 30°C for 3h. After the reaction was completed, the reaction solution was extracted with ethyl acetate (3*50mL); the organic phase was sequentially washed with 10% Na 2 CO 3 solution (3*50mL), deionized water (3*50mL), saturated sodium chloride solution (3*50mL) for washing; the organic phase was dehydrated with anhydrous sodium sulfate, the solvent was recovered by distillation, and finally obtained by vacuum distillation 3.84g of pedigrinone product was obtained. According to the gas chromatography analysis, the purity of pedigree ketone was 94.1%, the yield of pedigree ketone was 62.6%, and the conversion rate of cedrene was 81.3%. GC-MS: m / z=220[M] +

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