JPH0573736B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to an aliphatic N-substituted unsaturated amide compound and a method for producing the same. More specifically, the present invention relates to an aliphatic N-substituted unsaturated amide compound in which at least one hydroxyl group of the hydroxyl group-substituted aliphatic saturated and unsaturated compound is substituted with a w-unsaturated amide polymethyleneoxy group, and a method for producing the same. The compounds of the present invention have the general formula

[Chemical formula] (However, A is a halogen atom or a w-unsaturated amide polymethylene group (

[Formula]), hydroxyl group, alkoxy group, cyano group, nitro group, amino group, aldehyde group, acyl group, acyloxy group,
It is a carboxyl group, a carboxy ester group, a mercapto group, or a group consisting of a sulfonic acid or a salt thereof, B is an oxygen atom, a carbonyl group, a thio group, a sulfonyl group, or an azo group, and R is a hydrogen atom or a methyl group. l is an integer of 0 to 5, and when l is 2 or more, A may be different. m is 4
-20, and n is an integer of 1-4. α
is an integer from 1 to 30, and β is an integer from 0 to 3 smaller than α. p is an integer of 1 or 2, and q is 0
or an integer of 1. When p is 1, q is 0, and when p is 2, q is 1, and in this case, A, α, β, l, and n on the left and right may be different. ) It is an aliphatic N-substituted unsaturated amide compound represented by the following formula, and is a new compound that has not been described in any literature. The compounds of the present invention have the general formula

[C] (A', B, X, l, m, n, α, β, p, q
is the same as the general formula above. ) Aliphatic halogen-substituted ether compounds and general formula

It can be produced by reacting an unsaturated amide compound represented by the formula (R is the same as the general formula above) in an aprotic polar solvent in the presence of a strong basic substance. The compound of the present invention represented by formula (1) comprises at least one hydroxyl group-substituted aliphatic saturated and unsaturated compound.
In formula (1), A
The halogen represented by is chlorine, bromine, iodine or fluorine, and the halogen represented by X in formula (2) is
For example chlorine, bromine or iodine. Furthermore, in the present invention, among the various groups represented by A, alkoxy groups, acyl groups, acyloxy groups and carboxy ester groups each have the general formula RO
-, RCO-, RCOO-, -COOR, where R includes not only an alkyl group but also an alkenyl group and an aryl group. Further, in the case of a carboxyester group, the case where R represents the above-mentioned w-unsaturated amide polymethylene group is also included. In addition to the formula -COOH, the carboxyl group is
It also includes the case of the formula −COO ⁻ M ⁺ (M ⁺ represents an alkali metal ion). The amino group has the general formula

It is represented by [Formula], and R′ and R″ are hydrogen, a lower alkyl group, or a w-unsaturated amide polymethylene group, and may be different. and 4% less than monohydric alcohol.
This applies to polyhydric alcohols up to the hydroxyl group, and also those in which two of these alcohols are bonded via an oxygen atom, carbonyl group, thio group, sulfonyl group, or azo group, and at least one of these hydroxyl groups It is substituted with a w-unsaturated amide polymethyleneoxy group, and also includes those substituted with a substituent as shown in A above. Representative examples of the compounds of the present invention are illustrated below. However, the compounds of the present invention have a very wide range of
In addition, since there are a wide variety of compounds, in order to simplify the illustration of compounds, first, in general formula (1), m = 4 and R
are fixed on the hydrogen atom, A, B, α, β, l,
Examples will be given with n, p, and q changed in various ways. Then α=
3, fixing β=n=p=1 and l=q=0,
Examples will be given by changing R to a hydrogen atom or a methyl group and m to 4 to 20. First, examples of substituents for unsubstituted monohydric alcohols include N-(4-methoxybutyl)acrylamide, N-(4-ethoxybutyl)acrylamide, N-(4-n-propoxybutyl)acrylamide, and N-(4-methoxybutyl)acrylamide. -n-butoxybutyl)acrylamide, N-[4-(2-methylpropoxy)butyl]acrylamide, N-(4-pentyloxybutyl)acrylamide, N-[4-(3
-methylbutoxy)butyl]acrylamide, N
-[4-(2,2-dimethylpropoxy)butyl)
Acrylamide, N-(4-hexyloxybutyl)acrylamide, N-[4-(2-methylpentyloxy)butyl]acrylamide, N-[4
-(4-methylpentyloxy)butyl]acrylamide, N-[4-(3,3-dimethylbutoxy)butyl]acrylamide, N-[4-(2-ethylbutoxy)butyl]acrylamide, N-
(4-heptyloxybutyl)acrylamide,
N-(4-octyloxybutyl)acrylamide, N-[4-(2-ethylhexyloxy)butyl]acrylamide, N-[4-(2,4,4-trimethylpentyloxy)butyl]acrylamide, N-[4 -(2-ethyl-4-methylpentyloxy)butyl]acrylamide, N-(4-nonyloxybutyl)acrylamide, N-[4-
(3,5,5-trimethylhexyloxy)butyl]acrylamide, N-(4-decyloxybutyl)acrylamide, N-[4-(3,7-dimethyloctyloxy)butyl]acrylamide,
N-(4-undecyloxybutyl)acrylamide, N-(4-dodecyloxybutyl)acrylamide, N-(4-tridecyloxybutyl)
Acrylamide, N-(4-tetradecyloxybutyl)acrylamide, N-(4-pentadecyloxybutyl)acrylamide, N-(4-hexadecyloxybutyl)acrylamide, N-
(4-heptadecyloxybutyl)acrylamide, N-(4-octadecyloxybutyl)acrylamide, N-(4-nonadecyloxybutyl)
Acrylamide, N-(4-eicosyloxybutyl)acrylamide, N-(4-eicosyloxybutyl)acrylamide, N-(4-docosyloxybutyl)acrylamide, N-(4-eicosyloxybutyl)acrylamide, N-(4-eicosyloxybutyl)acrylamide,
-tricosyloxybutyl)acrylamide, N
-(4-tetracosyloxybutyl)acrylamide, N-(4-hexacosyloxybutyl)acrylamide, N-(4-triacontyloxybutyl)acrylamide, N-(4-allyloxybutyl)acrylimide, N-[4-(2-butenyloxy)butyl]acrylamide, N-[4-
(3-butenyloxy)butyl]acrylamide,
N-[4-(2-methyl-2-propenyloxy)
Butyl]acrylamide, N-[4-(3-methyl-2-butenyloxy)butyl]acrylamide, N-[4-(3-methyl-3-butenyloxy)butyl]acrylamide, N-[4-(2-hexenyloxy) ) butyl] acrylamide, N-
[4-(2,4-hexadienyloxy)butyl]
Acrylamide, N-[4-(3,7-dimethyl-
7-octenyloxy)butyl]acrylamide, N-[4-(3,7-dimethyl-2,6-octadienyloxy)butyl]acrylamide, N
-[4-10-undecenyloxy)butyl]acrylamide, N-[4-(3,7,11-trimethyl-2,6,10-dodecatrienyloxy)butyl]acrylamide, N-[4-( 9-octadecenyloxy)butyl]acrylamide, N-[4
-(3,7,11,15-tetramethyl-2-hexadecenyloxy)butyl]acrylamide, N-
[4-(2-propynyloxy)butyl]acrylamide, N-[4-(2-butynyloxy)butyl]acrylamide, N-[4-(2-pentynyloxy)butyl]acrylamide, N-[4-(3
-pentynyloxy)butyl]acrylamide,
N-[4-(2-hexynyloxy)butyl]acrylamide, N-[4-(3-heptynyloxy)
butyl]acrylamide, N-[4-(3-octynyloxy)butyl]acrylamide, N-[3
-nonynyloxy)butyl]acrylamide, N
-[4-(2-decynyloxy)butyl]acrylamide and the like. Examples of substituted monohydric alcohols include N-[4-(2-chloroethoxy)
butyl]acrylamide, N-[4-(2-bromoethoxy)butyl]acrylamide, N-[4-
(2,2,2-trichloroethoxy)butyl]acrylamide, N-[4-(3-chloropropoxy)butyl]acrylamide, N-[4-(2-chloro-1-methylethoxy)butyl]acrylamide, N- [4-(3-bromopropoxy)butyl]acrylamide, N-[4-(2,3-dichloropropoxy)butyl]acrylamide, N-
[4-(2,3-dibromopropoxy)butyl]acrylamide, N-[4-(4-chlorobutoxybutyl]acrylamide, N-[4-(6-chlorohexyloxy)butyl]acrylamide, N-
[4-(2-nitroethoxy)butyl]acrylamide, N-[4-(cyanomethoxy)butyl]acrylamide, N-[4-(2-cyanoethoxy)butyl]acrylamide, N-[4-(2-methyl) Amino)ethoxy)butyl]acrylamide, N-
[4-(2-methyl-2-nitropropoxy)butyl]acrylamide, N-[4-(2-nitrobutoxy)butyl]acrylamide, N-[4-(2-
(dimethylamino)ethoxy)butyl]acrylamide, N-[4-(2-(ethylamino)ethoxy)butyl]acrylamide, N-[4-(2-
(acetylamino)ethoxy)butyl]acrylamide, N-[4-(1-cyano-1-methylethoxy)butyl]acrylamide, N-[4-(2-
dimethylamino-1-methylethoxy)butyl]
Acrylamide, N-[4-(3-dimethylaminopropoxy)butyl]acrylamide, N-[4
-(2-(n-butylamino)ethoxy)butyl]
Acrylamide, N-[4-(2-(diethylamino)ethoxy)butyl]acrylamide, N-
[4-(2-(dimethylamino)-2-methylpropoxy)butyl]acrylamide, N-[4-(3-
(diethylamino)propoxy)butyl]acrylamide, N-[4-(4-n-butylamino)butoxy)butyl]acrylamide, N-[4-(2
-(diisopropylamino)ethoxy)butyl]
Acrylamide, N-[4-(2-(di-n-butylamino)ethoxy)butyl]acrylamide,
N-[4-(2-(dibutylamino)-1-methylethoxy)butyl]acrylamide, N-[4-(2
-(4-acrylamidobutylamino)ethoxy)
butyl]acrylamide, N-[4-(3-(4-
Acrylamidobutylamino)propoxy)butyl]acrylamide, N-[4-(2-(4-acrylamidobutylamino)-1-methylethoxy)
butyl]acrylamide, N-[4-(bis(4-
Acrylamidobutylaminomethyl)methoxy)
butyl]acrylamide, N-[4-(2-(4-
acrylamidebutylamino)butoxy)butyl]acrylamide, N-[4-(2-(4-acrylamidobutylamino)-2-methylpropoxy)butyl]acrylamide, 4-(4-acrylamidobutoxy)-2-(4-acrylamide butylamino)-n-4-acrylamidobutyl, N-[4-(3-(4-acrylamidobutylamino)-2,2-dimethylpropoxy)butyl]
Acrylamide, N-[4-(5-(4-acrylamidobutylamino)pentyloxy)butyl]
Acrylamide, N-[4-(4-diethylamino-2-butynyloxy)butyl]acrylamide, N-[4-(2-oxopropoxy)butyl]
Acrylamide, N-[4-(2-oxobutoxy)butyl]acrylamide, N-[4-(1-methyl-2-oxopropoxy)butyl]acrylamide, N-[4-(3-oxobutoxy)butyl]acrylamide , N-[4-(4-oxopentyloxy)butyl]acrylamide, N-[4
-(1,1-dimethyl-3-oxobutoxy)butyl]acrylamide, N-[4-(1-formyl-5-oxopentyloxy)butyl]acrylamide, (4-acrylamidobutoxy)sodium acetate, (4-acrylamide butoxy) 4-acrylamidobutyl acetate, 3-(4-acrylamidobutoxy)propionic acid 4-acrylamidobutyl, 3-(4-acrylamidobutoxy)
4-acrylamidobutyl propionate, (4-
(acrylamidobutoxy) di(4-acrylamidobutyl) malonate, (4-acrylamidobutoxy) di(4-acrylamidobutyl) succinate,
(4-acrylamidobutoxy) dimethyl succinate, (4-acrylamidobutoxy) di-n-butyl succinate, 2-(4-acrylamidobutoxy)-n-butyrate 4-acrylamidobutyl, 2-
(4-acrylamidobutoxy)-n-ethyl butyrate, 3-(4-acrylamidobutoxy)-n-butyrate 4-acrylamidobutyl, 3-(4-acrylamidobutoxy)-n-ethyl butyrate, 2-(4-
4-acrylamidobutyl (acrylamidobutoxy) propionate, methyl 2-(4-acrylamidobutoxy) propionate, n-butyl 2-(4-acrylamidobutoxy) propionate, 2
2-methylbutyl -(4-acrylamidobutoxy)propionate, 2-hexenyl 2-(4-acrylamidobutoxy)propionate, 2-(4-acrylamidobutoxy)propionate
-acrylamidobutoxy)propionate 3-hexenyl, 2-(4-acrylamidobutoxy)ethyl acrylate, 2-(4-acrylamidobutoxy)-1,2,3-propanetricarboxylic acid tri(4-acrylamidobutyl), 2- (4-acrylamidobutoxy)-1,2,3-propanetricarboxylic acid trimethyl, 2-(4-acrylamidobutoxy)1,2,3-propanetricarboxylic acid triethyl, 2-(4-acrylamidobutoxy)-1,2, Tri-n-butyl 3-propanetricarboxylate, 2-(4-acrylamidobutoxy)propyl acrylate, 2-methacrylate
(4-acrylamidobutoxy)ethyl, 3-(4
-acrylamidobutoxy)-3-methylglutarate di(4-acrylamidobutyl), 2-(4-
Acrylamidobutoxy)-4-methylvaleric acid 4
-Acrylamidobutyl, 2-(4-acrylamidobutoxy)-1,3-propanediol diacetate, 4-(4-acrylamidobutoxy)butyl acrylate, 1-(4-acrylamidobutoxy)-2,3-propanediol dibutyl rate, 1-(4-acrylamidobutoxy)2,3
-propanediol dilaurate, N- [4-
(3,3-dibutyryloxypropoxy)butyl]
Acrylamide, 4-acrylamidobutyl 3-(4-acrylamidobutoxy)-n-tetradecanoate, 2-hydroxy-n-hexadecanoic acid 4
-acrylamidobutyl, 4-acrylamidobutyl 12-(4-acrylamidobutoxy)oleate, methyl 12-(4-acrylamidobutoxy)oleate, ethyl 12-(4-acrylamidobutoxy)oleate, 12-(4-acrylamidobutoxy) ) n-butyl oleate, 12-(4-
Acrylamidobutoxy) cetyl oleate, 12
-(4-acrylamidobutoxy)oleyl oleate, 12-(4-acrylamidobutoxy)octadecanoate, 4-acrylamidobutyl, 1-
(4-acrylamidobutoxy)-2-stearoyloxypropane, 2-(4-acrylamidobutoxy)-1-stearoyloxypropane, (4
- Sodium acrylamide butoxy) methanesulfonate, 2-(4-acrylamidobutoxy)
Sodium ethanesulfonate, N-[4-(2-mercaptoethoxy)butyl]acrylamide, N
-[4-(2-(methylthio)ethoxy)butyl]
Acrylamide, N-[4-(2-mercapto-1
-methylethoxy)butyl]acrylamide, N
-[4-(2,3-dimercaptopropoxy)butyl]acrylamide, N-[4-(2-ethylthio)ethoxy)butyl]acrylamide, N-
[4-(3-(methylthio)propoxy)butyl]
Acrylamide, N-[4-(2-(isopropylthio)ethoxy,butyl]acrylamide, N-
[4-(2-(n-butylthio)ethoxy)butyl]
Acrylamide, N-[4-(2-isobutylthio)ethoxy)butyl]acrylamide, N-
[4-(2-(4-acrylamidobutylthio)ethoxy)butyl]acrylamide, N-[4-(2
-(4-acrylamidothio)-1-methylethoxy)butyl]acrylamide and the like. Examples of substituents of oxyalkylene compounds include N-[4-(2-methoxyethoxy)butyl]acrylamide, N-[4-(3-oxapentyloxy)butyl]acrylamide, and N-[4-(2-methoxyethoxy)butyl]acrylamide.
-(2-methoxy-1-methylethoxy)butyl]
Acrylamide, N-[4-(1-methoxymethylpropoxy)butyl]acrylamide, N-[4
-(3-methoxybutoxy)butyl]acrylamide, N-[4-(2-isopropoxyethoxy)
butyl]acrylamide, N-[4-(3-oxahexyloxy)butyl]acrylamide, N-
[4-(3,6-dioxaheptyloxy)butyl]acrylamide, N-[4-(3-methoxy-
3-methylbutoxy)butyl]acrylamide,
N-[4-(3-oxaheptyloxy)butyl]
Acrylamide, N-[4-(5-methyl-3-oxahexyloxy)butyl]acrylamide,
N-[4-(3,6-dioxaoctyloxy)butyl]acrylamide, N-[4-(1-methyl-
3-oxaheptyloxy)butyl]acrylamide, N-[4-(3,6-dioxanonyloxy)butyl]acrylamide, N-[4-(1-ethoxymethyl-3-oxapentyloxy)butyl]acrylamide, N-[4-(2,4-dimethyl-3,6-dioxaheptyloxy)butyl]
Acrylamide, N-[4-(2,5-dimethyl-
3,6-dioxaheptyloxy)butyl]acrylamide, N-[4-(1,4-dimethyl-3,
6-dioxaheptyloxy)butyl]acrylamide, N-[4-(1,5-dimethyl-3,6-
Dioxaheptyloxy)butyl]acrylamide, N-[4-(3-oxanonyloxy)butyl]acrylamide, N-[4-(3,6-dioxadecyloxy)butyl]acrylamide, N-
[4-(3,6-dioxadodecyloxy)butyl]acrylamide, N-[4-(3-oxapendadecyloxy)butyl]acrylamide, N-
[4-(3,6-dioxaoctadecyloxy)butyl]acrylamide, N-[4-(3,6-dioxatetracosyloxy)butyl]acrylamide, N-[4-(3-oxa-5-stearoyl) oxypentyloxy)butyl]acrylamide, N-
[4-(2-(2-hydroxyethoxy)ethoxy)
butyl]acrylamide, bis[2-(4-acrylamidobutoxy)ethyl]ether, dipropylene glycol mono(4-acrylamidobutyl)ether, dipropylene glycol bis(4-acrylamidobutyl)ether,
-acrylamidobutyl)ether, N-[4-
(3-hexadecyloxy-2-hydroxypropoxy)butyl]acrylamide, 1,2-bis(4-acrylamidobutoxy)-3-hexadecyloxypropane, N-[4-(2-allyloxyethoxy)butyl]acrylamide , N-[4-
(9-octadecenyloxypolyethoxy)butyl]acrylamide, N-[4-(2-(2-chloroethoxy)ethoxy)butyl]acrylamide, N-[4-(2-(2-(diethylamino)ethoxy) )ethoxy)butyl]acrylamide, N-
[4-(2-(2-(4-acrylamidobutylamino)ethoxy)ethoxy)butyl]acrylamide and the like. Next, as a substituent of polyhydric alcohol, for example, N-[4-(2-hydroxyethoxy)butyl]
Acrylamide, 1,2-bis(4-acrylamidobutoxy)ethane, N-[4-(2-hydroxypropoxy)butyl]acrylamide, 1,2
-Bis(4-acrylamidobutoxy)propane, N-[4-(3-hydroxypropoxy)butyl]acrylamide, 1,3-bis(4-acrylamidobutoxy)propane, N-[4-(2-hydroxyptoxy) Butyl] acrylamide,
1,2-bis(4-acrylamidobutoxy)butane, N-[4-(3-hydroxybutoxy)butyl]acrylamide, 1,3-bis(4-acrylamidobutoxy)butane, N-[4-(4-hydroxy) butoxy)butyl]acrylamide, 1,
4-bis(4-acrylamidobutoxy)butane, N-[4-(2,2-dimethyl-3-hydroxypropoxy)butyl]acrylamide, 1,3
-bis(4-acrylamidobutoxy)2,2-
Dimethylpropane, N-[4-(5-hydroxypentyloxy)butyl]acrylamide, 1,5
-bis(4-acrylamidobutoxy)pentane, N-[4-(6-hydroxyhexyloxy)
butyl]acrylamide, 1,6-bis(4-acrylamidobutoxy)hexane, 1,5-bis(4-acrylamidobutoxy)-3-methylpentane, N-[4-(1,2-dimethyl-3-hydroxybutoxy) ) butyl] acrylamide, 2,3
-bis(4-acrylamidobutoxy)-2,3
-dimethylbutane, N-[4-(2,2-diethyl-3-hydroxypropoxy)butyl]acrylamide, 1,3-bis(4-acrylamidobutoxy)-2,2-diethylpropane, N-[4-
(7-hydroxyheptyloxy)butyl]acrylamide, 1,7-bis(4-acrylamidobutoxy)heptane, 2,5-bis(4-acrylamidobutoxy)2,5-dimethylhexane,
N-[4-(2-ethyl-3-hydroxyhexyloxy)butyl]acrylamide, 1,3-bis(4-acrylamidobutoxy)-2-ethylhexane, N-[4-(8-hydroxyoctyloxy)butyl ] Acrylamide, 1,8-bis(4
-acrylamidobutoxy)octane, N-[4
-(3-hydroxy-2,2,4-trimethylpentyloxy)butyl]acrylamide, 1,3
-bis(4-acrylamidobutoxy)-2,2,
4-trimethylpentane, N-[4-(9-hydroxynonyloxy)butyl]acrylamide,
1,9-bis(4-acrylamidobutoxy)nonane, N-[4-(10-hydroxydecyloxy)
butyl] acrylamide, 1,10-bis(4-acrylamidobutoxy)decane, N-[4-(12-
hydroxydodecyloxy)butyl]acrylamide, 1,12-bis(4-acrylamidobutoxy)dodecane, N-[4-(16-hydroxyhexadecyloxy)butyl]acrylamide, 1,16
-bis(4-acrylamidobutoxy)hexadecane, N-[4-(2,3-dihydroxypropoxy)butyl]acrylamide, 1,3-bis(4
-acrylamidobutoxy)-2-propanol,
1,2,3-tris(4-acrylamidobutoxy)propane, N-[4-(2,3-dihydroxybutoxy)butyl]acrylamide, 1,2-bis(4-acrylamidobutoxy)-3-butanol, 1, 3-bis(4-acrylamidobutoxy)-2-butanol, N-[4-(3,4-dihydroxybutoxy)butyl]acrylamide, N
-[4-(2,4-dihydroxybutoxy)butyl]acrylamide, 1,4-bis(4-acrylamidobutoxy)-2-butanol, 1,2,
4-tris(4-acrylamidobutoxy)butane, N-[4-(2,2-bis(hydroxymethyl)propoxy)butyl]acrylamide, 2,
2-bis(4-acrylamidobutoxymethyl)
-1-propanol, 1,1,1-tris(4-
Acrylamidobutoxymethyl)ethane, N-
[4-(5,6-dihydroxyhexyloxy)butyl]acrylamide, 1,6-bis(4-acrylamidobutoxy)-2-hexanol, 1,
2,6-tris(4-acrylamidobutoxy)
Hexane, N-[4-(3,5-dihydroxy-3
-methylpentyloxy)butyl]acrylamide, 1,5-bis(4-acrylamidobutoxy)-3-methyl-3-pentanol, 1,3,
5-tris(4-acrylamidobutoxy)-3
-Methylpentane, N-[4-(2,2-bis(hydroxymethyl)butoxy)butyl]acrylamide, 1,1,1-tris(4-acrylamidobutoxymethyl)propane, N-[4-(2,3 ，
4-trihydroxybutoxy)butyl]acrylamide, 1,4-bis(4-acrylamidobutoxy)-2,3-butanediol, N-[4-(2,
2,2-tris(hydroxymethyl)ethoxy)
butyl] acrylamide, 2,2-bis(4-acrylamidobutoxymethyl)1,3-propanediol, 2,2,2-tris(4-acrylamidobutoxymethyl)ethanol, tetrakis(4-acrylamidobutoxymethyl)methane,
N-[4-(2,3,4,5-tetrahydroxypentyloxy)butyl]acrylamide, 1,5
-bis(4-acrylamidobutoxy)-2,3,
4-Pentanetriol, N-[4-(1,2,
3,4,5-pentahydroxyhexyloxy)
butyl]acrylamide, 1,6-bis(4-acrylamidobutoxy)-2,3,4,5-tetrahydroxyhexane, N-[4-(4-hydroxy-2-butenyloxy)butyl]acrylamide, 1,4- Bis(4-acrylamidobutoxy)-2-butene, N-[4-(5-hydroxy-
3-Hexenyloxy)butyl]acrylamide, 2,5-bis(4-acrylamidobutoxy)-3-hexane, N-[4-(4-hydroxy-2-butynyloxy)butyl]acrylamide, 1,4-bis(4 -acrylamidobutoxy)-2-butyne, N-[4-(5-hydroxy-
3-hexynyloxy)butyl]acrylamide, 2,5-bis(4-acrylamidobutoxy)-3-hexyne, N-[4-(2-hydroxy-1,1,2-trimethyl-3-butynyloxy)butyl]acrylamide, 3,4-bis(4
-acrylamidobutoxy)-3,4-dimethyl-1-pentyne, N-[4-(4-hydroxy-
1,1,4-trimethyl-2-pentynyloxy)butyl]acrylamide, 2,5-bis(4
-acrylamidobutoxy)-2,5-dimethyl-3-hexyne, N-[4-(6-hydroxy-
1,1,6-trimethyl-2,4-heptadiynyloxy)butyl]acrylamide, 2,7-bis(4-acrylamidobutoxy)-2,7-dimethyl-3,5-octadiyne, N-[4- (1,
4-dimethyl-1-ethyl-4-hydroxy-2
-hexynyloxy)butyl]acrylamide,
3,6-bis(4-acrylamidobutoxy)-
3,6-dimethyl-4-octyne, N-[4-(1
-isobutyl-4-hydroxy-1,4,6-trimethyl-2-heptynyloxy)butyl]acrylamide, 4,7-bis(4-acrylamidobutoxy)-2,4,7,9-tetramethyl-5
-Decine, 1-(4-acrylamidobutoxy)-
3-methoxy-2-propanol, 1,2-bis(4-acrylamidobutoxy)-3-methoxypropane, 3-[3-(4-acrylamidobutoxy)-2-hydroxypropoxy]-1,2-propanediol, bis[3-(4-acrylamidobutoxy)-2-hydroxypropyl]ether,
1-(4-acrylamidobutoxy)-3-[2,
3-bis(4-acrylamidobutoxy)propoxy]-2-propanol, bis[2,3-bis(4-acrylamidobutoxy)propyl]ether, 3-[3-(4-acrylamidobutoxy)
-2,2-bis(hydroxymethyl)propoxy]-2,2-bis(hydroxymethyl)-1-propanol, bis[3-(4-acrylamidobutoxy)2,2-bis(hydroxymethyl)propyl]ether, 3-[2,2-bis(4-acrylamidobutoxymethyl)-2-(hydroxymethyl)ethoxy]-2,2-bis(hydroxymethyl)-1-propanol, 2-(4-acrylamidobutoxymethyl)-3 −[2,2-bis(4-
Acrylamidobutoxymethyl)-2-(hydroxymethyl)ethoxy]-2-(hydroxymethyl)
-1-propanol, 2,2-bis(hydroxymethyl)-3-[2,2,2-tris(4-acrylamidobutoxymethyl)ethoxy]-1-propanol, 2-(4-acrylamidobutoxymethyl)-2 -(hydroxymethyl)-3-[2,2,
2-tris(4-acrylamidobutoxymethyl)ethoxy]-1-propanol, bis[2,
2-bis(4-acrylamidobutoxymethyl)
-2-(hydroxymethyl)ethyl]ether,
2,2-bis(4-acrylamidobutoxymethyl)-3-[2,2,2-tris(4-acrylamidobutoxymethyl)ethoxy]-1-propanol, bis[2,2,2-tris(4-acrylamidobutoxymethyl)ethoxy] butoxymethyl)ethyl]ether, 1-
(4-acrylamidobutoxy)-3-(allyloxy)-2-propanol, 1-(allyloxy)
-2,3-bis(4-acrylamidobutoxy)
Propane, 1-[2-(4-acrylamidobutoxy)ethoxy]-4-(2-hydroxyethoxy)
-2-butyne, 2-butyne-1,4diol-bis[2-(4-acrylamidobutoxy)ethyl]
Ether, N-[4-(3-chloro-2-hydroxypropoxy)butyl]acrylamide, 1,2
-bis(4-acrylamidobutoxy)-3-chloropropane, N-[4-(3-hydroxy-2-
Methyl-2-nitropropoxy)butyl]acrylamide, 1,3-bis(4-acrylamidobutoxy)-2-methyl-2-nitropropane, 2
-(4-acrylamidobutoxymethyl)-2-nitro-1,3-propanediol, tris(4-
acrylamide butoxymethyl) nitromethane,
Bis[2-(4-acrylamidobutoxy)ethyl]amine, tris(4-acrylamidobutoxymethyl)aminomethane, N,N-bis(2-
(4-acrylamidobutoxy)ethyl]methylamine, bis[2-(4-acrylamidobutoxy)propyl]amine, -[2-(4-acrylamidobutoxy)ethyl]-N-ethylethanolamine, N,N-bis[ 2-(4-acrylamidobutoxy)ethyl]ethylamine, N-[2-
(4-acrylamidobutoxy)ethyl]diethanolamine, tris[2-(4-acrylamidobutoxy)ethyl]amine, N-[2-(4-acrylamidobutoxy)ethyl]-N-n-butylethanolamine, N,N- Bis [2-(4-
Acrylamidobutoxy)ethyl]n-butylamine, N,N-bis[2-(4-acrylamidobutoxy)propyl]isopropanolamine,
Tris[2-(4-acrylamidobutoxy)propyl]amine, 1-[N-(2-(4-acrylamidobutoxy)ethyl)ethanolamino]-
2-(diethanolamino)ethane, 1,2-bis[N-(2-(4-acrylamidobutoxy)ethyl)ethanolamino]ethane, 1,2-bis[bis(2-(4-acrylamidobutoxy)ethyl) Amino]ethane, N-[2-(4-acrylamidobutoxy)ethyl]-N-laurylethanolamine, N,N-bis[2-(4-acrylamidobutoxy)ethyl]laurylamine, N-
[2-(4-acrylamidobutoxy)ethyl]-
N-stearylethanolamine, N,N-bis(2-(4-acrylamidobutoxy)ethyl]stearylamine, N-[w-(4-acrylamidobutoxy)polyoxyethylene]-N-(polyoxyethylene)alkylamine , N, N-bis [w
-(4-acrylamidobutoxy)polyoxyethylene]alkylamine, 6-(4-acrylamidobutoxy)-2-hydroxyhexanal,
2,6-bis(4-acrylamidobutoxy)hexanal, 3-(4-acrylamidobutoxy)
-2-hydroxypropanal, 2,3-bis(4-acrylamidobutoxy)propanal,
4-(4-acrylamidobutoxy)-2,3-dihydroxybutanal, 2,4-bis(4-acrylamidobutoxy)-3-hydroxybutanal, 2,3,4-tris(4-acrylamidobutoxy)butanal, (4-acrylamidobutoxy)-hydroxymalonate disodium, bis(4-acrylamidobutoxy)malonate disodium, 3-(4-acrylamidobutoxy)-2
-Sodium hydroxypropionate, 1,2,
Sodium 3-bis(4-acrylamidobutoxy)propionate, 1-acetyloxy-3-
(4-acrylamidobutoxy)-2-propanol, 1-acetyloxy-2,3-bis(4-acrylamidobutoxy)propane, 1-(4-acrylamidobutoxy)-3-propionyloxy-2-propanol, 1- (4-acrylamidobutoxy)-3-lauroyloxy-2-propanol, 1,2-bis(4-acrylamidobutoxy)-3-lauroyloxypropane, 1-
(4-acrylamidobutoxy)-3-stearoyloxy-2-propanol, 1,2-bis(4
-acrylamidobutoxy)-3-stearoyloxypropane, 2,3-bis(4-acrylamidobutoxy) disodium succinate, 2-(4
-Acrylamidobutoxy)-3-hydroxysuccinic acid disodium, 1-(4-acrylamidobutoxy)-3-(2,4-hexadienoyloxy)-2-propanol, 1,2-bis(4-acrylamidobutoxy) -3-(2,4-hexadienoyloxy)propane, 1-(4-acrylamidobutoxy)-3-(9-octadecenoyloxy)-2-propanol, 1-(4-acrylamidobutoxy)-3 -mercapto-2-propanol, 1,2-bis(4-acrylamidobutoxy)-3-mercaptopropane, 2-[2-(4-
Acrylamidobutoxy)ethylthio]ethanol, 1,1'-thiobis[2-(4-acrylamidobutoxy)ethane], 3-(4-acrylamidobutoxy)-1,4-dimercapto-2-butanol, 2,3-bis( 4-acrylamidobutoxy)-1,4-dimercaptobutane, N,N-bis[2-(4-acrylamidobutoxy)ethyl]
-2-Sodium aminoethanesulfonate, 1-
(4-acrylamidobutylthio)-2,3-bis(4-acrylamidobutoxy)propane, 2,
3-bis(4-acrylamidobutoxy)-1,
Examples include 4-bis(4-acrylamidobutylthio)butane. Next, in the general formula (1), α=3, β=n=p=1
An example will be given by fixing l=q=0, changing R to a hydrogen atom or a methyl group, and changing m to 4 to 20. Examples of these compounds include N-(4-allyloxybutyl)acrylamide, N-(4-allyloxybutyl)methacrylamide, N-(5-allyloxypentyl)acrylamide, N-(5-allyloxypentyl)methacrylamide, N-(6
-aryloxyhexyl)acrylamide, N-
(6-allyloxyhexyl)methacrylamide,
N-(8-allyloxyoctyl)acrylamide,
N-(8-allyloxyoctyl)methacrylamide, N-(10-allyloxydecyl)acrylamide, N-(10-allyloxydecyl)methacrylamide, N-(12-allyloxydodecyl)acrylamide, N-(12-allyloxydecyl) ) methacrylamide, N-(14-aryloxytetradecyl)
Acrylamide, N-(14-allyloxytetradecyl)methacrylamide, N-(16-allyloxyhekidecyl)acrylamide, N-(16-allyloxyhexadecyl)methacrylamide, N-(18
-aryloxyoctadecyl)acrylamide, N
-(18-allyloxyoctadecyl)methacrylamide, N-(20-allyloxyeicosyl)acrylamide, N-(20-allyloxyeicosyl)methacrylamide, and the like. The aliphatic N-substituted unsaturated amide compound exemplified above is, for example, a non-proton polar It is produced by reacting in a solvent in the presence of a strongly acidic substance. The structure of the aliphatic halogen-substituted ether compound and unsaturated amide compound that are the targets of the method of the present invention is exactly the same as the general formula detailed in the description of the aliphatic N-substituted unsaturated amide compound. Therefore, we will not discuss them in detail, but examples of aliphatic halogen-substituted ether compounds include hydroxyl-substituted aliphatic saturated and unsaturated compounds in which at least one hydroxyl group is substituted with a halogen-substituted ether group, and oxyalkylene compounds in which at least one hydroxyl group is substituted with a halogen-substituted ether group. Targets include those substituted with substituted ether groups. Among the various groups represented by A' in general formula (2),
The bonding mode of the halogen atom is the general formula (-CH ₂ ) _-nX
In addition, alkoxy groups, acyl groups, acyloxy groups and carboxy ester groups have the general formulas RO-, RCO-, RCOO-, respectively.
It is represented by -COOR, where R includes not only an alkyl group but also an alkenyl group and an aryl group. In addition, in the case of a carboxyester group, R is a w-halopolymethylene group ((-CH ₂ ) _-nX )
It further includes cases where it represents. In addition to the formula -COOH, the carboxyl group also includes the formula -COO ^- M ⁺ (M ⁺ represents an alkali metal ion). The amino group has the general formula

It is represented by [Formula], and R′ and R″ are hydrogen, a lower alkyl group, or a w-halopolymethylene group, and may be different from each other. Also, unsaturated amide compounds include acrylamide and methacrylamide. In the present invention, specific methods for conducting the reaction in the presence of a strongly basic substance include a method in which the reaction is initiated by dissolving the strongly basic substance in the reaction solution, and a method in which the reaction is initiated in the presence of the strongly basic substance in suspension. There is a method to start the process.In the case of the present invention, either method can be adopted.
Surprisingly, it is preferable to start the reaction under suspension of a strongly basic substance in terms of reaction efficiency such as suppression of side reactions. More specifically, methods for starting the reaction while suspending a strong basic substance include a method in which the three components are simultaneously supplied and mixed in an aprotic polar solvent to suspend the strong basic substance and the reaction is carried out; A method in which a strong basic substance is suspended in a protic polar solvent, and then an aliphatic halogen-substituted ether compound and an unsaturated amide compound are simultaneously supplied and reacted, and an aliphatic halogen-substituted ether is added to an aprotic polar solvent. An appropriate method may be employed, such as dissolving or suspending the compound and the unsaturated amide compound, and then adding and suspending a strong basic substance. The reaction solvent used in the present invention may be any aprotic polar solvent, such as acetonitrile,
Examples include N,N-dimethylformamide, N,N-dimethylacetamide, dimethylsulfoxide, sulfolane, tetraglyme, dioxane, and N-methylpyrrolidone. In the reaction system in the method of the present invention, it is preferable to start the reaction in a state where at least a part of the strong basic substance is suspended, and the amount of water in such a state is the amount of water in the reaction system. It is usually about 6% by weight. If the amount of water exceeds this value, side reactions such as hydrolysis of the dihalogen-substituted compound are likely to occur, resulting in a significant decrease in yield. To perform the reaction efficiently and increase the yield of the target product,
It is preferable that the water content of the reaction system is 5% by weight or less. The amount of solvent used is not particularly limited, but it is 5 to 95% by weight, preferably 10 to 90% by weight based on the total amount of reactants including the solvent.
% by weight. Next, the strong basic substance used in the present invention can be used as long as it is a solid substance and has an aqueous solution pH of 10 or higher, preferably 11 or higher when dissolved or suspended in water. Such basic substances include, for example, alkali metal hydroxides, alkali metal oxides, alkali metal carbonates, alkaline earth metal hydroxides, alkaline earth metal oxides, alkali metal hydrides, alkaline earth metal hydrogens. compounds, alkali metal amides, alkali metal alkoxides, etc. Examples of the above substances include alkali metal hydroxides such as sodium hydroxide, potassium hydroxide, lithium hydroxide, rubidium hydroxide, and cesium hydroxide. Examples of the alkali metal oxide include sodium oxide, potassium oxide, lithium oxide, rubidium oxide, and cesium oxide. Alkali metal carbonates are, for example, sodium carbonate, potassium carbonate, lithium carbonate, rubidium carbonate, and cesium carbonate. Examples of alkaline earth metal hydroxides include beryllium hydroxide, magnesium hydroxide, calcium hydroxide, strontium hydroxide, and barium hydroxide. Examples of alkaline earth metal oxides include beryllium oxide, magnesium oxide, calcium oxide, strontium oxide, and barium oxide. Examples of the alkali metal hydride include sodium hydride, potassium hydride, and lithium hydride. Examples of alkaline earth metal hydrides include beryllium hydride, magnesium hydride, and calcium hydride.
Alkali metal amides are alkali metal substituted compounds of ammonia, such as sodium amide, potassium amide, lithium amide, and the like. Alkali metal alkoxide is a compound in which the proton of the hydroxyl group of alcohol is replaced with an alkali metal.
Examples include sodium methoxide, sodium ethoxide, sodium t-butoxide, potassium methoxide, potassium ethoxide, potassium t-butoxide, and the like. Among the above-mentioned basic substances, those suitable for carrying out the method of the present invention are, for example, alkali metal hydroxides, alkaline earth metal hydroxides, alkali metal oxides, alkaline earth metal oxides, alkali metal Carbonates, etc. These strongly basic substances are usually used in the reaction in solid form, and the reaction is initiated while at least a portion of them is suspended in the reaction solution. In carrying out the present invention, the relative amounts of the raw materials, such as an aliphatic halogen-substituted ether compound, an unsaturated amide compound, and a strong basic substance, will vary depending on the reactivity of the aliphatic halogen-substituted ether compound and the unsaturated amide compound. Therefore, it cannot be specified uniformly. However, in general, the amount of aliphatic halogen-substituted ether compound used is 0.2 to 20% relative to the unsaturated amide compound.
twice the mole, preferably in the range of 0.3 to 10 times the mole,
The amount of strong basic substance used is 0.2 per amide compound.
It is in the range of ~15 times the mole, preferably 0.5 to 10 times the mole. Furthermore, a polymerization inhibitor may be added to prevent polymerization of raw materials and products during reaction and purification steps. In this case, the polymerization inhibitor is not particularly limited, but generally includes phenolic inhibitors, amine inhibitors, mercaptan inhibitors, copper powder, and the like. For the reaction method, a normal reaction vessel may be used, or if a strongly basic substance with low solubility is used, it is packed in a column and the aliphatic halogen-substituted ether compound and unsaturated amide compound are combined. A flow type method may also be used in which a mixed solution of is passed through and circulated. However, a reaction vessel is more convenient for equipment maintenance and management. The reaction temperature depends on the reactivity of the aliphatic halogen-substituted ether compound and unsaturated amide compound used, but if the reaction temperature is low, the reaction progresses slowly, while if the temperature is high, the unsaturated amide compound may undergo hydrolysis, etc. side reactions occur and the yield of the product decreases. Therefore, the temperature range is usually 30 to 100°C, preferably 20 to 70°C. As long as it is within this temperature range, it is not necessarily necessary to keep the temperature constant during the reaction, but it is sufficient to keep track of the progress of the reaction and appropriately set the reaction temperature to carry out the reaction efficiently. Further, the reaction time also varies depending on the aliphatic halogen-substituted ether compound and unsaturated amide compound used, as well as the reaction temperature, but it is 30 hours at the longest, and usually within 20 hours. The progress of the reaction can be understood by observing changes in the properties of the reaction system and the concentrations of raw materials and target products in the reaction solution by gas chromatography or high performance liquid chromatography. After the reaction, by-produced metal halides are filtered off and distilled under reduced pressure using a conventional method to obtain a highly pure target product. However, if the metal halide is dissolved in the reaction solution, after distilling off the solvent,
After removing the above substances with a combination of solvents forming two layers, such as water, benzene-water, or chloroform-water, the desired product can be obtained with high purity by distillation under reduced pressure. However, many of the compounds of the present invention generally have a high boiling point and are nonvolatile, and furthermore, they have highly polymerizable double bonds in their molecules, so distillation purification may not be possible. There are many. In such cases, the target product can be separated with high purity by a method using solvent extraction, recrystallization, or a purification method using an adsorbent such as silica gel, alumina, activated carbon, ion exchange resin, or adsorption resin.
Further, the above methods may be combined. The reaction solvent has a high affinity for water, such as dimethyl sulfoxide and N,N-dimethylformamide,
If the target product is highly lipophilic, after the reaction, add an aliphatic hydrocarbon solvent such as hexane to the reaction solution to extract the target product, or add water to the reaction solution to separate the target product as an oil layer. Alternatively, a method of extracting and separating the target product using a solvent that forms two layers with water such as benzene, toluene, or chloroform can also be applied. According to the present invention, a wide variety of aliphatic N-substituted unsaturated amide compounds can be produced in the same reactor using the same reaction mode, and is suitable for producing a wide variety of products in small quantities. As shown in the compound examples, the aliphatic N-substituted unsaturated amide compounds of the present invention have a wide variety of substituents introduced into their side chains, and can be applied in a wide variety of fields depending on the introduced substituents. It is possible. Specific applications include adhesives, paint and paper processing agents, fiber processing agents, emulsions, urethane curing agents, pigment dispersants, plastic additives, polymer flocculants, ion exchange resins, adsorption separation resins, chelate resins, optical lenses, Main raw materials, auxiliary raw materials, crosslinking agents, etc. for photosensitive resins, soft contact lenses, water absorbing resins, magnetic material binders, water absorbing resins, polymer catalysts, clinical reagents, biocompatible materials, enzyme immobilization base materials, etc. It can be applied in many fields. Next, the present invention will be further explained by examples. Example 1 1.16 g of acrylamide and 1-(4-bromobutoxy)- in 20 ml of N,N-dimethylformamide
4.0 g of n-dodecane was added, and while stirring, 0.74 g of flaky potassium hydroxide ground in a mortar was added, and the mixture was reacted at 0 to 5°C for 6 hours. In addition, 0.5% of phenothiazine was added to acrylamide. After reacting for a predetermined time, insoluble substances in the reaction solution were separated, and the solvent and unreacted raw materials were distilled off from the solution.
The residue was extracted with benzene-water to obtain the desired product in the benzene layer. Benzene is distilled off from the benzene layer, and N
3.11 g (yield: 80%) of -(4-n-dodecyloxybutyl)acrylamide was obtained. This product was further purified by column chromatography using silica gel as an adsorbent and benzene as a developing solvent.
Melting point measurement and elemental analysis showed melting point of 52-53℃, elemental analysis value: carbon 73.08% (calculated value 73.23), hydrogen 11.31
% (11.99%) and titanium 4.56% (4.45%). Example 2 A reaction was carried out using the combinations of raw materials, strong basic substances, and solvents listed in Table 1 under the conditions listed in Table 1. After the reaction, treatment was carried out in exactly the same manner as in Example 1, and the results shown in Table 2 were obtained.

【table】

[Table] Example 3 1.96 g of acrylamide and 4.0 g of 1-bromo-4-ethoxybutane were added to 20 ml of N,N-dimethylformamide, and while stirring, 1.44 g of flaky potassium hydroxide crushed in a mortar was added, 0～
The reaction was carried out at 5°C for 6 hours. In addition, 0.5% of phenothiazine was added to acrylamide. After reacting for a predetermined time, insoluble substances in the reaction solution were separated, and the solvent and unreacted raw materials were distilled off from the solution. The residue was extracted with benzene-water to obtain the desired product in the benzene layer.
Benzene was distilled off from the benzene layer to obtain 2.84 g of N-(4-ethoxybutyl)acrylamide (yield: 75
%) was obtained. This product was further purified by column chromatography using silica gel as an adsorbent and a benzene-methanol mixed solvent as a developing solvent, and the refractive index was measured up to 25°C and elemental analysis was performed.
Refractive index (25℃) 1.4719 and elemental analysis value: carbon
63.69% (calculated value 63.11%), hydrogen 10.72% (10.02
%), Chituso obtained a result of 8.57% (8.18%). Examples 4 to 24 Reactions were carried out using the combinations of raw materials, strong basic substances, and solvents listed in Tables 3 to 5 under the conditions listed in Table 3. After the reaction,
The treatment was carried out in exactly the same manner as in Example 3, and the results shown in Table 4 were obtained.

【table】

【table】

[Table] Example 25 <Production of water absorbing resin> Adding 1% of tert-butylperoxy-2-ethylhexanoate to N-acryloylpyrrolidine containing 0.2% of bis[2-(4-acrylamidobutoxy)ethyl]ether The mixture was left at 40° C. for 50 hours to carry out solvent-free polymerization to obtain a block-shaped polymer. The polymer was pulverized to obtain a product as a powder. 1.0 g of this product powder was put into a graduated cylinder containing 50 ml of distilled water, and the water absorption volume of the resin was measured at 25°C, and it was found to be 23 ml.

Claims (1)

[Scope of Claims] 1 General formula [formula] (where A is a halogen atom or a w-unsaturated amide polymethylene group (represents [formula]), a hydroxyl group, an alkoxy group, a cyano group, a nitro group, an amino group, aldehyde group, acyl group, acyloxy group,
It is a carboxyl group, a carboxy ester group, a mercapto group, or a group consisting of a sulfonic acid or a salt thereof, B is an oxygen atom, a carbonyl group, a thio group, a sulfonyl group, or an azo group, and R is a hydrogen atom or a methyl group. l is an integer of 0 to 5, and when l is 2 or more, A may be different. m is an integer of 4 to 20, and n is an integer of 1 to 4.
α is an integer from 1 to 30, and β is an integer from 0 to 3 smaller than α. p is an integer of 1 or 2, and q is an integer of 0 or 1. When p is 1, q is 0
When p is 2, q is 1, and in this case, A, α, β, l, and n on the left and right may be different. ) An aliphatic N-substituted unsaturated amide compound represented by: 2. General formula or a salt thereof, B is an oxygen atom, a carbonyl group, a thio group, a sulfonyl group, or an azo group, and X is a halogen atom. l is an integer of 0 to 5, and if l is 2 or more,
A′ may be different. m is an integer from 4 to 20,
n is an integer from 1 to 4. α is an integer from 1 to 30,
β is an integer from 0 to 3 smaller than α. p is an integer of 1 or 2, and q is an integer of 0 or 1. When p is 1, q is 0; when p is 2, q is 1; in this case, the left and right A', α, β, l,
n may be different. ) An aliphatic halogen-substituted ether compound represented by the following formula and an unsaturated amide compound represented by the general formula (R is a hydrogen atom or a methyl group) are combined in an aprotic polar solvent in the presence of a strong basic substance. Aliphatic N- represented by the general formula: (A, B, R, l, m, n, α, β, p, q are the same as the above general formula) A method for producing a substituted unsaturated amide compound.