JPS63233969A - Novel amphoteric compound - Google Patents

Abstract

NEW MATERIAL:A compound expressed by formula I (R1 is 1-22C alkyl; R2 and R3 are lower alkyl; n is 1-5). USE:A surfactant, bleaching activating agent and antimicrobial agent. PREPARATION:A tert. amine is reacted with a halocarboxylic acid to afford a quaternary amine, which is then hydrolyzed to give a compound expressed by formula II, which is then reacted with thionyl chloride to provide an acid chloride expressed by formula III, which is further reacted with p-phenol sulphonic acid disodium salt to give the compound expressed by formula I.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] This invention relates to a novel amphoteric compound having a functional group.

[Conventional technology and its problems]

Conventionally, (1) [where n is 3 to 25, R is an alkyl group, alkaryl group, allyl group, hydroxyalkyl group or polyoxyalkylene group, R2 and R3 are lower alkyl group or hydroxyalkyl group, or pyridine, morpholine , R2 selected from piperidine, an alkyl-substituted or unsubstituted nitrogen-containing heterocycle in which two bases of R3 form a ring, R4 is a phenyl group, X is chlorine or bromine, and is a quaternary ammonium salt. The total number of carbon atoms is less than 28. ] (US Pat. No. 4,397,757), an amphoteric compound represented by the following formula (2) L R+ N (C11z)-rcOO (CHzCIl
□0)ysOs" (2)■ CHlC In the formula, R3 represents an alkyl group having 14 to 20 carbon atoms, X represents 1 to 5, and y represents 6 to 12.] etc. are known.

However, no reports have been found to date that have investigated compounds containing -N- in the molecule and their usefulness.

[Means for solving problems]

Under these circumstances, the present inventors have completed the present invention by discovering that amphoteric compounds having specific functional groups exhibit excellent properties as surfactants, bleach activators, bactericidal agents, etc.

That is, the present invention provides a novel amphoteric compound represented by the following general formula (1).

I [In the formula, [R1 is an alkyl group having 1 to 22 carbon atoms, R2゜R3 is a lower alkyl group, and n is an integer of 1 to 5. ] As a particularly useful compound, in formula (I), R3 is 1 to 16
Examples include compounds in which the alkyl group, Rz, and R's are lower alkyl groups having 1 to 3 carbon atoms.

The amphoteric compound (1) of the present invention can be prepared, for example, by the following method.

A tertiary amine and a halocarboxylic acid are reacted using a solvent such as alcohol or acetone at room temperature or under reflux to obtain a quaternary amine of compound (n).

Ryu (R1, R2, R: l, Ra represents an alkyl group,
n is an integer from 1 to 5. X is a halogen atom. )next(
II) is hydrolyzed in a mixed solvent such as water/alcohol using an alkali catalyst such as 011 or NaOH to obtain an amphoteric compound (II[).

Rz H:1(ill)(
Acid chloride (IV) is obtained by reacting 1) with thionyl chloride using a solvent that does not contain a substance that reacts with acid chloride such as water or alcohol, such as dichloromethane or chloroform treated with ethanol.

Next, acid chloride (IV) was added to dimethoxyethane (DMB).
) etc. under reflux of a solvent capable of dissolving or uniformly dispersing (IV), p-phenolsulfone fI! Reaction with I2 sodium salt yields the desired amphoteric compound (I).

〔Effect of the invention〕

The compounds of the present invention obtained as described above are all new compounds, but among them, those in which R, R, R, and n are appropriately selected can be used as amphoteric surfactants as they are. It can be used in detergents. It also shows excellent effects as a bleach activator.

〔Example〕

The present invention will be explained below with reference to Examples.
It is not limited to these.

Example 1 62.8 g of dimethyloctylamine was dissolved in 300@l ethanol using a 11-nitro flask equipped with a cooling tube, and 78.0 g of ethyl bromobutyrate was added dropwise. After completion of the dropwise addition, the temperature was raised using an oil bath (temperature: 90° C.), and the reaction was carried out under ethanol reflux while checking with TLC until the raw material amine disappeared. After that, ethanol is distilled off and the following formula (I
140.5 g of quaternary salt of I-a) were obtained. Yield 9
9.8%.

C) 13 Next, 40.8 g of (If-a) was mixed with ethanol/water (1:3
) Dissolved in mixed solvent 41 and adjusted to pH-12 to 12.
The hydrolysis reaction was carried out at room temperature for 3 to 4 days while maintaining the temperature at 5°C.

After confirming by TLC that the raw material quaternary salt was gone, 20
% sulfuric acid, and when a salt was generated, the solvent was distilled off while performing a filtration operation. By desalting the remaining oily substance using dichloromethane, 28.0 g of an amphoteric surfactant of the following formula (I[I-a) was obtained. Yield 99.4%.

46.5 g (■
-a) was dissolved in 250 m7 of dichloromethane, and 20-thionyl chloride was added dropwise at room temperature, followed by reaction under reflux for 1 hour. When the solvent and excess thionyl chloride were distilled off, 57.0 g of the following formula (IV-a) was obtained as an orange oily substance. Yield 100%.

■ C.I.

Dimethoxyethane (DME) 400 g of acid chloride (rV-a) was dehydrated and distilled with lithium aluminum hydride using a 1,000-liter three-ring flask.
p-phenolsulfonic acid disodium salt prepared by the following method was dissolved in rL1 and suspended under reflux for 2 hours.
Allowed time to react. DME was decanted, acetone was added, the mixture was stirred at room temperature, and the acetone-soluble portion was removed by filtration to obtain a mixture of sodium chloride and (I-a). Recrystallization using ethanol/acetone yielded 26.8 g of white plate-like crystals. Yield 40.0%
.

Difficult, p, 217-227°C IR (KBr+ca-') 2932, 2860. 1758. 1491. 1
197. 1152. 1122°1029.1011
．． 687.567'H-N piece R (CD: IOD solvent, TMS internal standard, δ
)1.0(311,t), 1.3~1.5(1
2H91m), 2.1 ~ 2.2 (2H, m),
2.7 (2H, t), 3.05 (6H, s)
, 3.35-3.45 (2H, m), 7.2 (
2H, d), 7.85 (2H, d) p ~ Dissolve 278.4 g of sodium phenolsulfonate dihydrate in 200 g of water, add 52 g of sodium hydroxide, stir at room temperature for 2 hours, and dissolve the crystals. The precipitated p-phenolsulfonic acid disodium salt was filtered off. The filtrate was further recrystallized. The obtained crystals were dehydrated using toluene as a solvent using a Dean-Stark filter, and then refluxed and completely dehydrated while passing through molecular sieves. The obtained p-phenolsulfonic acid disodium salt was 228 g, and the yield was 87.4
%Met.

Example 2 (1-b) was obtained by using dimethyldodecylamine in place of dimethyloctylamine in Example 1. The yield was 53.8% through the 4-step reaction.

Steel, p, 213-216°C IR (KBr, cm-') 2920, 2854.1?55.1497.1470.
1221.1191°1122, 1032.1011.
693.567'H-NMR (CD20D, TMS
Internal standard, δ) 0.9 (3u, t), 1.2-1.
45 (20H, m), 1.7~1.9 (2H, n
+), 2.05-2.2 (2 fl, s), 2.
73 (2H.

t), 3.09 (6H, s), 3.3-3.45
(2H, m), 7.15 (2+1.d), 8.87
(2H, d) Example 3 (lh Using a 10100O three-lough flask, 52 g of ethyl bromoacetate was dissolved in 250 cc of acetone, and while stirring with a magnetic stirrer, dried triethylamine gas was bubbled with N as a carrier gas. After passing 2 equivalents of trimethylamine into ethyl bromoacetate over 3 hours, the mixture was sealed and stirred at room temperature overnight.The white crystals formed were filtered off, and 57.9 g of (U-c) was obtained. Yield: 85.4% Ha Next, 50.65 g of (U-c) was mixed with ethanol/water (l
:1) Dissolve in mixed solvent 11, pH = 12 ~ with KOH
The hydrolysis reaction was carried out at room temperature for 3 to 4 days while maintaining the temperature at 12.5. After confirming by TLC that the quaternary salt of the raw material was gone, it was neutralized with 20% sulfuric acid, and when salt was generated, the solvent was distilled off while performing a filtration operation. By desalting the remaining oily substance using methanol, 32.7 g of an amphoteric substance of the following formula (III-c) was obtained. Yield 99.0%.

The following is carried out in the same manner as in Example 1, so that (I-
c) was obtained. The yield was 42.5% over 4 steps.

IR (KBr, cn+-') 3034, 1?49.1593.1494.1194.
1071.1029°1011, 699.567 'II NMR (DzO, DSS internal standard, δ) 0.
9-2.5 (4H, m), 2.7 (2H, t),
3. H9tl,t).

7.2(2H,d), 7.9(211,d) Usage Example Compound Ia according to the present invention obtained as above,
I-b was tested for bleaching action. 1st
The table shows the results of evaluating the bleaching effect using the method below.

Bleaching method Hydrogen peroxide was added to 300 mf of water at 20° C. so that the effective oxygen content was 0.05%, and 1 g of sodium carbonate was added. Add I-a to this solution in an equimolar amount with hydrogen peroxide,
Or I-b was added, and a black tea-stained cloth prepared by the method described below was immersed in bleach for 30 minutes, washed with water, and dried, and then the bleaching rate was determined by the following formula. Sodium hypochlorite, a comparative product, was evaluated at 0.06% available chlorine.

Bleaching rate of black tea contaminated cloth: Reflectance is 460 for NDR-101DP manufactured by Nippon Denshoku Kogyo ■
Measured using an NRA filter.

Black tea contaminated cloth: Boil 80 g of Nitto black tea (yellow package) in 31 ion-exchanged water for about 15 minutes, strain it through desized dry cotton cloth, soak cotton training camp #2003 cloth in this liquid, and boil it for about 15 minutes. The sample was removed from the heat, left to stand for about 2 hours, then air-dried, washed with water until no color remained in the washing solution, dehydrated, and pressed to form a 10 cm x 10 cm test piece for use in experiments.

Table 1

Claims (1)

[Claims] 1 The following formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(I) [In the formula, R_1 is an alkyl group having 1 to 22 carbon atoms, R_2
, R_3 is a lower alkyl group, and n is an integer of 1 to 5. ] Amphoteric compound represented by