CN100358911C - N-acetylglucosamine derivatives and use thereof - Google Patents
N-acetylglucosamine derivatives and use thereof Download PDFInfo
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Abstract
The present invention relates to An N-acetylglucosamine derivative represented by the following formula (1), and a hyaluronic acid production promoting agent containing the same and a skin external preparation containing the same: wherein R<1> is a hydrogen atom or an alkyl group having 2 to 18 carbon atoms; R<2>, R<3>, and R<4> are hydrogen atoms or acyl groups having 2 to 18 carbon atoms and may be all the same or different from others; the steric structure at position 1 may be alpha or beta ; provided that R<1>, R<2>, R<3>, and R<4> must not be all hydrogen atoms. <>It is intended to provide an easily available hyaluronic acid production promoting agent and a skin external preparation whereby the production of hyaluronic acid can be promoted in the skin and thus the skin can be maintained in a vital and moist state so that it is expected that the human skin can be prevented from age.
Description
Technical field
Short agent or the external composition for skin of generating of hyaluronic acid that the present invention relates to the N-acetyl-glucosamine derivative and contain this compound.Can provide a kind of by the present invention and can keep the tension force of skin or moist external composition for skin.
Background technology
Hyaluronic acid is the macromolecule polysaccharide with high moisture hold facility, (the wine well advances I, too youth, " hyaluronic acid metabolism and the wrinkle formation " of aboveground gentry even also get most of the attention as important extracellular matrix components in skin, " Fragrance Journal ", Fragrance Journal society, distribution on April 15th, 1998, the 26th volume, No. 4,49～58 pages).
Also have, known hyaluronic acid has the resistibility that keeps cell, the oilness that keeps skin and external force such as flexibility, relative mechanical damage, prevent multiple function (" BIOINDUSTRY " such as infectation of bacteria, CMC Co., Ltd., distribution on May 1st, 1991, the 8th volume, No. 5,66 (346)-68 (346) pages).
On the other hand, there is report to claim aging decline (the Ludger J.M.Meyer and Robert Stern that can cause the hyaluronic acid staining power between epidermic cell, " Age-Dependent Changes ofHyaluronan in Human Skin ", " The Journal of Investigative Dermatology ", The Society for Investigative Dermatology, INC., in April, 1994, Vol.102, No.4, the 385-389 page or leaf), and the hyaluronic acid of solar elastosis (solarelastosis) portion that is caused by uviolizing almost detects to come out the tall and erect husband of (Tsuji, " physiological ageing of skin: and the difference of photoaging ", " clinical Dermatology Department ", medical science academy, distribution on April 15th, 1997, increase number of the edition the 51st volume, No. 5, the 53-57 page or leaf), its result can cause xerosis cutis, tension force, elastic decline, and then be the increase of wrinkle.In order to improve this state, what taked is to have cooperated the method for hyaluronic makeup with the moisture retention of maintenance skin surface by coating in the past, but is difficult to see through skin as high molecular hyaluronic acid, so can't fundamentally improve.Therefore, need develop the material that fundamentally improves skin function by improving the hyaluronic synthesis capability that cell self had.
As the short material that generates of the hyaluronic acid in the epidermis, known have a vitamin A acid, and it just is present in the epidermis originally, is with the propagation of epidermic cell or breaks up relevant material.But, have skin irritation from vitamin A acid, therefore wish to find the short material that generates of the hyaluronic acid that can avoid this point.
On the other hand, there is report to be referred to as the hyaluronic N-acetyl-glucosamine that constitutes sugar when concentration is 5mmol/L, can promotes to cultivate the hyaluronic growing amount of epidermic cell, it is reached about 1.5 times, and this point and cell proliferation are irrelevant.(" fine chemical (fine chemical) ", CMC Co., Ltd., distribution on December 15 calendar year 2001, the 30th volume, No. 22,5-11 page or leaf).But N-acetyl-glucosamine in order to use in fields such as makeup or medicine more widely, finds lower concentration also can demonstrate the material of effect of sufficient even wish if the short effect that generates of the matter acid that will show transparency just needs high density.
Summary of the invention
Therefore, the objective of the invention is to, provide by promote hyaluronic generation can keep skin tension force or moist and improve wrinkle, effect is higher than the short agent and the external composition for skin of generating of hyaluronic acid of N-acetyl-glucosamine.
For this reason, the inventor etc. are in view of above-mentioned situation, concentrate on studies to solving in the past the method for problem, found that, utilize the specific compound of aftermentioned can be easy as can and promote the hyaluronic acid in epidermis and the corium to generate strongly, thereby finished the present invention.
That is, the present invention is for the N-acetyl-glucosamine derivative of following general formula (1) expression, with external composition for skin that to contain this N-acetyl-glucosamine derivative be feature, with the short generation of the hyaluronic acid agent that is effective constituent of this N-acetyl-glucosamine derivative.
General formula (1)
(wherein, R
1Be that hydrogen atom or carbonatoms are 2～18 alkyl.R
2, R
3And R
4Be that hydrogen atom or carbonatoms are 2～18 acyl group, can be identical all, also can there be different groups.In addition, 1 D structure can be any among α or the β.But, R
1, R
2, R
3, R
4Can not all be hydrogen atom).
In addition, preferably use following general formula (2) or (3) expression the N-acetyl-glucosamine derivative, generate agent with external composition for skin that to contain this N-acetyl-glucosamine derivative be feature, with this N-acetyl-glucosamine derivative hyaluronic acid that is effective constituent is short.
General formula (2)
(wherein, R
5Be that carbonatoms is 2～18 alkyl.R
6Be hydrogen atom or ethanoyl.In addition, 1 D structure can be any among α or the β).
General formula (3)
(wherein, R
7Be that hydrogen atom or carbonatoms are 2～18 alkyl.R
8Be that carbonatoms is 2～18 acyl group.In addition, 1 D structure can be any among α or the β).
As N-acetyl-glucosamine derivative, can specifically enumerate compound with following general formula (4)～(15) expression with above-mentioned general formula (1) or (2) or (3) expression.
General formula (4)
(1 D structure can be any among α or the β).
General formula (5)
(1 D structure can be any among α or the β).
General formula (6)
(1 D structure can be any among α or the β).
General formula (7)
(1 D structure can be any among α or the β).
General formula (8)
(1 D structure can be any among α or the β).
General formula (9)
(1 D structure can be any among α or the β).
General formula (10)
(1 D structure can be any among α or the β).
General formula (11)
(1 D structure can be any among α or the β).
General formula (12)
(1 D structure can be any among α or the β).
General formula (13)
(1 D structure can be any among α or the β).
General formula (14)
(1 D structure can be any among α or the β).
General formula (15)
(1 D structure can be any among α or the β).
Also have, the present invention relates to short agent, the external composition for skin of generating of a kind of hyaluronic acid, it is characterized in that, with the N-acetyl-glucosamine derivative of following general formula (16) expression as effective constituent.
General formula (16)
(wherein, R
9Be that carbonatoms is 2～16 acyl group.In addition, 1 D structure can be any among α or the β).
As N-acetyl-glucosamine derivative, can specifically enumerate compound with following general formula (17) expression with above-mentioned general formula (16) expression.
General formula (17)
(1 D structure can be any among α or the β).
Description of drawings
Fig. 1 is the short figure that generates the result of test (test example 1) of hyaluronic acid of the expression epidermic cell that adopted Production Example 1～3 and 6～8.
Fig. 2 is the short figure that generates the result of test (test example 1) of hyaluronic acid of the expression epidermic cell that adopted Production Example 4 and 5.
Fig. 3 is that Production Example 9～12,2-acetamido-1,3,4 have been adopted in expression, the short figure that generates the result of test (test example 2) of the hyaluronic acid of the epidermic cell of 6-four-O-ethanoyl-2-deoxidation-β-D-glycopyranoside [compound of general formula (17)].
Fig. 4 is the short figure that generates the result of test (test example 3) of hyaluronic acid of the expression dermal cell that adopted Production Example 1 and 6.
Embodiment
The N-acetyl-glucosamine derivative of Shi Yonging can be represented with following general formula (1) or general formula (16) in the present invention.
General formula (1)
(wherein, R
1Be that hydrogen atom or carbonatoms are 2～18 alkyl.R
2, R
3And R
4Be that hydrogen atom or carbonatoms are 2～18 acyl group, can be identical all, also can there be different groups.In addition, 1 D structure can be any among α or the β.But, R
1, R
2, R
3, R
4Can not all be hydrogen atom).
General formula (16)
(wherein, R
9Be that carbonatoms is 2～16 acyl group.In addition, 1 D structure can be any among α or the β).
Here, R
1Be that hydrogen atom or carbonatoms are 2～18 straight or branched alkyl, preferred carbonatoms is 4～16, most preferably 8～12, can be saturated, and also can be unsaturated.R
2, R
3And R
4Be that hydrogen atom or carbonatoms are 2～18 straight or branched acyl group, can be identical all, also can there be different groups, but preferably all be hydrogen atom or ethanoyl.In addition, 1 of pyranose ring D structure can be any among α or the β.But, R
1, R
2, R
3, R
4Can not all be hydrogen atom.
As the N-acetyl-glucosamine derivative of representing with general formula 1, preferably use the compound of following general formula (2) or (3) expression.
General formula (2)
(wherein, R
5Be that carbonatoms is 2～18 alkyl.R
6Be hydrogen atom or ethanoyl.In addition, 1 D structure can be any among α or the β).
General formula (3)
(wherein, R
7Be that hydrogen atom or carbonatoms are 2～18 alkyl.R
8Be that carbonatoms is 2～18 acyl group.In addition, 1 D structure can be any among α or the β).
Here, R
5Be that carbonatoms is 2～18 straight or branched alkyl, preferred carbonatoms is 4～16, most preferably 8～12.R
6Being hydrogen atom or ethanoyl, preferably all is hydrogen atom or ethanoyl.R
7Be that hydrogen atom or carbonatoms are 2～18 straight or branched alkyl, preferred carbonatoms is 4～16, most preferably 8～12, can be saturated, and also can be unsaturated.R
8Be that carbonatoms is 2～18 straight or branched acyl group, preferred carbonatoms is 6～16, most preferably 8～12, can be saturated, and also can be unsaturated.R
9Be that carbonatoms is 2～16 straight or branched acyl group, preferred carbonatoms is 2～8, most preferably 2～4.
In addition, in general formula (1)～(17), 1 D structure of the pyranose ring of representing with wavy line can be any among α or the β.Perhaps also can use its mixture without any problem ground.
As N-acetyl-glucosamine derivative, can specifically enumerate compound with following general formula (4)～(15) expression with general formula (2) or (3) expression.
General formula (4)
(1 D structure can be any among α or the β).
General formula (5)
(1 D structure can be any among α or the β).
General formula (6)
(1 D structure can be any among α or the β).
General formula (7)
(1 D structure can be any among α or the β).
General formula (8)
(1 D structure can be any among α or the β).
General formula (9)
(1 D structure can be any among α or the β).
General formula (10)
(1 D structure can be any among α or the β).
General formula (11)
(1 D structure can be any among α or the β).
These compounds can use known glucosylation reaction to synthesize.For example, if roughly represent synthetic method, then with regard to R in the general formula (2)
6Be the compound of hydrogen atom, can by N-acetyl-glucosamine and the reaction of alcoholic acid glucosylation, make α, β blended glucoside under the effect of acid catalyst, if use silicagel column, α, β also can emanate.And then Ru fruit Shi oxazoline synthetic method then can be made single compound β-glucoside.In addition, with regard to regard to the compound of general formula (3) expression, react to the halogenide that wherein adds various lipid acid or acid anhydrides and suitable catalyzer behind the compound that can represent by heating for dissolving N-acetyl-glucosamine in solvent or with general formula (2) and make.
General formula (12)
(1 D structure can be any among α or the β).
General formula (13)
(1 D structure can be any among α or the β).
General formula (14)
(1 D structure can be any among α or the β).
General formula (15)
(1 D structure can be any among α or the β).
These compounds can pass through commercially available 2-acetamido-1; 3; 4,6-four-O-ethanoyl-2-deoxidation-β-D-glycopyranoside [compound of general formula (17)] derive materialization or adopt to utilize the oxazoline synthesis method of having known the glucosylation reaction pair its derive materialization and make.
As N-acetyl-glucosamine derivative, can specifically enumerate compound with following general formula (17) expression with general formula (16) expression.
General formula (17)
(1 D structure can be any among α or the β).
When being benchmark with the total composition, the N-acetyl-glucosamine derivative is preferably 0.00001～5.0 quality % of total composition amount to the short use level that generates agent, external composition for skin of hyaluronic acid, more preferably 0.001～3.0 quality %, most preferably 0.01～1.0 quality %.If in this scope, can give full play to purpose effect of the present invention.
The short generation of hyaluronic acid of the present invention agent, external composition for skin can make various doses of shapes such as ointment, lotion, emulsion, milk liquid, paste, parcel (pack) agent, sprays (mist), foam (foam) agent, particle, powder, gelifying agent.Also have, in the present invention, external composition for skin is meant that all skins with the health that comprises scalp are the preparation that is suitable for external application of object, also comprise bathing agents.With regard to matrix if normally used external-use substrate just is not particularly limited.In addition, final form can make makeup, medicine, non-pharmaceuticals.
In addition; in the short generation of hyaluronic acid of the present invention agent; in the external composition for skin except cooperating above-mentioned substance; can also in the scope that can reach purpose of the present invention, suitably cooperate following compound; it is tar class pigment; dimethyl polysiloxane; methyl phenyl silicone; silicone oil such as ring-type silicone; xenthophylls; astaxanthin (astaxanthin); fucoxanthine carotenoids pigments such as (fucoxanthin); painted pigment such as ferric oxide; p-Hydroxybenzoate; sanitass such as phenoxyethyl alcohol; paraffin; hydro carbons such as Vaseline; olive three decanes; rice three decanes; rice germ oil; Jojoba oil; Viscotrol C; Thistle oil; sweet oil; macadamia oil (macadamia nut oil); sunflower seeds wet goods vegetables oil; beeswax; haze tallow; wax classes such as carnauba wax; tetradecanoic acid octyl group dodecyl ester; hexadecyl palmitate; the different stearyl ester of Unimac 5680; ester oils such as Isopropyl myristate; lower alcohols such as ethanol; hexadecanol behenyl alcohol; stearyl alcohol; senior alcohols such as long-chain branched fatty alcohol; cholesterol; plant sterol; the branched chain fatty acid cholesteryl ester; steroid and derivatives such as macadamia fatty acid phytosterin ester; quenching wet goods treated oil class; stearic acid; tetradecanoic acid; Unimac 5680; oleic acid; different (iso) type longer chain fatty acid; anti--different (anteiso) senior lipid acid such as type longer chain fatty acid; limonene; terpenes such as hydrogenation bisabolol; the trioctylphosphine caprylin; 2 ethyl hexanoic acid glyceryl ester; three special-shaped long-chain fat acid glycerides; tri-glycerides such as tripalmitin; hexadecyl sodium sulfate; N-stearyl--anion surfactants such as L-glutaminate; polyethylene oxide alkyl ethers; polyoxyethylene fatty acid esters; the polyoxyethylene polyhydric alcohol fatty acid ester; polyoxyethylene solidifies Viscotrol C; polyhydric alcohol fatty acid ester; modified silicones such as polyoxyethylene modified silicone; polyglycerol fatty acid ester; nonionic surface active agent such as sucrose ester; cationic surfactants such as tetraalkylammonium salt; betaine type; the thetine type; amphotericses such as sulfo group amino acid; Yelkin TTS; lysolecithin; ceramide; natural class tensio-active agent such as cerebroside; titanium oxide; pigment such as zinc oxide; antioxidants such as butylated hydroxytoluene; sodium-chlor; magnesium chloride; sodium sulfate; saltpetre; sodium sulfate; water glass; inorganic salts such as calcium chloride; Trisodium Citrate; Potassium ethanoate; sodium succinate; Sodium L-aspartate; Sodium.alpha.-hydroxypropionate; dichloro acetic acid; mevalonic acid; organic acid and salt thereof such as glycyrrhetinic acid; diethanolamine hydrochloride; ammonium nitrate; arginine hydrochloride; the di-isopropyl amine salt; urea; organic amine and salt thereof such as decarboxylation carnosine; sequestrants such as ethylenediamine tetraacetic acid (EDTA); xanthane gum; carboxyvinyl polymer; carrageenin; pectin; the alkyl-modified carboxyl group vinyl polymer; thickening materials such as agar; potassium hydroxide; diisopropanolamine (DIPA); neutralizing agents such as trolamine; UV light absorber such as hydroxyl methoxy benzophenone sulfonate; dipropylene glycol; marvitol; 1; the 3-butyleneglycol; glycerine; propylene glycol; Sorbitol Powder; Glycerol dimer; multivalence alcohol such as raffinose; each seed amino acid, xitix; vitamin H; vitamins and xitix sulfuric acids such as tocopherol; xitix phosphonic acid ester salt; vitamin derivatives such as nicotinic acid tocopherol etc.
And then, by the suitable N-methyl-L-Serine that cooperates in the scope that can achieve the goal, the short generation of corium hyaluronic acids such as yeast extract agent, along silk agaric extract, black pine mushroom extract, Mo Jin (mokkin) extract, the terra japonica extract, hyaluronic acid decomposing inhibitors such as Flos Caryophylli extract, the Diisopropylamine dichloro acetic acid, nicotinic acid, mevalonic acid, thermal water, water glass, the uniform fruit of Particle Distribution angling promotor such as (homogenized fruit), beta-hydroxy-gamma-aminobutyric acid, barrier enhancer such as mevalonic acid etc. can obtain to keep the tension force of skin or moist effect, higher wrinkle improves effect.
Embodiment
Below, describe the present invention in detail by embodiment.But the present invention is not limited to following embodiment.
(1) about the Production Example of N-acetyl-glucosamine derivative
Production Example 1
The manufacturing of octyl group (2-acetamido-2-deoxidation) β-D-glycopyranoside [compound of general formula (4)]:
Dissolving 2-acetamido-1,3,4 in anhydrous chloroform 20mL, 6-four-O-ethanoyl-2-deoxidation-β-D-glycopyranoside 2g adds trifluoromethayl sulfonic acid TMS ester 1.0mL then, stirs 5 hours under the room temperature.Add chloroform in reaction mixture, after cleaning with saturated sodium bicarbonate aqueous solution, use the anhydrous magnesium sulfate drying chloroform layer, then decompression is distilled down to remove and is desolvated.Residue is dissolved among the ethylene dichloride 15mL, adds 1-octanol 0.89mL and (±)-camphor-10-sulfonic acid 119mg, stirred 2 hours down at 60 ℃.Add chloroform in reaction mixture, after cleaning with saturated sodium bicarbonate aqueous solution, use the anhydrous magnesium sulfate drying chloroform layer, decompression is distilled down to remove and is desolvated.Use silica gel column chromatography (eluting solvent; Normal hexane: vinyl acetic monomer=2: 3) residue that obtains is at last emanated and make refining thing.It is dissolved in methane 10mL and 1, in the mixed solvent of 4-diox 5mL, adds 28% methanol solution of sodium methylate of catalytic amount, stirred 1 hour under the room temperature.After the neutralization reaction mixed solution, distillation removes and desolvates.Water carries out crystallization to the residue that obtains at last, obtains the white crystal 840mg of octyl group (2-acetamido-2-deoxidation) β-D-glycopyranoside thus.
The 1H-NMR measurement result of having represented octyl group (2-acetamido-2-deoxidation) β-D-glycopyranoside below.
NMR(DMSO-d
6)δ：0.85(t，3H，J＝6.6Hz)，1.23(s，10H)，1.40-1.45(m，2H)，1.77(s，3H)，3.00-3.10(m，2H)，3.20-3.50(m，4H)，3.65-3.75(m，2H)，4.25(d，1H，J＝8.3Hz)，4.40(t，1H)，4.78(d，1H)，4.87(d，1H)，7.58(d，1H，J＝8.7Hz).
Production Example 2
The manufacturing of 2-acetamido-2-deoxidation-6-O-capryloyl-α-D-Glucopyranose [compound of general formula (5)]:
Add pyridine 5mL, N in N-acetyl-glucosamine 0.5g, N-DIMETHYL FORMAMIDE 5mL is heated to 70 ℃ when stirring, and the positive capryl(yl)chloride 0.46mL that drips makes its reaction 4 hours.After reaction finishes, use ethyl acetate extraction, use 2mol/L hydrochloric acid to clean, use anhydrous magnesium sulfate drying vinyl acetic monomer layer then, then decompression is distilled down to remove and is desolvated.Use silica gel column chromatography (eluting solvent; Chloroform: methyl alcohol=15: 1) residue that obtains is made with extra care, obtained the white crystal 170mg of 2-acetamido-2-deoxidation-6-O-capryloyl-α-D-Glucopyranose.
Represented 2-acetamido-2-deoxidation-6-O-capryloyl-α-D-Glucopyranose below
1The H-NMR measurement result.
NMR(DMSO-d
6)δ：0.92(t，3H，J＝6.8Hz)，1.33(s，10H)，1.55-1.60(m，2H)，1.89(s，3H)，2.34(t，2H)，3.15-3.20(m，1H)，3.55-3.60(m，1H)，3.65-3.70(m，1H)，3.85-3.90(m，1H)，4.08(d d，1H，J＝6.0，11.6Hz)，4.35(dd，1H，J＝2.1，11.8Hz)，4.70(d，1H，J＝5.4Hz)，4.96(t，1H，J＝3.5，4.3Hz)，5.13(d，1H，J＝5.8Hz)，6.54(d，1H，J＝4.7H)，7.61(d，1H，J＝8.1Hz).
Production Example 3
The manufacturing of octyl group (2-acetamido-2-deoxidation-6-O-capryloyl) β-D-glycopyranoside [compound of general formula (6)]:
In pyridine 1mL, the positive capryl(yl)chloride 61 μ L that drip make its reaction 4 hours with the compound shown in the Production Example 1 [general formula (4)] 100mg solvent.After reaction finishes, use chloroform extraction, use 2mol/L hydrochloric acid to clean, use anhydrous magnesium sulfate drying vinyl acetic monomer layer then, then decompression is distilled down to remove and is desolvated.Use silica gel column chromatography (eluting solvent; Chloroform: methyl alcohol=20: 1) residue that obtains is made with extra care, obtained the white crystal 170mg of octyl group (2-acetamido-2-deoxidation-6-O-capryloyl) β-D-glycopyranoside.
Represented octyl group (2-acetamido-2-deoxidation-6-O-capryloyl) β-D-glycopyranoside below
1The H-NMR measurement result.
NMR(DMSO-d
6)δ：0.85(t，3H，J＝6.8Hz)，1.23(s，18H)，1.40-1.45(m，2H)，1.50-1.55(m，2H)，1.78(s，3H)，2.28(t，2H)，3.05-3.10(m，1H)，3.25-3.40(m，4H)，3.60-3.65(m，1H)，4.05(dd，1H，J＝7.2，11.6Hz)，4.28(d，1H，J＝8.0Hz)，4.30(dd，1H，J＝1.6，11.6Hz)，4.90(d，1H，J＝4.8Hz)， 5.12(d，1H，J＝5.2Hz)，7.6 1(d，1H，J＝8.4Hz).
Production Example 4
The manufacturing of butyl (2-acetamido-2-deoxidation) β-D-glycopyranoside [compound of general formula (7)]:
Use the 1-butanols to replace 1-octanol in the Production Example 1, carry out the reaction identical, obtain white crystal butyl (2-acetamido-2-deoxidation) β-D-glycopyranoside 280mg with Production Example 1.
Represented butyl (2-acetamido-2-deoxidation) β-D-glycopyranoside below
1The H-NMR measurement result.
NMR(DMSO-d
6)δ：0.83(t，3H，J＝7.1Hz)，1.20-1.30(m，2H)，1.40-1.50(m，2H)，1.78(s，3H)，3.00-3.05(m，2H)，3.25-3.45(m，4H)，3.65-3.70(m，2H)，4.26(d，1H，J＝8.0Hz)，4.39(t，1H，J＝5.8Hz)，4.77(d，1H，J＝5.0Hz)，4.86(d，1H，J＝4.4Hz)，7.57(d，1H，J＝8.7Hz).
Production Example 5
The manufacturing of amyl group (2-acetamido-2-deoxidation) β-D-glycopyranoside [compound of general formula (8)]:
Use the 1-amylalcohol to replace 1-octanol in the Production Example 1, carry out the reaction identical, obtain white crystal amyl group (2-acetamido-2-deoxidation) β-D-glycopyranoside 150mg with Production Example 1.
Represented amyl group (2-acetamido-2-deoxidation) β-D-glycopyranoside below
1The H-NMR measurement result.
NMR(DMSO-d
6)δ：0.85(t，3H，J＝6.0Hz)，1.20-1.25(m，4H)，1.40-1.45(m，2H)，1.78(s，3H)，3.0 5-3.1 0(m，2 H)，3.2 0-3.4 5(m，4H)，3.65-3.75(m，2H)，4.26(d，1H，J＝8.0Hz)，4.40(t，1H，J＝6.0Hz)，4.78(d，1H，J＝4.8Hz)，4.87(d，1H)，7.58(d，1H，J＝8.8Hz).
Production Example 6
The manufacturing of lauryl (2-acetamido-2-deoxidation) β-D-glycopyranoside [compound of general formula (9)]:
Use the 1-dodecanol to replace 1-octanol in the Production Example 1, carry out the reaction identical, obtain white crystal lauryl (2-acetamido-2-deoxidation) β-D-glycopyranoside 450mg with Production Example 1.
Represented lauryl (2-acetamido-2-deoxidation) β-D-glycopyranoside below
1The H-NMR measurement result.
NMR(DMSO-d
6)δ：0.85(t，3H，J＝6.0Hz)，1.23(s，18H)，1.40-1.45(m，2H)，1.84(s，3H)，3.00-3.10(m，2H)，3.20-3.50(m，4H)，3.65-3.75(m，2H)，4.25(d，1H，J＝8.0Hz)，4.40(t，1H，J＝5.6Hz)，4.7 9(d，1H，J＝5.2Hz)，4.85(d，1H，J＝4.4Hz))，7.08(d，1H，J＝8.8Hz).
Production Example 7
The manufacturing of 2-acetamido-2-deoxidation-6-O-palmitoyl-α-D-Glucopyranose [compound of general formula (10)]:
Add pyridine 5mL, N in N-acetyl-glucosamine 1g, N-DIMETHYL FORMAMIDE 15mL is heated to 70 ℃ when stirring, and the palmityl chloride 1.37mL that drips makes its reaction 4 hours.After reaction finishes, use ethyl acetate extraction, use 2mol/L hydrochloric acid to clean, use anhydrous magnesium sulfate drying vinyl acetic monomer layer then, then decompression is distilled down to remove and is desolvated.Use silica gel column chromatography (eluting solvent; Chloroform: methyl alcohol=15: 1) residue that obtains is made with extra care, obtained the white crystal 710mg of 2-acetamido-2-deoxidation-6-O-palmitoyl-α-D-Glucopyranose.
Represented 2-acetamido-2-deoxidation-6-O-palmitoyl-α-D-Glucopyranose below
1The H-NMR measurement result.
NMR(DMSO-d
6)δ：0.85(t，3H，J＝6.5Hz)，1.25(s，24H)，1.45-1.55(m，2H)，1.82(s，3H)，2.30(t，2H)，3.05-3.15(m，1H)，3.45-3.65(m，2H)，3.75-3.85(m，1H)，4.00(dd，1H，J＝5.7，11.8Hz)，4.28(dd，1H，J＝2.0，11.8Hz)，4.65(d，1H，J＝5.7Hz)，4.90(t，1H，J＝3.7，4.1Hz)，5.07(d，1H，J＝5.7Hz)，6.45(d，1H，J＝4.5H)，7.55(d，1H，J＝8.1Hz).
Production Example 8
The manufacturing of geranyl (2-acetamido-2-deoxidation) β-D-glycopyranoside [compound of general formula (11)]:
Use the Mang geraniol to replace 1-octanol in the Production Example 1, carry out the reaction identical, obtain white crystal geranyl (2-acetamido-2-deoxidation) β-D-glycopyranoside 890mg with Production Example 1.
Represented geranyl (2-acetamido-2-deoxidation) β-D-glycopyranoside below
1The H-NMR measurement result.
NMR(DMSO-d
6)δ：1.57，1.60，1.65(3s，9H)，1.79(s，3H)，1.95-2.05(m，4H)，3.05-3.10(m，2H)，3.30-3.40(m，2H)，3.47(dt，1H，J＝5.2，12.0Hz)，3.68(dd，1H，J＝5.6，11.6Hz)，4.02(dd，1H，J＝7.2，12.0Hz)，4.17(dd，1H，J＝5.2Hz)，4.87(d，1H)，5.05-5.10(m，1H)，5.21(t，1H，J＝6.4Hz)，7.59(d，1H，J＝8.8Hz).
Production Example 9
The manufacturing of ethyl (2-acetamido-3,4,6-three-O-ethanoyl-2-deoxidation) β-D-glycopyranoside [compound of general formula (12)]:
Dissolving 2-acetamido-1,3,4 in anhydrous chloroform 10mL, 6-four-O-ethanoyl-2-deoxidation-β-D-glycopyranoside [compound of general formula (17)] 1g adds trifluoromethayl sulfonic acid trimethyl silane ester 0.5mL then, stirs 5 hours under the room temperature.Add chloroform in reaction mixture, after cleaning with saturated sodium bicarbonate aqueous solution, use the anhydrous magnesium sulfate drying chloroform layer, then decompression is distilled down to remove and is desolvated.Residue is dissolved among the ethylene dichloride 8mL, adds ethanol 0.17mL and (±)-camphor-10-sulfonic acid 60mg, stirred 2 hours down at 60 ℃.Add chloroform in reaction mixture, after cleaning with saturated sodium bicarbonate aqueous solution, use the anhydrous magnesium sulfate drying chloroform layer, decompression is distilled down to remove and is desolvated.Use ether and normal hexane that the residue that obtains is at last carried out crystallization, obtain the white solid 0.5g of ethyl (2-acetamido-3,4,6-three-O-ethanoyl-2-deoxidation) β-D-glycopyranoside thus.
Represented ethyl (2-acetamido-3,4,6-three-O-ethanoyl-2-deoxidation) β-D-glycopyranoside below
1The H-NMR measurement result.
NMR(CDCl
3)δ：1.18(t，3H，J＝7.3Hz)，1.93，2.00，2.05(4s，12H)，3.5 6(m，1H)，3.68(m，1H)，3.78(dt，1H，J＝8.4，8.8，10.4Hz)，3.88(m，1H)，4.12(dd，1H，J＝2.4，14Hz)，4.25(dd，1H，J＝4.8，12.4Hz)，4.69(d，1H，J＝8.4Hz)，5.03(t，1H，J＝9.6Hz)，5.30(t，1H，J＝9.2Hz)，5.43(d，1H，J＝8.8Hz).
Production Example 10
The manufacturing of amyl group (2-acetamido-3,4,6-three-O-ethanoyl-2-deoxidation) β-D-glycopyranoside [compound of general formula (13)]:
Dissolving 2-acetamido-1,3,4 in anhydrous chloroform 15mL, 6-four-O-ethanoyl-2-deoxidation-β-D-glycopyranoside 1.5g adds trifluoromethayl sulfonic acid trimethyl silane ester 0.75mL then, stirs 5 hours under the room temperature.Add chloroform in reaction mixture, after cleaning with saturated sodium bicarbonate aqueous solution, use the anhydrous magnesium sulfate drying chloroform layer, then decompression is distilled down to remove and is desolvated.Residue is dissolved among the ethylene dichloride 15mL, adds Pentyl alcohol 0.51mL and (±)-camphor-10-sulfonic acid 99mg, stirred 2 hours down at 60 ℃.Add chloroform in reaction mixture, after cleaning with saturated sodium bicarbonate aqueous solution, use the anhydrous magnesium sulfate drying chloroform layer, decompression is distilled down to remove and is desolvated.Use silica gel column chromatography (eluting solvent; Normal hexane: vinyl acetic monomer=2: 3) residue that obtains is at last emanated refining, obtain the white solid 1.1g of amyl group (2-acetamido-3,4,6-three-O-ethanoyl-2-deoxidation) β-D-glycopyranoside thus.
Represented amyl group (2-acetamido-3,4,6-three-O-ethanoyl-2-deoxidation) β-D-glycopyranoside below
1The H-NMR measurement result.
NMR(CDCl
3)δ：0.87(t，3H，J＝6.2Hz)，1.28(s，4H)，1.50-1.55(m，2H)，2.00，2.03，2.14(4s，12H)，3.45(dt，1H，J＝7.2，9.2Hz)，3.65-3.70(m，1H)，3.75-3.85(m，2H)，4.13(dd，1H，J＝2.4，12.4Hz)，4.25(dd，1H，J＝4.8，12.4Hz)，4.66(d，1H，J＝8.0Hz)，5.03(t，1H，J＝9.6Hz)，5.29(t，1H，J＝9.2Hz)，5.40(d，1H，J＝8.8Hz).
Production Example 11
The manufacturing of octyl group (2-acetamido-3,4,6-three-O-ethanoyl-2-deoxidation) β-D-glycopyranoside [compound of general formula (14)]:
Dissolving 2-acetamido-1,3,4 in anhydrous chloroform 20mL, 6-four-O-ethanoyl-2-deoxidation-β-D-glycopyranoside 2g adds trifluoromethayl sulfonic acid trimethyl silane ester 1.0mL then, stirs 5 hours under the room temperature.Add chloroform in reaction mixture, after cleaning with saturated sodium bicarbonate aqueous solution, use the anhydrous magnesium sulfate drying chloroform layer, then decompression is distilled down to remove and is desolvated.Residue is dissolved among the ethylene dichloride 15mL, adds 1-octanol 0.89mL and (±)-camphor-10-sulfonic acid 119mg, stirred 2 hours down at 60 ℃.Add chloroform in reaction mixture, after cleaning with saturated sodium bicarbonate aqueous solution, use the anhydrous magnesium sulfate drying chloroform layer, decompression is distilled down to remove and is desolvated.Use silica gel column chromatography (eluting solvent; Normal hexane: vinyl acetic monomer=2: 3) residue that obtains is at last emanated refining, obtain the white solid 1.5g of octyl group (2-acetamido-3,4,6-three-O-ethanoyl-2-deoxidation) β-D-glycopyranoside thus.
Represented octyl group (2-acetamido-3,4,6-three-O-ethanoyl-2-deoxidation) β-D-glycopyranoside below
1The H-NMR measurement result.
NMR(CDCl
3)δ：0.86(t，3H，J＝6.2Hz)，1.25(s，10H)，1.50-1.55(m，2H)，1.92，1.99，2.00，2.05(4s，12H)，3.40-3.45(m，1H)，3.65-3.70(m，1H)，3.75-3.90(m，2H)，4.10(d，1H，J＝12.2Hz)，4.23(d，1H，J＝4.8，12.2Hz)，4.65(d，1H，J＝8.3Hz)，5.03(t，1H，J＝9.8Hz)，5.28(t，1H，J＝9.8Hz)，5.41(d，1H，J＝8.7Hz).
Production Example 12
The manufacturing of geranyl (2-acetamido-3,4,6-three-O-ethanoyl-2-deoxidation) β-D-glycopyranoside [compound of general formula (15)]:
Dissolving 2-acetamido-1,3,4 in anhydrous chloroform 50mL, 6-four-O-ethanoyl-2-deoxidation-β-D-glycopyranoside 5g adds trifluoromethayl sulfonic acid trimethyl silane ester 2.6mL then, stirs 5 hours under the room temperature.Add chloroform in reaction mixture, after cleaning with saturated sodium bicarbonate aqueous solution, use the anhydrous magnesium sulfate drying chloroform layer, then decompression is distilled down to remove and is desolvated.Residue is dissolved among the ethylene dichloride 20mL, adds Mang geraniol 2.5mL and (±)-camphor-10-sulfonic acid 298mg, stirred 2 hours down at 60 ℃.Add chloroform in reaction mixture, after cleaning with saturated sodium bicarbonate aqueous solution, use the anhydrous magnesium sulfate drying chloroform layer, decompression is distilled down to remove and is desolvated.Use silica gel column chromatography (eluting solvent; Normal hexane: vinyl acetic monomer=2: 3) residue that obtains is at last emanated refining, obtain the white solid 4.3g of geranyl (2-acetamido-3,4,6-three-O-ethanoyl-2-deoxidation) β-D-glycopyranoside thus.
Represented geranyl (2-acetamido-3,4,6-three-O-ethanoyl-2-deoxidation) β-D-glycopyranoside below
1The H-NMR measurement result.
NMR(CDCl
3)δ：1.59，1.64，1.67(3s，9H)，1.91(s，3H)，1.99，2.00，2.05(3s，9H)，3.60-3.65(m，1H)，3.78(dt，1H，J＝2.8，12.4Hz)，4.10-4.30(m，3H)，4.68(d，1H，J＝8.8Hz)，5.00-5.10(m，2H)，5.20-5.40(m，2H).
(2) about having used the test example of N-acetyl-glucosamine derivative
Then, test example when using the N-acetyl-glucosamine derivative obtain to carry out the present invention estimates is described in above-mentioned Production Example.
Test example 1 (testing) at short generation of the hyaluronic acid of people's normal epidermis cell
Dull and stereotyped upper seeding wheel people's normal epidermis cell (Kurabo system) in 24 holes, cultivate up to merging (confluent) with substratum with propagation, being added in the above-mentioned Production Example 1～3,6～8 the N-acetyl-glucosamine derivative of making then, to make its ultimate density be 50 μ mol/L (having only Production Example 7 is 25 μ mol/L), and being added on the N-acetyl-glucosamine derivative of making in the Production Example 4,5 in addition, to make its ultimate density be 1mmol/L.After interpolation is cultivated 48 hours, measure the hyaluronic acid that in substratum, discharges.When measuring hyaluronic acid, used commercially available hyaluronic acid to measure test kit (kit) (Chugai system).
The hyaluronic acid growing amount is defined as: with add N-acetyl-glucosamine make its ultimate density be 1mmol/L comparative example 1 as 1 o'clock in the hyaluronic acid amount that contains the epidermic cell that the substances substratum cultivates.The result as depicted in figs. 1 and 2.
As shown in Figure 1; compare with N-acetyl-glucosamine; following compound is under the concentration of about 1/20 (being about 1/40 in Production Example 7); demonstrated 2.5～3.5 times the short effect that generates of hyaluronic acid, described compound is octyl group (2-acetamido-2-deoxidation) β-D-glycopyranoside [compound of general formula (4)] of Production Example 1; the 2-acetamido of Production Example 2-2-deoxidation-6-O-capryloyl-α-D-Glucopyranose [compound of general formula (5)]; the octyl group of Production Example 3 (2-acetamido-2-deoxidation-6-O-capryloyl) β-D-glycopyranoside [compound of general formula (6)]; 2-acetamido-2-deoxidation-6-O-palmitoyl-α-D-the Glucopyranose [compound of general formula (10)] of the lauryl of Production Example 6 (2-acetamido-2-deoxidation) β-D-glycopyranoside [compound of general formula (9)] and Production Example 7; the geranyl of Production Example 8 (2-acetamido-2-deoxidation) β-D-glycopyranoside [compound of general formula (11)].R in general formula (3) particularly
7The short generation of compound that is hydrogen is active higher.
In addition, as shown in Figure 2, following compound is under the concentration identical with N-acetyl-glucosamine, demonstrated 1.5 times～3 times the short effect that generates of hyaluronic acid, described compound is butyl (2-acetamido-2-deoxidation) β-D-glycopyranoside [compound of general formula (7)] of Production Example 4, amyl group (2-acetamido-2-deoxidation) β-D-glycopyranoside [compound of general formula (8)] of Production Example 5.
Test example 2 (testing) at short generation of the hyaluronic acid of people's normal epidermis cell
Dull and stereotyped upper seeding wheel people's normal epidermis cell (Kurabo system) in 24 holes; cultivate up to fusion with substratum with propagation; be added on 2-acetamido-1 then with above-mentioned general formula (17) expression; 3; 4; it is 100 μ mol/L that 6-four-O-ethanoyl-2-deoxidation-β-D-glycopyranoside makes its ultimate density; being added in the above-mentioned Production Example 9 the N-acetyl-glucosamine derivative of making in addition, to make its ultimate density be 1mmol/L, and being added on the N-acetyl-glucosamine derivative of making in the Production Example 10～12, to make its ultimate density be 100 μ mol/L.After interpolation is cultivated 48 hours, measure the hyaluronic acid that in substratum, discharges.When measuring hyaluronic acid, used commercially available hyaluronic acid to measure test kit (Chugai system).The result as shown in Figure 3.
As shown in Figure 3, the ethyl of Production Example 9 (2-acetamido-3,4,6-three-O-ethanoyl-2-deoxidation) β-D-glycopyranoside [compound of general formula (12)] has demonstrated 6.5 times the short effect that generates of hyaluronic acid under the concentration identical with N-acetyl-glucosamine.In addition; the amyl group of Production Example 10 (2-acetamido-3; 4; 6-three-O-ethanoyl-2-deoxidation) β-D-glycopyranoside [compound of general formula (13)]; the octyl group of Production Example 11 (2-acetamido-3; 4; 6-three-O-ethanoyl-2-deoxidation) β-D-glycopyranoside [compound of general formula (14)]; the geranyl of Production Example 12 (2-acetamido-3; 4; 6-three-O-ethanoyl-2-deoxidation) β-D-glycopyranoside [compound of general formula (15)]; 2-acetamido-1; 3; 4; [general formula (17 compounds) has demonstrated 3.8 respectively to 6-four-O-ethanoyl-2-deoxidation-β-D-glycopyranoside under 1/10 concentration; 2.8; 3.7; 3.0 the short effect that generates of hyaluronic acid doubly.
Test example 3 (testing) at short generation of the hyaluronic acid of people's normal dermal fibroblast
Dull and stereotyped upper seeding wheel people's normal dermal fibroblast (American Type CultureCollection system) in 24 holes, cultivate up to fusion with substratum with propagation, adding the N-acetyl-glucosamine derivative shown in the above-mentioned Production Example 1 then, to make its ultimate density be 100 μ mol/L, adds the N-acetyl-glucosamine derivative 25 μ mol/L shown in the Production Example 6 in addition.After interpolation is cultivated 48 hours, measure the hyaluronic acid that in substratum, discharges.When measuring hyaluronic acid, used commercially available hyaluronic acid to measure test kit (Chugai system).
The hyaluronic acid growing amount is defined as: with respect to the comparative example 2 of the N-acetyl-glucosamine that has added 1mmol/L in the hyaluronic acid amount that contains the corium fabric parent cell that the substances substratum cultivates.The result as shown in Figure 4.
As shown in Figure 4, compare with N-acetyl-glucosamine, these two kinds of compounds of lauryl (2-acetamido-2-deoxidation) β-D-glycopyranoside [compound of general formula (9)] of the octyl group of Production Example 1 (2-acetamido-2-deoxidation) β-D-glycopyranoside [compound of general formula (4)], Production Example 6 have all demonstrated 1.5～2 times the short effect that generates of hyaluronic acid under about 1/10～1/40 concentration.
Test example 4～7, comparative example 3,4 (by testee's evaluation)
40～60 years old women testee is divided into 8 groups, every group 20, give different groups respectively, 2 times on the 1st with creme of the composition shown in the table 1 (test example 4,5 and comparative example 3) and the astringent shown in the table 2 (testing example 6,7 and comparative example 4), be coated on the face logotype 3 months in right amount.After the logotype, estimate the tight sense of skin.
Evaluation divides significantly effective (the tight sense of skin has suitable improvement), effective (the tight sense of skin has good improvement), effective (the tight sense of skin has improvement), invalid (not changing) 4 stages carry out a little.Utilizing to answer significantly effectively, effectively adds up to the ratio (%) of number to come determine effect.
Table 1
| Test example 4 | Test example 5 | Comparative example 3 | |
| The compound of general formula (4) (Production Example 1) | 0.1 | - | - |
| The compound of general formula (17) | - | 0.1 | - |
| |
2 | ||
| |
2 | ||
| |
3 | ||
| Cholesterol | 0.5 | ||
| |
2 | ||
| Three decanes | 10 | ||
| Whiteruss | 10 | ||
| |
1 | ||
| The P-hydroxybenzoic acid butyl ester | 0.1 | ||
| The P-hydroxybenzoic acid methyl ester | 0.1 | ||
| N-stearoyl- |
1 | ||
| The glycerine dipropylene glycol | 5 | ||
| Purified Water | Residual content | ||
| Add up to | 100 | ||
| Estimate (%) | 80 | 80 | 45 |
*Content all is quality %.
Table 2
| Test example 4 | Test example 5 | Comparative example 3 | |
| The compound of general formula (4) (Production Example 1) | 0.01 | - | - |
| The compound of general formula (17) | - | 0.01 | - |
| Ethanol | 10 | ||
| Polyoxyethylene solidifies Viscotrol C (60E.O.) | 1 | ||
| |
3 | ||
| 1,3 |
2 | ||
| |
3 | ||
| Potassium primary phosphate | 0.05 | ||
| Dipotassium hydrogen phosphate | 0.05 | ||
| Disodium ethylene diamine tetraacetate | 0.05 | ||
| The P-hydroxybenzoic acid methyl ester | 0.1 | ||
| Purified Water | Residual content | ||
| Add up to | 100 | ||
| Estimate (%) | 55 | 55 | 30 |
*Content all is quality %.
By table 1 and table 2 as can be known, used the makeup of N-acetyl-glucosamine derivative of the present invention to have the effect of the tight sense that improves skin.
In addition, under the situation of the makeup that used any test example, that skin does not occur is rubescent, inflammation, other side reaction symptoms, can confirm the excellent in safety of makeup of the present invention.
(3) about embodiment
Embodiment 1 (protective skin cream)
Adopt the common method modulation to have the protective skin cream of following composition.
Material composition use level (quality %)
Beeswax 2.0
Stearic acid 5.0
Stearyl alcohol 5.0
Reduction hydrous wool 2.0
Squalene 20.0
Sorbitan monostearate 3.0
Polyoxyethylene (20) sorbitan monostearate 3.0
Propylene glycol 5.0
P-hydroxybenzoic acid methyl ester 0.2
The compound of general formula (4) (Production Example 1) 0.1
The Purified Water total amount is 100 o'clock a residual content
Embodiment 2 (protective skin cream)
Adopt the common method modulation to have the protective skin cream of following composition.
Material composition use level (quality %)
Beeswax 2.0
Stearic acid 5.0
Stearyl alcohol 5.0
Reduction hydrous wool 2.0
Squalene 20.0
Sorbitan monostearate 3.0
Polyoxyethylene (20) sorbitan monostearate 3.0
Propylene glycol 5.0
P-hydroxybenzoic acid methyl ester 0.2
The compound of general formula (5) (Production Example 2) 0.5
The Purified Water total amount is 100 o'clock a residual content
Embodiment 3 (skin lotion)
Adopt the common method modulation to have the skin lotion of following composition.
Material composition use level (quality %)
Sweet oil 10.0
Isopropyl myristate 1.0
Polyoxyethylene (6) nonylplenyl ether 0.5
Propylene glycol 1.0
Glycerine 2.0
P-hydroxybenzoic acid methyl ester 0.1
Ethanol 7.0
The compound of general formula (6) (Production Example 3) 0.5
The Purified Water total amount is 100 o'clock a residual content
Embodiment 4 (skin lotion)
Adopt the common method modulation to have the skin lotion of following composition.
Material composition use level (quality %)
Sweet oil 10.0
Isopropyl myristate 1.0
Polyoxyethylene (6) nonylplenyl ether 0.5
Propylene glycol 1.0
Glycerine 2.0
P-hydroxybenzoic acid methyl ester 0.1
Ethanol 7.0
The compound of general formula (8) (Production Example 5) 1.0
The Purified Water total amount is 100 o'clock a residual content
Embodiment 5 (bathing agents)
Adopt the common method modulation to have the bathing agents of following composition.
Material composition use level (quality %)
The compound of general formula (5) (Production Example 2) 1.0
The sodium bicarbonate balance
Yellow soda ash 20.0
Sodium sulfate 15.0
Sodium-chlor 7.5
Silicic anhydride 0.5
1,3 butylene glycol 1.0
Urea 1.0
Seaweed Extract 1.0
Pigment is an amount of
Dextrin is an amount of
Spices is an amount of
Adopt common method modulation protective skin cream according to following prescription.
Material composition use level (quality %)
Embodiment 678
The compound of general formula (4) (Production Example 1) 0.1--
The compound of general formula (5) (Production Example 2)-0.1-
The compound of general formula (6) (Production Example 3)--0.1
Unimac 5680--1
Glyceryl monostearate 222
Behenyl alcohol 222
Cetyl myristate 111
Sesquialter oleic acid sorbitan ester 111
N-stearyl phytosphingosine 0.1 0.1 0.1
Hydrolecithin 0.1 0.1 0.1
Plant three decanes 555
Tetradecanoic acid octyl group dodecyl ester 555
Cork tree extract 0.1 1 0.1
Fire sour jujube extract 0.1 0.3-
Water-soluble Radix Glycyrrhizae extract--0.1
1,3 butylene glycol 5 10 5
Concentrated glycerin 555
P-Hydroxybenzoate 0.2 0.2 0.2
N-acetyl-glucosamine oligopolymer 0.1 0.1 0.1
Ascorbic acid phosphoric acid esters Mg salt 0.1 0.1 0.1
Ascorbic acid phosphoric acid esters Na salt 0.1 0.1 0.1
γ-An Jidingsuan 0.1 0.1 0.1
N-stearoyl-glutamic acid sodium 0.2 0.2 0.2
Alkyl-modified carboxyl group vinyl polymer * 1 0.05 0.05 0.05
Niacinamide 0.1 0.1 0.1
Sarkosine 0.1 0.1 0.1
Purified Water residual content residual content residual content
* 1; B.F.Goodrich system PEMULEN TR-1
Embodiment 9～11 (lotion)
Adopt common method modulation lotion according to following prescription.
Material composition use level (quality %)
Embodiment 9 10 11
The compound of general formula (4) (Production Example 1) 0.1--
The compound of general formula (5) (Production Example 2)-0.1-
The compound of general formula (6) (Production Example 3)--0.1
Cork tree extract 0.1 0.3 0.3
Rose of Sharon extract 0.2 0.5 0.5
Lactic acid bacteria culture solution 0.1 0.1 0.1
1,3 butylene glycol 555
Dipropylene glycol 555
Raffinose 111
Ethanol 111
Phenoxyethyl alcohol 0.2 0.2 0.2
Pectin 0.05 0.05 0.05
Xanthane gum 0.1 0.1 0.1
Trisodium Citrate 0.05 0.05 0.05
Nib dish extraction liquid 0.1 0.1 0.1
Tensicor 0.2 0.2 0.2
γ-amido-beta-hydroxy-butanoic acid 0.2 0.2 0.2
Hyaluronate sodium 0.001 0.001 0.01
Glycyrrhetinic acid dipotassium 0.2 0.2 0.2
Along silk agaric extract 0.05 0.05 0.05
Decarboxylation carnosine hydrochloride 0.05 0.05 0.05
Spices 0.02 0.02 0.02
Purified Water residual content residual content residual content
Embodiment 12～14 (gel)
Adopt the common method modulated gel according to following prescription.
Material composition use level (quality %)
Embodiment 12 13 14
The compound of general formula (4) (Production Example 1) 0.1--
The compound of general formula (5) (Production Example 2)-0.1-
The compound of general formula (6) (Production Example 3)--0.1
Decamethylcyclopentasiloxane 10 10 10
The different stearyl ester 1 of Unimac 5680--
Sweet oil-1-
Macadamia oil--1
Oil of Eucalyptus 0.1-0.1
Nicotinic acid d1 alpha-tocopherol-0.1-
Polyoxyethylene (60) solidifies Viscotrol C 222
Spherical silicone powder * 2115
Cork tree extract 0.1 1 0.1
Chlorophillins 0.02 0.02 0.02
Ocean Soviet Union extract-0.3 0.1
1,3 butylene glycol 5 10 5
D-sorbitol solution 333
Macrogol 4000 111
Carboxyvinyl polymer 0.2 0.2 0.2
Glycosyl ceramide * 3 0.1 0.1 0.1
P-Hydroxybenzoate 0.2 0.2 0.2
First hydroxyl valerolactone (mevalonolactone) 0.5 0.5 0.5
Edetate 0.02 0.02 0.02
Potassium hydroxide 0.05 0.05 0.05
Purified Water residual content residual content residual content
* 2; The silicone system tospearl of GE Toshiba
* 3: the biological ceramide of the civilian food chemistry system of recording
Embodiment 15～17 (lipophilicity creme)
Adopt common method modulation lipophilicity creme according to following prescription.
Material composition use level (quality %)
Embodiment 15 16 17
The compound of general formula (4) (Production Example 1) 0.1--
The compound of general formula (5) (Production Example 2)-0.1-
The compound of general formula (6) (Production Example 3)--0.1
Be total to modified silicone * 4222
Polyoxyethylene modified silicone dispersion liquid * 5-2-
Three decanes--10
Decamethylcyclopentasiloxane 15 20 10
Methyl polysiloxane 523
Long-chain branched chain fatty acid cholesteryl ester * 6--3
Silicone elastomer dispersion liquid * 752
Cork tree extract 111
Radix Glycyrrhizae extract 0.1 0.1 0.1
Chlorophillins 0.02 0.02 0.02
Sodium-chlor 111
Dipropylene glycol 555
Concentrated glycerin 555
Raffinose 111
P-Hydroxybenzoate 0.3 0.3 0.3
N-methyl-L-Serine 0.5 0.5 0.5
Purified Water residual content residual content residual content
* 4; Goldschmidt system ABIL EM90
* 5:Toray Dow Corning silicone makes siliconeBY22-008
* 6; Japan refines and makes YOFCO CLE-NH
* 7; Toray Dow Corning silicone makes Trefil
Embodiment 18～20 (sunscreen)
Adopt common method modulation sunscreen according to following prescription.
Material composition use level (quality %)
Embodiment 18 19 20
The compound of general formula (4) (Production Example 1) 0.1--
The compound of general formula (5) (Production Example 2)-0.1-
The compound of general formula (6) (Production Example 3)--0.1
Dioctyl ether 10 10 10
Be total to modified silicone * 4222
Three 2 ethyl hexanoic acid glyceryl ester 555
Solidified oil 0.1 0.1 0.1
Methyl phenyl silicone 523
Macadamia fatty acid phytosterin ester--2
P-methoxycinnamic acid 2-ethylhexyl-7 7
Titanium oxide 554
Zinc oxide 554
Cork tree extract 111
Magnesium chloride 111
1,3 butylene glycol 555
Phenoxyethyl alcohol 0.3 0.3 0.3
Rose of Sharon extract 111
Aloe extract 0.1 0.1 0.1
Yeast extract * 8111
Purified Water residual content residual content residual content
* 4; Goldschmidt system ABIL EM90
* 8:PentaFarm makes Dismutin
Embodiment 21 (astringent)
Ethanol 10
Polyoxyethylene (60) solidifies Viscotrol C 1
1,3 butylene glycol 2
Polyethylene glycol 1500 1
Phosphoric acid salt is an amount of
Edetate is an amount of
The P-hydroxybenzoic acid methyl ester is an amount of
The compound of general formula (10) (Production Example 7) 0.1
Antioxidant is an amount of
The Purified Water residual content
Embodiment 22,23 (emulsion)
Embodiment 22 embodiment 23
Stearic acid 11
Stearin 22
Hexadecanol 11
Cholesterol 0.5 0.5
Vaseline 22
Three decanes 55
Whiteruss 55
Silicone oil 11
Acyl glutamate 11
Xanthane gum 0.5 0.5
Glycerine 22
Dipropylene glycol 33
The compound of general formula (5) (Production Example 2) 0.1-
The compound of general formula (10) (Production Example 7)-0.1
The P-hydroxybenzoic acid butyl ester is an amount of
Antioxidant is an amount of
Purified Water residual content residual content
Embodiment 24,25 (creme)
Embodiment 24 embodiment 25
Stearic acid 22
Stearin 22
Hexadecanol 33
Cholesterol 0.5 0.5
Vaseline 22
Three decanes 55
Whiteruss 10 10
Silicone oil 11
Acyl glutamate 11
Xanthane gum 0.5 0.5
Glycerine 55
Dipropylene glycol 33
The compound of general formula (5) (Production Example 2) 0.1-
The compound of general formula (10) (Production Example 7)-0.1
The P-hydroxybenzoic acid butyl ester is an amount of
Antioxidant is an amount of
Purified Water residual content residual content
Embodiment 26,27 (sunscreen)
Embodiment 26 embodiment 27
Ethanol 10 10
Octyl methoxycinnamate 77
POE/POP modification dimethyl polysiloxane 22
Titanium oxide microparticle 55
Zinc oxide 55
Ring-type silicone 10 10
Dimethyl polysiloxane (6cs) 10 10
The compound of general formula (5) (Production Example 2) 0.1-
The compound of general formula (10) (Production Example 7)-0.1
Antioxidant is an amount of
Purified Water residual content residual content
Embodiment 28 (protective skin cream)
Adopt the common method modulation to have the protective skin cream of following composition.
Material composition use level (quality %)
Beeswax 2.0
Stearic acid 5.0
Stearyl alcohol 5.0
Reduction hydrous wool 2.0
Squalene 20.0
Sorbitan monostearate 3.0
Polyoxyethylene (20) sorbitan monostearate 3.0
Propylene glycol 5.0
P-hydroxybenzoic acid methyl ester 0.2
The compound 0.1 of general formula (17)
The Purified Water total amount is 100 o'clock a residual content
Embodiment 29 (protective skin cream)
Adopt the common method modulation to have the protective skin cream of following composition.
Material composition use level (quality %)
Beeswax 2.0
Stearic acid 5.0
Stearyl alcohol 5.0
Reduction hydrous wool 2.0
Squalene 20.0
Sorbitan monostearate 3.0
Polyoxyethylene (20) sorbitan monostearate 3.0
Propylene glycol 5.0
P-hydroxybenzoic acid methyl ester 0.2
The compound of general formula (12) (Production Example 9) 0.5
The Purified Water total amount is 100 o'clock a residual content
Embodiment 30 (skin lotion)
Adopt the common method modulation to have the skin lotion of following composition.
Material composition use level (quality %)
Sweet oil 10.0
Isopropyl myristate 1.0
Polyoxyethylene (6) nonylplenyl ether 0.5
Propylene glycol 1.0
Glycerine 2.0
P-hydroxybenzoic acid methyl ester 0.1
Ethanol 7.0
The compound 0.5 of general formula (17)
The Purified Water total amount is 100 o'clock a residual content
Embodiment 31 (bathing agents)
Adopt the common method modulation to have the bathing agents of following composition.
Material composition use level (quality %)
The compound 1.0 of general formula (17)
The sodium bicarbonate balance
Yellow soda ash 20.0
Sodium sulfate 15.0
Sodium-chlor 7.5
Silicic anhydride 0.5
1,3 butylene glycol 1.0
Urea 1.0
Seaweed Extract 1.0
Pigment is an amount of
Dextrin is an amount of
Spices is an amount of
Embodiment 32,33 (protective skin cream)
Adopt common method modulation protective skin cream according to following prescription.
Material composition use level (quality %)
Embodiment 32 33
The compound 0.1 of general formula (17)-
The compound of general formula (14) (Production Example 11)-0.1
Stearic acid 1-
Unimac 5680-1
Glyceryl monostearate 22
Behenyl alcohol 22
Chinese wax 11
Cetyl myristate 11
Sesquialter oleic acid sorbitan ester 11
N-stearyl phytosphingosine 0.1 0.1
Hydrolecithin 0.1 0.1
Plant three decanes 55
Tetradecanoic acid octyl group dodecyl ester 55
Cork tree extract 0.1 1
Fire sour jujube extract 0.1 0.3
Water-soluble Radix Glycyrrhizae extract 0.1 0.1
1,3 butylene glycol 5 10
Concentrated glycerin 55
P-Hydroxybenzoate 0.2 0.2
N-acetyl-glucosamine oligopolymer 0.1 0.1
Ascorbic acid phosphoric acid esters Mg salt 0.1 0.1
Ascorbic acid phosphoric acid esters Na salt 0.1 0.1
γ-An Jidingsuan 0.1 0.1
N-stearoyl-glutamic acid sodium 0.2 0.2
Alkyl-modified carboxyl group vinyl polymer * 1 0.05 0.05
Niacinamide 0.1 0.1
Sarkosine 0.1 0.1
Purified Water residual content residual content
* 1; B.F.Goodrich system PEMULEN TR-1
Embodiment 34,35 (lotion)
Adopt common method modulation lotion according to following prescription.
Material composition use level (quality %)
Embodiment 34 35
The compound 0.1 of general formula (17)-
The compound of general formula (12) (Production Example 9)-0.1
Cork tree extract 0.1 0.3
Rose of Sharon extract 0.2 0.5
Lactic acid bacteria culture solution 0.1 0.1
1,3 butylene glycol 55
Dipropylene glycol 55
Raffinose 11
Ethanol 11
Phenoxyethyl alcohol 0.2 0.2
Pectin 0.05 0.05
Xanthane gum 0.1 0.1
Trisodium Citrate 0.05 0.05
Nib dish extraction liquid 0.1 0.1
Diisopropylamine dichloro acetic acid 0.2 0.2
γ-amido-beta-hydroxy-butanoic acid 0.2 0.2
Hyaluronate sodium 0.001 0.001
Glycyrrhetinic acid dipotassium 0.2 0.2
Along silk agaric extract 0.05 0.05
Decarboxylation carnosine hydrochloride 0.05 0.05
Spices 0.02 0.02
Purified Water residual content residual content
Embodiment 36,37 (gel)
Adopt the common method modulated gel according to following prescription.
Material composition use level (quality %)
Embodiment 36 37
The compound of general formula (13) (Production Example 10) 0.1-
The compound of general formula (15) (Production Example 12)-0.1
Decamethylcyclopentasiloxane 10 10
The different stearyl ester 1 of Unimac 5680-
Sweet oil-1
Macadamia oil 0.1 0.1
Oil of Eucalyptus 0.1-
Nicotinic acid d1 alpha-tocopherol-0.1
Polyoxyethylene (60) solidifies Viscotrol C 22
Spherical silicone powder * 211
Cork tree (phellodendron bark) extract 0.1 1
Chlorophillins 0.02 0.02
Ocean Soviet Union extract-0.3
1,3 butylene glycol 5 10
D-sorbitol solution 33
Macrogol 4000 11
Carboxyvinyl polymer 0.2 0.2
Glycosyl ceramide * 3 0.1 0.1
P-Hydroxybenzoate 0.2 0.2
First hydroxyl valerolactone 0.5 0.5
Edetate 0.02 0.02
Potassium hydroxide 0.05 0.05
Purified Water residual content residual content
* 2; The silicone system Tospearl of GE Toshiba
* 3: the biological ceramide of the civilian food chemistry system of recording
Embodiment 38,39 (lipophilicity creme)
Adopt common method modulation lipophilicity creme according to following prescription.
Material composition use level (quality %)
Embodiment 38 39
The compound 0.1 of general formula (17)-
The compound of general formula (15) (Production Example 12)-0.1
Be total to modified silicone * 422
Polyoxyethylene modified silicone dispersion liquid * 5-2
Three decanes 22
Decamethylcyclopentasiloxane 15 20
Methyl polysiloxane 52
Long-chain branched chain fatty acid cholesteryl ester * 611
Silicone elastomer dispersion liquid * 752
Cork tree extract 11
Radix Glycyrrhizae extract 0.1 0.1
Chlorophillins 0.02 0.02
Sodium-chlor 11
Dipropylene glycol 55
Concentrated glycerin 55
Raffinose 11
P-Hydroxybenzoate 0.3 0.3
N-methyl-L-Serine 0.5 0.5
Purified Water residual content residual content
* 4; Goldschmidt system ABIL EM90
* 5:Toray Dow Corning silicone makes siliconeBY22-008
* 6; Japan refines and makes YOFCO CLE-NH
* 7; Toray Dow Corning silicone makes Trefil
Embodiment 40,41 (sunscreen)
Adopt common method modulation sunscreen according to following prescription.
Material composition use level (quality %)
Embodiment 40 41
The compound 0.1 of general formula (17)-
The compound of general formula (14) (Production Example 11)-0.1
Dioctyl ether 10 10
Be total to modified silicone * 422
Three 2 ethyl hexanoic acid glyceryl ester 55
Solidified oil 0.1 0.1
Methyl phenyl silicone 33
Macadamia fatty acid phytosterin 11
(phytosteryl) ester
P-methoxycinnamic acid 2-ethylhexyl-7
Titanium oxide 55
Zinc oxide 55
Cork tree extract 11
Magnesium chloride 11
1,3 butylene glycol 55
Phenoxyethyl alcohol 0.3 0.3
Rose of Sharon extract 11
Aloe extract 0.1 0.1
Yeast extract * 811
Purified Water residual content residual content
* 4; Goldschmidt system ABIL EM90
* 8:PentaFarm makes Dismutin
Embodiment 42 (astringent)
Ethanol 10
Polyoxyethylene (60) solidifies Viscotrol C 1
1,3 butylene glycol 2
Polyethylene glycol 1500 1
Phosphoric acid salt is an amount of
Edetate is an amount of
The P-hydroxybenzoic acid methyl ester is an amount of
The compound of general formula (15) (Production Example 12) 0.1
Antioxidant is an amount of
The Purified Water residual content
Stearic acid 11
Stearin 22
Hexadecanol 11
Cholesterol 0.5 0.5
Vaseline 22
Three decanes 55
Whiteruss 55
Silicone oil 11
Acyl glutamate 11
Xanthane gum 0.5 0.5
Glycerine 22
Dipropylene glycol 33
The compound 0.1 of general formula (17)-
The compound of general formula (15) (Production Example 12)-0.1
The P-hydroxybenzoic acid butyl ester is an amount of
Antioxidant is an amount of
Purified Water residual content residual content
Embodiment 45,46 (creme)
Embodiment 45 embodiment 46
Stearic acid 22
Stearin 22
Hexadecanol 33
Cholesterol 0.5 0.5
Vaseline 22
Three decanes 55
Whiteruss 10 10
Silicone oil 11
Acyl glutamate 11
Xanthane gum 0.5 0.5
Glycerine 55
Dipropylene glycol 33
The compound of general formula (13) (Production Example 10) 0.1-
The compound of general formula (15) (Production Example 12)-0.1
The P-hydroxybenzoic acid butyl ester is an amount of
Antioxidant is an amount of
Purified Water residual content residual content
Embodiment 47,48 (sunscreen)
Embodiment 47 embodiment 48
Ethanol 10 10
Octyl methoxycinnamate 77
POE/POP modification dimethyl polysiloxane 22
Titanium oxide microparticle 55
Zinc oxide 55
Ring-type silicone 10 10
Dimethyl polysiloxane (6cs) 10 10
The compound of general formula (13) (Production Example 10) 0.1-
The compound of general formula (15) (Production Example 12)-0.1
Antioxidant is an amount of
Purified Water residual content residual content
Industrial utilizability
By above record as can be known, the present invention can provide and can urge to generate agent by hyaluronic acid easy and that easily synthesize, epidermis. In addition, can realize anti-aging (the tension force fire elasticity of skin, moist the keeping) of skin by the present invention.
Claims (13)
1, a kind of N-acetyl-glucosamine derivative is characterized in that, with following general formula (1) expression, general formula (1)
Wherein: R
1Be that carbonatoms is 2～18 alkyl, R
2, R
3Be hydrogen atom, R
4Be that hydrogen atom or carbonatoms are 2～18 acyl group; Perhaps R
1Be-CH
2CH=C (CH
3) CH
2CH
2CH=C (CH
3)
2, R
2, R
3, R
4Be hydrogen atom or simultaneously simultaneously for ethanoyl; And 1 D structure is among α or the β any.
2, N-acetyl-glucosamine derivative according to claim 1 is characterized in that, described general formula (1) is with following general formula (4) expression,
General formula (4)
3, N-acetyl-glucosamine derivative according to claim 1 is characterized in that, described general formula (1) is with following general formula (6) expression,
General formula (6)
4, N-acetyl-glucosamine derivative according to claim 1 is characterized in that, described general formula (1) is with following general formula (7) expression,
General formula (7)
5, N-acetyl-glucosamine derivative according to claim 1 is characterized in that, described general formula (1) is with following general formula (8) expression,
General formula (8)
6, N-acetyl-glucosamine derivative according to claim 1 is characterized in that, described general formula (1) is with following general formula (9) expression,
General formula (9)
7, N-acetyl-glucosamine derivative according to claim 1 is characterized in that, described general formula (1) is with following general formula (11) expression,
General formula (11)
8, N-acetyl-glucosamine derivative according to claim 1 is characterized in that, described general formula (1) is with following general formula (15) expression,
General formula (15)
9, a kind of external composition for skin is characterized in that, with any one described N-acetyl-glucosamine derivative in the claim 1～8 as effective constituent.
10, external composition for skin according to claim 9 is characterized in that, described N-acetyl-glucosamine derivative content is 0.01～3.0 quality %.
11, external composition for skin according to claim 9 is characterized in that, described N-acetyl-glucosamine derivative content is 0.01～1.0 quality %.
12., it is characterized in that also containing more than one materials of selecting from N-methyl-L-Serine, yeast extract, an edge silk agaric extract, black pine mushroom extract, not golden extract, terra japonica extract, Flos Caryophylli extract, Diisopropylamine dichloro acetic acid, nicotinic acid, mevalonic acid, thermal water, water glass, fruit extract, beta-hydroxy-gamma-aminobutyric acid according to any one described external composition for skin in the claim 9～11.
13. be used as the external composition for skin that resisting age of skin is used according to any one described external composition for skin in the claim 9～11.
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP295733/2002 | 2002-10-09 | ||
| JP2002295733 | 2002-10-09 | ||
| JP9365/2003 | 2003-01-17 | ||
| JP79595/2003 | 2003-03-24 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2007101823114A Division CN101177438B (en) | 2002-10-09 | 2003-07-25 | N-acetylglucosamine derivatives and use thereof |
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| CN1688595A CN1688595A (en) | 2005-10-26 |
| CN100358911C true CN100358911C (en) | 2008-01-02 |
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| CN2007101823114A Expired - Fee Related CN101177438B (en) | 2002-10-09 | 2003-07-25 | N-acetylglucosamine derivatives and use thereof |
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|---|---|---|---|---|
| KR101831756B1 (en) * | 2010-09-16 | 2018-02-26 | (주)아모레퍼시픽 | Cosmetic composition for improving wrinkles and the patch for the skin around eyes using the same |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6236306A (en) * | 1985-08-12 | 1987-02-17 | Taiyo Kagaku Kk | Skin-beautifying cosmetic |
| JPH02243611A (en) * | 1989-03-16 | 1990-09-27 | Kobayashi Kose Co Ltd | Cosmetic |
| JPH08143588A (en) * | 1994-11-24 | 1996-06-04 | Kose Corp | Glucosamine derivative and cosmetic containing the same |
| US5696246A (en) * | 1995-05-16 | 1997-12-09 | Hoechst Aktiengesellschaft | Process for the specific synthesis of β-glycosidically linked N-acetylpyranoside derivatives |
| JP2001002551A (en) * | 1999-06-18 | 2001-01-09 | Kanebo Ltd | Agent for increasing hyaluronic acid content of horny layer |
| CN1283413A (en) * | 1999-08-09 | 2001-02-14 | 烧津水产化学工业株式会社 | Skin-care agent, health and face-care foodstuff |
-
2003
- 2003-07-25 CN CNB038240866A patent/CN100358911C/en not_active Expired - Fee Related
- 2003-07-25 CN CN2007101823114A patent/CN101177438B/en not_active Expired - Fee Related
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6236306A (en) * | 1985-08-12 | 1987-02-17 | Taiyo Kagaku Kk | Skin-beautifying cosmetic |
| JPH02243611A (en) * | 1989-03-16 | 1990-09-27 | Kobayashi Kose Co Ltd | Cosmetic |
| JPH08143588A (en) * | 1994-11-24 | 1996-06-04 | Kose Corp | Glucosamine derivative and cosmetic containing the same |
| US5696246A (en) * | 1995-05-16 | 1997-12-09 | Hoechst Aktiengesellschaft | Process for the specific synthesis of β-glycosidically linked N-acetylpyranoside derivatives |
| JP2001002551A (en) * | 1999-06-18 | 2001-01-09 | Kanebo Ltd | Agent for increasing hyaluronic acid content of horny layer |
| CN1283413A (en) * | 1999-08-09 | 2001-02-14 | 烧津水产化学工业株式会社 | Skin-care agent, health and face-care foodstuff |
Non-Patent Citations (2)
| Title |
|---|
| "Enzymatic procedure catalysed by lipase from Candidaantarctica for the regioprotection-deprotection ofglucosamine". Giovanni Nicolosi et al.Tetrahedron: Asymmetry,No.10. 1999 * |
| "The Asymmetric Dihydroxylation of Some Alkenyl2-Acetylamino-2-deoxy-β-D-glucopyranosides:thePreparation of Optically Pure Epoxides as Putative Inhibitorsof Chitinases". Jon k. Fairweather et al.Aust J. Chem,Vol.51 No.6. 1998 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101177438A (en) | 2008-05-14 |
| CN101177438B (en) | 2012-05-23 |
| CN1688595A (en) | 2005-10-26 |
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