Synthesis method of aggregation pheromone (E)-cis-6, 7-epoxy-2-nonenal of Aromia bungii

A technology for gathering pheromones and pink-necked beetles, which is applied in the new synthesis field of natural product pheromone components, can solve the problems of harsh conditions, expensive raw materials, unsuitable for industrial production, etc., and achieve the effect of simple operation and mild conditions

Active Publication Date: 2019-04-26
江苏宁录科技股份有限公司
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  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

Its raw material is more expensive, and condition is harsh, is not suitable for industrialized production (K.Mori.Pheromone synthesis.Part 263:Synthesis of the racemate and theenantiomers of (E)-cis-6,7-epoxy-2-nonenal, the male-produced pheromone of the red-necked longhorn beetle, Aromia bungii. Tetrahedron, 2018, 74, 1444-1448)

Method used

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  • Synthesis method of aggregation pheromone (E)-cis-6, 7-epoxy-2-nonenal of Aromia bungii

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0027] Example 1: Add p-toluenesulfonic acid monohydrate (2.3g, 12mmol) to a tetrahydrofuran / dichloromethane mixed solution (220mL) of 1,4-butanediol (13.0g, 144mmol), cool to 0°C, drop Add 3,4-dihydro-2H-pyran (10.8mL, 120mmol), and stir at room temperature for 6h. TLC detection, after the reaction was completed, quenched by adding water, extracted with dichloromethane, combined organic phases, dried over anhydrous sodium sulfate, concentrated under reduced pressure, purified by column chromatography to obtain a colorless liquid 3 (15.56g, yield 75% ). 1 H NMR (400MHz, CDCl 3 ): δ4.53(t, J=3.5Hz, 1H), 3.76-3.81(m, 1H), 3.69-3.73(m, 1H), 3.57(t, J=6.0Hz, 2H), 3.43-3.46( m,1H),3.34-3.37(m,1H),2.98(s,1H),1.72-1.76(m,1H),1.61-1.65(m,5H),1.44-1.53(m,4H); 13 C NMR (100MHz, CDCl 3 ): δ99.8, 67.5, 62.4, 62.3, 30.6, 29.8, 26.4, 25.3, 19.5.

Embodiment 2

[0028] Example 2: Pyridinium p-toluenesulfonate (0.31g, 1.2mmol) was added to a mixed solution of 1,4-butanediol (1.3g, 14.4mmol) in tetrahydrofuran dichloromethane (22mL), and after cooling to 0°C, Add 3,4-dihydro-2H-pyran (1.1 mL, 12 mmol) dropwise and stir at room temperature for 6 h. TLC detection, after the reaction was completed, quenched by adding water, extracted with dichloromethane, combined organic phases, dried over anhydrous sodium sulfate, concentrated under reduced pressure, purified by column chromatography to obtain a colorless liquid 3 (1.5g, yield 70% ). Compared with Example 1, p-toluenesulfonic acid monohydrate was changed to p-toluenesulfonic acid pyridinium salt, and other conditions were unchanged. product of 1 H NMR and 13 CNMR is completely consistent with Example 1.

Embodiment 3

[0029]Example 3: Add p-toluenesulfonic acid monohydrate (0.23g, 12mmol) to a mixed solution of 1,4-butanediol (1.08g, 12mmol) in tetrahydrofuran dichloromethane (22mL), after cooling to 0°C, drop Add 3,4-dihydro-2H-pyran (1.1 mL, 12 mmol), and stir at room temperature for 6 h. TLC detection, after the reaction was completed, quenched by adding water, extracted with dichloromethane, combined organic phases, dried over anhydrous sodium sulfate, concentrated under reduced pressure, purified by column chromatography to obtain a colorless liquid 3 (1.3g, yield 62% ). Compared with Example 1, the equivalent of 1,4-butanediol is reduced, and other conditions remain unchanged. product of 1 H NMR and 13 C NMR is completely consistent with Example 1.

[0030] Step 2: Preparation of 4-((tetrahydro-2H-pyran-2-yl)oxy)butyraldehyde (4)

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Abstract

The invention relates to a synthesis method of aggregation pheromone (E)-cis-6, 7-epoxy-2-nonenal of Aromia bungii, which belongs to the field of pharmaceutical synthesis. The synthesis method comprises the following steps: taking 1, 4-butanediol as a raw material, singly protecting diol with DHP (dihexylphthalate) and then oxidizing TEMPO (tetramethylpiperidine oxide) into 4-((tetrahydro-2H-pyran-2-base) oxy) butyraldehyde; performing a Wittig reaction, so as to obtain (Z)-2-(hepta-4- alkene-1-base-oxy) tetrahydro-2H-pyran; removing the protection of the DHP and oxidizing TEMPO, so as to obtain (Z)-4-heptenal; performing a Wittig reaction, so as to obtain (2E, 6Z)-nona-2, 6-heptadienal; finally, performing epoxidation, so as to obtain the aggregation pheromone (E)-cis-6, 7-epoxy-2-nonenalof the Aromia bungii. The total yield is 6.5%. In the synthesis method, the 1, 4-butanediol with low cost is taken as the starting raw material; the synthesis method has the advantages of being simple in operation and mild in conditions, therefore, the synthesis method is suitable for large-scale preparation.

Description

technical field [0001] The present invention relates to a novel synthetic method of a natural product pheromone component, in particular to a synthetic method of the aggregation pheromone (E)-cis-6,7-epoxy-2-nonenal of the pink-necked longhorn beetle Aromia bungii , which is insect-attractive, non-toxic and harmless, and belongs to the field of drug synthesis. Background technique [0002] The pink-necked longhorn Aromia bungii (Coleoptera: Cyperididae) is a species of wood beetle native to China, Korea, Mongolia, and eastern Russia. It has recently invaded countries such as Japan, Italy, and Germany, and has also been found in countries such as the United States, the United Kingdom, and Australia. It mainly parasitizes trees of the genus Prunus, including some economic fruit trees, such as cherry trees, cherry trees, peach trees, plum trees and apricot trees. It is one of only four species found in the entire world. As with many geranium beetles, the developing larvae fe...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07D303/32C07D301/14
CPCC07D301/14C07D303/32
Inventor 何佳怡陈志立赵帅夏冉吴林盛侯苏童周骏涛陈新
Owner 江苏宁录科技股份有限公司
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