A kind of synthetic method of piperonone

A synthetic method and technology of piperonone, applied in the field of synthesis of piperonone, can solve the problems of difficult starting materials, toxicity, high cost, etc., and achieve the effects of improving the three wastes, improving operating conditions, and mild reaction conditions

Active Publication Date: 2015-09-09
SHANGHAI WANXIANG FLAVORS & FRAGRANCES
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

[0008] In the relevant synthetic methods, either starting materials that are difficult to obtain, or toxic raw materials and intermediates are used, which makes the cost quite high or the environmental protection and safety problems are prominent, and the practicability is not strong

Method used

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  • A kind of synthetic method of piperonone
  • A kind of synthetic method of piperonone
  • A kind of synthetic method of piperonone

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0030] Synthesis of 3-isopropyl-3-buten-2-one (II)

[0031] Install an electric stirring device on a 2000ml four-necked bottle and place it in a water bath, and install a thermometer and a gas absorption device.

[0032] Add 1000g of methyl isobutyl ketone to a 2000ml three-necked flask under stirring, cool in a cold bath to -5°C, and pass in dry hydrogen chloride for 20 minutes while stirring; then pass in formaldehyde produced by the decomposition of 68g of paraformaldehyde for about 3 hours finished. Keep hydrogen chloride flowing slowly and steadily. Stir for 16 hours. The product was washed with 10% sodium hydroxide solution, 200mlx3; washed with 8% sodium sulfate aqueous solution until neutral; dried over anhydrous sodium sulfate.

[0033] 30g of white oil and 30g of quinoline were added to the material; excess methyl isobutyl ketone was distilled off by water ring pump vacuum distillation. Collect 65-68°C / 2000Pa. Yield 47%.

Embodiment 2

[0035] Synthesis of 2-acetyl-4-isopropyl-5-oxo-hexanoic acid methyl ester (III)

[0036] Install an electric stirring device on a 1000ml three-necked flask and place it in a water bath, add 126g of methyl acetoacetate, 200g of methanol, and 6g of 30% methanol solution of sodium methoxide; keep the reaction temperature below 25°C in the water bath; add 112g of 3-iso Propyl-3-buten-2-one was added dropwise in about 2 hours. The reaction was continued for 18 hours while maintaining the reaction temperature below 30°C. Gas chromatography detected that the reaction was complete. Add 2.4 g of glacial acetic acid. Methanol was recovered at normal pressure; 85-90°C / 1mm was collected by vacuum distillation to obtain 2-acetyl-4-isopropyl-5-oxo-hexanoic acid methyl ester, 178.5g (75%).

Embodiment 3

[0038] Synthesis of Methyl Piperonone Carboxylate (IV)

[0039] Install an electric stirring device on a 2000ml three-necked flask and place it in a water bath, add 10g of 30% sodium methoxide methanol solution, 600g of toluene, and distill out the methanol; cool to 50°C, add dropwise 45g of 2-acetyl-4-isopropyl - Methyl 5-oxo-hexanoate, the dropwise addition was completed in about 3 hours; continue to stir at 50-55°C for 12 hours, and the reaction was detected by gas chromatography until the reaction was complete. Cool, add 3.4g of glacial acetic acid to neutralize, and wash with 100ml of saturated brine. The upper oily phase was separated. The oil phase was recovered toluene under reduced pressure with a water ring pump; the crude product was 42g.

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Abstract

The invention discloses a synthesis method for piperitone. The synthesis method comprises the following steps: A: taking methyl isobutyl ketone as a raw material to react with formaldehyde under the catalysis of hydrogen chloride to obtain 3-isopropyl-3-butene-2-ketone; B: carrying out Michael addition on the 3-isopropyl-3-butene-2-ketone and acetyl acetate under the effect of an alkaline catalyst to obtain a 2-acetyl-4-isopropyl-5-oxo-methyl caproate intermediate; C: carrying out intramolecular aldol condensation on the 2-acetyl-4-isopropyl-5-oxo-methyl caproate intermediate under an alkaline condition to obtain a carboxylic ester of the piperitone; D: carrying out hydrolysis and acidification decarboxylation on the carboxylic ester of the piperitone under the alkaline condition to obtain the piperitone. According to the synthesis method, a synthesis route uses conventional chemical raw materials and a reaction condition is moderate; related synthesis steps are classic methods. The three-waste condition and the operation condition are greatly improved so that the synthesis method is a novel synthesis route.

Description

technical field [0001] The invention belongs to the field of organic synthesis, and in particular relates to a synthetic method of piperonone. Background technique [0002] As a naturally occurring cyclic terpene ketone, piperonone (formula I) is one of the characteristic components of peppermint oil; it also exists in Asian peppermint oil and peppermint oil; it has a camphor-like smell, spicy peppermint flavor. It can be applied to the formulation of daily chemical flavors, and it is also used in beverages, ice cream, candies and baked goods. It is also used in the preparation of menthone, menthol and its sulfur derivatives. Therefore, its synthetic method has always attracted attention. [0003] [0004] Khimiya Prirodnykh Soedinenii, Nos.3,4, pp.335–338, May–August, 1992. reported a synthetic method of piperonone published by V.V.Bazyl′chik, etc., using expensive thymol methyl ether As the starting material, under the action of lithium metal and ethylenediamine-iso...

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): C07C49/603C07C45/65
CPCC07C45/676C07C45/75C07C67/327C07C67/347C07C2601/16C07C49/603C07C69/757C07C69/716C07C49/203
Inventor 黄战鏖侯峰陈文杰张长征钱正刚裴继红
Owner SHANGHAI WANXIANG FLAVORS & FRAGRANCES
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