Synthesis method of (3Z,6Z)-9,10-epoxy-octadecadiene

A technology of octadecadiene and a synthesis method, applied in the field of pharmaceutical synthesis, can solve the problems of unsuitability for large-scale preparation, high price of natural linolenic acid, etc., and achieves the effects of low cost, simple operation and high yield

Inactive Publication Date: 2019-02-15
CHANGZHOU UNIV +1
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  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

Its disadvantage is that natural linolenic acid is expensive and not suitable for large-scale preparation

Method used

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  • Synthesis method of (3Z,6Z)-9,10-epoxy-octadecadiene
  • Synthesis method of (3Z,6Z)-9,10-epoxy-octadecadiene

Examples

Experimental program
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Effect test

Embodiment 1

[0037] Step 1: Preparation of Undec-2-yn-1-ol

[0038] Embodiment 1: join propynyl alcohol (2g, 35.7mmol) and hexamethylphosphoric triamide (21mL, 107mmol) in anhydrous THF (100mL), under N 2 Under protection, cool down to -78°C, slowly add n-butyllithium (28.6mL, 71.4mmol, 2.5M in hexane), stir for 10min, then add bromooctane (7.5g, 39.3mmol), stir overnight at room temperature . After the reaction was complete, 10 mL of dilute hydrochloric acid was added to quench at 0°C. Extracted with 10% hydrochloric acid and methyl tert-butyl ether (MTBE), washed with saturated brine, collected the organic phase, dried with anhydrous sodium sulfate, and purified by column chromatography to obtain 4.1 g (yield 68%) of brown oily liquid One carbon-2-yn-1-ol. 1 H NMR (300MHz, CDCl 3 ):δ0.85(t,J=6.9Hz,3H),1.24-1.36(m,10H),1.43-1.50(m,2H),2.15-2.21(m,3H),4.21-4.23(m,2H ); 13 C NMR (75MHz, CDCl 3 ): δ14.2, 18.8, 22.7, 28.7, 28.9, 29.2, 29.3, 31.9, 51.3, 78.4, 86.6.

Embodiment 2

[0039] Embodiment 2: join propynyl alcohol (2g, 35.7mmol) and hexamethylphosphoric triamide (21mL, 107mmol) in anhydrous tetrahydrofuran (100mL), under N 2 Under protection, cool down to -10°C, slowly add n-butyllithium (28.6mL, 71.4mmol, 2.5M in hexane), stir for 10min, then add bromooctane (7.5g, 39.3mmol), stir overnight at room temperature . After the reaction was complete, 10 mL of dilute hydrochloric acid was added to quench at 0°C. Extracted with 10% hydrochloric acid and methyl tert-butyl ether (MTBE), washed with saturated brine, collected the organic phase, dried with anhydrous sodium sulfate, and purified by column chromatography to obtain 3 g (yield 50%) of brown oily liquid eleven Carbo-2-yn-1-ol. Compared with embodiment 1, change reaction temperature, other conditions are constant. product of 1 H NMR and 13 CNMR is completely consistent with Example 1.

[0040] Step 2: Preparation of cis-undec-2en-1-ol

Embodiment 3

[0041] Embodiment 3: Ni(OAc)·4H 2 O (6.4g, 25.9mmol) was dissolved in 60mL methanol, under N 2 Under protection, the temperature was cooled to 0°C, sodium borohydride (0.98g, 25.9mmol) was added, and reacted at room temperature for 20 minutes, then 1,2-ethylenediamine (3.2g, 51.8mmol) was added, and undecyl- 2-Alkyn-1-ol (8.7g, 51.8mmol) was added to the reaction solution, and reacted for 5 hours under hydrogen gas. After the reaction was complete, the insoluble matter was removed by suction filtration with diatomaceous earth, the filtrate was extracted with ethyl acetate and water, and the organic phase was collected and dried with anhydrous sodium sulfate. Spin-dry to obtain 7.9 g (90% yield) of cis-undec-2en-1-ol as a light yellow liquid. 1 H NMR (300MHz, CDCl 3 ): δ0.87(t,J=6.9Hz,3H),1.26-1.37(m,13H),2.02-2.10(m,4H),2.02-2.09(m,2H),4.12-4.19(m,2H ),5.49-5.63(m,2H); 13 C NMR (75MHz, CDCl 3 ): δ14.2, 22.8, 27.5, 29.3, 29.4, 29.6, 29.7, 31.9, 58.6, 128.5, 133.2.

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Abstract

The invention discloses a synthesis method of (3Z,6Z)-9,10-epoxy-octadecadiene which is one of tea geometrid sex pheromone components. The synthesis method comprises the following steps: coupling propynyl alcohol with bromooctane to produce undec-2-yn-1-ol, and catalytically hydrogenating the undec-2-yn-1-ol to obtain cis-undec-2-en-1-ol; performing a reaction on the cis-undec-2-en-1-ol and m-chloroperoxybenzoic acid to obtain undec-2,3-epoxy-1-ol; sulfonylating hydroxyl groups of the undec-2,3-epoxy-1-ol by p-methylsufonyl chloride to obtain p-methylsulfonyl ester; performing ring opening onan epoxidized compound under the conditions of tri-tert-butylphosphine and chlorosuccinimide to obtain 3-chloro-2-hydroxyundecyl methanesulfonate, and then performing ring closure under an alkali condition to obtain 3-chloro-1,2-epoxyundecane; then, performing ring opening under the conditions of n-butyl lithium and boron trifluorideetherate, and performing ring closure under the condition of potassium carbonate to obtain 2-octyl-3-(prop-2-yn-1-yl)oxirane; then, obtaining 2-(octane-2,5-diyn-1-yl)-3-octyloxirane under the condition of an iodo coupling reagent; and finally, performing hydrogenation catalysis to obtain a final product. The synthesis method is relatively low in cost, and is suitable for scale preparation.

Description

technical field [0001] The invention relates to a novel synthesis method of a natural product sex pheromone component, in particular to a synthesis method of (3Z,6Z)-9,10-epoxy-octadecadiene, which belongs to the field of drug synthesis. Background technique [0002] my country's tea region has a vast territory, and the ecological characteristics of each region are different. There are many types of tea tree pests, among which tea inchworm is one of the most common and most harmful species in tea garden inchworms. The flood of tea inchworm has brought great loss to tea production. Previously, the prevention and control of tea inchworms mainly used organophosphorus pesticides to kill them. However, due to the extensive use of pesticides, pests have developed resistance to pesticides. Moreover, the pollution of chemical pesticides to the environment and the residues of pesticides in tea are also worrying. In recent years, with the rapid increase of productivity and the contin...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07D301/00C07D303/04
CPCC07D301/00C07D303/04
Inventor 陈新单明伟赵帅
Owner CHANGZHOU UNIV
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