JPS58162553A - 1,5-dimethyl-2-isopentylhexanol ester of higher fatty acid and cosmetic containing the same - Google Patents

Abstract

NEW MATERIAL:A compound of formulaI(R is 9-21C aliphatic hydrocarbon group). EXAMPLE:1,5-Dimethyl-2-isopentylhexyl myristate. USE:Useful as a component in cosmetics or drugs for external use in direct contact with the skin or an oily component incorporated with an oil or emulsion, e.g. a medicine, in the liquid state at room temperatue, and having a lower cloud point than expected from the molecular weight without giving the irritation to the skin surface even in continuous use, and having improved stability in air for the ester of a saturated fatty acid. PROCESS:1,5-Dimethyl-2-isopentylhexanol of formula II or a reactive derivative thereof and a 10-22C fatty acid or a reactive derivative thereof, e.g. an acid halide, are reacted with a dehydrohalogenating agent, e.g. pyridine, in a solvent, e.g. benzene, at 50-100 deg.C under heating and stirring to give the aimed compound of formulaI.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to higher fatty acid esters of 1,5-dimethy-2-isopentylhexanol and cosmetics containing the same. More particularly, the present invention provides a compound represented by the general formula (1) (wherein R represents a saturated or unsaturated aliphatic hydrocarbon group having 9 to 21 carbon atoms) and a scissors compound. The present invention relates to cosmetics containing.

One of the present inventors and his co-inventors previously discovered that 6-methyl-5-hebuten-2-one, an important intermediate in the synthesis of terpenoids, is a by-product produced from phrenyl chloride and a7tone. 6-methyl-5
By hydrogenating 1,1-diisopentenyl acetone obtained by the condensation reaction of -hebuten-2-one and pnonyl halide, the T1 formula ( II) 1,5-dimethyl-2-isopentylhexanol represented by the following was provided (see JP-A-56-135431).

The present inventors have recently synthesized a new compound represented by the general formula (1), which is a higher fatty acid ester of 1,5-dimethyl-2-isopentylhexanol, and have discovered that the esters can be used as cosmetic ingredients. The present inventors have discovered that it has various properties suitable for use, and have completed the present invention.

As a specific example of the compound of the present invention represented by the general formula (1),
Saturated fatty acid esters of 5-dimethyl-2-isopentylhexanol such as capric acid, undecylic acid, lauric acid, myristic acid, palmitic acid, stearic acid, isostearic acid, behenic acid and 1.5-dimethyl-2
-Isopentylhexanoltotecylenic acid, Kundecylenic acid, Palmitoleic acid, Oleic acid, Rirun II! ,
Unsaturated fatty acid esters such as linoleic acid can be mentioned. When these esters are used in cosmetics, esters with saturated fatty acids are preferred from the viewpoint of stability in the air.

The compound of the present invention is higher fatty acid ester of 1,5-dimethyl-2-isopentylhexanol - Fil, 5
-dimethyl-2-isopengylhexanol or a reactive derivative thereof with 10 to 2 carbon atoms as mentioned above;
It is easily obtained by reacting two fatty acids or their reactive derivatives (eg, acid halides or h-esters).

The esterification reaction or the transesterification reaction can be carried out using methods and conditions known per se.

One of the highly reactive derivatives is an acid halide of a fatty acid, and in a preferred example, first, thionyl chloride, thionyl bromide,
Using 1 to 2 moles of a halogenating reagent such as phosphorus trichloride, the two are reacted at 0 to 100°C to form an acid halide. Then, 1 to 3 mol of 1.5-
Using dimethyl-2-isopentyl-hexanol and 1 to 3 moles of a dehydrogenating agent such as pyridine or quinoline, these are heated and stirred at 50 to 100°C in a solvent such as benzene or methylene chloride to react. let The hydrogen halogenide amine layer produced from the reaction mixture is removed, and the desired esters are obtained by performing the desired treatments such as washing with water, drying, and distilling off the solvent, followed by purification by distillation.

The esters of the present invention can also be produced by directly reacting fatty acids with 1,5-dimethyl-2-chopentylhexanol without using highly reactive derivatives. At this time, an esterification catalyst may or may not be used. Kt when using a catalyst
i. Heating fatty acids and 1,5-dimethyl-2-isobenthylhexanol in an inert solvent such as benzene or toluene in the presence of a catalyst such as para-toluenesulfonic acid or zinc chloride, and co-producing water. A method in which the reaction is carried out while distilling off by distillation (17) is preferred. K when no esterification catalyst is used
Fi, it is preferable to carry out the reaction at a high temperature such as 200 to 230° C. while distilling off the produced water under reduced pressure.

The desired ester can also be obtained easily and economically by a transesterification reaction between a lower alkyl ester such as methyl ester or ethyl ester of the fatty acid and 1,5-dimethyl-2-isopentylhexanol.

The ester 1llFi of the present invention represented by general formula (1) is liquid at room temperature and has a lower cloudiness than expected from its molecular weight. Furthermore, regular use of the esters on the skin does not cause irritation, and changes in the cough ester field over time are small. In particular, saturated fatty esters of 1,5-dimethyl-2-isopentylhexanol have excellent stability in air. In addition, in the feel tests when the esters of the present invention were applied to the skin, they were found to be 1) non-sticky, 2) spreadable, 3) light, and 4) absorbent and permeable. Results included 5) good blendability, 6) no heat sensation, 7) no glare, and 8) good clarity.

The esters and saturated fatty acid esters of the present invention are useful as components of cosmetics or external preparations (for example, ointments, etc.) that are used directly on the skin, and have characteristics that improve the feeling.

Therefore, the cosmetic provided by the present invention has the general formula (1)
) It is characterized by containing (blending) the compound shown in the following. When the compound represented by the general formula (1) is incorporated into cosmetics, an effective amount may be incorporated into a system containing water and other oily substances. Generally, in the whole composition (cosmetic), 1 part of water
~99% weight, preferably 20-90% I! The compound represented by the general formula (1) is 0.01 to . 25 layer fil favorite
L< is o1~1o heavy aS and other oily substances 0.1~9
It is appropriate to mix it so that it is 0 TLt%, preferably Fi 1 to 50% by weight. Examples of the above [-other oily substances] include liquid paraffin, squalane, natural oils and fats,
Any of the oily substances known to be incorporated into cosmetics, such as higher fatty acids, higher aliphatic alcohols, and their esters, can be used. Anything that can be blended can be included, such as humectants, thickeners, preservatives, emulsifiers, medicinal ingredients, fragrances, emulsion stabilizers, etc. The compounds of the present invention are particularly suitable as described above. It is useful as a cosmetic ingredient, but it can also be used as a medicine, capsule medicine, etc.
It is also useful as an oily component added to oils or emulsions such as polymeric materials.

Examples of manufacturing the compounds of the present invention and formulation examples of the cosmetics of the present invention are shown below. The invention is not limited to these examples.

Example 1 Myristic acid 77,·f (0,337 mol) was placed in a flask, heated in a 100°C oil bath, scaled, and then added to thionyl chloride 31WI! (0.42 mol
) was added dropwise over 15 minutes. After heating under reflux for 4.5 hours and cooling to 50°C, unreacted thionyl chloride was removed under reduced pressure with a water jet pump, and methylene chloride 150111
: was added to prepare a methylene chloride solution of myristoyl chloride.

To another flask add 1,5-dimethyl-2-1/hex'r/k 67.56 f (0,337 mo
l), pyridine 41/(0,51 mol) and 4-
N,N-cy)f ruaminopyridine 0.41 f (3,
4 mmol) methylene chloride<340 Il/) solution was added, and the previously prepared methylene chloride solution of ristoyl chloride was added dropwise at room temperature. After the addition was completed, the mixture was stirred at room temperature for 13 hours, and then heated under reflux for an additional 1.5 hours. A cooling bale and hexane 40011/ml were added, the precipitate was separated, and the mouth plate was washed with dilute hydrochloric acid and a saturated aqueous solution of NaHCOs. The hexane layer was dried over anhydrous Mg5Oa, and the hexane was removed under reduced pressure, resulting in a brown liquid 133. Of was obtained.

Distill this liquid at 230-250℃ i 1 To
rr) followed by column chromatography on silica gel [hexane:isopropyl ether-95:5 color clear liquid 96. I got Of. The analysis results of this liquid are shown below.

CI-MS (M raw calculated value 410) 409, 393 1H-NMR (δ, TMS standard, CDUs solution] 4.9
2 (m, IH), 2.21 (t, 2H).

1.801.04 (m, 33H), 0.8'2 (m
, 18H) IR [KBr;
The yield of dimethyl-2-isopentylhexyl was 69.

Next, the 1,5-dimethyl-2-isopentylhexyl myristic acid obtained in the above procedure was deodorized. This ester96. OF and water 100t'6 preparation,
Heat the water to 60-70″C under vacuum with a water jet pump.
f was distilled off. After cooling, the organic layer was separated from the residue, washed with a saturated aqueous solution of NaHCOs, and dried using anhydrous MgSO4 to remove the MgSO4.

The mixture was left at room temperature for 1 hour under reduced pressure with a vacuum pump to obtain a colorless and transparent liquid 8301.

Myristic acid 1.5- purified and deodorized by the above procedure
The cloud point of dimethyl-2-isopentylhexyl was determined according to the Japanese Industrial Standards Petroleum Products Cloud Point Test Method and was -31°C.

- The compatibility of this ester with other fats and oils was also tested at 11°C. The results are shown in the table below. M elf 2 Execution a1) Perform the same operation as in 1 and change to m+) stenoic acid and τ stear 1J >#95.99 (0,337 mol
) and purified by column chromatography using silica gel to obtain a colorless and transparent liquid [022]. The analysis results of this liquid are shown below.

'H-NMR [δ, TM8 standard, CDα3 solution] 4.9
2 (m, I H)? 2.20 (t-2H) T
1.801.05 (m, 41H), 0.81 (”+
188)l R (KBr film) 1735t?llI From the analysis results in
It was confirmed that it was dimethyl-2-isopentylhexyl. The yield was 6511.

Example 3 The same operation as in Example 1 was carried out using 115 f (0,337 mol) of behenic acid instead of myristic acid, and 97.3 f of a colorless and transparent liquid was obtained by chromatographic purification using nine columns using silica gel. The analysis results of this liquid are shown below □ 'H-NMR [δ, TM8 standard, CDα3 solution] 4.9
1(m, 1)L), 2.20(t, 2)1).

1.80-1.04 (m, 49H), 0.82 (m
, 18) 1) JR [KBr film] 17356R-1 From the analysis results in F, this liquid is Behenil 1.5-
It was confirmed to be dimethyl-2-isopentylhexyl. The yield was 55t4.

Example 4 The same operation as in Example 1 was carried out using 95.2 F (0,337 mol) of oleic acid instead of myristic acid, and a colorless and transparent liquid of 89.9 F was obtained by column chromatography purification using silica gel. The analysis results of this liquid are shown below.

'H, -NMR [: δ, TMS standard, CDC18 solution] 5.30 (m, 2H), 4.91 (rn, IH).

2.24 (t, zH), 1.97 (m, nH).

1678-1. (15 (m, 43 H), 0-81
(m + 18 H) ■RCKBr film] 1735m-1 From the analysis results described in E, it was confirmed that this liquid was 1.5-dimethyl-2-isopentylhexyl oleate. The yield was 57 mm.

Example 5 Myristic acid K instead of fogging in Example 1: 1rl
If using t 58.1 f (0,337 mol)
Except for this, the same operation as u'JNI Example 1 was carried out, and a colorless and transparent liquid 710 was purified by nine column chromatography using silica gel.
I got f. The analysis results of this liquid are shown below.

'H-NMR [δ, TMS standard, CDα3 solution] 4.9
z (mt IH), 2.20 (t, 2H)
.

1.80-1.05 (m, 25 H) to, s
2 (mt 18 H) IR [KBr film] 1735 (:Ill”) According to the analysis results of Uemachi, this liquid was
It was confirmed to be dimethyl-2-isopentylhexyl. The yield tli was 72%.

Example 6 Lauric acid 67 instead of myristic acid in Example 1
．． The same operation as in Example 1 was carried out except that 7f (0,337 mol) was used, and a colorless and transparent liquid 76.32 was obtained by nine column chromatographic purification using silica gel. The analysis results of this liquid are shown below.

'H-NMRCJ, TMS standard, CDα3 solution] 4.9
2(m, IJ, 2.19(t, 2H).

1.80-1.04 (m, 29H), 0.82 (rn,
18H) IR [KBr; yIlmuco 1735tM' From the analysis results in section h, it was confirmed that this liquid was 1,5-dimethyl-2-isopentyl laurate. The yield was 709I.

Example 7 Palmitic acid 8 was used instead of myristic acid in Actual Example 1.
The same procedure as in Example 1 was carried out except that 6.4 F (0,337 mol) was used, and 88.2 F, a colorless and transparent liquid, was obtained by column chromatographic purification using silica gel. The analysis results of this liquid are shown below.

') i-NMR [δ, TM8 standard, CDα3 solution] 4.
91 (m, 1) (), 2.21 (tt2H) 11.80
-1.05 (m, 37H), 0.83 (m, 1
8H) IR [KBr) (Rum:] 1735ml From the analysis results of t-1kj, this liquid is palmitic acid 1
．． It was determined to be 5-dimethyl-2-isopentylhexyl. The yield was 69 cm.

Example 8 (Example of formulation in cream) (Nutritional cream) (
Stearic acid 3.00 (Setanol 1.5011) 2.5
04 (Self-emulsifying type) Stearyl alcohol 1,50 dehydrated lanolin 2.001G liquid paraffin 15.004 Triethanolamine 1.00 Propylene glycol 60〇-Purified water 611O Tatami preservative (rose oxybenzoic acid ester) 0.10 Fragrance 0.30 Among the ingredients, the oil and fat components were mixed and dissolved at 75 to 80°C. Separately, dissolve and heat the aqueous ingredients excluding fragrance.7
It was set as the aqueous phase of 5-80 degreeC. The oil phase was added to the aqueous solution while stirring to emulsify it, and the fragrance was added at a temperature of 60 to 65° C., and the mixture was cooled to room temperature to prepare a product.

This product had a significantly better feel when applied to the skin than a cream with the same composition as above except that 1,5-dimethyl-2-isopentylhexanol ester was not blended.

Example 9 (Formulation into cream) (Nutritional cream) (Weight 9!i) Stearic acid 3.001 Cetano 150 Glycerin monostearate (self-emulsifying fl) 2.5
01 Stearyl alcohol 1.50 Dehydrated lanolin 200-Liquid paraffin 10.001!1 Squalane 5.001 Triethanolamine 1.00 Propylene glycol 6.00 YI'fI water
61.10 Preservative (paraoxybenzoic acid ester) 0.10 Flavor 0304 1. The ingredients were combined in the same manner as in Example 8 to obtain a product. This product had a good feeling when applied to the skin.

Example 10 (Example of blending into emulsion) (Nutritional emulsion) (weight 11 l
-11) Stearic acid 2.801 Cethanol 170L4 dehydrated lanolin 0504 Sorbitan monolaure) 1.20% Squalane
200% propylene glycol
250 Glycerin
2.501 triethanolamine
+, (01 Preservative (rose oxybenzoate ester) 0.10'11 Purified water
82.80 Shizuku fragrance 020
Regrettably, the ingredients were blended in the same manner as in Example 8 to produce a product, L.
: I, ta. This product had good filling when applied to the skin.

1 set 1,5-dimethyl-2-palmitate instead of 1,5-dimethyl-2-isopentylhexyl colistate
Isopentylhexyl, 1,5-dimethyl-2-isopentylhexyl stearate, 1,5-dimethyl-2-isopentylhexyl laurate or 1,5 behenic acid
An emulsion containing -dimethyl-2-isopentylhexyl was similarly applied to the skin and had a good feel when applied.

Patent applicant: Rishi Co., Ltd. Representative Patent Attorney Tate Honda

Claims (1)

[Scope of Claims] 1. A compound represented by the general formula (1) % formula % (wherein R represents a saturated or unsaturated aliphatic hydrocarbon group having 9 to 21 carbon atoms). 2. The compound according to claim 1, wherein R in the general formula (1) is a saturated aliphatic hydrocarbon group □ having 9 to 21 carbon atoms. 3. Contains a compound represented by the general formula (1) % formula % (3 (wherein R represents a saturated or unsaturated aliphatic hydrocarbon group having 9 to 21 carbon atoms) 4. The cosmetic composition according to claim 3, which contains a compound of general formula (1) in which R in K is a saturated aliphatic hydrocarbon group having 9 to 21 carbon atoms.