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US 4,400,550 AGranted
Synthesis of the navel orange worm pheromone (Z,Z)-11,13-hexadecadienal
AssigneeAlbany International Corp.
InventorsClyde E. Bishop, Gary W. Morrow
Life of this patent
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Abstract
A process for the synthesis of (Z,Z)-11-13-hexadecadienal is disclosed, starting with undecylenic alcohol.
Claims3
A process for preparing (Z,Z)-11,13-hexadecadienal, which comprises;
- halogenating undecylenic alcohol at a temperature below room temperature to obtain 10,11-dihalo-1-undecanol;
- dehydrohalogenating the 10,11-dihalo-1-undecanol by reaction with a strong base to obtain 10-undecyn-1-ol;
- chlorinating the 10-undecyn-1-ol to obtain 11-chloro-1-undecyne;
- converting the 11-chloro-1-undecyne to the 11-chlorododecyne Grignard reagent;
- complexing the Grignard reagent with acrolein at a temperature of from about 15.degree. to about 30.degree. C.;
- hydrolyzing the complex to obtain 14-chloro-1-tetradecen-4-yn-3-ol;
- acylating the 14-chloro-1-tetradecen-4-yn-3-ol with an acyl radical of the formula ##STR14## wherein R represents hydrocarbyl;
- reacting the acylate with methylmagnesium bromide in the presence of a catalytic proportion of cuprous ion to obtain 15-chloro-(Z)-3-pentadecen-5-yne at a temperature of less than about -30.degree. C.;
- reducing the 15-chloro-(Z)-3-pentadecen-5-yne to 15-chloro-(Z,Z)-3,5-pentadecadiene at a temperature of from about -20.degree. C. to room temperature by hydroboration of the 15-chloro-(Z)-3-pentadecen-5-yne followed by protonolysis of the product borane;
- converting the 15-chloro-(Z,Z)-3,5-pentadecadiene to the (Z,Z)-11,13-hexadecadienal dialkyl acetal by reaction with a compound of the formula ##STR15## wherein R is as previously defined;
- and cleaving the acetal to obtain the (Z,Z)-11,13-hexadecadienal by acid hydrolysis of the acetal.
8 more elements
A process for preparing (Z,Z)-11,13-hexadecadienal, which comprises;
- brominating undecylenic alcohol at a temperature below room temperature to obtain 10,11-dibromo-1-undecanol;
- dehydrobrominating the 10,11-dibromo-1-undecanol by reaction with a strong base to obtain 10-undecyn-1-ol;
- chlorinating the 10-undecyn-1-ol to obtain the 11-chloro-1-undecyne;
- converting the 11-chloro-1-undecyne to a Grignard reagent and complexing the Grignard reaction product with acrolein at a temperature of from about 15.degree. to about 30.degree. C.
- hydrolyzing the complex to obtain 14-chloro-1-tetradecen-1-yn-3-ol;
- acylating the 14-chloro-1-tetradecen-4-yn-3-ol with acetic anhydride to obtain the 14-chloro-1-tetradecen-4-yn-3-acetate;
- reacting said acylate with methylmagnesium bromide at a temperature of less than about -30.degree. C. in the presence of a catalytic proportion of dilithium tetrachlorocuprate to obtain 15-chloro-(Z)-3-pentadecen-5-yne;
- reducing the 15-chloro-(Z)-3-pentadecen-5-yne with dicyclohexyl borane followed by protonolysis of the product borane with acetic acid to obtain 15-chloro-(Z,Z)-3,5-pentadecadiene;
- converting the 15-chloro-(Z,Z)-3,5-pentadecadiene to the corresponding (Z,Z)-11,13-hexadecadienal diethyl acetal by reaction with triethyl orthoformate;
- and
- cleaving the acetal to obtain the (Z,Z)-11,13-hexadecadienal, by acid hydrolysis of the acetal.
8 more elements
Dependencies are inferred from the claim text.