Method for preparing thujopsanone under catalysis of MTO

Abstract

The invention discloses a method for preparing thujopsanone 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 the thujopsanone . The MTO is used as the catalyst, so that the thujopsanone 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; and the prepared thujopsanone 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

[0026] Get 6.12g pagodarene (content 68%), 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), and saturated sodium chloride solution (3*50mL) for washing; the organic phase was dehydrated with anhydrous sodium sulfate, the solvent was recovered by distillation, and then rectified under reduced pressure to obtain Arhat The crude product 3.14g of cedrene, gas chromatographic analysis of cedrene content is 81.9%, calculated, cedrene yield is 57.3%, the conversion rate of cedrene is 76.8%; crude product by column chromatography , the purity of 94.6% was obtained, and it was determined to be luohan cedryl ketone by GC-MS characterization.

Embodiment 2

[0028] Get 6.12g pagoda ene (content 68%), 0.018g methyl rhenium trioxide, 0.612g 3-methylpyrazole, 15mL methylene chloride, 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), and saturated sodium chloride solution (3*50mL) for washing; the organic phase was dehydrated with anhydrous sodium sulfate, the solvent was recovered by distillation, and then rectified under reduced pressure to obtain Arhat The crude product 3.53g of cedrene, gas chromatographic analysis of cedrene content is 76.8%, calculated, cedrene yield is 60.4%, the conversion rate of cedrene is 80.7%; crude product is passed through column chromatography , the purity of 93.7% was obtained, and it was determined to be luohancypressanone through GC-MS characteri...

Embodiment 3

[0030] Get 6.12g pagodarene (content 68%), 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), and saturated sodium chloride solution (3*50mL) for washing; the organic phase was dehydrated with anhydrous sodium sulfate, the solvent was recovered by distillation, and then rectified under reduced pressure to obtain Arhat The crude product 3.84g of cedrene, gas chromatographic analysis of cedrene content is 73.2%, calculated, cedrene yield is 62.6%, the conversion rate of cedrene is 81.3%; crude product is passed through column chromatography , the purity of 94.1% was obtained, and it was determined to be luohan cedrynone through GC-MS characterization....

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

[0026] Get 6.12g pagodarene (content 68%), 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), and saturated sodium chloride solution (3*50mL) for washing; the organic phase was dehydrated with anhydrous sodium sulfate, the solvent was recovered by distillation, and then rectified under reduced pressure to obtain Arhat The crude product 3.14g of cedrene, gas chromatographic analysis of cedrene content is 81.9%, calculated, cedrene yield is 57.3%, the conversion rate of cedrene is 76.8%; crude product by column chromatography , the purity of 94.6% was obtained, and it was determined to be luohan cedryl ketone by GC-MS characterization.

Embodiment 2

[0028] Get 6.12g pagoda ene (content 68%), 0.018g methyl rhenium trioxide, 0.612g 3-methylpyrazole, 15mL methylene chloride, 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), and saturated sodium chloride solution (3*50mL) for washing; the organic phase was dehydrated with anhydrous sodium sulfate, the solvent was recovered by distillation, and then rectified under reduced pressure to obtain Arhat The crude product 3.53g of cedrene, gas chromatographic analysis of cedrene content is 76.8%, calculated, cedrene yield is 60.4%, the conversion rate of cedrene is 80.7%; crude product is passed through column chromatography , the purity of 93.7% was obtained, and it was determined to be luohancypressanone through GC-MS characteri...

Embodiment 3

[0030] Get 6.12g pagodarene (content 68%), 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), and saturated sodium chloride solution (3*50mL) for washing; the organic phase was dehydrated with anhydrous sodium sulfate, the solvent was recovered by distillation, and then rectified under reduced pressure to obtain Arhat The crude product 3.84g of cedrene, gas chromatographic analysis of cedrene content is 73.2%, calculated, cedrene yield is 62.6%, the conversion rate of cedrene is 81.3%; crude product is passed through column chromatography , the purity of 94.1% was obtained, and it was determined to be luohan cedrynone through GC-MS characterization....

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