WO2019078185A1 - 2,2,6-トリメチルシクロヘキサンカルボン酸誘導体を含有する冷感剤組成物 - Google Patents
2,2,6-トリメチルシクロヘキサンカルボン酸誘導体を含有する冷感剤組成物 Download PDFInfo
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- WO2019078185A1 WO2019078185A1 PCT/JP2018/038425 JP2018038425W WO2019078185A1 WO 2019078185 A1 WO2019078185 A1 WO 2019078185A1 JP 2018038425 W JP2018038425 W JP 2018038425W WO 2019078185 A1 WO2019078185 A1 WO 2019078185A1
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- Prior art keywords
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- vanillyl
- ether
- care products
- ethyl
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- 0 C**C(C1C(C)(C)CCCC1C)=O Chemical compound C**C(C1C(C)(C)CCCC1C)=O 0.000 description 4
- JUUFWGPNYSHIAN-UHFFFAOYSA-N CC(CCCC1(C)C)C1C(NC(Cc1ccccc1)CO)=O Chemical compound CC(CCCC1(C)C)C1C(NC(Cc1ccccc1)CO)=O JUUFWGPNYSHIAN-UHFFFAOYSA-N 0.000 description 1
- XJXRIZKIFOGUHD-UHFFFAOYSA-N CC(CCCC1(C)C)C1C(NCC(c1cccc(O)c1)O)=O Chemical compound CC(CCCC1(C)C)C1C(NCC(c1cccc(O)c1)O)=O XJXRIZKIFOGUHD-UHFFFAOYSA-N 0.000 description 1
- RPRNSZAYSVEIRY-UHFFFAOYSA-N CC(CCCC1(C)C)C1C(NCC(c1ccccc1)O)=O Chemical compound CC(CCCC1(C)C)C1C(NCC(c1ccccc1)O)=O RPRNSZAYSVEIRY-UHFFFAOYSA-N 0.000 description 1
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- BEICMBYBCFEOBI-UHFFFAOYSA-N CC(CCCC1(C)C)C1C(NCCc1ccccc1)=O Chemical compound CC(CCCC1(C)C)C1C(NCCc1ccccc1)=O BEICMBYBCFEOBI-UHFFFAOYSA-N 0.000 description 1
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- RPRNSZAYSVEIRY-OGVSOVDVSA-N CC(CCCC1(C)C)C1C(NC[C@H](c1ccccc1)O)=O Chemical compound CC(CCCC1(C)C)C1C(NC[C@H](c1ccccc1)O)=O RPRNSZAYSVEIRY-OGVSOVDVSA-N 0.000 description 1
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- ADEXCXWWURBXKL-UHFFFAOYSA-N CC(CCCC1(C)C)C1C(Nc(cc1)ccc1F)=O Chemical compound CC(CCCC1(C)C)C1C(Nc(cc1)ccc1F)=O ADEXCXWWURBXKL-UHFFFAOYSA-N 0.000 description 1
- QLLJBZRWGCRUHK-UHFFFAOYSA-N CC(CCCC1(C)C)C1C(Nc(cc1)ccc1O)=O Chemical compound CC(CCCC1(C)C)C1C(Nc(cc1)ccc1O)=O QLLJBZRWGCRUHK-UHFFFAOYSA-N 0.000 description 1
- LHTXEAOPMRROAE-UHFFFAOYSA-N CC(CCCC1(C)C)C1C(Nc(cc1)ccc1OC)=O Chemical compound CC(CCCC1(C)C)C1C(Nc(cc1)ccc1OC)=O LHTXEAOPMRROAE-UHFFFAOYSA-N 0.000 description 1
- JMGGXBKNHKPVHU-UHFFFAOYSA-N CC(CCCC1(C)C)C1C(Nc(cc1CC2)ccc1C2=O)=O Chemical compound CC(CCCC1(C)C)C1C(Nc(cc1CC2)ccc1C2=O)=O JMGGXBKNHKPVHU-UHFFFAOYSA-N 0.000 description 1
- ZQVLWNQBFANPMJ-UHFFFAOYSA-N CC(CCCC1(C)C)C1C(Nc1ccc(CO)cc1)=O Chemical compound CC(CCCC1(C)C)C1C(Nc1ccc(CO)cc1)=O ZQVLWNQBFANPMJ-UHFFFAOYSA-N 0.000 description 1
- BBYBAXBBMWSGRU-UHFFFAOYSA-N CC(c(cc1)ccc1NCC1(C(C)(C)CCCC1C)C=O)O Chemical compound CC(c(cc1)ccc1NCC1(C(C)(C)CCCC1C)C=O)O BBYBAXBBMWSGRU-UHFFFAOYSA-N 0.000 description 1
- PEVHFOLBHOAIST-KPMSDPLLSA-N CCCCCC(C)[C@@H](CC)C(NCc(cc1)ccc1OC)=O Chemical compound CCCCCC(C)[C@@H](CC)C(NCc(cc1)ccc1OC)=O PEVHFOLBHOAIST-KPMSDPLLSA-N 0.000 description 1
- SASNBVQSOZSTPD-UHFFFAOYSA-N CNCCc1ccccc1 Chemical compound CNCCc1ccccc1 SASNBVQSOZSTPD-UHFFFAOYSA-N 0.000 description 1
- AJJUWXPSCKVXOT-PIVQAISJSA-N C[C@@H](CCCC1(C)C)C1C(NCCc(cc1OC)ccc1OC)=O Chemical compound C[C@@H](CCCC1(C)C)C1C(NCCc(cc1OC)ccc1OC)=O AJJUWXPSCKVXOT-PIVQAISJSA-N 0.000 description 1
- MPLGIGIOVUTMJA-IENPIDJESA-N C[C@@H](CCCC1(C)C)C1C=O Chemical compound C[C@@H](CCCC1(C)C)C1C=O MPLGIGIOVUTMJA-IENPIDJESA-N 0.000 description 1
- UJOQZRKKQQRFMJ-TZMCWYRMSA-N C[C@H](CCCC1(C)C)[C@@H]1C(NCCc1ccc[s]1)=O Chemical compound C[C@H](CCCC1(C)C)[C@@H]1C(NCCc1ccc[s]1)=O UJOQZRKKQQRFMJ-TZMCWYRMSA-N 0.000 description 1
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- C07D317/08—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3
- C07D317/44—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 ortho- or peri-condensed with carbocyclic rings or ring systems
- C07D317/46—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 ortho- or peri-condensed with carbocyclic rings or ring systems condensed with one six-membered ring
- C07D317/48—Methylenedioxybenzenes or hydrogenated methylenedioxybenzenes, unsubstituted on the hetero ring
- C07D317/62—Methylenedioxybenzenes or hydrogenated methylenedioxybenzenes, unsubstituted on the hetero ring with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to atoms of the carbocyclic ring
- C07D317/66—Nitrogen atoms not forming part of a nitro radical
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D333/00—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom
- C07D333/02—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings
- C07D333/04—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom
- C07D333/06—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to the ring carbon atoms
- C07D333/14—Radicals substituted by singly bound hetero atoms other than halogen
- C07D333/20—Radicals substituted by singly bound hetero atoms other than halogen by nitrogen atoms
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/20—Organic compounds containing oxygen
- C11D3/2075—Carboxylic acids-salts thereof
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/20—Organic compounds containing oxygen
- C11D3/2093—Esters; Carbonates
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/26—Organic compounds containing nitrogen
- C11D3/32—Amides; Substituted amides
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/34—Organic compounds containing sulfur
- C11D3/3409—Alkyl -, alkenyl -, cycloalkyl - or terpene sulfates or sulfonates
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/34—Organic compounds containing sulfur
- C11D3/3427—Organic compounds containing sulfur containing thiol, mercapto or sulfide groups, e.g. thioethers or mercaptales
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/50—Perfumes
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
- D06M13/005—Compositions containing perfumes; Compositions containing deodorants
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
- D06M13/10—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing oxygen
- D06M13/224—Esters of carboxylic acids; Esters of carbonic acid
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
- D06M13/244—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing sulfur or phosphorus
- D06M13/248—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing sulfur or phosphorus with compounds containing sulfur
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
- D06M13/322—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing nitrogen
- D06M13/402—Amides imides, sulfamic acids
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K2800/00—Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
- A61K2800/20—Chemical, physico-chemical or functional or structural properties of the composition as a whole
- A61K2800/24—Thermal properties
- A61K2800/244—Endothermic; Cooling; Cooling sensation
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K2800/00—Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
- A61K2800/80—Process related aspects concerning the preparation of the cosmetic composition or the storage or application thereof
- A61K2800/92—Oral administration
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
- C07B2200/00—Indexing scheme relating to specific properties of organic compounds
- C07B2200/07—Optical isomers
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2601/00—Systems containing only non-condensed rings
- C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
- C07C2601/14—The ring being saturated
Definitions
- the present invention relates to a cooling agent composition containing a novel 2,2,6-trimethylcyclohexanecarboxylic acid derivative. Furthermore, the present invention relates to a organoleptic composition containing the cooling agent composition, a perfume composition containing the organoleptic composition, the organoleptic composition or a product containing the perfume composition, The invention relates to a process for the preparation of such products and to novel 2,2,6-trimethylcyclohexanecarboxylic acid derivatives.
- a cooling agent that gives a refreshing sensation (cool sensation) or a cold sensation (cool sensation) to human skin, mouth, nose, and throat, that is, a cooling sensation effect
- a toothpaste eg, chewing gum, candy Etc.
- l-menthol (El-menthol) is widely used at present as a fragrant substance that gives a feeling of coolness or coolness, its coolness effect lacks sustainability, and if the amount used is increased, the coolness effect is obtained. Although enhanced, it has the disadvantage that it may be accompanied by different stimuli such as bitterness. Furthermore, l-menthol has a problem that it has a characteristic strong minty odor and high volatility.
- N-monosubstituted non-cyclic carboxamides represented by N, 2,3-trimethyl-2-isopropylbutanamide see, for example, Patent Document 21
- icillin analogs see, for example, Patent Document 22
- N-phenyl-N-pyridinyl benzamide and benzene sulfonamide see, for example, Patent Document 23
- aryl carboxamides see, for example, Patent Document 24 and Patent Document 25
- aromatic ring compound group for example, Patent Document 26) Reference
- ⁇ -keto enamine derivatives see, for example, Patent Document 27
- N, 2,2,6-tetramethylcyclohexanecarboxamide is mentioned as a compound having a cooling effect.
- the above-mentioned conventional compounds having a cooling sensation effect have their own cooling sensation effect, but are still not sufficiently satisfactory in terms of the durability of the cooling sensation effect and the like.
- the main commercially available cooling agents including N-substituted-p-menthane-carboxamides commercially known as “WS series” are derivatives of l-menthol Because of this, the synthesis process is complicated in multiple steps. Thus, it is expensive to produce on an industrial scale, and many of these compounds are relatively expensive components.
- the object of the present invention is to use as a cooling agent or a sensory stimulant having less unpleasant sensation and having a sustained coolness or coolness, and having a carbon skeleton structurally different from l-menthol It is an object of the present invention to provide a cooling agent composition comprising a novel 2,2,6-trimethylcyclohexanecarboxylic acid derivative which is a novel compound having as a mother nucleus and which can be synthesized very easily and at low cost from inexpensive raw materials. .
- Another object of the present invention is to provide a sensory stimulant composition containing the cooling agent composition. Furthermore, the present invention provides a perfume composition containing the organoleptic composition, the organoleptic composition or a product containing the perfume composition, a method of producing the product, and a novel 2,2,6-trimethyl compound. It is also an object to provide cyclohexane carboxylic acid derivatives.
- the symbol * represents an asymmetric carbon atom
- X is NH, N (ZAr 2 ), O or S
- Z is a single bond or an alkylene group of 1 to 3 carbon atoms which may have a substituent
- Ar 2 is a substituent
- Y is each independently a methylene group which may have a substituent
- n is an integer of 0 to 3
- Ar 1 is an aryl group having 6 to 20 carbon atoms which may have a substituent or an aromatic heterocyclic group having 2 to 15 carbon atoms which may have a substituent.
- the cooling agent composition according to any one of [1] to [7], which further contains at least one cooling agent other than the 2,2,6-trimethylcyclohexanecarboxylic acid derivative.
- the cold sensation substance is Menthol, Menthon, Camphor, Pregol, Isopregol, Cineole, Cubenol, Menthyl Acetate, Pregyl Acetate, Isopregyl Acetate, Menthyl Salicylate, Pregyl Salicylate, Isoprigyl Salicylate, 3- (l-Mentoxy) propane-1,2-diol, 2-Methyl -3- (l-menthoxy) propane-1,2-diol, 2- (l-menthoxy) ethane-1-ol, 3- (l-menthoxy) propan-1-ol, 4- (l-menthoxy) butane -1-ol, menthyl 3-hydroxybutanoate, menthyl glyoxylate, p-menthane-3
- the warming substance is Vanillyl methyl ether, vanillyl ethyl ether, vanillyl propyl ether, vanillyl isopropyl ether, vanillyl butyl ether, vanillyl amyl ether, vanillyl isoamyl ether, vanillyl hexyl ether, isovanillyl methyl ether, isovanillyl ethyl ether , Isovanillyl propyl ether, isovanillyl isopropyl ether, isovanillyl butyl ether, isovanillyl amyl ether, isovanillyl isoamyl ether, isovanillyl hexyl ether, ethyl vanillyl methyl ether, ethyl vanillyl ether, ethyl vanillyl Prop
- the present invention can be used as a cooling agent or a sensory stimulant having less unpleasant sensation and having a long lasting feeling of coolness or coolness, and has a carbon skeleton structurally different from l-menthol. It is possible to provide a cooling agent composition containing the core novel 2,2,6-trimethylcyclohexanecarboxylic acid derivative. By blending the cooling agent composition of the present invention into various products, it is possible to impart to these products a refreshing feeling or a cooling feeling excellent in durability.
- the 2,2,6-trimethylcyclohexanecarboxylic acid derivative is a novel compound having a carbon skeleton which is structurally different from l-menthol as a mother nucleus, and using inexpensive citronellal as a raw material, it is very easy and inexpensive. It is possible to synthesize.
- the scent composition of the fragrance composition is enhanced and the residual odor is enhanced, and the fragrance composition is perfumed.
- the product is also given a high aroma quality improvement effect.
- the 2,2,6-trimethylcyclohexanecarboxylic acid derivative exhibits an excellent property of hardly causing an unpleasant skin irritation to the human body.
- the cooling agent composition according to the present invention is characterized by containing a novel 2,2,6-trimethylcyclohexanecarboxylic acid derivative represented by the following general formula (1) as a cooling agent.
- the symbol * represents an asymmetric carbon atom
- X is NH, N (ZAr 2 ), O or S
- Z is a carbon optionally having a single bond or a substituent
- Ar 2 is an alkylene group of 1 to 3 and Ar 2 is an aryl group of 6 to 20 carbon atoms which may have a substituent or an aromatic complex of 2 to 15 carbon atoms which may have a substituent
- Y each independently represents a methylene group which may have a substituent
- n is an integer of 0 to 3
- Ar 1 may have a substituent It is an aryl group having 6 to 20 carbon atoms or an aromatic heterocyclic group having 2 to 15 carbon atoms which may have a substituent.
- the 2,2,6-trimethylcyclohexanecarboxylic acid derivative represented by the general formula (1) has a cyclohexane ring structure, and has asymmetric carbons at the 1- and 6-positions as shown in the following formula.
- n, X, Y and Ar 1 are as defined above.
- the 2,2,6-trimethylcyclohexanecarboxylic acid derivative represented by the general formula (1) is preferably a trans form, particularly preferably a (1R, 6S) -form (1-a).
- X is NH, N (ZAr 2 ), O or S.
- X is preferably NH or N (ZAr 2 ) from the viewpoint of cooling sensation strength.
- Z is a single bond or an alkylene group having 1 to 3 carbon atoms which may have a substituent.
- alkylene group having 1 to 3 carbon atoms which may have a substituent include a methylene group, an ethylene group and a propylene group.
- Z is preferably a single bond or an ethylene group which may have a substituent, and more preferably an ethylene group which may have a substituent, from the viewpoint of cooling strength. .
- Y is each independently a methylene group which may have a substituent, and n is an integer of 0 to 3. Among these, n is preferably 0 or 2 and more preferably 2 from the viewpoint of the cooling sensation strength.
- Ar 1 and Ar 2 are each independently an aryl group having 6 to 20 carbon atoms which may have a substituent or an aromatic heterocyclic group having 2 to 15 carbon atoms which may have a substituent It is.
- the aryl group having 6 to 20 carbon atoms which may have a substituent include, for example, an aromatic monocyclic group having 6 to 20 carbon atoms, an aromatic polycyclic group, or an aromatic fused ring group. It can be mentioned. Specifically, a phenyl group, a naphthyl group, an anthryl group, a phenanthryl group, an indenyl group etc. are mentioned, A phenyl group is mentioned as a preferable specific example.
- the aromatic heterocyclic group having 2 to 15 carbon atoms which may have a substituent is, for example, 5 to 20 carbon atoms, which contains at least one, preferably 1 to 3 different elements.
- Examples thereof include 8-membered rings, preferably 5- or 6-membered aromatic heterocyclic (heteroaryl) groups such as monocyclic, polycyclic or fused cyclic.
- Examples of the hetero atom include hetero elements such as nitrogen atom, oxygen atom and sulfur atom.
- aromatic heterocyclic group having 2 to 15 carbon atoms which may have a substituent are, for example, furyl group, thienyl group, pyridyl group, pyrinidyl group, pyrazinyl group, pyradazinyl group, tetrazinyl group, imidazoyl group.
- oxazoyl group, thiazolyl group, benzofuryl group, benzothienyl group, quinolyl group, isoquinolyl group, quinoxanoyl group, phthalazinyl group, quinazolinyl group, naphthyldinyl group, cinnolinyl group, benzoimidazolin group, benzoxazolyl group, benzothiazolyl group, indolyl A group etc. are mentioned and a thienyl group is mentioned as a preferable specific example.
- Examples of the substituent which the above-mentioned alkylene group of 1 to 3 carbon atoms, aryl group of 6 to 20 carbon atoms and aromatic heterocyclic group of 2 to 15 carbon atoms may have are, for example, methyl group, ethyl group Alkyl groups having 1 to 6 carbon atoms such as n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, pentyl and hexyl; cyclopentyl, cyclohexyl and cyclopropyl Cycloalkyl group having 5 to 8 carbon atoms such as heptyl group; hydroxy group; hydroxymethyl group, hydroxyethyl group, 2-hydroxyethyl group, 1-hydroxypropyl group, 2-hydroxypropyl group and 1-hydroxybutyl group C 1-4 hydroxyalkyl group; methoxy group, ethoxy group, n-propoxy group, isoprop
- the 2,2,6-trimethylcyclohexanecarboxylic acid derivative represented by the general formula (1) is synthesized, for example, by the method represented by the following scheme 1 to scheme 6.
- the synthesis method of the carboxylic acid derivative is not limited to the methods of the following schemes 1 to 6.
- a solid line and a dotted double line are a double bond or a single bond, and when a solid line and a dotted double line are a single bond, Z 1 is a hydroxy group or a methoxy group.
- Ac is an acetyl group, and the symbol * is as defined above.
- the step [A], the step [B] and the step [C] can be carried out by the method described in Patent Document 29. That is, the step [A] can be performed by an enol acetylation reaction, the step [B] can be performed by a cyclization reaction with an acid catalyst, and the step [C] can be performed by an oxidation reaction.
- process [D], process [E], process [F], and process [G] can be performed with the method of patent document 30. That is, step [D] can be performed by Grignard reaction, step [E] can be performed by oxidation reaction, step [F] can be performed by enol acetylation reaction, and step [G] is an acid catalyst It can be carried out by a cyclization reaction.
- step [H] can be synthesized by the method described in Patent Document 31. That is, the step [H] can be carried out by nitric acid oxidation.
- secondary amide compound (10 ) May be synthesized from carboxylic acid compound (5), for example, according to the method shown in Scheme 2 below.
- the secondary amide compound (10) can also be synthesized from the carboxylic acid compound (5), for example, according to the method shown in Scheme 3 below.
- Step [J] can be carried out by mesylation of the carboxylic acid compound (5) to convert it into an active acyl intermediate, and then reacting with an amine.
- X ' represents a chlorine atom, a bromine atom or an iodine atom, * mark, n, Y, Z, Ar 1 and Ar 2 are as defined above.
- Step [K] can be performed by the same method as the method described in Non-Patent Document 2.
- Process [I] and process [J] can be performed by the above-mentioned method.
- ester compound (13) Is sometimes synthesized from carboxylic acid compound (5), for example, according to the method shown in the following scheme 5.
- Step [L] can be performed by the same method as the method described in Patent Document 29.
- thioester compound (14) May be synthesized from carboxylic acid compound (5), for example, according to the method shown in Scheme 6 below.
- Step [M] can be performed by the same method as the method described in Non-Patent Document 5. That is, the step [M] can be carried out by a condensation reaction.
- Preferred specific examples of the 2,2,6-trimethylcyclohexanecarboxylic acid derivative represented by the general formula (1) include a secondary amide compound (10), a tertiary amide compound (11), an ester compound (13) and a thioester
- a compound (14) is mentioned, it is not limited to these.
- the following compounds are mentioned as a preferable specific example of a secondary amide compound (10), It is not limited to these.
- Me represents a methyl group and * represents an asymmetric carbon.
- Preferred specific examples of the thioester compound (14) include, but are not limited to, the following compounds.
- Me represents a methyl group and * represents an asymmetric carbon.
- 2,2,6-trimethylcyclohexanecarboxylic acid derivative represented by the general formula (1) is a 2,2,6-trimethyl represented by the following general formula (1-1) from the viewpoint of the cooling sensation strength.
- Preferred are cyclohexanecarboxylic acid derivatives.
- * represents an asymmetric carbon atom
- R, R ′ and R ′ ′ each independently represent a hydrogen atom, a hydroxy group or a methoxy group. It is preferable that R, R ′ and R ′ ′ each independently represent a hydrogen atom or a hydroxy group from the viewpoint of the cooling sensation strength.
- the 2,2,6-trimethylcyclohexanecarboxylic acid derivative represented by the general formula (1) thus obtained has a strong and persistent cooling effect and can be used alone as a cooling agent or sensation. It can also be used as a stimulant.
- the 2,2,6-trimethylcyclohexanecarboxylic acid derivative represented by the general formula (1) can also be contained in various products.
- the application range and application method need to be changed appropriately according to the type of product, purpose of use, etc., but the carboxylic acid derivative is usually 0.00001 to 50% by mass, preferably the entire composition of the product. Is used at a concentration of 0.0001 to 20% by weight, particularly preferably 0.001 to 5% by weight.
- the content of the 2,2,6-trimethylcyclohexanecarboxylic acid derivative represented by the general formula (1) in the cooling agent composition of the present invention needs to be suitably changed according to the purpose of use of the cooling agent composition, etc. However, it is usually 0.00001 to 50% by mass, preferably 0.0001 to 20% by mass, and particularly preferably 0.001 to 5% by mass.
- the cooling agent composition of the present invention further comprises a cooling sensation strength by further containing at least one cooling sensation substance other than the 2,2,6-trimethylcyclohexanecarboxylic acid derivative represented by the general formula (1). It can be an enhanced cooling agent composition. Furthermore, it is possible to prepare a organoleptic composition containing the cooling agent composition, which has increased cooling sensation strength.
- Examples of the cooling substance other than the 2,2,6-trimethylcyclohexanecarboxylic acid derivative represented by the general formula (1) include: Menthol, Menthon, Camphor, Pregol, Isopregol, Cineole, Cubenol, Menthyl Acetate, Pregyl Acetate, Isopregyl Acetate, Menthyl Salicylate, Pregyl Salicylate, Isoprigyl Salicylate, 3- (l-Mentoxy) propane-1,2-diol, 2-Methyl -3- (l-menthoxy) propane-1,2-diol, 2- (l-menthoxy) ethane-1-ol, 3- (l-menthoxy) propan-1-ol, 4- (l-menthoxy) butane -1-ol, menthyl 3-hydroxybutanoate, menthyl glyoxylate, p-menthane-3,8-diol, 1- (2-hydroxy-4-methylcyclohexyl)
- the cooling agent preferably includes at least one cooling agent selected from the group consisting of a compound ( ⁇ ), a sugar alcohol ( ⁇ ) and a natural product ( ⁇ ).
- the 2,2,6-trimethylcyclohexanecarboxylic acid derivative represented by the general formula (1) and the cooling agent other than the carboxylic acid derivative impair the effects of the present invention.
- the preferred use ratio of the carboxylic acid derivative and the cooling agent other than the carboxylic acid derivative is in the range of 1:99 to 90:10 by mass ratio.
- the cooling agent composition of the present invention is used for a spice composition, a beverage, a food, a cosmetic, a toiletry product, an air care product, a daily use / general goods, a composition for oral cavity, a hair care product, a skin care product, a body care product, clothing. It can be formulated into products such as detergents, fabric softeners, quasi drugs and pharmaceuticals.
- the cooling agent composition of the present invention has a strong and persistent cooling effect
- the sensory stimulation of the present invention having a cooling effect by containing the cooling agent composition
- An agent composition can be prepared.
- the amount is usually 0.00001 to 50% by mass, preferably 0.0001 to 20% by mass, and particularly preferably 0.001 to 4% by mass, based on the total composition of the agent composition.
- the organoleptic composition of the present invention is a composition that provides an effect of stimulating a sense.
- the effect of stimulating the sense includes a cold sensation effect and / or a warm sensation effect. Therefore, in the present invention, the sensory stimulant composition is used as a concept including a cooling agent composition and / or a warming agent composition.
- the stimulation effect of the sensory stimulation composition can be adjusted by further containing at least one kind of warming substance.
- the warming substance preferably includes at least one warming substance selected from the group consisting of a compound ( ⁇ ) and a natural product ( ⁇ ).
- the mixing ratio of the warming substance to the cooling agent composition should be such that the warming effect is not imparted by the blending of the warming substance. Just do it.
- the blending amount of the warming substance is usually 0.001 to 0.95 times, preferably 0.01 to 0.5 times the total mass of the cooling agent composition.
- the addition of the warming substance to the cooling agent composition in the above proportion can further improve the cooling effect.
- the blending ratio of the warming substance to the cooling agent composition may be in the range where the cooling effect is not imparted by the blending of the cooling agent composition.
- the blending amount of the cooling agent composition is usually 0.001 to 0.95 times, preferably 0.01 to 0.5 times the total mass of the warming substance.
- the fragrance composition of the present invention contains the organoleptic composition of the present invention.
- the perfume composition of the present invention can contain a perfume component.
- the flavor component include various types of synthetic flavors, natural essential oils, synthetic essential oils, citrus oils, animal flavors, etc.
- a wide variety of flavor components as described in Non-Patent Document 1 can be used. It can be used.
- the content of the sensory stimulant composition of the present invention can be adjusted according to the types of the spice and other components to be formulated together, the purpose of use of the spice composition, etc. It is preferably 0.00001 to 90% by mass, more preferably 0.0001 to 20% by mass, and still more preferably 0.001 to 4% by mass with respect to the total mass of
- the content of the organoleptic composition of the present invention is usually 0.00001 to 50% by mass, preferably 0. It is preferably 001 to 50% by mass, particularly preferably 0.01 to 20% by mass.
- the fragrance composition of the present invention is for beverages and foods
- the content of the organoleptic composition of the present invention is 0.0001 to 50% by mass with respect to the total mass of the fragrance composition. Preferably, it is 0.001 to 30% by mass.
- the perfume composition of the present invention may optionally contain other perfume retention agents commonly used in perfume compositions.
- perfume retention agents in that case, for example, ethylene glycol, propylene glycol, dipropylene glycol, glycerin, hexyl glycol, benzyl benzoate, triethyl citrate, diethyl phthalate, hercholine, medium-chain fatty acid triglyceride, medium-chain fatty acid diglyceride, etc. And one or more of these may be contained.
- the product of the present invention contains the organoleptic composition of the present invention or the fragrance composition of the present invention for the purpose of imparting a cold sensation or sensory irritation.
- the above products are not particularly limited, but, for example, beverages; food products; toiletry products such as detergents, kitchen detergents and bleaches; air care products such as deodorants and fragrances; oral compositions; fragrance products, basic cosmetics Hair care products such as finishing cosmetics, hair cosmetics, tanning cosmetics, medicated cosmetics, etc. Hair care products, skin care products such as soaps, body care products such as body cleansers, bath agents, detergents for clothes, softeners for clothes, aerosol agents Daily use, miscellaneous goods; quasi-drugs or medicines.
- beverage examples include beverages such as fruit juices, fruit wines, milk drinks, carbonated drinks, soft drinks, drinks and the like; green tea, oolong tea, black tea, persimmon leaf tea, chamomile tea, Kumazasa tea, persimmon tea, dokudami tea, Tea of Pouar tea, yerba mate, rooibos tea, gymnema tea, guava tea, coffee, tea beverages such as cocoa, cocoa or beverages; Japanese-style soup, Western-style soup, soups such as Chinese soup; Various instant beverages etc.
- beverages such as fruit juices, fruit wines, milk drinks, carbonated drinks, soft drinks, drinks and the like
- green tea oolong tea, black tea, persimmon leaf tea, chamomile tea, Kumazasa tea, persimmon tea, dokudami tea, Tea of Pouar tea, yerba mate, rooibos tea, gymnema tea, guava tea, coffee, tea beverages such as cocoa
- Examples of the food include ice creams, sorbets, frozen desserts such as ice lollies; desserts such as jellies and puddings; cakes, cookies, chocolates, chocolate confections such as chewing gum, and the like; Jams, candies, breads, flavored seasonings, various instant foods, various snack foods, etc.
- the composition for oral cavity includes toothpaste, mouthwash, mouthwash, troche, chewing gum and the like; As said fragrance products, perfume, eau de perfume, eau de toilette, eau de cologne, etc .; As said basic cosmetics, face-wash cream, burnishing cream, cleansing cream, cold cream, massage cream, milky lotion, lotion, essence, pack, makeup remover, etc .; As the finishing cosmetics, foundations, powder, solid powder, talcum powder, lipstick, lip balm, blusher, eyeliner, mascara, eye drop, ink, eye pack, nail enamel, enamel rim bar, etc .; Examples of the cosmetic for hair include pomade, brilliantin, set lotion, hair lotion, hair solid, hair oil, hair treatment, hair cream, hair tonic, hair liquid, hair spray, bandrin, hair restorer, hair dye, etc .; As said suntan cosmetics, a suntan product, a sunscreen product etc .; As the above-mentioned cosmeceuticals, antiperspirants, after shaving lotions and gels,
- the shape of the organoleptic composition or perfume composition is the same as that of the organoleptic composition or perfume composition itself. It can take shapes or other shapes.
- Liquids dissolved in alcohols polyhydric alcohols such as propylene glycol, glycerin, dipropylene glycol, etc., esters such as triethyl citrate, benzyl benzoate, diethyl phthalate; Emulsified state emulsified with an emulsifier such as glycerin fatty acid ester or sucrose fatty acid ester; Natural gums such as gum arabic and tragacanth gum, powdery coated with excipients such as gelatin and dextrin; Solubilised or dispersed solubilized or dispersed using a surfactant such as a nonionic surfactant, an anionic surfactant, a cationic surfactant, an amphoteric surfactant or the like; Microcapsules obtained by treatment with an encapsulating agent; An arbitrary shape is selected and used according to the purpose.
- a sensory stimulant composition Or perfume composition may be added or given directly to the product;
- the organoleptic composition or the flavor composition may be added or applied to a product by dissolving it in a polyhydric alcohol such as alcohols, propylene glycol, glycerin and the like, for example; Natural gums such as gum arabic and tragant gum, surfactants (for example, nonionic surfactants such as glycerin fatty acid ester and sucrose fatty acid ester, anionic surfactants, cationic surfactants, amphoteric surfactants, etc.) It may be added or imparted to the product in the form of solubil
- the addition amount or application amount of the sensory stimulant composition or the flavor composition to the product when cold sensation or sensory stimulation is applied is the kind or form of the product, the cooling sensation or sensory stimulation effect or action required for the product, etc. It can be adjusted accordingly.
- the addition amount or application amount of the sensory stimulant composition or the fragrance composition is preferably 0.00001 to 50% by mass from the viewpoint of the cooling sensation strength with respect to the mass of the product, and it is preferably 0.
- the content is more preferably 0001 to 20% by mass, and still more preferably 0.001 to 4% by mass.
- combination of a carboxylic acid compound (5) is as follows. l-Citronellal: 96.6% e. e. d-citronellal: 97.8% e. e.
- trans isomer hereinafter sometimes referred to as “(1R, 6S) -5”
- cis isomer hereinafter, referred to as “(1R, 6S) -5”
- optically active carboxylic acid compounds (5) synthesized according to the method described in Patent Document 29.
- the isomer ratio of “(1R, 6R) -5” may be mentioned, and the optical purity is as follows.
- Me represents a methyl group and Et represents an ethyl group.
- Methanesulfonyl chloride (0.55 mL, 1.2 eq.) Is slowly added dropwise at room temperature, and after stirring for 20 minutes at room temperature, phenethylamine (0.81 mL, 1.1 eq.) Is added, and 45 at room temperature. I was allowed to react for a minute. After diluting the reaction solution with ethyl acetate (15 mL), 2N hydrochloric acid (15 mL) was slowly added for workup. The oil layer was washed twice with saturated aqueous sodium bicarbonate solution (15 mL), further washed once with saturated brine (10 mL), and dried over sodium sulfate. The resulting solution was concentrated under reduced pressure, and recrystallized with heptane / ethyl acetate to give the title compound (1.08 g, yield 68%) as a white solid.
- Methanesulfonyl chloride (0.55 mL, 1.2 eq.) Is slowly added dropwise at room temperature, and after stirring for 5 hours at room temperature, phenacylamine hydrochloride (1.11 g, 1.1 eq.) And triethylamine (0 .98 mL, 1.2 eq.) was added and allowed to react at room temperature for 45 minutes. After diluting the reaction solution with ethyl acetate (15 mL), 2N hydrochloric acid (15 mL) was slowly added for workup. The oil layer was washed twice with saturated aqueous sodium bicarbonate solution (15 mL), further washed once with saturated brine (10 mL), and dried over sodium sulfate.
- Methanesulfonyl chloride (0.55 mL, 1.2 eq.) Is slowly added dropwise at room temperature, and after stirring for 5 hours at room temperature, phenacylamine hydrochloride (1.11 g, 1.1 eq.) And triethylamine (0 .98 mL, 1.2 eq.) was added and allowed to react at room temperature for 45 minutes. After diluting the reaction solution with ethyl acetate (15 mL), 2N hydrochloric acid (15 mL) was slowly added for workup. The oil layer was washed twice with saturated aqueous sodium bicarbonate solution (15 mL), further washed once with saturated brine (10 mL), and dried over sodium sulfate.
- dopamine hydrochloride (1.23 g, 1.10 eq.) was added and allowed to react at 50 ° C. for 1 hour. After diluting the reaction solution with ethyl acetate (15 mL), 2N hydrochloric acid (15 mL) was slowly added for workup. The oil layer was washed twice with saturated aqueous sodium bicarbonate solution (15 mL), further washed once with saturated brine (10 mL), and dried over sodium sulfate.
- Methanesulfonyl chloride (0.55 mL, 1.20 eq.) Is slowly added dropwise at room temperature, and after stirring for 25 minutes at room temperature, 2- (aminomethyl) thiophene (0.59 mL, 1.20 eq.) Is slowly added. And allowed to react at room temperature for one and a half hours. After diluting the reaction solution with ethyl acetate (10 mL), 2N hydrochloric acid (10 mL) was slowly added for workup. The oil layer was washed twice with saturated aqueous sodium bicarbonate solution (15 mL), further washed once with saturated brine (10 mL), and dried over sodium sulfate. The obtained solution was concentrated under reduced pressure, and recrystallized with hexane to give the title compound (1.14 g, yield 73%) as a pale yellow solid.
- Methanesulfonyl chloride (0.55 mL, 1.20 eq.) Is slowly added dropwise at room temperature, and after stirring for 15 minutes at room temperature, 2- (aminoethyl) thiophene (0.69 mL, 1.20 eq.) Is slowly added. And allowed to react at room temperature for 1 hour. After diluting the reaction solution with ethyl acetate (10 mL), 2N hydrochloric acid (15 mL) was slowly added for workup. The oil layer was washed twice with saturated aqueous sodium bicarbonate solution (15 mL), further washed once with saturated brine (10 mL), and dried over sodium sulfate. The resulting solution was concentrated under reduced pressure, and recrystallized with hexane to give the title compound (1.11 g, yield 67%) as a pale brown solid.
- reaction solution was transferred to a separatory funnel and washed by adding dilute hydrochloric acid and ethyl acetate.
- the oil layer was washed once with dilute hydrochloric acid, then once with saturated brine, and dried over anhydrous magnesium sulfate.
- the resulting solution was concentrated under reduced pressure, and recrystallized with heptane / ethyl acetate to give the title compound (1.07 g, yield 66%) as white crystals.
- reaction solution was transferred to a separatory funnel and washed by adding dilute hydrochloric acid and ethyl acetate.
- the oil layer was washed once with dilute hydrochloric acid, then once with saturated brine, and dried over anhydrous magnesium sulfate.
- the resulting solution was concentrated under reduced pressure, and recrystallized with heptane / ethyl acetate to give the title compound (1.13 g, yield 66%) as white crystals.
- Bispalladium dibenzylideneacetone (71 mg, 1 mol%), dicyclohexyl (1,1-diphenyl-1-propen-2-yl) phosphine ligand (97 mg, 4 mol%) and toluene (20 mL) under nitrogen atmosphere Add and stir at room temperature for 1 hour. Subsequently, phenethylamine (1.00 g, 7.80 mmol), bromoanisole (0.97 ml, 1.0 eq.) And sodium tert-butoxide (0.90 g, 1.2 eq.) Are added and the mixture is heated to 100 ° C. Heating and stirring were performed for 5 hours.
- reaction solution was cooled to room temperature, extracted and washed with ethyl acetate / water.
- the oil layer was dried over anhydrous magnesium sulfate, filtered and concentrated, and the obtained residue was isolated and purified by silica gel column chromatography to obtain the title compound (1.05 g, yield 59%) as a pale yellow oil.
- a fluorescent calcium indicator (Fluo4-AM: manufactured by Dojindo Laboratories) is added, incubated at 37 ° C. for 30 minutes, and transferred to a fluorescent microplate reader (FlexStation3: manufactured by Molecular Devices). did. It was added the compound and comparative compounds obtained in Examples in the range of 1000 ⁇ M from a final concentration of 0.1 [mu] M, and measuring the change in fluorescence wavelength 525nm when excited at a wavelength of 485nm at the temperature in the apparatus 32 ° C., EC 50 The value was calculated.
- the EC 50 values in TRPM8 activation activity of each compound obtained in the examples and the comparative compound are as shown in Tables 1 to 6 below.
- each of the compounds obtained in the examples has a TRPM8 activation activity much superior to that of N, 2,2,6-tetramethylcyclohexanecarboxamide shown in Table 6.
- the compounds obtained in these examples have a much stronger cooling effect than N, 2,2,6-tetramethylcyclohexanecarboxamide.
- each compound obtained in the Examples is compared with existing cooling agents such as l-menthol, WS-3, WS-5 and WS-23 shown in Table 6 Even if it shows the same or more strong cold sensation effect.
- Example 37 Preparation of 30 ppm aqueous solution of exemplified compound ((1R, 6S) -10-1) and 30 ppm aqueous solution of comparative compound (N, 2,2,6-tetramethylcyclohexanecarboxamide, l-menthol, WS-3, WS-5) And the evaluation was carried out using the aqueous solution. The evaluation was conducted by four flavorists. Each of the above aqueous solutions was put in the mouth, garnished and then exhaled, and the intensity of cold sensation in the oral cavity, the persistence of cold sensation, and the quality of cold sensation were evaluated.
- the exemplary compound ((1R, 6S) -10-1) had a very strong cold sensation strength and was clearly stronger than the comparative compound N, 2, 2, 6-tetramethylcyclohexanecarboxamide, l-menthol, WS-3. The cold sensation lasted for more than 30 minutes.
- the exemplary compound ((1R, 6S) -10-1) had a higher level of cooling sensation compared to WS-5, and the cooling sensation continued for 30 minutes or more. With regard to the quality of the cooling sensation, the exemplified compound ((1R, 6S) -10-1) had almost the same level of sensation as the WS-5.
- Toothpaste powder aromatizing evaluation Toothpaste powders (A) to (C) were prepared according to the following formulation.
- Two-Spaced Flavor BASE The prescription of Two-Spaced Flavor BASE is as follows.
- the toothpaste base formulation is as follows.
- toothpaste (B) and toothpaste (C) have a stronger cooling effect than toothpaste (A), and toothpaste (C) has a cooling sensation equal to or better than toothpaste (B). It was effective. Moreover, compared with toothpaste (B), toothpaste (C) exhibited the same flavor profile of Two-space flavor BASE, and almost no stimulation other than feeling of cold sensation. Both toothpaste (B) and toothpaste (C) felt a cold feeling of 30 minutes or more.
- Mouthwash liquid fragrance evaluation According to the following composition, mouthwash liquids (D) to (F) were prepared.
- the formulation of the mouthrinse liquid base is as follows.
- mouthwash (E) and mouthrinse (F) have a stronger cooling effect than mouthrinse (D), and mouthrinse (F) has mouthwash There was a cold feeling effect equal to or more than the liquid (E).
- the expression of the flavor profile of the mint of the mouthwash flavor BASE was equivalent to that of the mouthwash (E), and almost no stimulus other than a sensation of cold sensation was felt. Both the mouthrinse (E) and mouthrinse (F) felt a cold feeling of 30 minutes or more.
- Chewing gum flavor evaluation Chewing gums (G) to (I) were prepared according to the following formulation.
- (G) 990.0 g of chewing gum base + peppermint flavor BASE 6.3 g + l-menthol 0.7 g + ethyl alcohol (EtOH) 3.0 g
- (H) 990.0 g of chewing gum base + peppermint flavor BASE 6.3 g + l-menthol 0.7 g + comparative compound (WS-5) (1% by mass in EtOH) 3.0 g
- the formulation of peppermint flavor BASE is as follows.
- formulation of chewing gum base is as follows.
- chewing gum (H) and chewing gum (I) have a stronger cooling effect than chewing gum (G), and chewing gum (I) has a cooling sensation equal to or better than chewing gum (H). It was effective.
- chewing gum (I) was bitten, a somewhat sharp cold sensation was developed from the beginning of chewing, and a good cold sensation with a snout was spread in the oral cavity, and no miscellaneous taste or other irritation was felt.
- a cold feeling of 30 minutes or more was felt.
- Example 41 Candy aromatization evaluation Candy (J) to (L) of the following formulation were prepared according to the following production method.
- (J) candy base 998.0 g + herb flavor BASE 0.9 g + 1-menthol 0.8 g + ethyl alcohol (EtOH) 0.3 g
- (L) candy base 998.0 g + herb flavor BASE 0.9 g + 1-menthol 0.8 g + exemplified compound ((1R, 6S) -10-1) (10% by mass in EtOH) 0.3 g
- the prescription of herb flavor BASE is as follows.
- the formulation of the candy base is as follows.
- the candy (K) and the candy (L) have a cooling effect than the candy (J), and the candy (L) has a cooling effect equal to or more than the candy (K) was there.
- the candy (L) was licked, a sharp refreshing feeling was felt from the beginning of the licking, and after a while it became a refreshing feeling that stimulates the back of the throat, and miscellaneous tastes and other stimuli were not felt.
- a feeling of coolness of 30 minutes or more was felt.
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Abstract
Description
現在、冷感剤として商業化されている化合物の多くが、これらl-メントールの誘導体である。
さらに、本発明は、当該感覚刺激剤組成物を含有する香料組成物、当該感覚刺激剤組成物又は当該香料組成物を含有する製品、当該製品の製造方法、及び新規2,2,6-トリメチルシクロヘキサンカルボン酸誘導体を提供することも目的とする。
[1]下記一般式(1)で表される2,2,6-トリメチルシクロヘキサンカルボン酸誘導体を含有する冷感剤組成物。
Xは、NH、N(ZAr2)、O又はSであり、Zは、単結合又は置換基を有していてもよい炭素数1~3のアルキレン基であり、Ar2は、置換基を有していてもよい炭素数6~20のアリール基又は置換基を有していてもよい炭素数2~15の芳香族複素環基であり、
Yは、それぞれ独立して置換基を有していてもよいメチレン基であり、
nは、0~3の整数であり、
Ar1は、置換基を有していてもよい炭素数6~20のアリール基又は置換基を有していてもよい炭素数2~15の芳香族複素環基である。]
[2]前記2,2,6-トリメチルシクロヘキサンカルボン酸誘導体が、前記Xは、NH又はN(ZAr2)である[1]に記載の冷感剤組成物。
[3]前記2,2,6-トリメチルシクロヘキサンカルボン酸誘導体が、前記Xは、NH又はN(ZAr2)であり、(1R,6S)-体である[1]に記載の冷感剤組成物。
[4]前記2,2,6-トリメチルシクロヘキサンカルボン酸誘導体が、前記Xは、NH又はN(ZAr2)であり、前記nは、0又は2であり、前記Zは、単結合又は置換基を有していてもよいエチレン基である[1]に記載の冷感剤組成物。
[5]前記2,2,6-トリメチルシクロヘキサンカルボン酸誘導体が、前記Xは、NH又はN(ZAr2)であり、前記nは、0又は2であり、前記Zは、単結合又は置換基を有していてもよいエチレン基であり、(1R,6S)-体である[1]に記載の冷感剤組成物。
[6]前記2,2,6-トリメチルシクロヘキサンカルボン酸誘導体が、前記Xは、NH又はN(ZAr2)であり、前記nは、2であり、前記Zは、置換基を有していてもよいエチレン基である[1]に記載の冷感剤組成物。
[7]前記2,2,6-トリメチルシクロヘキサンカルボン酸誘導体が、前記Xは、NH又はN(ZAr2)であり、前記nは、2であり、前記Zは、置換基を有していてもよいエチレン基であり、(1R,6S)-体である[1]に記載の冷感剤組成物。
[8]前記2,2,6-トリメチルシクロヘキサンカルボン酸誘導体以外の冷感物質を少なくとも1種更に含有する[1]~[7]のいずれか1つに記載の冷感剤組成物。
[9]前記冷感物質が、
メントール、メントン、カンファー、プレゴール、イソプレゴール、シネオール、キュベノール、酢酸メンチル、酢酸プレギル、酢酸イソプレギル、サリチル酸メンチル、サリチル酸プレギル、サリチル酸イソプレギル、3-(l-メントキシ)プロパン-1,2-ジオール、2-メチル-3-(l-メントキシ)プロパン-1,2-ジオール、2-(l-メントキシ)エタン-1-オール、3-(l-メントキシ)プロパン-1-オール、4-(l-メントキシ)ブタン-1-オール、3-ヒドロキシブタン酸メンチル、グリオキシル酸メンチル、p-メンタン-3,8-ジオール、1-(2-ヒドロキシ-4-メチルシクロヘキシル)エタノン、乳酸メンチル、メントングリセリンケタール、メンチル-2-ピロリドン-5-カルボキシラート、モノメンチルスクシナート、モノメンチルスクシナートのアルカリ金属塩、モノメンチルスクシナートのアルカリ土類金属塩、モノメンチルグルタラート、モノメンチルグルタラートのアルカリ金属塩、モノメンチルグルタラートのアルカリ土類金属塩、N-[[5-メチル-2-(1-メチルエチル)シクロヘキシル]カルボニル]グリシン、p-メンタン-3-カルボン酸グリセロールエステル、メントールプロピレングリコールカルボナート、メントールエチレングリコールカルボナート、p-メンタン-2,3-ジオール、2-イソプロピル-N,2,3-トリメチルブタンアミド、N-エチル-p-メンタン-3-カルボキサミド、3-(p-メンタン-3-カルボキサミド)酢酸エチル、N-(4-メトキシフェニル)-p-メンタンカルボキサミド、N-エチル-2,2-ジイソプロピルブタンアミド、N-シクロプロピル-p-メンタンカルボキサミド、N-(4-シアノメチルフェニル)-p-メンタンカルボキサミド、N-(2-ピリジン-2-イル)-3-p-メンタンカルボキサミド、N-(2-ヒドロキシエチル)-2-イソプロイル-2,3-ジメチルブタンアミド、N-(1,1-ジメチル-2-ヒドロキシエチル)-2,2-ジエチルブタンアミド、シクロプロパンカルボン酸(2-イソプロピル-5-メチルシクロヘキシル)アミド、N-エチル-2,2-ジイソプロピルブタンアミド、N-[4-(2-アミノ-2-オキソエチル)フェニル]-p-メンタンカルボキサミド、2-[(2-p-メントキシ)エトキシ]エタノール、2,6-ジエチル-5-イソプロピル-2-メチルテトラヒドロピラン、及びトランス-4-tert-ブチルシクロヘキサノールから選ばれる1種以上の化合物;
キシリトール、エリスリトール、デキストロース、及びソルビトールから選ばれる1種以上の糖アルコール;並びに
和種ハッカオイル、ペパーミントオイル、スペアーミントオイル、及びユーカリプタスオイルから選ばれる1種以上の天然物;
からなる群より選ばれる少なくとも1種の冷感物質である[8]に記載の冷感剤組成物。
[10][1]~[9]のいずれか1つに記載の冷感剤組成物を含有する感覚刺激剤組成物。
[11]少なくとも1種の温感物質を更に含有する[10]に記載の感覚刺激剤組成物。
[12]前記温感物質が、
バニリルメチルエーテル、バニリルエチルエーテル、バニリルプロピルエーテル、バニリルイソプロピルエーテル、バニリルブチルエーテル、バニリルアミルエーテル、バニリルイソアミルエーテル、バニリルヘキシルエーテル、イソバニリルメチルエーテル、イソバニリルエチルエーテル、イソバニリルプロピルエーテル、イソバニリルイソプロピルエーテル、イソバニリルブチルエーテル、イソバニリルアミルエーテル、イソバニリルイソアミルエーテル、イソバニリルヘキシルエーテル、エチルバニリルメチルエーテル、エチルバニリルエチルエーテル、エチルバニリルプロピルエーテル、エチルバニリルイソプロピルエーテル、エチルバニリルブチルエーテル、エチルバニリルアミルエーテル、エチルバニリルイソアミルエーテル、エチルバニリルヘキシルエーテル、バニリンプロピレングリコールアセタール、イソバニリンプロピレングリコールアセタール、エチルバニリンプロピレングリコールアセタール、バニリルブチルエーテル酢酸エステル、イソバニリルブチルエーテル酢酸エステル、エチルバニリルブチルエーテル酢酸エステル、4-(l-メントキシメチル)-2-(3’-メトキシ-4’-ヒドロキシフェニル)-1,3-ジオキソラン、4-(l-メントキシメチル)-2-(3’-ヒドロキシ-4’-メトキシフェニル)-1,3-ジオキソラン、4-(l-メントキシメチル)-2-(3’-エトキシ-4’-ヒドロキシフェニル)-1,3-ジオキソラン、カプサイシン、ジヒドロカプサイシン、ノルジヒドロカプサイシン、ホモジヒドロカプサイシン、ホモカプサイシン、ビスカプサイシン、トリスホモカプサイシン、ノルノルカプサイシン、ノルカプサイシン、カプサイシノール、バニリルカプリルアミド(オクチル酸バニリルアミド)、バニリルペリラゴンアミド(ノニル酸バニリルアミド)、バニリルカプロアミド(デシル酸バニリルアミド)、バニリルウンデカンアミド(ウンデシル酸バニリルアミド)、N-トランス-フェルロイルチラミン、N-5-(4-ヒドロキシ-3-メトキシフェニル)-2E,4E-ペンタジエノイルピペリジン、N-トランス-フェルロイルピペリジン、N-5-(4-ヒドロキシ-3-メトキシフェニル)-2E-ペンテノイルピペリジン、N-5-(4-ヒドロキシフェニル)-2E,4E-ペンタジエノイルピペリジン、ピペリン、イソピペリン、シャビシン、イソシャビシン、ピペラミン、ピペレチン、ピペロレインB、レトロフラクタミドA、ピペラシド、グイネンサイド、ピペリリン、ピペラミドC5:1(2E)、ピペラミドC7:1(6E)、ピペラミドC7:2(2E,6E)、ピペラミドC9:1(8E)、ピペラミドC9:2(2E,8E)、ピペラミドC9:3(2E,4E,8E)、ファガラミド、サンショオール-I、サンショオール-II、ヒドロキシサンショオール、サンショウアミド、ジンゲロール、ショウガオール、ジンゲロン、メチルジンゲロール、パラドール、スピラントール、カビシン、ポリゴジアール(タデオナール)、イソポリゴジアール、ジヒドロポリゴジアール、及びタデオンから選ばれる1種以上の化合物;並びに
トウガラシ油、トウガラシオレオレジン、ジンジャーオレオレジン、ジャンブーオレオレジン(キバナオランダセンニチ抽出物)、サンショウエキス、サンショウアミド、黒胡椒エキス、白胡椒エキス、及びタデエキスから選ばれる1種以上の天然物;
からなる群より選ばれる少なくとも1種の温感物質である[11]に記載の感覚刺激剤組成物。
[13][10]~[12]のいずれか1つに記載の感覚刺激剤組成物を含有する香料組成物。
[14]前記感覚刺激剤組成物を0.00001~90質量%含有する[13]に記載の香料組成物。
[15]飲料、食品、香粧品、トイレタリー製品、エアケア製品、日用・雑貨品、口腔用組成物、ヘアケア製品、スキンケア製品、ボディケア製品、衣料用洗剤、衣料用柔軟仕上げ剤、医薬品部外品及び医薬品からなる群より選ばれるいずれかの製品であって[10]~[12]のいずれか1つに記載の感覚刺激剤組成物を含有する製品。
[16]前記感覚刺激剤組成物を0.00001~50質量%含有する[15]に記載の製品。
[17]飲料、食品、香粧品、トイレタリー製品、エアケア製品、日用・雑貨品、口腔用組成物、ヘアケア製品、スキンケア製品、ボディケア製品、衣料用洗剤、衣料用柔軟仕上げ剤、医薬品部外品及び医薬品からなる群より選ばれるいずれかの製品であって、[13]又は[14]に記載の香料組成物を含有する製品。
[18]前記香料組成物を0.00001~50質量%含有する[17]に記載の製品。
[19]飲料、食品、香粧品、トイレタリー製品、エアケア製品、日用・雑貨品、口腔用組成物、ヘアケア製品、スキンケア製品、ボディケア製品、衣料用洗剤、衣料用柔軟仕上げ剤、医薬品部外品及び医薬品からなる群より選ばれるいずれかの製品の製造方法であって、[10]~[12]のいずれか1つに記載の感覚刺激剤組成物を配合する、製品の製造方法。
[20]飲料、食品、香粧品、トイレタリー製品、エアケア製品、日用・雑貨品、口腔用組成物、ヘアケア製品、スキンケア製品、ボディケア製品、衣料用洗剤、衣料用柔軟仕上げ剤、医薬品部外品及び医薬品からなる群より選ばれるいずれかの製品の製造方法であって、[13]又は[14]に記載の香料組成物を配合する、製品の製造方法。
[21]下記一般式(1-1)で表される2,2,6-トリメチルシクロヘキサンカルボン酸誘導体。
[22]下記構造式(10-1)で表される2,2,6-トリメチルシクロヘキサンカルボン酸誘導体。
(一般式(1)で表される2,2,6-トリメチルシクロヘキサンカルボン酸誘導体)
本発明にかかる冷感剤組成物は、下記一般式(1)で表される新規2,2,6-トリメチルシクロヘキサンカルボン酸誘導体を冷感物質として含有することを特徴とする。
これらの中でもXは、冷感強度の観点から、NH又はN(ZAr2)であることが好ましい。
置換基を有していてもよい炭素数1~3のアルキレン基としては、例えば、メチレン基、エチレン基、プロピレン基が挙げられる。
これらの中でもZは、冷感強度の観点から、単結合又は置換基を有していてもよいエチレン基であることが好ましく、置換基を有していてもよいエチレン基であることがより好ましい。
これらの中でもnは、冷感強度の観点から、0又は2であることが好ましく、2であることがより好ましい。
置換基を有していてもよい炭素数6~20のアリール基としては、例えば、炭素数6~20の芳香族単環式基、芳香族多環式基、又は芳香族縮合環式基が挙げられる。具体的には、フェニル基、ナフチル基、アントリル基、フェナントリル基、インデニル基等が挙げられ、好ましい具体例としてはフェニル基が挙げられる。
一般式(1)で表される2,2,6-トリメチルシクロヘキサンカルボン酸誘導体は、例えば、以下のスキーム1~スキーム6で表される方法により合成される。しかし、当該カルボン酸誘導体の合成方法は以下のスキーム1~スキーム6の方法に限定されるものではない。
工程[I]は、特許文献2又は特許文献19に記載の手法と同様な手法によって行うことができる。
工程[J]は、カルボン酸化合物(5)をメシル化して活性アシル中間体へと変換した後、アミンと反応させることで行うことができる。
工程[K]は、非特許文献2に記載の手法と同様な手法によって行うことができる。工程[I]及び工程[J]は、前記の手法によって行うことができる。
工程[L]は、特許文献29に記載の手法と同様な手法によって行うことができる。
工程[M]は、非特許文献5に記載の手法と同様な手法によって行うことができる。即ち、工程[M]は、縮合反応により行うことができる。
また、2級アミド化合物(10)の好ましい具体例としては、以下の化合物が挙げられるが、これらに限定されるものではない。
以下の化合物中、Meはメチル基を、*印は不斉炭素を表す。
以下の化合物中、Meはメチル基を、*印は不斉炭素を表す。
以下の化合物中、Meはメチル基を、*印は不斉炭素を表す。
以下の化合物中、Meはメチル基を、*印は不斉炭素を表す。
冷感強度の観点から、R、R’及びR’’は、それぞれ独立して水素原子若しくはヒドロキシ基であることが好ましい。
メントール、メントン、カンファー、プレゴール、イソプレゴール、シネオール、キュベノール、酢酸メンチル、酢酸プレギル、酢酸イソプレギル、サリチル酸メンチル、サリチル酸プレギル、サリチル酸イソプレギル、3-(l-メントキシ)プロパン-1,2-ジオール、2-メチル-3-(l-メントキシ)プロパン-1,2-ジオール、2-(l-メントキシ)エタン-1-オール、3-(l-メントキシ)プロパン-1-オール、4-(l-メントキシ)ブタン-1-オール、3-ヒドロキシブタン酸メンチル、グリオキシル酸メンチル、p-メンタン-3,8-ジオール、1-(2-ヒドロキシ-4-メチルシクロヘキシル)エタノン、乳酸メンチル、メントングリセリンケタール、メンチル-2-ピロリドン-5-カルボキシラート、モノメンチルスクシナート、モノメンチルスクシナートのアルカリ金属塩、モノメンチルスクシナートのアルカリ土類金属塩、モノメンチルグルタラート、モノメンチルグルタラートのアルカリ金属塩、モノメンチルグルタラートのアルカリ土類金属塩、N-[[5-メチル-2-(1-メチルエチル)シクロヘキシル]カルボニル]グリシン、p-メンタン-3-カルボン酸グリセロールエステル、メントールプロピレングリコールカルボナート、メントールエチレングリコールカルボナート、p-メンタン-2,3-ジオール、2-イソプロピル-N,2,3-トリメチルブタンアミド、N-エチル-p-メンタン-3-カルボキサミド、3-(p-メンタン-3-カルボキサミド)酢酸エチル、N-(4-メトキシフェニル)-p-メンタンカルボキサミド、N-エチル-2,2-ジイソプロピルブタンアミド、N-シクロプロピル-p-メンタンカルボキサミド、N-(4-シアノメチルフェニル)-p-メンタンカルボキサミド、N-(2-ピリジン-2-イル)-3-p-メンタンカルボキサミド、N-(2-ヒドロキシエチル)-2-イソプロイル-2,3-ジメチルブタンアミド、N-(1,1-ジメチル-2-ヒドロキシエチル)-2,2-ジエチルブタンアミド、シクロプロパンカルボン酸(2-イソプロピル-5-メチルシクロヘキシル)アミド、N-エチル-2,2-ジイソプロピルブタンアミド、N-[4-(2-アミノ-2-オキソエチル)フェニル]-p-メンタンカルボキサミド、2-[(2-p-メントキシ)エトキシ]エタノール、2,6-ジエチル-5-イソプロピル-2-メチルテトラヒドロピラン、トランス-4-tert-ブチルシクロヘキサノール等の化合物(α)並びにこれらのラセミ体及び光学活性体;
キシリトール、エリスリトール、デキストロース、ソルビトール等の糖アルコール(β);
和種ハッカオイル、ペパーミントオイル、スペアーミントオイル、ユーカリプタスオイル等の天然物(γ);
日本国特開2001-294546号公報、日本国特開2005-343915号公報、日本国特開2007-002005号公報、日本国特開2009-263664号公報、日本国特開2010-254621号公報、日本国特開2010-254622号公報、日本国特開2011-079953号公報、米国特許第4136163号明細書、米国特許第4150052号明細書、米国特許第4178459号明細書、米国特許第4190643号明細書、米国特許第4193936号明細書、米国特許第4226988号明細書、米国特許第4230688号明細書、米国特許第4032661号明細書、米国特許第4153679号明細書、米国特許第4296255号明細書、米国特許第4459425号明細書、米国特許第5009893号明細書、米国特許第5266592号明細書、米国特許第5698181号明細書、米国特許第5725865号明細書、米国特許第5843466号明細書、米国特許第6231900号明細書、米国特許第6277385号明細書、米国特許第6280762号明細書、米国特許第6306429号明細書、米国特許第6432441号明細書、米国特許第6455080号明細書、米国特許第6627233号明細書、米国特許第7078066号明細書、米国特許第6783783号明細書、米国特許第6884906号明細書、米国特許第7030273号明細書、米国特許第7090832号明細書、米国特許出願公開第2004/0175489号明細書、米国特許出願公開第2004/0191402号明細書、米国特許出願公開第2005/0019445号明細書、米国特許出願公開第2005/0222256号明細書、米国特許出願公開第2005/0265930号明細書、米国特許出願公開第2006/015819号明細書、米国特許出願公開第2006/0249167号明細書、欧州特許出願公開第1689256号明細書、国際公開第2005/082154号、国際公開第2005/099473号、国際公開第2006/058600号、国際公開第2006/092076号、国際公開第2006/125334号に記載の化合物(δ);
等を例示することができる。
これらは、1種又は2種以上を適宜配合して用いることができる。中でも、上記冷感物質は、化合物(α)、糖アルコール(β)及び天然物(γ)からなる群より選ばれる少なくとも1種の冷感物質を含むことが好ましい。
本発明の冷感剤組成物は、強く、かつ持続性のある冷感効果を有していることから、この冷感剤組成物を含有させることにより、冷感効果を有する本発明の感覚刺激剤組成物を調製することができる。
バニリルメチルエーテル、バニリルエチルエーテル、バニリルプロピルエーテル、バニリルイソプロピルエーテル、バニリルブチルエーテル、バニリルアミルエーテル、バニリルイソアミルエーテル、バニリルヘキシルエーテル、イソバニリルメチルエーテル、イソバニリルエチルエーテル、イソバニリルプロピルエーテル、イソバニリルイソプロピルエーテル、イソバニリルブチルエーテル、イソバニリルアミルエーテル、イソバニリルイソアミルエーテル、イソバニリルヘキシルエーテル、エチルバニリルメチルエーテル、エチルバニリルエチルエーテル、エチルバニリルプロピルエーテル、エチルバニリルイソプロピルエーテル、エチルバニリルブチルエーテル、エチルバニリルアミルエーテル、エチルバニリルイソアミルエーテル、エチルバニリルヘキシルエーテル、バニリンプロピレングリコールアセタール、イソバニリンプロピレングリコールアセタール、エチルバニリンプロピレングリコールアセタール、バニリルブチルエーテル酢酸エステル、イソバニリルブチルエーテル酢酸エステル、エチルバニリルブチルエーテル酢酸エステル、4-(l-メントキシメチル)-2-(3’-メトキシ-4’-ヒドロキシフェニル)-1,3-ジオキソラン、4-(l-メントキシメチル)-2-(3’-ヒドロキシ-4’-メトキシフェニル)-1,3-ジオキソラン、4-(l-メントキシメチル)-2-(3’-エトキシ-4’-ヒドロキシフェニル)-1,3-ジオキソラン、カプサイシン、ジヒドロカプサイシン、ノルジヒドロカプサイシン、ホモジヒドロカプサイシン、ホモカプサイシン、ビスカプサイシン、トリスホモカプサイシン、ノルノルカプサイシン、ノルカプサイシン、カプサイシノール、バニリルカプリルアミド(オクチル酸バニリルアミド)、バニリルペリラゴンアミド(ノニル酸バニリルアミド)、バニリルカプロアミド(デシル酸バニリルアミド)、バニリルウンデカンアミド(ウンデシル酸バニリルアミド)、N-トランス-フェルロイルチラミン、N-5-(4-ヒドロキシ-3-メトキシフェニル)-2E,4E-ペンタジエノイルピペリジン、N-トランス-フェルロイルピペリジン、N-5-(4-ヒドロキシ-3-メトキシフェニル)-2E-ペンテノイルピペリジン、N-5-(4-ヒドロキシフェニル)-2E,4E-ペンタジエノイルピペリジン、ピペリン、イソピペリン、シャビシン、イソシャビシン、ピペラミン、ピペレチン、ピペロレインB、レトロフラクタミドA、ピペラシド、グイネンサイド、ピペリリン、ピペラミドC5:1(2E)、ピペラミドC7:1(6E)、ピペラミドC7:2(2E,6E)、ピペラミドC9:1(8E)、ピペラミドC9:2(2E,8E)、ピペラミドC9:3(2E,4E,8E)、ファガラミド、サンショオール-I、サンショオール-II、ヒドロキシサンショオール、サンショウアミド、ジンゲロール、ショウガオール、ジンゲロン、メチルジンゲロール、パラドール、スピラントール、カビシン、ポリゴジアール(タデオナール)、イソポリゴジアール、ジヒドロポリゴジアール、タデオン等の化合物(ε)並びにこれらのラセミ体及び光学活性体;
トウガラシ油、トウガラシオレオレジン、ジンジャーオレオレジン、ジャンブーオレオレジン(キバナオランダセンニチ抽出物)、サンショウエキス、サンショウアミド、黒胡椒エキス、白胡椒エキス、タデエキス等の天然物(ζ);
日本国特開平8-225564号公報、日本国特開2007-015953号公報、日本国特表2007-510634号公報、日本国特表2008-505868号公報、国際公開第2007/013811号、国際公開第2003/106404号、欧州特許出願公開第1323356号明細書、独国特許出願公開第10351422号明細書、米国特許出願公開第2005/0181022号明細書、米国特許出願公開第2008/0038386号明細書に記載の化合物(η);
等を例示することができる。
これらは、1種又は2種以上を適宜配合して用いることができる。中でも、上記温感物質は、化合物(ε)、及び天然物(ζ)からなる群より選ばれる少なくとも1種の温感物質を含むことが好ましい。
本発明の香料組成物は、本発明の感覚刺激剤組成物を含有する。また、本発明の香料組成物は、香料成分を含有することができる。
当該香料成分としては、各種の合成香料、天然精油、合成精油、柑橘油、動物性香料等を挙げることができ、例えば、非特許文献1に記載されているような広範な種類の香料成分を使用することができる。
さらに、本発明の香料組成物が飲料用や食品用の場合、本発明の感覚刺激剤組成の含有量は、香料組成物の全質量に対して、0.0001~50質量%であることが好ましく、0.001~30質量%であることがより好ましい。
本発明の製品は、冷感又は感覚刺激の付与を目的として、本発明の感覚刺激剤組成物又は本発明の香料組成物を含有する。
前記食品としては、アイスクリーム類、シャーベット類、アイスキャンディー類の如き冷菓類;ゼリー、プリン等のデザート類;ケーキ、クッキー、チョコレート、チューインガム等の洋菓子類;饅頭、羊羹、ウイロウ等の和菓子類;ジャム類;キャンディー類;パン類;風味調味料;各種インスタント食品類;各種スナック食品類等;
前記口腔用組成物としては、歯磨き、口腔洗浄料、マウスウオッシュ、トローチ、チューインガム等;
前記フレグランス製品としては、香水、オードパルファム、オードトワレ、オーデコロン等;
前記基礎化粧品としては、洗顔クリーム、バニシングクリーム、クレンジングクリーム、コールドクリーム、マッサージクリーム、乳液、化粧水、美容液、パック、メイク落とし等;
前記仕上げ化粧品としては、ファンデーシヨン、粉おしろい、固形おしろい、タルカムパウダー、口紅、リップクリーム、頬紅、アイライナー、マスカラ、アイシャドゥ、眉墨、アイパック、ネイルエナメル、エナメルリムバー等;
前記頭髪化粧品としては、ポマード、ブリランチン、セットローション、ヘアーステック、ヘアーソリッド、ヘアーオイル、ヘアートリートメント、ヘアークリーム、ヘアートニック、ヘアーリキッド、ヘアースプレー、バンドリン、養毛剤、染毛剤等;
前記日焼け化粧品としては、サンタン製品、サンスクリーン製品等;
前記薬用化粧品としては、制汗剤、アフターシェービングローション及びジェル、パーマネン卜ウェーブ剤、薬用石鹸、薬用シャンプー、薬用皮膚化粧料等;
前記ヘアケア製品としては、シャンプー、リンス、リンスインシャンプー、コンディショナー、トリートメン卜、ヘアーパック等;
前記石鹸としては、化粧石鹸、浴用石鹸、香水石鹸、透明石鹸、合成石鹸等;
前記身体洗浄剤としては、ボディソープ、ボディシャンプー、ハンドソープ、フェースクリーム等;
前記浴用剤としては、入浴剤(バスソルト、バスタブレット、バスリキッド等)、フォームバス(バブルバス等)、バスオイル(バスパヒューム、バスカプセル等)、ミルクバス、バスジェリー、バスキユーブ等;
前記衣料用洗剤としては、衣料用重質洗剤、衣料用軽質洗剤、液体洗剤、洗濯石鹸、コンパクト洗剤、粉石鹸等;
前記衣料用柔軟仕上げ剤としては、ソフナー、ファーニチァケアー等;
前記洗浄剤としては、クレンザー、ハウスクリーナー、トイレ洗浄剤、浴室用洗浄剤、ガラスクリーナー、カビ取り剤、排水管用洗浄剤等;
前記台所用洗剤としては、台所用石鹸、台所用合成石鹸、食器用洗剤等;
前記漂白剤としては、酸化型漂白剤(塩素系漂白剤、酸素系漂白剤等)、還元型漂白剤(硫黄系漂白剤等)、光学的漂白剤等;
前記エアゾール剤としては、スプレータイプ、パウダースプレー等;
前記消臭・芳香剤としては、固形状タイプ、ゲル状タイプ、リキッドタイプ(水性、油性)等;
前記日用・雑貨品としては、ティッシュペーパー、トイレットペーパー等;
前記医薬部外品としては、液体入浴剤、洗口液、忌避剤等、前記忌避剤としてはミストスプレータイプ、水性液体タイプ等;
前記医薬品としては、薬用化粧品、薬用ローション等;
の種々の形態を挙げることができる。
アルコール類、プロピレングリコール、グリセリン、ジプロピレングリコール等の多価アルコール類、トリエチルシトレート、ベンジルベンゾエート、ジエチルフタレート等のエステル類に溶解した液体状;
グリセリン脂肪酸エステル、ショ糖脂肪酸エステル等の乳化剤で乳化した乳化状;
アラビアガム、トラガントガム等の天然ガム質類、ゼラチン、デキストリン等の賦形剤を用いて被膜させた粉末状;
界面活性剤、例えば、非イオン界面活性剤、アニオン界面活性剤、カチオン界面活性剤、両性界面活性剤等を用いて可溶化あるいは分散化した可溶化状或いは分散化状;
カプセル化剤で処理して得られるマイクロカプセル等;
その目的に応じて任意の形状を選択して用いられている。
冷感又は感覚刺激が付与される製品の種類や製品の最終形態(例えば、液体状、固体状、粉末状、ゲル状、ミスト状、エアゾール状等の製品形態)に応じて、感覚刺激剤組成物又は香料組成物を、その製品に直接添加又は付与してもよいし;
感覚刺激剤組成物又は香料組成物を、例えば、アルコール類、プロピレングリコール、グリセリン等の多価アルコール類に溶解して液体状にして製品に添加又は付与してもよいし;
アラビアガム、トラガントガム等の天然ガム質類、界面活性剤(例えば、グリセリン脂肪酸エステル、ショ糖脂肪酸エステル等の非イオン界面活性剤、アニオン界面活性剤、カチオン界面活性剤、両性界面活性剤等)を用いて可溶化或いは乳化分散させた可溶化状或いは分散状にして製品に添加又は付与してもよいし;
アラビアガム、トラガントガム等の天然ガム質類、ゼラチン、デキストリン等の賦形剤を用いて被膜形成した粉末状で製品に添加又は付与してもよいし;
カプセル化剤で処理してマイクロカプセルにして製品に添加又は付与してもよい。
さらに、サイクロデキストリン等の包接剤に包接して、感覚刺激剤組成物又は香料組成物を安定化すると共に徐放性にして用いてもよい。
l-シトロネラール:96.6%e.e.
d-シトロネラール:97.8%e.e.
トランス/シス比 (1R,6S)-5/(1R,6R)-5=90/10
光学純度 (1R,6S)-5:93.1%e.e.
(1R,6R)-5:>99.0%e.e.
トランス/シス比 (1S,6R)-5/(1S,6S)-5=91/9
光学純度 (1S,6R)-5:96.3%e.e.
(1S,6S)-5:>99.0%e.e.
従って、本実施例中の化合物は、少量若しくは極少量のジアスレテオマー及びエナンチオマーを含有する。
核磁気共鳴スペクトル:1H-NMR:AM-500(500MHz)(ブルッカー社製)
外部標準物質:テトラメチルシラン
ガスクロマトグラフ(GC):GC-2010AF(島津製作所製)、GC-4000Plus(GLサイエンス社製)
カラム:DB-WAX(30m×0.32nm×0.5μm)(ヒューレット・パッカード社製)、IC-1(30m×0.25mm×0.25μm)(ヒューレット・パッカード社製)、Rtx-1(30m×0.25mm×0.25μm)(ReStek社製)、Inert Cap1(30m×0.25mm×0.25μm)(GLサイエンス社製)高分解能質量スペクトル(HRMS):JMS-T100GCV(日本電子社製)
融点:融点測定装置(シリアルナンバー:2678)(柳本製作所製)
HRMS:質量273.2093 実測値273.2080([M]+)
1H-NMR(500MHz,CDCl3):δ0.84(d,3H,J=6.4Hz),0.85-0.92(m,1H),0.93(s,3H),1.04(s,3H),1.11(dt,1H,J=4.8,12.9Hz),1.36-1.42(m,2H),1.45-1.59(m,2H),1.70-1.78(m,1H),1.84-1.95(m,1H),3.80(s,3H),4.34(dd,1H,J=5.2,14.3,Hz),4.44(dd,1H,J=4.8,14.4,Hz),5.55(br,1H),6.84-6.88(m,2H),7.19-7.23(m,2H).
HRMS:質量290.2115 実測値290.2115([M+H]+)
1H-NMR(500MHz,CDCl3):δ0.78-0.94(m,7H),0.96-1.04(m,3H),1.06-1.16(m,1H),1.35-1.55(m,4H),1.69-1.76(m,1H),1.81-1.91(m,1H),3.32-3.46(m,1H),3.66-3.81(m,2H),4.82-4.89(m,1H),5.81-5.91(br,1H),7.25-7.29(m,1H),7.31-7.39(m,4H).
HRMS:質量290.2115 実測値290.2115([M+H]+)
1H-NMR(500MHz,CDCl3):δ0.78-0.95(m,7H),0.95-1.04(m,3H),1.06-1.17(m,1H),1.36-1.55(m,4H),1.67-1.78(m,1H),1.79-1.91(m,1H),3.32-3.46(m,1H),3.63-3.77(m,2H),3.86-3.95(m,1H),4.82-4.89(m,1H),5.89-5.97(m,1H),7.25-7.29(m,1H),7.31-7.39(m,4H).
1H-NMR(500MHz,CDCl3):δ0.84(d,3H,J=6.3Hz),0.83-0.91(m,1H),0.91(s,3H),1.00(s,3H),1.07-1.15(m,1H),1.35-1.54(m,4H),1.68-1.77(m,1H),1.82-1.91(m,1H),3.31-3.39(m,1H),3.74-3.79(m,2H),4.82-4.88(m,1H),5.84(br,1H),7.24-7.29(m,1H),7.31-7.39(m,4H).
HRMS:質量290.2115 実測値290.2115([M+H]+)
1H-NMR(500MHz,CDCl3):δ0.88(d,3H,J=6.3Hz),0.80-0.87(m,1H),0.89(s,3H),1.00(s,3H),1.06-1.14(m,1H),1.34-1.43(m,1H),1.44-1.52(m,1H),1.67-1.87(m,2H),3.41(ddd,1H,J=5.3,7.6,14.1Hz),3.65(ddd,1H,J=3.3,6.6,14.1Hz),3.90-3.97(m,1H),4.04(d,1H,J=3.6Hz),4.79-4.86(m,1H),6.08(br,1H),7.24-7.28(m,1H),7.30-7.38(m,4H).
HRMS:質量290.2115 実測値290.2113([M+H]+)
1H-NMR(500MHz,CDCl3):δ0.78(d,3H,J=6.3Hz),0.81-0.87(m,1H),0.89(s,3H),1.00(s,3H),1.06-1.14(m,1H),1.32-1.55(m,4H),1.68-1.90(m,2H),3.42(ddd,1H,J=5.3,7.4,14.1Hz),3.66(ddd,1H,J=3.3,6.6,14.1Hz),3.90-3.97(m,1H),4.82-4.86(m,1H),5.97(br,1H),7.24-7.29(m,1H),7.31-7.39(m,4H).
1H-NMR(500MHz,CDCl3):δ0.84(d,3H,J=6.3Hz),0.85-0.91(m,1H),0.91(s,3H),0.99(s,3H),1.11(dt,1H,J=5.9,12.8Hz),1.36-1.54(m,4H),1.70-1.77(m,1H),1.82-1.91(m,1H),3.36(dq,1H,J=2.0,5.3Hz),3.72-3.79(m,2H),4.84-4.89(m,1H),5.86(br,1H),7.24-7.29(m,1H),7.32-7.39(m,4H).
HRMS:質量290.2115 実測値290.2114([M+H]+)
1H-NMR(500MHz,DMSO-d6):δ0.69(d,3H,J=6.3Hz),0.75-0.87(m,4H),0.90(s,3H),1.02-1.11(m,1H),1.26-1.32(m,1H),1.40-1.47(m,2H),1.50(d,1H,J=11.1Hz),1.61-1.76(m,2H),2.58(t,2H,J=6.7Hz),3.22(dt,1H,J=6.7,7.9Hz),6.63-6.68(m,2H),6.99(d,2H,J=8.5Hz),7.72(br,1H),9.12(s,1H)
HRMS:質量290.2115 実測値290.2113([M+H]+)
1H-NMR(500MHz,DMSO-d6):δ0.69(d,3H,J=6.3Hz),0.75-0.87(m,4H),0.90(s,3H),1.02-1.11(m,1H),1.26-1.32(m,1H),1.40-1.47(m,2H),1.50(d,1H,J=11.1Hz),1.61-1.76(m,2H),2.58(t,2H,J=6.7Hz),3.22(dt,1H,J=6.7,7.9Hz),6.63-6.68(m,2H),6.99(d,2H,J=8.5Hz),7.72(br,1H),9.12(s,1H)
融点:85~87℃
HRMS:質量288.1958 実測値288.1972([M+H]+)
1H-NMR(500MHz,CDCl3):δ0.86(d,3H,J=6.4Hz),0.86-0.98(m,1H),0.98(s,3H),1.04(s,3H),1.19(dt,1H,J=12.8,5.0Hz),1.39-1.45(m,2H),1.49-1.58(m,2H),1.63(d,1H,J=11.1Hz),1.73-1.79(m,1H),1.84-1.97(m,1H),4.80(d,2H,J=4.3Hz),6.47(br,1H),7.48-7.53(m,2H),7.60-7.65(m,1H),7.96-8.02(m,2H).
HRMS:質量288.1958 実測値288.1945([M+H]+)
1H-NMR(500MHz,CDCl3):δ0.89(d,3H,J=6.3Hz),0.93(s,3H),1.02(s,3H),1.09-1.14(m,1H),1.34-1.52(m,2H),1.59-2.00(m,5H),4.75(d,2H,J=4.0Hz),6.48(br,1H),7.48-7.53(m,2H),7.58-7.65(m,1H),7.96-8.01(m,2H).
融点:86~87℃
HRMS:質量288.1958 実測値288.1934([M+H]+)
1H-NMR(500MHz,CDCl3):δ0.86(d,3H,J=6.4Hz),0.86-0.98(m,1H),0.98(s,3H),1.04(s,3H),1.19(dt,1H,J=12.8,5.0Hz),1.37-1.45(m,2H),1.49-1.58(m,2H),1.63(d,1H,J=11.1Hz),1.73-1.79(m,1H),1.85-1.97(m,1H),4.80(d,2H,J=4.3Hz),6.47(br,1H),7.48-7.53(m,2H),7.60-7.65(m,1H),7.96-8.01(m,2H).
HRMS:質量288.1958 実測値288.1990([M+H]+)
1H-NMR(500MHz,CDCl3):δ0.89(d,3H,J=6.3Hz),0.93(s,3H),1.02(s,3H),1.09-1.14(m,1H),1.34-1.52(m,2H),1.59-1.98(m,5H),4.75(d,2H,J=4.0Hz),6.48(br,1H),7.46-7.53(m,2H),7.58-7.65(m,1H),7.94-8.02(m,2H).
HRMS:質量304.2271 実測値304.2299([M+H]+)
1H-NMR(500MHz,CDCl3):δ0.80(d,3H,J=6.4Hz),0.81-0.87(m,1H),0.88(s,3H),1.00(s,3H),1.09(dt,1H,J=12.7,5.0Hz),1.29(d,1H,J=11.1Hz),1.34-1.38(m,1H),1.42-1.54(m,2H),1.68-1.90(m,2H),2.75(t,2H,J=6.9Hz),3.45-3.60(m,2H),3.79(br,3H),6.80-6.86(m,2H),7.10-7.14(m,2H).
HRMS:質量304.2271 実測値304.2276([M+H]+)
1H-NMR(500MHz,CDCl3):δ0.77(d,3H,J=6.4Hz),0.81-0.85(m,1H),0.85(s,3H),0.98(s,3H),1.08(dt,1H,J=5.2,12.9Hz),1.29(d,1H,J=11.1Hz),1.32-1.39(m,1H),1.44-1.53(m,2H),1.64-1.75(m,1H),1.78-1.87(m,1H),2.83(t,2H,J=6.8Hz),3.45-3.58(m,2H),3.84(s,3H),5.55(br,1H),6.85-7.02(m,2H),7.15(dd,1H,J=1.4,7.5Hz),7.21(dt,1H,J=1.8,7.8Hz).
1H-NMR(500MHz,DMSO-d6):δ0.70(d,3H,J=6.3Hz),0.76-0.85(m,5H),0.86-0.93(m,4H),1.01-1.11(m,1H),1.26-1.33(m,1H),1.39-1.47(m,2H),1.50(d,1H,J=11.0Hz),1.61-1.75(m,2H),3.14-3.22(m,2H),6.43(dd,1H,J=8.0,2.0Hz),6.57(d,1H,J=1.9Hz),6.61(d,1H,J=7.9Hz),7.71(br,1H),8.60(s,1H),8.68(s,1H).
HRMS:質量356.2196 実測値356.2203([M+Na]+)
1H-NMR(500MHz,CDCl3):δ0.80(d,3H,J=6.4Hz),0.81-0.87(m,1H),0.88(s,3H),1.00(s,3H),1.09(dt,1H,J=12.7,5.0Hz),1.31(d,1H,J=11.1Hz),1.34-1.38(m,1H),1.42-1.54(m,2H),1.68-1.90(m,2H),2.76(t,2H,J=7.0Hz),3.55-3.60(m,2H),3.86(br,6H),6.70-6.83(m,3H).
HRMS:質量313.2274 実測値313.2276([M+H]+)
1H-NMR(500MHz,CDCl3):δ0.80(d,3H,J=6.4Hz),0.80-0.86(m,1H),0.87(s,3H),1.00(s,3H),1.07(dt,1H,J=5.0,12.9Hz),1.29(d,1H,J=11.1Hz),1.32-1.38(m,1H),1.43-1.54(m,2H),1.67-1.74(m,1H),1.78-1.90(m,1H),2.98(t,2H,J=6.8Hz),3.67-3.71(m,2H),5.58(br,1H),7.02(d,1H,J=2.3Hz),7.12(dt,1H,J=1.0,7.0Hz),7.20(dt,1H,J=1.0,7.1Hz),7.37(dt,1H,J=0.9,8.0Hz),7.61(dd,1H,J=0.5,8.0Hz),8.27(br,1H).
HRMS:質量261.1961 実測値261.1962([M+H]+)
1H-NMR(500MHz,CDCl3):δ0.82(d,3H,J=6.4Hz),0.84-0.92(m,1H),0.88(s,3H),1.04(s,3H),1.16(dt,1H,J=5.0,13.0Hz),1.36-1.43(m,1H),1.45-1.54(m,2H),1.56(d,1H,J=11.2Hz),1.71-1.77(m,1H),1.85-1.95(m,1H),4.54(dd,1H,J=5.0,16.1Hz),4.60(dd,1H,J=5.2,16.1Hz),6.66(br,1H),7.17-7.21(m,1H),7.29(d,1H,J=7.8Hz),7.65(dt,1H,J=1.8,7.8Hz),8.51-8.54(m,1H).
HRMS:質量275.2118 実測値275.2118([M+H]+)
1H-NMR(500MHz,CDCl3):δ0.86(d,3H,J=6.4Hz),0.78-0.89(m,1H),0.84(s,3H),0.98(s,3H),1.10(dt,1H,J=5.1,12.9Hz),1.33-1.48(m,2H),1.44-1.53(m,2H)),1.67-1.75(m,1H),1.78-1.88(m,1H),3.00(t,2H,J=6.4Hz),3.63-3.74(m,2H),6.25(br,1H),7.11-7.17(m,1H),7.18(d,1H,J=7.8Hz),7.60(dt,1H,J=1.9,7.8Hz),8.51-8.54(m,1H).
HRMS:質量266.1573 実測値266.1577([M+H]+)
1H-NMR(500MHz,CDCl3):δ0.84(d,3H,J=6.3Hz),0.85-0.92(m,1H),0.94(s,3H),1.06(s,3H),1.12(dt,1H,J=5.1,12.9Hz),1.36-1.44(m,2H),1.46-1.55(m,2H),1.71-1.78(m,1H),1.84-1.95(m,1H),4.60(dd,1H,J=5.5,15.2Hz),4.66(dd,1H,J=5.7,15.2Hz),5.55(br,1H),6.92-6.98(m,2H),7.18-7.24(m,1H).
HRMS:質量266.1573 実測値266.1562([M+H]+)
1H-NMR(500MHz,CDCl3):δ0.84(d,3H,J=6.4Hz),0.85-0.92(m,1H),0.93(s,3H),1.04(s,3H),1.12(dt,1H,J=12.8,5.0Hz),1.36-1.42(m,2H),1.45-1.60(m,2H),1.70-1.78(m,1H),1.84-1.95(m,1H),4.56-4.69(m,2H),5.69(br,1H),6.91-6.98(m,2H),7.19-7.23(m,1H).
HRMS:質量266.1573 実測値266.1571([M+H]+)
1H-NMR(500MHz,CDCl3):δ0.84(d,3H,J=6.3Hz),0.85-0.92(m,1H),0.93(s,3H),1.03(s,3H),1.12(dt,1H,J=5.1,13.0Hz),1.35-1.43(m,2H),1.46-1.55(m,2H),1.66-1.77(m,1H),1.84-1.95(m,1H),4.42(dd,1H,J=5.6,14.9Hz),4.50(dd,1H,J=5.9,14.9Hz),5.67(br,1H),7.03(d,1H,J=5.0Hz),7.12-7.16(m,1H),7.28(dd,1H,J=3.0,5.0Hz).
HRMS:質量280.1730 実測値280.1730([M+H]+)
1H-NMR(500MHz,CDCl3):δ0.81(d,3H,J=6.3Hz),0.81-0.88(m,1H),0.88(s,3H),1.01(s,3H),1.10(dt,1H,J=4.8,12.4Hz),1.36(t,2H,J=12.4Hz),1.44-1.55(m,2H),1.66-1.92(m,2H),3.04(t,2H,J=9.7Hz),3.47-3.64(m,2H),5.58(br,1H),6.81-6.97(m,2H),7.15(d,1H,J=5.0Hz).
HRMS:質量280.1730 実測値280.1740([M+H]+)
1H-NMR(500MHz,CDCl3):δ0.81(d,3H,J=6.4Hz),0.83-0.89(m,1H),0.89(s,3H),1.00(s,3H),1.10(dt,1H,J=12.8,5.0Hz),1.32-1.40(m,2H),1.45-1.56(m,2H),1.68-1.75(m,1H),1.81-1.89(m,1H),2.99-3.07(m,2H),3.49-3.64(m,2H),5.48(br,1H),6.84(dd,1H,J=3.3,0.9Hz),6.94(dd,1H,J=5.1,3.4Hz),7.16(dd,1H,J=5.3,1.1Hz).
HRMS:質量262.1802 実測値262.1804([M+H]+)
1H-NMR(500MHz,DMSO-d6):δ0.79(d,3H,J=6.0Hz),0.82-0.92(m,1H),0.92(s,3H),0.96(s,3H),1.10-1.17(m,1H),1.32-1.38(m,1H),1.43-1.52(m,2H),1.67-1.84(m,3H),2.48-2.52(m,1H),6.63-6.68(m,2H),7.31-7.37(m,2H),9.47(br,1H).
HRMS:質量276.1958 実測値276.1985([M+H]+)
1H-NMR(500MHz,CDCl3):δ0.80(d,3H,J=6.4Hz),0.81-0.87(m,1H),0.88(s,3H),1.00(s,3H),1.18(dt,1H,J=12.7,5.0Hz),1.40-1.48(m,1H),1.49-1.60(m,3H),1.76-1.81(m,1H),1.90-2.00(m,1H),3.78(s,3H),6.82-6.87(m,2H),6.95(br,6H),7.37-7.44(m,2H).
HRMS:質量289.2042 実測値289.2031([M]+)
1H-NMR(500MHz,CDCl3):δ0.84(d,3H,J=6.4Hz),0.85-0.92(m,1H),0.93(s,3H),1.04(s,3H),1.11(dt,1H,J=12.9,4.8Hz),1.36-1.42(m,2H),1.45-1.59(m,2H),1.70-1.78(m,1H),1.84-1.95(m,1H),3.80(s,3H),4.34(dd,1H,J=14.3,5.2Hz),4.44(dd,1H,J=14.4,4.8Hz),5.55(br,1H),6.84-6.88(m,2H),7.19-7.23(m,2H).
HRMS:質量290.1751 実測値290.1754([M+H]+)
1H-NMR(500MHz,CDCl3):δ0.91(d,3H,J=6.4Hz),0.91-1.00(m,1H),1.02(s,3H),1.07(s,3H),1.18(dt,1H,J=5.5,12.8Hz),1.40-1.47(m,1H),1.49-1.58(m,2H),1.74-1.82(m,1H),1.91-2.00(m,1H),5.93(s,2H),6.72(d,1H,J=8.3Hz),6.77(dd,1H,J=2.1,8.3Hz),7.02(br,1H),7.24(d,1H,J=2.1Hz).
HRMS:質量288.1958 実測値288.1952([M+H]+)
1H-NMR(500MHz,CDCl3):δ0.91(d,3H,J=6.4Hz),0.93-1.00(m,1H),1.04(s,3H),1.08(s,3H),1.19(dt,1H,J=5.9,13.0Hz),1.40-1.56(m,3H),1.61(d,1H,J=11.2Hz),1.75-1.83(m,1H),1.93-2.05(m,1H),2.57(s,3H),7.43(br,1H),7.62-7.67(m,2H),7.91-7.95(m,2H).
HRMS:質量290.2115 実測値290.2111([M+H]+)
1H-NMR(500MHz,CDCl3):δ0.91(d,3H,J=6.4Hz),0.93-1.00(m,1H),1.03(s,3H),1.07(s,3H),1.19(dt,1H,J=5.4,13.1Hz),1.42-1.47(m,1H),1.49-1.56(m,2H),1.58(d,1H,J=11.0Hz),1.67(br,1H),1.75-1.83(m,1H),1.91-2.02(m,1H),2.80-2.84(m,2H),3.78-3.86(m,2H),7.14-7.23(m,3H),7.42-7.47(m,2H).
HRMS:質量304.1907 実測値304.1914([M+H]+)
1H-NMR(500MHz,CDCl3):δ0.91(d,3H,J=6.4Hz),0.92-1.01(m,1H),1.03(s,3H),1.07(s,3H),1.14-1.24(m,1H),1.42-1.49(m,2H),1.52-1.59(m,2H),1.61(d,1H,J=11.1Hz),1.75-1.83(m,1H),1.94-2.02(m,1H),3.89(s,3H),7.32(br,1H),7.57-7.64(m,2H),7.96-8.02(m,2H).
HRMS:質量292.1730 実測値292.1734([M+H]+)
1H-NMR(500MHz,CDCl3):δ0.91(d,3H,J=6.4Hz),0.92-1.00(m,1H),1.02(s,3H),1.07(s,3H),1.18(dt,1H,J=5.7,13.0Hz),1.42-1.47(m,1H),1.50-1.59(m,3H),1.74-1.82(m,1H),1.92-2.00(m,1H),2.46(s,3H),7.09(br,1H),7.24(dt,2H,J=2.7,8.7Hz),7.46(dt,2H,J=2.1,8.7Hz).
HRMS:質量284.1848 実測値284.1838([M]+)
1H-NMR(500MHz,CDCl3):δ0.91(d,3H,J=6.4Hz),0.93-1.00(m,1H),1.04(s,3H),1.07(s,3H),1.19(dt,1H,J=5.1,12.8Hz),1.41-1.47(m,3H),1.51-1.61(m,3H),1.76-1.83(m,1H),1.92-2.01(m,1H),3.71(s,2H),7.29(br,1H),7.25-7.28(m,2H),7.52-7.58(m,2H).
HRMS:質量247.1805 実測値247.1807([M+H]+)
1H-NMR(500MHz,CDCl3):δ0.87(d,3H,J=6.4Hz),0.83-0.90(m,1H),1.00(s,3H),1.05(s,3H),1.11(dt,1H,J=5.5,12.9Hz),1.36-1.43(m,1H),1.45-1.54(m,2H),1.72(d,1H,J=11.1Hz),1.68-1.78(m,1H),1.88-2.00(m,1H),7.52-7.58(m,2H),8.39-8.44(m,2H),8.70(br,1H).
1H-NMR(500MHz,CDCl3):δ7.42-7.28(m,5H),4.96(brd,J-8Hz,1H),4.31(ddd,J=3.6,9.2,12.0Hz,1H),4.19(ddd,J=8.0,10.4,11.6Hz,1H),2.57(brs,1H),1.89-1.82(m,2H),1.73(ddd,J=1.2,3.2,14.0Hz,1H),1.51(tt,J=3.2,10.0Hz,2H),1.41(dtd,J=1.2,3.2,13.2Hz,1H),1.20-1.13(m,1H),0.96(d,J=2.4Hz,3H),0.93(s,3H),0.88(ddd,J=3.4,6.8,16.0Hz,1H),0.81(dd,J=1.8,5.8Hz,3H).
HRMS:質量290.4030 実測値290.4073([M+H]+)
1H-NMR(500MHz,CDCl3):δ7.40-7.28(m,5H),4.32(ddd,J=3.6,9.2,12.0Hz,1H),4.17(ddd,J=8.0,10.4,11.6Hz,1H),2.57(brs,1H),1.89-1.82(m,2H),1.72(ddd,J=1.2,3.2,14.0Hz,1H),1.51(tt,J=3.2,10.0Hz,2H),1.41(dtd,J=1.2,3.2,13.2Hz,1H),1.20-1.13(m,1H),0.96(d,J=2.4Hz,3H),0.93(s,3H),0.88(ddd,J=3.4,6.8,16.0Hz,1H),0.81(dd,J=1.8,5.8Hz,3H).
HRMS:質量290.4030 実測値290.4058([M+H]+)
1H-NMR(500MHz,CDCl3):δ7.40-7.28(m,5H),4.96(brd,J-8Hz,1H),4.30(ddd,J=3.6,9.2,12.0Hz,1H),4.19(ddd,J=8.0,10.4,11.6Hz,1H),2.57(brs,1H),1.89-1.82(m,2H),1.73(ddd,J=1.2,3.2,14.0Hz,1H),1.51(tt,J=3.2,10.0Hz,2H),1.41(dtd,J=1.2,3.2,13.2Hz,1H),1.20-1.13(m,1H),0.96(d,J=2.4Hz,3H),0.93(s,3H),0.88(ddd,J=3.4,6.8,16.0Hz,1H),0.81(dd,J=1.8,5.8Hz,3H).
,3.36(t,2H,J=7.1Hz),3.75(s,3H),6.57-6,61(m,2H),6.75-6.80(m,2H),7.20-7.37(m,6H).
一般的に、メントール等の冷感効果を有する化合物は、冷刺激受容体であるTRPM8(メラスタチン一過性受容体電位チャンネル8)を活性化することで、冷感を誘発することが知られている(例えば、非特許文献3参照)。そこで、冷感強度を評価するため、以下の手順に従い、実施例で得られた各化合物及び比較化合物(特許文献29に記載の方法に従って合成したN,2,2,6-テトラメチルシクロヘキサンカルボキサミド、並びに、l-メントール、WS-3、WS-5及びWS-23)のTRPM8活性化作用におけるEC50値を測定した。
なお、WS-3、WS-5及びWS-23は以下の表6に示される化合物である。
全長ヒトTRPM8遺伝子は、プラスミドRC220615(オリジーン社製)よりPCR法を用いて増幅した。得られたPCR産物をpcDNA5/FRT/TO(サーモフィッシャーサイエンティフィック社製)へサブクローニングした後、Flp-InT-RExシステム(サーモフィッシャーサイエンティフィック社製)を用いてFlp-In293293細胞(サーモフィッシャーサイエンティフィック社製)に導入し、ヒトTRPM8安定発現細胞株を作製した。
培養したヒトTRPM8安定発現細胞を、ポリ-D-リジンコートされた96ウェルマイクロプレート(コーニング社製)に対して50,000細胞/ウェルの割合で播種し、1μg/mLドキシサイクリン(タカラバイオ社製)を添加した後、37℃で一晩培養することでヒトTRPM8の発現誘導を行った。
実施例で得られた各化合物及び比較化合物のTRPM8活性化作用におけるEC50値は以下の表1~表6に示すとおりであった。
例示化合物((1R,6S)-10-1)の30ppm水溶液及び比較化合物(N,2,2,6-テトラメチルシクロヘキサンカルボキサミド、l-メントール、WS-3、WS-5)の30ppm水溶液を調製し、当該水溶液を用いて評価を行った。
評価はフレーバリスト4人により行った。前記水溶液をそれぞれ口に含み、うがいをした後吐き出し、口腔内における冷感強度、冷感持続性、冷感の質について評価した。
例示化合物((1R,6S)-10-1)は、WS-5と比較して、冷感強度は強く、その冷感は30分以上続いた。
冷感の質については、例示化合物((1R,6S)-10-1)は、WS-5と比較して、ほぼ同程度のピリピリ感を有した。
下記の配合に従い、歯磨き粉(A)~(C)を調製した。
(A)歯磨き粉基剤990.0g+ツースペーストフレーバーBASE4.0g+l-メントール3.0g+エチルアルコール(EtOH)3.0g
(B)歯磨き粉基剤990.0g+ツースペーストフレーバーBASE4.0g+l-メントール3.0g+比較化合物(WS-5)(1質量% in EtOH)3.0g
(C)歯磨き粉基剤990.0g+ツースペーストフレーバーBASE4.0g+l-メントール3.0g+例示化合物((1R,6S)-10-1)(1質量% in EtOH)3.0g
評価はフレーバリスト3人により行った。上記フレーバリスト3人は、歯ブラシに各歯磨き粉約1gをとり、通常歯を磨く方法で約5分間歯を磨いた。上記フレーバリスト3人は、歯磨き後にうがいをし、口腔内における冷感の強度、持続性、質等について評価した。
また、歯磨き粉(C)では歯磨き粉(B)と比較して、ツースペーストフレーバーBASEの香味プロファイルの発現は同等で、且つ冷感感覚以外の刺激もほとんど感じられなかった。歯磨き粉(B)及び歯磨き粉(C)では共に30分以上の冷感が感じられた。
下記の配合に従い、洗口液(D)~(F)を調製した。
(D)洗口液基剤999.0g+マウスウォッシュフレーバーBASE0.35g+l-メントール0.35g+エチルアルコール(EtOH)0.3g
(E)洗口液基剤999.0g+マウスウォッシュフレーバーBASE0.35g+l-メントール0.35g+比較化合物(WS-5)(10質量% in EtOH)0.3g
(F)洗口液基剤999.0g+マウスウォッシュフレーバーBASE0.35g+l-メントール0.35g+例示化合物((1R,6S)-10-1)(10質量% in EtOH)0.3g
評価はフレーバリスト3人により行った。上記フレーバリスト3人は、各洗口液20mLを口に含み、うがいをした後吐き出し、口腔内における冷感の強度、持続性、質等について評価した。
また、洗口液(F)では洗口液(E)に比べるとマウスウォッシュフレーバーBASEのミントの香味プロファイルの発現は同等で、且つ冷感感覚以外の刺激もほとんど感じられなかった。洗口液(E)及び洗口液(F)では共に30分以上の冷感が感じられた。
下記の配合に従い、チューイングガム(G)~(I)を調製した。
(G)チューイングガム基剤990.0g+ペパーミントフレーバーBASE6.3g+l-メントール0.7g+エチルアルコール(EtOH)3.0g
(H)チューイングガム基剤990.0g+ペパーミントフレーバーBASE6.3g+l-メントール 0.7g+比較化合物(WS-5)(1質量% in EtOH)3.0g
(I)チューイングガム基剤990.0g+ペパーミントフレーバーBASE6.3g+l-メントール0.7g+例示化合物((1R,6S)-10-1)(1質量% in EtOH)3.0g
評価はフレーバリスト3人により行った。上記フレーバリスト3人は、各チューイングガム1gを口に含み、5分程度噛み吐き出した。上記フレーバリスト3人は、吐き出した後の口腔内における冷感の強度、持続性、質等について評価した。
また、チューイングガム(I)を噛んだ場合は噛み始めからややシャープな冷感が発現し、鼻抜けの良い冷感が口腔内に広がり、雑味、他の刺激は感じられなかった。さらに、チューイングガム(I)吐き出し後も30分以上の冷感が感じられた。
下記の配合のキャンディー(J)~(L)を、下記製法に従って調製した。
(J)キャンディー基剤998.0g+ハーブフレーバーBASE0.9g+l-メントール0.8g+エチルアルコール(EtOH)0.3g
(K)キャンディー基剤998.0g+ハーブフレーバーBASE0.9g+l-メントール0.8g+比較化合物(WS-5)(10質量% in EtOH)0.3g
(L)キャンディー基剤998.0g+ハーブフレーバーBASE0.9g+l-メントール0.8g+例示化合物((1R,6S)-10-1)(10質量% in EtOH)0.3g
上記処方のキャンディー基剤1100.0gのうち998.0gを150℃まで火詰めした。その後、火を止め、生地を計量し、上記(J)~(L)に示すキャンディー基剤以外の材料をそれぞれ混合し、135~140℃に保ちながらモールドに流し、成型した。冷却後、モールドから外し、1粒約3gのキャンディー(J)~(L)を作製した。
評価はフレーバリスト3人により行った。上記フレーバリスト3人は、キャンディー1粒を口に含み、舐め溶かし、キャンディーが完全に無くなった後の口腔内における冷感の強度、持続性、質等について評価した。
また、キャンディー(L)を舐めた場合は舐め始めからシャープな清涼感が感じられ、しばらくすると喉奥を刺激する清涼感になり、雑味、他の刺激は感じられなかった。さらに、キャンディー(L)が完全になくなった後も30分以上の冷感が感じられた。
Claims (22)
- 下記一般式(1)で表される2,2,6-トリメチルシクロヘキサンカルボン酸誘導体を含有する冷感剤組成物。
[式(1)中、*印は、不斉炭素原子を表し、
Xは、NH、N(ZAr2)、O又はSであり、Zは、単結合又は置換基を有していてもよい炭素数1~3のアルキレン基であり、Ar2は、置換基を有していてもよい炭素数6~20のアリール基又は置換基を有していてもよい炭素数2~15の芳香族複素環基であり、
Yは、それぞれ独立して置換基を有していてもよいメチレン基であり、
nは、0~3の整数であり、
Ar1は、置換基を有していてもよい炭素数6~20のアリール基又は置換基を有していてもよい炭素数2~15の芳香族複素環基である。] - 前記2,2,6-トリメチルシクロヘキサンカルボン酸誘導体が、前記Xは、NH又はN(ZAr2)である請求項1に記載の冷感剤組成物。
- 前記2,2,6-トリメチルシクロヘキサンカルボン酸誘導体が、前記Xは、NH又はN(ZAr2)であり、(1R,6S)-体である請求項1に記載の冷感剤組成物。
- 前記2,2,6-トリメチルシクロヘキサンカルボン酸誘導体が、前記Xは、NH又はN(ZAr2)であり、前記nは、0又は2であり、前記Zは、単結合又は置換基を有していてもよいエチレン基である請求項1に記載の冷感剤組成物。
- 前記2,2,6-トリメチルシクロヘキサンカルボン酸誘導体が、前記Xは、NH又はN(ZAr2)であり、前記nは、0又は2であり、前記Zは、単結合又は置換基を有していてもよいエチレン基であり、(1R,6S)-体である請求項1に記載の冷感剤組成物。
- 前記2,2,6-トリメチルシクロヘキサンカルボン酸誘導体が、前記Xは、NH又はN(ZAr2)であり、前記nは、2であり、前記Zは、置換基を有していてもよいエチレン基である請求項1に記載の冷感剤組成物。
- 前記2,2,6-トリメチルシクロヘキサンカルボン酸誘導体が、前記Xは、NH又はN(ZAr2)であり、前記nは、2であり、前記Zは、置換基を有していてもよいエチレン基であり、(1R,6S)-体である請求項1に記載の冷感剤組成物。
- 前記2,2,6-トリメチルシクロヘキサンカルボン酸誘導体以外の冷感物質を少なくとも1種更に含有する請求項1~7のいずれか1項に記載の冷感剤組成物。
- 前記冷感物質が、
メントール、メントン、カンファー、プレゴール、イソプレゴール、シネオール、キュベノール、酢酸メンチル、酢酸プレギル、酢酸イソプレギル、サリチル酸メンチル、サリチル酸プレギル、サリチル酸イソプレギル、3-(l-メントキシ)プロパン-1,2-ジオール、2-メチル-3-(l-メントキシ)プロパン-1,2-ジオール、2-(l-メントキシ)エタン-1-オール、3-(l-メントキシ)プロパン-1-オール、4-(l-メントキシ)ブタン-1-オール、3-ヒドロキシブタン酸メンチル、グリオキシル酸メンチル、p-メンタン-3,8-ジオール、1-(2-ヒドロキシ-4-メチルシクロヘキシル)エタノン、乳酸メンチル、メントングリセリンケタール、メンチル-2-ピロリドン-5-カルボキシラート、モノメンチルスクシナート、モノメンチルスクシナートのアルカリ金属塩、モノメンチルスクシナートのアルカリ土類金属塩、モノメンチルグルタラート、モノメンチルグルタラートのアルカリ金属塩、モノメンチルグルタラートのアルカリ土類金属塩、N-[[5-メチル-2-(1-メチルエチル)シクロヘキシル]カルボニル]グリシン、p-メンタン-3-カルボン酸グリセロールエステル、メントールプロピレングリコールカルボナート、メントールエチレングリコールカルボナート、p-メンタン-2,3-ジオール、2-イソプロピル-N,2,3-トリメチルブタンアミド、N-エチル-p-メンタン-3-カルボキサミド、3-(p-メンタン-3-カルボキサミド)酢酸エチル、N-(4-メトキシフェニル)-p-メンタンカルボキサミド、N-エチル-2,2-ジイソプロピルブタンアミド、N-シクロプロピル-p-メンタンカルボキサミド、N-(4-シアノメチルフェニル)-p-メンタンカルボキサミド、N-(2-ピリジン-2-イル)-3-p-メンタンカルボキサミド、N-(2-ヒドロキシエチル)-2-イソプロイル-2,3-ジメチルブタンアミド、N-(1,1-ジメチル-2-ヒドロキシエチル)-2,2-ジエチルブタンアミド、シクロプロパンカルボン酸(2-イソプロピル-5-メチルシクロヘキシル)アミド、N-エチル-2,2-ジイソプロピルブタンアミド、N-[4-(2-アミノ-2-オキソエチル)フェニル]-p-メンタンカルボキサミド、2-[(2-p-メントキシ)エトキシ]エタノール、2,6-ジエチル-5-イソプロピル-2-メチルテトラヒドロピラン、及びトランス-4-tert-ブチルシクロヘキサノールから選ばれる1種以上の化合物;
キシリトール、エリスリトール、デキストロース、及びソルビトールから選ばれる1種以上の糖アルコール;並びに
和種ハッカオイル、ペパーミントオイル、スペアーミントオイル、及びユーカリプタスオイルから選ばれる1種以上の天然物;
からなる群より選ばれる少なくとも1種の冷感物質である請求項8に記載の冷感剤組成物。 - 請求項1~9のいずれか1項に記載の冷感剤組成物を含有する感覚刺激剤組成物。
- 少なくとも1種の温感物質を更に含有する請求項10に記載の感覚刺激剤組成物。
- 前記温感物質が、
バニリルメチルエーテル、バニリルエチルエーテル、バニリルプロピルエーテル、バニリルイソプロピルエーテル、バニリルブチルエーテル、バニリルアミルエーテル、バニリルイソアミルエーテル、バニリルヘキシルエーテル、イソバニリルメチルエーテル、イソバニリルエチルエーテル、イソバニリルプロピルエーテル、イソバニリルイソプロピルエーテル、イソバニリルブチルエーテル、イソバニリルアミルエーテル、イソバニリルイソアミルエーテル、イソバニリルヘキシルエーテル、エチルバニリルメチルエーテル、エチルバニリルエチルエーテル、エチルバニリルプロピルエーテル、エチルバニリルイソプロピルエーテル、エチルバニリルブチルエーテル、エチルバニリルアミルエーテル、エチルバニリルイソアミルエーテル、エチルバニリルヘキシルエーテル、バニリンプロピレングリコールアセタール、イソバニリンプロピレングリコールアセタール、エチルバニリンプロピレングリコールアセタール、バニリルブチルエーテル酢酸エステル、イソバニリルブチルエーテル酢酸エステル、エチルバニリルブチルエーテル酢酸エステル、4-(l-メントキシメチル)-2-(3’-メトキシ-4’-ヒドロキシフェニル)-1,3-ジオキソラン、4-(l-メントキシメチル)-2-(3’-ヒドロキシ-4’-メトキシフェニル)-1,3-ジオキソラン、4-(l-メントキシメチル)-2-(3’-エトキシ-4’-ヒドロキシフェニル)-1,3-ジオキソラン、カプサイシン、ジヒドロカプサイシン、ノルジヒドロカプサイシン、ホモジヒドロカプサイシン、ホモカプサイシン、ビスカプサイシン、トリスホモカプサイシン、ノルノルカプサイシン、ノルカプサイシン、カプサイシノール、バニリルカプリルアミド(オクチル酸バニリルアミド)、バニリルペリラゴンアミド(ノニル酸バニリルアミド)、バニリルカプロアミド(デシル酸バニリルアミド)、バニリルウンデカンアミド(ウンデシル酸バニリルアミド)、N-トランス-フェルロイルチラミン、N-5-(4-ヒドロキシ-3-メトキシフェニル)-2E,4E-ペンタジエノイルピペリジン、N-トランス-フェルロイルピペリジン、N-5-(4-ヒドロキシ-3-メトキシフェニル)-2E-ペンテノイルピペリジン、N-5-(4-ヒドロキシフェニル)-2E,4E-ペンタジエノイルピペリジン、ピペリン、イソピペリン、シャビシン、イソシャビシン、ピペラミン、ピペレチン、ピペロレインB、レトロフラクタミドA、ピペラシド、グイネンサイド、ピペリリン、ピペラミドC5:1(2E)、ピペラミドC7:1(6E)、ピペラミドC7:2(2E,6E)、ピペラミドC9:1(8E)、ピペラミドC9:2(2E,8E)、ピペラミドC9:3(2E,4E,8E)、ファガラミド、サンショオール-I、サンショオール-II、ヒドロキシサンショオール、サンショウアミド、ジンゲロール、ショウガオール、ジンゲロン、メチルジンゲロール、パラドール、スピラントール、カビシン、ポリゴジアール(タデオナール)、イソポリゴジアール、ジヒドロポリゴジアール、及びタデオンから選ばれる1種以上の化合物;並びに
トウガラシ油、トウガラシオレオレジン、ジンジャーオレオレジン、ジャンブーオレオレジン(キバナオランダセンニチ抽出物)、サンショウエキス、サンショウアミド、黒胡椒エキス、白胡椒エキス、及びタデエキスから選ばれる1種以上の天然物;
からなる群より選ばれる少なくとも1種の温感物質である請求項11に記載の感覚刺激剤組成物。 - 請求項10~12のいずれか1項に記載の感覚刺激剤組成物を含有する香料組成物。
- 前記感覚刺激剤組成物を0.00001~90質量%含有する請求項13に記載の香料組成物。
- 飲料、食品、香粧品、トイレタリー製品、エアケア製品、日用・雑貨品、口腔用組成物、ヘアケア製品、スキンケア製品、ボディケア製品、衣料用洗剤、衣料用柔軟仕上げ剤、医薬品部外品及び医薬品からなる群より選ばれるいずれかの製品であって請求項10~12のいずれか1項に記載の感覚刺激剤組成物を含有する製品。
- 前記感覚刺激剤組成物を0.00001~50質量%含有する請求項15に記載の製品。
- 飲料、食品、香粧品、トイレタリー製品、エアケア製品、日用・雑貨品、口腔用組成物、ヘアケア製品、スキンケア製品、ボディケア製品、衣料用洗剤、衣料用柔軟仕上げ剤、医薬品部外品及び医薬品からなる群より選ばれるいずれかの製品であって、請求項13又は14に記載の香料組成物を含有する製品。
- 前記香料組成物を0.00001~50質量%含有する請求項17に記載の製品。
- 飲料、食品、香粧品、トイレタリー製品、エアケア製品、日用・雑貨品、口腔用組成物、ヘアケア製品、スキンケア製品、ボディケア製品、衣料用洗剤、衣料用柔軟仕上げ剤、医薬品部外品及び医薬品からなる群より選ばれるいずれかの製品の製造方法であって、請求項10~12のいずれか1項に記載の感覚刺激剤組成物を配合する、製品の製造方法。
- 飲料、食品、香粧品、トイレタリー製品、エアケア製品、日用・雑貨品、口腔用組成物、ヘアケア製品、スキンケア製品、ボディケア製品、衣料用洗剤、衣料用柔軟仕上げ剤、医薬品部外品及び医薬品からなる群より選ばれるいずれかの製品の製造方法であって、請求項13又は14に記載の香料組成物を配合する、製品の製造方法。
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CA3078909A CA3078909A1 (en) | 2017-10-16 | 2018-10-16 | Cool-sensation imparter composition containing 2,2,6-trimethylcyclohexanecarboxylic acid derivative |
SG11202003286YA SG11202003286YA (en) | 2017-10-16 | 2018-10-16 | Cool-sensation imparter composition containing 2,2,6-trimethylcyclohexanecarboxylic acid derivative |
EP18867351.1A EP3699250A4 (en) | 2017-10-16 | 2018-10-16 | COMPOSITION PROVIDING A FRESHNESS FEELING CONTAINING A DERIVATIVE OF 2,2,6-TRIMETHYLCYLCYCLOHEXANECARBOXYLIC ACID |
US16/756,015 US11344488B2 (en) | 2017-10-16 | 2018-10-16 | Cool-sensation imparter composition containing 2,2,6-trimethylcyclohexanecarboxylic acid derivative |
JP2019549282A JP7157072B2 (ja) | 2017-10-16 | 2018-10-16 | 2,2,6-トリメチルシクロヘキサンカルボン酸誘導体を含有する冷感剤組成物 |
CN201880067163.8A CN111212884A (zh) | 2017-10-16 | 2018-10-16 | 含有2,2,6-三甲基环己烷羧酸衍生物的冷感剂组合物 |
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Also Published As
Publication number | Publication date |
---|---|
EP3699250A1 (en) | 2020-08-26 |
EP3699250A4 (en) | 2021-08-25 |
CN111212884A (zh) | 2020-05-29 |
SG11202003286YA (en) | 2020-05-28 |
JPWO2019078185A1 (ja) | 2020-09-17 |
US11344488B2 (en) | 2022-05-31 |
CA3078909A1 (en) | 2019-04-25 |
US20200297607A1 (en) | 2020-09-24 |
JP7157072B2 (ja) | 2022-10-19 |
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