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Novel method for preparing 3-methylene nopinone

A technology of methylene nopinone and nopinone, which is applied in the field of organic synthesis, can solve the problems of harsh experimental environment, long synthesis route, complicated processing, etc., and achieves improved production safety, good product quality, and simplified synthesis The effect of craftsmanship

Inactive Publication Date: 2014-01-08
NANJING FORESTRY UNIV +1
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

[0005] This method has the following disadvantages: in the process of preparing nopinone, the oxidant OsO used 4 Not only the toxicity is high, the price is high, but also two-step oxidation is required, the post-reaction treatment is complicated and the yield is low
[0010] Taking a broad view of the existing bibliographical reports, the techniques for synthesizing 3-methylenenopinone all have different shortcomings at present, and OsO 4 and O 3 Existence of high toxicity and high cost, NaNH 2 , NaOMe, NaOC 2 h 5 Equal hydroxymethylation catalysts need to be used in an anhydrous environment, the experimental environment is harsh, and the entire synthetic route is long

Method used

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  • Novel method for preparing 3-methylene nopinone
  • Novel method for preparing 3-methylene nopinone

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Experimental program
Comparison scheme
Effect test

Embodiment 1

[0029] In a 100ml three-neck flask equipped with a magnetic stirrer, a thermometer and a reflux condenser, add 13.8g (0.10mol) nopinone, 50ml of 30.2% (0.50mol) formaldehyde solution and 5g of NaOH, stir evenly, and control the temperature at 80~90℃, heat and reflux for 4~6h. Through gas chromatography analysis, the conversion rate is about 98.7%. The reaction process was tracked and detected by GC. After the reaction was completed, ethyl acetate was added for extraction three times, and the extracts were combined and washed with saturated brine until neutral. with anhydrous Na 2 SO 4After drying, filter, and recover ethyl acetate by rotary evaporator to obtain light yellow crude product, after separation by silica gel column chromatography [V cyclohexane: V ethyl acetate = 50:3], obtain light yellow product 3-methylene Nopinone, yield 95.5%. The product was analyzed by GC and the purity was 98.1%; the analysis conditions were: 80°C (2min) to 250°C (10min), the heating ra...

Embodiment 2

[0031] In a 100ml three-neck flask equipped with magnetic stirring, a thermometer, and a reflux condenser, add 13.8g (0.1mol) nopinone, 50ml of 15% formaldehyde solution and 6g KOH, stir evenly with a magnetic constant temperature stirrer, and control the temperature at 80~ 90°C, heat to reflux for 8~9h. Through gas chromatography analysis, the conversion rate is about 96.5%. The reaction process was tracked and detected by GC. After the reaction was completed, toluene was added for layered extraction four times, and the extracts were combined and washed with saturated brine until neutral. with anhydrous Na 2 SO 4 After drying, filter, and recover toluene by rotary evaporator to obtain light yellow crude product, after separation by silica gel column chromatography [V cyclohexane: V ethyl acetate = 50:3], obtain light yellow product 3-methylenenopine Ketone, yield 94.8%.

Embodiment 3

[0033] The preparation method of 3-methylene nopinone is the same as embodiment 1, wherein, the consumption of nopinone is 0.1mol, and the consumption of 30.2% formaldehyde solution is 10ml, and the yield of product 3-methylene nopinone is 75.. 3%.

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Abstract

The invention discloses a novel method for preparing 3-methylene nopinone. The method comprises the following steps of: performing aldol condensation on nopinone serving as a raw material and formaldehyde aqueous solution under the catalytic action of NaOH or KOH; and dehydrating to obtain 3-methylene nopinone. Compared with the prior art, the method has the outstanding advantages: the synthesis process of 3-methylene nopinone is simplified, the defect that a target product can only be obtained by performing hydroxyl methylenenation and oxidation steps on nopinone in the conventional synthetic method is overcome, and the disadvantages of the need of using hydroxyl methylenenation catalysts such as NaNH2, NaOM3, NaOC2H5 and the like in the anhydrous environment and severe requirement on the experimental environment existing in the conventional process are overcome. Meanwhile, solid potassium permanganate is taken as an oxidant, so that the defects of high toxicity, high price and the like existing in the conventional oxidants, i.e., OsO4 and O3 are overcome, the production cost of 3-methylene nopinone is reduced, and the production safety is enhanced. The novel method has high practicability, and good economic and social benefits can be generated.

Description

technical field [0001] The present invention relates to the synthetic method of organic matter, be specifically related to a kind of new method of preparing 3-methylene nopinone, this method uses β-pinene as raw material, obtains nopinone through potassium permanganate oxidation, and then NaOH or Under the catalysis of KOH, carry out aldol condensation and dehydration with aqueous formaldehyde solution to obtain 3-methylenenopinone. Background technique [0002] 3-methylenenopinone, the chemical name is 6,6-dimethyl-3-methenylbicyclo[3.1.1]heptan-2-one, the English name is 6,6-dimethyl-3-methylenebicyclo[ 3.1.1] heptan-2-one, molecular formula C 10 h 14 O, with a molecular weight of 150, is a bicyclic monoterpenoid compound, a colorless transparent liquid, slightly soluble in hot water, insoluble in cold water, soluble in ethanol, ether, benzene and other organic solvents, and can be used as an important organic synthesis intermediate or biological Active substances are w...

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): C07C49/653C07C45/75
Inventor 王石发兰蓝杨益琴汪建新谷文曲玲樊媛媛徐晓维魏柏松孟兆杰
Owner NANJING FORESTRY UNIV