JPH08198864A - Spiculisporic acid derivative and its production - Google Patents

Abstract

PURPOSE: To easily obtain in high yield from an inexpensive and readily available stock the subject new compound excellent as an emulsifier, lubricant, or a base such as for skin cosmetics, hair cosmetics and household or industrial surfactants. CONSTITUTION: This new compound (or a salt thereof) is expressed by formula I [R is a 1-21C hydrocarbon group; M is H, an alkali (alkaline earth) metal ion, ammonium ion, or an alkanolammonium ion[, e.g. a compound of formula II. Another version of this new compound (or a salt thereof) of formula III (e.g. a compound of formula IV) is obtained by opening the lactone ring of the compound of formula I with an alkali hydroxide. The compound of formula I is obtained by reaction of spiculisporic acid with an equimolar amount of an isocyanate of formula R-NCO, and the compound of formula II can be obtained by opening the lactone ring of the compound of formula I with an alkali hydroxide.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to novel spiculisporic acid derivatives and a method for producing them, and more specifically, novel spiculisporic acid useful as a skin cosmetic, hair cosmetic, household or industrial surfactant. The present invention relates to an acid derivative and a method for producing the same.

[0002]

2. Description of the Related Art Conventionally, spiculisporic acid is a natural polyvalent carboxylic acid obtained by fermentation, and its salt has little skin irritation, and it has been proposed in the cosmetics industry to use it as a raw material for cosmetics from an early stage. However, as a raw material for cosmetics, it was unsatisfactory in terms of performance because it was poorly compatible with the skin and had low surface activity. Therefore, in the cosmetics industry, spiculisporic acid derivatives or salts thereof, which have low toxicity and low skin irritation of natural spiculisporic acid and have further excellent functions, for example, mild and familiar to the skin, and sufficiently surface active, are used. Was desired.

[0003]

DISCLOSURE OF THE INVENTION As a result of intensive studies conducted by the present inventors in order to solve the above problems, the compounds represented by the following general formulas (1) and (2) are skin cosmetics and hair cosmetics. The present invention has been completed by finding that it is excellent as a base such as a surfactant, an emulsifier, and a lubricant, and that it can be produced at a high yield by a simple operation from raw materials that are easily available at low cost. General formula (1) General formula (2) [In the general formulas (1) and (2), R is 1 to 1 carbon atoms.
21 represents a saturated or unsaturated hydrocarbon group, and M represents a hydrogen atom, an alkali metal ion, an alkaline earth metal ion, an ammonium ion or an alkanol ammonium ion. The compounds represented by the above general formulas (1) and (2) of the present invention are novel compounds produced by the following synthetic routes.

Synthetic route [I] Synthetic route [II] [In the general formulas (1) and (2), R has 1 to 2 carbon atoms.
1 represents a saturated or unsaturated hydrocarbon group, and M represents a hydrogen atom, an alkali metal ion, an alkaline earth metal ion, an ammonium ion or an alkanol ammonium ion. In the present invention, examples of the saturated or unsaturated hydrocarbon group having 1 to 21 carbon atoms represented by R include methyl, ethyl and n-
Propyl, n-butyl, isobutyl, n-pentyl, allyl, octyl, 4-octenyl, 2-octenyl, 2
-Ethylhexyl, oleyl, palmityl, hexyl,
2-hexenyl, 11-hexadecenyl, hexadecyl, cyclohexyl, stearyl, geranyl and the like can be mentioned.

The novel compounds represented by the above general formulas (1) and (2) of the present invention are, as shown in the above synthetic routes [I] to [II], the equimolar R-NC with spiculisporic acid.
A step of reacting an isocyanate represented by O (R is a saturated or unsaturated hydrocarbon group having 1 to 21 carbon atoms) to obtain a compound represented by the general formula (1) (synthesis route [I]) And a compound represented by the general formula (1) are hydrolyzed to open a lactone ring (synthesis route [II]).

Next, each synthetic route of the present invention will be described.

Synthetic Route [I] Spiculisporic acid and R-NCO (R is a carbon number of 1 to 21)
Represents a saturated or unsaturated hydrocarbon group. The reaction)) is carried out in an organic solvent which is not reactive with isocyanate groups. Particularly desirable organic solvents are tetrahydrofuran, acetone, methyl ethyl ketone, dioxane, acetonitrile and the like. The reaction temperature is 0 to 100 ° C, preferably 20
~ 80 ° C.

[0008] The reaction time is 1 to 12 hours, but since it largely changes depending on the reaction temperature, it ends when the raw material is no longer confirmed by thin layer chromatography. After the reaction, it can be easily obtained by distilling off the solvent used. When purification is required, ordinary operations such as column chromatography are performed. In the compound thus obtained, M of the compound of the general formula (1) is a hydrogen atom, so that it can be changed to a salt suitable for the purpose of use if necessary.

Synthetic Route [II] The compound of the general formula (1) obtained by distilling the solvent from the reaction liquid synthesized by the synthetic route [I] is treated with a methanol solution of sodium hydroxide for 2 to 20 hours, particularly preferably. Is heated to reflux at the boiling point of methanol for 5 to 10 hours. After the completion of the reaction, the target compound of the general formula (2) is obtained by cooling.
If necessary, this sodium salt can be changed to another salt according to the intended purpose by a commonly known method.

For example, when a sodium salt is dissolved in water and neutralized with hydrochloric acid, sulfuric acid, phosphoric acid or the like, a compound in which M of the general formula (2) is a hydrogen atom can be easily taken out.
As a raw material, various salts can be prepared according to the purpose of use.

[0011]

The present invention will be described in detail with reference to the following examples.

Example 1 Synthesis of

12.73 g of spiculisporic acid was added to THF.
Dissolve in 50 ml. To this, 9.83 g of stearyl isocyanate is added and heated at room temperature for 3 hours and at 65 ° C. for 5 hours. Then it is left at room temperature and the traces of precipitated precipitate are filtered off. The filtrate is heated under reduced pressure and the THF is distilled off. The lactone form of the title compound is quantitatively obtained as a transparent oil. Sodium hydroxide 3
g and a solution of 100 ml of water are added, and the mixture is heated under reflux for 10 hours.
Next, it is cooled, and the precipitated crystals are collected by filtration, washed with methanol and ethanol, and dried. The sodium salt is obtained as a white powder. The filtered methanol mother liquor is acidified with dilute hydrochloric acid, and the deposited precipitate is collected by filtration, washed with methanol and dried to obtain 9.76 g of an off-white waxy substance. A small amount is purified by chromatography for NMR measurement. _{0.9 (m, 6H -CH 3 ×} 2) 1.2 (s, 50H) 2.3~3.4 (m, 7H) 9.5 (s, 1H -CON H -) dicarboxylic acid (CCl _{4 -d 6 DMSO) 0.8 (t,} 6H -CH 3 × 2) 1.2 (s, 50H) 1.6~3.1 (m, 7H) 7.6 (m, 1H -CON H -) Example 2

6.56 g of spiculisporic acid and 1.7 g of propyl isocyanate are dissolved in 30 ml of THF, stirred at room temperature for 2 hours and heated under reflux for 10 hours, and then the solvent is distilled off. Purification by column chromatography gives a colorless transparent oily substance. _{0.9 (t, 6H -CH 3 ×} 2) 1.3 (s, 18H -CH 2 - × 2) 1.9~2.8 (m, 9H) 9.2 (m, 1H -CON H - The free carboxylic acid according to this example is compatible with mink oil, which is important as a cosmetic raw material, at an arbitrary mixing ratio and can be used as a cosmetic product.

Example of Use The sensitivity evaluation as a cream when the spiculisporic acid derivative according to the present invention was added to a cosmetic cream was carried out. Evaluation criteria are skin elongation, richness, familiarity,
The moist feeling was compared with the cream containing no spiculisporic acid derivative, and was shown by the following evaluation scores.

1 ... Very low 2 ... Low 3 ... Equivalent 4 ... High 5 ... Very high Manufacturing method 1. Liquid paraffin 20.0% 2. Sorbitan monostearic acid 3.0% 3. Sorbitan monostearate POE (20) 3.0% 4. Paraoxybenzoic acid ester 0.2% 5. 1,3-butylene glycol 6.0% 6. Triethanolamine 0.2% 7. 1% carboxyvinyl polymer 20.0% 8. Spiclisporic acid derivative 5.0% 9. Purified water 42.6% 1-3 Heat to 70 ° C. Add 4-6, 7, 8 to this
Add what was heated to 0 ° C and emulsify uniformly. Add 9 to this, mix and quench to make a cream. The results are shown in Table 1.

[0017]

As can be seen from Table 1, the spiculisporic acid derivative of the present invention is comprehensively excellent in elongation, richness, familiarity and moistness.

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Claims (4)

[Claims] 1. A compound represented by the following general formula (1) or a salt thereof. General formula (1) [In the formula, R represents a saturated or unsaturated hydrocarbon group having 1 to 21 carbon atoms, and M represents a hydrogen atom, an alkali metal ion, an alkaline earth metal ion, an ammonium ion, or an alkanol ammonium ion. ] 2. A compound represented by the following general formula (2) or a salt thereof. General formula (2) [In the formula, R represents a saturated or unsaturated hydrocarbon group having 1 to 21 carbon atoms, and M represents a hydrogen atom, an alkali metal ion, an alkaline earth metal ion, an ammonium ion, or an alkanol ammonium ion. ] 3. A spiculisporic acid is reacted with an equimolar amount of an isocyanate represented by R—NCO (wherein R represents a saturated or unsaturated hydrocarbon group having 1 to 21 carbon atoms), and if necessary, a salt. A method for producing a compound represented by the following general formula (1): General formula (1) [In the formula, R represents a saturated or unsaturated hydrocarbon group having 1 to 21 carbon atoms, and M represents a hydrogen atom, an alkali metal ion, an alkaline earth metal ion, an ammonium ion, or an alkanol ammonium ion. ] 4. A method for producing a compound represented by the following general formula (2) by opening the lactone ring of the compound represented by the following general formula (1) with an alkali hydroxide and performing salt exchange if necessary. General formula (1) General formula (2) [In the formula, R represents a saturated or unsaturated hydrocarbon group having 1 to 21 carbon atoms, and M represents a hydrogen atom, an alkali metal ion, an alkaline earth metal ion, an ammonium ion, or an alkanol ammonium ion. ]