JPS638932B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to novel esters of side-chain higher mixed dibasic acids useful as bases for oils or emulsions in cosmetics, pharmaceuticals, etc., or as industrial oils. More specifically, the present invention relates to general formulas ()() and () (However, in the formula, R represents a straight-chain alkyl group, a straight-chain alkenyl group, or a hydroxyalkyl group having 1 or more carbon atoms, or a side-chain alkyl group having 3 or more carbon atoms.) It concerns esters of basic acids. Specific compounds obtained in the present invention include formulas () (), and () Dimethyl ester, diethyl ester, dipropyl ester, dibutyl ester, dipentyl ester, dihexyl ester, dioctyl ester, didecyl ester, dilauryl ester, ditetradecyl ester, dihexadecyl ester, of side chain higher dibasic acids represented by Dioctadecyl ester, dioleyl ester, dilinoleyl ester, dipalmitol ester, dimyristol ester, diisopropyl ester, diisobutyl ester, di-sec-butyl ester, di-
(3-methylbutyl) ester, di-(2-ethylhexyl) ester, diisostearyl ester, di-2-octyldodecyl ester, di-12
-Ester bodies such as hydroxyoctadecyl ester are exemplified. The compounds of the present invention represented by general formulas ()() and () can be produced, for example, by the following method. That is, the expressions () () and ()
The desired reaction can be easily achieved by carrying out a normal esterification reaction with dicarboxylic acids represented by the formula or their reactive derivatives, linear saturated alcohols, linear unsaturated alcohols, and side chain alcohols or their reactive derivatives. Esters represented by the general formulas () () and () are obtained. For example, industrially, the formulas () () and ()
Heating the dicarboxylic acids represented by and the above alcohols at 200 to 250° for about 4 to 15 hours, or
Alternatively, the dicarboxylic acids of formulas (), () and () may be reacted with the above alcohols in the presence of a dehydrating agent such as a mineral acid such as sulfuric acid or a benzenesulfonic acid such as para-toluenesulfonic acid. It is better to carry out the above reaction under a stream of an inert gas such as nitrogen gas or carbon dioxide gas to prevent coloring, and thus to obtain preferable results from the viewpoint of product purity. If it is colored, good results can be obtained by treating it with activated carbon or activated clay. If even higher purity is required, reactive derivatives of dicarboxylic acids of formulas ()() and (), such as halogenating agents such as thionyl bromide and thionyl chloride, can be used to It can be obtained in high yield by reacting dibromide or dichloride with the above-mentioned alcohols in the presence of a basic catalyst such as trimethylamine or pyridine. Further treatment with column chromatography etc. yields a highly pure diester form of the target product. Also, the expressions () () and ()
The alkali metal salt of the dicarboxylic acid may be reacted with the halogen of the alcohol. Of course,
It can also be manufactured by known methods other than those described above. The raw material carboxylic acid used is usually 2 moles of cyclohexanone mixed with Fenton's reagent (a solution of hydrogen peroxide and a ferrous salt such as ferrous sulfate or ferrous chloride) to form a radical, and then 1 mole of cyclohexanone is added to the radical. The reaction with isoprene yields unsaturated forms of these compounds (), (), and () before catalytic reduction, and they are synthesized by catalytic reduction, so the reaction product has the formula () ( ) and () in the form of a mixture. Therefore, since the above esterification reaction is usually carried out as a mixture, the ester product produced is a mixture of general formulas () () and (). Of course, each carboxylic acid as a raw material may be separated by a known appropriate method such as column chromatography, and each may be esterified by the above method. In the case of general formulas (), () and (), the ester may be separated into each ester by a known appropriate method such as column chromatography. In fact, from an economic point of view, it is preferable to use it in the form of a mixed ester as a base for cosmetics, pharmaceuticals, etc. Now, conventionally, oil-based bases such as cosmetics and pharmaceuticals,
Emulsifiers, absorption enhancers, etc. include castor oil, squalane,
Many natural oils and fats have been used, such as lanolin, olive oil, coconut oil, cacao oil, and camellia oil. Furthermore, in recent years, various synthetic oils that can replace natural oils and fats have come into use. The components of natural oils and fats rarely have a single structure, and generally consist of monoglycerides, diglycerides, triglycerides, and various higher fatty acids.
Synthetic oils are generally in the form of mixed glycerides or mixed esters of higher alcohols and higher fatty acids like lanolin, whereas synthetic oils are generally esters of higher alcohols, intermediate alcohols, or lower alcohols and higher fatty acids. It is often used as a base material. Incidentally, natural oils and fats have been used as bases for cosmetics and pharmaceuticals for a long time, but they have many drawbacks that make them difficult to use. For example, since it is a natural product, there are high and low harvests depending on the weather and other factors, and there are concerns about supply. In addition, there is also variation in components between lots, and problems with odor and hue are considered to be major drawbacks. On the other hand, synthetic oils are produced by hydrolyzing the natural oils and fats mentioned above as raw materials, separating them, and then using extracted and purified higher fatty acids or higher alcohols obtained by reducing them as raw materials and reacting them to esterify them. Alternatively, higher fatty acids or higher alcohols obtained from petrochemistry are generally esterified with appropriate combinations of higher fatty acids or higher alcohols obtained from nature, and used as a single substance as a base. It's summery. Therefore, since it is a synthetic product, there is little variation between lots, and since it is generally colorless, tasteless, and odorless, synthetic oil is often used as a base for modern cosmetics. However, depending on the type of base used in synthetic oils, some synthetic oils can cause skin irritation, poor moisture permeability, and reduced skin respiration, especially those with relatively small molecular weights and those whose entire molecule is linear. It is said that the problem of the above-mentioned drawbacks is included in the combination. As described above, many oil-based bases are known, but at present there are still very few ideal ones. Recently, the presence of side chain higher fatty acids in sebum has been discovered and has attracted attention. Side-chain higher fatty acid esters or side-chain higher alcohol esters are less likely to be hydrolyzed than straight-chain esters, so they are less irritating to the skin than straight-chain esters, and their water permeability is lower than that of straight-chain esters. Mystic acid-2-
Higher fatty acid esters of side-chain higher alcohols, such as octyldodecyl, 2-octyldodecyl oleate, and 2-octyldodecyl ricinoleate, are increasingly being used. The present inventors have continued to research synthetic oil bases from all angles, and have been searching for a synthetic oil substance that is as close to the ideal as possible over a long period of time. We have proposed the general formulas ()() and ()
The present invention was completed by synthesizing various esters of mixed side chain higher dibasic acids shown in the literature and discovering that they have excellent characteristics as oil bases for cosmetics, pharmaceuticals, etc. For example, it has excellent softening properties when used as an oil-based base for cosmetics such as creams, emulsions, lipsticks, foundations, white powders, pomades, hair creams, perfume oils, and hair nourishing products. It has various advantages such as giving a very satisfying feeling when applied to the skin surface, sealing the skin surface and preventing skin respiration, and is tasteless, colorless, and odorless. It has characteristics such as excellent chemical, physical, and bacteriological stability. Furthermore, it can be used as an ointment base for pharmaceuticals, an absorption enhancer, a suppository base, etc., so it has a wide range of applications. The present compounds also have excellent properties as plasticizers and industrial oils such as synthetic lubricants. Furthermore, the metal salts of the present compounds have a wide range of uses, including heavy metal removal agents. Next, the substance of the present invention will be explained with reference to Examples, but of course the invention is not limited thereto. Note that the reference example shows a production example in which unsaturated raw material compounds of and catalytic reduction thereof were carried out. Reference example 1 Dissolve 70g of isoprene in 300ml of methanol,
Add to this 80g of cyclohexanone and 80g of 35% hydrogen peroxide.
After stirring at 20±5°C for 0.5 hour, 250g of ferrous sulfate (heptahydrate) was gradually added while maintaining the temperature at 0 to -5°C. After the reaction,
After adding 18 g of 60% sulfuric acid and stirring, the mixture was allowed to stand until it separated into two layers. The upper layer was separated, washed with dilute sulfuric acid and water, and dried to form an oily mixture of compounds (), (), and dimethyl esters of unsaturated forms of () 132
I got g. This product was purified by column chromatography using silica gel and then subjected to the following instrumental analysis. (a) Infrared absorption spectrum (liquid film method, cm ^-1 ) −
2925, 2850, 1735, 1430, 1390, 1370. (b) Gas chromatography - mass spectrometry - Γ Model used: Shimadzu GCMS QP-100 Γ Analysis conditions: Separation column Silicon OV-17
2% on Chromosorb W 2m; column temperature 150-310°C, vaporization chamber temperature 270°C, ion source temperature 250°C, ionization method EI method, ionization voltage 70eV & 20eV, scanning range 40-500 mass. Γ analysis results (m/e): 326 (M ⁺ ), 295 (M ⁺ −
OCH ₃ ), 294 (M ⁺ −CH ₃ OH), 198 [M ⁺ −
CH ₃ OCO (CH ₂ ) ₄ CH], 197 (M ⁺ −CH ₃ OCO
−(CH ₂ ) ₅ ], 184 [M ⁺ −CH ₃ OCO
(CH ₂ ) ₅ CH], 183 [M ⁺ −CH ₃ OCO
(CH ₂ ) ₅ CH ₂ ], 165 (198−OCH ₃ ), 152 (183−
_OCH3 ), 151 (183− _CH3OH ). (c) Gas chromatography - Γ Model used: Shimadzu GC-9A Γ Analysis conditions Column: Inner diameter 3 mm, length 2.1 m Packing material Silicon OV-1, 1.5%, 80~
100mesh Detector FID/Carrier gas N ₂ Column temperature 130°C to 300°C (temperature increase) Vaporizing chamber temperature 320°C Γ analysis results (weight% of each compound relative to the entire mixture) Dimethyl ester of unsaturated form of compound ()
79.1% Dimethyl ester of unsaturated form of compound ()
17.1% Dimethyl ester of unsaturated compound ()
3.8% Regarding the proportion of unsaturated ester of compounds () () and (), the reaction was carried out more than 10 times under the same conditions as in the above reference example, and the resulting product was analyzed by gas chromatography. , the same results as above were obtained, and the proportions were as follows. Dimethyl ester of unsaturated compound ()
Approximately 76-82% Dimethyl ester of unsaturated form of compound ()
Approximately 15-19% Dimethyl ester of unsaturated form of compound ()
Approximately 2.5-6% Compound () obtained above, a mixture of () and dimethyl ester of an unsaturated product of () was hydrolyzed in a dilute aqueous sodium hydroxide solution under heating according to a conventional method, and the compound Unsaturated dibasic acids (), () and () were obtained. It was confirmed by gas chromatography similar to the above that the mixing ratio of unsaturated substances in these compounds (), (), and () did not change even due to hydrolysis. Furthermore, the mixing ratio of the three types of dibasic acids in the oily substances (), () and () obtained by catalytic reduction of these unsaturated bodies is the same as that of the compounds (), () obtained in the above reference example. It was similar to the unsaturated form of and (). Reference Example 2 Method for producing side chain higher mixed dibasic acids (), () and () Dissolve 50 g of the mixture of unsaturated forms of compounds (), () and () obtained in Reference Example 1 above in 500 ml of acetic acid. After catalytic hydrogenation for about 12 hours at 60℃ and 5 atm hydrogen pressure using 2g of 5% PD/C as a catalyst, the catalyst was filtered off and the filtrate was concentrated under reduced pressure, washed with hot water, dehydrated and the desired product was obtained. (), () and ()
47g of the product was obtained as a colorless and transparent oil. Vinegar value 372,
Saponification value 374, iodine value 1.2, mixture ratio is approximately 79% (), 17% by gas chromatography
(), 4% (). The existence of a double bond is ruled out based on the iodine value, and it is certain that the compounds (), (), and () have undergone catalytic reduction. In addition, in the infrared absorption spectrum, absorption peculiar to carboxylic acids is clearly observed at 1730 to 1740 cm ^-1 Example 1 Method for producing sodium salts of dibasic acids (), (), () Dissolve 0.82 g of caustic soda in 10 ml of water. Then, 3 g of a mixture of dibasic acids (), (), and () are added and heated for 1 hour, and the solution becomes transparent. The solution was concentrated under reduced pressure to obtain 3.4 g of the sodium salt of the target product as a paste-like substance. Example 2 Method for producing diisopropyl esters of dibasic acids (), (), () Compounds in which R in (), (), () is (CH ₃ ) _2.CH- Dibasic acids (), ( When about 20 g of thionyl chloride is added to 3 g of a mixture of ) and () and heated at 70-80°C, hydrochloric acid gas is rapidly generated. Gas generation stopped after 1 hour, and the mixture was heated and stirred for an additional 30 minutes. After the reaction is completed, excess thionyl chloride is distilled off under reduced pressure. Furthermore, in order to completely distill off thionyl chloride, chloroform
Add 50ml and evaporate under reduced pressure. 50 ml of benzene was added to the residue, 5 g of isopropanol was added thereto, and 2.0 g of pyridine was gradually added dropwise as a deoxidizing agent while stirring. After dropping, the mixture is further heated at 70-80°C for 30 minutes to complete the reaction. After cooling, add 50 ml of 10% hydrochloric acid to separate the benzene layer, and further extract the aqueous layer with benzene. The benzene layer is washed once with water and then dried with anhydrous sodium sulfate. The solvent was distilled off by filtration, followed by decolorization and deodorization to obtain 3.7 g of the target diisopropyl ester as a colorless and transparent oil. Yield 96%,
Acid value 0.3, saponification value 290 Example 3 Method for producing dihexyl ester of dibasic acids (), (), () Compound where R in (), (), () is CH ₃ (CH ₂ ) ₅ Dibasic acid 3 g of a mixture of (), (), and () and 2.1 g of hexyl alcohol were reacted under the same conditions as in Example 2 to obtain 4.6 g of dihexyl ester as a colorless and transparent oil. Yield 98%, acid value
0.2, saponification 239 Example 4 Method for producing di-2-ethylhexyl ester of dibasic acids (), (), () R of (), (), () is

Compound of [Formula] 3g of mixture of dibasic acid (), (), () and 2
- Example 2 from 2.6g of ethylhexyl alcohol
Di-2-ethylhexyl ester was obtained as a colorless and transparent oil by reacting under the same conditions as in the case of
I got g. Yield 95%, acid value 0.5, saponification value 212 Example 5 Method for producing dioleyl esters of dibasic acids (), (), () (), (), R in () is CH ₃ (CH ₂ ) ₇ CH＝
CH(CH ₂ ) ₇・CH ₂ - Compound 3 g of a mixture of dibasic acids (), (), () and 5.4 g of oleyl alcohol were reacted under the same conditions as in Example 2 to form a colorless and transparent oil. 7.9 g of dioleyl ester was obtained. Yield 99%, acid value
0.7, saponification value 139, iodine value 62.1 Example 6 Method for producing di-2-octyldodecyl ester of dibasic acids (), (), ()

Compound of [Formula] 6g of mixture of dibasic acid (), (), () and 2
- When 12.4 g of octyldodecanol is mixed and heated and stirred at 230 to 250 degrees for about 8 hours under Chituso's surrounding atmosphere,
16.8 g of the desired di-2-octyldodecyl ester compound was obtained as a pale yellow oil. This product is obtained as a colorless oil by treatment with activated carbon or activated clay. Acid value 3.5, hydroxyl value 7.2, saponification value 128 Example 7 Method for producing dioctadecyl ester of dibasic acids (), (), () (), (), R in () is CH ₃ (CH ₂ ) ₁₇ - Compound 6 g of a mixture of dibasic acids (), (), () and 11 g of stearyl alcohol were mixed and
By heating and stirring at 230 to 250°C for about 5 hours, 15.4 g of the desired dioctadecyl ester is obtained as a pale yellow wax. Acid value 2.1, hydroxyl value 4.7, saponification value 141 For confirmation of the ester compounds obtained in Examples 2 to 7, the raw material compounds (), (), ()
As described above, the structure has been estimated from various instrumental analyzes, synthetic methods, synthetic reagents, etc., and these structures are certain. However, although attempts were made to separate them using methods such as column chromatography, vacuum distillation, thin layer chromatography, gas chromatography, and mass spectrometry, it was not possible to separate each component individually. In addition, for each ester of R, a unique sharp absorption based on the ester was observed in the infrared absorption spectrum at 1700 to 1740 cm ^-1 , which was different from the infrared absorption spectrum of the raw material, and it was estimated that a diester was formed from each alcohol used. It is certain that it is.

Claims (1)

[Claims] 1. General formula () (), and () (However, in the formula, R represents a straight-chain alkyl group, a straight-chain alkenyl group, or a hydroxyalkyl group having 1 or more carbon atoms, or a side-chain alkyl group having 3 or more carbon atoms.) Basic acid esters. 2. The compound according to claim 1, wherein R in the general formulas ()() and () is a methyl group. 3. The compound according to claim 1, wherein R in the general formulas ()() and () is an ethyl group. 4 R in general formulas () () and () is n-
The compound according to claim 1, which is a propyl group. 5 R in general formulas () () and () is n-
The compound according to claim 1, which is a butyl group. 6 R in general formulas () () and () is n-
The compound according to claim 1, which is a pentyl group. 7 R in general formulas () () and () is n-
The compound according to claim 1, which is a hexyl group. 8 R in general formulas () () and () is n-
The compound according to claim 1, which is an octyl group. 9 Claim 1 in which R in the general formulas ()() and () is a straight-chain alkyl group having 10 carbon atoms.
Compounds described in Section. 10. The compound according to claim 1, wherein R in the general formulas ()() and () is a straight-chain alkyl group having 12 carbon atoms. 11. The compound according to claim 1, wherein R in the general formulas ()() and () is a straight-chain alkyl group having 14 carbon atoms. 12. The compound according to claim 1, wherein R in the general formulas () () and () is a straight-chain alkyl group having 16 carbon atoms. 13. The compound according to claim 1, wherein R in the general formulas ()() and () is a straight-chain alkyl group having 18 carbon atoms. 14. The compound according to claim 1, wherein R in the general formulas () () and () is a straight chain alkenyl group having 18 carbon atoms, and the straight chain alkenyl group has a double bond at the 9th to 10th positions. 15. The compound according to claim 1, wherein the side chain alkyl group of R in the general formulas () () () and () is an isopropyl group. 16. The compound according to claim 1, wherein R in the general formulas ()() and () is an isobutyl group. 17 R in general formulas () () and () is sec
The compound according to claim 1, which is a -butyl group. 18 General formula () () and R in () is 3
The compound according to claim 1, which is a -methylbutyl group. 19 General formula () () and R in () is 2
The compound according to claim 1, which is -ethylhexyl group. 20. The compound according to claim 1, wherein the side chain alkyl group of R in the general formulas () () () and () is a 2-octyldodecyl group. 21. The compound according to claim 1, wherein R in the general formulas ()() and () is a side chain alkyl group having 16 carbon atoms. 22. The compound according to claim 1, wherein the side chain alkyl group of R in the general formulas () () and () is an isostearyl group. 23 In the general formulas () () and (), R is a straight chain alkyl group having 18 carbon atoms, and 12 of the straight chain alkyl group
The compound according to claim 1, which has a hydroxyl group at this position.