Recent trend of the development of cosmetic raw materials has its importance in finding function and efficacy for skin. We discuss about cosmetic raw materials such as oil, humectant, surfactant and pigment in related to their function and efficacy in this review.

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(-) -Ambrox (1) and (+) -8-demethylisoambrox (2), which give out a strong ambergris-type odor, were efficiently synthesized from (-) -levopimaric acid (3). The keto diester (8) was obtained by ozonolysis of methyl levopimalate. By the Wittig reaction, followed by epoxidation and reduction, the methyl and hydroxyl groups at C-8 were introduced. The triol (15) was convefted to the 8 α, 12-epoxy mesylate (16) by dehydration with methanesulfonyl chloride. The reduction of 16 with sodium iodide and zinc dust gave (-) -ambrox (1).

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Reverse phase HPLC analysis of amino compounds labeled with N-succinimidyl benzoates (1) was carried out. Aliphatic primary and secondary amines labeled with N-succinimidyl pnitrobenzoate (1) (X=p-NO2) could be separated by using aqueous acetonitrile containing 0.1% phosphoric acid as an eluent. The secondary amines with 1-branched chains could not be detected since they did not react with (1) (X=p-NO2). Good erythro/threo separation of synthetic dihydrosphingosines (4) labeled with (1) was observed, and the erythro content was about 70%, which is in good agreement with that determined by the previously reported GLC method.

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The effects of metal salts added to the water phase on the properties of the monolayer of a surface-active crown ether compound with long-chain formed at the oil/water interface were examined by surface pressure measurements, and the ζ-potentials of an O/W emulsion and crown ether compounds were also examined under various salt conditions.
Once crown ether compounds have complexed with metal ions at the O/W interface, they become more capable of remaining there owing to the increment in the hydrophilicity of their headgroups. With increase in the degree of complexing the stability of the monolayer becomes greater. The stability of monolayer was found to be influenced not only by the metal cation, but by its counter-anion in the water phase as well; i.e., in the case of potassium salts, this stability is controlled by the degree of the hydration free energy of the anion. Especially, when picric ion, a lipid soluble anion, is used, the monolayer becomes unstable with respect to desorption of a crown ether compound from the O/W interface. That is, crown ether compound complexes including the picric anion are easily transferred from the water phase to the oil phase by compression of the monolayer.

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Spiculisporic acid (1), produced by Penicillium spiculisporum, is well known as a member of microbial biosurfactants. (1) is a polyfunctional compound having a five-membered lactone and two carboxylic groups. However, relatively little work has been reported on the preparation of its derivatives. (1) readily reacted with diazomethane to give an optically active ester (2) in 93% yield and was also converted to 3-decyl-4- (2-carboxyethyl) maleic anhydride (4) in 87% yield by heating it under reduced pressure. We describe here the preparation of other derivatives from (2) and (4). (4) reacted with various alcohols by refluxing in benzene in the presence of p-TsOH as an acid catalyst to give terminal esters (5) in high yields. Conversion to the terminal ethyl ester of (4) in 95% yield was easily achieved by treating (6), prepared from (4) and 1, 3-thiazolidine-2-thione, in ethyl alcohol at room temperature in the presence of K2CO3 as a base catalyst. The lactone ring of (2) reacted with dodecylamine under high pressure (8, 000kg/cm2) at 60°C to give an optically active hydroxy amide (7) in 86% yield. Reactions of (4) via the acyl chloride with amines afforded terminal amides (8) in low yields, together with triamides (9) and amide-imides (10). (8) were also obtained in high yields by only mixing (6) with amines in CH2Cl2. Imides (11) were prepared in good yields by refluxing a benzene solution of (4) and equimolar amounts of amines. When (4) was refluxed in toluene with two equimolar amounts of amines, (10) and (11) were obtained in a 1 : 1 molar ratio.

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The influences of six representative surfactants on hair and the scalp were investigated under various conditions such as : irritation, protein denaturation, sorption onto commercial hide powder or keratin powder, change in turnover time of the stratum corneum, dandruff and disintegration of the cuticle.
1. Influence of surfactants on scalp.
Although the cumulative irritation test, 48-hour closed patch test, and immersion test were performed to assess the irritating effects of surfactants, the results did not agree with each other. The immersion test, which makes essentially the same use of surfactants, gave results in close agreement with those for sorption of sufactants or protein denaturation by surfactants.
Amounts of surfactants sorbed by hide powder.
Irritation score of immersion test : r=0.671.
Amounts of surfactants sorbed by keratin powder.
Irritation score of immersion test : r=0.930.
Per cent denaturation of OVA by surfactants.
Irritation score of immersion test : r=0.880.
Turnover times of the stratum corneum due to the surfactants were found to follow the order, AMT≤AGS≤L-Soap≤AP<LS≤ES.
Examination of the amounts of dandruff as observed when using AMT shampoo and ES shampoo, each with a different effect on the turnover time of the stratum corneum, showed the amounts to differ remarkably according to the surfactant used.
2. Influence of surfactants on hair.
The extent of disintegration of cuticle by a surfactant supersonic treatment was found to have the following order :
AMT≤AGS≤AP≤ES<LS<L-Soap.
Based on the above results, AMT can be a good surfactant as a detergent for the hair and scalp.

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The polymorphism of mixtures of POP, POS and SOS was analyzed by using samples composed of pure compounds (>99%). Three mixture systems were prepared, A : POP (18.2%), SOS (34.0%), POS (47.8%), B : POP (44.5%), SOS (39.2%), POS (16.3%) and C : POP (58.1%), SOS (41.9%). The presence of polymorphism and its thermal transformation were examined by X-ray diffraction (XRD) and DSC, both applicable to the same sample at the same time, The three mixture systems exhibited almost identical polymorphic behavior : namely, α, pseudo-β', β2 and β1 occurred either via melt crystallizaion or polymorphic transformation. Melting points increased in the order, α to β1. In mixture C, the γ form was also detectable, with its melting point lying between those of α and pseudo β.
The transformation rates from β2 to β1 were highest in mixture C, and slowest in mixture A.
Both XRD short spacing patterns and DSC melting behavior of β2 and β1 of the three mix-tures were completely identical to those of pure POP and SOS, and to Forms V and VI of cocoa butter. Since mixture A has the same triacylglycerol composition as cocoa butter, the conversion from Form V to Form VI may be concluded to be the same as a solid-state-transformation.

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A quantitative determination of surface-active components in Nekal-type surfactants of isopropyl style was carried out by HPLC. Surface-active substances separated from products prepared by Lederer's method and commercial products were converted quantitatively to methyl esters, and the following 17 components were subsequently separated from these esters by silica gel column chromatography. Their structures were determined by MS and NMR spectrometry as 5 triisopropyl-, 7 diisopropyl-, and 5 monoisopropyl-derivatives. Each component present in the mixtures was determined quantitatively by HPLC (Zorbax SIL, φ 4.6×250mm) using two eluents, such as CHCl3-C6H14 (60/40, vol/vol) [Solvent system I] and CHCl3-C6H14-i-PrOH (4.8/95/0.2, vol/vol/vol) [Solvent system II].
In these determinations, it was necessary to use calibration factors for each component, to make correction for defferences in molar absorption coefficients at the detecting wave length (294nm) and methyl 5, 8-diisopropyl-2-naphthalenesulfonate was used as the internal standard.
The components and their compositions were found to vary according to the reaction condition. The commercial products were classified as two types, on the basis of composition.

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