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Novel method for preparing 6,6-dimethylbicycol[3.1.1]heptane-2, 3-dione

A technology of pinedione and a new method, which is applied in the field of preparing 2,3-pinedione, can solve the problems of poor selectivity of pine carvone, difficulty in large-scale application, high ozone toxicity, etc., and achieves simple preparation, low cost, and high-quality products. good quality effect

Inactive Publication Date: 2013-05-08
NANJING FORESTRY UNIV
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

[0005] This method pine carvone selectivity is poor, and the yield is low, only about 16%, and the reagent SeO used 2 and ozone are highly toxic and easy to explode; the reaction process of preparing 2,3-pinedione by oxidation of pine carvone must be carried out at ultra-low temperature, and the reaction time is as long as 72h, which makes it difficult to apply this method on a large scale
Kulhánek and others also use β-pinene as raw material, but their synthesis method is completely different from that of Christophe

Method used

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  • Novel method for preparing 6,6-dimethylbicycol[3.1.1]heptane-2, 3-dione
  • Novel method for preparing 6,6-dimethylbicycol[3.1.1]heptane-2, 3-dione
  • Novel method for preparing 6,6-dimethylbicycol[3.1.1]heptane-2, 3-dione

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Experimental program
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Effect test

Embodiment 1

[0036] Add 0.01mol of 3-methylenenopinone, 20mL of solvent acetone, and 2mL of deionized water into a 100mL four-neck flask equipped with a stirrer, thermometer, and reflux condenser. The finely ground potassium permanganate was added in about 30 minutes. After the addition was completed, the reaction was maintained at 5°C for 6 hours, and the reaction progress was tracked and detected by GC. After the reaction, the MnO was removed by filtration through a sand core funnel. 2 , and the solid residue was washed with acetone (2 x 20 mL). Acetone was recovered with a rotary concentrator, and the residue was dissolved in ethyl acetate, washed with saturated brine until neutral, and washed with anhydrous Na 2 SO 4 The organic layer was dried, and ethyl acetate was evaporated with a rotary evaporator to obtain a yellow liquid. After separation by silica gel column chromatography V (dichloromethane): V (methanol) = 50:1, a light yellow liquid was obtained, and then 1.14 g of light ...

Embodiment 2

[0038] Add 0.02mol of 3-methylenenopinone, 40mL of solvent acetone, and 4mL of deionized water into a 100mL four-neck flask equipped with a stirrer, thermometer, and reflux condenser. Cool in an ice bath, and add 0.06mol of Finely ground potassium permanganate, reacted at 15°C for 6 hours after the addition was completed, and tracked and detected the reaction progress with GC. After the reaction, the MnO was removed by filtration through a sand core funnel. 2 , and the solid residue was washed with acetone (2 x 20 mL). Acetone was recovered with a rotary concentrator, and the residue was dissolved in ethyl acetate, washed with saturated brine until neutral, and washed with anhydrous Na 2 SO 4 The organic layer was dried, and ethyl acetate was evaporated with a rotary evaporator to obtain a yellow liquid. After separation by silica gel column chromatography V (dichloromethane): V (methanol) = 50:1, a light yellow liquid was obtained, and then crystallized by methanol to obta...

Embodiment 3

[0040] The method for preparing 2,3-pinedione by oxidation of 3-methylenenopinene is the same as in Example 1, wherein the consumption of 3-methylenenopinene is 0.02mol, potassium permanganate 0.04mol, acetone 40mL, water 2 mL, reaction temperature 0°C, reaction time 3 h, 1.25 g of 2,3-pinedione was obtained with a yield of 41.14%.

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Abstract

The invention discloses a novel method for preparing 6,6-dimethylbicycol[3.1.1]heptane-2, 3-dione. According to the method, through taking beta-pinene as a raw material, taking acetone as a solvent and taking acidic potassium permanganate as an oxidant, beta-pinene is subjected to selective oxidation so as to generate nopinone; through taking KOH as a catalyst, 37% formaldehyde solution as a hydroxymethylation reagent is subjected to continuous hydroxymethylation-digestion reaction with nopinone so as to generate 3-methylene nopinone; and through taking potassium permanganate as an oxidant and adopting an acetone-water mixed solvent, 3-methylene nopinone is subjected to selective oxidation so as to generate 6,6-dimethylbicycol[3.1.1]heptane-2, 3-dione. The method has the outstanding advantages that the synthetic process of 6,6-dimethylbicycol[3.1.1]heptane-2, 3-dione is simplified, the defects of the traditional method that used reagents such as SeO2 and ozone are large in toxicity, explosion is easily caused, reaction time is long, energy consumption is large due to too low reaction temperature and the like are overcome, the production cost of 6,6-dimethylbicycol[3.1.1]heptane-2, 3-dione is reduced, and the production safety is improved, therefore, the method has good practicability.

Description

technical field [0001] The invention relates to a method for synthesizing organic matter, in particular to a new method for preparing 2,3-pinedione. Background technique [0002] 2,3-pinedione, the chemical name is 6,6-dimethylbicyclo[3.1.1]heptane-2,3-dione, the English name is 6,6-dimethylbicyclo[3.1.1]heptane-2, 3-dione, the molecular formula is C 9 h 12 o 2 , with a molecular weight of 152, is a yellow crystal, slightly soluble in hot water, insoluble in cold water, soluble in ethanol, ethyl acetate, toluene and other organic solvents, is an important organic synthesis intermediate, and also an important biologically active substances. 2,3-pinedione reacts with diazomethane to generate a-epoxyketone active monomer with high reactivity; 2,3-pinedione is also an important chiral ligand for the synthesis of new Double helixene; 2,3-pinedione reacts with hydroxylamine and primary amine, and then cyclizes with aldehyde to generate cyclic terpene-based imidazole derivativ...

Claims

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Application Information

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IPC IPC(8): C07C45/28C07C49/433
Inventor 杨益琴王石发徐徐曲玲鲍明凯吴君彭晗牛丹丹
Owner NANJING FORESTRY UNIV
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