JPH0122258B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to an N-substituted polyamine and a method for producing the same. [ _Wherein ,

[Formula] (M represents hydrogen, a metal atom or an ammonium group), p represents 0 or 1. Y is a general formula [However, R ₁ and R ₂ are hydrogen, hydroxyl group, phenyl group, or -COOR ₆ group (R ₆ is a metal atom, ammonium group, lower alkyl group, lower alkoxy lower alkyl group, lower alkenyl group , lower alkylamino lower alkyl group, mono- or polyhydroxy lower alkyl group, phenyl group or substituted phenyl group, or benzyl group or substituted benzyl group). R ₃ and R ₄ are hydrogen,
Represents a hydroxyl group, a lower alkyl group, a phenyl group or a substituted phenyl group, -OM group (M is a metal atom),
1, m and n represent 0 or 1. R and
R' is hydrogen, a cyano group, -COR ₅ group (R ₅ represents an amino group or lower alkylamino group), -COOR ₆ group (R ₆ is the same as above), or R and R' are -NH- or - A
represents hydrogen or hydroxyl group. ], and Y' represents a lower amino lower alkyl group, a mono- or dihydroxy lower alkyl group, a disodium carbonyl lower alkyl group, or hydrogen. ], and is particularly useful as an intermediate for N-substituted polyalkylene bisdithiocarbamates. It is known that N-substituted amines can be obtained by the addition reaction of aliphatic amines to activated olefins. describes reaction examples and references between various monoamines and olefins. Among them, Org.Synth.
, 258 (1955) and J.Am.Chem.Soc., 71 ,
2124 (1949) gives an example of the reaction of monomethylamine to a carboxylic ester with an olefin, providing an N-substituted amine. For example, according to the former, 2CH ₂ = CHCO ₂ C ₂ H ₅ + CH ₃ NH ₂ --------→ CH ₃ N (CH ₂ CH ₂ CO ₂ C ₂ H ₅ ) ₂ in ethanol at 40℃, and According to the latter, CH ₂ = CHCO ₂ C ₂ H ₅ + CH ₃ NH ₂ ―――――――――→ CH ₃ NHCH ₂ CH ₂ CO ₂ C ₂ H ₅ in absolute ethanol. However, an N-substituted polyamine in which a substituent having two or more carboxyl groups is substituted with nitrogen is an undescribed compound, and there are also examples in which a polyamine is reacted with a monoethylenically unsaturated compound having such a substituent. I can't find it. As shown in the above general formula (), the present invention includes:
N- in which a substituent having two or more carboxyl groups or a substituent having that functional group is substituted with nitrogen.
An object of the present invention is to provide a substituted polyamine. The manufacturing method for providing the compound of the present invention includes:
Possible methods include adding a polyamine to a monoethylenically unsaturated compound having a carboxyl group or its functional group, or an epoxidized compound, or substituting the polyamine with a halogenated compound having a carboxyl group. and,
Taking this as a reaction example, the former addition reaction is as follows. or In the case of a substitution reaction, the reaction is as follows. The polyamines used in the present invention include alkylene diamines, polyalkylene polyamines, hydrazine, etc. Specific examples include ethylene diamine, 1,2-propylene diamine,
1,3-propylene diamine, 1,2-diaminobutane, 2,3-diaminobutane, 1,2-diamino-2-methylpropane, 1,3-diamino-
2-methylpropane, 1,2-diamino-2,2
-dimethylethane, 1,4-diaminobutane,
1,5-diaminopentane, 1,6-diaminohexane, 1,7-diaminoheptane, 1,8-diaminooctane, 1,12-diaminododecane,
1,2-diamino-2-methylbutane, 1,2-
Diaminopentane, 1,2-diaminohexane,
1,2-diaminoheptane, 1,2-diaminooctane, 2,3-diaminopentane, 2,3-diaminohexane, 2,3-diaminoheptane,
2,3-diaminooctane, 1,2-diamino-
2-methylpentane, 2,3-diamino-3-methylpentane, 1,2-diamino-2-ethylbutane, 1,2-diamino-2-methylhexane,
1,2-diamino-2-ethylpentane, 3,4
- Diaminohexane, 1,2-diamino-3-methylbutane, hydrazine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, 2,5-diamino-2,5-dimethylhexane, bisaminoethylpropylenediamine, methylenediamine, etc. can be mentioned. To prepare N-substituted polyamines from the above polyamines, itaconic acid and its functional derivatives, maleic acid and its functional derivatives, fumaric acid and its functional derivatives, citraconic acid and its functional derivatives, mesaconic acid and Functional derivatives thereof, 1,2-dicarboxyacetylene and functional derivatives thereof, especially monoethylenically unsaturated compounds such as esters, amides, nitrile salts thereof, or epoxy compounds are subjected to an addition reaction. Specific examples of these compounds reacted with the above polyamine include sodium fumarate, potassium fumarate, ammonium fumarate, lithium fumarate, calcium fumarate, magnesium fumarate, trimethylammonium fumarate, triethylammonium fumarate, fumaric acid Triethanolammonium, sodium-potassium fumarate, sodium-ammonium fumarate, monosodium fumarate, monopotassium fumarate, monoammonium fumarate, monolithium fumarate,
Fumaric acid, methyl fumarate, ethyl fumarate, propyl fumarate, isopropyl fumarate, butyl fumarate, sec-butyl fumarate, tert-butyl fumarate, pentyl fumarate, hexyl fumarate, fuptyl fumarate, octyl fumarate , decyl fumarate, dodecyl fumarate, hexadecyl fumarate, octadecyl fumarate, vinyl fumarate,
Allyl fumarate, butenyl fumarate, hydroxyethyl fumarate, ethoxyethyl fumarate, dimethylaminoethane fumarate, phenyl fumarate,
Chlorphenyl fumarate, tolyl fumarate, methoxyphenyl fumarate, benzyl fumarate, chlorbenzyl fumarate, sodium maleate, potassium maleate, ammonium maleate, lithium maleate, calcium maleate, magnesium maleate, trimethyl maleate Ammonium, triethanolammonium maleate, tetramethylammonium maleate,
Sodium-potassium maleate, sodium-ammonium maleate, monosodium maleate, monopotassium maleate, monoammonium maleate, monolithium maleate, maleic acid, methyl maleate, ethyl maleate, propyl maleate, butyl maleate , octyl maleate, octadecyl maleate, hydrazide maleate, sodium itaconate, potassium itaconate, ammonium itaconate, lithium itaconate, calcium itaconate, magnesium itaconate, trimethylammonium itaconate, sodium-potassium itaconate, itaconate Sodium-ammonium, potassium-ammonium itaconate, monopotassium itaconate, monosodium itaconate, monoammonium itaconate, itaconic acid, methyl itaconate,
Ethyl itaconate, propyl itaconate, isopropyl itaconate, butyl itaconate, sec-butyl itaconate, tert-butyl itaconate, pentyl itaconate, (1-methyl)butyl itaconate,
(1-ethyl)propyl itaconate, hexyl itaconate, heptyl itaconate, octyl itaconate, nonyl itaconate, decyl itaconate, undecyl itaconate, dodecyl itaconate, tridecyl itaconate, tetradecyl itaconate, pentadecyl itaconate, itaconate hexadecyl itaconate, octadecyl itaconate, vinyl itaconate, allyl itaconate, butenyl itaconate, hydroxyethyl itaconate, methoxyethyl itaconate, ethoxyethyl itaconate, dibutylaminoethyl itaconate, phenyl itaconate,
Tolyl itaconate, methoxyphenyl itaconate, benzyl itaconate, chlorbenzyl itaconate, sodium citraconate, potassium citraconate, ammonium citraconate, trimethylammonium citraconate, triethanolammonium citraconate, tetramethylammonium citraconate, citraconic acid Lithium, Calcium Citraconate, Magnesium Citraconate, Sodium-Potassium Citraconate, Sodium Ammonium Citraconate, Monosodium Citraconate, Monopotassium Citraconate, Monoammonium Citraconate, Monolithium Citraconate, Citraconic Acid, Methyl Citraconate, Citraconic Acid Ethyl, propyl citraconate, butyl citraconate, octyl citraconate, dodecyl citraconate, hydroxyethyl citraconate, allyl citraconate, dibutylaminoethyl citraconate, phenyl citraconate, benzyl citraconate, p-methylbenzyl citraconate, citracone Chlorbenzyl acid, ethoxyethyl citraconate, methoxypropyl citraconate, sodium mesaconate, potassium mesaconate, ammonium mesaconate, lithium mesaconate, trimethylammonium mesaconate, sodium-potassium mesaconate, potassium-ammonium mesaconate, monomethaconate Sodium, monopotassium mesaconate, monoammonium mesaconate, mesaconic acid, methyl mesaconate, ethyl mesaconate, propyl mesaconate, butyl mesaconate, octyl mesaconate, sodium 3-sodiumoxycarbonyl-2,3-epoxypropionate, Methyl 3-methoxycarbonyl-2,3-epoxypropionate, 3-ethoxy-2,3
-Ethyl epoxypropionate, propyl 3-propoxycarbonyl-2,3-epoxypropionate, butyl 3-butoxycarbonyl-2,3-epoxypropionate, octyl 3-octyloxycarbonyl-2,3-epoxypropionate, 3 -Carboxy-2,3-epoxypropionic acid, 3-potassiumoxycarbonyl-2,3-
Potassium epoxypropionate, sodium 3-sodiumoxycarbonyl-3,4-epoxylactate, 3-carboxy-3,4-epoxylacic acid, methyl 3-methoxycarbonyl-3,4-epoxylactate, 3-ethoxycarbonyl -3,4
-Ethyl epoxy lactate, propyl 3-propoxycarbonyl-3,4-epoxy lactate, butyl 3-butoxycarbonyl-3,4-epoxy lactate, sodium phenyl maleate, potassium phenyl maleate, ammonium phenyl malate, Lithium phenylmaleate, trimethylammonium phenylmaleate, sodium-potassium phenylmaleate, phenylmaleic acid, p-chlorophenylmaleic acid, m-chlorophenylmaleic acid, o-chlorophenylmaleic acid, Sodium p-chlorophenyl maleate, sodium m-chlorphenyl maleate,
Sodium o-chlorphenyl maleate, p-
Sodium bromphenyl maleate, sodium p-iodophenyl maleate, sodium 2,4-dichlorophenyl maleate, sodium 2,5-dichlorophenyl maleate, 2,6-
Sodium dichlorophenyl maleate, 3,5
- Sodium dichlorophenyl maleate, 3,
Sodium 4-dichlorophenylmaleate,
Sodium 2,3-dichlorophenyl maleate, sodium trichlorophenyl maleate,
Sodium tetrachlorphenyl maleate, p
- Sodium chlorfumarate, p-sodium tolylfumarate, methyl p-chlorofumarate, p-
Ethyl chlorofumarate, sodium acetylene dicarboxylate, potassium acetylene dicarboxylate,
Ammonium acetylene dicarboxylate, sodium-potassium acetylene dicarboxylate, acetylene dicarboxylic acid, methyl acetylene dicarboxylate, ethyl acetylene dicarboxylate, propyl acetylene dicarboxylate, butyl acetylene dicarboxylate, octyl acetylene dicarboxylate, dodecyl acetylene dicarboxylate, 1,1- Dicarboxyethylene, 1,1-disodiumoxycarbonylethylene, 1,1-dipotassiumoxycarbonylethylene, 1,1-diammoniumoxycarbonylethylene, 1,1-ditrimethylammoniumoxycarbonylethylene, 1,1-dimethoxycarbonylethylene Ethylene, 1,1-diethoxycarbonylethylene, 1,1-dipropoxycarbonylethylene, 1,1-diisopropoxycarbonylethylene, 1,1-dibutoxycarbonylethylene, 1,1-dioctyloxycarbonylethylene, benzalmalonic acid , methyl benzalmalonate, ethyl benzalmalonate, isopropyl benzalmalonate, butyl benzalmalonate,
Hexyl benzalmalonate, octyl benzalmalonate, dodecyl benzalmalonate, sodium benzalmalonate, potassium benzalmalonate,
Ammonium benzalmalonate, lithium benzalmalonate, sodium-potassium benzalmalonate, p-chlorobenzalmalonic acid, sodium p-chlorobenzalmalonate, potassium p-chlorobenzalmalonate, ammonium p-chlorobenzalmalonate, p-chlorobenzalmalonate -Lithium chlorbenzalmalonate, sodium dichlorobenzalmalonate,
Sodium trichlorobenzalmalonate, sodium brombenzalmalonate, sodium p-tolylbenzalmalonate, sodium p-methoxybenzalmalonate, sodium p-nitrobenzalmalonate, oxalacetic acid, sodium oxalacetate, oxalacetic acid Potassium, ammonium oxalacetate, lithium oxalacetate, dimethyloxalacetate, sodium diethyloxalacetate, sodium disodium oxalacetate, sodium dipropyloxalacetate, sodium diisopropyloxalacetate, sodium dibutyloxalacetate, dioctyloxal Sodium acetate, sodium didodecyloxalacetate, sodium diallyloxalacetate, di(2-hydroxyethyl)
Sodium oxalacetate, disodium methoxymethylenemalonate, disodium ethoxymethylenemalonate, disodium isopropoxymethylenemalonate, disodium propoxymethylenemalonate, disodium butoxymethylenemalonate, disodium octyloxymalonate, methoxymethylenemalonate dimethyl acid, diethyl ethoxymethylenemalonate, diisopropyl isopropoxymethylenemalonate, dipropyl propoxymethylenemalonate, dibutyl butoxymethylenemalonate, dioctyloxymethylenemalonate, didodecyl didodecyloxymethylenemalonate, diallyloxymethylenemalonate, 3-anilinomalonate, sodium 3-anilinomalonate, potassium 3-anilinomalonate,
Ammonium 3-anilinomalonate, lithium 3-anilinomalonate, tetramethylammonium 3-anilinomalonate, methyl 3-anilinomalonate, ethyl 3-anilinomalonate, aconitic acid, trisodium aconitate, tripotassium aconitate, triammonium aconitate,
Trilithium aconitate, trimethylammonium aconitate, tetramethylammonium aconitate, trimethyl aconitate, triethyl aconitate, triisopropyl aconitate, tripropyl aconitate, tributyl aconitate, trioctyl aconitate, tridecyl aconitate, triallyl aconitate, 3-
p-Chloranilinomalonate, sodium 3-p-chloroanilinomalonate, disodium trans-glutaconate, dipotassium trans-glutaconate, diammonium trans-glutaconate, dilithium trans-glutaconate, ditrans-glutaconate tetramethylammonium,
Dimethyl trans-glutaconate, diethyl trans-glutaconate, dipropyl trans-glutaconate, diisopropyl trans-glutaconate, dibutyl trans-glutaconate, dioctyl trans-glutaconate, didodecyl trans-glutaconate, cis-glutaconic acid, cis-
Disodium glutaconate, dipotassium cis-glutaconate, diammonium cis-glutaconate, dilithium cis-glutaconate, ditrimethylammonium cis-glutaconate, methyl cis-glutaconate, ethyl cis-glutaconate, propyl cis-glutaconate, Isopropyl cis-glutaconate, Butyl cis-glutaconate, Octyl cis-glutaconate, Octadecyl cis-glutaconate, α-dihydromuconic acid, Sodium α-dihydromuconate, Potassium dihydromuconate, Ammonium α-dihydromuconate, α
-tetramethylammonium dihydromuconate,
α-Dihydromuconic acid sodium-potassium, α
-Methyl dihydromuconate, ethyl α-dihydromuconate, propyl α-dihydromuconate, α-
Isopropyl dihydromuconate, butyl α-dihydromuconate, octyl α-dihydromuconate,
α-dihydromuconic acid dodecyl, β-dihydromuconic acid, β-dihydromuconic acid sodium, β-
Potassium dihydromuconate, ammonium β-dihydromuconate, lithium β-dihydromuconate, trans-transmuconic acid, sodium trans-trans-muconate, potassium trans-transmuconate, ammonium trans-transmuconate, trans-trans-muconic acid Methyl, trans-trans-ethyl muconate,
Trans-trans-propyl muconate, trans-trans-butyl muconate, cis-cis-muconic acid, sodium cis-cis-muconate, potassium cis-cis-muconate, ammonium cis-cis-muconate, cis-cis -Methyl muconate,
cis-cis-ethyl muconate, cis-trans-
Muconic acid, cis-trans-sodium muconate, cis-trans-methyl muconate, 1,1,
2-tricarboxyethylene, 1,1,2-trisodiumoxycarbonylethylene, 1,1,
2-trimethoxycarbonylethylene, 1,1,
3-tricarboxypropene-1,1,1,3-
Trisodium oxycarbonylpropene-1,
1,1,3-trimethoxycarbonylpropene
1,1,1,3-triethoxycarbonylpropene-1,1,1,3-triisopropoxypropene-1,1,1,3-tributoxycarbonylpropene-1,1,5-dicarboxypentene-
1,1,5-Disodium oxycarbonylpentene-1, 1,5-dipotassiumoxycarbonylpentene-1, 1,5-dimethoxycarbonylpentene-1, 1,5-diethoxycarbonylpentene-1,1,5 -diisopropoxycarbonylpentene-1, 1,5-dibutoxycarbonylpentene-1, 1,3-carboxy-2-methylpropene-1, 1,3-disodiumoxycarbonyl-2-methylpropene-1,1 ,3-dimethoxycarbonyl-2-methylpropene-1,
1,3-diethoxycarbonyl-2-methylpropene-1,1,3-dipropoxycarbonyl-2
-Methylpropene-1,1,3-dibutoxycarbonyl-2-methylpropene-1,1,3-dioctyloxycarbonyl-2-methylpropene-
1,1,3-dicarboxy-1-methylpropene-1,1,3-disodiumoxycarbonyl-
1-Methylpropene-1,1,3-dimethyloxycarbonyl-1-methylpropene-1, hydroxymaleic acid, sodium hydroxymaleate, potassium hydroxymaleate, ammonium hydroxymaleate, lithium hydroxymaleate, trimethyl hydroxymaleate Ammonium, sodium-potassium hydroxymaleate, potassium-ammonium hydroxymaleate, methyl hydroxymaleate, ethyl hydroxymaleate, propyl hydroxymaleate, butyl hydroxymaleate, hexyl hydroxymaleate, octyl hydroxymaleate, dodecyl hydroxymaleate , octadecyl hydroxymaleate, hydroxyfumarate, sodium hydroxyfumarate, potassium hydroxyfumarate, ammonium hydroxyfumarate, lithium hydroxyfumarate, trimethylammonium hydroxyfumarate, tetramethylammonium hydroxyfumarate, methyl hydroxyfumarate, hydroxyfumarate Ethyl acid, propyl hydroxyfumarate, butyl hydroxyfumarate, octyl hydroxyfumarate, dodecyl hydroxyfumarate, octadecyl hydroxyfumarate, allyl hydroxyfumarate, hydroxymaleic acid, sodium hydroxymaleate, potassium hydroxymaleate, dihydroxymaleic acid Ammonium, methyl dihydroxy maleate, ethyl dihydroxy maleate, dihydroxy fumaric acid, sodium dihydroxy fumarate, potassium dihydroxy fumarate, ammonium dihydroxy fumarate, lithium dihydroxy fumarate, methyl dihydroxy fumarate, ethyl dihydroxy fumarate, propyl dihydroxy fumarate , butyl dihydroxy fumarate, dodecyl dihydroxy fumarate, fumaric acid amide, maleic acid amide, itaconic acid amide, citraconic acid amide, mesaconic acid amide, fumaric acid N-methylamide, maleic acid N-methylamide, itaconic acid N-methylamide, citracon Acid N-methylamide, mesaconic acid N-methylamide, fumaric acid N-
Ethylamide, maleic acid N-ethylamide, itaconic acid N-ethylamide, fumaric acid N-butylamide, fumaric acid N-benzylamide, maleic acid N-benzylamide, itaconic acid N-benzylamide, mesaconic acid N-benzylamide, citraconic acid N-benzylamide, fumaric acid nitrile,
Maleic nitrile, mesaconic nitrile, itaconic nitrile, citraconic nitrile, ileimide, fumarimide, itaconimide, mesaconimide, citraconimide, benzylidenemalonic acid amide, p-chlorobenzylidenemalonic acid amide, benzylidenemalononitrile, p-chlorobenzylidenemalononitrile , aconitic acid triamide, aconitic acid trinitrile, trans-glutaconic acid amide, trans-glutaconic acid nitrile, cis-glutaconic acid amide, cis-glutaconic acid nitrile, α-dihydromuconic acid amide, α-dihydromuconic acid nitrile, trans-
trans-muconic acid amide, trans-trans-muconic acid nitrile, 1,1,3-triaminocarbonylpropene-1, 1,1,3-trinitrilepropene-1,1,3-diaminocarbonyl-
2-methylpropene-1,1,3-dicyano-2
-Methylpropene-1, hydroxymaleic acid amide, hydroxymaleic acid nitrile, dihydroxymaleic acid amide, dihydroxyfumaric acid amide, dihydroxymaleic acid nitrile, dihydroxyfumaric acid nitrile, maleic acid monoamide, fumaric acid monoamide, itaconic acid monoamide, citraconic acid Examples include monoamide, mesaconic acid monoamide, and the like. The above addition reaction is carried out at 0-15°C, preferably at 30-15°C.
This can be easily carried out by dropping the monoethylenically unsaturated compound or epoxy compound into an excess polyamine or a solution thereof in water or an inert solvent at a temperature of 80°C.
These reactions can be carried out without a solvent or with water, alcohols, acetone, ethers,
This is carried out using an organic solvent such as dimethylformamide, dimethyl sulfoxide, or hexamethylene phosphoramide. The reaction temperature, which normally occurs during this reaction, can be controlled by adjusting the dropwise addition rate of the compound, but if the heat generation is severe, the temperature can be controlled by cooling the reaction vessel. After the addition reaction is completed in this way, the excess polyamine is recovered under reduced pressure to quantitatively obtain the N-substituted polyamine.
On the other hand, it is also possible to obtain an addition reaction product containing N,N'-disubstituted polyamine as the main component by reducing the excess amount of polyamine or increasing the dropping rate of ethylenically unsaturated compound or epoxy compound. can. At this time, if one or more N-substituted polyamines are produced, N-
It can be separated and purified into monosubstituted polyamines, N,N'-disubstituted polyamines, etc. These N-mono-substituted polyamines and N,N'-disubstituted polyamines are used as starting materials, but without separating and purifying both of them and the addition reaction product, the N-substituted polyamines can be used as raw materials as they are. It is also possible to subject the product to the same method, and this can be said to be a preferable method. Further, N-monodithiocarbamoylamine, which is obtained by introducing a dithiocarbamoyl group into the above-mentioned amine, can also be used in these addition reactions.
The method for producing these N-monodicarbamoylamines is to produce the inner salt according to the method in Org.Synth.Col.Vol. () P.394, and then treat it with an equivalent amount of alkali to produce these water-soluble salts. is obtained and can be used as a raw material amine in the present invention. This is illustrated by a simple reaction example as follows. Although N-monodithiocarbamoyl polyamines can be obtained from all of the polyamines mentioned above, some specific examples thereof are as follows. 2-Aminoethyldithiocarbamic acid, 2-aminopropyldithiocarbamic acid, 3-aminopropyldithiocarbamic acid, 2-aminobutyldithiocarbamic acid, 2-amino-1-methyldithiocarbamic acid, 3- Amino-2-methyldithiocarbamic acid, 2-amino-2,2-dimethyldithiocarbamic acid, 4-aminobutyldithiocarbamic acid, 6-aminohexyldithiocarbamic acid, N-dithiocarbamoyldiethylenetriamine, N- Examples include dithiocarbamoyltriethylenetetramine, N-dithiocarbamoylpolyethyleneimine, and N-aminodithiocarbamic acid. These N-monodithiocarbamoyl polyamines can be used as free acids, soluble salts, ammonium salts, esters, etc. The addition reaction between N-monodithiocarbamoyl polyamine and ethylenically unsaturated compound or epoxy compound can be carried out using equivalent amounts of both.
There is no need to use an excess of N-monodithiocarbamoyl polyamine like the polyamines mentioned above. Therefore, a recovery process becomes unnecessary. When the functional derivative is an ester, in the former method using an excess of polyamine, generally N
-The reaction may not be completed with substituted polyamines and further cyclization or substitution reactions may occur, so piperazine-
Often produces 2-one derivatives, polymers, etc. Therefore, when the functional derivative is an ester, N-substituted polyamines can be obtained by using N-monodithiocarbamoyl polyamines instead of polyamines, which is a desirable method. On the other hand, the N-substituted polyamine of the present invention can also be produced by carrying out a substitution reaction between a polyamine and a halogenated compound, neutralizing by-produced hydrogen halide with an alkali, and then performing a purification treatment as necessary. It is possible. In this reaction, the halides used include compounds obtained by adding hydrogen halide to the compounds specifically exemplified as the ethylenically unsaturated compounds or epoxy compounds. The following are typical examples. Sodium chlorosuccinate, potassium chlorosuccinate, ammonium chlorosuccinate, lithium chlorosuccinate, chlorsucciamide, chlorosuccinimide, chlorsuccinic hydrazide,
Nitrile chlorosuccinate, methyl chlorosuccinate, ethyl chlorosuccinate, allyl chlorosuccinate, 1,2-(disodiumoxycarbonyl)-3-chloropropane, 1,2-(dipotassiumoxycarbonyl)-3-chloropropane,
1,2-(diammoniumoxycarbonyl)-
3-chloropropane, 1,2-(diaminocarbonyl)-3-chloropropane, 1,2-diamino-3-chloropropane, 1,2-(dimethoxycarbonyl)-3-chloropropane, 1,2-(diaminocarbonyl)-3-chloropropane Sodium oxy)-2-chloropropane, 1,
2-(dipotassiumoxycarbonyl)-2-chloropropane, 1,2-(diaminocarbonyl)-
2-chloropropane, 1,2-dicyano-2-chloropropane, 1,2-(dimethoxycarbonyl)-2-chloropropane, 2-chloromethylmalonic acid, sodium 2-chloromethylmalonate,
Potassium 2-chloromethylmalonate, ammonium 2-chloromethylmalonate, lithium 2-chloromethylmalonate, 2-chloromethylmalonic acid amide, 2-chloromethylmalononitrile, methyl 2-chloromethylmalonate, 2-chlor Ethyl methylmalonate, allyl 2-chloromethylmalonate, chlormalonic acid, sodium chlormalonate, potassium chlormalonate, ammonium chlormalonate, lithium chlormalonate, chlormalonic acid amide, chlormalonic acid imide, chlormalononitrile, methyl chlormalonate, chlormalonic acid Ethyl, octyl chlormalonate, allyl chlormalonate, 1,3-dicarboxy-2-chloropropane, 1,3-disodium oxy-2
-Chlorpropane, 1,3-dipotassium oxy-
2-chloropropane, 1,3-diaminocarbonyl-2-chloropropane, 1,3-dicyano-2
-Chlorpropane, 1,3-dimethoxycarbonyl-2-chloropropane, 1,3-disodiumoxy-1-chloropropane, 1,3-dipotassiumoxycarbonyl-1-chloropropane, 1,
3-diaminocarbonyl-1-chloropropane,
1,3-dicyano-1-chloropropane, 1,3
-dimethoxycarbonyl-1-chloropropane,
Examples include 1,3-diethoxycarbonyl-1-chloropropane. This substitution reaction is also carried out at 0-150°C, preferably at 30-150°C.
This can be carried out by dropping the halogenated alkyl derivative into excess polyamine at a temperature range of 80°C. The reaction medium is the same as described above. This reaction is generally accompanied by intense heat generation, but the temperature is controlled by adjusting the dropwise addition rate of the alkyl halide derivative and cooling the reaction vessel. After the dropwise addition of the halogenated alkyl derivative is completed, heating is continued and maintained at a constant temperature to complete the substitution reaction. Neutralization of the secondary hydrohalic acid in the obtained reaction product can be easily carried out with alkali hydroxide, but it is more advantageous to introduce ammonia gas. Next, by recovering excess polyamine from the reaction product under reduced pressure, the target N-monosubstituted polyamine is quantitatively obtained, which is purified by distillation or the like. This reaction is usually carried out using an excess of polyamine, but it is possible to produce an N-disubstituted polyamine in which two identical substituents have been introduced by reducing the amount of polyamine and adjusting the dropping rate and reaction temperature. is also possible, and this is exactly the same as in the case of the addition reaction described above. In the present invention, by using an N-monosubstituted polyamine as a raw material instead of the above-mentioned polyamine raw material, N-monosubstituted polyamine with another substituent,
N′-disubstituted polyamines can also be produced.
Also useful are N-substituted polyamines obtained by reacting polyamines with compounds containing two or more reactive functional groups. Specific examples of the polyfunctional compound include glycidyl itaconate, glycidyl maleate, glycidyl fumarate, glycidyl citraconate, glycidyl mesaconate, and the like. This reaction also contains 0 to 0 in excess polyamine.
This is carried out by dropping the polyfunctional compound at a temperature of 150°C, preferably from 30 to 80°C, and the same number of polyamines as the number of functional groups are introduced into the resulting N-substituted polyamine. The desired N-substituted polyamine is prepared by recovering excess polyamine and neutralizing by-product hydrohalic acid, if present. Next, the present invention will be explained using specific examples. Examples 1-47 Ethylenediamine (purity
99%) Add 250ml. To this, 89 g of sodium maleate monohydrate was dissolved in 200 ml of water and gradually added dropwise.
The reaction mixture became cloudy at the same time as the dropwise addition, but when heated to about 110° C. after the dropwise addition, the cloudy reaction mixture turned into a transparent solution. When the temperature was further raised and stirring was continued for 30 minutes under reflux (114-115°C), colloidal white crystals were precipitated. This was continued to be stirred under reflux for 8 hours. Then add this reaction mixture to 100
350 ml of excess ethylenediamine-water was recovered under reduced pressure (water pump) at ~110°C. Then 50~
Continuing to collect at 100℃/5mmHg, the final value was 130
The mixture was collected at ℃/5 mmHg until the distillation completely stopped. The time required for recovery was 6 hours. The amount of white crystals of N-(1,2-disodiumoxycarbonylethyl)ethylenediamine remaining in the flask was 125 g. The results of TLC (thin layer chromatography) analysis of this were almost uniform, and free ethylenediamine was not observed. The structure was confirmed by C13-NMR. In addition, compounds of Examples 2 to 47 were obtained by reacting various amines with unsaturated carboxylates and the like using the same recipe.

【table】

【table】

【table】

【table】

【table】

[Table] 〓Maleic acid salt in 2 moles of polyethyleneimine〓

Claims (1)

[Claims] 1. General formula [Wherein, X represents a linear or branched lower alkylene chain, or a mono- or polyamino residue of polylower alkylene, and R _q represents hydrogen or [Formula] (M represents hydrogen, a metal atom, or an ammonium group.) , p represents 0 or 1. Y is a general formula [However, R ₁ and R ₂ are hydrogen, hydroxyl group, phenyl group, or -COOR ₆ group (R ₆ is a metal atom, ammonium group, lower alkyl group, lower alkoxy lower alkyl group, lower alkenyl group , lower alkylamino lower alkyl group, mono- or polyhydroxy lower alkyl group, phenyl group or substituted phenyl group, or benzyl group or substituted benzyl group). R ₃ and R ₄ are hydrogen,
Represents a hydroxyl group, a lower alkyl group, a phenyl group or a substituted phenyl group, -OM group (M is a metal atom),
1, m and n represent 0 or 1. R and
R' is hydrogen, a cyano group, -COR ₅ group (R ₅ represents an amino group or lower alkylamino group), -COOR ₆ group (R ₆ is the same as above), or R and R' are -NH- or - A
represents hydrogen or hydroxyl group. ], and Y' represents a lower amino lower alkyl group, a mono- or dihydroxy lower alkyl group, a disodium oxycarbonyl lower alkyl group, or hydrogen. ] N-substituted polyamine. 2 General formula NH ₂ -(X) _p -NH- _{R q [} wherein, ] (M represents hydrogen, a metal atom or an ammonium group), p represents 0 or 1. ] The amine shown in and the general formula [In the formula, B is directly bonded to represent a double bond, or
or an oxygen atom, R ₁ and R ₂ are hydrogen, hydroxyl group, phenyl group, or -COOR ₆ group (R ₆ is a metal atom, ammonium group, lower alkyl group, lower alkoxy lower alkyl group, lower alkenyl group, lower alkylamino group) lower alkyl group, mono- to polyhydroxy lower alkyl group, phenyl group to substituted phenyl group, or benzyl group to substituted benzyl group). R ₃ and R ₄ are hydrogen, hydroxyl group,
It represents a lower alkyl group, a phenyl group or a substituted phenyl group, -OM group (M is a metal atom), and 1, m and n represent 0 or 1. R and R' are hydrogen,
Cyano group, -COR ₅ group (R ₅ represents an amino group or lower alkylamino group), -COOR ₆ group (R ₆ is the same as above), or R and R' are -NH- or -NHNH
-Including cases of association through. A general formula characterized by reacting an ethylenic compound or an epoxy compound represented by ] at 0 to 150°C without a solvent or in an inert solvent. [Wherein, X represents a linear or branched lower alkylene chain, or a mono- or polyamino residue of polylower alkylene, and R _q represents hydrogen or [Formula] (M represents hydrogen, a metal atom, or an ammonium group.) , p represents 0 or 1. Y is a general formula [However, R ₁ and R ₂ are hydrogen, hydroxyl group, phenyl group, or -COOR ₆ group (R ₆ is a metal atom, ammonium group, lower alkyl group, lower alkoxy lower alkyl group, lower alkenyl group , lower alkylamino lower alkyl group, mono- or polyhydroxy lower alkyl group, phenyl group or substituted phenyl group, or benzyl group or substituted benzyl group). R ₃ and R ₄ are hydrogen,
Represents a hydroxyl group, a lower alkyl group, a phenyl group or a substituted phenyl group, -OM group (M is a metal atom),
1, m and n represent 0 or 1. R and
R' is hydrogen, a cyano group, -COR ₅ group (R ₅ represents an amino group or lower alkylamino group), -COOR ₆ group (R ₆ is the same as above), or R and R' are -NH- or - A
represents hydrogen or hydroxyl group. ], and Y' represents a lower amino lower alkyl group, a mono- or dihydroxy lower alkyl group, a disodium oxycarbonyl lower alkyl group, or hydrogen. ] A method for producing an N-substituted polyamine. 3 General formula NH ₂ -(X) _p -NH- _{R q [} wherein, ] (M represents hydrogen, a metal atom or an ammonium group), p represents 0 or 1. ] The amine represented by the general formula [In the formula, J represents a halogen atom, R ₁ and
R ₂ is hydrogen, hydroxyl group, phenyl group or -COOR ₆
Group (R ₆ is a metal atom, ammonium group, lower alkyl group, lower alkoxy lower alkyl group, lower alkenyl group, lower alkylamino lower alkyl group, mono- to polyhydroxy lower alkyl group,
phenyl group or substituted phenyl group or benzyl group or substituted benzyl group). _R3 and _R4
is hydrogen, hydroxyl group, lower alkyl group, phenyl group or substituted phenyl group, -OM group (M is a metal atom)
1, m and n represent 0 or 1. R
and R' is hydrogen, cyano group, -COR ₅ group (R ₅ represents amino group or lower alkylamino group), -
COOR ₆ groups (R ₆ is the same as above) or R and R' are -
Including the case of association via NH- or -NHNH-, A represents hydrogen or a hydroxyl group. ] without a solvent or in an inert solvent.
General formula characterized by reacting at ~150℃ [Wherein, X represents a linear or branched lower alkylene chain, or a mono- or polyamino residue of polylower alkylene, and R _q represents hydrogen or [Formula] (M represents hydrogen, a metal atom, or an ammonium group.) , p represents 0 or 1. Y is a general formula [However, R ₁ and R ₂ are hydrogen, hydroxyl group, phenyl group, or -COOR ₆ group (R ₆ is a metal atom, ammonium group, lower alkyl group, lower alkoxy lower alkyl group, lower alkenyl group , lower alkylamino lower alkyl group, mono- or polyhydroxy lower alkyl group, phenyl group or substituted phenyl group, or benzyl group or substituted benzyl group). R ₃ and R ₄ are hydrogen,
Represents a hydroxyl group, a lower alkyl group, a phenyl group or a substituted phenyl group, -OM group (M is a metal atom),
1, m and n represent 0 or 1. R and
R' is hydrogen, a cyano group, -COR ₅ group (R ₅ represents an amino group or lower alkylamino group), -COOR ₆ group (R ₆ is the same as above), or R and R' are -NH- or - A
represents hydrogen or hydroxyl group. ], and Y' represents a lower amino lower alkyl group, a mono- or dihydroxy lower alkyl group, a disodium oxycarbonyl lower alkyl group, or hydrogen. ] A method for producing an N-substituted polyamine.