Process for preparing a 5-alken-1-yne compound, (6Z)-1,1-dialkoxy-6-nonen-2-yne compound, (2E,6Z)-2,6-nonadienal and (2E)-cis-6,7-epoxy-2-nonenal, and 1,1-dialkoxy-6-nonen-2-yne compound

Patent metadata

Field	Value
Publication number	US-10781146-B2
Application number	US-201916533254-A
Country	US
Kind code	B2
Filing date	Aug 6, 2019
Priority date	Aug 10, 2018
Publication date	Sep 22, 2020
Grant date	Sep 22, 2020

Abstract

The object of the present invention is to provide a process for preparing a 5-alken-1-yne compound efficiently at low costs and a process for preparing (2E,6Z)-2,6-nonadienal by making use of the aforesaid process for preparing the 5-alken-1-yne compound.
There is provided a process for preparing a 5-alken-1-yne compound of the following formula (4): Y—Z—CR 1 ═CR 2 —(CH 2 ) 2 —C≡CH (4) in which Y in formula (4) represents a hydrogen atom or a hydroxyl group, the process comprising at least steps of: subjecting (i) an alkenylmagnesium halide compound prepared from a haloalkene compound of the following formula (1): Y—Z—CR 1 ═CR 2 —(CH 2 ) 2 —X 1 (1) and (ii) an alkyne compound of the following formula (2): X 2 —C≡C—Si(R 3 )(R 4 )(R 5 ) (2) to a coupling reaction to form a silane compound of the following formula (3): Y—Z—CR 1 ═CR 2 —(CH 2 ) 2 —C≡C—Si(R 3 )(R 4 )(R 5 ) (3); and subjecting the silane compound (3) to a desilylation reaction to form the 5-alken-1-yne compound (4).

First claim

The invention claimed is:

1. A process for preparing a 5-alken-1-yne compound of the following formula (4):
Y—Z—CR 1 ═CR 2 —(CH 2 ) 2 —C≡CH  (4)

in which Y in formula (4) represents a hydrogen atom or a hydroxyl group, Z represents a divalent hydrocarbon group having from 1 to 15 carbon atoms, and R 1 and R 2 represent, each independently, a hydrogen atom or a monovalent hydrocarbon group having from 1 to 6 carbon atoms or bond together to form a divalent hydrocarbon group having from 1 to 6 carbon atoms, R 1 -R 2 ,
the process comprising at least steps of:
subjecting (i) an alkenylmagnesium halide compound prepared from a haloalkene compound of the following formula (1):
Y—Z—CR 1 ═CR 2 —(CH 2 ) 2 —X 1   (1)

in which Y, Z, R 1 and R 2 are as defined above and X 1 represents a halogen atom, and (ii) an alkyne compound of the following formula (2):
X 2 —C≡C—Si(R 3 )(R 4 )(R 5 )  (2)

in which X 2 represents a halogen atom, R 3 represents a hydrogen atom or a monovalent hydrocarbon group having from 1 to 6 carbon atoms, and R 4 and R 5 represent, each independently, a monovalent hydrocarbon group having from 1 to 6 carbon atoms or bond together to represent a divalent hydrocarbon group having from 2 to 6 carbon atoms, R 4 -R 5 , to a coupling reaction to form a silane compound of the following formula (3):
Y—Z—CR 1 ═CR 2 —(CH 2 ) 2 —C≡C—Si(R 3 )(R 4 )(R 5 )  (3)

in which Y, Z, R 1 , R 2 , R 3 , R 4 , and R 5 are as defined above; and
subjecting the silane compound (3) to a desilylation reaction to form the 5-alken-1-yne compound (4).

2. The process according to claim 1 , wherein the haloalkene compound (1) is a (3Z)-1-halo-3-hexene compound of the following formula (1-1), Y in formula (1) represents a hydrogen atom, Z represents an ethylene group, and R 1 and R 2 each represent a hydrogen atom:

in which X 1 represents a halogen atom;
the silane compound (3) is a silane compound of the following formula (3-1):

in which R 3 , R 4 , and R 5 are as defined above; and
the 5-alken-1-yne compound (4) is (5Z)-5-octen-1-yne of the following formula (4-1):

3. A process for preparing a (6Z)-1,1-dialkoxy-6-nonen-2-yne compound of the following formula (7a):

in which R 6 may be the same or different at each occurrence and represents a monovalent hydrocarbon group having from 1 to 6 carbon atoms,
the process comprising at least steps of:
each of the steps of the process according to claim 2 for preparing (5Z)-5-octen-1-yne of the following formula (4-1):

preparing, from the (5Z)-5-octen-1-yne (4-1) thus obtained, an acetylide compound of the following formula (5):

in which M represents Li, Na, K, or MgX 3 , and X 3 represents a halogen atom; and
subjecting the acetylide compound (5) and an orthoformic acid ester compound of the following formula (6):

in which R 6 may be the same or different at each occurrence and represents a monovalent hydrocarbon group having from 1 to 6 carbon atoms, to a nucleophilic substitution reaction to form the (6Z)-1,1-dialkoxy-6-nonen-2-yne compound (7a).

4. A process for preparing a process for preparing (2E,6Z)-2,6-nonadienal of the following formula (9):

the process comprising at least steps of:
each of the steps of the process according to claim 3 for preparing (6Z)-1,1-dialkoxy-6-nonen-2-yne compound (7a);
subjecting the (6Z)-1,1-dialkoxy-6-nonen-2-yne compound (7a) thus obtained to a reduction reaction to form a (6Z)-1,1-dialkoxy-2,6-nonadiene compound of the following formula (8):

in which R 6 may be the same or different at each occurrence and represents a monovalent hydrocarbon group having from 1 to 6 carbon atoms; and
hydrolyzing the (6Z)-1,1-dialkoxy-2,6-nonadiene compound (8) to form (2E,6Z)-2,6-nonadienal (9).

5. A process for preparing (2E)-cis-6,7-epoxy-2-nonenal of the following formula (10):

the process comprising at least steps of:
each of the steps of the process according to claim 4 for preparing (2E,6Z)-2,6-nonadienal (9); and
epoxidizing the (2E,6Z)-2,6-nonadienal (9) thus obtained to form (2E)-cis-6,7-epoxy-2-nonenal (10).

Assignees

• Shinetsu Chemical Co

Inventors

• Watanabe Tomohiro
• Kinsho Takeshi
• Miyake Yuki

Classifications

• C07F7/0805

  comprising only Si, C or H atoms · CPC title

• C07F1/00

  Compounds containing elements of Groups 1 or 11 of the Periodic Table · CPC title

• C07C41/20

  by hydrogenation of carbon-to-carbon double or triple bonds · CPC title

• C07D301/14

  with organic peracids, or salts, anhydrides or esters thereof · CPC title

• C07C41/48

  Preparation of compounds having [IMAGE cpc-sch-C07C-0958.gif] groups · CPC title