JP2001048851A - Quaternary ammonium salt - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide the subject novel compound that comprises a specific ammonium salt, has high safety, good biodegradability, imparts excellent flexibility to fibers and hairs and is useful as a softening base agent with excellent biodegradability in combination with anionic surfactant. SOLUTION: This novel compound is represented by formula I [R1 is a 8-22C alkyl or the like; R2 is a 1-3C alkyl or the like; R3 is H, 1-22C alkyl or the like; (m) is 1-6; (n) is 2-6; (p) is 1-10; and X is an anion], typically N-(3- trimethylammoniopropylaminocarbonylmethyl)-N,N-dimethyloctadecylammonium chloride of formula II. The compound of formula I is prepared by allowing a tertiary amine of formula III to react with a halogenated carboxylic acid of the formula: X-(CH2)m-CO2Y (X is halogen; and Y is H, a 1-22C alkyl or the like), allowing the resultant quaternary ammonium salt of formula IV to react with a diamine of formula V to form an amino cation of formula VI and finally allowing the amino cation to react with a quaternizatio agent of the formula: X-R3.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION The present invention relates to a novel quaternary surfactant used as a softening base for fabrics, hair and the like.
The present invention relates to a quaternary ammonium salt and a method for producing the same.

[0002]

2. Description of the Related Art
A commercially available product as a fabric softener is a composition containing a quaternary ammonium salt having two long-chain alkyl groups in one molecule represented by di (long-chain alkyl) dimethylammonium chloride. However, when the quaternary ammonium salt is released into the natural world such as a river, there is a problem that most of the quaternary ammonium salt is accumulated without being biodegraded.

[0003] As an improved product of such a problem, N-methyl-N, N-bis (long-chain alkanoyloxyethyl)-
N- (2-hydroxyethyl) ammonium methyl sulfate, N, N-dimethyl-N, N-bis (alkanoyloxyethyl) ammonium chloride and the like are commercially available, but are more biodegradable than the above quaternary ammonium salts. Although the properties are improved, it cannot be said that the base material has sufficient flexibility.

On the other hand, a method in which a compound having at least two cationic groups in one molecule is used as a flexible base is described in E.
P225281, JP-A-2-11545 and WO9414938. However, these compounds are too hydrophilic,
Flexible performance was weak. Japanese Patent Application Laid-Open No. Hei 9-111660 discloses a softener containing a polycation and an anion. However, this polycation is excellent in flexibility performance but not satisfactory in biodegradability.

An object of the present invention is to provide a compound which is excellent in flexibility and suitable as a flexible base having good biodegradability.

[0006]

According to the present invention, there is provided a compound represented by the general formula (1):
And a method for producing the quaternary ammonium salt.

[0007]

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[0008] (In the formula, R ¹ represents a linear or branched alkyl or alkenyl group having 8 to 22 carbon atoms, an amido group, may be interrupted by an ester group or an ether group .R ² carbon R ³ represents a hydrogen atom or a linear or branched alkyl group, hydroxyalkyl group or alkenyl group having 1 to 22 carbon atoms, and represents an amide group or an ester group. Or m may represent a number from 1 to 6, n represents a number from 2 to 6, and p represents a number from 1 to 10.
X represents an anionic group. Note that 2p + 2 R ² , p +
One X may be the same or different. )

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION In the quaternary ammonium salt (1), R ¹ is preferably an alkyl or alkenyl group having 12 to 18 carbon atoms. R ² is preferably an alkyl group having 1 to ² carbon atoms or a hydroxyalkyl group. R ³ is preferably a hydrogen atom, an alkyl group having 1 to 22 carbon atoms, a hydroxyalkyl group or an alkenyl group, and may be interrupted by an amide group, an ester group or an ether group. m is preferably 1 to 3.
n is preferably 2 to 6. p is preferably 1 to 3. X is preferably chloro or methyl sulfate.

As the quaternary ammonium salt (1), for example, the following compounds can be mentioned.

[0011]

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(In the series of formulas, R is a residue obtained by removing a carbonyl group from hardened tallow fatty acid, tallow fatty acid, and coconut fatty acid;
R 'represents a methyl group or a hydrogen atom. The quaternary ammonium salt (1) is prepared in the following steps (a), (b) and
(d) or by performing steps (a), (b), (c) and (d). <Step (a)> General formula (2)

[0013]

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(Wherein R ¹ and R ² have the same meanings as described above), and X- (CH ₂ ) _m —CO ₂ Y (3) (Wherein, X represents a halogen atom, Y represents a hydrogen atom, or a linear or branched alkyl or alkenyl group having 1 to 22 carbon atoms, and m represents the same meaning as described above). With a carboxylic acid or an ester thereof,
General formula (4)

[0015]

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(Wherein, R ¹ , R ² , m, X and Y have the same meanings as described above). <Step (b)> The quaternary ammonium salt represented by the general formula (4) is converted into a compound represented by the general formula (5)

[0017]

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(Wherein R ² and n have the same meanings as described above), and reacted with a diamine represented by the general formula (6):

[0019]

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(Wherein, R ¹ , R ² , m, n and X have the same meanings as described above). <Step (c)> Instead of the tertiary amine in step (a),
The step (a) and the step (b) are repeated 1 to 9 times using the amino cation obtained in the step (b) to obtain a compound represented by the general formula (7):

[0021]

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(Wherein R ¹ , R ² , m, n and X have the same meaning as described above, and p ′ represents a number of 2 to 10). <Step (d)> With respect to the amino cation represented by the general formula (6) or the aminopolycation represented by the general formula (7), X-R ³ (8) X and R ³ have the same meanings as described above) or a quaternizing agent represented by the general formula (9) HX (9) (wherein, X has the same meanings as described above). A step of reacting an acid to obtain a quaternary ammonium salt (1).

Hereinafter, each step will be described in detail. <Step (a)> Tertiary amine (2) used in this step
As N, N-dimethyloctadecylamine or the like;
N-methyl-N-hydroxyethylalkylamine such as N-dimethylalkylamine, N-methyl-N-hydroxyethyloctadecylamine, N, N-dihydroxyethylalkylamine such as N, N-dihydroxyethyloctadecylamine; N-dimethyl-N-alkanoylaminopropylamine, N, N-dimethyl-N-alkanoyloxyethylamine, N, N-dimethyl-N
-Alkanoyloxypropylamine and the like. The alkyl group represented by R ¹ may be a single composition or a mixed composition, and may be a residue obtained by removing a carboxyl group from hardened tallow fatty acid, tallow fatty acid, or coconut fatty acid.

The halogenated carboxylic acid or its ester (3) includes, for example, monochloroacetic acid, monochlorobutyric acid, monochlorohexanoic acid and their methyl esters, ethyl esters, isopropyl esters and the like.

In the case of the reaction of this step, methyl alcohol, ethyl alcohol, isopropyl alcohol, butyl alcohol, hexane, acetone, chloroform and the like can be used as a reaction solvent. Reaction temperature is 30 ~ 120 ℃
Is preferable, and 50 to 90 ° C. is more preferable. In this reaction, the molar ratio of [halogenated carboxylic acid or its ester (3) / tertiary amine (2)] is preferably 0.5 to 2.0, more preferably 0.8 to 1.5. 0.5 ~ 10 in this condition
If the quaternization reaction is carried out over time, the reaction is completed. Thereafter, post-treatment is carried out according to a conventional method to obtain a quaternary ammonium salt (4) having an ester group. If necessary, recrystallization may be performed with acetone or the like.

<Step (b)> As the diamine (5) used in this step, for example, N, N-dimethylaminoethylamine, N-methyl-N-hydroxyethylaminoethylamine, N, N-dihydroxyethylaminoethylamine N, N-dimethylaminopropylamine, N-methyl-N-hydroxyethylaminopropylamine,
N, N-dihydroxyethylaminopropylamine,
N, N-dimethylaminobutylamine, N-methyl-N
-Hydroxyethylaminobutylamine, N, N-dihydroxyethylaminobutylamine, N, N-dimethylaminohexylamine, N-methyl-N-hydroxyethylaminohexylamine, N, N-dihydroxyethylaminohexylamine and the like. it can.

In the case of the reaction of this step, methyl alcohol, ethyl alcohol, isopropyl alcohol, acetone or the like is used as a solvent. The reaction temperature is preferably from 50 to 150 ° C, more preferably from 70 to 120 ° C. The molar ratio of [diamine (5) / quaternary ammonium salt (4)] in this reaction is preferably 0.5 to 2.0, and more preferably 0.8 to 1.2. If the reaction is carried out for 0.5 to 10 hours under these conditions, the amidation reaction is completed. Thereafter, the solvent is removed by a conventional method to obtain the amino cation (6).

<Step (c)> The amino cation (6) needs to be reacted with a halogenated carboxylic acid or its ester (3) and a diamine (5) in the same manner as in the above steps (a) and (b). The aminopolycation (7) can be obtained by repeating the process a number of times.

<Step (d)> Examples of the quaternizing agent (8) used in this step include lower alkyl halides such as methyl chloride, di-lower alkyl sulfates such as dimethyl sulfate and diethyl sulfate, and monochloroacetic acid alkyl esters. No. Water, methyl alcohol,
Ethyl alcohol, isopropyl alcohol, acetone and the like can be mentioned.

The reaction temperature of the aminocation (6) or aminopolycation (7) with the quaternizing agent (8) is 30 to 150 ° C.
Is preferably 40 to 100 ° C. Also, this 4
The molar ratio of [quaternizing agent (8) / aminocation (6) or aminopolycation (7)] in the grading reaction is 0.5.
To 10, preferably 0.8 to 2.0. Under this condition
The reaction is completed if the quaternization reaction is carried out without a solvent or in a solvent over 0.1 to 20 hours. Thereafter, post-treatment is performed according to a conventional method, and if necessary, salt exchange is performed using an ion exchange resin or the like. For example, a quaternary ammonium salt (1) having a necessary counter ion can be obtained.

The acid (9) used for neutralizing the amino cation (6) or the amino polycation (7) includes
Hydrochloric acid, sulfuric acid, phosphoric acid, nitric acid, p-toluenesulfonic acid,
Examples thereof include inorganic acids such as methanesulfonic acid and the like, and organic acids such as formic acid, acetic acid, propionic acid, malic acid and citric acid, alone or in combination. Examples of the solvent for this neutralization reaction include water, methyl alcohol, ethyl alcohol, isopropyl alcohol, and acetone.

The structure of the quaternary ammonium salt (1) of the present invention can be confirmed by infrared absorption spectrum and nuclear magnetic resonance spectrum.

[0033]

The quaternary ammonium salt of the present invention (1)
Is a novel surfactant with high safety and good biodegradability, which can be used in combination with an anionic surfactant to give excellent flexibility to fibers, hair, etc. It is useful as an excellent soft base.

[0034]

EXAMPLES Example 1 (1) N, N-dimethyloctadecylamine 17 was added to a flask.
8.8 g (0.601 mol) and 238.0 g of acetone were charged, heated to 50 ° C. and dissolved. Then, 98.5 g (0.721 mol) of monochloroacetic acid isopropyl ester was added dropwise at 20 ° C over 5 minutes,
The temperature was raised to 60 ° C., and the reaction was performed for 4 hours. After the reaction,
The white crystals obtained by cooling to 20 ° C. were recrystallized with acetone according to a conventional method to give 213.5 g (0.492 mol) of N- (isopropoxycarbonylmethyl) -N, N-dimethyloctadecyl ammonium chloride of the following structural formula. I got

[0035]

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Results of IR analysis and NMR analysis <IR analysis> Strong ester-specific absorption was observed at 1731 cm ^-1 . <NMR analysis> The solvent CDCl _3, internal standard TMS 4.31ppm -C H - (m, 1H) 4.20ppm N + -C H 2 -COO (s, 2H) 3.30ppm N + - (C H 3) 2 (s ^{, 6H) 3.24ppm N + -C H} 2 - (t, 2H) 1.35ppm C- (C H 3) 2 (s, 6H) (2) in a flask, N- chloride obtained in (1) ( Dissolve 207.4 g (0.478 mol) of isopropoxycarbonylmethyl) -N, N-dimethyloctadecyl ammonium in 66.1 g of isopropyl alcohol, add 58.7 g (0.574 mol) of N, N-dimethylaminopropylamine and raise the temperature to 90 ° C. Warm and react for 5 hours. After completion of the reaction, excess N, N-
Dimethylaminopropylamine and isopropyl alcohol were distilled off under reduced pressure, and N- (3-dimethylaminopropylaminocarbonylmethyl) -N,
218.8 g (pure content: 97 wt%) of an isopropyl alcohol solution of N-dimethyloctadecyl ammonium was obtained.

[0037]

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Results of IR analysis and NMR analysis <IR analysis> Strong absorption unique to amide was observed at 1680 cm ^-1 . <NMR analysis> Solvent CDCl ₃ , internal standard TMS 4.13 ppm N ⁺ -CH ₂ -CONH (s, 2H) 3.30 ppm N ⁺ -(CH ₃ ) ₂ (s, 6H) 3.22 ppm N ⁺ -CH ₂ -, CONH-C H _{2- (4H) 2.36ppm -C H 2 -N} (CH 3) 2 (t, 2H) 2.27ppm N- (C H 3) 2 (s, 6H) (3) in an autoclave, chloride obtained in (2) N- (3-
Dimethylaminopropylaminocarbonylmethyl)-
100 g of N, N-dimethyloctadecyl ammonium (0.21
0 mol), 12.7 g (0.252 mol) of methyl chloride and 27 g of isopropyl alcohol, and the temperature was raised to 90 ° C. The mixture was stirred at the same temperature for 6 hours to complete the reaction. After the reaction,
The excess methyl chloride is distilled off, and
135 g (0.203 mol) of-(3-trimethylammoniopropylaminocarbonylmethyl) -N, N-dimethyloctadecyl ammonium was obtained.

[0039]

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Results of IR analysis and NMR analysis <IR analysis> Strong absorption peculiar to amide was observed at 1672 cm ^-1 . <NMR analysis> Solvent CDCl ₃ , internal standard TMS 4.13 ppm N ⁺ -CH ₂ -CONH (s, 2H) 3.30 ppm N ⁺ -(CH ₃ ) ₂ , N ⁺ -(CH ₃ ) ₃ (s, _{^{15H) 3.23ppm N + -C H 2}} -, a _{CONH-C H 2 -CH 2 -C} H 2 -N + (CH 3) 3 (6H) example 2 flask, resulting in the example 1 (2) N- (3-
Dimethylaminopropylaminocarbonylmethyl)-
100 g of N, N-dimethyloctadecyl ammonium (0.21
0 mol) and 50 g of isopropyl alcohol, and the mixture was heated to 50 ° C. and dissolved. Then 38.7 g (0.231 mol) of 6N hydrochloric acid
Was added and stirred for 10 minutes to perform a neutralization reaction. After the neutralization reaction,
The mixture was cooled to 20 ° C., and the obtained white crystals were recrystallized with acetone according to a conventional method to give N- (3-dimethylammoniopropylaminocarbonylmethyl) chloride of the following structural formula.
86 g of N, N-dimethyloctadecyl ammonium (0.168
mol).

[0041]

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Results of IR analysis and NMR analysis <IR analysis> Strong absorption peculiar to amide was observed at 1674 cm ^-1 . <NMR analysis> Solvent CDCl ₃ , internal standard TMS 4.13 ppm N ⁺ -CH ₂ -CONH (s, 2H) 3.30 ppm N ⁺ -(CH ₃ ) ₂ (s, 6H) 3.21 ppm N ⁺ -CH _{2 -, NH-C H 2 -CH} 2 -C H 2 -NH + (CH 3) 2 (6H) 2.90ppm NH + - (C H 3) 2 (s, 6H) example 3 example 1 (1 )), Using N, N-dimethylhexadecylamine in place of N, N-dimethyloctadecylamine, and performing the same operation as in Example 1 to give N- (3-trimethylammoniopropylaminocarbonylmethyl chloride having the following structural formula. ) -N, N-dimethylhexadecyl ammonium was obtained.

[0043]

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Results of IR analysis and NMR analysis <IR analysis> Strong absorption peculiar to amide was observed at 1672 cm ^-1 . <NMR analysis> Solvent CDCl ₃ , internal standard TMS 4.13 ppm N ⁺ -CH ₂ -CONH (s, 2H) 3.30 ppm N ⁺ -(CH ₃ ) ₂ , N ⁺ -(CH ₃ ) ₃ (s, _{^{15H) 3.23ppm N + -C H 2}} -, NH-C H 2 -CH 2 -C H 2 -N + (CH 3) 3 (6H) N- chloride in example 4 example 2 (3-dimethylamino The same operation as in Example 2 was carried out using N- (3-dimethylaminopropylaminocarbonylmethyl) -N, N-dimethylhexadecyl ammonium chloride instead of (propylaminocarbonylmethyl) -N, N-dimethyloctadecyl ammonium. And N- (3-dimethylammoniopropylaminocarbonylmethyl) -N, N-dimethylhexadecyl ammonium chloride. IR analysis and NMR analysis results <IR analysis> Strong absorption peculiar to amide was observed at 1674 cm ^-1 . <NMR analysis> Solvent CDCl ₃ , internal standard TMS 4.13 ppm N ⁺ -CH ₂ -CONH (s, 2H) 3.30 ppm N ⁺ -(CH ₃ ) ₂ (s, 6H) 3.21 ppm N ⁺ -CH _{2 -, NH-C H 2 -CH} 2 -C H 2 -NH + (CH 3) 2 (6H) 2.90ppm NH + - (C H 3) 2 (s, 6H) example 5 example 1 (1 )), Using N, N-dimethyldodecylamine in place of N, N-dimethyloctadecylamine to carry out the same operation as in Example 1 to obtain NCl
-(3-Trimethylammoniopropylaminocarbonylmethyl) -N, N-dimethyldodecylammonium was obtained.

[0045]

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Results of IR analysis and NMR analysis <IR analysis> Strong absorption peculiar to amide was observed at 1672 cm ^-1 . <NMR analysis> Solvent CDCl ₃ , internal standard TMS 4.13 ppm N ⁺ -CH ₂ -CONH (s, 2H) 3.30 ppm N ⁺ -(CH ₃ ) ₂ , N ⁺ -(CH ₃ ) ₃ (s, _{^{15H) 3.24ppm N + -C H 2}} -, NH-C H 2 -CH 2 -C H 2 -N + (CH 3) 3 (6H) N- chloride in example 6 example 2 (3-dimethylamino The same operation as in Example 2 was performed by using N- (3-dimethylaminopropylaminocarbonylmethyl) -N, N-dimethyldodecylammonium chloride instead of (propylaminocarbonylmethyl) -N, N-dimethyloctadecylammonium, N- (3-Dimethylammoniopropylaminocarbonylmethyl) -N, N-dimethyldodecylammonium chloride was obtained. IR analysis and NMR analysis results <IR analysis> Strong absorption peculiar to amide was observed at 1674 cm ^-1 . <NMR analysis> Solvent CDCl ₃ , internal standard TMS 4.13 ppm N ⁺ -CH ₂ -CONH (s, 2H) 3.30 ppm N ⁺ -(CH ₃ ) ₂ (s, 6H) 3.24 ppm N ⁺ -CH _{2 -, NH-C H 2 -CH} 2 -C H 2 -NH + (CH 3) 2 (6H) 2.90ppm NH + - (C H 3) 2 (s, 6H) example 7 example 1 (1 )) And using monochlorobutyric acid methyl ester in place of chloroacetic acid isopropyl ester, the same operation as in Example 1 was carried out.
[3- (3-Trimethylammoniopropylaminocarbonyl) propyl] -N, N-dimethyloctadecyl ammonium was obtained.

[0047]

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Results of IR analysis and NMR analysis <IR analysis> Strong absorption peculiar to amide was observed at 1672 cm ^-1 . <NMR analysis> Solvent CDCl ₃ , internal standard TMS 3.30 ppm N ⁺ -(CH ₃ ) ₂ , N ⁺ -(CH ₃ ) ₃ (s, 15H) 3.21 ppm -CH ₂ -N ⁺ -CH ₂ -, NH-C H ₂ -CH ₂ -C H ₂ -N ⁺ (CH ₃ ) ₃ (8H) 2.18ppm -C H ₂ -CONH (t, 2H) Example 8 Instead of N- (3-dimethylaminopropylaminocarbonylmethyl) -N, N-dimethyloctadecyl ammonium chloride in Example 2, N- [3- (3-dimethylaminopropylaminocarbonyl chloride) was used. ) Propyl]-
The same operation as in Example 2 was performed using N, N-dimethyloctadecyl ammonium to obtain N- [3- (3-dimethylammoniopropylaminocarbonyl) propyl] chloride.
-N, N-dimethyloctadecyl ammonium was obtained. Results of IR analysis and NMR analysis <IR analysis> Strong absorption unique to amide was observed at 1676 cm ^-1 . <NMR analysis> The solvent CDCl _3, internal standard ^{TMS 3.30ppm N + - (C H} 3) 2 (s, 6H) 3.22ppm -C H 2 -N + -C H 2 -, NH-C H 2 -CH 2 -C H ₂ -N ⁺ (CH ₃ ) ₃ (8H) 2.90 ppm NH ⁺ -(C H ₃ ) ₂ (s, 6H) 2.18 ppm -C H ₂ -CONH (t, 2H) Example 9 Example 1 The same operation as in Example 1 was carried out using monochlorohexanoic acid methyl ester in place of the monochloroacetic acid isopropyl ester in (1) above, to give N- [6- (3-trimethylammoniopropylaminocarbonyl) chloride of the following structural formula. [Hexyl] -N, N-dimethyloctadecyl ammonium was obtained.

[0049]

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Results of IR analysis and NMR analysis <IR analysis> Strong absorption peculiar to amide was observed at 1672 cm ^-1 . <NMR analysis> Solvent CDCl ₃ , internal standard TMS 3.30 ppm N ⁺ -(CH ₃ ) ₂ , N ⁺ -(CH ₃ ) ₃ (s, 15H) 3.24 ppm -CH ₂ -N ⁺ -CH ₂ -, NH-C H ₂ -CH ₂ -C H ₂ -N ⁺ (CH ₃ ) ₃ (8H) 2.18ppm -C H ₂ -CONH (t, 2H) Example 10 Instead of N- (3-dimethylaminopropylaminocarbonylmethyl) -N, N-dimethyloctadecyl ammonium chloride in Example 2, N- [6- (3-dimethylaminopropylaminocarbonyl chloride) was used. ) Hexyl]-
The same operation as in Example 2 was performed using N, N-dimethyloctadecyl ammonium to obtain N- [6- (3-dimethylammoniopropylaminocarbonyl) hexyl chloride].
-N, N-dimethyloctadecyl ammonium was obtained. Results of IR analysis and NMR analysis <IR analysis> Strong absorption unique to amide was observed at 1676 cm ^-1 . <NMR analysis> The solvent CDCl _3, internal standard ^{TMS 3.30ppm N + - (C H} 3) 2 (s, 6H) 3.22ppm -C H 2 -N + -C H 2 -, NH-C H 2 -CH 2 _{^{-C H 2 -NH + (CH 3}} ) 2 (8H) 2.90ppm NH + - (C H 3) 2 (s, 6H) 2.18ppm -C H 2 -CONH (t, 2H) example 11 example 1 (2) was replaced with N, N-dimethylaminoethylamine in the same manner as in Example 1 to obtain N- (2-trimethylammonioethyl chloride having the following structural formula. (Aminocarbonylmethyl) -N, N-dimethyloctadecyl ammonium was obtained.

[0051]

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Results of IR analysis and NMR analysis <IR analysis> Strong absorption unique to amide was observed at 1675 cm ^-1 . <NMR analysis> The solvent CDCl _3, internal standard _{^{TMS 4.13ppm N + -C H 2 -CONH}} (s, 2H) 3.64ppm NH-C H 2 -CH 2- N + - (CH 3) 3 (t, 4H) _{3.50ppm NH-CH 2 -C H 2-} N + - (CH 3) 3 (t, 4H) 3.30ppm N + - (C H 3) 2, N + - (C H 3) 3 (t, 15H) 3.24ppm N ⁺ -C H _2- (t, 2H) Example 12 Instead of N- (3-dimethylaminopropylaminocarbonylmethyl) -N, N-dimethyloctadecyl ammonium chloride in Example 2, N- (2-dimethylaminoethylaminocarbonylmethyl)-chloride was used. The same operation as in Example 2 was performed using N, N-dimethyloctadecyl ammonium to obtain N- (2-dimethylammonioethylaminocarbonylmethyl) -N, N-dimethyloctadecyl ammonium chloride. Results of IR analysis and NMR analysis <IR analysis> Strong absorption peculiar to amide was observed at 1679 cm ^-1 . <NMR analysis> The solvent CDCl _3, internal standard _{^{TMS 4.13ppm N + -C H 2 -CONH}} (s, 2H) 3.64ppm NH-C H 2 -CH 2- N + - (CH 3) 2 (t, 2H) 3.50ppm NH-CH ₂ -C H _2- N ⁺ -(CH ₃ ) ₂ (t, 2H) 3.30ppm N ⁺ -(C H ₃ ) ₂ (s, 6H) 3.24ppm N ⁺ -C H _2- (t, 2H) 2.90ppm NH ⁺ -(C H ₃ ) ₂ (s, 6H) Example 13 The same procedure as in Example 1 was carried out except for using N, N-dimethylaminohexylamine in place of N, N-dimethylaminopropylamine in (2) of Example 1, to obtain the following compound N- (6-trimethylammoniohexylaminocarbonylmethyl) -N, N-dimethyloctadecyl ammonium chloride of the formula was obtained.

[0053]

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Results of IR analysis and NMR analysis <IR analysis> 1670 cm^-1, Strong absorption peculiar to the amide was observed. <NMR analysis> Solvent CDCl_Three, Internal standard TMS 4.13ppm N⁺-CH ₂ -CONH (s, 2H) 3.30ppm N⁺-(CH ₃ )_Two, N⁺-(CH ₃ )_Three (t, 15H) 3.50ppm N⁺-CH ₂ -, CONH-CH ₂ -, -CH ₂ -N⁺(CH_Three)_Three (6H) Example 14 N- (3-Dimethylaminopropyl chloride in Example 2
Laminocarbonylmethyl) -N, N-dimethylocta
N- (6-dimethyl chloride) instead of decyl ammonium
Aminohexylaminocarbonylmethyl) -N, N-di
Same as Example 2 using methyloctadecyl ammonium
The same operation was performed to obtain N- (6-dimethylammonium chloride).
Xylaminocarbonylmethyl) -N, N-dimethylo
Cutadecyl ammonium was obtained. IR analysis and NMR analysis results <IR analysis> 1674cm^-1Strong absorption characteristic of amide
Admitted. <NMR analysis> Solvent CDCl_Three, Internal standard TMS 4.13ppm N⁺-CH ₂ -CONH (s, 2H) 3.30ppm N⁺-(CH ₃ )_Two       (s, 6H) 3.23ppm N⁺-CH ₂ -, CONH-CH ₂ -, -CH ₂ -NH⁺(CH_Three)_Two (6H) 2.90ppm NH⁺-(CH ₃ )_Two    (s, 6H) Example 15 N, N-dimethyloctadecyl in (1) of Example 1
Instead of the amine, the N-chloride obtained in (2) of Example 1 was used.
(3-dimethylaminopropylaminocarbonylmethyl
G) using -N, N-dimethyloctadecyl ammonium
And the same operation as in Example 1 was carried out.
-'N'-(3-trimethylammoniopropylamino
Carbonylmethyl) -N ', N'-dimethylammonio
Propylaminocarbonylmethyl) {-N, N-dimethyl
Luoctadecyl ammonium was obtained.

[0055]

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Results of IR analysis and NMR analysis <IR analysis> Strong absorption unique to amide was observed at 1675 cm ^-1 . <NMR analysis> Solvent CDCl ₃ , internal standard TMS 4.13 ppm N ⁺ -CH ₂ -CONH (s, 4H) 3.30 ppm N ⁺ -(CH ₃ ) ₃ , N ⁺ -(CH ₃ ) ₂ (s, _{^{21H) 3.22ppm N + -C H 2}} -, NH-C H 2 -CH 2 -C H 2 -N + (CH 3) 3 (10H) N- chloride in example 16 example 2 (3-dimethylamino Propylaminocarbonylmethyl) -N, N-dimethyloctadecylammonium instead of N- {N '-(3-
Dimethylaminopropylaminocarbonylmethyl)-
(N ′, N′-dimethylammoniopropylaminocarbonylmethyl)}-N, N-dimethyloctadecylammonium was used to perform the same operation as in Example 2 to obtain N-chloride.
{N '-(3-dimethylammoniopropylaminocarbonylmethyl) -N', N'-dimethylammoniopropylaminocarbonylmethyl)}-N, N-dimethyloctadecyl ammonium was obtained. Results of IR analysis and NMR analysis <IR analysis> Strong absorption peculiar to amide was observed at 1679 cm ^-1 . <NMR analysis> Solvent CDCl ₃ , internal standard TMS 4.13 ppm N ⁺ -CH ₂ -CONH (s, 4H) 3.30 ppm N ⁺ -(CH ₃ ) ₂ ^{(s, 12H) 3.22ppm N +} -C H 2, NH-C H 2 -CH 2 -C H 2 -N + (10H) 2.90ppm NH + - (C H 3) 2 (s, 6H) Example 17 The same operation as in Example 1 was performed using N, N-dihydroxyethylaminopropylamine in place of N, N-dimethylaminopropylamine in (2) of Example 1,
N- (N ', N'-dihydroxyethyl-N'-methylammoniopropylaminocarbonylmethyl) -N, N-dimethyloctadecyl ammonium chloride having the following structural formula was obtained.

[0057]

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Results of IR analysis and NMR analysis <IR analysis> Strong absorption peculiar to amide was observed at 1672 cm ^-1 . <NMR analysis> The solvent CDCl _3, internal standard _{^{TMS 4.13ppm N + -C H 2 -CONH}} (s, 2H) 3.97ppm N + -CH 2 -C H 2 -OH (t, 4H) 3.43ppm N ⁺ -C H ₂ -CH ₂ -OH (t, 4H) 3.30 ppm N ⁺ -(C H ₃ ) ₂ , N ⁺ -C H ₃ ^{(S, 9H) 3.24ppm N +} -C H 2 -, NH-C H 2 -CH 2 -C H 2 -N + -CH 3 (6H) Example 18 N-chloride in Example 2 (3-Dimethylamino Example 2 was repeated using N- (N ', N'-dihydroxyethylaminopropylaminocarbonylmethyl) -N, N-dimethyloctadecyl ammonium chloride instead of (aminopropylaminocarbonylmethyl) -N, N-dimethyloctadecyl ammonium. The same operation was performed to obtain N- (N ′, N ′) chloride.
-Dihydroxyethylammoniopropylaminocarbonylmethyl) -N, N-dimethyloctadecyl ammonium was obtained. Results of IR analysis and NMR analysis <IR analysis> Strong absorption unique to amide was observed at 1676 cm ^-1 . <NMR analysis> The solvent CDCl _3, internal standard _{^{TMS 4.13ppm N + -C H 2 -CONH}} (s, 2H) 3.97ppm N + -CH 2 -C H 2 -OH (t, 4H) 3.43ppm N ⁺ -C H ₂ -CH ₂ -OH (t, 4H) 3.30ppm N ⁺ -(C H ₃ ) ₂ (s, 6H) 3.24ppm N ⁺ -C H _2- , NH _{-C H 2 -CH 2 -C H 2} -NH + (CH 3) 2 (6H) N in (2) of example 19 example 1, N- hydroxyethyl -N instead of N- dimethylaminopropylamine The same operation as in Example 1 was carried out using -methylaminopropylamine, and N- (N'-hydroxyethyl-N ', N'-dimethylammoniopropylaminocarbonylmethyl) -N, N -Dimethyloctadecyl ammonium was obtained.

[0059]

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Results of IR analysis and NMR analysis <IR analysis> Strong absorption unique to amide was observed at 1670 cm ^-1 . <NMR analysis> The solvent CDCl _3, internal standard _{^{TMS 4.13ppm N + -C H 2 -CONH}} (s, 2H) 3.97ppm N + -CH 2 -C H 2 -OH (t, 2H) 3.43ppm N ⁺ -C H ₂ -CH ₂ -OH (t, 2H) 3.30ppm N ⁺ -(C H ₃ ) ₂ ^{(S, 12H) 3.22ppm N +} -C H 2 -, NH-C H 2 -CH 2 -C H 2 -N + (6H) N- chloride in Example 20. Example 2 (3-dimethylamino-propylamino Same as Example 2 except that N- (N'-hydroxyethyl-N'-methylaminopropylaminocarbonylmethyl) -N, N-dimethyloctadecyl ammonium chloride was used instead of (carbonylmethyl) -N, N-dimethyloctadecyl ammonium. Operation, chloride N-
(N′-hydroxyethyl-N′-methylammoniopropylaminocarbonylmethyl) -N, N-dimethyloctadecyl ammonium was obtained. Results of IR analysis and NMR analysis <IR analysis> Strong absorption peculiar to amide was observed at 1670 cm ^-1 . <NMR analysis> The solvent CDCl _3, internal standard _{^{TMS 4.13ppm N + -C H 2 -CONH}} (s, 2H) 3.97ppm N + -CH 2 -C H 2 -OH (t, 2H) 3.43ppm N ⁺ -C H ₂ -CH ₂ -OH (t, 2H) 3.30ppm N ⁺ -(C H ₃ ) ₂ (s, 6H) 3.22ppm N ⁺ -C H _2- , NH -C H ₂ -CH ₂ -C H ₂ -N ⁺ H (9H) 2.90 ppm NH ⁺ -(C H ₃ ) (d, 3H) Example 21 Instead of N, N-dimethyloctadecylamine in (1) of Example 1, N, N-dimethyl-N-octadecanoyl The same operation as in Example 1 was performed using aminopropylamine to give N- (3-trimethylammoniopropylaminocarbonylmethyl) -N, N-dimethyl-N-octadecanoylaminopropylammonium chloride having the following structural formula. Obtained.

[0061]

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Results of IR analysis and NMR analysis <IR analysis> Strong absorption peculiar to amide was observed at 1672 cm ^-1 . <NMR analysis> Solvent CDCl ₃ , internal standard TMS 4.13 ppm N ⁺ -CH ₂ -CONH (s, 2H) 3.30 ppm N ⁺ -(CH ₃ ) ₂ , N ⁺ -(CH ₃ ) ₃ (s, 15H) 3.22ppm NH-C H ₂ -CH ₂ -C H ₂ -N ⁺ (8H) 2.18ppm CH ₂ -C H ₂ -CONH (T, 2H) Example 22 The same operation as in Example 1 was carried out except that N, N-dimethyl-N-octadecyloxypropylamine was used instead of N, N-dimethyloctadecylamine in (1) of Example 1. Thus, N- (3-trimethylammoniopropylaminocarbonylmethyl) -N, N-dimethyl-N-octadecyloxypropylammonium chloride having the following structural formula was obtained.

[0063]

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Results of IR analysis and NMR analysis <IR analysis> Strong absorption peculiar to amide was observed at 1670 cm ^-1 . <NMR analysis> The solvent CDCl _3, internal standard _{^{TMS 4.14ppm N + -C H 2 -CONH}} (s, 2H) 3.37ppm -C H 2 -OC H 2 - (s, 4H) 3.30ppm N + - (C H ^{_{3) 2, N + - (}} C H 3) 3 (s, 15H) 3.22ppm N + C H 2 -, NH-C H 2 -CH 2 -C H 2 -N + (6H) Example 23 The same operation as in Example 1 was carried out except that octadecyl chloroacetate was used instead of methyl chloride in (3) of Example 1, to give N- (N′-octadecyloxycarbonylmethyl chloride) having the following structural formula. -N ', N'-dimethylammoniopropylaminocarbonylmethyl) -N, N-dimethyl-
N-octadecyl ammonium was obtained.

[0065]

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Results of IR analysis and NMR analysis <IR analysis> Strong absorption peculiar to the ester was observed at 1731 cm ^-1 .

At 1670 cm ^-1 , strong absorption characteristic of amide was observed. <NMR analysis> Solvent CDCl ₃ , internal standard TMS 4.20 ppm N ⁺ -CH ₂ -COO (s, 2H) 4.13 ppm N ⁺ -CH ₂ -CONH (s, 2H) 4.08ppm COO-C H _2- ^{(t, 2H) 3.30ppm N +} - (C H 3) 2 (s, 12H) 3.22ppm N + -C H 2 -, NH-C H 2 -CH 2 -C H 2 -N + (6H)

 ────────────────────────────────────────────────── ─── Continuing on the front page (72) Inventor Ken Takeshi 1334 Minato, Wakayama-shi, Wakayama Pref. BA50 BA52 BB14 BB16 BC10 BC31 BE63 BU50 BV34

Claims (2)

[Claims] 1. A quaternary ammonium salt represented by the general formula (1). Embedded image (In the formula, R ¹ represents a linear or branched alkyl or alkenyl group having 8 to 22 carbon atoms, an amide group, an .R ² be interrupted by an ester group or an ether group 1 carbon atoms And R ³ represents a hydrogen atom or a linear or branched alkyl group, hydroxyalkyl group or alkenyl group having 1 to 22 carbon atoms, and an amide group, an ester group or an ether group. M is a number from 1 to 6, and n is 2
Represents a number from 1 to 6, and p represents a number from 1 to 10. X represents an anionic group. Note that 2p + 2 R ² and p + 1 X may be the same or different. ) 2. The following steps (a), (b) and (d), or steps:
The method for producing a quaternary ammonium salt according to claim 1, comprising (a), (b), (c) and (d). <Step (a)> General formula (2) (Wherein, R ¹ and R ² have the same meanings as described above), and X- (CH ₂ ) _m —CO ₂ Y (3) , X represents a halogen atom, Y represents a hydrogen atom, or a linear or branched alkyl or alkenyl group having 1 to 22 carbon atoms, and m represents the same meaning as described above.) Or reacting with its ester,
General formula (4) (Wherein, R ¹ , R ² , m, X and Y have the same meanings as described above). <Step (b)> The quaternary ammonium salt represented by the general formula (4) is converted into a compound represented by the general formula (5): (Wherein R ² and n have the same meanings as described above), and are reacted with a diamine represented by the general formula (6). (Wherein, R ¹ , R ² , m, n and X have the same meanings as described above). <Step (c)> Instead of the tertiary amine in step (a),
Using the amino cation obtained in the step (b), the steps (a) and (b) are repeated 1 to 9 times to obtain a compound represented by the general formula (7). (Wherein, R ¹ , R ² , m, n and X have the same meaning as described above, and p ′ represents a number of 2 to 10). <Step (d)> With respect to the amino cation represented by the general formula (6) or the aminopolycation represented by the general formula (7), X-R ³ (8) X and R ³ have the same meanings as described above) or a quaternizing agent represented by the general formula (9) HX (9) (wherein, X has the same meanings as described above). A step of reacting an acid to obtain a quaternary ammonium salt represented by the general formula (1).