Method for synthesizing violet dienone with homogeneous phase reaction and heterogeneous phase separation

A technology of ionodienone and ionone, which is applied in the synthesis of ester derivatives and ketone-substituted α-ionone, can solve the problems of unfavorable economy and environment, the catalyst cannot be recovered and can only be treated as waste liquid, etc. The effect of recycling, quantity reduction, and volume reduction

Inactive Publication Date: 2010-06-09
CHINA TOBACCO GUIZHOU IND +1
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

And when the catalyst consumption of use is 10~20% of substrate amount, the time required for reaction is shorter, but because copper salt is made catalyzer when aftertreatment promptly adds 10% sodium sul...

Method used

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  • Method for synthesizing violet dienone with homogeneous phase reaction and heterogeneous phase separation
  • Method for synthesizing violet dienone with homogeneous phase reaction and heterogeneous phase separation
  • Method for synthesizing violet dienone with homogeneous phase reaction and heterogeneous phase separation

Examples

Experimental program
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Effect test

Embodiment 1

[0098] Example 1, add 5mol α-ionone and its ester, g pyridinium ionic liquid, 0.01mol copper chloride in a 25ml reactor equipped with a stirrer and a condenser, keep the temperature at 40°C, and add tert-butyl dropwise under stirring After 20 hours of reaction, butanol and unconsumed tert-butyl hydroperoxide were distilled off under reduced pressure, and diethyl ether was added for solid-liquid extraction. Extraction was carried out for ~10 times with 5ml each time, filtered, combined extracts, and reduced Concentrate under reduced pressure to remove the solvent, and then use silica gel column chromatography to separate (eluent V 石油醚 :V 乙酸乙酯 =4:1), 2.50~2.6mol of 3-keto-α-ionone and its ester were obtained, and the yield was 50~52%. Or combine the extracts, concentrate under reduced pressure to remove the solvent, and rectify under reduced pressure to obtain 2.40-2.50 mol of the product 3-keto-α-ionone and its ester, with a yield of 48-50%. The filter cake was distilled at 5...

Embodiment 2

[0099] Example 2, add 5mol α-ionone and its ester, 5g pyridinium ionic liquid, 0.01mol copper chloride into a 25ml reactor equipped with a stirrer and a condenser, keep the temperature at 80°C, and add tert-butyl dropwise under stirring After 20 hours of reaction, distill out butanol and unconsumed tert-butyl hydroperoxide under reduced pressure, add ether for solid-liquid extraction, extract 6-10 times with 5ml each time, filter, and combine the extracts, Concentrate under reduced pressure to remove solvent, and then use silica gel column chromatography to separate (eluent V 石油醚 :V 乙酸乙酯 =4:1), to obtain 3.05~3.15mol of 3-keto-α-ionone and its ester, and the yield was 61~63%. Or combine the extracts, concentrate under reduced pressure to remove the solvent, and rectify under reduced pressure to obtain 2.95-3.05 mol of the product 3-keto-α-ionone and its ester, with a yield of 59-61%. The filter cake was distilled at 50°C to remove the residual extractant ether, and dried in ...

Embodiment 3

[0100] Embodiment 3, in the 25ml reactor that stirrer and condenser tube are equipped with, add 5mol with the ether of α-ionone and the ether of β-ionone or its ester, 5g pyridinium ionic liquid, 0.2mol cobalt chloride at 50 ℃, add 1-2 mol of tert-butyl hydroperoxide dropwise under stirring, react for 0.3h-1h, distill off butanol and unconsumed tert-butyl hydroperoxide under reduced pressure, add diethyl ether for solid-liquid extraction, extract 6-10 Use 5ml each time, filter, combine the extracts, concentrate under reduced pressure to remove the solvent, and then separate with silica gel column chromatography (eluent V 石油醚 :V 乙酸乙酯 =4:1), to obtain 2.15-2.25mol of the ether of 3-keto α-ionone and the ether of β-ionone or its ester, with a yield of 43-45%. Or combine the extracts, concentrate under reduced pressure to remove the solvent, and rectify under reduced pressure to obtain 2.05-2.15 mol of the product 3-keto-α-ionone and its ester, with a yield of 41-43%. The filter...

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Abstract

The invention provides a method for transforming alpha-irisone, beta-irisone and ether and ester derivatives thereof into relevant ketenes, and then forming keto-alpha-irisone, keto-beta-irisone and ether and ester derivatives thereof by using pyridinium ionic liquid as a reaction medium, a simple copper salt or manganese salt or cobalt salts as a catalyst and tert-butyl hydroperoxide as an oxidant,. The catalyst and the reaction medium in the method can be recycled, and the method has the characteristics that the unique phase changes are presented along with reaction and separation, and the method has good selection and high yield when the reaction is carried out in homogeneous phases, and is convenient for operation and the recycling of the catalyst and the reaction medium when the separation is carried out in heterogeneous phase. Therefore, the method for synthesizing the keto-alpha-irisone, the keto-beta-irisone and the ether and ester derivatives thereof is an efficient and environmental-friendly method having the characteristics of high-efficiency reaction of the homogeneous phases and convenient separation of the heterogeneous phase.

Description

technical field [0001] The invention relates to a method for synthesizing ketone α-ionone, β-ionone and ether and ester derivatives thereof. In particular, it involves recyclable and reusable reaction medium and catalyst, has the characteristics of homogeneous high-efficiency reaction, heterogeneous and convenient separation, and forms ketone-substituted α-ionone, keto-substituted β-ionone and its ether and ester derivatives. method. Background technique [0002] α-ionone, β-ionone and their ether and ester derivatives are important fragrance components of natural aromatic plants such as osmanthus, violet, passion flower, tea, tobacco, etc., and are widely used in fine chemicals, pharmaceuticals and In the fragrance industry, the oxidation of the allylic position of the cyclohexene structure (and the oxidation of the 3rd position and the 4th position) can not only introduce the active group of carbonyl for further derivation to other compounds, but more importantly, this ki...

Claims

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Application Information

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IPC IPC(8): C07B41/06C07C69/145C07C67/29C07C45/28C07C49/647C07C49/753
CPCY02P20/584
Inventor 彭黔荣杨敏谢如刚白云峰刘钟祥惠建权
Owner CHINA TOBACCO GUIZHOU IND
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