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Synthesis of conjugated diene pheromones and related compounds

A technology of conjugated dienes and dienes, applied in the field of synthesis of conjugated diene pheromones and related compounds

Pending Publication Date: 2021-08-17
PROVIVI
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

The preparation of conjugated diene pheromone compounds in which the alkene geometry is controlled at both positions remains particularly challenging

Method used

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  • Synthesis of conjugated diene pheromones and related compounds
  • Synthesis of conjugated diene pheromones and related compounds
  • Synthesis of conjugated diene pheromones and related compounds

Examples

Experimental program
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preparation example Construction

[0089] A. Preparation of Starting Materials

[0090] In some embodiments, the alkene has a structure according to Formula Va:

[0091]

[0092] where R 1a is C 1-6 Acyl (eg, acetyl). In some embodiments, the olefin is a terminal olefin, wherein R 3a and R 3b It is H. In some embodiments, the olefin is an internal olefin, wherein R 3a and R 3b At least one of is an alkyl group. can be obtained by acylating the corresponding enol with an acylating agent (for example, a compound of formula Va, where R 1a , R 3a and R 3b is H) to prepare acylated olefins. Any acylating agent suitable for forming an acylated olefin according to Formula Va can be used in the methods provided herein. Examples of suitable acylating agents include acid anhydrides (e.g., acetic anhydride), acid chlorides (e.g., acetyl chloride), activated esters (e.g., pentafluorophenyl esters of carboxylic acids) and coupling agents such as dicyclohexylcarbodiimide or Carboxylic acid used with carbonyld...

Embodiment 1

[0159] Embodiment 1. the synthesis of oct-7-en-1-yl acetate (7-OAc)

[0160] Under an inert atmosphere, a vessel was charged with oct-7-en-1-ol (1 molar equivalent) and a catalytic amount of anhydrous sodium acetate (0.1 molar equivalent). The suspension was stirred and heated to ~55°C. Acetic anhydride (1.2 molar equivalents) was added to the mixture over about 1 hour at a rate such that the reaction temperature did not exceed 60°C. The mixture was stirred for an additional hour at -60°C, then allowed to cool to ambient temperature. The crude mixture was washed once with one reaction volume of deionized (DI) water, twice with one reaction volume of saturated sodium carbonate solution, and finally twice with one reaction volume of DI water. The crude mixture was then dried via azeotropic distillation with toluene at -45°C and 15 torr to give a pale yellow oil. The oil was then purified by vacuum distillation to give the final product in ~85-90% molar yield and ~93% overall ...

Embodiment 2

[0161] Example 2. Synthesis of E-9-oxononon-7-en-1-yl acetate via cross-metathesis of 7-OAc and crotonaldehyde

[0162] Under an inert atmosphere, a vessel was charged with 7-OAc (200 g, 1 molar equiv) and freshly distilled crotonaldehyde (2 molar equiv). Inert gas was introduced under agitation through a cannula below the feed surface, with the outlet directed first through a -10°C condenser and finally through a silicone oil bubbler. Metathesis Catalyst ) Ruthenium(II) (0.015 mol % relative to all starting materials) was added as a solution in toluene. Propylene gas evolution was observed immediately and slowly subsided over the next two hours. The progress of the reaction was monitored by GC-FID analysis of an aliquot of the reaction mixture. The conversion of 7-OAc in all products was determined to be >80 mole%, the E-selectivity at the 7-position >97%, and the selectivity of conjugated aldehydes to other metathesis co-products >85%. Excess crotonaldehyde was stripped ...

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Abstract

Methods for preparing conjugated dienes are described. An alpha, beta-unsaturated E olefin intermediate may be prepared via cross-metathesis using a catalyst comprising a transition metal (e.g., ruthenium), a first carbene ligand (e.g., a substituted indenylidene) and an N-heterocyclic carbene ligand (e.g., an imidazolidinylidene). The catalyst further includes a phenylphosphine ligand, a tri(isopropoxy)phosphine ligand, a dimethylsulfoxide ligand, an acetonitrile ligand, or a pyridine ligand. Following the cross metathesis-step, the alpha, beta-unsaturated aldehyde intermediate may be converted to the conjugated diene product via reaction with a phosphonium ylide. Products obtained via the methods of the disclosure include (7E,9Z)-dodeca-7,9-dien-1-yl acetate, a pheromone produced by Lobesia botrana (European grapevine moth), and other insect pheromones.

Description

[0001] Cross References to Related Applications [0002] This application claims priority to U.S. Provisional Patent Application No. 62 / 777,680, filed December 10, 2018, which is hereby incorporated by reference in its entirety. [0003] Background of the invention [0004] Insect infestation is a major cause of crop failure around the world. Various chemical insecticides have been relied upon in the past to control pests. However, environmental concerns as well as consumer safety concerns have led to the deregistration of many pesticides and reluctance to use others on agricultural products that are ultimately consumed as food. Therefore, it is desirable to develop alternative biocontrol agents. [0005] Pheromones are chemical substances secreted outside the body of insects and can be classified according to the type of behavioral responses they induce. Pheromone categories include aggregation pheromones, sex pheromones, trail pheromones and alarm pheromones. For example,...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07C17/263C07C11/12C07C29/38
CPCC07C45/68C07C67/343C07F15/0046C07C47/21C07C69/145B01J31/2442B01J2531/821
Inventor 基思·M·万普勒李春宇戴维·罗泽尔
Owner PROVIVI