Process for preparing an alkoxymethyl alkynyl ether compound having a terminal triple bond

Patent metadata

Field	Value
Publication number	US-2021198172-A1
Application number	US-202017128306-A
Country	US
Kind code	A1
Filing date	Dec 21, 2020
Priority date	Dec 25, 2019
Publication date	Jul 1, 2021
Grant date	—

Abstract

The present invention provides a process for preparing an alkoxymethyl alkynyl ether compound having a terminal triple bond of the following formula (4): H—C≡C(CH2)aOCH2OCH2R (4), wherein R represents a hydrogen atom, an n-alkyl group having 1 to 9 carbon atoms, or a phenyl group, and “a” represents an integer of 1 to 10, the method comprising subjecting an alkynol compound having a terminal triple bond of the following formula (1): H—C≡C(CH2)aOH (1), wherein “a” is as defined above, to an alkoxymethylation with a halomethyl alkyl ether compound of the following formula (3): RCH2OCH2X (3), wherein X represents a halogen atom, and R is as defined above, in the presence of a dialkylaniline compound of the following formula (2): [CH3(CH2)b][CH3(CH2)c]NC6H5 (2), wherein b and c represent, independently of each other, an integer of 0 to 9, to form the alkoxymethyl alkynyl ether compound (4) having a terminal triple bond.

First claim

1 . A process for preparing an alkoxymethyl alkynyl ether compound having a terminal triple bond of the following formula (4):
H—C═C(CH 2 ) a OCH 2 OCH 2 R  (4)

wherein R represents a hydrogen atom, an n-alkyl group having 1 to 9 carbon atoms, or a phenyl group, and “a” represents an integer of 1 to 10, the method comprising
subjecting an alkynol compound having a terminal triple bond of the following formula (1):
H—C≡C(CH 2 ) a OH  (1)

wherein a is as defined above,
to an alkoxymethylation with a halomethyl alkyl ether compound of the following formula (3):
RCH 2 OCH 2 X  (3)

wherein X represents a halogen atom, and R is as defined above,
in the presence of a dialkylaniline compound of the following formula (2):
[CH 3 (CH 2 ) b ][CH 3 (CH 2 ) c ]NC 6 H 5   (2)

wherein b and c represent, independently of each other, an integer of 0 to 9,
to form the alkoxymethyl alkynyl ether compound (4) having a terminal triple bond.

2 . The process for preparing an alkoxymethyl alkynyl ether compound (4) having a terminal triple bond according to claim 1 , wherein the alkynol compound (1) and the dialkylaniline compound (2) are added dropwise to the halomethyl alkyl ether compound (3) to proceed with the alkoxymethylation.

3 . The process for preparing an alkoxymethyl alkynyl ether compound (4) having a terminal triple bond according to claim 1 the method further comprising reacting a dialkoxymethane compound of the following formula (5):
RCH 2 OCH 2 OCH 2 R  (5)

wherein R is as defined above,
with a halogenating agent (7) in the presence of a zinc compound (6) to form the halomethyl alkyl ether compound (3).

4 . The process for preparing an alkoxymethyl alkynyl ether compound (4) having a terminal triple bond according to claim 1 , wherein the halomethyl alkyl ether compound (3) is selected from the group consisting of chloromethyl methyl ether, chloromethyl ethyl ether, chloromethyl propyl ether, chloromethyl butyl ether, and chloromethyl benzyl ether.

5 . The process for preparing an alkoxymethyl alkynyl ether compound (4) having a terminal triple bond according to claim 1 , wherein the dialkylaniline compound (2) is selected from the group consisting of N,N-dimethylaniline, N,N-diethylaniline, N,N-dipropylaniline, and N,N-dibutylaniline.

6 . The process for preparing an alkoxymethyl alkynyl ether compound (4) having a terminal triple bond according to claim 1 , wherein the alkynol compound (1) is selected from the group consisting of 2-propyn-1-ol, 3-butyn-1-ol, 4-pentyn-1-ol, and 5-hexyn-1-ol.

7 . The process for preparing an alkoxymethyl alkynyl ether compound (4) having a terminal triple bond according to claim 1 , the method further comprising recovering the dialkylaniline compound (2) after the alkoxymethylation.

8 . The process for preparing an alkoxymethyl alkynyl ether compound (4) having a terminal triple bond according to claim 7 , the method further comprising recycling the recovered dialkylaniline compound (2) to a subsequent alkoxymethylation.

9 . The process for preparing an alkoxymethyl alkynyl ether compound (4) having a terminal triple bond according to claim wherein the dialkylaniline compound (2) is recovered from one batch of the alkoxymethylation and then the recovered dialkylaniline compound (2) is recycled to a subsequent alkoxymethylation; or a plurality of batches of the alkoxymethylation is carried out, and the dialkylaniline compound (2) is recovered from each one batch, and the recovered dialkylaniline compound (2) is collected, and then the collected dialkylaniline compound (2) is recycled to a subsequent alkoxymethylation.

10 . The process for preparing an alkoxymethyl alkynyl ether compound (4) having a terminal triple bond according to claim 8 , wherein the dialkylaniline compound (2) is recovered from one batch of the alkoxymethylation and then the recovered dialkylaniline compound (2) is recycled to a subsequent alkoxymethylation; or a plurality of batches of the alkoxymethylation is carried out, and the dialkylaniline compound (2) is recovered from each one batch, and the recovered dialkylaniline compound (2) is collected, and then the collected dialkylaniline compound (2) is recycled to a subsequent alkoxymethylation.

11 . The process for preparing an alkoxymethyl alkynyl ether compound (4) having a terminal triple bond according to claim 2 , the method further comprising reacting a dialkoxymethane compound of the following formula (5):
RCH 2 OCH 2 OCH 2 R  (5)

wherein R is as defined above,
with a halogenating agent (7) in the presence of a zinc compound (6) to form the halomethyl alkyl ether compound (3).

12 . The process for preparing an alkoxymethyl alkynyl ether compound (4) having a terminal triple bond according to claim 2 , wherein the halomethyl alkyl ether compound (3) is selected from the group consisting of chloromethyl methyl ether, chloromethyl ethyl ether, chloromethyl propyl ether, chloromethyl butyl ether, and chloromethyl benzyl ether.

13 . The process for preparing an alkoxymethyl alkynyl ether compound (4) having a terminal triple bond according to claim 2 , wherein the dialkylaniline compound (2) is selected from the group consisting of N,N-dimethylaniline, N,N-diethylaniline, N,N-dipropylaniline, and N,N-dibutylaniline.

14 . The process for preparing an alkoxymethyl alkynyl ether compound (4) having a terminal triple bond according to claim 2 , wherein the alkynol compound (1) is selected from the group consisting of 2-propyn-1-ol, 3-butyn-1-ol, 4-pentyn-1-ol, and 5-hexyn-1-ol.

15 . The process for preparing an alkoxymethyl alkynyl ether compound (4) having a terminal triple bond according to claim 2 , the method further comprising recovering the dialkylaniline compound (2) after the alkoxymethylation.

16 . The process for preparing an alkoxymethyl alkynyl ether compound (4) having a terminal triple bond according to claim 3 , wherein the halomethyl alkyl ether compound (3) is selected from the group consisting of chloromethyl methyl ether, chloromethyl ethyl ether, chloromethyl propyl ether, chloromethyl butyl ether, and chloromethyl benzyl ether.

17 . The process for preparing an alkoxymethyl alkynyl ether compound (4) having a terminal triple bond according to claim 3 , wherein the dialkylaniline compound (2) is selected from the group consisting of N,N-dimethylaniline, N,N-diethylaniline, N,N-dipropylaniline, and N,N-dibutylaniline.

18 . The process for preparing an alkoxymethyl alkynyl ether compound (4) having a terminal triple bond according to claim 3 , wherein the alkynol compound (1) is selected from the group consisting of 2-propyn-1-ol, 3-butyn-1-ol, 4-pentyn-1-ol, and 5-hexyn-1-ol.

19 . The process for preparing an alkoxymethyl alkynyl ether compound (4) having a terminal triple bond according to claim 3 the method further comprising recovering the dialkylaniline compound (2) after the alkoxymethylation.

20 . The process for preparing an alkoxymethyl alkynyl ether compound (4) having a terminal triple bond according to claim 4 , wherein the dialkylaniline compound (2) is selected from the group consisting of N,N-dimethylaniline, N,N-diethylaniline, N,N-dipropylaniline, and N,N-dibutylaniline.

Assignees

• Shinetsu Chemical Co

Inventors

• Miyake Yuki
• Yamashita Miyoshi
• Kinsho Takeshi
• Baba Akihiro

Classifications

• C07C41/16 Primary

  by reaction of esters of mineral or organic acids with hydroxy or O-metal groups · CPC title

• C07C41/52 Primary

  by substitution of halogen only · CPC title

• C07C41/34

  Separation; Purification; Stabilisation; Use of additives · CPC title

• C07C41/22

  by introduction of halogens; by substitution of halogen atoms by other halogen atoms · CPC title