USRE44339E1 - N-substituted P-menthane carboxamides - Google Patents

N-substituted P-menthane carboxamides Download PDF

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USRE44339E1
USRE44339E1 US13/222,947 US201113222947A USRE44339E US RE44339 E1 USRE44339 E1 US RE44339E1 US 201113222947 A US201113222947 A US 201113222947A US RE44339 E USRE44339 E US RE44339E
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menthanecarboxamide
product
compound
menthyl
cyanomethylphenyl
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Christophe C. Galopin
Pablo Victor Krawec
Jay Patrick Slack
Lori W. Tigani
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Givaudan SA
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C255/00—Carboxylic acid nitriles
    • C07C255/49—Carboxylic acid nitriles having cyano groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton
    • C07C255/58—Carboxylic acid nitriles having cyano groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton containing cyano groups and singly-bound nitrogen atoms, not being further bound to other hetero atoms, bound to the carbon skeleton
    • C07C255/60—Carboxylic acid nitriles having cyano groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton containing cyano groups and singly-bound nitrogen atoms, not being further bound to other hetero atoms, bound to the carbon skeleton at least one of the singly-bound nitrogen atoms being acylated
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
    • A61K8/40—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing nitrogen
    • A61K8/42—Amides
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q11/00—Preparations for care of the teeth, of the oral cavity or of dentures; Dentifrices, e.g. toothpastes; Mouth rinses
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q19/00—Preparations for care of the skin
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C233/00—Carboxylic acid amides
    • C07C233/57—Carboxylic acid amides having carbon atoms of carboxamide groups bound to carbon atoms of rings other than six-membered aromatic rings
    • C07C233/60—Carboxylic acid amides having carbon atoms of carboxamide groups bound to carbon atoms of rings other than six-membered aromatic rings having the nitrogen atom of at least one of the carboxamide groups bound to a carbon atom of a hydrocarbon radical substituted by singly-bound oxygen atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C233/00—Carboxylic acid amides
    • C07C233/57—Carboxylic acid amides having carbon atoms of carboxamide groups bound to carbon atoms of rings other than six-membered aromatic rings
    • C07C233/61—Carboxylic acid amides having carbon atoms of carboxamide groups bound to carbon atoms of rings other than six-membered aromatic rings having the nitrogen atom of at least one of the carboxamide groups bound to a carbon atom of a hydrocarbon radical substituted by doubly-bound oxygen atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C255/00—Carboxylic acid nitriles
    • C07C255/01—Carboxylic acid nitriles having cyano groups bound to acyclic carbon atoms
    • C07C255/32—Carboxylic acid nitriles having cyano groups bound to acyclic carbon atoms having cyano groups bound to acyclic carbon atoms of a carbon skeleton containing at least one six-membered aromatic ring
    • C07C255/42—Carboxylic acid nitriles having cyano groups bound to acyclic carbon atoms having cyano groups bound to acyclic carbon atoms of a carbon skeleton containing at least one six-membered aromatic ring the carbon skeleton being further substituted by singly-bound nitrogen atoms, not being further bound to other hetero atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C255/00—Carboxylic acid nitriles
    • C07C255/01—Carboxylic acid nitriles having cyano groups bound to acyclic carbon atoms
    • C07C255/32—Carboxylic acid nitriles having cyano groups bound to acyclic carbon atoms having cyano groups bound to acyclic carbon atoms of a carbon skeleton containing at least one six-membered aromatic ring
    • C07C255/42—Carboxylic acid nitriles having cyano groups bound to acyclic carbon atoms having cyano groups bound to acyclic carbon atoms of a carbon skeleton containing at least one six-membered aromatic ring the carbon skeleton being further substituted by singly-bound nitrogen atoms, not being further bound to other hetero atoms
    • C07C255/44—Carboxylic acid nitriles having cyano groups bound to acyclic carbon atoms having cyano groups bound to acyclic carbon atoms of a carbon skeleton containing at least one six-membered aromatic ring the carbon skeleton being further substituted by singly-bound nitrogen atoms, not being further bound to other hetero atoms at least one of the singly-bound nitrogen atoms being acylated
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C311/00—Amides of sulfonic acids, i.e. compounds having singly-bound oxygen atoms of sulfo groups replaced by nitrogen atoms, not being part of nitro or nitroso groups
    • C07C311/30—Sulfonamides, the carbon skeleton of the acid part being further substituted by singly-bound nitrogen atoms, not being part of nitro or nitroso groups
    • C07C311/45—Sulfonamides, the carbon skeleton of the acid part being further substituted by singly-bound nitrogen atoms, not being part of nitro or nitroso groups at least one of the singly-bound nitrogen atoms being part of any of the groups, X being a hetero atom, Y being any atom, e.g. N-acylaminosulfonamides
    • C07C311/46—Y being a hydrogen or a carbon atom
    • 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
    • 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

  • Cooling compounds that is, chemical compounds that impart a cooling sensation to the skin or the mucous membranes of the body, are well known to the art and are widely used in a variety of products such as foodstuffs, tobacco products, beverages, dentifrices, mouthwashes and toiletries.
  • cooling compounds can be represented by formula I
  • Y and Z are selected independently from the group consisting of H, OH, C1-C4 straight or branched alkyl, and a C1-C4 straight or branched alkoxy;
  • X is (CH 2 ) n —R, where n is 0 or 1 and R is a group with non-bonding electrons, with the provisos that:
  • An embodiment provides for compounds of formula I wherein X is in the 4-position. Additional embodiments provide for compounds of formula I wherein X is in the 4-position and Y and Z are H, OH, Me or OMe. In certain embodiments, Y and Z are selected independently.
  • Useful groups with non-bonding electrons are halogens, OH, OMe, NO 2 , CN, Ac, SO 2 NH 2 , CHO, CO 2 H and C 1 -C 4 alkyl carboxylates such as CO 2 Et.
  • Other C 1 -C 4 alkyl carboxylates with non-bonding electrons may be useful.
  • the compounds of formula I have 3 chiral centres, giving rise to 8 stereoisomers. All possible stereoisomers are included in the scope of the compounds represented by formula I.
  • the cooling compounds may be prepared by reacting an arylalkylamine derivative with an appropriate acid chloride or carbonyl chloride.
  • the carbonyl chloride can be prepared from 1-menthol ((1R,2S,5R)-2-isopropyl-5-methylcyclohexanol).
  • the cooling compounds are distinguished from similar compounds of the prior art by their surprisingly high cooling effect (up to 10 times higher than that of similar known compounds) and by the longevity of the cooling effect, which adds to their attractiveness in a large variety of products.
  • the subject cooling compounds may be used in products that are applied to the mouth or the skin to give a cooling sensation.
  • applying is meant any form of bringing into contact, for example, oral ingestion or, in the case of tobacco products, inhalation.
  • applying to the skin it may be, for example, by including the compound in a cream or salve, or in a sprayable composition.
  • a method is directed to providing a cooling effect to the mouth or skin by applying thereto a product comprising a compound as hereinabove described.
  • the subject cooling compounds may be used alone or in combination with other cooling compounds known in the art, e.g., menthol, menthone, isopulegol, N-ethyl p-menthanecarboxamide (WS-3), N,2,3-trimethyl-2-isopropylbutanamide (WS-23), menthyl lactate (FrescolatTM ML), menthone glycerine acetal (FrescolatTM MGA), mono-menthyl succinate (PhyscoolTM), mono-menthyl glutarate, O-menthyl glycerine (CoolActTM 10), menthyl-N,N-dimethylsuccinamate or 2-sec-butylcyclohexanone (FreskomentheTM).
  • other cooling compounds known in the art, e.g., menthol, menthone, isopulegol, N-ethyl p-menthanecarboxamide (WS-3), N,2,3-tri
  • the starting compound p-menthane-3-carbonyl chloride as used for the preparation of the compounds in Example 1-6 was prepared from 1-menthol.
  • the ingredients are mixed. 30 mL of obtained solution is put in the mouth, swished around, gargled and spit out. An intense cooling is felt in every area of the mouth as well as the lips. The cooling perception lasts for several hours.
  • Peppermint oil Terpeneless 0.500 g
  • the materials are mixed in the toothgel, and a panelist's teeth are brushed using this toothgel.
  • the mouth is rinsed with water and the water spit out.
  • An intense cooling sensation is felt by the panelist in all areas of the mouth. The cooling perception lasts for several hours.

Abstract

Cooling compounds are provided having the formula:
Figure USRE044339-20130702-C00001
wherein, m is 0 or 1, Y and Z are selected independently from the group consisting of H, OH, C1-C4 straight or branched alkyl, and a C1-C4 straight or branched alkoxy, X is (CH2)n—R, where n is 0 or 1 and R is a group with non-bonding electrons, with the provisos that: (a) when Y and Z are H, X is not F, OH, MeO or NO2 in the 4-position and is not OH in the 2 or 6-position (b) when Y or Z is H then X, Y and Z are such that
    • (i) the groups in the 3- and 4-positions are not both OMe,
    • (ii) the groups in the 4- and 5-positions are not both OMe,
    • (iii) the groups in 3- and 5-positions are not OMe if the group in the 4-position is OH, and
    • (iv) the groups in the 3- and 5-positions are not OH if the group in the 4-position is methyl.

Description

CROSS REFERENCE TO RELATED APPLICATIONS
This application is a reissue application of U.S. Ser. No. 11/437,294 filed May 19, 2006, now U.S. Pat. No. 7,414,152, which is a continuation-in-part of International Application No. PCT/CH2004/000646 filed Oct. 28, 2004, under 35 USC §120 and §365(c), and which claims the benefit of the filing date of U.S. Provisional Application No. 60/523,977 filed Nov. 21, 2003.
COOLING COMPOUNDS ARE PRESENTED
Cooling compounds, that is, chemical compounds that impart a cooling sensation to the skin or the mucous membranes of the body, are well known to the art and are widely used in a variety of products such as foodstuffs, tobacco products, beverages, dentifrices, mouthwashes and toiletries.
One class of cooling compounds that have enjoyed substantial success consists of N-substituted p-menthane carboxamides. Examples of these compounds are described in, for example, British Patents GB 1,351,761-2 and U.S. Pat. No. 4,150,052.
It has now been found that a particular selection of such compounds exhibits a cooling effect that is both surprisingly strong and long-lasting. In one embodiment, the cooling compounds can be represented by formula I
Figure USRE044339-20130702-C00002
in which m is 0 or 1, Y and Z are selected independently from the group consisting of H, OH, C1-C4 straight or branched alkyl, and a C1-C4 straight or branched alkoxy; X is (CH2)n—R, where n is 0 or 1 and R is a group with non-bonding electrons, with the provisos that:
  • (a) when Y and Z are H, X is not F, OH, MeO or NO2 in the 4-position and is not OH in the 2 or 6-position
  • (b) when Y or Z is H then X, Y and Z are such that
    • (i) the groups in the 3- and 4-positions are not both OMe,
    • (ii) the groups in the 4- and 5-positions are not both OMe,
    • (iii) the groups in 3- and 5-positions are not OMe if the group in the 4-position is OH, and
    • (iv) the groups in the 3- and 5-positions are not OH if the group in the 4-position is methyl.
An embodiment provides for compounds of formula I wherein X is in the 4-position. Additional embodiments provide for compounds of formula I wherein X is in the 4-position and Y and Z are H, OH, Me or OMe. In certain embodiments, Y and Z are selected independently.
Useful groups with non-bonding electrons are halogens, OH, OMe, NO2, CN, Ac, SO2NH2, CHO, CO2H and C1-C4 alkyl carboxylates such as CO2Et. Other C1-C4 alkyl carboxylates with non-bonding electrons may be useful.
The compounds of formula I have 3 chiral centres, giving rise to 8 stereoisomers. All possible stereoisomers are included in the scope of the compounds represented by formula I.
The cooling compounds may be prepared by reacting an arylalkylamine derivative with an appropriate acid chloride or carbonyl chloride. The carbonyl chloride can be prepared from 1-menthol ((1R,2S,5R)-2-isopropyl-5-methylcyclohexanol).
The cooling compounds are distinguished from similar compounds of the prior art by their surprisingly high cooling effect (up to 10 times higher than that of similar known compounds) and by the longevity of the cooling effect, which adds to their attractiveness in a large variety of products.
For example, a small group of panelists was asked to taste various solutions of cooling compounds and indicate which solutions had a cooling intensity similar or slightly higher than that of a solution of menthol at 2 ppm. In a second experiment, the same panel was asked to taste the solutions at the chosen concentrations and to record the cooling intensity at regular time intervals until no cooling could be sensed in the mouth. Results are shown in table 1.
TABLE 1
experiment on cooling intensity and longevity.
Chemical Concentration Longevity
1-Menthol 2.0 ppm 35 minutes
N-ethyl p-menthanecarboxamide (WS-3) 1.5 ppm 57 minutes
Formula 1, m = 0,Y = Z = H, 0.5 ppm 90 minutes
X = 4-CN
Formula 1, m = 0, Y = Z = H, 0.2 ppm 93 minutes
X = 4-CH2CN
From Table 1, it can be seen that the compounds of Formula I are up to 10 times stronger and last up to 3 times longer than menthol, the reference cooling compound. Compounds of Formula I are also much stronger and last longer than WS-3, a known cooling compound of the prior art.
The subject cooling compounds may be used in products that are applied to the mouth or the skin to give a cooling sensation. By “applying” is meant any form of bringing into contact, for example, oral ingestion or, in the case of tobacco products, inhalation. In the case of application to the skin, it may be, for example, by including the compound in a cream or salve, or in a sprayable composition. A method is directed to providing a cooling effect to the mouth or skin by applying thereto a product comprising a compound as hereinabove described.
The subject cooling compounds may be used alone or in combination with other cooling compounds known in the art, e.g., menthol, menthone, isopulegol, N-ethyl p-menthanecarboxamide (WS-3), N,2,3-trimethyl-2-isopropylbutanamide (WS-23), menthyl lactate (Frescolat™ ML), menthone glycerine acetal (Frescolat™ MGA), mono-menthyl succinate (Physcool™), mono-menthyl glutarate, O-menthyl glycerine (CoolAct™ 10), menthyl-N,N-dimethylsuccinamate or 2-sec-butylcyclohexanone (Freskomenthe™).
The subject cooling compounds and related methods are further described by the following non-limiting examples.
The starting compound p-menthane-3-carbonyl chloride as used for the preparation of the compounds in Example 1-6 was prepared from 1-menthol.
EXAMPLE 1 Preparation of N-(4-cyanomethylphenyl) p-menthanecarboxamide
To a flask, were added 6.6 g (50 mmol) of 4-aminobenzyl cyanide, 4.04 mL of pyridine and 100 mL MtBE. To this mixture, 10 g of p-menthane-3-carbon*yl chloride were added dropwise over 5 minutes. The reaction mixture was stirred for 24 h. To the reaction mixture, 50 mL of water were added. The mixture was separated. The organic layer was washed with 50 mL of water and 50 mL of brine. The organic layer was dried over MgSO4. The solvent was evaporated in vacuo to afford the crude product, which was recrystallized from hexanes to afford 10.1 g of the desired product with the following spectroscopic properties:
MS: 299 ([M+1]), 298 ([M+]), 132, 83. 1H NMR (300 MHz; CDCl3) δ; 7.58 (d, 2H), 7.49 (s, 1H), 7.27 (d, 2H), 3.73 (s, 2H), 2.2 (t, 1H), 1.96-1.57 (m, 5H), 1.48-1.21 (m, 2H), 1.172-0.99 (m, 2H), 0.94 (d, 3H), 0.93 (d, 3H), 0.85 (d, 3H). 13C NMR (75 MHz; CDCl3)δ: 174.4, 137.8, 128.3, 125.1, 120.3, 118.2, 50.5, 44.3, 39.25, 34.3, 32.1, 28.7, 23.8, 22.9, 22.1, 21.2, 16.1
EXAMPLE 2 Preparation of N-(4-sulfamoylphenyl) p-menthanecarboxamide
A preparation similar to that described in example 1 gives the desired product with the following spectroscopic properties:
MS: 339 ([M+1]), 338 ([M+]), 172, 83. 1H NMR (300 MHz; DMSO) δ: 10.21 (s, 1H), 7.76 (d, 1H) 7.73 (d, 2H), 7.23 (s, 2H), 2.26-2.42 (m, 1H), 1.45-1.85 (m, 5H), 1.29-1.44 (m, 2H), 0.89 (d, 3H), 0.86 (d, 3H), 0.78 (d, 3H). 13C NMR (75 MHz; DMSO) δ: 174.6, 142.3, 138.3, 126.7, 118.8, 48.9, 43.7, 34.3, 31.9, 28.6, 23.7, 22.35, 21.3, 16.25
EXAMPLE 3 Preparation of N-(4-cyanophenyl) p-menthanecarboxamide
A preparation similar to that described in example 1 gives the desired product with the following spectroscopic properties:
MS: 285 ([M+1]), 284 ([M+]), 139, 83. 1H NMR (300 MHz; CDCl3) δ: 7.69 (d, 2H), 7.6 (d, 2 H), 7.5 (s, 1H), 1.85-1.97 (m, 1H), 1.69-1.84 (m, 3H), 1.55-1.69 (m, 2H), 1.21-1.47 (m, 2H), 0.979-1.16 (m, 2H), 0.95 (d, 3H), 0.93 (d, 3H), 0.82 (d, 3H). 13C NMR (300 MHz; CDCl3) δ: 174.6, 133.1, 119.4, 118.7, 100.35, 50.7, 44.4, 39.25, 34.2, 32.1, 28.8, 23.7, 22.0, 21.2, 16.1, 14.0
EXAMPLE 4 Preparation of N-(4-acetylphenyl) p-menthanecarboxamide
A preparation similar to that described in example 1 gives the desired product with the following spectroscopic properties:
MS: 302 ([M+1]), 301 ([M+]), 135, 83. 1H NMR (300 MHz; CDCl3) δ: 7.93 (d, 2H), 7.66 (d, 2H), 7.63 (s, 1H), 2.57 (s, 3H), 2.09-2.31 (m, 1H), 1.84-1.98 (m, 1H), 1.68-1.85 (m, 5H), 1.56-1.68 (m, 1H), 1.17-1.48 (m, 2H), ), 0.93 (d, 3H), 0.91 (d, 3H), 0.83 (d, 3H). 13C NMR (75 MHz; CDCl3) δ: 197.1, 174.9, 142.7, 129.9, 119.2, 51.2, 44.9, 39.8, 34.8, 32.6, 29.2, 26.6, 24.3, 22.4, 21.5, 16.6
EXAMPLE 5 Preparation of N-(4-hydroxymethylphenyl) p-menthanecarboxamide
A preparation similar to that described in example 1 gives the desired product with the following spectroscopic properties:
MS: 290 (M+1), 289 (M+), 123, 83. 1HNMR (300 MHz, DMSO) δ: 9.9 (s, 1H), 7.54 (d, 2H), 7.21 (d, 2H), 4.2 (s, 2H), 2.36-2.1 (m, 1H), 1.8-1.59 (m, 6H), 1.57-1.44 (m, 1H), 1.21-0.9 (m, 4H), 0.87 (dd, 3H), 0.85 (dd, 3H), 0.79 (d, 2H). 13C NMR (75 MHz; DMSO) δ: 173.7, 137.7, 137.1, 126.7, 118.9, 62.6, 48.6, 43.6, 34.2, 31.7, 28.3, 23.6, 22.2, 21.1, 16.1
EXAMPLE 6 Preparation of N-(3-hydroxy-4-methoxyphenyl) p-menthanecarboxamide
A preparation similar to that described in example 1 gives the desired product with the following spectroscopic properties:
MS: 306 ([M+1]), 305 ([M+]), 139, 83. 1H NMR (300 MHz; CDCl3) δ: 7.14 (s, 1H), 7.08 (d, 1H), 6.78 (d, 1H), 5.7 (s, 1H), 3.8 (s, 3H), 2.02-2.21 (m, 2H), 1.53-1.94 (m, 5H), 1.17-1.48 (m, 2H), 0.97-1.17 (m, 2H), 0.92 (dd, 3H), 0.91 (dd, 3H), 0.82 (d, 3H). 13C NMR (75 MHz; CDCl3) δ: 173.9, 145.6, 143.3, 131.7, 111.65, 110.8, 107.4, 56.1, 50.5, 44.4, 39.2, 32.15, 34.4, 28.6, 23.8, 22.1, 21.2, 16.1
EXAMPLE 7 Application in Mouthwash
Alcohol 95% 177 mL
Sorbitol 70% 250 g
Compound of example 1 as a 1% solution in alcohol 50 mL
Peppermint oil, Terpeneless 0.300 g
Methyl salicylate 0.640 g
Eucalyptol 0.922 g
Thymol 0.639 g
Benzoic acid 1.500 g
Pluronic ™ F127 5.000 g
Sodium Saccharin 0.600 g
Sodium Citrate 0.300 g
Citric Acid 0.100 g
Water q.s. 1 liter
The ingredients are mixed. 30 mL of obtained solution is put in the mouth, swished around, gargled and spit out. An intense cooling is felt in every area of the mouth as well as the lips. The cooling perception lasts for several hours.
EXAMPLE 9 Application in Toothpaste
Opaque toothgel 97.000 g
Compound of example 2 as a 2% solution in PG 2.500 g
Peppermint oil, Terpeneless 0.500 g
The materials are mixed in the toothgel, and a panelist's teeth are brushed using this toothgel. The mouth is rinsed with water and the water spit out. An intense cooling sensation is felt by the panelist in all areas of the mouth. The cooling perception lasts for several hours.
It will be understood that the embodiments described herein are merely exemplary, and that one skilled in the art may make variations and modifications without departing from the spirit and scope of the invention. All such variations and modifications are intended to be included within the scope of the invention as described hereinabove. Further, all embodiments disclosed are not necessarily in the alternative, as various embodiments of the invention may be combined to provide the desired result.

Claims (23)

What is claimed is:
1. A compound selected from the group consisting of N-(4-cyanomethylphenyl) p-menthanecarboxamide, N-(4-sulfamoylphenyl) p-menthanecarboxamide, N-(4-cyanophenyl) p-menthanecarboxamide, N-(4-acetylphenyl) p-menthanecarboxamide, N-(4-hydroxymethylphenyl) p-menthanecarboxamide and N-(3-hydroxy-4-methoxyphenyl) p-menthanecarboxamide.
2. A method of providing a cooling effect to the mouth or skin by applying thereto a product comprising a compound according to claim 1 selected from the group consisting of N-(4-cyanomethylphenyl) p-menthanecarboxamide, N-(4-sulfamoylphenyl) p-menthanecarboxamide, N-(4-cyanophenyl) p-menthanecarboxamide, N-(4-acetylphenyl) p-menthanecarboxamide, N-(4-hydroxymethylphenyl) p-menthanecarboxamide and N-(3-hydroxy-4-methoxyphenyl) p-menthanecarboxamide.
3. A product that is applied to the mouth or the skin foodstuff, tobacco product, beverage, dentrifice, mouthwash, or toiletry composition comprising an amount of a compound according to claim 1 selected from the group consisting of N-(4-cyanomethylphenyl) p-menthanecarboxamide, N-(4-sulfamoylphenyl) p-menthanecarboxamide, N-(4-cyanophenyl) p-menthanecarboxamide, N-(4-acetylphenyl) p-menthanecarboxamide, N-(4-hydroxymethylphenyl) p-menthanecarboxamide and N-(3-hydroxy-4-methoxyphenyl) p-menthanecarboxamide, wherein the amount is effective to give a cooling sensation to the mouth or the skin.
4. A compound comprising formula I
Figure USRE044339-20130702-C00003
in which m is 0 or 1, Y and Z are selected independently from the group consisting of H, OH, C1-C4 straight or branched alkyl, and C1-C4 straight or branched alkoxy; X is (CH2)n—R, where n is 0 or 1 and R is a group with non-bonding electrons; said compound selected from the group consisting of N-(4-cyanomethylphenyl) p-menthanecarboxamide, N-(4-sulfamoylphenyl) p-menthanecarboxamide, N-(4-cyanophenyl) p-menthanecarboxamide, N-(4-acetylphenyl) p-menthanecarboxamide, N-(4-hydroxymethylphenyl) p-menthanecarboxamide and N-(3-hydroxy-4-methoxyphenyl) p-menthanecarboxamide.
5. A method of providing a cooling effect to the mouth or skin by applying thereto a product comprising a compound according to claim 4.
6. A product that is applied to the mouth or the skin comprising an amount of a compound according to claim 4, wherein the amount is effective to give a cooling sensation to the mouth or the skin.
7. The product of claim 6 comprising at least one of foodstuffs, tobacco products, beverages, dentifrices, mouthwashes, or toiletries.
8. The product composition of claim 7 comprising 3 wherein the product comprises a cream or salve.
9. The product composition of claim 7 comprising 3 wherein the product comprises a sprayable composition.
10. The product of claim 6 further comprising an additional cooling compound.
11. The product of claim 10 wherein the additional cooling compound comprises at least one of menthol, menthone, isopulegol, N-ethyl p-menthanecarboxamide, N,2,3-trimethyl-2-isopropylbutanamide, menthyl lactate, menthone glycerine acetal, mono-menthyl succinate, mono-menthyl glutarate, O-menthyl glycerine, menthyl-N,N-dimethylsuccinamate or 2-sec-butylcyclohexanone.
12. The method of claim 5 wherein said applying comprises inhalation.
13. The method of claim 5 wherein said applying comprises oral ingestion.
14. The product of claim 3 comprising at least one of foodstuffs, tobacco products, beverages, dentifrices, mouthwashes, or toiletries.
15. The product of claim 14 comprising a cream or salve.
16. The product of claim 14 comprising a sprayable composition.
17. The product composition of claim 3 further comprising an additional cooling compound.
18. The product composition of claim 17 wherein the additional cooling compound comprises at least one of menthol, menthone, isopulegol, N-ethyl p-menthanecarboxamide, N,2,3-trimethyl-2-i sopropylbutanami de, menthyl lactate, menthone glycerine acetal, mono-menthyl succinate, mono-menthyl glutarate, O-menthyl glycerine, menthyl-N,N-dimethylsuccinamate or 2-sec-butylcyclohexanone.
19. The method of claim 2 wherein said applying comprises inhalation.
20. The method of claim 2 wherein said applying comprises oral ingestion.
21. The compound of claim 1, wherein said compound is N-(4-cyanomethylphenyl) p-menthanecarboxamide.
22. The method of claim 2, wherein said compound is N-(4-cyanomethylphenyl) p-menthanecarboxamide.
23. The composition of claim 3, wherein said compound is N-(4-cyanomethylphenyl) p-menthanecarboxamide.
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Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US10123953B2 (en) 2012-06-21 2018-11-13 The Procter & Gamble Company Reduction of tooth staining derived from cationic antimicrobials
US10299999B2 (en) 2011-02-23 2019-05-28 Givaudan S.A. Flavour composition comprising menthol and menthane carboxamides
US10871363B2 (en) 2018-05-28 2020-12-22 The Procter & Gamble Company Oral care composition with improved deposition efficacy of a cooling sensate agent in the oral cavity
US11191709B2 (en) 2019-04-26 2021-12-07 The Procter & Gamble Company Reduction of tooth staining derived from cationic antimicrobials
US11236042B2 (en) 2017-01-10 2022-02-01 Takasago International Corporation Methylmenthol derivative and cool-sensation imparter composition containing same
US11344488B2 (en) 2017-10-16 2022-05-31 Takasago International Corporation Cool-sensation imparter composition containing 2,2,6-trimethylcyclohexanecarboxylic acid derivative

Families Citing this family (171)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
ES2352563T3 (en) * 2005-03-01 2011-02-21 Givaudan Sa MENTANOCARBOXAMIDE DERIVATIVES THAT HAVE COOLING PROPERTIES.
GB0504194D0 (en) * 2005-03-02 2005-04-06 Givaudan Sa Organic compounds
BRPI0610087A2 (en) * 2005-05-27 2008-12-02 Givaudan Sa cooling compound
JP5383191B2 (en) 2005-08-15 2014-01-08 ジボダン エス エー Refreshing compound
EP1940791B1 (en) * 2005-10-25 2009-09-16 Givaudan SA Organic compounds
EP1996535A2 (en) * 2006-03-15 2008-12-03 Givaudan SA Para-substituted 2-alkoxyphenol compounds
US20090312384A1 (en) * 2006-07-14 2009-12-17 Stefan Michael Furrer Benzimidazole As Cooling Compounds
BRPI0721140A2 (en) * 2006-12-20 2014-04-01 Givaudan Nederland Services Bv P-MENTANE-3-N-REPLACED CARBOXAMIDE AND USES OF THE SAME.
GB0704163D0 (en) * 2007-03-02 2007-04-11 Quest Int Serv Bv Compositions comprising a physiological coolant
JP2010527943A (en) 2007-05-23 2010-08-19 ジボダン エス エー Buton derivatives useful as coolants
EP2162018B1 (en) 2007-06-06 2012-10-17 Givaudan SA Salt enhancement
US8655677B2 (en) * 2007-06-12 2014-02-18 Bruce Reiner Productivity workflow index
WO2008151460A2 (en) 2007-06-13 2008-12-18 Givaudan Sa Cooling compounds
US7880011B2 (en) 2007-07-23 2011-02-01 Givandan, S.A. Amide addition reaction
EP2033688B1 (en) 2007-08-20 2012-10-17 Symrise AG Oxalic acid derivatives and their use as physiological cooling agents
US20090098173A1 (en) * 2007-10-11 2009-04-16 Robinson Ronni L Topical pain relief product
WO2009062332A2 (en) * 2007-11-16 2009-05-22 Givaudan Sa Cooling compounds
WO2009070910A2 (en) 2007-12-07 2009-06-11 Givaudan Sa Carboxamide derivatieves having cooling properties
WO2009076792A1 (en) 2007-12-19 2009-06-25 Givaudan Sa Cooling compounds
EP2250154A1 (en) * 2008-01-17 2010-11-17 Givaudan SA Benzimidazole derivatives and their use as cooling agents
EP2244745B1 (en) * 2008-02-22 2015-03-25 The Procter and Gamble Company Absorbent article comprising lotion composition comprising a cooling agent
DE102008015425A1 (en) * 2008-03-20 2010-01-21 Beiersdorf Ag Cosmetic or dermatological preparations for the reduction of itching and other dermatological abnormalities, which may occur particularly in the case of aging skin, containing (1R, 2S, 5R) -2-isopropyl-5-methyl-N- (2- (pyridine-2-) yl) ethylcyclohexanecarboxamide and / or (1R, 2S, 5R) -N- (4- (cyanomethyl) -phenyl) -2-isopropyl-5-methylcyclohexanecarboxamide
DE102008015424A1 (en) * 2008-03-20 2009-09-24 Beiersdorf Ag Cooling cosmetic or dermatological preparations containing (1R, 2S, 5R) -2-isopropyl-5-methyl-N- (2- (pyridyn-2-yl) -ethyl-cyclohexanecarboxamide and / or (1R, 2S, 5R) -N- (4- (cyanomethyl) -phenyl) -2-isopropyl-5-methylcyclohexanecarboxamide with menthoxypropanediol
DE102008015426A1 (en) 2008-03-20 2009-09-24 Beiersdorf Ag Cooling cosmetic or dermatological preparations containing (1R, 2S, 5R) -2-isopropyl-5-methyl-N- (2- (pyridyn-2-yl) -ethyl-cyclohexanecarboxamide and / or (1R, 2S, 5R) -N- (4- (cyanomethyl) -phenyl) -2-isopropyl-5-methylcyclohexanecarboxamide to reduce reddening of the skin
DE102008015428A1 (en) * 2008-03-20 2009-09-24 Beiersdorf Ag Cooling preparations for human skin and / or mucosal contact containing (1R, 2S, 5R) -2-isopropyl-5-methyl-N- (2- (pyridin-2-yl) -ethyl-cyclohexanecarboxamide and / or ( 1R, 2S, 5R) -N- (4- (cyanomethyl) phenyl) -2-isopropyl-5-methylcyclohexanecarboxamide
EP2296759B1 (en) * 2008-05-22 2019-10-02 Givaudan SA Cooling composition
AU2009282004A1 (en) * 2008-08-15 2010-02-18 The Procter & Gamble Company Solution of menthane carboxamides for use in consumer products
BRPI0917999A2 (en) * 2008-08-15 2015-11-17 Procter & Gamble synthesis of cyclohexane derivatives useful as sensory elements in consumer products
AU2009318056B2 (en) * 2008-11-20 2014-07-24 The Procter & Gamble Company Personal care compositions providing enhanced cooling sensation
FR2944790B1 (en) * 2009-04-23 2012-06-01 Mane Fils V NOVEL COMPOUNDS WITH PHYSIOLOGICAL EFFECT
US7923577B2 (en) 2009-04-27 2011-04-12 International Flavors & Fragrances Inc. Menthylcarboxamides and their use as cooling agents
US8664261B2 (en) 2009-05-05 2014-03-04 Givaudan S.A. Organic compounds having cooling properties
BR112012001599A2 (en) 2009-07-29 2016-03-08 Unilever Nv dentifrice composition
US20120196018A1 (en) * 2009-07-29 2012-08-02 Francisco Valentino Villagran Organic Compounds
EP2295031B1 (en) 2009-08-05 2018-01-10 Symrise AG Use of pterocarpans as anti-cellulite agents
CN102802732B (en) 2009-09-11 2016-04-27 宝洁公司 For the method and composition of oral surfaces hydrophobically modified
US20110195042A1 (en) 2010-02-10 2011-08-11 Thomas Edward Huetter Compositions, Methods and Kits Useful for Treating a Respiratory Symptom
EP2553444B1 (en) 2010-04-01 2018-09-26 The Procter and Gamble Company Whole mouth malodor control by a combination of antibacterial and deodorizing agents
EP2555745B1 (en) 2010-04-08 2016-12-21 Symrise AG Use of dihydrodehydrodiisoeugenol and preparations comprising dihydrodehydrodiisoeugenol
EP2389922A1 (en) 2010-05-25 2011-11-30 Symrise AG Cyclohexyl carbamate compounds as anti-ageing actives
BR112013001142A2 (en) 2010-07-19 2016-05-17 Procter & Gamble compositions comprising derivatives of essential oil compounds and use in personal care products
EP2613649A1 (en) 2010-09-09 2013-07-17 Kraft Foods Global Brands LLC Chewing gum compositions providing flavor release profiles
AU2011308857B2 (en) 2010-10-01 2015-11-05 The Procter & Gamble Company Oral care compositions with improved flavor
US20120116113A1 (en) 2010-11-05 2012-05-10 Erman Mark B PROCESS FOR MAKING NEO-ENRICHED p-MENTHANE COMPOUNDS
EP2286908A3 (en) 2010-11-19 2011-06-01 Symrise AG Solubilizer for cosmetic preparations
EP2356977B1 (en) 2011-02-02 2017-12-27 Symrise AG Preparations with wood extracts of Gleditsia
AU2012217908B2 (en) 2011-02-14 2016-03-03 The Procter & Gamble Company Filmcoated solid dosage forms comprising honey in the coating
WO2013014235A2 (en) 2011-07-26 2013-01-31 Givaudan Sa Rinse-off compositions
US20130042482A1 (en) 2011-08-16 2013-02-21 Valerie Jean Bradford Skin Engaging Member Comprising An Anti-Irritation Agent
ES2689171T3 (en) 2011-09-01 2018-11-08 The Procter & Gamble Company Compositions for oral care with improved rheology
US9802885B2 (en) 2011-09-01 2017-10-31 Takasago International Corporation (Usa) Substituted cyclohexane compounds
GB201205444D0 (en) * 2012-03-28 2012-05-09 Givaudan Sa Composition
BR112014027633A2 (en) * 2012-05-22 2017-06-27 Unilever Nv personal care composition, methods for providing a refreshing feel and use of a copolymer
US20130315843A1 (en) 2012-05-25 2013-11-28 The Procter & Gamble Company Composition for reduction of trpa1 and trpv1 sensations
EP2861304B1 (en) 2012-06-15 2018-08-08 Symrise AG Compositions comprising hyaluronan biosynthesis promoting agents
US20130344120A1 (en) 2012-06-21 2013-12-26 Douglas Craig Scott Mouth Rinse Emulsions
WO2014005614A1 (en) 2012-07-02 2014-01-09 Symrise Ag A method of flavouring a smoking product
EP2695597B1 (en) 2012-08-07 2019-07-24 Symrise AG Cosmetic compositions
US20140090255A1 (en) * 2012-09-28 2014-04-03 The Gillette Company Skin Engaging Member Comprising At Least One Thermally Resilient Sensate
SG11201501430VA (en) 2012-09-28 2015-03-30 Gillette Co A skin engaging member comprising at least one thermally resilient sensate
WO2014052389A2 (en) * 2012-09-28 2014-04-03 The Gillette Company A skin engaging shaving aid member comprising at least one thermally resilient sensate
EP2745878B1 (en) 2012-12-19 2023-01-25 Symrise AG Cosmetic compositions
AU2014209162B2 (en) 2013-01-25 2016-03-24 Wintermute Biomedical, Llc Therapeutic compounds
EP2764860A1 (en) 2013-02-06 2014-08-13 Basf Sa Cupuassu fatty acid amidoamines and their derivatives
CA2899492C (en) 2013-02-13 2019-09-17 The Procter & Gamble Company Anise flavored medication
ES2701758T3 (en) 2013-02-27 2019-02-25 Symrise Ag Ginger extract for the protection of stem cells
ES2647784T3 (en) 2013-03-08 2017-12-26 Symrise Ag Cosmetic compositions
PL2774481T3 (en) 2013-03-08 2019-03-29 Symrise Ag Antimicrobial compositions
EP2783578A1 (en) 2013-03-26 2014-10-01 Symrise AG Catechin reaction products
EP2789369B1 (en) 2013-04-14 2018-06-06 Symrise AG A composition for lightening skin and hair
EP2807925A1 (en) 2013-05-26 2014-12-03 Symrise AG Antimicrobial compositions
EP2810934A1 (en) 2013-06-09 2014-12-10 Symrise AG New succinate derivatives
EP3127583A1 (en) 2013-06-24 2017-02-08 The Procter and Gamble Company A method of demonstrating stain-proof efficacy of an oral care composition
EP2842607B1 (en) 2013-09-02 2018-05-30 Symrise AG A skin and/or hair whitening mixture
EP3046634A1 (en) 2013-09-22 2016-07-27 Cutech S.R.L. Extracts fo halimione portulacoides and their application
EP2853254B1 (en) 2013-09-26 2017-11-08 Symrise AG A composition for lightening skin and/or hair
EP2859883B1 (en) 2013-10-13 2019-05-15 Symrise AG Active mixtures comprising acylated oligopeptides and troxerutin
EP2862852B1 (en) 2013-10-18 2018-07-04 Symrise AG Urea derivatives for the protection of stem cells
WO2015062629A1 (en) 2013-10-29 2015-05-07 Cutech Srl Use of mono ornithine ketoglutarate (mokg)
US9884130B2 (en) 2013-11-13 2018-02-06 The Procter & Gamble Company Compositions for delivery of oral comfort sensations
EP3110510A1 (en) 2014-02-27 2017-01-04 The Procter & Gamble Company Oral care compositions with a reduced bitter taste perception
ES2643590T3 (en) 2014-03-18 2017-11-23 Symrise Ag Titanium dioxide coated to reduce the effect of skin whitening
US20150272847A1 (en) * 2014-03-26 2015-10-01 The Gillette Company Skin Engaging Shaving Aid Comprising A Thermally Resilient Sensate And A TRPA1 Receptor Inhibitor
US20150273711A1 (en) * 2014-03-26 2015-10-01 The Gillette Company Razor Comprising A Molded Shaving Aid Composition Comprising A Thermally Resilient Sensate
AU2015249706A1 (en) 2014-04-23 2016-11-03 The Procter & Gamble Company Cyclohexanecarboxamide with cooling properties
EP2962678A1 (en) 2014-06-30 2016-01-06 Symrise AG Flavour and fragrance compositions comprising acetophenone derivatives
EP2979682B1 (en) 2014-07-30 2018-09-05 Symrise AG A fragrance composition
BR112017002061A2 (en) 2014-08-15 2017-12-26 Procter & Gamble oral treatment compositions and regimens
CN106659650A (en) 2014-08-15 2017-05-10 宝洁公司 Oral care compositions with an enhanced sensory experience
CN111939090A (en) 2014-08-15 2020-11-17 宝洁公司 Dentifrice with extending chemical
EP3023090B1 (en) 2014-11-21 2019-08-07 Symrise AG Compositions
KR20170070196A (en) 2014-11-26 2017-06-21 더 질레트 컴퍼니 엘엘씨 A skin engaging member comprising ethylene vinyl acetate
CA2971390A1 (en) 2014-12-18 2016-06-23 The Gillette Company Llc Lubricating members having hydrophobic components for razor cartridges
RU2017118504A (en) 2014-12-18 2019-01-18 Дзе Жиллетт Компани Ллс Lubricating elements for shaving cartridges
EP3045161A1 (en) 2015-01-18 2016-07-20 Symrise AG Active compositions comprising 1,2-hexanediol and 1,2-octanediol
US9951295B2 (en) 2015-02-19 2018-04-24 The Procter & Gamble Company Compositions for deposition on biological surfaces
CN107532063B (en) * 2015-03-25 2020-03-10 高砂香料工业株式会社 Methylmenthol derivative and cold-sensitive composition containing the same
EP3280411B1 (en) 2015-04-09 2020-02-19 The Procter and Gamble Company Reduction in cpc taste aversion by reducing cpc activation of trpa1 receptors, tprv1 receptors, or both
EP3081207B1 (en) 2015-04-16 2022-09-21 Symrise AG Use of a liposome composition
US10391071B2 (en) 2015-04-28 2019-08-27 Cutech Srl Compositions comprising valerian extracts
EP3097905B1 (en) 2015-05-28 2020-11-04 Symrise AG Cosmetic compositions
BR112018006735A2 (en) * 2015-10-22 2018-10-16 Procter & Gamble chromatographic separation method
MX2018004814A (en) 2015-10-22 2019-04-01 Procter & Gamble Synthesis of cyclohexane carboxamide derivatives useful as sensates in consumer products.
WO2017071752A1 (en) 2015-10-28 2017-05-04 Symrise Ag Method for inhibiting or masking fishy odours
MX2018005796A (en) 2015-11-15 2018-08-01 Symrise Ag Reduction of stinging sensation on skin.
WO2017097434A1 (en) 2015-12-06 2017-06-15 Symrise Ag A fragrance composition
WO2017097362A1 (en) 2015-12-10 2017-06-15 Symrise Ag Composition with stabilized taste and odor
EP3390352A1 (en) 2015-12-18 2018-10-24 The Procter and Gamble Company Synthesis of cyclohexane ester derivatives useful as sensates in consumer products
ES2733201T3 (en) 2015-12-21 2019-11-28 Thiocyn Gmbh Cosmetic composition comprising a combination of active substances
EP3090727B8 (en) 2016-01-13 2019-06-19 Thiocyn GmbH Hair growth composition
KR20180124121A (en) 2016-03-30 2018-11-20 시므라이즈 아게 Active mixture
AU2017240032B2 (en) 2016-04-01 2019-07-18 The Procter & Gamble Company Oral care compositions containing gel networks and potassium nitrate
WO2017173272A1 (en) 2016-04-01 2017-10-05 The Procter & Gamble Company Oral care compositions containing potassium nitrate and peroxide
MX2018011991A (en) 2016-04-01 2019-02-13 Procter & Gamble Oral care compositions with an effective flavor display.
US20170334082A1 (en) 2016-05-18 2017-11-23 The Gillette Company Llc Skin Engaging Member Comprising Ethylene Vinyl Acetate
US20230190633A1 (en) 2016-05-23 2023-06-22 Symrise Ag A wheat bran extract in a hair care blend
WO2018036625A1 (en) 2016-08-20 2018-03-01 Symrise Ag A preservative mixture
BR112018073863B1 (en) 2016-10-11 2022-08-23 Symrise Ag USE OF A COMPOUND OF FORMULA (I), ANTIFUNGAL MIXTURE, COMPOSITIONS COMPRISING SUCH COMPOUND OF FORMULA (I) OR SUCH ANTIFUNGAL MIXTURE AND METHOD TO PREVENT MICROBIAL DETERIORATION OF SUCH COMPOSITIONS
WO2018081190A1 (en) 2016-10-25 2018-05-03 The Procter & Gamble Company Fibrous structures
US20180117780A1 (en) 2016-11-03 2018-05-03 The Gillette Company Llc Skin engaging member comprising ethylene vinyl acetate
BR112019009754B1 (en) 2016-11-17 2022-11-22 The Gillette Company Llc SKIN CONTACT MEMBERS COMPRISING ETHYLENE VINYL ACETATE AND A FRAGRANCE
WO2018099570A1 (en) 2016-12-02 2018-06-07 Symrise Ag Cosmetic blends
WO2018148763A1 (en) 2017-02-13 2018-08-16 Wintermute Biomedical, Inc. Anti-pathogenic therapeutic compositions
IT201700090929A1 (en) 2017-08-07 2019-02-07 Cutech S R L Cosmetic and medical uses of extracts of Coprinus comatus fungus for the regulation of pilo sebaceous unity.
EP4331684A2 (en) 2017-08-09 2024-03-06 Symrise AG 1,2-alkanediols
WO2019037844A1 (en) 2017-08-23 2019-02-28 Symrise Ag Novel compositions of natural butters and uses thereof
CN111032015A (en) 2017-08-23 2020-04-17 西姆莱斯有限公司 New use of extract of Isochrysis galbana
KR102637288B1 (en) 2017-10-10 2024-02-16 시므라이즈 아게 Compositions containing benzoic acid derivatives or furoic acid derivatives and uses of the derivatives for emulsion and foam stability
EP3700352B1 (en) 2017-10-23 2021-09-22 Symrise AG Aroma composition
JP6981243B2 (en) * 2017-12-27 2021-12-15 ライオン株式会社 Toothpaste composition
EP3813795A1 (en) 2018-03-08 2021-05-05 Symrise AG Mixtures comprising a protein extract for the treatment of human skin and/or hair
EP3823455A1 (en) 2018-07-16 2021-05-26 Symrise AG Composition for substituting sugar in baked goods
US20210337793A1 (en) 2018-08-27 2021-11-04 Symrise Ag Antimicrobial mixtures comprising at least one hydroxyphenone derivative
CN113226267A (en) 2018-09-14 2021-08-06 西姆莱斯股份公司 Hair care composition
CA3113475A1 (en) 2018-09-20 2020-03-26 Symrise Ag Compositions comprising odorless 1,2-pentanediol
EP3860585A4 (en) 2018-10-01 2022-06-22 Wintermute Biomedical, Inc. Therapeutic compositions
WO2020069762A1 (en) 2018-10-05 2020-04-09 Symrise Ag A method for fighting female body odors
JP2020070263A (en) * 2018-11-01 2020-05-07 ライオン株式会社 Liquid composition for oral cavity
CN113164792A (en) 2018-11-02 2021-07-23 西姆莱斯股份公司 Liquid transparent mixtures of UV filters
EP3877494A1 (en) 2018-11-08 2021-09-15 Symrise AG An antimicrobial surfactant based composition
KR20210117294A (en) 2019-01-17 2021-09-28 시므라이즈 아게 antibacterial mixture
US20220071933A1 (en) 2019-01-18 2022-03-10 Symrise Ag Combination remedy
CN113891750A (en) 2019-03-11 2022-01-04 西姆莱斯股份公司 Method for improving performance of spice or spice mixture
CA3131978A1 (en) 2019-03-12 2020-09-17 Symrise Ag An antimicrobial mixture
CN113766911A (en) 2019-03-22 2021-12-07 西姆莱斯股份公司 Plant peptides and uses thereof (II)
WO2020192865A1 (en) 2019-03-22 2020-10-01 Symrise Ag Plant peptides and their applications
CN113993500A (en) 2019-06-13 2022-01-28 德国德之馨香精香料公司 Cool preparation
EP3993767A1 (en) 2019-07-02 2022-05-11 Symrise AG Blend of beeswax and a lactylate ester
CN114364773A (en) 2019-09-04 2022-04-15 西姆莱斯股份公司 Aromatic oil mixture
JP2023510996A (en) 2019-10-16 2023-03-16 シムライズ アーゲー Non-disposable multi-use product intended for indirect penetration of active agents into the skin
WO2021228352A1 (en) 2020-05-11 2021-11-18 Symrise Ag A fragrance composition
EP4149419A1 (en) 2020-05-11 2023-03-22 Symrise AG A solid mucoadhesive composition
MX2023003549A (en) 2020-09-28 2023-04-21 Procter & Gamble Oral care composition comprising hops and flavor.
WO2022111793A1 (en) 2020-11-24 2022-06-02 Symrise Ag Medicament for accelerated wound healing
WO2022111829A1 (en) 2020-11-30 2022-06-02 Symrise Ag Essential oils of citrus fruits for use as medicament for induced, increased and/or accelerated autophagy in human keratinocytes
WO2022122122A1 (en) 2020-12-08 2022-06-16 Symrise Ag Medicament for fighting inflammatory conditions of human skin (i)
WO2022122134A1 (en) 2020-12-09 2022-06-16 Symrise Ag Compositions with (bio)-alkanediols and cooling agents
WO2022122167A1 (en) 2020-12-11 2022-06-16 Symrise Ag Medicament for preventing or treating pathologic conditions of human skin (i)
WO2022128051A1 (en) 2020-12-14 2022-06-23 Symrise Ag Medicament for fighting inflammatory conditions of human skin (ii)
WO2022128052A1 (en) 2020-12-14 2022-06-23 Symrise Ag Medicament for fighting inflammatory conditions of human skin
WO2022128048A1 (en) 2020-12-14 2022-06-23 Symrise Ag Medicament for preventing or treating pathologic conditions of human skin
WO2022128054A1 (en) 2020-12-14 2022-06-23 Symrise Ag Medicament for fighting inflammatory conditions of human skin (iv)
WO2022128057A1 (en) 2020-12-14 2022-06-23 Symrise Ag Medicament for prevention and treatment of collagen degradation in human connecting tissue
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Citations (30)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1351762A (en) 1971-02-14 1974-05-01 Wilkinson Sword Ltd Tobacco and tobacco-containing manufactures
GB1351761A (en) 1971-02-04 1974-05-01 Wilkinson Sword Ltd Substituted p-menthane carboxamides and compositions containing them
GB1353381A (en) 1971-02-04 1974-05-15 Wilkinson Sword Ltd Substituted p-menthanes and compositions containing them
GB1421744A (en) 1972-04-18 1976-01-21 Wilkinson Sword Ltd Aliphatic n-substituted tertiary amides possessing physiological cooling activity
GB1457671A (en) 1974-01-31 1976-12-08 Wilkinson Sword Ltd Flavour
US4136163A (en) 1971-02-04 1979-01-23 Wilkinson Sword Limited P-menthane carboxamides having a physiological cooling effect
US4150052A (en) 1971-02-04 1979-04-17 Wilkinson Sword Limited N-substituted paramenthane carboxamides
US4226988A (en) 1971-02-04 1980-10-07 Wilkinson Sword Limited N-substituted paramenthane carboxamides
US4248859A (en) 1973-12-12 1981-02-03 Wilkinson Sword Limited Alicyclic amides having a physiological cooling effect
US4296093A (en) 1973-04-16 1981-10-20 Wilkinson Sword Limited Cyclic carboxamides having a physiological cooling effect
US6348625B1 (en) 2000-11-10 2002-02-19 Gloria Long Anderson Method for preparing some 1-adamantancecarboxamides
US6399614B1 (en) 1997-08-01 2002-06-04 Recordati S.A. Chemical And Pharmaceutical Company 1-(N-phenylaminoalkyl)piperazine derivatives substituted at position 2 of the phenyl ring
WO2004089416A2 (en) 2003-04-11 2004-10-21 Novo Nordisk A/S Combination of an 11beta-hydroxysteroid dehydrogenase type 1 inhibitor and an antihypertensive agent
WO2005002582A2 (en) 2003-07-02 2005-01-13 Genentech, Inc. Trp-p8 active compounds and therapeutic treatment methods
WO2005015158A2 (en) 2003-08-06 2005-02-17 Senomyx Inc. T1r hetero-oligomeric taste receptors, cell lines that express said receptors, and taste compounds
WO2005020897A2 (en) 2003-08-22 2005-03-10 Dendreon Corporation Compositions and methods for the treatment of disease associated with trp-p8 expression
US20050084447A1 (en) 2003-10-15 2005-04-21 Wei Edward T. Radioligands for the TRP-M8 receptor and methods therewith
US20050159394A1 (en) 2003-12-31 2005-07-21 Wei Edward T. Aryl-substituted derivatives of cycloalkyl and branched chain alkyl carboxylic acids useful as antinociceptive drugs for peripheral targets
US20050187211A1 (en) 2004-02-23 2005-08-25 Wei Edward T. N-arylsalkyl-carboxamide compositions and methods
US20050207993A1 (en) 2003-11-13 2005-09-22 Russel Bazemore Method and composition for breath freshening
US20060051301A1 (en) 2002-10-28 2006-03-09 Givaudan Sa Coolant solutions and compositions comprising the same
WO2006056087A1 (en) 2004-11-23 2006-06-01 Givaudan Sa Carboxamides and their use
WO2006056096A1 (en) 2004-11-29 2006-06-01 Givaudan Sa Substrate care product
WO2006092074A1 (en) 2005-03-01 2006-09-08 Givaudan Sa Menthane carboxamide derivatives having cooling properties
WO2006099762A1 (en) 2005-03-24 2006-09-28 Givaudan Sa Cooling compounds
WO2006125334A1 (en) 2005-05-27 2006-11-30 Givaudan Sa Cooling compounds
WO2007019719A1 (en) 2005-08-15 2007-02-22 Givaudan Sa Cooling compounds
US20080176945A1 (en) 2005-03-02 2008-07-24 Galopin Christophe C Carboxilic Acid Amides Provoking A Cooling Sensation
WO2009007091A2 (en) 2007-07-09 2009-01-15 Bayer Bioscience N.V. Brassica plant comprising mutant fatty acyl-acp thioesterase alleles
WO2009070910A2 (en) 2007-12-07 2009-06-11 Givaudan Sa Carboxamide derivatieves having cooling properties

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CA2134977C (en) * 1992-05-18 1998-12-15 Deanna K. Furman Coolant compositions
BRPI0113421B8 (en) * 2000-08-24 2016-05-10 Givaudan Sa use of unsubstituted p-menthane carboxamide compounds as insect repellent
CN1845741A (en) * 2003-07-02 2006-10-11 健泰科生物技术公司 TRP-P8 active compounds and therapeutic treatment methods

Patent Citations (36)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1351761A (en) 1971-02-04 1974-05-01 Wilkinson Sword Ltd Substituted p-menthane carboxamides and compositions containing them
GB1353381A (en) 1971-02-04 1974-05-15 Wilkinson Sword Ltd Substituted p-menthanes and compositions containing them
US4136163A (en) 1971-02-04 1979-01-23 Wilkinson Sword Limited P-menthane carboxamides having a physiological cooling effect
US4150052A (en) 1971-02-04 1979-04-17 Wilkinson Sword Limited N-substituted paramenthane carboxamides
US4226988A (en) 1971-02-04 1980-10-07 Wilkinson Sword Limited N-substituted paramenthane carboxamides
GB1351762A (en) 1971-02-14 1974-05-01 Wilkinson Sword Ltd Tobacco and tobacco-containing manufactures
GB1421744A (en) 1972-04-18 1976-01-21 Wilkinson Sword Ltd Aliphatic n-substituted tertiary amides possessing physiological cooling activity
US4296093A (en) 1973-04-16 1981-10-20 Wilkinson Sword Limited Cyclic carboxamides having a physiological cooling effect
US4318900A (en) 1973-12-12 1982-03-09 Wilkinson Sword Limited Alicyclic amides having a physiological cooling effect
US4248859A (en) 1973-12-12 1981-02-03 Wilkinson Sword Limited Alicyclic amides having a physiological cooling effect
GB1457671A (en) 1974-01-31 1976-12-08 Wilkinson Sword Ltd Flavour
US6399614B1 (en) 1997-08-01 2002-06-04 Recordati S.A. Chemical And Pharmaceutical Company 1-(N-phenylaminoalkyl)piperazine derivatives substituted at position 2 of the phenyl ring
US6348625B1 (en) 2000-11-10 2002-02-19 Gloria Long Anderson Method for preparing some 1-adamantancecarboxamides
US20060051301A1 (en) 2002-10-28 2006-03-09 Givaudan Sa Coolant solutions and compositions comprising the same
WO2004089416A2 (en) 2003-04-11 2004-10-21 Novo Nordisk A/S Combination of an 11beta-hydroxysteroid dehydrogenase type 1 inhibitor and an antihypertensive agent
WO2005002582A2 (en) 2003-07-02 2005-01-13 Genentech, Inc. Trp-p8 active compounds and therapeutic treatment methods
WO2005015158A2 (en) 2003-08-06 2005-02-17 Senomyx Inc. T1r hetero-oligomeric taste receptors, cell lines that express said receptors, and taste compounds
WO2005020897A2 (en) 2003-08-22 2005-03-10 Dendreon Corporation Compositions and methods for the treatment of disease associated with trp-p8 expression
US20050084447A1 (en) 2003-10-15 2005-04-21 Wei Edward T. Radioligands for the TRP-M8 receptor and methods therewith
US20050207993A1 (en) 2003-11-13 2005-09-22 Russel Bazemore Method and composition for breath freshening
US20050159394A1 (en) 2003-12-31 2005-07-21 Wei Edward T. Aryl-substituted derivatives of cycloalkyl and branched chain alkyl carboxylic acids useful as antinociceptive drugs for peripheral targets
US20050187211A1 (en) 2004-02-23 2005-08-25 Wei Edward T. N-arylsalkyl-carboxamide compositions and methods
US20080112899A1 (en) 2004-11-23 2008-05-15 Galopin Christophe C Carboxamides and Their Use
WO2006056087A1 (en) 2004-11-23 2006-06-01 Givaudan Sa Carboxamides and their use
WO2006056096A1 (en) 2004-11-29 2006-06-01 Givaudan Sa Substrate care product
US20080305051A1 (en) 2005-03-01 2008-12-11 Lucienne Cole Menthane Carboxamide Derivatives Having Cooling Properties
WO2006092074A1 (en) 2005-03-01 2006-09-08 Givaudan Sa Menthane carboxamide derivatives having cooling properties
US20080176945A1 (en) 2005-03-02 2008-07-24 Galopin Christophe C Carboxilic Acid Amides Provoking A Cooling Sensation
WO2006099762A1 (en) 2005-03-24 2006-09-28 Givaudan Sa Cooling compounds
US20080319055A1 (en) 2005-03-24 2008-12-25 Givaudan Sa Cooling Compounds
WO2006125334A1 (en) 2005-05-27 2006-11-30 Givaudan Sa Cooling compounds
US20090105237A1 (en) 2005-05-27 2009-04-23 Karen Ann Bell Cooling compounds
WO2007019719A1 (en) 2005-08-15 2007-02-22 Givaudan Sa Cooling compounds
US20100035938A1 (en) 2005-08-15 2010-02-11 Karen Ann Bell Cooling Compounds
WO2009007091A2 (en) 2007-07-09 2009-01-15 Bayer Bioscience N.V. Brassica plant comprising mutant fatty acyl-acp thioesterase alleles
WO2009070910A2 (en) 2007-12-07 2009-06-11 Givaudan Sa Carboxamide derivatieves having cooling properties

Non-Patent Citations (10)

* Cited by examiner, † Cited by third party
Title
Database Beilstein, Beilstein Insitut zur Förderung der Chemischen Wissenschaften; XP002382093 accession No. 3422960, abstract & BUU-HOI: Z. Physiol. Chem., vol. 279, 1943.
Database Beilstein, Beilstein Institut zur Förderung der Chemischen Wissenschaften; XP002382094 accession No. 2328224, abstract & Inagaki, Shingaki: Chem. Lett., 1981.
Database Chemcats, Accession NR. 2004:1396439: ChemBridge Screening Library, Order NR. 5380996, Jan. 12, 2005, XP 002384344, abstract.
Database Chemcats, Chemical Abstracts Service, Columbus, Ohio, US; Jan. 12, 2005, XP002382091, order No. 6383438, abstract.
Database Chemcats, Chemical Abstracts Service, Columbus, Ohio, US; Jan. 12, 2005, XP002382092, order No. 6399044, abstract.
Database Chemcats, Chemical Abstracts Service, Columbus, Ohio, US; Jan. 18, 2005, XP002382089, order No. STK013323, abstract.
Database Chemcats, Chemical Abstracts Service, Columbus, Ohio, US; Jan. 18, 2005, XP002382090, order No. BAS 08858028, abstract.
Database Chemicals [Online], Chemical Abstracts Service, Columbus, Ohio, US; Jan. 12, 2005, XP002382088, retrieved from STN, order No. 6489078, abstract.
Patani et al., Chemical Review, 1996, vol. 96, pp. 3147-3176.
Watson H.R., et al., "New Compounds with the Menthol Cooling Effect," Journal of Society of Cosmetic Chemists, New York, NY, U.S., vol. 29, No. 4, 1978, pp. 185-200.

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US10123953B2 (en) 2012-06-21 2018-11-13 The Procter & Gamble Company Reduction of tooth staining derived from cationic antimicrobials
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US11236042B2 (en) 2017-01-10 2022-02-01 Takasago International Corporation Methylmenthol derivative and cool-sensation imparter composition containing same
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US10871363B2 (en) 2018-05-28 2020-12-22 The Procter & Gamble Company Oral care composition with improved deposition efficacy of a cooling sensate agent in the oral cavity
US11191709B2 (en) 2019-04-26 2021-12-07 The Procter & Gamble Company Reduction of tooth staining derived from cationic antimicrobials
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