JPS5927844A - D-mannitol alkyl ether and cosmetic containing the same - Google Patents

Abstract

NEW MATERIAL:The compound of formula I (R is 8-24C saturated or unsaturated straight or branched chain aliphatic hydrocarbon group). EXAMPLE:3-O-methyl branched-isostearyl-D-mannitol. USE:It has high chemical stability and surface active property, and low irritation to the skin, and is useful as an emulsifier, lubricant (emollient), self-emulsifiable lubricant, wetting agent, and thickener, and especially useful as a component of cosmetics. PROCESS:The compound of formula I can be prepared by (1) reacting D-mannitol of formula II with acetone to obtain 1,2,5,6-di-O-isopropylidene-D-mannitol having four protected OH groups and two free OH groups at 3 and 4 positions, (2) etherifying the compound of formula III in the presence of a phase-transfer catalyst (e.g. quaternary onium salt), (3) distilling the resultant reaction product to separate monoalkyl ether from dialkyl ether, and (4) removing the protecting groups from the product.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a novel chemically stable alkyl ether and a cosmetic containing the same.

In the oil and fat chemical industry, polyhydric alcohols such as glycerin, diglycerin, sorbitol, mannitol, and sugars are widely used as one of the important groups of highly hydrophilic raw materials. In addition, these polyhydric alcohol esters and ethers are widely distributed in the natural world, and play an important role in the life activities of living things, as well as in many other applications such as detergents, foods, industrial chemicals, and pharmaceuticals. As an industrial product, it greatly contributes to human daily life.

Conventionally, attempts have been made in various fields to synthesize and apply nonionic surfactants by subjecting polyhydric alcohols to esterification reactions or etherification reactions (however, in this case, alkylene oxide type ether compounds are used in most cases). It's here.

For example, regarding the application of polyhydric alcohol esters to emulsifiers or cosmetics, JP-A-56-32407 and JP-A-56-32407;
Examples can be found in No. 6-32408 and No. 56-38127. Also, emulsifiers or cosmetics for polyhydric alcohol ether esters obtained by adding alkylene oxide to polyhydric alcohol and then performing partial esterification to obtain the desired HLB value (balance between lipophilic groups and hydrophilic groups). Examples of applications to materials include U.S. Pat. No. 395,465.8, U.S. Pat. Furthermore, as an application example as a lubricating oil additive or a metal cutting oil additive, JP-A No. 52-78661,
Also included are No. 52-96951 and No. 56-63935.

In addition, among these polyhydric alcohol salt conductors, sorbitan fatty acid ester derived from sorbitol, a linear monosaccharide, is used as a base material for cosmetics, including industrial chemicals, due to its characteristic emulsifying properties and safety. Canchichi is used in a wide range of fields such as food additives and pharmaceutical bases.

However, with conventional techniques, it is difficult to selectively react only specific hydroxyl groups in polyhydric alcohols, and all hydroxyl groups in polyhydric alcohols competitively participate in chemical reactions, resulting in complex products. Often obtained as a mixture. Therefore, there is a strong possibility that the advantages and disadvantages of each of the six products will be canceled out, and that the very distinctive and valuable properties of one product with a specific structure will be significantly impaired.

The present inventors focused on D-mannitol and conducted intensive research to obtain a new and useful polyhydric alcohol derivative using it as a raw material. As a result, the hydroxyl group of D-mannitol was partially protected with a protecting group, When an etherifying agent is applied to this, a derivative of D-mannitol in which the 6-position or the 6- and 4-position hydroxyl groups are selectively etherified can be obtained, and the derivative is useful as a cosmetic base. They discovered this and completed the present invention.

That is, the present invention provides the following formula (1), OR' OH0H CH2-aH-cH-aH-aH-aH2(1)l
D-mannitol alkyl represented by 11 OHOHOR (wherein, R represents a saturated or unsaturated linear or branched aliphatic hydrocarbon group having 8 to 24 carbon atoms, and R' represents a water-earth atom or R) The present invention provides an ether and a cosmetic containing the same.

The D-mannitol alkyl ether (1) of the present invention is
Preferably, □4 is produced by the reaction shown in the following formula.

Below is a blank space (in the formula, R has the above-mentioned meaning, and X represents a halodane atom, etc.) That is, first, in order to introduce a retention group into D-mannitol (If), four groups were added using acetone according to a known method. 1 with two free hydroxyl groups at the 6 and 4 positions by protecting the hydroxyl group
, 2, 5. (S-di0-isozolobylidene-D-mannitol (Ir[) (hereinafter abbreviated as D-mannitol diacetonide or diacetonide) is obtained. At this time, in addition to diacetonide (1), triacetonide (IV) (1,
2, 3, 4, 5, 6-) 17-0-'f soderopylidene-D-mannitol) is also produced, but since triacetonide (IV) does not contain any free hydroxyl groups, it does not participate at all in the substitution reaction in the next step. It remains in the reaction system as it is. Therefore, since triacetonide (IV) can be recovered by distillation etc., triacetonide (IV) can be recovered from the reaction product.
is recovered, the protective group is removed by hydrolysis, etc., and it is used again as the raw material D-mannitol.

Next, the obtained D-mannitol diacetonide (1) is etherified by a known method. An industrially advantageous method includes etherification in an alkaline aqueous solution using a phase transfer catalyst typified by a quaternary onium salt. In this method, etherification proceeds under mild conditions,
The desired mixture of D-mannitol monoalkyl ether diacetonide (Va) and D-mannitol dialkyl ether diacetonide (Vb) is obtained. The compounds (Va) and (Vb) are then separated by distillation using the difference in boiling points.

Furthermore, if the separated D-mannitol monoalkyl ether diacetonide (Va) and D-mannitol monoalkyl ether diacetonide (Vb) are hydrolyzed with mineral acid to remove the protecting groups, the final product is obtained. Certain D-mannitol monoalkyl ethers (Ia) and D-maynitol dialkyl ethers (Ib) are obtained.

More detailed reaction conditions for the above reaction are as follows.

The etherification reaction of D-mannitol diacetonide (II) is preferably carried out in the presence of an alkaline substance. Examples of alkaline substances include alkali metal hydroxides, alkali metal carbonates, alkali metal phosphate groups, etc. Among these, alkali metal hydroxides such as sodium hydroxide and potassium hydroxide are particularly used industrially. suitable. The appropriate amount of the alkaline substance used is 1 to 10 mol per 1 mol of D-mannitol diacetonide (III), and the alkaline substance is preferably 10 to 80%, more preferably,
It is preferable to use an aqueous solution of 40 to 60 g.

As the etherification agent, alkyl halide R, alkyl sulfonate 8 sprue, sulfuric acid alkyl ester, etc. are used. Among these, suitable etherification agents include alkyl halides, and preferably alkyl zolomy V,
Alkyl iodite is good. These etherifying agents include those having a saturated or unsaturated, linear or branched aliphatic hydrocarbon group having 8 to 24 carbon atoms, preferably 8 to 20 carbon atoms.

The alkyl group of the etherification agent includes octyl, decyl, lauryl, cetyl, and linear aliphatic hydrocarbon groups.
Examples of branched aliphatic hydrocarbon groups are 2-ethylhexyl, 2-hebutylundecyl, 5,7.7-dolimethyl-2-(1,3,3-
trimethylp-tyl) octyl, and the following formula % formula %) (where m is an integer of 4 to 10, n is 5 to 11
represents an integer of , m+n represents 11 to 17, and m
= 7, n = 8 as the apex). The appropriate amount of the etherifying agent to be used is 2 to 10 moles, preferably 2 to 4 moles, per mole of D-mannitol diacetoni P.

The etherification reaction of D-mannitol diacetonide (■) is preferably carried out in the presence of a catalytic amount of a quaternary onium salt. Ammonium salts are preferred because of their ease of use. Specific examples of quaternary ammonium salts include:
Tetraalkylammonium salts (e.g., tetrabutylammonium chloride, tetrazotylammonium sulfate aqueous salt, trioctylmethylammonium chloride, lauryltrimethylammonium chloride, stearyltrimethylammonium chloride, benzyltrimethylammonium chloride, etc.), or polyoxyalkylene-based salts Examples include a group of alkyl ammonium salts (for example, tetraoxyethylene stearyl dimethyl ammonium chloride, bistetraoxyethylene stearyl methyl ammonium chloride, etc.), betaine compounds, crown ethers, amine oxide compounds, ion exchange resins, and the like. These quaternary onium salts are D-mannitol diacetonide (■
) 0.01 to 0.20 mole per mole, especially 0.01 to 0.20 mole per mole.
05 to 0.10 mol is good.

Further, as the reaction solvent, any solvent that does not adversely affect the reaction can be used. Among these, aliphatic hydrocarbons such as hexane, heptane and octane, alicyclic hydrocarbons such as cyclopentane and cyclohexane, and aromatic hydrocarbons such as benzene, toluene and xylene are particularly preferred.

Additionally, ether compounds such as diethyl ether, THF, diglyme, and dioxane can also be used.

The reaction temperature for etherification is 25 to 80°C, preferably 40°C.
~60°C, and etherification is completed in several hours with vigorous stirring.

The reaction product is treated in a conventional manner and then distilled under reduced pressure to separate D-mannitol monoalkyl ether diacetonide (vlL) and D-mannitol dialkyl ether diacetonide (Vb), thus separating. The hydrolysis of compounds (Va) and (Vb) can be carried out by any known method, but hydrolysis in water using a protonic acid catalyst such as sulfuric acid, hydrochloric acid, nitric acid, phosphoric acid, benzenesulfonic acid, or acetic acid, It is best to heat it up. The amount of acid catalyst used is not particularly limited, but is 0.5 to 6
．． 0 normality is sufficient, and 0.5 to 2.0 normality is particularly suitable. Water includes water-soluble organic solvents, such as lower alcohols such as methanol, ethanol, and isopropanol,
THF, dioxane, etc. can be added, and the reaction temperature is preferably 50 to 100°C.

If the hydrolysis reaction is carried out under such conditions, D-mannitol monoalkyl ether cyacetoni)' (Va) can be almost quantitatively converted to the final target product, D-mannitol monoalkyl ether (Ia), D-mannitol dialkyl. From ether diacetonide (Vb), D-mannitol alkyl ether was obtained in a more or less quantitative manner.The properties of a representative compound of D-mannitol alkyl ether (I) are as follows. Among the ethers in rll total margin 1), D-mannitol monoalkyl ether (1a) has ambiguous emulsifying power and hygroscopicity when R in the formula has 8 to 12 carbon atoms, and is used as a moisturizing agent for cosmetics. It is particularly useful as a In addition, as the number of carbon atoms in R increases, its properties as an oil become stronger, and when R has 12 to 18 carbon atoms, when used as an oil component in cosmetics, it blends into the skin as an emollient agent that also has hydrophilic properties. It is useful because it improves.

4, D-mannitol monoalkyl ether (lb)
has strong emulsifying power and is particularly useful as an emulsifier for cosmetics, and also has strong properties as an oil agent, so it is also useful as an oil component for cosmetics.

The amount of D-mannitol alkyl ether (I) blended into cosmetics varies depending on the application and various factors, but generally, when used as an emulsifier, it is about 0.2 to 15 N.C.
% is suitably about 5 to 50 times higher when used as an oil agent.

As shown in E, the D-mannitol alkyl ether (I) of the present invention is chemically stable because it does not have easily decomposable bonds such as ester groups, and is less irritating to the skin.
Because it has surfactant ability, it is a useful compound as an emulsifier, an oil (emollient), a self-emulsifying oil, a wetting agent, and a thickener, and can be particularly advantageously used as a cosmetic ingredient.

The present invention will be explained in more detail below using reference examples and examples, but the present invention is not limited to these examples.

Reference Example 1 Synthesis of monomethyl branched stearyl alcohol: In a 201 autoclave, isostearate isopropyl ester (Bmery 2310 isostearate isopropyl ester, commercially available from Emery, USA) 4770.9 and a copper chromium catalyst (8
Prepare 239.9 (volatilized). Next, 150 kg/c
Fill with hydrogen gas at a pressure of IrL2, and then heat the reaction mixture to 275°C.

After hydrogenation at 150 kg/cm"/275°C for about 7 hours, the reaction product was cooled and the catalyst residue was removed by filtration to obtain a crude product of 3500.!i'. By distillation T, colorless and transparent instearyl alcohol DOy was obtained as a fraction of 80 to 167°O10.6.The obtained isostearyl alcohol (monomethyl branched instearyl alcohol) was It showed a value of 0.05, a saponification value of 5.5, and a hydroxyl value of 181.4.In IR (liquid film), it was 6640.1055α-1.
In NMR (0014 solvent), δ3.50 (
Absorption was shown in the broad triplet line (-0f-OH). The main component of this alcohol, the gas chromatograph, shows that about 75% of the alkyl groups have a total carbon number of 18, and the remaining components have a total of 14.16 carbon atoms, and the branched methyl groups are was also found to be a mixture of those located near the center of the alkyl main chain.

Reference Example 2 Synthesis of methyl branched isostearyl bromide: Temperature poor 1
, a reflux condenser, and a stirrer.
Methyl branched isostearyl alcohol 816 obtained in
g (6 mol), 47 thihydrobromide aqueous solution 1062 g (
6,1 mol), and trimethylstearylammonium chloride 50.1 &(0,'15 mol)
100~120℃ in a mantle heater while stirring.
Heat to ℃.

After stirring at this temperature for about 6 hours, it was observed in the gas chromatograph of the reaction mixture that the peak of methyl branched isostearyl alcohol had disappeared. The reaction product is
After cooling, the organic layer is collected by liquid separation. Add ether (1,51) to the lower layer (aqueous layer) and perform ether extraction. Collect the ether layer by liquid separation. The organic layers obtained earlier are combined and an aqueous sodium bicarbonate solution is added to neutralize the remaining acid. An ether layer was collected by liquid separation, and after drying with the addition of Glauber's salt, the ether was distilled off under reduced pressure, and then distilled under reduced pressure to obtain 800 g of methyl branched instearyl bromide. Yield 80% Boiling point 145-169
℃(0,'rynmHg) Engineering R(liquid film, crn')
1200-1300.720.640.56O N)ilR (C0I4, δ, TH9 internal standard)6. RoO
(Triple line, "~7, LI H2,0H2Er) Elemental analysis C] As 8H37Br (calculated value) C! 6
Section 4.7 (section 64, 85); Section H11, 2 (section 11,
1991 = ): Br 24.4% (23,97%
) Average molecule ff1 (vpo method/HOO13) 527
(Calculated value 666) Reference Example 6 Synthesis of D-mannitol diacetonide: 875 ME of dimethoxyethane, 520 g of acetone dimethyl ketal (
5 mol) and 0.44.9% of stannous chloride dihydrate were added and stirred. Next, D-mannitol 36151 (2
Mol) Add one small amount. After adding D-mannitol, the reaction mixture is heated to reflux at 0'C.

After refluxing for about 60 minutes, the reaction product is cooled and neutralized by adding triethylamine 1y. The reaction product was dissolved in dibutyl ether 1100mA and recrystallized,
Obtain 1,2,5,6-di-0-isoprohyritene-D-mannitol 238&, which is a white crystal. Yield: 44% Melting point: 118°C (literature value: 117-119°C) Blue:
Carbohydrate Research,
84.650'352 (1980) Example 1 6-0-Methyl branched isostearyl-D-mannitol and 6,4-diO-methyl branched instearyl-D-
Synthesis of mannitol: (1) In a 51 reaction vessel equipped with a reflux condenser, a thermometer, a dropping funnel, and a stirrer, 197% of D-mannitol diacetonide obtained in Reference Example 6 was added. ,! i' (0,75 mol).

50 sodium hydroxide aqueous solution filtration Q Q jJ (Na
150FC3.75 mol as OH), hexane 21
and tetra-n-butylammonium hydrogen sulfate 25.5
,! 0.075 mol) and stir vigorously. Then, from a dropping funnel, 500 g (1.5 mol) of the methyl branched isostearyl bromide obtained in Reference Example 2 was added.
Drip little by little. During this time, the temperature of the reaction mixture was 25
Keep at ℃. After the dropwise addition of isostearylderomide is finished, heat the reaction mixture to 6o-65"C [1].
Continue stirring at M degree for about 6 hours. When it was confirmed by chromatography that the instearyl bromide in the reaction mixture had completely disappeared, the reaction product was cooled, and then water 11 was added thereto and stirred. Hexane J~ is collected by liquid separation, dried by this method, and then the hexane is distilled off under reduced pressure. Further, by distillation under reduced pressure, 260 g (0,50
mole) f? f (yield: 67).

In addition, 165 g (0,215 mol) of 5,4-di-methyl-branched instearyl-D-mannitol diacetonide as a colorless and odorless liquid was obtained as a distillation residue for 7 hours (yield 2B).
, Z section).

[Rho-0-methyl branched isostearyl-D --q 7
Nitole diacetonide] Boiling point 265-265°C (0.4 Hg) IR (liquid film, C1n”) 3470.1675.1565.1250
, 1207.115o, 1000-1160, 845 NMR (0014, δ, TMS internal standard) 6.20-4
．． 20 (Multiplet, 11J (0000H2R × - Elemental analysis "30H5806 (total a-value) 20
70.9% (70,00chi); H ll, 9 section (11,36 section”l; 017.7% (18,
65chi) Average molecule f (VPO method 7Hco1.') 509
(Calculated value 515) Hydroxyl value 100 (Calculated value 109) [6,4-di-0-methyl branched isostearyl-D-mannitol diacetonide] Engineering R (liquid film, Crl1-Re 1680.1670.124
7.1210.1160.1140 ~1000.855 NMR (0014, δ, TMS internal standard) elemental analysis
As 04EIH940fl (calculated value) C75°5%
(75, 14 section); HI3.3% CI 2.35%); 012.5% (12,51%) Average molecular weight (VPO method/HeC13) 750 (calculated value 767) Hydroxyl value 1.0 (calculated value 0.0) (11) 154 g of 6-0-methyl branched instearyl-D-mannitol diacetonide obtained in (1) of Example 1 was placed in a 61 reaction vessel equipped with a reflux condenser, a thermometer, and a stirrer.
(0.3 mol), 6Q Q ml of methanol, and QQ ml of tap water. To this, 98% concentrated sulfuric acid 1
5.5,! 9 and reflux at 75-88°C. After heating under reflux for about 6 hours, it was confirmed from the IR spectrum and gas chromatography of the reaction mixture that diacetonide completely disappeared and hydrolysis was completed.

After the reaction product is cooled, the acid content is neutralized with an aqueous sodium hydroxide solution, and then ether (1,21) is added, stirred, and subjected to liquid separation. After collecting the ether layer, the ether was distilled off under reduced pressure and then heated and dried at 100°C/6 Hg for about 6 hours to obtain 125 g of 6-O-methyl branched stearyl-D-mannitol as a colorless and transparent semi-solid. (0,2
9 mol) was obtained. Yield 96% Melting point 65-38°C IR (IR membrane, CIIL) 3400.1ooo-1
16°NMR (0014, δ, TMS internal standard) 0GH
OH OH0HOOH2R" Elemental analysis 024H5006 (calculated value) 066.7 section (
Hl 2.1% (11,6096); 021.3 (22,08) Average molecular weight (VPO method/Hcct3) 425 (calculated value 435) Hydroxyl value 650 (calculated value 645) ( 149 g of 3,4-di-0-methyl branched instearyl-D-mannitol cyacetoni) obtained in (1)
0,194 mol) 'Y+I11 When treated in the same manner as 6.4-di-0-methyl branched instea, it becomes a colorless transparent liquid! J
Lou D-Mann Thor 130g (0,189 mol) I
R (liquid film, crIl") 3400.1000~116O
NMR (0014, δ, TMEI internal standard) elemental analysis
As 042H1l+606 (calculated value) 074.1% (
73, 41 Section); H12, 8 Chi (12, 68 Chi); 01
3.4 inches (13,97 inches) average molecular weight (VPO method/HO
O13) 661 (calculated value 687) Hydroxyl value 615 (calculated value 627) Example 2 Synthesis of 6-O-oleyl-D-mannitol and 6°4-di0-oleyl-D-mannitol: (1) Example 1 131.2 g of D-mannitol diacetonide obtained in Reference Example 6 (0,
5%), 50% NaOH aqueous solution 400,! i' (
200.9 (5 moles) as NaOH, 1.
51. #Tetrabutylammonium hydrogen chloride 17.9
(0.05 mol) 7ml, stir vigorously.

Then add oleyl bromide 331.4 &
(1.0 mol) was added dropwise little by little. During this time, the temperature of the reaction mixture is maintained at 25°C. After dropping oleyl bromide, mix the reaction! II! Heat to 160-65℃ for about 1
Stir for 0 hours.

It was confirmed by chromatography that oleyl bromide had almost disappeared from the reaction mixture. The reaction product was treated in the same manner as +11 of Example 1, and the fraction was distilled under reduced pressure to obtain 3-o-oleyl-D-mannitol diacetonide 140I as a colorless transparent oil (yield 55 cm), and the distillation residue was colorless. Clear oily 6゜4-di-O-oleyl-D-mannitol diacetonide 167,! i/(yield 44%) was obtained.

[Ro-0-oleyl-D-mannitol diacetonide] Boiling point 256-276°O (0,6 Hg) IR (liquid film, m-1) 3470, Ro000.138o, 1370.
1255.1207. 1155, 1000-1140, 5O NMR (C(!14, δ, TMS internal standard) 0.88
(6 lanes, 6H, oleyl terminal methyl) methylene flotons + 1.7 to 2.6 (pro F multiplet, oleyl terminal methyl).

-C0H=CHOH! -・, 4) To 1)? 5.3 (Triplet, cis-oleyl, 2H) elemental analysis 0
As 30H5606 (calculated value) 071.4% (71,
11th); H10, 6 section (9,95%); o 18
．． 5% (18,94%) molecule-11 (VPO method/HC (
E13) 506 (calculated value 507) Hydroxyl value 10
7 (calculated value 110.7) Iodine 160.2 (calculated value 50.1) [6,4-di-0-oleyl-D-mannitol diacetone] Engineering R (liquid film, a-1) filter 000. 1ro85.1375.
1260.1220.1170. 1000-1140.86O NMR (δ, 001., TMS internal standard) 0.87 (
Triplet line, terminal methyl of 6H12 oleyl groups) Elemental analysis 048H9006 (calculated value) 075.
8% (75,54%); H12,2% (11,89chi)
-,012,8 ti (12,58 ti) Molecular weight (VPO method/HC013) 752 (calculated value 766) Hydroxyl group value 6.0 (calculated value 0.0) Iodine value 68.5 (calculated value 66.5) ( :1) 6-0-oleyl-D-mannitol diacetonide 127,!i' (0 , 242 mol) methanol (300 ml) and tap water (300 ml) are mixed together. Add 98% concentrated sulfuric acid (15.5 &') to this and reflux at 75 - so'c. After heating under reflux for about 6 hours, the reaction mixture is mixed. From the IR spectrum, it was confirmed that the diacetonide peak completely disappeared, indicating that 0 water decomposition occurred.

The reaction product was treated in the same manner as in Example 1 (11) to obtain a viscous pale yellow oil, 6-0-oleyl-D-mannitol 106I. Yield 98.1% Melting point 40℃ Engineering R (liquid film, Cr/L') 3350.1000-115
0,9O NMR (QC!1., δ, TMS internal standard) 0.86
(Triple line, 6H, oleyl group terminal methyl) 1.1-1.8 (broad single line, methylene group of oleyl group, 24 a) 1.8-2.6 (broad multiplet line, oleyl group terminal methyl) 10
H20H=OHC! H2, -14H)3.2~5.6(
Broad multiplet, OHOHQC! H2-R 5,26 (3, i line, cis-olefin proton, 2
H) Elemental analysis C24H4806' (calculated value) 066.9%
(66, 63 section); Hll, 8% (11, 18%); 0
22.0 coefficient (22,19 coefficient) molecular weight (VPO method/HO
OI3) 435 (calculated value 466) Hydroxyl value 640
(Calculated value 649) Iodine value 64.7 (Calculated value 58.7) (lit)
(l 6,4-di-0-oleyl-D obtained in l
-Mannitol diacetonide 154 F (0,201
mol) was treated in the same manner as in (11) to obtain 6,4-di-0-oleyl-D-mannitol 1 as a viscous pale yellow oil.
65g was obtained. Yield 98.5 Thie R (liquid film, σ-1) 3400.1000-115ON
MR (δ, CCl4, TMS internal standard) 0.84 (triplet, 6H terminal methyl of 12 oleyl groups) 1.1-1.8 (broad single line, methylene group of 2 oleyl groups, 48H) 1.8-2.3 (broad multiplet, -C0H=OHCH8!-18H of two oleyl groups) 5.2-4.4 (
Multiplet, 0dan 0dan oadan 2. R" 5.27 (triplet, cis-olefin protons of two oleyl groups, 4H) Elemental analysis 042H5206 (calculated value) 074.
Section 2 (73,85%); n12.4qIj (12,10
014.1 (14,05) molecular weight (VPO
Method/HOO13) 653 (calculated value 645) Hydroxyl value 6'5B (calculated value 628.6) Iodine value 711.
6 (calculated value 74.3) Example 6 Synthesis of 3-〇-lauryl-D-mannitol and 6゜4-dirolauryl-D-mannitol: (1) Example 1
D-mannitol diacetonide 161 & (0,5
mol), 200 g of 50% NaOH aqueous solution (100 g (2.5 mol) as Na1), 11 hexane, 1.7/i/i of tetra-n-butylammonium hydrogen sulfate (
0.05 mol) Add heat and stir vigorously. Then,
Lauryl bromide 49El (2 mol) from the dropping funnel
Drip little by little. During this time, the temperature of the reaction mixture was increased to 25°C.
Keep at ℃. After the addition of lauryl bromide is complete, the reaction mixture is heated to 60-65°C and stirred for about 6 hours. After confirming that the D-mannitol diacetonide peak had completely disappeared in the gas chromatograph of the reaction mixture, the reaction product was cooled, water (1,51) was added, vigorously stirred, and further subjected to liquid separation. . After collecting the hexane layer,
After drying with Glauber's salt, hexane was distilled off under reduced pressure.
Then, by distillation under reduced pressure, 80 g of 3-〇-lauryl-D-mannitol diacetonide (
0,186 mol) (yield: 67 mm), and from the distillation residue, 58 g (0,097 mol) of 3.4-di-O-lauryl-D-mannitolzoacetonide was obtained as a colorless transparent liquid (yield: 20chi).

[Ro-0-lauryl-D-mannitol diacetonide] Boiling point 202-210'C (0,65+++mHg)
IR (liquid film, Crn”) 3475.1685.1 filter 70
．． 1255.1220.1160. 1050-1140.850, NMR (cc14, δ, TMEI internal standard) 0.85
(Triple line, 5H, Osu(OH2)10) 1.0~1
．． 4 (broad straight line, 20H1OH3 (C!H2)
1°-) Elemental analysis C24H4606 (calculated value) c 67.0
% (66,94%); Hll, 0 section (10,77%)
;021.9 ratio (22,29%) molecular weight (vpo method/H
OO13) 424 (Total n value 431) Hydroxyl value 125
(Calculated value 1 RO O) [3,4-di-O-lauryl-D-mannitol diacetonide] Boiling point 245-260 "CC0,55 Dragon Hg) Engineering R (
Liquid film, Bo-1) 1385.1670.1255.122
0.1165.1000~1140.86O NMR (001,, δ, TM8 internal standard) 0.87 (
Triple line, 6H52XOH30H2-)1.0~1.4(
Broad-heavy line, 40H12×CH3 (C). -) Elemental analysis 036H7006 (calculated value) 072.
0% (72nd, 19th section); H11, 8th (11th, 78th section)
;016.5ti (16,03ti) molecular weight (vpo method 10
o13H) 590 (calculated value 599) Hydroxyl value 2.5 (
Total 1! -fiiO,o) (11) Into 11 reaction vessels equipped with the apparatus of Example 1 (11), 10-lauryl-D-mannitol-diacetonide 1
Stir 28 g (0,298 mol) methanol 200 ml and tap water 20011 (l).
Concentrated sulfuric acid 15.5,! Add i' and reflux at 75-80°C. After heating under reflux for about 6 hours, the diacetonide peak completely disappeared from the R spectrum and gas chromatograph of the reaction mixture, indicating that the hydrolysis was complete.

The reaction product was treated in the same manner as in Example 1 (11) to obtain 6-0-lauryl-D-mannitol 93, which is a white crystal.
I got g. Yield 89 Melting point 79.5-81℃ Engineering R (KBr, on') 3400.1000-11
8ONMR (cannot be measured due to insolubility in solvent) Elemental analysis 018H3806 (calculated value) Section 061.5 (
61,68%) ; H10,8% (10,98 section)'
1027.8 (27,39%) Hydroxyl value 780 (calculated value 800) (Ill) (+ 110 g (0,1
84 mol) was treated in the same manner as in (11) to obtain 93 g of 6,4-di-0-lauryl-p-mannitol as white crystals.

Yield: 97°C Melting point: 68-69.5°C Engineering R (KBr, crrr-') 3400.10
00~117ONMR (0CI4, δ, TMS internal standard) 0.87 (triple line, 6H12X0H3(OH,)1
゜-) 1.6 (broad-double line, 40) 1.2 XGH
a(OHz),. -) Elemental analysis As C30H6206 (calculated value) 069.0% (69,45chi): H12,
Section 1 (12,05%): 018.8% (18,50
%) Molecular weight (vpo method/HOO13) 514 (calculated value 516) Hydroxyl value 400 (calculated value 466) Example 4 3-6-octyl-D-mannitol and 6゜4-di-0-octyl-D-mannitol Synthesis: (1) D-mannitol diacetonide 157 obtained in Reference Example 6 was placed in 31 reaction vessels equipped with the apparatus (1) of Example 1. l'
(0.6 mol), 50% aqueous sodium hydroxide solution 480
,! l' (Na, 240i6.0 mol as OR)
), Hexa/11! , 20.4 & (0.06 mol) of tetra-n-butylammonium hydrogen sulfate and stir vigorously. Then, octylde-Umite 46 filter 9 (2.4 mol) was added dropwise through the dropping funnel. After adding the octyl bromide dropwise, the reaction mixture is heated to 60-65°C and stirred for about 6 hours. A gas chromatograph of the reaction mixture revealed that D-mannitol diacetonide had completely disappeared. The reaction product was treated in a conventional manner. 113. 6-0-Octyl-D-mannitol diacetonide was obtained as a colorless transparent liquid from the distillate under reduced pressure. @(0
, 30 mol) (yield 50%), and from the distillation residue 6,
4-O-octyl-D-mannitol diacetonide 1059 (0.22 mol) ff: obtained (yield 67).

[6-0-octyl-D-mannitol cyacetoni V] Boiling point 175-175℃ (0.7mmHg, ) Engineering R (
liquid film, cml, ) 3475.1680.1370.12
55.1220.1155. 1110.1100-1000, 5O NMR (cal, δ, TMS internal standard) [ ], 85
(Triple line, 3H, 0H3(OH2)7) 1.0
~1,5 (broad singlet, 12H0H3 (OH2)
60H2) 1.3 (-lane, 12H54 infropylidene methyl) 064.2% (64,14%); H10,4CH (1
0.23%); 025.5% (25.63%) Molecular weight (
vpo method 10HOI3) 425 (calculated value 461)
Hydroxyl value 125 (calculated value 160) [6,4-di-0-octyl-D-mannitol diacetonide] Boiling point 199-201°C (0.6 degrees Hg) IR (liquid film, crrL') 1380.1570.1255 .122
0.1160,1140~1000.855 NMR (001,, δ, TMS internal standard) 0.85 (
Three is, 6H12 C! H3(C'H2)6C! H2
) 1.0 to 1.5 (broad single line, 24H12L
^1's 0H3 (C! Kaken 2) 60H2-) 1.33 (
-M line, 12H14 infropylidenemethyl) 6.20-4.30 (multiplet, 12H10000H2
R" × - Elemental analysis 028H5406 (calculated value) 06B,
4% (69,09%); Hll, 2chi (11,18chi)
;019.8 (19,72) molecular weight (vpo method/H
OO13”) 487 (calculated value 482) Hydroxyl value
1.1 (calculated value 0.0) (II) 6-o-octyl-D obtained in Example 4 (1) was placed in 11 reaction vessels equipped with the apparatus of Example 1 (11).
- Mannitol diacetonide 102.7 g (0,27
mol), methanol 200 ml. and tap water 2QQm
Stir around Ai. Add to this 98% concentrated sulfuric acid 11.3.9
and reflux at 75-80°C. Hydrolysis was completed in the same manner as in Example 1. Generate wJ in Example 1 (
11), white crystals of 6-0-octyl-D-mannitol 79I! I got it. Yield: 98% Melting point: 87.5-88.5°C IR (KBr, cm") 6400.1000-118
5NMR (cannot be measured due to insolubility in solvent) Elemental analysis 014H3006 (measurement value) 057.5 section (57, 12 section); H9.9% (10, 27 section);
062.3% (32,61%) Hydroxyl value 960 (calculated value 953) 1ii1 (l 111.7 g (0
, 23 mol) was treated in the same manner as in (11) to obtain 92 g of 6,4-di-0-octyl-D-mannitol as white crystals.
got '.

Yield 98% Melting point 84.5-85.5°C Engineering R (KBr-C1n-') 3400.1000-
1175NMR (cal, δ, TMS internal standard) 0.
88 (triple line, 6H12 0H3(OH2)60H
2) 1.0-1.6 (broad single line, 24I (,2
0H3(OH2)6cH2-) Elemental analysis 022H4606 (calculated value) 064.
6th section (64,99chi); H11,4% (11,40th section)
;024.0 ratio (23,61 ratio) molecular weight (VPO method 10
HO13) 420 (calculated value 427) Hydroxyl value 56
5 (calculated value 552) Example 5 Next, a hygroscopicity test was conducted on the YD-mannitol monoalkyl ether shown below to examine its ability as a wetting agent.

The moisture absorption test was carried out by storing 90 ml of test compounds that had been air-dried in advance at a constant humidity and temperature of 25° C., and examining the rate of weight increase. The results are shown in Table 2.

Table 2 Hygroscopicity = As is clear from the results in the above h1, among the D-mannitol monoalkyl ethers of the present invention, R has 8 to 8 carbon atoms.
No. 12 had particularly high hygroscopicity.

Example 6 An emulsification test was conducted on the following D-mannitol dialkyl ether of the present invention to examine its emulsifying power.

The emulsification test was conducted under the following conditions using liquid paraffin as the oil. Two parts of the test compound are mixed with 20 parts of liquid paraffin and heated to 75°C. Separately, add 78 parts of ion-exchanged water to 7
The mixture was heated to 5°C and added to liquid paraffin and the test compound under stirring to emulsify. After emulsification, cool to room temperature while stirring.

The emulsifying power plan is based on the state of the immediately produced emulsion and the 25°
This was done by observing the state of separation after storage at C for 7 days. The results are shown in Table 6.

As is clear from the above results, the compound of the present invention has excellent emulsifying power, and has superior emulsion stability to glycerol ester yanbitan esters, which are known substances that are said to have strong emulsifying power. Did.

male side 7 Cosmetic cream: A cosmetic cream was prepared with the following composition.

Composition] Manufacturing method] Mix component A and heat to 75°C. During this mixture,
Two portions of B, which have been mixed in advance and heated (70°C), are added under stirring to emulsify. Then, while stirring, cool to room temperature.
An emulsion was obtained. The obtained milk product was a WlO type cream, which had good emulsion stability, did not cause separation over a long period of time, and when applied to skin (JI), it blended well with the skin and had a good feeling of use.

Example 8 Cosmetic cream: A cosmetic cream was prepared with the following composition.

〔composition〕

Mix ingredients A and heat to 75°C. Component B, which had been mixed in advance and heated to 70° C., was added to this mixture while stirring and emulsified. Thereafter, the mixture was cooled to room temperature while stirring to obtain an emulsion. The obtained emulsion was a W2O type cream, had extremely good emulsion stability, did not cause separation over a long period of time, and when applied to the skin, it blended well with the skin and had a good feeling of use.

Example 9 eye shadow: The following composition was mixed to prepare an eye shadow.

〔composition〕

Carnauba wax 3 (Li amount%) Ceresin wax 10 Microcrystalline wax 5 Castor oil
36 squalane
606-0-oleyl-D-
Mannitol Ibititan filtrate
8 mica titanium
2 Ultramarine Blue 6 The obtained mixture was a soft, bluish-white solid that blended well with the skin as an eye shadow.

Example 10 Lip rouge: A lipstick was prepared with the following composition.

〔composition〕

Component A is heated to 85° C. and mixed uniformly. Component IcB is added thereto and thoroughly stirred to emulsify the mixture. Immediately thereafter, the mixture is poured into a molding machine and cooled.

The obtained emulsion was a slightly soft solid W10 emulsion with a milky white luster, and when molded into a rod shape, it had excellent properties as a lipstick.

Example 11 Lotion: A lotion was prepared by mixing the following composition.

〔composition〕

6-0-Rau') Lukoomannitol 3.0 (
1% by volume) Ethanol 1
5.0 Glycine 1.
0 Polyoxyethylene cetyl ether 1.5 Sodium pyrrolidone carboxylate 1.0 Fragrance 0.2 Purified water
The lotion containing the product of the present invention obtained in this way is
It had a non-sticky and moist feeling after use.

that's all Patent attorney Nobuo Komachi, ゛i

Claims (1)

[Claims] (11) The following formula (1) %Formula% (In the formula, R represents a saturated or unsaturated straight-chain or branched aliphatic hydrocarbon group having 8 to 24 carbon atoms, and R' represents a hydrogen atom or R) (2) The following formula (I) OR' OHOH 111 HOHOR (wherein, R is a saturated or unsaturated group having 8 to 24 carbon atoms) a straight-chain or branched aliphatic hydrocarbon group, and R' represents a hydrogen atom or R) A cosmetic containing a D-mannitol alkyl ether represented by: