# US 4,400,550 A · Synthesis of the navel orange worm pheromone (Z,Z)-11,13-hexadecadienal

> Agents: this data is available as JSON from the patentgrep API and MCP server — see https://patentgrep.com/llms.txt

- Number: US 4,400,550 A
- Document ID: US4400550A
- Status: Granted
- Kind: A
- Application number: 06/348,501
- Filed: 1982-02-12
- Granted: 1983-08-23
- Earliest claimed: 1982-02-12
- Assignees: Albany International Corp.
- Inventors: Clyde E. Bishop; Gary W. Morrow
- Web page: https://patentgrep.com/patent/US4400550A

## CPC

- C07C 29/62: by introduction of halogen; by substitution of halogen atoms by other halogen atoms
- C07C 17/2632: {involving an organo-magnesium compound, e.g. Grignard synthesis}
- C07C 17/354: by hydrogenation
- C07C 17/395: by treatment giving rise to a chemical modification of at least one compound
- C07C 21/22: containing carbon-to-carbon triple bonds
- C07C 29/40: with compounds containing carbon-to-metal bonds
- C07C 29/58: by elimination of halogen, e.g. by hydrogenolysis, splitting-off (C07C29/124 takes precedence)
- C07C 41/50: by reactions producing [IMAGE cpc-sch-C07C-0958.gif] groups
- C07C 45/515: {the singly bound functional group being an acetalised, ketalised hemi-acetalised, or hemi-ketalised hydroxyl group (cyclic acetals or ketals C07C45/59, C07C45/60)}
- C07C 67/08: by reacting carboxylic acids or symmetrical anhydrides with the hydroxy or O-metal group of organic compounds
- C07F 3/02: Magnesium compounds
- C07C: ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07F: ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM (metal-containing porphyrins C07D487/22)

## Abstract

A process for the synthesis of (Z,Z)-11-13-hexadecadienal is disclosed, starting with undecylenic alcohol.

## Claims

### Claim 1

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.

### Claim 2 (depends on 1)

The process of claim 1 wherein the cuprous ion is provided by dilithium tetrachlorocuprate.

### Claim 3

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.