JPH04124165A - Compound having two or three chains and two hydrophilic groups - Google Patents

Abstract

NEW MATERIAL:The compound of formula I or formula II [R<1> and R<3> are 8-30C alkyl or alkylaryl; R<2> and R<4> are methyl, 8-30C alkyl or alkylaryl; Z<1> and Z<2> are SO3M1, (CH2)nSO3M2, CH2COOM3, group of formula III or (CH2CH2 O)mH (M1 to M5 are H<+>, NH, Na<+>, K<+> or cation derived from alkanolamine; (n) is 2-4; (m) is 1-40)]. USE:A surfactant having low critical micelle concentration and excellent surface- tension-lowering performance and expected to have high performance (e.g. detergency and emulsifiability) and various composite functions (e.g. formation of liposome and formation of complex with metallic cation). PREPARATION:The compound of formula I or formula II can be produced by reacting a compound of formula IV or formula V with chlorosulfonic acid, a haloacetic acid salt or a polyphosphoric acid, thereby modifying the hydroxyl group of the starting compound. The compounds of formula IV and formula V are new compounds and useful as an oil-soluble surfactant, an additive for cosmetics, an emulsifier, etc.

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to a novel compound having excellent interfacial properties,
More specifically, in the fields of cosmetics and pharmaceuticals,
Emulsifier 1 Dispersant, solubilizer, detergent 1 Limestone A novel compound that can be used as a dispersant and liposome forming agent (compounds (I) and (II)).

Compounds (compound (I), (
Regarding IV)).

[Conventional technology]

Up until now, amphiphilic compounds consisting of one molecule of a hydrophobic group and a hydrophilic group have mainly been of the "-chain one hydrophilic group type" (Sekken, S
DS, lauryl polyglycol ether),
- chain two-hydrophilic group type (such as alkyl/L nophenyl ether cis sulfonate), and one-chain two-chain hydrophilic group type (such as one-chain, n-alkylnomethylammonium chloride). ing.

The one-chain hydrophilic type surfactant is the most common surfactant, and is widely used in various fields due to its effects on emulsification, dispersion, foaming, solubilization, and FJC permeation.

Compounds with one set of two hydrophilic groups have better water solubility than those with one chain and one hydrophilic group, and are also characterized by superior surfactant ability, and are now available as industrial products. .

On the other hand, among the two-chain hydrophilic group type compounds represented by natural lentin, those with short hydrophobic chains are used as penetrants, and those with long hydrophobic chains are used as biomembrane model bilayer vesicle constructors. As such, research has progressed rapidly over the past 10 years.

(Problem to be solved by the invention) However, the combination of one hydrophilic group and one hydrophobic group, the combination of one hydrophilic group and two hydrophobic groups, as described above,
Or a combination of two hydrophilic groups and one hydrophobic group,
Since there is a limit to improving the critical micelle concentration and surface tension lowering ability, it is possible to improve detergency and emulsifying properties (higher performance), and in small amounts, to form membranes such as bilayer membranes and LB membranes, and complexes with metal cations. There was also a limit to the ability to add performance (complex functionality) that could be used to create such things.

Therefore, an object of the present invention is to provide a novel amphiphilic compound that has a lower critical micelle concentration than conventional surfactants, has excellent surface tension lowering ability, and is expected to have high performance and various complex functions. be.

[Means to solve the problem]

The present invention has the following features: (1) The following - 0 represented by (I) or (I
2'Z Z2 (However, Rl, R" is a straight chain or branched alkyl group or alkylar group having 8 to 30 carbon atoms, R", R
' is a methyl group)
, z' are SO. M.

(CHz)nsO. Mz, CH2C00M3, P(
OM. )(OM+).

(CH2CHJ)represents any of mH, M, -M+, H", 'NH4', ha", ni', represents any of the cations derived from alkanolamine, and n is 2 to 4. m represents an integer of 1 to 40, and (2) a two-chain or three-chain dihydrophilic group type compound represented by the following general formula (■) or (IV) (wherein R represents). be.

~R4 is the same as in claim (1), and by the way, R', R' or CH, compounds (I) ~ (IV)
Compounds (1) to (■) in which R' and R' are linear or branched alkyl groups or alkylaryl groups having 8 to 30 carbon atoms are two-chain type.

Compounds (I) and (■) of the present invention are generally amphiphilic, and exhibit surface activity in aqueous solutions or organic solvents such as lower alcohol acetone, chlorinated hydrocarbons, hydrocarbons, Hensen, and toluene. In particular, the two-chain type has a lower critical micelle concentration surface tension lowering ability than the two-chain type, and acts as a higher performance surfactant.

Compounds (II[) and (IV) of the present invention are generally insoluble in water or can be used as oil-soluble surfactants, cosmetic formulations, emulsifiers, etc.
It is useful as an intermediate for synthesizing I) and (II).

The two-chain or three-chain dihydrophilic group type compound of the present invention is, for example,
Using N-acyljetanolamine or 0-alkylglycerol, which are industrially easily available materials, as starting materials, their diglynonyl etherification and oxirane ring opening with long-chain alcohols were performed.2. Subsequently, it can be synthesized by carrying out a series of operations in which the two hydroxyl groups of the resulting nohydroquino compound are modified.

The intermediate compound represented by the general formula (I) can be synthesized, for example, as follows.

N-acyljetanolamine is treated with a phase transfer catalyst such as penciltrioctylammonium chloride, and Na,
Diglycidyl etherification is achieved by reacting with shrimp chlorohydrin in the presence of an alkali metal hydroxide such as OH or KOH (Koikeda, Okahara, 5YNTHESIS,
1985.

649-651), then in the presence of an alkali metal,
The compound (I
[[) can be obtained.

The compound represented by general formula (I) can be obtained by modifying two hydroxyl groups of compound (I[) by the method shown below.

Methods for modifying hydroxyl groups include reaction with chlorosulfonic acid to generate a sulfuric ester salt, reaction with sultones or isethionic acid to generate a terminal sulfonate alkyl ether, and reaction with a haloacetate to generate an alkyl terminal carboxylate salt. Examples include production of ether, phosphate ester salt by reaction with polyphosphoric acid, and production of polyoxyethylene ether by reaction with ethylene oxide.

The crude product is recrystallized from lower alcohols.

Alternatively, it can be purified by phosphoric gel chromatography using a suitable solvent system (for example, a mixed solvent of ethanol and hexane) as an eluent.

Compounds represented by general formulas (n) and (IV) can be similarly synthesized by using 1-0-alkylglycerol in place of N-acylgetanolamine in the above method.

Compound (I) of the present invention thus obtained.

(n) has two hydrophilic groups and two or three hydrophobic groups in its molecule, so compared to conventional surfactants, it has a significantly lower critical micelle concentration (CMC) and surface tension lowering ability ( γC
MC) (see Table 1).

However, L, compound 8 (r), (I[) no M, ~
M or hydrogen ion compounds can exhibit surface activity when used together with isotropic soda, triethanolamine, etc.

The surface tension lowering ability referred to here means the minimum surface tension exhibited by an aqueous surfactant solution at or above the critical micelle concentration, and the smaller this value, the higher the surface tension. A certain R502Na (R=CI H
1? , Cl0H1)゜Cl-H□), the CMC is on the order of 10-'M, and the γCMC is on the order of 40m.
The value is N/m or more.

The compounds (1) and (II) of the present invention can be used, for example, in the fields of cosmetics and pharmaceuticals, as emulsifiers, dispersants, solubilizers, detergents, limestone dispersants, and liposome forming agents.

At that time, as the emulsifier 1 dispersant and liposome forming agent,
Solubilizers with relatively long hydrophobic chains.

As a cleaning agent, one having a relatively short hydrophobic length is particularly preferable.

Compounds (T) and (I[) of the present invention can also be used in appropriate combination with other known surfactants (nonionic, anionic, cationic mono-ampholytic) and the like.

The compounds of the invention have CMC, γ. . Because the surfactant is low, a sufficient effect can be obtained with a smaller amount than ordinary surfactants.

〔Example〕

Hereinafter, the present invention will be explained in more detail with reference to Examples.

The surface tension of the sample solution was measured by the Wilhelmy glass plate method at 20°C, and from the plot of the relationship between surface tension and logarithmic concentration, CMC and γ were determined. . I asked for

Example 1 (Compound (I[I); Cm)-A where R' = C, , H, , R' = CH,] Epichlorohydrin 55
．． 51g (0.60mol, tetrabutylammonium hydrogen sulfate (catalytic amount), sodium hydroxide 5.05
g (0.12m O1), stirred at 40°C, and added 4.41 g of N-acetylgetanolamine.
(Drop 0.03 mo! over 1 hour, then add 50 mo!
Stirred at °C for 1 hour. This was filtered and distilled to give N-acetyldiethanolamine diglynodyl ether 5.1
9 g (0.02 m o R) was obtained.

Put 28.5 g (0.18 mol) of n-decyl alcohol into another 200 mR four-lower flask, and add 7
1.17g (0.03mol) of metallic potassium at 0゛C
was dissolved. There, 5.19 g (0.02 m
of) was added dropwise over 1 hour, and the mixture was stirred at 80°C for 12 hours. Thereafter, it was cooled to room temperature, neutralized with 10% hydrochloric acid, transferred to a separating liquid, and diluted with methylene chloride (150mAX 3 times).
Extracted with water (150ml) system. After collecting the methylene chloride layer and drying it with anhydrous magnesium sulfate, remove the insoluble matter. ls, and the Hama liquid was distilled under reduced pressure to remove methylene chloride and excess n-decyl alcohol. The residue was purified by glue gel chromatography using acetone-hexane as eluent to obtain a colorless liquid compound (I[[)-A5,30
g (46% yield) was isolated.

(III) Physical properties of -A IR (ne at): v (cm-')34
00, 2930. +630.1460.1)20MA
SS: m/e (relative intensity) 576 [(M+1)”, 15], 344 [IQO]
.

+(-NMR(CDC1,): δ(ppm)0.89(
t, 6H), 1.30-1.65(m, 32)t)
.

2.16(s, 3)1), 3.15-4.05(m
, 24H) Example 2 (F!'=C,.H,,,R'
Compound (III) where =C,H,; (I)-
B) Following the production method of Example 1, 4.41 g (0.03 mol) of N-decanoyl ethanolamine (0.0
3mo! Compound (I)-BIo, a colorless liquid, was prepared using
．． 6 g (77% yield) was obtained.

Physical properties of (I[)-B IR (neat): v (cm-') 3400,
2930, 2850, +620. 1460.

MASS: m/e (relative intensity) 688 [(M+ 1)”, +3], 456 [10
0]1(-NMR (CDCI!3'): δ(ppm
)0, 88(t, 9H), 1. 18-1
．． 67 (m, 46H).

Z35 (t, 2H), 2.81 (s, 2H).

3, 37-3. 93 (m. 22H) Example 3
(R' = C,.H2,, R'' =C.H,.

The compound (I
); (I)-B. ) 200m! ! Put 50 ml of distilled and dried tetrahydrofuran (THF) into a three-row flask, and add 0.80 g (0.0 g) of sodium hydride treated with hexane.
2 mol) was added, and while stirring at 30°C, the compound (
IN)-83.44g (0.005mol) THF
(I Om! After adding the solution dropwise over 30 minutes, the reaction system was heated to 60°C, and then propane sultone 14
A solution of 4 g (0.0 2 moA) in THF (10 ml) was added dropwise. The mixture was stirred for 24 hours under THF reflux conditions, and after cooling to room temperature, 20 ml of methanol was added to deactivate unreacted sodium hydride and the solvent was removed. was distilled off under reduced pressure.The residue was diluted with n-butanol (100 mfXa times) and water (15
0mj? ) system, the organic layer was dried over anhydrous magnesium sulfate, the solids were separated by filtration, and the solvent was distilled off from the filtrate.

The residue was purified by silica gel column chromatography using ethanol-hexane eluent to obtain 3.22 g of white waxy compound (I) B (yield: 66%).
) was isolated.

(I)-B. Physical properties of IR (ne at): v (cm-')2
930, 2840. 1620. 1,440. 1
200.

1) O H-NMR (CDCf,): δ (ppm) 0, 87 (
t. 9H), 1.2G-1.80 (m.46H).

2, 00-2. , 1.5 (m, 4H), Z
37-2. 50 (m.

2) 1), 2. , 88-3. 12 (m. 4
H), 3. 33-4,35 (m. 26H) Soluble in water at 0-100°C at a concentration of 0.05% by weight or less CMC: 7.8XI O-'M7 CIIC: 2 8. O mN/m Example 4 (R' = C,.H !l+ R' = C *
H l@+Z ' ” C H t C O O N
Compound (I) which is a; (1)-B. ') 200mj' Compound (III)-
83.44 g (0.005mol,
t-Butanol 80mi! and dissolve 0.69 g (0.03 mof) of metallic sodium at 60°C.

A solution of 2.08 g (0,015 mof) of bromoacetic acid in t-butanol (20 to 1) was added dropwise over Io minutes, and then stirred at 80°C for 24 hours. Cool to room temperature and evaporate the solvent under reduced pressure. The obtained residue was extracted with n-butanol (100 to 1 x 3 times) and water (150 mL), and the organic layer was dried over anhydrous magnesium sulfate, the solid content was separated by filtration, and the solvent was distilled off from the filtrate. The residue was purified by silica gel column chromatography using inoprobanol-Hensen eluent to isolate 2.33 g (55% yield) of compound (I)-B as a white wax.

Physical properties of (I)-B, TR (ne at): v (cm'')29
50, 2850.1650.16+0.1460゜'H
-NMR (CDCAt) δ (ppm) 0.88 (t
, 9H), 1.20-1.80 (m, 46) 1).

2-42 (m, 2H), 3.30-4.20 (m,
22)1).

4,35(s, 4)1) CMC soluble in water from 0 to 100'C at a concentration of 0.05% by weight or less: 1.2X 10'M (pH 1) in aqueous solution) γ.2, : 30. OmN/m' Example 5 (Compound (IV) where R3 = C, H,, R' = CH, (IV)-A) Sodium hydroxide 5.05 g (0.12 m o r ) to 10, 1.
g (0.24 mol), N-acetyl lenoethanolamine: /4.41 g (0.03 mon)
1-0-methylglycerol 6,36 g (0,0
6 m o r! ), n-denyl alcohol 28.5
g (0,18 moA) with n-octyl alcohol 23
The procedure was carried out in the same manner as in Example 1 except that ゜4 g (0.18 mof) was used. 1. Colorless liquid compound (IV) -A9
．． 52 g (66% yield) were isolated.

(IV) Physical properties of -A IR (ne at): ν (cm-') 342
02900, 2840.1460.1370MASS:
m/e (relative intensity) 479 [(M+I)'', 48], 57 [100
]H-NMR (CDCffi,) δ (ppm)
0.85 (t, 6H), 1.20-1.60 (m,
4H).

'l 69(s, 2H), 3.26-3.98(
m, 22t() Example 6 (R' = C, H, , R
'=C,. Compound (IV) which is H21; (IV
)-B) N-acetylgetanolamine 4.4 +,
g (0.03 mof) to 1-0-denulglycerol 6.96 g (0.03 m o I), n-desol alcohol 28.5 g (0.18 mol) to n-octyl alcohol 15.6 g ( 0,+2 m o
l! ), 1.17 g (0.03 m
The procedure was repeated in the same manner as in Example 1, except that 0.78 g (0.02 mof) was used for the colorless liquid compound (I
V)-88.95 g (74% yield) were isolated.

(IV) Physical properties of -B IR, (ne at); v (cm-')3
450, 2930.2860.1470.1) 20MA
SS: m/e (relative intensity) 605 [(M+II)'', 26], 69 [100
]'H-NMR (CDC1', ) ・δ (ppm
)0, 86(t, 91(), 1.20-1.59
(m, 40H>'l 63(s, 2H), 3.
38-4.02 (m, 2H1) Example 7 (R' =
C, H, □, R' = C,. H2Z” ” (CH2)
Compound (II) which is 2SOzNa; (II)-B
) 0.80g (0.02mol) of sodium hydride
．． 96g (0,024mof), (I)-B3,4
4 g (0,005 mol) of (IV)-B3
．． (IV)-B instead of 63g (0,006mof)
The same procedure as in Example 3 was carried out except that the dropwise addition time of the THF solution was changed from 30 minutes to 20 minutes, and 3.32 g (yield: 62%) of compound (If) B+ in the form of a white wax was isolated.

Physical properties of (n)-B, IR (ne a t): v (cm-') 2940,
2840.1450.1200.1) 10゜'H-NM
R(CDCj7.) δ(pprn)0.88(t,
9H), 1.15-1.61 (m, 40H).

L 95-2.20 (m, 4H), :! ,,90-
3.14 (m.

48), 3.35-3.95 (m, 25H) 0.05
CMC soluble in water at 0-100°C at a concentration of not more than 1.9 x 1. O-'MγCMC・28
-3 m N/m Example 8 (R' = Ci HIT, R'2C1°H2,
.

Compound (IIm) ([)-B where Z1=SOz Na
) 100m! ! Compound (IV)-83,6 in a round bottom flask
3g (0,006mof), sodium carbonate 2.54
g (0,024 mo!, chloroform 50 mj2
Add chlorosulfonic acid Z80 and stir at 0°C.
g (0,024 moA) was added dropwise over 30 minutes. 0
After stirring at °C for 6 hours, ION sodium hydroxide alcoholic solution was added to the system to adjust the pH to 10, and the solvent was distilled off under reduced pressure. Add 45 mj' of hot ethanol to the residue,
Insoluble matter was filtered off while hot, and ethanol was distilled off from the filtrate.

The residue was diluted with n-butanol (30 ml 3 times) and water (3 times).
After drying the organic layer over anhydrous magnesium sulfate, the insoluble matter was filtered off, the filtrate was concentrated under reduced pressure, and the residue was purified by gel column chromatography using ethanol-chloroform eluent. 822.91 g of compound (I[) as a white solid (yield: about 67%)
) was isolated.

Physical properties of (In)-B IR (KBr): v (cm-') 3500, 2950. +640.1480.1240
．． 1) 10'H-NMR (CDC13) δ (ppm
)0.88(t,9)1), 1.20-1.70(
m, 40H) 3, 35-4.00 (m, 19H),
4.60-4.80 (m.

2H).

CMC soluble in water at 0-100°C at a concentration of 0.1% by weight or less: 8.0xlO-'M γCMC: 2 8. Om N /m Example 9 (R
'=C,H+,,R'=C,. H71゜Z2=P
(=0)(OH), Compound (II); (IF)
-B, ) Hensen 50 dehydrated and dried in a 200ml four-lower Scotch
rr+I! , polyphosphoric acid 6.08 g (HCO1+P
4 conversion 0. Compound (IV)-83,63g (0,006rn
Hensen (20ml> solution of) was added dropwise over 30 minutes. Then, the reaction was carried out at 45°C for 24 hours. Cooled to around room temperature, 50ml of water was added, and the system was subsequently stirred at 50°C for 6 hours. Add 150 mA of ether to the mixture and transfer to a separating funnel to remove the aqueous layer.Additionally 100 mA of water
100 mj of N hydrochloric acid? The ether layer was washed twice with 00 mA of water. Next, 5% sodium hydroxide aqueous solution 1
500mj of ether solution while adding 50ml! Transferred to a Mayer flask and stirred the system for 1 hour. After that, it was transferred to a separating funnel again, the aqueous layer was collected, concentrated hydrochloric acid was added to the aqueous layer to adjust the pI (l), and the ether layer was extracted three times with 150 ml of ether.The ether layer was collected, washed with water at 150 mA, and then After drying, it was filtered, and the ether was distilled off from the filtrate to obtain a white waxy compound (II) B+3.80 g (yield: 83%).
) was isolated.

In addition, TLC and HPLC (methanol eluent.

When analyzed using an ODS column, it was confirmed to be a pure compound.

Physical properties of (II)-B IR (ne at): v (cm-') 35
00, 2950.2860.2300.1640.1,
220°') l-NMR (CDCA, ), δ (ppm)
0.88 (+, 9H), 1.20-1.70 (m,
40)1).

3, 36-4.05 (m, 19H), 4.40-4
．． 60 (m.

2H), 7.50-8.70(br, 4H)I)f
H++”P-NMR (CDC1,/CHCA, 85%
D, PO, external standard) δ (ppm) 0 (±0.5) (S) Example 1o (R': C# HIT, R4=c
Compound (II) where 1°H71°Z2= (P-○)(ONa); (I[)-B, ) Compound (II)-
8,3,80g (0,005mol) in a 100ml Meyer flask, 0.85g of sodium hydroxide
(0,02mof) ethanol (50ml) solution and 1
By stirring for an hour and then distilling off the ethanol under reduced pressure, a white waxy compound (III)-B, 4.2
5g (0,005mof) was obtained.

Physical properties of (II)-B Soluble in water at 0 to 100°C at a concentration of 0.1% by weight or less Example 1) (R,” = C+ H++, R' = C
3゜H71゜Zt” (CHt CHl 0)-
Compound (1) [) (II)-B, ) H (m is 20 on average) Compound (IV) -83.63 g in a reaction tube for gas blowing
(0,006moA'), sodium hydroxide 0,0
Add 4 g and stir with a magnetic rotor.
Ethylene oxide dried at 150°C was blown into the reactor. Blowing was stopped when the weight of the system reached about 15 g, and unreacted ethylene oxide remaining in the system was purged by blowing nitrogen gas, and the system was cooled to around room temperature. 100 ml of water was added to the system, transferred to a separating funnel, and extracted five times with 200 ml of methylene chloride. The organic layer was collected, dried over anhydrous magnesium sulfate, and filtered. The solvent was distilled off from the filtrate, and the residue was subjected to preparative GPC liquid chromatography to remove molecules of about 1,000 ml. About 1.5 g of unreacted (■)-B was cut off by treatment with chloroform (solvent) to obtain a viscous liquid compound (Ir) Ba.

Physical properties of (I[)-Bs IR(ne at) ν(cm-') 3400,
2900.1640.1450.1)l100H-N
(CDCf, ): δ (ppm) 0.88 (t, 9) 1)
, ], 20-1. TO (m, 40H) 3, 30
-4.10 (m, about 1801 ()) Cloud point near 5°C of 1% solution by weight CMC・<IO-'M γ CMC: 8°0 m N/m Comparative example ~ 3 Regarding known surfactants , CMC, and γtic [Effects of the Invention] As described above, it is clear that the present invention provides a high-performance compound with a low critical micelle concentration and excellent ability to lower surface tension, and an intermediate flavor useful for the production thereof. be.

Claims (1)

[Claims] (1) Two-chain or three-chain dihydrophilic group type compound represented by the following general formula (I) or (II)▲There are mathematical formulas, chemical formulas, tables, etc.▼...(I)▲Mathematical formulas, chemical formulas, tables, etc. etc.▼...(II) (However, R^1 and R^2 are straight chain or branched alkyl groups or alkylaryl groups having 8 to 30 carbon atoms, R^
2, R^4 is a methyl group or a linear or branched alkyl group or alkylaryl group having 8 to 30 carbon atoms, and Z^1, Z^2 are SO_3M_1, (CH_2)nSO_2M_2, CH_2COOM_3
,▲There are mathematical formulas, chemical formulas, tables, etc.▼, (CH_2CH
_2O) mH, M_1 to M_5 are H
^+, NH_4^+, Na^+, K^+, represents any cation derived from alkanolamine, n represents an integer of 2 to 4, and m represents an integer of 1 to 40. ) (2) Two-chain or three-chain dihydrophilic group type compound represented by the following general formula (III) or (IV) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ ... (III) ▲ Numerical formulas, chemical formulas, There are tables, etc.▼...(IV) (However, R^1 to R^4 represent the same thing as claim (1).)