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Method for synthesizing sex pheromone of carposina niponensis

A technology of peach borer and synthetic method, which is applied in the direction of organic chemical methods, chemical instruments and methods, and the preparation of organic compounds, and can solve problems such as expensive reagents, lengthy reaction routes, and harsh reaction conditions

Active Publication Date: 2019-07-05
CHINA AGRI UNIV
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

[0010] Although some progress has been made in the synthesis of the sex pheromone of the peach borer, there are still some problems, such as: lengthy reaction route, harsh reaction conditions, expensive reagents, etc.

Method used

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  • Method for synthesizing sex pheromone of carposina niponensis

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0029] Synthesis of 1-tetrahydropyranyloxy-3-bromopropane 2

[0030] At room temperature, add dichloromethane (200 mL) and p-toluenesulfonic acid (1.72 g, 10 mmol) into a 500 mL round bottom flask, stir to dissolve. Then 3-bromo-1-propanol (13.90g, 100mmol) and 2,3-dihydropyran (12.60g, 150mmol) were added successively, and the reaction was stirred for 12h. After the reaction was completed, water was added to quench, and the organic phase was separated. The aqueous phase was extracted with dichloromethane (3 x 100 mL), and the organic phases were combined. The organic phase was washed with saturated NaCl aqueous solution, washed with anhydrous NaCl 2 SO 4 Dry and concentrate under reduced pressure to obtain crude product. Finally, it was purified by silica gel column chromatography (petroleum ether / ethyl acetate 30:1) to obtain yellow-green oily liquid 1-tetrahydropyranyloxy-3-bromopropane 2 (19.68 g, yield 88%). 1 H NMR (300MHz, CDCl 3)δ4.67(dd,J=12.5,3.5Hz,1H),3.84–3.7...

Embodiment 2

[0032] Synthesis of 1-tetrahydropyranyloxy-4-undecyne 3

[0033] Under argon protection, add anhydrous tetrahydrofuran (100 mL) and 1-octyne (8.82 g, 80 mmol) into a 200 mL Schlenk reaction flask, and stir to dissolve. The temperature of the mixture was cooled to -40°C, and n-butyllithium (39.0 mL, 2.4M n-hexane solution, 88 mmol) was slowly added dropwise, and stirred for 4 h after the drop was completed. Then HMPA (6.83 mL, 80 mmol) was slowly added dropwise, and the reaction was stirred for 0.5 h. 1-Tetrahydropyranyloxy-3-bromopropane 2 (8.92 g, 40 mmol) was added dropwise, and after the addition was completed, the temperature was slowly raised to room temperature to continue the reaction for 24 h. After the reaction was completed, the reaction was quenched with saturated aqueous ammonium chloride solution, and the organic phase was separated. The aqueous phase was extracted with ether (3 x 80 mL), and the organic phases were combined. The organic phase was washed with s...

Embodiment 3

[0035] Synthesis of (Z)-1-tetrahydropyranyloxy-4-undecene 4

[0036] At room temperature, nickel acetate tetrahydrate (4.69 g, 26.5 mmol) was added into a 250 mL reaction flask. Vacuumize the reaction flask and fill it with hydrogen gas, slowly drop into ethanol solution of sodium borohydride (1.00 g, 26.5 mmol), and stir for 1 h. Then ethylenediamine (6.38g, 106mmol) was added dropwise, and after stirring for 10min, 1-tetrahydropyranyloxy-4-undecyne 3 (6.71g, 26.5mmol) was added dropwise, and the stirring reaction was continued for 8h. After the reaction was completed, it was concentrated under reduced pressure, the mixture was extracted with ether, and washed with anhydrous Na 2 SO 4 Dry and concentrate under reduced pressure to obtain crude product. Finally, it was purified by silica gel column chromatography (petroleum ether / ethyl acetate 50:1) to obtain light yellow oily liquid (Z)-1-tetrahydropyranyloxy-4-undecene 4 (6.62g, yield 98 %). 1 H NMR (300MHz, CDCl 3 )δ5....

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Abstract

The invention belongs to the technical field of green pesticide synthesis, and discloses a new method for synthesizing sex pheromone of carposina niponensis. According to the method, 3-bromo-1-propanol serves as an initial raw material, alcoholic hydroxyl groups are protected first, and THP protected bromhydrin is obtained; then, the THP protected bromhydrin and 1-octyne are coupled to obtain THPprotected alkynol; hydrogenation reduction is carried out under the catalysis of nickel acetate and sodium borohydride to obtain THP protected Z type enol; then, deprotection and PDC oxidation are carried out to obtain Z type olefine aldehyde; finally, the Z type olefine aldehyde and N-octylmagnesiumromide or N-nonylmagnesiumromide are subjected to an addition reaction and PDC oxidation, and the target product sex pheromone of the carposina niponensis is obtained, namely (Z)-13-eicosylene-10-one and (Z)-12-nonadecene-9-one. According to the method, a triple bond is subjected to hydrogenation reduction under the catalysis of the nickel acetate and the sodium borohydride to construct a Z type double bond, reaction conditions are mild, and the method is environmentally friendly.

Description

technical field [0001] The invention belongs to the technical field of green pesticide synthesis, and in particular relates to a new method for synthesizing the sex pheromone of the peach borer. Background technique [0002] The small peach borer (Carposina niponensis Walsingham) belongs to the family Lepidoptera and is mainly harmful to various fruit trees such as peaches, apples, pears, hawthorns, jujubes, and plums (Liu Wanda; Zhao Weibei Horticulture 2011, 135-136. Yu Guang Wei; Zhang Wei Modern Agricultural Science and Technology 2015, 130-131.). The sex pheromone of the peach borer has the biological activity of attracting male moths (Liu Mengying; Zeng Kaonong; Yan Zhongzhong Insect Knowledge 1980, 120-122.), and is widely used in population monitoring, trapping and interfering mating of such pests (Liu Mengying; Su Xiping; Yan Zhongcheng; Yao Ying Biological Control Bulletin 1990, 184. Yin Helong; Liu Xianqian; Ma Ruiyan Forestry Practical Technology 2010, 33-34. Li...

Claims

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Application Information

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IPC IPC(8): C07C49/203C07C45/68C07D309/12C07C33/025C07C29/10C07C47/21C07C45/29
CPCC07B2200/09C07C29/10C07C45/004C07C45/292C07C45/68C07C49/203C07D309/12C07C33/025C07C47/21
Inventor 钟江春孙效边庆花王敏周云袁谷城
Owner CHINA AGRI UNIV
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