# US 4,391,984 A · Alkynyl halide compounds and alkenyl acetate compounds therefrom

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- Number: US 4,391,984 A
- Document ID: US4391984A
- Status: Granted
- Kind: A
- Application number: 06/266,614
- Filed: 1981-05-22
- Granted: 1983-07-05
- Earliest claimed: 1980-05-26
- Assignees: Schin-Etsu Chemical Co., Ltd.
- Inventors: Toshinobu Ishihara; Akira Yamamoto; Kenichi Taguchi
- Web page: https://patentgrep.com/patent/US4391984A

## CPC

- C07C 17/2632: {involving an organo-magnesium compound, e.g. Grignard synthesis}
- C07C 67/11: being mineral ester groups
- C07C 67/283: by hydrogenation of unsaturated carbon-to-carbon bonds
- C07C: ACYCLIC OR CARBOCYCLIC COMPOUNDS

## Abstract

The invention provides a novel method for the synthetic preparation of an .omega.-haloalkyne compound of the general formula R--C.tbd.C--CH.sub.2).sub.n X, in which X is a halogen atom, R is a monovalent hydrocarbon group and n is 4, 5 or 6, by the coupling reaction of a Grignard reagent RMgX' and an .omega.-halo-1-bromoalkyne compound of the formula X--CH.sub.2).sub.n C.tbd.C-Br. The .omega.-haloalkyne compound obtained in the above can be readily converted to the corresponding alkenyl acetate of the formula R--CH.dbd.CH--CH.sub.2).sub.n OCOCH.sub.3 by first acetylating and then partially hydrogenating in the presence of a Lindlar catalyst. In particular, 7, 11-hexadecadienyl acetate, which is a sexual pheromone compound of a noxious insect, is obtained in the same route of synthesis starting with the Grignard reagent of a 1-halo-3-octene and 1, 8-dibromo-1-octyne.

## Claims

### Claim 1

A method for the preparation of an alkenyl acetate having the general formula
R--CH.dbd.CH--CH.sub.2).sub.n OCOCH.sub.3
in which R is a monovalent hydrocarbon group and n is a number of 4, 5 or 6, which comprises the steps of
(a) reacting a Grignard reagent represented by the general formula
RMgX',
in which R has the same meaning as defined above and X' is a halogen atom, and an .omega.-halo-1-bromoalkyne compound represented by the general formula
X--CH.sub.2).sub.n C.tbd.C--Br,
in which X and n each have the same meaning as defined above, to form an alkynyl halide compound having the general formula
R--C.tbd.C--CH.sub.2).sub.n X,
in which R, X and n each have the same meaning as defined above,
(b) acetylating the alkynyl halide compound to form an alkynyl acetate compound having the general formula
R--C.tbd.C--CH.sub.2).sub.n OCOCH.sub.3,
in which R and n each have the same meaning as defined above, and
(c) partially hydrogenating the alkynyl acetate compound in the presence of a Lindlar catalyst.

### Claim 2

A method for the preparation of 7,11-hexadecadienyl acetate having the formula
CH.sub.3 (CH.sub.2).sub.3 CH.dbd.CH(CH.sub.2).sub.2 CH.dbd.CH(CH.sub.2).sub.6 OCOCH.sub.3
which comprises the steps of
(a) reacting the Grignard reagent of a 1-halo-3-octene expressed by the formula
CH.sub.3 (CH.sub.2).sub.3 CH.dbd.CH(CH.sub.2).sub.2 X',
in which X' is a halogen atom, and 1,8-dibromo-1-octyne having the formula
Br--CH.sub.2).sub.6 C.tbd.C--Br,
to form 1-bromohexadeca-11-en-7-yne having the formula
CH.sub.3 (CH.sub.2).sub.3 CH.dbd.CH(CH.sub.2).sub.2 C.tbd.C(CH.sub.2).sub.6 Br,
(b) acetylating the 1-bromohexadeca-11-en-7-yne to form hexadeca-11-en-7-ynyl acetate having the formula
CH.sub.3 (CH.sub.2).sub.3 CH.dbd.CH(CH.sub.2).sub.2 C.tbd.C(CH.sub.2).sub.6 OCOCH.sub.3,
and
(c) partially hydrogenating the hexadeca-11-en-7-ynyl acetate in the presence of a Lindlar catalyst.

### Claim 3

A method for the preparation of an alkenyl acetate having the formula
R--CH.dbd.CH--CH.sub.2).sub.n OCOCH.sub.3,
in which R is a monovalent hydrocarbon group and n is a number of 4, 5 or 6, which comprises the steps of:
(a) reacting from 1.0 to 1.5 moles of the Grignard reagent having the formula
RMgX',
in which X' is a halogen atom, and 1.0 mole of an .omega.-halo-bromoalkyne compound having the formula
X--CH.sub.2).sub.n C.tbd.C--Br,
in a tetrahydrofuran solution at a temperature in the range from -5.degree. to +10.degree. C. in the presence of a catalytic amount of a copper halide to form an alkynyl halide compound having the formula
R--CH.tbd.C--CH.sub.2).sub.n X,
(b) acetylating the alkynyl halide compound by reacting it under the heating with an alkali metal acetate as diluted with acetic acid to form an alkynyl acetate compound having the formula
R--C.tbd.C--CH.sub.2).sub.n OCOCH.sub.3,
and
(c) partially hydrogenating the alkynyl acetate compound in the presence of a Lindlar catalyst at a temperature of 4 to 10 atmospheres.

### Claim 4

A method for the preparation of 7,11-hexadecadienyl acetate having the formula
CH.sub.3 (CH.sub.2).sub.3 CH.dbd.CH(CH.sub.2).sub.2 CH.dbd.CH(CH.sub.2).sub.6 OCOCH.sub.3
which comprises the steps of
(a) reacting from 1.0 to 1.5 moles of the Grignard reagent of a 1-halo-3-octene expressed by the formula
CH.sub.3 (CH.sub.2).sub.3 CH.dbd.CH(CH.sub.2).sub.2 X',
in which X' is a halogen atom, and 1,8-dibromo-1-octyne having the formula
Br--CH.sub.2).sub.6 C.tbd.C--Br,
to form 1-bromohexadeca-11-en-7-yne having the formula
CH.sub.3 (CH.sub.2).sub.3 CH.dbd.CH(CH.sub.2).sub.2 C.tbd.C(CH.sub.2).sub.6 Br,
(b) acetylating the 1-bromohexadeca-11-en-7-yne to form hexadeca-11-en-7-ynyl acetate having the formula
CH.sub.3 (CH.sub.2).sub.3 CH.dbd.CH(CH.sub.2).sub.2 C.dbd.C(CH.sub.2).sub.6 OCOCH.sub.3,
and
(c) partially hydrogenating the hexadeca-11-en-7-ynyl acetate in the presence of a Lindlar catalyst.