JP2907517B2 - 2- or 3-chain bihydrophilic compound - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to a novel compound having excellent interfacial properties, and more particularly, to an emulsifier, a dispersant, a solubilizer, a washing agent in the fields of cosmetics and pharmaceuticals. The present invention relates to a novel compound usable as an agent, a limestone dispersant, and a liposome-forming agent.

[Conventional technology]

Until now, as amphiphilic compounds in which one molecule is composed of a hydrophobic group and a hydrophilic group, the “single-chain one-hydrophilic group type” (Soken, S
DS, lauryl polyglycol ether), "single-chain two-hydrophilic group" (alkyldiphenyl ether disulfonate, etc.) and "two-chain, single hydrophilic group" (lecithin, dialkyldimethylammonium chloride, etc.) are known.

Single-chain / one-hydrophilic groups are the most common surfactants and are used in various fields based on their actions such as emulsification, dispersion, foaming, solubilization, washing, and penetration.

The single-parent / two-hydrophilic type has better water solubility as compared with the single-chain / single-hydrophilic type and also has excellent surface activity, and is already available as an industrial product.

On the other hand, among the two-chain single hydrophilic group type compounds represented by natural lecithin, those having a short hydrophobic group length are used as penetrants, and those having a long hydrophobic group length are used as biological membrane models. Research has progressed rapidly over the last decade.

[Problems to be solved by the invention]

However, in the case of the combination of one hydrophilic group and one hydrophobic group, the combination of one hydrophilic group and two hydrophobic groups, or the combination of two hydrophilic groups and one hydrophobic group as described above, the critical micelle concentration and surface tension Since there is a limit in improving the lowering ability, it is necessary to improve the washing and emulsifying properties (higher performance), and to form a membrane such as a bilayer membrane or LB membrane or a complex with metal cations in a small amount. There is also a limit to the performance that can be added (multifunctionalization).

Accordingly, an object of the present invention is to reduce the critical micelle concentration compared to conventional surfactants, and to excel in surface tension lowering ability, high performance,
Another object of the present invention is to provide a novel amphiphilic compound which can be expected to have various composite functions.

[Means for solving the problem]

The present invention provides (1) a two-chain or three-chain bihydrophilic compound represented by the following general formula ( 3 ): (Where R ¹ is a straight-chain alkyl group having 8 or 10 carbon atoms,
R ² represents a methyl group or a linear alkyl group having 9 or 11 carbon atoms, Z represents (CH ₂ ) ₃ SO ₃ M, and M represents H ⁺ , NH ^{4 +} , Na
⁺ , K ⁺ , a cation selected from alkanol ammonium ions. (2) A two-chain or three-chain bihydrophilic compound represented by the following general formula ( 4 ) (However, R ¹ and R ² represent the same as in claim (1).)

Incidentally compound of R ² are CH ₃ group (3) a two-chain form, the compounds of the straight-chain alkyl group R ² carbon atoms 9 or 11 (3) is a three-chain type.

The compound ( 3 ) of the present invention is generally amphiphilic and exhibits surface activity in an aqueous solution or an organic solvent such as lower alcohol, acetone, chlorinated hydrocarbon, hydrocarbon, benzene, toluene, etc. The chain type has lower critical micelle concentration and surface tension lowering ability than the two-chain type, and can act as a higher performance surfactant.

The compound ( 4 ) of the present invention is generally insoluble in water, but it can be used as an oil-soluble surfactant, cosmetic / cosmetic compounding agent, emulsifier, etc., as well as an intermediate for synthesizing the compound ( 3 ) of the present invention. Useful with the body. The two-chain or three-chain two-hydrophilic compound of the present invention uses, for example, O-alkylglycerol, which is a commercially available material, as a starting material, diglycidyl etherification thereof, and an oxirane ring with a long-chain alcohol. The compound can be synthesized by performing a series of operations such as a ring opening reaction and a modification reaction of two hydroxyl groups of the resulting dihydroxy compound.

More specifically, the intermediate compound represented by the general formula ( 4 ) can be synthesized, for example, as follows.

N-acyldiethanolamine is reacted with a phase transfer catalyst such as benzyltrioctylammonium chloride and NaO
Diglycidyl etherification by reacting with epichlorohydrin in the presence of alkali metal hydroxides such as H and KOH (Ken, Ikeda, Okahara, SYNTHESIS, 1985, 649-651)
Page). Next, compound ( 4 ) is obtained by opening the ring with a long-chain alcohol in the presence of an alkali metal.

The compound represented by the general formula ( 3 ) can be obtained by modifying two hydroxyl groups of the compound ( 4 ).

Examples of the method for modifying the hydroxyl group include production of an alkyl ether having a sulfonate at the terminal by reaction with a sultone or isethionic acid.

The crude product can be purified by recrystallization from lower alcohols or silica gel chromatography using a suitable solvent system (for example, a mixed solvent of ethanol and hexane) as an eluent.

Compounds ( 3 ), ( 4 ) of the present invention thus obtained
Has two hydrophilic groups and two or three hydrophobic groups in the molecule, and therefore has significantly lower critical micelle concentration (CMC) and lower surface tension (γ _CMC ) than conventional surfactants. (See Table 1).

However, when the compound ( 3 ) is a compound in which M is a hydrogen ion, the surfactant activity can be exhibited by using it together with caustic soda or triethanolamine at the time of use.

The term "surface tension lowering ability" as used herein means the minimum surface tension exhibited by a surfactant aqueous solution at or above the critical micelle concentration. The smaller this value is, the more excellent the surface tension lowering ability is. That is to say.

In contrast, for example, a known surfactant RSO ₃ Na
(R = C ₈ H ₁₇ , C ₁₀ H ₂₁ , C ₁₂ H ₂₅ )
Both the order of 10 ⁻³ M and γ _CMC are values of 40 mN / m or more.

The compounds ( 3 ) and ( 4 ) of the present invention can be used as emulsifiers, dispersants, solubilizers, detergents, limestone dispersants, and liposome-forming agents, for example, in the fields of cosmetics and pharmaceuticals.

As the emulsifier, dispersant, and liposome-forming agent, those having a relatively short hydrophobic chain length are particularly preferable.

Since the compound of the present invention has a low CMC and γ _CMC , a sufficient effect can be obtained with an amount smaller than that of a general surfactant.

〔Example〕

Hereinafter, the present invention will be described in more detail with reference to examples.

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

Example 1 Compound (R ¹ = C ₁₀ H ₂₁ , R ² = CH ₃ (( 4 ); ( 4 ) -A) 55.51 g of epichlorohydrin in a 200 ml four-necked flask
(0.60 mol), tetrabutylammonium hydrogen sulfate (catalytic amount), 5.05 g (0.12 mol) of sodium hydroxide,
Stir at ℃, N-acetyldiethanolamine
4.41 g (0.03 mol) was added dropwise over 1 hour, and the mixture was further stirred at 50 ° C. for 1 hour. This was filtered and distilled, and N-acetyldiethanolamine diglycidyl ether 5.19 g (0.02 mol
l) got.

In another 200 ml four-necked flask, add n-decyl alcohol 2
Put 8.5g (0.18mol), and at 70 ℃ 1.17g of metallic potassium
(0.03 mol) was dissolved. There, 5.19 g of N-acetyldiethanolamine diglycidyl ether (0.02m
ol) was added dropwise over 1 hour and stirred at 80 ° C. for 12 hours. Thereafter, the mixture was cooled to room temperature, neutralized with 10% hydrochloric acid, transferred to a separating funnel, and extracted with methylene chloride (150 ml × 3 times) -water (150 ml). After collecting methylene chloride and drying over anhydrous magnesium sulfate, the insoluble matter was filtered off, and the filtrate was distilled under reduced pressure to distill off methylene chloride and excess n-decyl alcohol. The residue was purified by silica gel chromatography using acetone-hexane as an eluent to isolate 5.3 g of an anhydrous liquid compound ( 4 ) -A (about 46% yield).

( 4 ) Physical properties of -A IR (neat): ν (cm ^-1 ) 3400, 2930, 1630, 1460, 1120 MASS: m / e (relative strength) 576 [(M + 1) ⁺ , 15], 344 [100] , ¹ H-NMR (CDCl ₃ ): δ (ppm) 0.89 (t, 6H), 1.30-1.65 (m, 32H), 2.16 (s, 3H), 3.1
5-4.05 (m, 24H) Example 2 (Compound ( 4 ) wherein R ¹ ＣC ₁₀ H ₂₁ , R ² ＣC ₉ H ₁₉ ; ( 4 ) -B) Following the production method of Example 1, N- Instead of 4.41 g (0.03 mol) of acetyldiethanolamine, 7.77 g (0.03 mol) of N-decanoyldiethanolamine was used to obtain 10.6 g (yield: about 77%) of a colorless liquid compound ( 4 ) -B.

( 4 ) Physical properties of -B IR (neat): ν (cm ⁻¹ ) 3400, 2930, 2850, 1620, 1460, 1120 MASS: m / e (relative strength) 688 [(M + 1) ⁺ , 13], 456 [ 100], ¹ H-NMR (CDCl ₃ ): δ (ppm) 0.88 (t, 9H), 1.18-1.67 (m, 46H), 2.35 (s, 2H), 2.8
1 (s, 2H), 3.37-3.93 (m, 22H) Example _{^{3 (R 1 = C 10 H}} 21, R 2 = C 9 H 19, Z = (CH 2) 3 SO
₃ Na, compound (3) 200 ml distilled purified necked flask was placed in dried tetrahydrofuran (THF) 50 ml, treated with sodium hydride 0.80g of (0.02 mol) was added with hexane, stirring at 30 ° C. , Compound ( 4 ) -B 3.44 g (0.005 mol) in THF (10
ml) solution was added dropwise over 30 minutes, and the reaction system was heated to 60 ° C., followed by 2.44 g (0.02 mol) of propane sultone in THF (1
0 ml) solution was added dropwise. Stir for 24 hours under THF reflux conditions,
After cooling to room temperature, 20 ml of methanol was added to inactivate unreacted sodium hydride, and the solvent was distilled off under reduced pressure. The residue was extracted with an n-butanol (100 ml × 3 times) -water (150 ml) system, the organic layer was dried over anhydrous magnesium sulfate, the solid was filtered off, and the solvent was distilled off from the filtrate. The residue was purified by silica gel chromatography using an ethanol-hexane eluent to give 3.22 g of a white wax compound ( 3 ).
(About 66% yield).

Physical properties of ( 3 ) IR (neat): ν (cm ⁻¹ ) 2930, 2840, 1620, 1440, 1220, 1110 ¹ H-NMR (CDCl ₃ ): δ (ppm) 0.87 (t, 9H), 1.20 to 1.80 (M, 46H), 2.00-2.15 (m, 4
H), 2.37-2.50 (m, 2H), 2.88-3.12 (m, 4H), 3.33-4.35
(M, 26H) Soluble in water at 0 to 100 ° C. at a concentration of 0.05% by weight or less CMC: 7.8 × 10 ⁻⁶ M γ _CMC : 28.0 mN / m Comparative Examples 1 to 3 For known surfactants, CMC and Table 2 shows the results of examining γ _CMC .

〔The invention's effect〕

As described above, it is apparent that the present invention provides a high-performance compound having a low critical micelle concentration and excellent surface tension lowering ability, and an intermediate useful for the production method thereof.

Claims (2)

(57) [Claims] 1. A two-chain or three-chain bihydrophilic compound represented by the following general formula ( 1 ): (Where R ¹ is a straight-chain alkyl group having 8 or 10 carbon atoms,
R ² represents a methyl group or a linear alkyl group having 9 or 11 carbon atoms, Z represents (CH ₂ ) ₃ SO ₃ M, and M represents H ⁺ , NH ^{4 +} , Na
⁺ , K ⁺ , a cation selected from alkanol ammonium ions. ) 2. A two-chain or three-chain bihydrophilic compound represented by the following general formula ( 2 ): (However, R ¹ and R ² represent the same as in claim (1).)