Synthesis of 5-decenyl acetate and other pheromone components
AssigneeTillieChem, Inc.
InventorsRichard L. Pederson, Robert H. Grubbs
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Abstract
The present invention relates to syntheses of 5-decenyl acetate, the major component in Peach Twig Borer pheromone, and other pheromone components. The syntheses entails few reaction steps, use commercially available starting materials, and have relatively short process times. A preferred embodiment of the syntheses involves self-metathesizing 1-hexene in the presence of Grubbs' catalyst, [(PCy3)2Cl2]Ru═CHPh. The resulting 5-decene is then reacted with an alcohol or acetate protected hexene under vacuum to yield 5-decenyl acetate. These syntheses produce good yields without the need for expensive or sophisticated equipment.
Claims26
A method for synthesizing 5-decenyl acetate, comprising the steps of:
- self-metathesizing 1-hexene in the presence of a first catalyst to form a product;
- cross-metathesizing the product with an alcohol- or acetate-protected hexene or derivative thereof in the presence of a second catalyst to form 5-decenyl acetate or derivative thereof and a side product.
A method for synthesizing 5-decenyl acetate comprising the steps of:
- self-metathesizing 1-hexene in the presence of Grubbs' catalyst to form a mixture of 5-decene and ethylene;
- removing the ethylene from the mixture;
- cross-metathesizing the 5-decene with a protected hexene having a formula 5-hexene-1-R, where R includes an alcohol, acetate, ether, halide, or ester, in the presence of Grubbs' catalyst to form 1-hexene and 5-decenyl acetate having a trans:cis ratio of greater than 80:20;
- performing the cross-metathesizing step under vacuum to remove the 1-hexene as it is formed;
- and
- producing a gross yield of 5-decenyl acetate that is greater than 30 percent.
A method for synthesizing 5-decenyl acetate, comprising the steps of:
- self-metathesizing 5-hexenyl acetate under vacuum and in the presence of a catalyst to form 1,10-diacetoxy-5-decene;
- and
- cross-metathesizing 1,10-diacetoxy-5-decene with 5-decene in the presence of the catalyst to form 5-decenyl acetate.
A method for synthesizing olefinic alcohols, acetates, aldehydes, carboxylic acids or derivatives thereof in a reaction chamber, comprising:
- self-metathesizing a first alpha olefin in an exemplary form of CH2CH(CH2)n(CHX)(CH2)mCH3, where X is selected from a hydrogen, an alcohol, an acetate, a halide, or a tosylate, mesylate or derivative thereof, and n and m are each selected from zero and an integer less than or equal to 20, in the presence of a first catalyst to form a product in the form of CH2CH(CH)p(CHX)(CH2)qCH3, where p and q are each selected from zero and an integer such that at least p is greater than n or at least q is greater than m and a first side product in the form of CH2Y, where Y is selected from CH2 or CH(CH2)n(CHX)(CH2)mCH3;
- and
- cross-metathesizing the product with a second alpha olefin in an exemplary form of NCH(CH2)rM, where N is selected from CH2 or CH(CH2)rM, r is selected from zero and an integer less than or equal to 20, and M is selected from an alcohol, acetate, aldehyde, halide or carboxylic acid or derivative thereof in the presence of a second catalyst to form a second product in the form of CH3(CH2)m(CHX)(CH2)nCHCH(CH2)rM or derivatives thereof and a second side product in the form of CH2Z, where Z is selected from CH2 or CH(CH2)n(CHX)(CH2)mCH3 under conditions of sufficiently high temperature and/or sufficiently low pressure such that the second side product evaporates out of the reaction chamber.
Dependencies are inferred from the claim text.