US 20110081393A1 (19) United States (12) Patent Application Publication (10) Pub. No.: US 2011/008 1393 A1 Komatsuki et al. (43) Pub. Date: Apr. 7, 2011

(54) COOLING SENSATION AGENT A6IP27/00 (2006.01) COMPOSITION, SENSORY STIMULATION A6IP 700 (2006.01) AGENT COMPOSITION AND USE OF THE (52) U.S. Cl...... 424/402:560/194: 514/548; 560/193; SAME 424/443 (75) Inventors: Yasuhiro Komatsuki, Kanagawa (57) ABSTRACT (JP); Tomoko Yamamoto, Disclosed is a cooling sensation agent composition or sensory Kanagawa (JP): Takashi Aida, stimulation agent composition which contains at least one of Tokyo (JP); Kenya Ishida, diester compounds of dicarboxylic acid represented by the Kanagawa (JP) formula (1) wherein A represents CH or CH=CH, in repre sents an integer of 0 to 4 when A is CH, or 1 when A is (73) Assignee: TAKASAGO INTERNATIONAL CH=CH, B is an alcohol residue having 10 to 18 carbon CORPORATION atoms and containing a para-menthane skeleton, which may have a substituent, and C is an alcohol residue having 6 to 18 (21) Appl. No.: 12/898,939 carbonatoms, which may have a Substituent as well as a flavor or fragrance composition, a beverage, a food product, a per (22) Filed: Oct. 6, 2010 fume or cosmetic product, a toiletry product, daily utensil products or groceries, a fiber, a fiber product, clothes, clothing (30) Foreign Application Priority Data or a medicine, wherein the cooling sensation agent composi tion or the sensory stimulation agent composition is com Oct. 7, 2009 (JP) ...... 2009-233059 pounded.

Publication Classification (1) (51) Int. Cl. A6 IK 3L/225 (2006.01) CD7C 69/40 (2006.01) 46R 9/00 (2006.01) 1. A 6LX 9/70 (2006.01) US 2011/008 1393 A1 Apr. 7, 2011

COOLING SENSATION AGENT skin (WO 94/06441 A), and the like are mentioned. In addi COMPOSITION, SENSORY STIMULATION tion to them, there are known many patents that utilize release AGENT COMPOSITION AND USE OF THE of a fragrance molecule by decomposition of a fragrance SAME precursor based on a chemical change or an enzyme reaction (JP 45-26872 B, EP 1077251 A, WO 95/04809 A, WO FIELD OF THE INVENTION 97/16523 A, JP 8-225564A, JP 2009-520701 A, and Angew. Chem. Int. Ed, 2007, 46, 5836-5863). JP 45-26872 B, for 0001. The present invention relates to novel esters of example, discloses cosmetics in which monomenthyl or dicarboxylic acid, a cooling sensation agent composition dimenthyl esters of dicarboxylic acid is contained. The esters containing the same, a sensory stimulation agent composition in the cosmetics are decomposed by an ester-hydrolyzing containing the cooling sensation agent composition as well as enzyme present in a skin or an alkali included in an alkaline a flavor or fragrance composition, a beverage, a food product, cosmetic that is already applied on the skin to release men a perfume or cosmetic product, a toiletry product, a daily thol. However, it is not known that the aforementioned dimen utensil product or grocery, fibers, fiber products, clothes, thyl esters of dicarboxylic acid themselves have an excellent clothing or a medicine, which contains the cooling sensation cooling sensation effect. In addition, when a precursor of a agent composition or the sensory stimulation agent compo flavor or fragrance compound is used, there are still some sition and a method for producing the same. The present problems that quite a long time is required till the decompo invention also relate to a method for providing long-lasting sition reaction of the precursor starts and a flavor or fragrance cooling sensation or a cool refreshment processing method compound is released after adhesion of the precursor to using the cooling sensation agent composition or the sensory clothes or a skin, the strength of cooling sensation is signifi stimulation agent composition. cantly weak, and so on. Thus, it is not a fundamental solution. 0005. Other studies on the method for providing clothes BACKGROUND OF THE INVENTION with cooling action, for example, using microcapsules or the 0002. A cooling sensation agent that endows the skin, oral like have been conducted, and many patent applications have cavity, nose and throat of a person with a refresh feeling been filed. Examples thereof include a fiber processing (refresh sensation) and cool feeling (cooling sensation), that method by use of microcapsules containing mint oil or 1-men is cooling sensation effect, is used in various products such as thol (JP 2000-96443A), a fiber processing method by use of toothpastes, confectioneries such as chewing gums and can a microcapsulated Substance which melts at a temperature not dies, tobacco, cataplasms, bath agents and cosmetics. Men higher than the body temperature, so that the substance gives thol, which is the representative cooling sensation agent persons a cooling action reversibly by latent heat when con material, has an excellent cooling sensation effect. However tacting with skin (JP 2006-161226 A), or the like. However, as menthol is highly volatile, the cooling sensation effect they have also problems. That is, in the former method, pro thereof does not last so long. Therefore, studies have been cessed clothes, of course, loses its action after releasing of all carried out to maintain a cooling sensation action for a long cooling sensation agent by destruction of the microcapsules, period of time. Examples of the compounds having been and it is actually impossible to re-process the clothes at home. developed to maintain the cooling sensation for a prolonged Further, because the stage of releasing the cooling sensation period of time include menthoxypropanediol that is glycerin agent by destruction of the microcapsules is the rate-deter ether of menthol, lacticester of menthol, ethylene glycol ether mining step in this method, similar to a chemical reaction, it of menthol and the like. is not currently at the technological level where the cooling 0003. However, under influence of recent global warming, action can be provided to persons just after wearing of the there has been a demand for cool feeling processing of cloth clothes. In the latter method which relies on phase transition ing Such as clothes and the like to make people feel more between solid and liquid, the cooling action cannot be pro comfortable even in hot Summer. Most cooling sensation vided to persons in constantly hot areas where the microcap agents including menthol, however, are highly volatile and sulated substance does not return to the solid state after melt also highly water-soluble, and thus, the cool feeling process ing. ing of clothes and the like by use of the cooling sensation 0006 An object of the present invention is to provide a agents often results in loss of the action within a short period cooling sensation agent composition by which the conven of time. For example, even if a cooling sensation agent is tional problems described above are solved, i.e., to provide a compounded with a detergent or a softener, the cooling sen cooling sensation agent composition which shows the long sation agent hardly remains on the clothing fiber after wash lasting cooling action for an extended period of time. ing because of its water Solubility and further, no cooling 0007 Another object of the present invention is to provide sensation agent remains after drying because of its high Vola a sensory stimulation agent composition which contains the tility. cooling sensation agent composition. 0004 To solve these problems, sustained-release cooling 0008 Still another object of the present invention is to sensation agents utilizing a chemical change has been devel provide a flavor or fragrance composition, a beverage, a food oped. For example, a method for giving a refresh feeling to product, a perfume or cosmetic product, a toiletry product, gas to be breathed at Smoking by releasing a cooling sensation daily utensil products and groceries, and a medicine, which agent, menthol due to thermal decomposition of chlorocar contain the cooling sensation agent composition or the sen bonic esters or carbonic esters contained in tobacco on com sory stimulation agent composition, and also a production bustion of tobacco (U.S. Pat. No. 3,312.226), a method for method of the same. releasing a fragrance component by decomposition of car 0009 Further, still another object of the present invention bonic esters on the skinto elongate the diffusion period of the is to provide a method for providing a prolonged cooling fragrance (JP 10-95752A), a method for releasing a fragrance action by applying one of the aforementioned products con due to decomposition of orthoesters by perspiration on the taining the cooling sensation agent composition or the sen US 2011/008 1393 A1 Apr. 7, 2011 sory stimulation agent composition directly onto a skin or a 2 The cooling sensation agent composition described in Scalp, administering it into an oral cavity, or applying it on above item 1, wherein C in the formula (1) is an alcohol fibers, a fiber product, clothes or clothing; or a cool refresh residue having a para-menthane skeleton, which may have a ment processing method of fibers, a fiber product, clothes or substituent. clothing by compounding a cooling sensation agent compo 3 The cooling sensation agent composition described in sition or the sensory stimulation agent composition with above item 2, wherein Band C in the formula (1) are not the those or processing those with a cooling sensation agent same residue. composition or the sensory stimulation agent composition. 4The cooling sensation agent composition described in any one of above items 1 to 3, wherein the alcohol residue for 0010 Furthermore, another object of the present invention B or B and C in the formula (1) having a para-menthane is to provide novel diesters of dicarboxylic acid. skeleton, which may have a substituent, is one selected from 0011. As a result of intensive studies to solve the problems alcohol residues consisting of 1-menthol, l-isopulegol, 3-(1- described above, inventors of the invention found that a menthoxy)propane-1,2-diol. 2-(1-menthoxy)ethan-1-ol. 3-(1- diester compound of dicarboxylic acid where at least one of menthoxy)propan-1-ol. 2-methyl-3-(1-menthoxy)propane-1, the diester includes an alcohol residue having a para-men 2-diol and para-menthane-3,8-diol. thane skeleton, which may have a substituent, but not all of 5The cooling sensation agent composition described in any the alcohol residues are a menthol residue, has an excellent one of above items 1 to 4), wherein the diester compounds and long-lasting cooling sensation effect. In addition, the of dicarboxylic acid represented by the formula (1) have inventors also found that the diesters may easily remain in ClogP of 3.0 or more and the molecular weight of 250 to 600. clothes when it is compounded with a detergent, a fabric 6The cooling sensation agent composition described in any softener or the like and the clothes are washed using the one of above items 1 to 5, which further comprises at least detergent or rinsed using the softer, and the clothes after one kind of cooling sensation Substances other than the com washing or rinsing exhibit a gentle and long-lasting cooling pounds corresponding to the formula (1). sensation at the time of wearing or after the wearing. Further, 7. The cooling sensation agent composition described in the inventors found that a long-lasting cool refreshing action above item 6., wherein the cooling sensation Substances was obtained even when the diester compound is com other than the compounds corresponding to the formula (1) pounded for a beverage, a food product, a perfume or cos are menthol, menthone, camphor, pulegol, isopulegol, cin metic product, a toiletry product, daily utensil products or eole, mint oil, peppermint oil, spearmint oil, eucalyptus oil, groceries, tobacco, a medicine and the like. The present 3-(1-menthoxy)propane-1,2-diol, N-alkyl-p-menthane-3-car invention was made based on these findings. boxamide, 2-methyl-3-(1-menthoxy)propane-1,2-diol, p-menthane-3,8-diol. 2-(1-menthoxy)ethan-1-ol. 3-(1-men SUMMARY OF THE INVENTION thoxy)propan-1-ol. 4-(1-menthoxy)butan-1-ol, menthyl 3-hy droxybutanoate, menthyl lactate, menthone glycerin ketal, 0012 Specifically, the present invention relates to a cool N-methyl-2.2-isopropylmethyl-3-methylbutane amide and ing sensation agent composition and a sensory stimulation menthylglyoxylate. agent composition as well as the flavor or fragrance agent 8. A sensory stimulation agent composition which contains composition containing the compositions. The present inven the cooling sensation agent composition described in any one tion also relates to a beverage, a food product, a perfume or of above items 1 to 7. cosmetic product, a toiletry product, daily utensil products or 9. The sensory stimulation agent composition described in groceries, a fiber, a fiber product, clothes, clothing or the above item 8), which further comprises at least one kind of medicine, a method for producing the same, a method for warming and pungent Substances. providing a long-lasting cool refreshing action, and a cool 10 The sensory stimulation agent composition described in refreshment processing method for a fiber, a fiber product, above item 9, wherein the warming and pungent Substances clothes or clothing described in the followings items 1 to are vanillyl ethyl ether, Vanillyl propyl ether, vanillin propy 16. Further, the present invention also relates to novel lene glycol acetal, ethylvanillin propylene glycol acetal, cap diester compounds of dicarboxylic acid described in the fol saicin, gingerol, Vanillylbutyl ether, 4-(1-menthoxymethyl)- lowings items 17 to 20. 2-(3'-methoxy-4'-hydroxy-phenyl)-1,3-dioxolane, pepper 1 A cooling sensation agent composition which contains at oil, pepper oleoresin, ginger oleoresin, nonylic acid Vanilly least one of diester compounds of dicarboxylic acid repre lamide, jamboo oleoresin, Zanthoxylum Piperitum Peel sented by the formula (1): Extract, Sanshool-I, Sanshool-II, Sanshoamide, black pepper extract, chavicine, piperine and spilanthol. 11 A flavor or fragrance composition, a beverage, a food (1) product, a perfume or cosmetic product, a toiletry product, O O daily utensil products or groceries, a fiber, a fiber product, clothes, clothing or a medicine, which comprises the cooling sensation agent composition or the sensory stimulation agent 1. composition described in any one of above items 1 to 10. 12 A method for providing a long-lasting cooling sensation wherein. A represents CH or CH=CH, in represents an inte effect, which comprises applying directly any one of products ger of 0 to 4 when A is CH, or 1 when A is CH-CH, B is an described in above item 11 onto a skin or a scalp, adminis alcohol residue having 10 to 18 carbon atoms and containing tering any one of them into an oral cavity, or applying any one a para-menthane skeleton, which may have a Substituent, and of them to a fiber, a fiber product, clothes or clothing. C is an alcohol residue having 6 to 18 carbon atoms, which 13 A flavor or fragrance agent composition described in may have a Substituent. above item 11, wherein the content of the cooling sensation US 2011/008 1393 A1 Apr. 7, 2011 agent composition or the sensory stimulation agent compo compounding the cooling sensation agent composition or the sition is 0.0001 to 90% by mass. sensory stimulation agent composition with a flavor or fra 14 Abeverage, a food product, a perfume or cosmetic prod grance composition, a beverage, a food product, a perfume or uct, a toiletry product, daily utensil products or groceries, a cosmetic product, a toiletry product, daily utensil products or fiber, a fiber product, clothes, clothing or a medicine groceries, a fiber, a fiber product, clothes, clothing and a described in above item 11, wherein the content of the medicine, it is possible to prepare the products providing the cooling sensation agent composition or the sensory stimula cooling sensation effect or the sensation stimulating effect, tion agent composition is 1x107 to 20% by mass. which lasts for a long period of time. Furthermore, when these 15. A cool refreshment processing method for a fiber, a fiber products are directly applied onto a skin or a scalp or admin product, clothes or clothing, which comprises compounding istered into an oral cavity, a cooling sensation effect or the the cooling sensation agent composition or the sensory stimu sensation stimulating effect lasting for a long period of time lation agent composition described in any one of above items can be given to the skin, the scalp or the oral cavity, etc. and 1 to 10 to a fiber, a fiber product, clothes or clothing, or when they are applied to a fiber, a fiber product, clothes or processing a fiber, a fiber product, clothes or clothing with the clothing, etc., a gentle cooling sensation effect is given at the cooling sensation agent composition or the sensory stimula time of wearing and also agentle prolonged cooling sensation tion agent composition described in any one of above items effect is given even after wearing. Further, when the cooling 1 to 10. sensation agent composition or the sensory stimulation agent 16 A method for producing a flavor or fragrance composi composition is compounded with a detergent, a fabric Soft tion, a beverage, a food product, a perfume or cosmetic prod ener or the like, a gentle or prolonged gentle cooling effect uct, a toiletry product, daily utensil products or groceries, a can be given at the time of wearing the clothes or clothing fiber, a fiber product, clothes, clothing or a medicine, which after washing or rinsing using the detergent, the fabric Soft comprises compounding the cooling sensation agent compo ener or the like and after wearing the cloth, in the present sition or the sensory stimulation agent composition described invention. Furthermore, the present invention provides novel in any one of above items 1 to 10 with a beverage, a food compounds. product, a perfume or cosmetic product, a toiletry product, daily utensil products or groceries, a fiber, a fiber product, DETAILED DESCRIPTION OF THE INVENTION clothes, clothing or a medicine. 0014. Herein after, the invention will be described in more 17 Diester compounds of dicarboxylic acid represented by detail. As described above, the invention relates to a cooling the formula (1"): sensation agent composition, a sensory stimulation agent composition as well as a flavor or fragrance composition, a beverage, a food product, a perfume or cosmetic product, a (1) toiletry product, daily utensil products or groceries, a fiber, a fiber product, clothes, clothing or a medicine containing these compositions, a method for producing the same, a method for ---, providing a long-lasting cooling sensation effect, a cool refreshment processing method for a fiber, a fiber product, clothes, and clothing and novel compounds. First, the cooling wherein. A represents CH2, n represents an integer of 0 to 4. sensation agent composition of the invention will be B is an alcohol residue of an alcohol having 10 to 18 carbon explained in detail. atoms and containing a para-menthane skeleton, which may 0015 The cooling sensation agent composition of the have a Substituent, and C is an alcohol residue of an alcohol invention contains at least one of diester compounds of dicar having 6 to 18 carbon atoms, which may have a Substituent, boxylic acid that are represented by the following Formula however when B or C is an alcohol residue of menthol, another is not an alcohol residue of menthol. (1). 18. The diester compounds of dicarboxylic acid described in above item 17, wherein C in the formula (1") is an alcohol (1) residue of an alcohol having a para-menthane skeleton, which O O may have a Substituent. 19. The diester compounds of dicarboxylic acid described in above item (18), wherein B and C in the formula (1") are not 1. the same residue. 20. The diester compounds of dicarboxylic acid described in wherein. A represents CH or CH=CH, in represents an inte any one of above items 17 to 19, wherein the alcohol ger of 0 to 4 when A is CH, or 1 when A is CH=CH, B is an residue for B or B and C in the formula (1") having a alcohol residue having 10 to 18 carbon atoms and containing para-menthane skeleton, which may have a Substituent, is any a para-menthane skeleton, which may have a substituent, and one selected from alcohol residues of 1-menthol, l-isopulegol, C is an alcohol residue having 6 to 18 carbon atoms, which 3-(1-menthoxy)propane-1,2-diol. 2-(1-menthoxy)ethan-1-ol. may have a substituent. 3-(1-menthoxy)propan-1-ol, 2-methyl-3-(1-menthoxy)pro 0016. Meanwhile, as described in “Background of the pane-1,2-diol and para-menthane-3,8-diol. invention', there are already well known cosmetics contain 0013 The present invention provides a cooling sensation ing dimenthyl esters of a dicarboxylic acid such as phthalic agent composition imparting along-lasting cooling sensation acid, Succinic acid, maleic acid, and adipic acid, which are the effect and a sensory stimulation agent composition with a compounds closely related to the compounds represented by long-lasting cooling sensation effect containing the cooling the formula (1), and that fresh feeling can be provided after sensation agent composition. Further, in the invention, by putting make-up using the cosmetics (JP-B 45-26872). How US 2011/008 1393 A1 Apr. 7, 2011

ever, these dimenthyl esters of dicarboxylic acid release men but also an increased molecular weight has a ClogP of 4.5, thol due to a degradation reaction by an alkali or an enzyme and thus, dimenthyl carbonate is highly oleophilic and less present in a skin to give cool feeling. In other words, the soluble in water. The ClogP values of the compounds of the dimenthyl esters of dicarboxylic acid are precursors of a formula (1) used in the cooling sensation agent composition Substance which gives cool feeling and it is not known from of the present invention are preferably in the range of 3.0 or the document that the dimenthyl esters of dicarboxylic acid more, more preferably 4.0 or more. themselves give an excellent cooling sensation effect. In addi 0021. As alcohols which are used for forming alcohol tion, it is not disclosed in the document at all that an excellent residues of B in the formula (1) of the invention, which have long-lasting cooling sensation effect can be given by their use 10 to 18 carbonatoms and apara-menthane skeleton, and may in combination with other sensory stimulating component have a Substituent, e.g., a hydroxyl group, an ether group and like a cooling sensation agent, a warming agent and the like. the like, there may be preferably exemplified 1-menthol, 0017. Furthermore, the dimenthyl diesters having a sym 1-isopulegol, 3-(1-menthoxy)propane-1,2-diol. 2-(1-men metrical construction are generally in a wax state with a high thoxy)ethan-1-ol. 3-(1-menthoxy)propan-1-ol, 2-methyl-3- Viscosity or in a solid form, and are hard to handle and have a (1-menthoxy)propane-1,2-diol and para-menthane-3,8-diol. poor yield when they are compounded with a product. Sur 0022. In addition, as alcohols which are used for forming prisingly, however, non-symmetric diesters of dicarboxylic alcohol residues of C in the formula (1) which have 6 to 18 acid like the diesters of dicarboxylic acid represented by the carbon atoms and may have a substituent, e.g., a hydroxyl above Formula (1) are generally oily Substances having a low group, an ether group and the like, there may be exemplified Viscosity and can be easily compounded with a flavor or alcohols having 10 to 18 carbon atoms and a para-menthane fragrance and other various products and have a good yield. skeleton, which may have a Substituent, and other alcohols Further, they themselves have a excellent long-lasting cool except for the aforementioned alcohols, that are linear, ing sensation effect compared to the dimenthyl esters branched or cyclic alcohols having 10 to 18 carbon atoms, described above, and also by using it in combination with which may have an unsaturated bond, an ether group, an other sensory stimulating component Such as a cooling sen aromatic ring and/oran fused ring derived from the aromatic sation agent, a warming agent and the like, an excellent long ring. lasting cooling sensation effect can be given. 0023. As alcohols having 10 to 18 carbon atoms and a 0.018. Furthermore, as described above, the document para-menthane skeleton, which may have a substituent and shown in the prior art describes dimenthyl esters in which are used for forming alcohol residues having 6 to 18 carbon both two alcohol residues are menthol in regard to the dicar atoms, which may have a substituent, of C in the formula (1), boxylic esters represented by the formula (1), however there there may be preferably exemplified 1-menthol, l-isopulegol, exists no description of a dicarboxylic ester compound or 3-(1-menthoxy)propane-1,2-diol. 2-(1-menthoxy)ethan-1-ol. dicarboxylic ester compound mixture excluding the above 3-(1-menthoxy)propan-1-ol, 2-methyl-3-(1-menthoxy)pro dimenthyl esters, i.e., a dicarboxylic ester compound which pane-1,2-diol and para-menthane-3,8-diol, similar to B. contains one selected from alcohol residues of alcohols with 0024. As liner or branched saturated alcohols among the 10 to 18 carbon atoms and a para-menthane skeleton, which linear or cyclic alcohols having 6 to 18 carbon atoms, which may have a Substituent, Such as 1-menthol, l-isopulegol, 3-(1- may have an unsaturated bond, an ether group, an aromatic menthoxy)propane-1,2-diol. 2-(1-menthoxy)ethan-1-ol. 3-(1- ring and/oran fused ring derived from an aromatic ring in C menthoxy)propan-1-ol. 2-methyl-3-(1-menthoxy)propane-1, of the formula (1), there may be exemplified, but not particu 2-diol, para-menthane-3,8-diol and the like and one selected larly limited to, hexanol, heptanol, octanol, nonanol, decanol, from alcohol residues with 6 to 18 carbon atoms. Therefore, undecanol, dodecanol, tridecanol, tetradecanol, 2-methyl these are novel Substances. hexanol, 3-methylhexanol, 4-methylhexanol, 5-methylhex 0019 Volatility and oleophilicity of the compounds rep anol, 2-methylheptanol, 3-methylheptanol, 4-methylhep resented by the formula (1) will be disclosed below. Volatility tanol, 5-methylheptanol, 6-methylheptanol, of a compound is significantly affected by a functional group 2-methyloctanol, 3-methyloctanol, 4-methyloctanol, 5-me attached to a molecule of the compound. On the other hand, thyloctanol, 6-methyloctanol, 7-methyloctanol, 2-methyl flash point or boiling point can be increased by increasing the nonanol, 3-methylnonanol, 4-methylnonanol, 5-methyl molecular weight and a compound having a molecular weight nonanol, 6-methylnonanol, 7-methylnonanol, of approximately 250 to 600, preferably 300 to 500, is a less 8-methylnonanol, 2-methyldecanol, 3-methyldecanol, 4-me Volatile compound. In addition, a compound having a thyldecanol, 5-methyldecanol, 6-methyldecanol, 7-methyl molecular weight of more than 600 shows almost no cool decanol, 8-methyldecanol, 9-methyldecanol, 2,3-dimethyl feeling. For that reason, the compounds represented by the pentanol. 2,4-dimethylpentanol. 2,2-dimethylpentanol, 3.3- formula (1) used in the cooling sensation agent composition dimethylpentanol, 3,4-dimethylpentanol, 4.4- of the present invention preferably have a molecular weight in dimethylpentanol, 2,2-dimethylhexanol, 2,3- the range of preferably 250 to 600, and more preferably 300 dimethylhexanol, 2,4-dimethylhexanol, 2.5- to 600. dimethylhexanol, 3.3-dimethylhexanol, 3,4- 0020. The oleophilicity of a compound is influenced sig dimethylhexanol, 3,5-dimethylhexanol, 4.4- nificantly by the functional group attached to a molecule of dimethylhexanol, 4,5-dimethylhexanol, 5,5- the compound and the number of carbons thereof, and pres dimethylhexanol, 2,2-dimethylheptanol, 2,3- ence of a hydroxyl group leads to decrease of oleophilicity, dimethylheptanol, 2,4-dimethylheptanol, 2.5- while increase in the number of carbons leads to increase of dimethylheptanol, 2,6-dimethylheptanol, 3,3- oleophilicity. Water/octanol distribution coefficient (ClogP) dimethylheptanol, 3,4-dimethylheptanol, 3,5- is normally used as the indicator of oleophilicity. Menthol, for dimethylheptanol, 3,6-dimethylheptanol, 4.4- example, has a ClogP of 2.5, while dimenthyl carbonate hav dimethylheptanol, 4,5-dimethylheptanol, 4.6- ing not only the hydroxyl group blocked with carbonic esters dimethylheptanol, 5,5-dimethylheptanol, 5,6- US 2011/008 1393 A1 Apr. 7, 2011

dimethylheptanol. 6,6-dimethylheptanol, 2,2-dimethyloc 5-decen-2-ol, 9-decen-1-ol, 5-undecen-2-ol, 10-undecen-1- tanol. 2,3-dimethyloctanol. 2,4-dimethyloctanol. 2,5-dim ol, 5-tetradecen-2-ol. 3-methyl-4-hexen-2-ol. 4-methyl-4- ethyloctanol. 2,6-dimethyloctanol. 2,7-dimethyloctanol, 3.3- hexen-2-ol. 5-methyl-4-hexen-2-ol. 3-methyl-4-hepten-2-ol. dimethyloctanol, 3,4-dimethyloctanol, 3,5-dimethyloctanol, 4-methyl-4-hepten-2-ol. 5-methyl-4-hepten-2-ol, 6-methyl 3,6-dimethyloctanol. 3,7-dimethyloctanol, 4.4-dimethyloc 4-hepten-2-ol. 3-methyl-3-octen-2-ol. 1,4-methyl-3-octen-2- tanol. 4,5-dimethyloctanol. 4,6-dimethyloctanol, 4.7-dim ol, 5-methyl-3-octen-2-ol, 6-methyl-3-octen-2-ol, 7-methyl ethyloctanol, 5,5-dimethyloctanol, 5,6-dimethyloctanol, 5,7- 3-octen-2-ol, 3-methyl-5-nonen-2-ol. 4-methyl-5-nonen-2- dimethyloctanol. 6,6-dimethyloctanol. 6,7-dimethyloctanol, ol, 5-methyl-5-nonen-2-ol. 6-methyl-5-nonen-2-ol. 7,7-dimethyloctanol, 2,2-dimethylnonanol, 2,3-dimethyl 7-methyl-5-nonen-2-ol, 8-methyl-5-nonen-2-ol. 3-methyl-5- nonanol. 2,4-dimethylnonanol. 2,5-dimethylnonanol. 2.6- decen-2-ol. 4-methyl-5-decen-2-ol. 4-methyl-3-decen-5-ol. dimethylnonanol. 2,7-dimethylnonanol, 2,8-dimethyl 5-methyl-5-decen-2-ol, 6-methyl-5-decen-2-ol, 7-methyl-5- nonanol, 3.3-dimethylnonanol, 3,4-dimethylnonanol. 3.5- decen-2-ol, 8-methyl-5-decen-2-ol, 9-methyl-5-decen-2-ol. dimethylnonanol, 3,6-dimethylnonanol, 3,7- 3,4-dimethyl-3-penten-2-ol. 3.3-dimethyl-4-hexen-2-ol. 3,4- dimethylnonanol, 3.8-dimethylnonanol, 4.4- dimethyl-4-hexen-2-ol. 3,5-dimethyl-4-hexen-2-ol. 4,5-dim dimethylnonanol, 4.5-dimethylnonanol, 4.6- ethyl-4-hexen-2-ol. 3,3-dimethyl-4-hepten-2-ol. 3,4-dim dimethylnonanol, 4,7-dimethylnonanol, 4,8- ethyl-4-hepten-2-ol. 3,5-dimethyl-4-hepten-2-ol. 3,6- dimethylnonanol, 5,5-dimethylnonanol, 5,6- dimethyl-4-hepten-2-ol. 4,5-dimethyl-4-hepten-2-ol. 4.6- dimethylnonanol, 5,7-dimethylnonanol, 5,8- dimethyl-4-hepten-2-ol. 5,6-dimethyl-4-hepten-2-ol. 6,6- dimethylnonanol, 6,6-dimethylnonanol, 6,7- dimethyl-4-hepten-2-ol. 3,4-dimethyl-3-octen-2-ol. 3.5- dimethylnonanol, 6,8-dimethylnonanol, 7,7- dimethyl-3-octen-2-ol. 3,6-dimethyl-3-octen-2-ol. 3,7- dimethylnonanol, 7,8-dimethylnonanol, 8.8- dimethyl-3-octen-2-ol. 4,5-dimethyl-3-octen-2-ol. 4.6- dimethylnonanol, 3-methyl-2-hexanol, 4-methyl-2-hexanol, dimethyl-3-octen-2-ol. 4,7-dimethyl-3-octen-2-ol. 5.5- 5-methyl-2-hexanol, 3-methyl-2-heptanol, 4-methyl-2-hep dimethyl-3-octen-2-ol. 5,6-dimethyl-3-octen-2-ol. 5,7- tanol, 5-methyl-2-heptanol, 6-methyl-2-heptanol, 3-methyl dimethyl-3-octen-2-ol. 6,6-dimethyl-3-octen-2-ol. 6,7- 2-octanol, 4-methyl-2-octanol, 5-methyl-2-octanol, 6-me dimethyl-3-octen-2-ol. 7,7-dimethyl-3-octen-2-ol. 3.3- thyl-2-octanol, 7-methyl-2-octanol, 3-methyl-2-nonanol, dimethyl-5-nonen-2-ol. 3,4-dimethyl-5-nonen-2-ol. 3.5- 4-methyl-2-nonanol, 5-methyl-2-nonanol, 6-methyl-2- dimethyl-5-nonen-2-ol. 3,6-dimethyl-5-nonen-2-ol. 3,7- nonanol, 7-methyl-2-nonanol, 8-methyl-2-nonanol, 3-me dimethyl-5-nonen-2-ol. 3.8-dimethyl-5-nonen-2-ol. 4.4- thyl-2-decanol, 4-methyl-2-decanol, 5-methyl-2-decanol, dimethyl-5-nonen-2-ol. 4.5-dimethyl-5-nonen-2-ol. 4.6- 6-methyl-2-decanol, 7-methyl-2-decanol, 8-methyl-2-de dimethyl-5-nonen-2-ol. 4,7-dimethyl-5-nonen-2-ol. 4.8- canol, 9-methyl-2-decanol, 3.3-dimethyl-2-pentanol, 3,4- dimethyl-5-nonen-2-ol. 5,6-dimethyl-5-nonen-2-ol. 5,7- dimethyl-2-pentanol, 4.4-dimethyl-2-pentanol, 3.3-dim dimethyl-5-nonen-2-ol. 5,8-dimethyl-5-nonen-2-ol. 6,7- ethyl-2-hexanol, 3,4-dimethyl-2-hexanol, 3,5-dimethyl-2- dimethyl-5-nonen-2-ol. 6,8-dimethyl-5-nonen-2-ol. 7,7- hexanol, 4.4-dimethyl-2-hexanol. 4,5-dimethyl-2-hexanol, dimethyl-5-nonen-2-ol. 7,8-dimethyl-5-nonen-2-ol, 8.8- 5,5-dimethyl-2-hexanol, 3.3-dimethyl-2-heptanol, 3,4-dim dimethyl-5-nonen-2-ol. 2,6-nonadien-1-ol. linalool, ethyl-2-heptanol, 3,5-dimethyl-2-heptanol. 3,6-dimethyl-2- ethyllinalool, dihydrolinalool, geraniol, nerol, citronellol, heptanol, 4.4-dimethyl-2-heptanol. 4.5-dimethyl-2-heptanol, rhodinol, myrcenol, lavandulol, isodihydrolavandulol, dihy 4,6-dimethyl-2-heptanol, 5,5-dimethyl-2-heptanol, 5,6-dim dromyrcenol, allocimenol, and the like. Even if geometrical ethyl-2-heptanol. 6,6-dimethyl-2-heptanol. 3,3-dimethyl-2- or optical isomers are present, the individual isomer or the octanol. 3,4-dimethyl-2-octanol. 3.5-dimethyl-2-octanol, mixture thereof may be used. 3,6-dimethyl-2-octanol. 3,7-dimethyl-2-octanol, 4.4-dim 0026. As ether group-containing liner or branched satu ethyl-2-octanol. 4,5-dimethyl-2-octanol. 4,6-dimethyl-2-oc rated alcohols among the linear, branched or cyclic alcohols tanol, 4,7-dimethyl-2-octanol, 5,5-dimethyl-2-octanol, 5,6- having 6 to 18 carbon atoms, which may have an unsaturated dimethyl-2-octanol, 5,7-dimethyl-2-octanol. 6,6-dimethyl-2- bond, an ether group, an aromatic ring and/or an fused ring octanol. 6,7-dimethyl-2-octanol. 7,7-dimethyl-2-octanol, derived from an aromatic ring in C of the formula (1), there 3.3-dimethyl-2-nonanol, 3,4-dimethyl-2-nonanol. 3,5-dim may be exemplified, but not particularly limited to, 3-meth ethyl-2-nonanol. 3,6-dimethyl-2-nonanol. 3,7-dimethyl-2- oxy-3-methyl-butanol, 3-methoxyhexanol, 3-methoxyhep nonanol. 3.8-dimethyl-2-nonanol, 4.4-dimethyl-2-nonanol, tanol, 3-methoxyoctanol, 3-methoxynonanol, 3-methoxyde 4.5-dimethyl-2-nonanol. 4,6-dimethyl-2-nonanol, 4.7-dim canol, 3-methoxytridecanol, 2-methyl-3-methoxyhexanol, ethyl-2-nonanol, 4,8-dimethyl-2-nonanol, 5,5-dimethyl-2- 3-methyl-3-methoxyhexanol, 4-methyl-3-methoxyhexanol, nonanol, 5,6-dimethyl-2-nonanol, 5,7-dimethyl-2-nonanol, 5-methyl-3-methoxyhexanol, 2-methyl-3-methoxyheptanol, 5,8-dimethyl-2-nonanol. 6,6-dimethyl-2-nonanol. 6,7-dim 3-methyl-3-methoxyheptanol, 4-methyl-3-methoxyhep ethyl-2-nonanol, 6,8-dimethyl-2-nonanol. 7,7-dimethyl-2- tanol, 5-methyl-3-methoxyheptanol, 6-methyl-3-methoxy nonanol. 7,8-dimethyl-2-nonanol, 8,8-dimethyl-2-nonanol, heptanol, 2-methyl-3-methoxyoctanol, 3-methyl-3-meth 3.5.5-trimethyl-1-hesanol, and the like. Even if optical iso oxyoctanol, 4-methyl-3-methoxyoctanol, 5-methyl-3- mers are present, the individual isomer or the mixture thereof methoxyoctanol, 6-methyl-3-methoxyoctanol, 7-methyl-3- may be used. methoxyoctanol, 2-methyl-3-methoxynonanol, 3-methyl-3- 0025. As liner or branched unsaturated alcohols among methoxynonanol, 4-methyl-3-methoxynonanol, 5-methyl-3- the linear, branched or cyclic alcohols having 6 to 18 carbon methoxynonanol, 6-methyl-3-methoxynonanol, 7-methyl-3- atoms, which may have an unsaturated bond, an ether group, methoxynonanol, 8-methyl-3-methoxynonanol, 2,3- an aromatic ring and/or an fused ring derived from an aro dimethyl-3-methoxypentanol, 2,4-dimethyl-3- matic ring in C of the formula (1), there may be exemplified, methoxypentanol. 2,2-dimethyl-3-methoxypentanol. 3,4- but not particularly limited to, 2-hexen-1-ol, 3-hexen-1-ol. dimethyl-3-methoxypentanol, 4,4-dimethyl-3- 4-hepten-2-ol, 3-octen-2-ol. 1-octen-3-ol, 5-nonen-2-ol. methoxypentanol. 2,2-dimethyl-3-methoxyhexanol, 2.3- US 2011/008 1393 A1 Apr. 7, 2011 dimethyl-3-methoxyhexanol, 2,4-dimethyl-3- 2-heptenol. 2,6-dimethyl-5-methoxy-2-heptenol, 3,4- methoxyhexanol. 2,5-dimethyl-3-methoxyhexanol, 3,4- dimethyl-5-methoxy-2-heptenol. 3,5-dimethyl-5-methoxy dimethyl-3-methoxyhexanol, 3,5-dimethyl-3- 2-heptenol. 3,6-dimethyl-5-methoxy-2-heptenol, 4.4- methoxyhexanol, 4.4-dimethyl-3-methoxyhexanol. 4.5- dimethyl-5-methoxy-2-heptenol. 4,5-dimethyl-5-methoxy dimethyl-3-methoxyhexanol, 5,5-dimethyl-3- 2-heptenol. 4,6-dimethyl-5-methoxy-2-heptenol, 5,6- methoxyhexanol. 2,2-dimethyl-3-methoxyheptanol, 2.3- dimethyl-5-methoxy-2-heptenol. 6,6-dimethyl-5-methoxy dimethyl-3-methoxyheptanol, 2,4-dimethyl-3- 2-heptenol, 2,3-dimethyl-5-methoxy-2-octenol, 2,4- methoxyheptanol. 2,5-dimethyl-3-methoxyheptanol. 2,6- dimethyl-5-methoxy-2-octenol. 2,5-dimethyl-5-methoxy-2- dimethyl-3-methoxyheptanol, 3,4-dimethyl-3- octenol. 2,6-dimethyl-5-methoxy-2-octenol. 2,7-dimethyl-5- methoxyheptanol. 3,5-dimethyl-3-methoxyheptanol, 3.6- methoxy-2-octenol, 3,4-dimethyl-5-methoxy-2-octenol, 3.5- dimethyl-3-methoxyheptanol, 4,4-dimethyl-3- dimethyl-5-methoxy-2-octenol. 3,6-dimethyl-5-methoxy-2- methoxyheptanol. 4,5-dimethyl-3-methoxyheptanol, 4.6- octenol. 3,7-dimethyl-5-methoxy-2-octenol, 4.4-dimethyl-5- dimethyl-3-methoxyheptanol, 5,5-dimethyl-3- methoxy-2-octenol. 4,5-dimethyl-5-methoxy-2-octenol. 4.6- methoxyheptanol, 5,6-dimethyl-3-methoxyheptanol. 6,6- dimethyl-5-methoxy-2-octenol, 4,7-dimethyl-5-methoxy-2- dimethyl-3-methoxyheptanol, 2,2-dimethyl-3- octenol, 5,6-dimethyl-5-methoxy-2-octenol, 5,7-dimethyl-5- methoxyoctanol. 2,3-dimethyl-3-methoxyoctanol. 2,4- methoxy-2-octenol. 6,6-dimethyl-5-methoxy-2-octenol. 6,7- dimethyl-3-methoxyoctanol, 2,5-dimethyl-3- dimethyl-5-methoxy-2-octenol. 7,7-dimethyl-5-methoxy-2- methoxyoctanol. 2,6-dimethyl-3-methoxyoctanol, 2.7- octenol. 2,3-dimethyl-5-methoxy-2-nonenol. 2,4-dimethyl dimethyl-3-methoxyoctanol, 3,4-dimethyl-3- 5-methoxy-2-nonenol. 2,5-dimethyl-5-methoxy-2-nonenol, methoxyoctanol. 3,5-dimethyl-3-methoxyoctanol, 3.6- 2,6-dimethyl-5-methoxy-2-nonenol. 2,7-dimethyl-5-meth dimethyl-3-methoxyoctanol, 3,7-dimethyl-3- oxy-2-nonenol. 2,8-dimethyl-5-methoxy-2-nonenol. 3,4- methoxyoctanol, 4.4-dimethyl-3-methoxyoctanol. 4.5- dimethyl-5-methoxy-2-nonenol. 3,5-dimethyl-5-methoxy-2- dimethyl-3-methoxyoctanol, 4,6-dimethyl-3- nonenol. 3,6-dimethyl-5-methoxy-2-nonenol. 3,7-dimethyl methoxyoctanol, 4,7-dimethyl-3-methoxyoctanol, 5.5- 5-methoxy-2-nonenol, 3.8-dimethyl-5-methoxy-2-nonenol, dimethyl-3-methoxyoctanol, 5,6-dimethyl-3- 4,4-dimethyl-5-methoxy-2-nonenol. 4,5-dimethyl-5-meth methoxyoctanol. 5,7-dimethyl-3-methoxyoctanol, 6.6- oxy-2-nonenol. 4,6-dimethyl-5-methoxy-2-nonenol. 4.7- dimethyl-3-methoxyoctanol, 6,7-dimethyl-3- dimethyl-5-methoxy-2-nonenol. 4,8-dimethyl-5-methoxy-2- methoxyoctanol. 7,7-dimethyl-3-methoxyoctanol, and the nonenol, 5,6-dimethyl-5-methoxy-2-nonenol. 5,7-dimethyl like. Even if optical isomers are present, the individual isomer 5-methoxy-2-nonenol. 5,8-dimethyl-5-methoxy-2-nonenol, or the mixture thereof may be used. 6,6-dimethyl-5-methoxy-2-nonenol. 6,7-dimethyl-5-meth 0027. As ether group-containing liner or branched unsat oxy-2-nonenol. 6,8-dimethyl-5-methoxy-2-nonenol. 7,7- urated alcohols having among the linear, branched or cyclic dimethyl-5-methoxy-2-nonenol. 7,8-dimethyl-5-methoxy-2- alcohol having 6 to 18 carbon atoms, which may have an nonenol, 8,8-dimethyl-5-methoxy-2-nonenol, 5-methoxy-3- unsaturated bond, an ether group, an aromatic ring and/or an heptenol, 5-methoxy-3-octenol, 5-methoxy-3-nonenol, fused ring derived from an aromatic ring in C of the formula 5-methoxy-3-decenol, 5-methoxy-3-undecenol, 2-methyl-5- (1), there may be exemplified, but not particularly limited to, methoxy-3-hexenol, 3-methyl-5-methoxy-3-hexenol, 4-me 5-methoxy-2-hexenol, 5-methoxy-2-heptenol, 5-methoxy-2- thyl-5-methoxy-3-hexenol, 5-methyl-5-methoxy-3-hexenol, octenol, 5-methoxy-2-nonenol. 5-methoxy-2-decenol, 2-methyl-5-methoxy-3-heptenol, 3-methyl-5-methoxy-3- 5-methoxy-2-tridecenol, 5-methoxy-2-undecenol, 2-methyl heptenol, 4-methyl-5-methoxy-3-heptenol, 5-methyl-5- 5-methoxy-2-hexenol, 3-methyl-5-methoxy-2-hexenol, methoxy-3-heptenol, 6-methyl-5-methoxy-3-heptenol, 4-methyl-5-methoxy-2-hexenol, 5-methyl-5-methoxy-2- 2-methyl-5-methoxy-3-octenol, 3-methyl-5-methoxy-3- hexenol, 2-methyl-5-methoxy-2-heptenol, 3-methyl-5-meth octenol, 4-methyl-5-methoxy-3-octenol, 5-methyl-5-meth oxy-2-heptenol, 4-methyl-5-methoxy-2-heptenol, 5-methyl oxy-3-octenol, 6-methyl-5-methoxy-3-octenol, 7-methyl-5- 5-methoxy-2-heptenol, 6-methyl-5-methoxy-2-heptenol, methoxy-3-octenol, 2-methyl-5-methoxy-3-nonenol, 2-methyl-5-methoxy-2-octenol, 3-methyl-5-methoxy-2- 3-methyl-5-methoxy-3-nonenol, 4-methyl-5-methoxy-3- octenol, 4-methyl-5-methoxy-2-octenol, 5-methyl-5-meth nonenol, 5-methyl-5-methoxy-3-nonenol, 6-methyl-5-meth oxy-2-octenol, 6-methyl-5-methoxy-2-octenol, 7-methyl-5- oxy-3-nonenol, 7-methyl-5-methoxy-3-nonenol, 8-methyl methoxy-2-octenol, 2-methyl-5-methoxy-2-nonenol, 5-methoxy-3-nonenol, 2-methyl-5-methoxy-3-decenol, 3-methyl-5-methoxy-2-nonenol, 4-methyl-5-methoxy-2- 3-methyl-5-methoxy-3-decenol, 4-methyl-5-methoxy-3-de nonenol, 5-methyl-5-methoxy-2-nonenol, 6-methyl-5-meth cenol, 5-methyl-5-methoxy-3-decenol, 6-methyl-5-meth oxy-2-nonenol, 7-methyl-5-methoxy-2-nonenol, 8-methyl oxy-3-decenol, 7-methyl-5-methoxy-3-decenol, 8-methyl-5- 5-methoxy-2-nonenol, 2-methyl-5-methoxy-2-decenol, methoxy-3-decenol, 9-methyl-5-methoxy-3-decenol and the 3-methyl-5-methoxy-2-decenol, 4-methyl-5-methoxy-2-de like. Even if geometrical or optical isomers are present, the cenol, 5-methyl-5-methoxy-2-decenol, 6-methyl-5-meth individual isomer or the mixture thereof may be used. oxy-2-decenol, 7-methyl-5-methoxy-2-decenol, 8-methyl-5- 0028. As alcohols which may have an alicyclic structure methoxy-2-decenol, 9-methyl-5-methoxy-2-decenol, 2.3- among the linear, branched or cyclic alcohols having 6 to 18 dimethyl-4-methoxy-2-pentenol. 2,4-dimethyl-4-methoxy carbon atoms, which may have an unsaturated bond, an ether 2-pentenol. 3,4-dimethyl-4-methoxy-2-pentenol. 2.3- group, an aromatic ring and/oran fused ring derived from an dimethyl-5-methoxy-2-hexenol. 2,4-dimethyl-5-methoxy-2- aromatic ring in C of the formula (1), there may be exempli hexenol. 2,5-dimethyl-5-methoxy-2-hexenol, 3,4-dimethyl fied, but not particularly limited to, cyclohexanol, 2-methyl 5-methoxy-2-hexenol, 3,5-dimethyl-5-methoxy-2-hexenol, cyclopentanol, 3-methylcyclopentanol, 2-methyl-1-cyclo 4,4-dimethyl-5-methoxy-2-hexenol. 4,5-dimethyl-5-meth pentenol, 3-methyl-1-cyclopentenol, 4-methyl-1- oxy-2-hexenol. 2,3-dimethyl-5-methoxy-2-heptenol. 2,4- cyclopentenol, 5-methyl-1-cyclopentenol, 2-methyl-2- dimethyl-5-methoxy-2-heptenol. 2,5-dimethyl-5-methoxy cyclopentenol, 3-methyl-2-cyclopentenol, 4-methyl-2- US 2011/008 1393 A1 Apr. 7, 2011

cyclopentenol, 5-methyl-2-cyclopentenol, 2-methyl-3- a condensation agent, or the carboxylic acid residue of the cyclopentenol, 3-methyl-3-cyclopentenol, 4-methyl-3- halfester is converted into an activated ester or acid halide to cyclopentenol, 5-methyl-3-cyclopentenol, 2.2- react with the alcohol. It is also possible to use a lipase dimethylcyclopentanol. 2,3-dimethylcyclopentanol. 2,4- enzyme as an esterifying agent. dimethylcyclopentanol. 2,5-dimethylcyclopentanol, 3.3- 0032. As the condensation agent, there may be exempli dimethylcyclopentanol, 3,4-dimethylcyclopentanol. 2,4- fied dicyclohexyl carbodiimide, diisopropyl carbodiimide, dimethyl-3-cyclohexenylmethanol, 2-cyclopentylethan-1-ol. 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide, and 2-me 2-(2,2,3-trimethyl-3-cyclopentenyl)-ethan-1-ol. 1-cyclohex thyl-6-nitrobenzoic acid anhydride, and the like. Further, as enol, 2-cyclohexenol, 3-cyclohexenol, 2-methyl-1-cyclohex the acid catalyst, there may be exemplified Sulfuric acid, enol, 3-methyl-1-cyclohexenol, 4-methyl-1-cyclohexenol, hydrochloric acid, phosphoric acid, Sodium hydrogen Sulfate, 4-isopropyl-1-cyclohexanol, 4-isopropyl-1-cyclohexyl methane Sulfonic acid, para-toluene Sulfonic acid, and the methanol. 1-(4-isopropyl-1-cyclohexyl)ethanol, 5-methyl-1- like. As the base catalyst, there may be exemplified sodium cyclohexenol, 6-methyl-1-cyclohexenol, 2-methyl-2-cyclo carbonate, potassium carbonate, sodium methoxide, potas hexenol, 3-methyl-2-cyclohexenol, 4-methyl-2- sium butoxide, Sodium acetate, pyridine, dimethylamino cyclohexenol, 5-methyl-2-cyclohexenol, 6-methyl-2- pyridine, triethylamine, and the like. In addition, as the lipase cyclohexenol, 2-methyl-3-cyclohexenol, 3-methyl-3- enzyme, there may be exemplified Lipase PS (trade name, cyclohexenol, 4-methyl-3-cyclohexenol, 5-methyl-3- manufactured by AMANO Corporation), Lipase AY (trade cyclohexenol, 6-methyl-3-cyclohexenol, 2.2.6- name, manufactured by AMANO Corporation), Novozyme trimethylcyclohexyl alcohol, 2.2,6-trimethyl-6- 435 (trade name, manufactured by Novozymes), Novozyme cyclohexenol, 2.2,6-trimethyl-5-cyclohexenol, 2.2.6- 525 (trade name, manufactured by Novozymes), and the like. trimethyl-4-cyclohexenol, 2,2-dimethyl-6-exomethyl-6- 0033. The diester compounds of dicarboxylic acid accord cyclohexenol, 4-tert-butylcyclohexanol, 2-tert ing to the invention represented by the formula (1), which is butylcyclohexanol, terpineol, borneol, nopol, ambrinol, and obtained as above, have a long-lasting cooling sensation the like. Even if geometrical or optical isomers are present, effect even if they are used alone or as a mixture of two or the individual isomer or the mixture thereof may be used. more. Therefore, it can be utilized as a cooling sensation 0029. As alcohols which may have an aromatic ring agent or a sensory stimulation agent either alone or as a among the linear, branched or cyclic alcohols having 6 to 18 mixture of two or more. carbon atoms, which may have an unsaturated bond, an ether 0034. Although the diester compound ofdicarboxylic acid group, an aromatic ring and/oran fused ring derived from an of the invention, that is obtained as above, is needed to alteran aromatic ring in C of the formula (1), there may be exempli amount compounded or an application method according to fied, but not particularly limited to, benzyl alcohol, styrallyl types and purposes of use of the product, an amount for a alcohol, hydroquinone, furfuryl alcohol, 4-hydroxystyrallyl flavor or fragrance agent composition, generally, is preferably alcohol, Vanillyl alcohol, cuminic alcohol, 2-methylbenzyl 0.0001 to 90% by mass to the total mass of the composition. alcohol, 3-methylbenzyl alcohol, 4-methylbenzyl alcohol, On the other hand, an amount for a beverage, a food product, C.-dimethylbenzyl alcohol, C-phenethyl alcohol, B-phenethyl a perfume or cosmetic product, a toiletry product, daily uten alcohol, cinnamic alcohol, 4-hydroxy-3-methoxystyrallyl sil products or groceries, a fiber, a fiber product, clothes, alcohol, anisyl alcohol, catechol, 5-methylfurfuryl alcohol, clothing or a medicine or the like is 1x107 to 20% by mass, 2-pyridinylethanol and the like. Even if geometrical or optical preferably 0.0001 to 20% by mass, and more preferably 0.001 isomers are present, the individual isomer or the mixture to 5% by mass to the total mass of the composition. thereof may be used. 0035. The cooling sensation agent composition of the 0030. Furthermore, as the alcohols which may have a invention contains at least one of the dicarboxylic esters fused ring derived from an aromatic ring among the linear, described above. That is, the cooling sensation agent compo branched or cyclic alcohols with 6 to 18 carbon atoms which sition of the invention may comprise one of the dicarboxylic may have an unsaturated bond and an ether group, an aro esters or two or more of the dicarboxylic esters. Further, the matic ring and/or a fused ring derived from an aromatic ring dicarboxylic ester compound of the invention may be used as in C of the formula (1), there may be exemplified, but not it is for a cooling sensation agent composition or used as a particularly limited to, 6-methyl-1-indanol, alpha tetralol, Solution in alcohol, propylene glycol, benzyl benzoate and 1-naphthyl methanol, 2-naphthyl methanol, piperonyl alco the like or as an emulsion admixed with an emulsifying agent hol, 3-chromon alcohol, 2-benzofurfuryl alcohol and the like. for a cooling sensation agent composition. Even if geometrical or optical isomers are present, the indi 0036 Furthermore, a cooling sensation agent composition vidual isomer or the mixture thereof may be used. having increased cooling sensation strength may be obtained 0031 Compounds of the invention may be synthesized using the dicarboxylic ester compounds of the invention according to a technique that is well known in the art. together with at least one selected from cooling sensation Although not specifically limited, they can be obtained by an Substances that are not included in the ester compounds of the one-step or preferably two-step condensation of a dicarboxy invention. lic acid such as Oxalic acid, malonic acid. Succinic acid, 0037. As the cooling substances which are not included in glutaric acid, adipic acid, fumaric acid and maleic acid with the dicarboxylic ester compounds of the invention, there may alcohols which can form the alcohol residue of the formula be exemplified menthol, menthone, camphor, pulegol, isop (1) in the presence of an appropriate condensation agent. A ulegol, cineole, mint oil, peppermint oil, spearmint oil, euca desired diester may be obtained as follows. That is, an acid lyptus oil, 3-(1-menthoxy)propane-1,2-diol, N-alkyl-p-men anhydride of the aforementioned dicarboxylic acid is reacted thane-3-carboxamide, 3-1-menthoxy-2-methylpropane-1,2- with the aforementioned alcohols in the absence or presence diol, p-menthane-3,8-diol, 2-1-menthoxyethan-1-ol. 3-1- of an acid or base catalyst to synthesize a halfester, and then menthoxypropan-1-ol. 4-1-menthoxybutan-1-ol (menthyl the half ester is condensed with an alcohol in the presence of 3-hydroxybutanoate), menthyl lactate, menthone glycerin US 2011/008 1393 A1 Apr. 7, 2011 ketal, N-methyl-2.2-isopropylmethyl-3-methylbutane 0043. The cooling sensation agent composition and the amide, menthylglyoxylate and the like. These can be used sensory stimulation agent composition of the invention can be alone or as an appropriate mixture of two or more. compounded with a flavor or fragrance composition. When 0038. The dicarboxylic ester compounds of the invention the cooling sensation agent composition or the sensory stimu and the cooling sensation Substances which are not included lation agent composition is compounded with the flavor or in the dicarboxylic ester compounds of the invention may be fragrance composition, the compounding amount thereof used at any ratio within a range in which the effect of the should be altered properly according to the scope, application invention is not impaired. However, the ratio is preferably, in method, kind and purpose of use of the flavor or fragrance terms of mass ratio of the dicarboxylic ester compounds of the composition, but is preferred in the range of normally 0.0001 invention to the cooling Substance which is not included in the to 90% by mass with respect to the total amount of the flavor compounds, in the range of 1:99 to 70:30. or fragrance composition. In addition, the cooling sensation 0039. Further, in the invention, since the aforementioned agent composition and the sensory stimulation agent compo cooling sensation agent composition of the invention has a sition of the present invention can be compounded with a strong and long-lasting cooling sensation effect, a sensory flavor or fragrance composition, a beverage, a food product, a stimulation agent composition having a cooling sensation perfume or cosmetic product, a toiletry product, daily utensil effect can be produced by containing this cooling sensation products and groceries, a medicine and others. when the agent composition. In addition, the sensory stimulation agent cooling sensation agent composition or the sensory stimula composition of the invention is a composition having an tion agent composition is compounded in Such a product, the action to stimulate senses. The sense-stimulating action compounding amount thereof may vary according to the kind includes both cooling action and warming action, and thus in of the product to be compounded, but is preferably 1x107 to the present invention, the sensory stimulation agent compo 20% by mass, more preferably 0.0001 to 20% by mass, par sition is a concept including both the cooling sensation agent ticularly preferably 0.001 to 5% by mass, with respect to the composition and warming and pungent agent composition. total amount of the product composition. The products can be 0040. In preparing a sensory stimulation agent composi applied directly onto a skin or a scalp, administered into an tion, the field and method of application of the cooling sen oral cavity, or applied to fibers, fiber products, clothes or sation agent composition should be altered properly accord clothing. Especially when the cooling sensation agent com ing to the kind and application purpose of the product, and the position of the present invention is used, long-lasting cooling cooling sensation agent composition is normally used in a feeling is provided to the skin, Scalp, or oral cavity since the compounding amount of 0.0001 to 20% by mass, particularly cooling sensation agent composition has a strong, long-last preferably 0.001 to 5% by mass, in the entire sensory stimu ing cool action. Alternatively, the cooling sensation agent lation agent composition. composition or the sensory stimulation agent composition 0041. The sensory stimulation agent composition may be can be used in processing of a fiber, a fiber product, clothes, prepared by using a warming and pungent Substance in com clothing, resin and the like. The compounding amount thereof bination with the cooling sensation agent composition of the should be altered properly according to the application scope, invention. Examples of the warming Substances include purpose of use, kind and application method of the product vanillyl ethyl ether, vanillyl propyl ether, vanillin propylene and others, but is normally 0.0001 to 20% by mass, particu glycol acetal, ethylvanillin propylene glycol acetal, capsai larly preferably 0.001 to 5% by mass in concentration. cin, gingerol, Vanillylbutyl ether, 4-(1-menthoxy-methyl)-2- 0044) For example, the cooling sensation agent composi (3'-methoxy-4'-hydroxyphenyl)-1,3-dioxolane, pepper oil, tion or the sensory stimulation agent composition of the pepper oleoresin, ginger oleoresin, nonanoic Vanillylamide, present invention may be directly sprayed on, adsorbed in or jamboo oleoresin, Zanthoxylum Piperitum Peel Extract, san permeated to the fibers, resins, cloth materials, clothes or shool-I, sanshool-II, Sanshoamide, black pepper extract, clothing, or may be used for modification or processing of the chavicine, piperine, spilanthol and the like. These substances surface or internal region of the fiber or the resin surface by may be used alone or as a mixture of two or more. using a suitable solvent, a dispersion medium or microcap 0042. If the cooling action is desirable, the compounding sules. The compounding amount thereof is preferably 0.0001 ratio of the warming and pungent Substance to the cooling to 100% by mass, particularly preferably 0.001 to 100% by sensation Substance is in the range where the warming action mass with respect to the total amount of the fragrance com by the warming substance is not distinctively observed by position, the processing agent composition or the internal compounding of the warming Substance, and thus, the com composition in the microcapsule. pounding amount of the warming and pungent Substance is 0045. The fiber material to be processed is not particularly normally 0.001 to 0.95 part, preferably 0.01 to 0.5 part, with limited, and examples thereof include natural fibers such as respect to the total amount of the cooling sensation agent cellulose, cotton, hemp, silk and wool; regenerated fibers composition. In this case, the cooling action is further Such as rayon, cupra, polynosic, Tencel (trade name), and improved and strengthened by addition of the warming and Lyocell (trade name); semi-synthetic fibers such as acetates; pungent Substance to the cooling sensation agent composition chemically synthetic fibers such as nylon, polyester, and in the amount described above in the sensory stimulation acrylic; and the like. These fibers may be used alone or as a agent composition of the present invention. Alternatively if fiber obtained by mixed spinning or mixed weaving in which the warming action is desirable, the cooling sensation agent two kind or more of fibers are used. The forms of the fibers composition is added to a warming composition in an amount include yarn, woven and knitted fabrics, nonwoven fabric, not distinctively showing the cooling action by the cooling paper and the like, but are not particularly limited thereto. sensation agent composition compounded, and the com 0046) Wall materials of the microcapsule is preferably an pounding amount is normally 0.001 to 0.95 part, preferably organic material, and examples thereof include polystyrene, 0.01 to 0.5 part, with respect to the total amount of the warm ethylcellulose, polyamide, polyacrylic acid, melamine, sili ing and pungent agent. cone resin and the like, but are not limited thereto. US 2011/008 1393 A1 Apr. 7, 2011

0047. The average particle diameter of the microcapsule is 0053. The content of the cooling sensation agent compo not particularly limited, but preferably 20 Lum or less, more sition or the sensory stimulation agent composition in the preferably 10 Lum or less, still more preferably 5 um or less, flavor or fragrance composition containing the cooling sen because of dispersibility when used as a processing solution, sation agent composition or the sensory stimulation agent prevention of breakage of microcapsules under pressure dur composition of the invention may be adjusted properly ing processing as they are adhered to fibers, and prevention of according to the kind and purpose of use of the flavor or hardening in texture. fragrance and other components to be mixed. For example, in the case of a fragrance composition, the content of the cooling 0048. The method for producing the microcapsule is not sensation agent composition is normally 0.0001 to 50% by particularly limited and includes known methods, for mass, preferably 0.001 to 50% by mass, and more preferably example those described in JP-A Nos. 62-1452, 62-45680, 0.01 to 20% by mass with respect to the total mass of the 62-149334, 62-225241, 63-115718, 63-217 196, and fragrance composition. 2-258052, JP Patent No. 3,059,558 and others. 0054 Alternatively, in the case of a flavor composition, the 0049. The adhesion methods of the microcapsule-dis content of the cooling sensation agent composition is prefer persed processing solution to fibers or resins include, for ably 0.0001 to 50% by mass and more preferably 0.001 to example, a pad drying method, a spraying method, a printing 30% by mass with respect to the total mass of the flavor method, a coating method and the like, but are not particularly composition. limited thereto. 0055. The cooling sensation agent composition and the 0050 Cool feeling may be given to fiber products, clothes sensory stimulation agent composition of the present inven and the like by compounding the cooling sensation agent tion may contain, as needed, one or more odorant-retaining composition or the sensory stimulation agent composition of agents commonly used in flavor or fragrance compositions. the invention with a detergent, a fabric softener or the like in Example of the odorant-retaining agents used include ethyl advance, and then adhering the cooling sensation agent com ene glycol, propylene glycol, dipropylene glycol, glycerol, position or the sensory stimulation agent composition of the hexyl glycol, benzyl benzoate, triethylcitrate, diethyl phtha invention onto the fiber products, clothes or the like at the time late, hercolin, medium-chain fatty acid triglycerides, of washing or rinsing. The compounding amount of these medium-chain fatty acid diglycerides and the like. These compositions in a detergent, a fabric softener or the like is not compounds may be contained alone or as a mixture of two or particularly limited, but should be an amount of a level where O. cool feeling is recognized at the time of touching to or wear 0056. The cooling sensation agent composition and the ing a fiber product, clothes or clothing after washing and sensory stimulation agent composition of the present inven drying. The amount is normally 0.0000001 to 10% by mass, tion can be used for providing cooling action to various prod preferably 0.000001 to 5% by mass with respect to the total ucts, as described above, by using the cooling sensation agent composition of a detergent, a fabric softener or the like. composition alone or as a flavor or fragrance containing the 0051. The cooling sensation agent composition and the cooling sensation agent composition. The products to which sensory stimulation agent composition of the present inven the cooling action can be provided using the cooling sensation tion may be compounded directly with various products Such agent composition itself or the flavor or fragrance composi as flavor or fragrance compositions, beverage, food products, tion containing the cooling sensation agent composition of perfume or cosmetic products, toiletry products, daily utensil the present invention include beverages, food products, per products and groceries, fibers, fiber products, clothes, cloth fume or cosmetic products, daily utensil products and grocer ing and medicines. In addition, the cooling sensation agent ies, toiletry products, fibers, fiber products, clothes, clothing, composition and the sensory stimulation agent composition medicines and the like, as described above. may be first compounded with a flavor or fragrance compo 0057. Unlimited examples of the beverages and food prod sition to give a flavor or fragrance composition containing the ucts of the invention capable of giving the cooling sensation cooling sensation agent composition or the sensory stimula or the like by the cooling sensation agent composition, the tion agent composition, and then, the cooling sensation agent sensory stimulant composition or the flavor composition con composition, the sensory stimulation agent composition, or taining these composition include beverages Such as fruit the flavor or fragrance composition containing the cooling beverages, fruit spirits, milk-based drinks, carbonated drinks, sensation agent composition or the sensory stimulation agent soft drinks and health and nutrient drinks; frozen deserts such composition may be compounded with the product. as ice creams, sherbets and popsicles; deserts such as jelly and 0052 Examples of the flavor or fragrance components puddings; confectionary Such as cakes, cookies, chocolates contained in combination with the cooling sensation agent and chewing gums, Japanese Sweets such as bean-jam buns, composition and the sensory stimulation agent composition thickjellied sweet made of azuki bean paste and thick jellied of the present invention include various synthesis aroma Sweet made of powdered rice paste;jams; candies; breads; tea chemicals, natural essential oils, synthetic essential oils, cit drinks and other favorite drinks such as green tea, oolong tea, rus oils, animal aromachemicals and the like, and there also black tea, persimmon leaf tea, chamomile tea, Sasa Veitchii may be used various kinds of flavor or fragrance components tea, mulberry leaf tea, Houttuynia cordata tea, puaar tea, mate such as those described, for example, in “Collection of Well tea, rooibos tea, gymnema tea, guava tea, coffee and cocoa: known Prior Arts (Flavor or Fragrances) 1st part, Japanese Soups such as Japanese style soups, Western style soups and Patent Office, Jan. 29, 1999. Typical examples thereof include Chinese style soups: flavored seasonings; various instant C-pinene, limonene, cis-3-hexenol, phenylethyl alcohol, drinks and foods; various Snacks; and oral products Such as styralyl acetate, eugenol, Oxyde de rose, linalool, benzalde toothpaste, tooth powder, oral wash, mouth wash, throat loZ hyde, l-muscone (Takasago International Corporation), Musk enge, and chewing gums. T (Takasago International Corporation). Thesaron (Takasago 0.058 Examples of the perfume or cosmetic products, toi International Corporation) and the like. letry products or daily utensil products and groceries of the US 2011/008 1393 A1 Apr. 7, 2011 invention capable of giving the cooling sensation or the like tion or the flavor or fragrance composition containing these by the cooling sensation agent composition, the sensory compositions include, but are not limited to, skin external stimulant composition or the fragrance composition contain preparations such as poultice and ointment, internal prepara ing these composition include perfume or cosmetic products, tions and the like. skin-care cosmetics, make-up cosmetics, hair cosmetics, 0079. When the cooling sensation agent composition, the anti-Sunburn cosmetics, medicinal cosmetics, hair-care prod sensory stimulation agent composition or the flavor or fra ucts, soaps, body lotions, bath utensils, detergents, soft fin grance composition containing these compositions according ishing agents, cleaning agents, kitchen detergents, breaching to the invention is used for providing the aforementioned agents, aerosol agents, deodorant-aromatics, repellents, and various products with cooling sensation or the like, they may other groceries. be added various forms or various methods according to the 0059 More specifically, the examples include: kind of the products and final product forms such as liquid, 0060 perfume, Eau de Parfum, Eau de Toilette, and Eau de Solid, powder, gel, mist, aerosol, or the like. For example, they Cologne as the perfume or cosmetic products; may be added directly to the product; as a liquid dissolved in 0061 face washing cream, Vanishing cream, cleansing an alcohol or a polyvalent alcohol Such as, propylene glycol, cream, cold cream, massage cream, milky lotion, skin lotion, or glycerol; as a solution or dispersion dissolved or dispersed beauty wash, beauty pack, and make-up remover as the skin with a natural gum Such as gum arabic or tragacanth gum or care cosmetics; a Surfactant such as nonionic Surfactant, e.g. glycerol fatty 0062 foundation, face powder, pressed powder, talcum acid ester or Sucrose fatty acid ester, anionic Surfactant, cat powder, rouge, lip Stick, lip cream, cheek rouge, eye liner, ionic Surfactant and amphoteric Surfactant; as a powder mascara, eye shadow, eyebrow-color, eye pack, nail enamel, formed with a natural gum Such as gum arabic or a shape and enamel remover as the make-up cosmetics; and imparting agent Such as gelatin or dextrin; or as microcap 0063 pomade, brilliantine, set lotion, hair stick, hair solid, Sules treated with an encapsulating agent. hair oil, hair treatment, hair cream, hair tonic, hair liquid, hair 0080. Alternatively, the cooling sensation agent composi spray, bandlin, hair-growing agent, and hair dye as the hair tion, the sensory stimulation agent composition or the flavor cosmetics. or fragrance composition containing these may be stabilized 0064. Examples of the anti-sunburn cosmetics include and provided with Sustained-release property by inclusion Suntan products and Sunscreen products; using an inclusion agent such as cyclodextrin. 0065 examples of the medicinal cosmetics include anti perspirant, after-shaving lotion and gel, permanent wave EXAMPLES agent, medicinal Soap, medicinal shampoo, and medicinal skin-care cosmetics. 0081. Hereinafter, the invention will be described more 0066 Examples of the hair-care products include sham specifically with reference to Examples, but it should be poo, rinse, rinse-in-shampoo, hair conditioner, hair treatment, understood that the present invention is not restricted by these and hair pack; Examples, and various modifications are possible within the 0067 examples of the soaps include toilet soap, bath soap, Scope of the present invention. perfume soap, clear Soap, and synthetic Soap: I0082. The products obtained in the Synthetic examples 0068 examples of the body cleaners include body soap, and Examples described below were analyzed by using the body shampoo, and hand Soap: following instruments and apparatuses: 0069 examples of the bath utensils include bath agent I0083) Nuclear magnetic resonance spectrum: "H-NMR: such as bath salt, bath tablet and bath liquid, foam bath such OXFORD 300 MHz FT-NMR (300 MHz), manufactured by as bubble bath, bath oil such as bath perfume and bath cap Varian, Inc. sule, milk bath, bathjelly, and bath cube; and I0084 External standard substance: tetramethylsilane 0070 examples of the detergents include heavy detergent I0085 TLC: SILICAGEL 60 F254 (trade name, manufac for clothes, light detergent for clothes, liquid laundry deter tured by Merck & Co., Inc.) gent, laundry Soap, compact detergent, and powder detergent. Synthetic Example 1 0071 Examples the soft finishing agents include softener and furniture care; Synthesis of 1-menthyl-(1-menthoxyethyl)succinic 0072 examples of the cleaning agents include cleanser, ester house wash, toilet cleaner, bath cleaner, glass cleaner, fungi cide, and cleaner for drain pipe; Compound 1 0073 examples of the kitchen detergents include kitchen I0086 To a 100 ml autoclave, 10.00 g (63.99 mmol) of Soap, kitchen synthetic Soap, and dish wash; 1-menthol and 6.40 g (63.96 mmol) of succinic anhydride 0074 examples of the bleaching agents include oxidant were added, flushed with nitrogen gas, and then stirred at 110° bleach Such as chlorine bleach and oxygen bleach, reductive C. for 8 hours. After cooling to room temperature, 100 ml of bleach Such as Sulfur containing bleach, and optical bleach; hexane was added thereto. The precipitated crystals were 0075 examples of the aerosol agents include spray type filtered and the filtrate, hexane phase was concentrated to aerosol and powder spray; obtain 16.61 g of 1-menthylsuccinic acid. The yield was >99. 0076 examples of the deodorant-aromatics include solid, 9%. gel and liquid deodorizer and aromatics; and I0087. To a 20 ml two-neck flask, 6.00 g (23.42=1) of 0077 examples of the groceries include tissue paper and 1-menthylsuccinic acid and 20.0 mg of DMF were added, and toilet paper. 6.00 g (50.43 mmol) of thionyl chloride was added dropwise 0078 Examples of the medicines of the invention capable thereto at room temperature. Upon the completion of the of giving the cooling sensation or the like by the cooling dropwise addition, the mixture was stirred for 2 hours and sensation agent composition, the sensory stimulant composi excess thionyl chloride was removed by distillation under US 2011/008 1393 A1 Apr. 7, 2011

reduced pressure to obtain 6.45 g of 1-menthylsuccinic acid (3H, m), 1.65 (3H, s), 1.30-1.60 (6H, m), 0.96-1.11 (6H, m), chloride. The yield was >99.9%. 0.88-0.94 (9H, m), 0.75 (6H, t, J=6.9) I0088. To a 50 ml two-neck flask, 1.99 g (9.93 mol) of 1-menthoxyethanol. 20 ml of toluene and 2.01 g (19.86 mmol) Synthetic Example 4 of triethylamine were added, and 3.00 g (10.92 mmol) of 1-menthylsuccinic acid chloride obtained was added drop Synthesis of 1-menthyl-(1-citronellyl)succinic ester wise thereto at room temperature. After stirring for 2 hours at room temperature, disappearance of the spot of 1-methoxy Compound 4 ethanol was confirmed by the thin layer chromatography (TLC) (ethyl acetate:hexane=1:3), and then the reaction was 0094. The synthesis was carried out in the same manner as terminated. The reaction solution was diluted with 150 ml of Synthetic example 1 except for using 1-citronellol instead of toluene and washed twice with 30 ml of purified water. The 1-menthoxyethanol to obtain 1-menthyl-(1-citronellyl)suc organic layer was dried over sodium sulfate and concentrated cinic ester. The yield was 78.6%. to obtain 4.84 g of a colorless liquid. Column purification was carried out using 73 g of silica gel and development Solution Physical property of 1-menthyl-(1-citronellyl)succinic of ethyl acetate:hexane=1:30 to obtain 3.95 g of 1-menthyl ester (1-menthoxyethyl)succinic ester. The yield was 79.2%. (0.095 'H-NMR (CDC1,300 MHz): O 5.08 (1H, t, J–72), Physical property of 4.69 (1H, ddd, J=10.8, 10.8, 4.2), 405-4.17 (2H, m), 2.61 1-menthyl-(1-menthoxyethyl)Succinic ester (3H, s), 1.93-2.02 (3H, m), 1.81-1.90 (1H, m), 1.64-1.71 (5H, m), 1.60 (3H, s), 1.29-1.57 (6H, m), 1.07-124 (2H, m), 0.88 0089 'H-NMR (CDC1, 300 MHz): O 4.70 (1H, ddd, 0.98 (9H, m), 0.75 (3H, J=6.9) J=10.8, 10.8, 4.5), 4.22 (2H, t, J=6.8), 3.79 (1H, dt, J=11.1, 9.3), 3.52(1H, dt, J=11.1, 10.8), 3.05 (1H, ddd, J=10.8, 10.8, Synthetic Example 5 4.5), 2.64 (4H, m), 2.22 (1H, m), 2.02 (2H, m), 1.85 (1H, q, J=7.2), 1.84 (1H, m), 1.20-1.33 (4H, m), 0.97-1.07 (4H, m), Synthesis of 1-menthyl-(phenylethyl)succinic ester 0.81-0.93 (12H, m), 0.77 (6H, t, J=8.1) Compound 5 Synthetic Example 2 0096. The synthesis was carried out in the same manner as Synthesis of 1-menthyl-3-(1-menthoxy)-2-(hydrox Synthetic example 1 except for using phenethyl alcohol ypropyl)succinic ester instead of 1-menthoxyethanol to obtain 1-menthyl-(phenyl Compound 2 ethyl)succinic ester. The yield was 69.0%. 0090 The synthesis was carried out in the same manner as Synthetic example 1 except for using 1-menthylglycerol Physical property of 1-menthyl-(phenylethyl)succinic instead of 1-menthoxyethanol to obtain 1-menthyl-3-(1-men ester thoxy)-2-(hydroxyl-propyl)succinic ester. The yield was (0097 H-NMR (CDC1, 300 MHz): o 7.20-7.33 (59, m), 75.4%. 4.69 (1H, ddd, J=10.8, 10.8, 4.2), 4.30 (2H, t, J=7.2), 2.94 (2H, t, J=7.2), 2.60 (4H, t, J=7.2), 1.98 (1H, d, J=12.0), 1.85 Physical property of (1H, t, J=6.9), 1.67 (2H, d, J=12.8), 1.31-1.56 (3H, m), 0.98 1-menthyl-3-(1-menthoxy)-2-hydroxypropyl-Succinic 1.11 (2H, m), 0.92 (6H, d. J=11.4), 0.75 (3H, d, J–6.6) ester I0091 'H-NMR (CDC1, 300 MHz): O 4.69 (1H, ddd, Synthetic Example 6 J=10.8, 10.8, 4.5), 3.97-4.23 (2H, m), 3.80 (1H, br), 3.61-3.72 (1H, m), 3.28-3.39 (1H, m), 3.08 (1H, ddd, J=10.8, 10.8, 4.5), Synthesis of 1-menthyl-(phenylethyl)glutaric ester 2.64 (4H, m), 1.82-2.17 (4H, m), 1.60- 1.68 (4H, m), 1.20-1. 46 (6H, m), 0.99-1.11 (4H, m), 0.88-1.06 (12H, m), 0.77 (6H, Compound 6 t, J=6.9) (0098. To a 200 ml autoclave, 39.00 g (0.25 mol) of 1-men thol and 28.5 g (0.25 mol) of glutaric anhydride were added, Synthetic Example 3 flushed with nitrogen gas, and stirred at 90° C. for 18 hours. Synthesis of 1-menthyl-(1-isopulegyl)succinic ester Upon the completion of the reaction, bigelow distillation (Bottom 180 to 195° C., Top 150 to 155° C., 30 Pa) was Compound 3 carried out to obtain 59.64 g of 1-menthylglutaric acid. The 0092. The synthesis was carried out in the same manner as yield was 88.4%. Synthetic example 1 except for using l-isopulegol instead of (0099 Subsequently, to a 200 ml four-neck flask, 10.00 g 1-menthoxyethanol to obtain 1-menthyl-(1-isopulegyl)suc (36.99 mmol) of 1-menthylglutaric acid, 4.52 g (37.00 mmol) cinic ester. The yield was 72.4%. of phenethyl alcohol, 100 ml of hexane and 0.50 g (5.0% by weight) of Novozyme 435 were added, and then stirred at 60° Physical property of 1-menthyl-(1-isopulegyl)succinic C. for 13 hours. After confirming the conversion ratio of ester 90.9%, the reaction solution was filtered to remove Novozyme 435. The organic layer was concentrated to obtain 0093. H-NMR (CDC1, 300 MHz): O 4.81 (1H, ddd, 14.39 g of a colorless liquid. Column purification was carried J=11.0, 11.0, 4.2), 4.65-4.72 (3H, m), 2.56 (3H, s), 1.81-2.15 out using 300g of silica gel and development solution of ethyl US 2011/008 1393 A1 Apr. 7, 2011 acetate:hexane=1:30 to obtain 9.51 g of 1-menthyl-(phenyl instead of phenethyl alcohol to obtain 1-menthyl-(1-men ethyl)glutaric ester. The yield was 68.7%. thoxyethyl)glutaric ester. The yield was 65.2%. Physical property of Physical property of 1-menthyl-(phenylethyl)glutaric 1-menthyl-(1-menthoxyethyl)glutaric ester ester 0104 'H-NMR (CDC1, 300 MHz): O 4.68 (1H, ddd, J=10.8, 10.8, 4.5), 4.21 (2H, t, J=6.8), 3.79 (1H, dt, J=11.1, 0100 'H-NMR (CDC1,300 MHz): O 720-7.33 (5H, m), 9.3), 3.52(1H, dt, J=11.1, 10.8), 3.05 (1H, ddd, J=10.8, 10.8, 4.67 (1H, ddd, J=10.8, 10.8, 4.5), 4.30 (2H, t, J=7.2), 2.94 4.5), 2.36 (4H, m), 2.18 (1H, m), 2.05 (1H, m), 1.96 (2H, q, (2H, t, J=7.2), 2.33 (2H, ddd, J=7.5, 7.5, 3.9), 1.81-199 (4H, J=7.2), 1.84 (1H, m), 1.59-1.69 (10H, m), 1.03-1.50 (5H, m), m), 1.68 (2H, m), 1.32-1.59 (3H, m), 1.30-1.40 (2H, m), 0.79-0.93 (12H, m), 0.76 (6H, t, J=6.6) 1.03-1.08 (2H, m), 0.95 (6H, m), 0.75 (3H, d, J=6.9) Test Example 1 Synthetic Example 7 Test of a Cooling Towel Direct Spraying Synthesis of 1-menthyl-(1-citronellyl)glutaric ester 0105. Each of Compounds 1 to 8 that were obtained by the above synthetic examples and Mixture 1 which is an equiva Compound 7 lent-weight mixture of Compounds 1 to 4, Mixture 2 which is an equivalent-weight mixture of Compounds 5 to 8, Mixture 0101 The synthesis was carried out in the same manner as 3 which is an equivalent-weight mixture of Compounds 2, 3 Synthetic example 6 except for using 1-citronellol instead of and 8, and dimenthylglutaric acid and 1-menthol as compara phenethyl alcohol to obtain 1-menthyl-(1-citronellyl)glutaric tive compounds was prepared in 1% ethanol solution. The 1% ester. The yield was 70.0%. ethanol solutions were then sprayed respectively by 1 g to different pure cotton hand towels (white plain towel made in Physical property of 1-menthyl-(1-citronellyl)glutaric Japan, 20 cmx20 cm, degrease-finished). Those which were air-dried for 10 minutes, 3 hours or 24 hours after spraying ester were sensory evaluated. The sensory evaluation was carried out by touching the cooling towel with the inside of upper 0102 'H-NMR (CDC1,300 MHz): O 5.09 (1H, t, J–72), parts of arms, and cooling action at that time was determined. 4.69 (1H, ddd, J=10.8, 10.8, 4.2), 4.11 (2H, m), 2.35 (4H, t, Results are shown in Table 1. J–7.5), 1.90-2.03 (6H, m), 1.84 (1H, t, J=9.3), 1.64-1.68 (8H, 01.06 Meanwhile, the evaluation was carried out by five m), 1.60(3H, d, J=4.2), 1.31-1.55 (4H, m), 1.02-1.24 (2H, m), panelists having 5 years or longer experience. Compounds 1 0.88-0.98 (9H, m), 0.75 (3H, J=6.9) to 8 and mixtures 1 to 3 were divided into three groups of A to C, wherein group A consists of Compound 1, mixture 1, Synthetic Example 8 Compound 2. dimenthylglutaric acid, and 1-menthol; group B consists of mixture 2, Compound 3. Compound 6, dimenth Synthesis of 1-menthyl-(1-menthoxyethyl)-glutaric ylglutaric acid, and 1-menthol; and group C consists of Com ester pound 7. Compound 8, Compound 4, mixture 3, and dimen thylglutaric acid. Then, different 5 kinds of samples were Compound 8 ranked from the strongest to weakest in action respectively by the panelists in each three groups. The results are shown by 0103) The synthesis was carried out in the same manner as the total score of the ranking numbers. In other words, Smaller Synthetic example 6 except for using 1-menthoxyethanol total score means to show a better cooling sensation effect.

TABLE 1 Results of comparison concern with lasting properties of cooling effect on treated hand towel at direct spraying Group A Group B Group C

After After After After After After After After After Materials 10 min 3 hr 24 hr 10 min 3 hr 24 hr 10 min 3 hr 24hr Example 1 Compound 1 18 12 11 Example 2 Mixture 1 11 6 5 Example 3 Compound 2 18 13 13 Example 4 Mixture 2 13 7 7 Example 5 Compound 3 16 10 10 Example 6 Compound 6 17 14 14 Example 7 Compound 7 15 17 18 Example 8 Compound 8 13 12 11 Example 9 Compound 4 16 18 16 Example 10 Mixture 3 9 7 7 Comparative Dimenthylglutaric 22 2O 21 22 2O 19 22 21 23 example 1 acid Comparative 1-Menthol 6 24 25 7 24 25 example 2

Numbers in Table are the total score of the ranking numbers, US 2011/008 1393 A1 Apr. 7, 2011 13

0107 As obvious from the results in Table 1, menthol 0109 Meanwhile, the evaluation was carried out by five showed the strongest cooling action after air drying for 10 panelists having 5 years or longer experience. The above minutes, but the action was found to be less consistent. On the compounds, mixtures and menthoxypropanediol were other hand, the compounds of the invention showed long lasting cooling action and the effects are better than that of divided into three groups of A to C (group A; Compound 1. dimenthylglutaric acid. In particular, the mixture of the com mixture 1, Compound 2, menthoxypropanediol: group B; pounds of the invention appeared to be excellent cooling mixture 2, Compound 3, Compound 6, menthoxypro action in the initial strength and the consistency. panediol: group C; Compound 8, Compound 4, mixture 3, menthoxypropanediol). Then, different 4 kinds of samples Test Example 2 were ranked from the strongest to weakest in action respec Test of a Cooling Towel tively by the panelists in each three groups. The results are shown by the total score of the ranking numbers. The results Washing Processed are expressed by the total score of the rankings. In other 0108. Each of Compounds 1 to 4 and 6 that were obtained words, Smaller total score means to show a better cooling by the above synthetic examples, Mixture 1 which is an sensation effect.

TABLE 2

Results of comparison concern with lasting properties of cooling effect on treated hand towel after washing Group A Group B Group C

After After After After After After After After After Materials 6 hr 24 hr 48 hr 6 hr 24 hr 48 hr 6 hr 24 hr 48 hr

Example 11 Compoun 11 10 13 Example 12 Mixture 1 7 7 6 Example 13 Compoun 13 11 12 Example 14 Mixture 2 8 7 6 Example 15 Compoun 11 10 10 Example 16 Compoun 13 14 14 Example 17 Compoun 13 13 13 Example 18 Compoun 10 12 11 Example 19 Mixture 3 7 5 7 Comparative Menthoxypropanediol 19 2O 19 18 19 2O 19 2O 19 example 4

Numbers in Table are the tota score of the ranking numbers, equivalent-weight mixture of Compounds 1 to 4, Mixture 2 0110. According to Table 2, it was found that overall the which is an equivalent-weight mixture of Compounds 5 to 8, compounds of the invention showed an excellent cooling action compared with 1-menthoxypropanediol and the effect Mixture 3 which is an equivalent-weight mixture of Com was not weakened even after 48 hours. In addition, interms of pounds 2, 3 and 8, and 1-menthoxypropanediol as a compara the effect, the mixture appeared to be better like Test example tive compound was compounded with a base composition for 1. Meanwhile, after the washing treatment and 6 hours of air drying, almost no cooling action was observed from 1-men washing detergent at a concentration of 1%, and then a pure thoxypropanediol alone. cotton hand towel (white plain towel made in Japan, 20 cmx20 cm, degrease-finished) was hand-washed for three Example 20 minutes by using the detergent at pre-determined concentra Body shampoo tion (water 10 L, detergent 3 g, and water temperature 17°C.). 0111. A fragrance composition containing the sensory After rinsing with the same amount of water for 2 minutes, stimulation agent was produced from 35 parts by mass of the sensory stimulation agent composition containing the com water was removed from the towel by brief squeezing, and pound of the invention that were obtained from the above then the towel was air-dried for 6 hours inside the building. Synthetic examples and 65 parts by mass of a citrus-herbal The hand towel thus prepared and those after further air-dried mixed fragrance (manufactured by Takasago International Corporation), and eight kinds of body shampoos. A to H were for 24 hours or 48 hours were brought into contact with the prepared according to the following prescription by using the inside of upper parts of arms, and the cooling action thereof fragrance composition (addition amount is based on parts by was determined organoleptically. Results are shown in Table mass). The shampoos had excellent cool feeling and also were 2. excellent in lasting property. US 2011/008 1393 A1 Apr. 7, 2011 14

TABLE 3 Prescription for body shampoo Amount compounded Ingredients A. B C D E F G H

Triethanolamine 9.00 9.OO 9.00 9.OO 9.00 9.OO 9.00 9.OO Lauric acid 6.OO 6.OO 6.OO 6.OO 6.OO 6.OO 6.OO 6.OO Myristic aci 9.00 9.OO 9.00 9.OO 9.00 9.OO 9.00 9.OO Lauryl polyoxyethylene SulfoSuccinate 10.00 1O.OO 10.00 1O.OO 10.00 1O.OO 10.00 1O.OO disodium salt (1 E.O.) (42%) Alkyl (C8 to C16) glucoside 8.00 8.OO 8.00 8.OO 8.00 8.OO 8.00 8.OO Glyceryl laurate 1.00 1.OO 1.00 1.OO 1.00 1.OO 1.00 1.OO 2-Hydroxyethyl distearate 2.50 2.50 2.50 2.50 2.50 2.50 2.50 2.50 Coconut oil fatty acid diethanol amide 3.00 3.00 3.00 3.00 3.00 3.00 3.00 3.00 Propylene glycol S.OO S.OO S.OO S.OO S.OO S.OO S.OO S.OO Dibutylhydroxytoluene O.OS O.OS O.OS O.OS O.OS O.OS O.OS O.OS Edetic acid disodium salt O.10 O.10 O.10 O.10 O.10 O.10 O.10 O.10 Ethyl p-oxybenzoate O.20 O.2O O.20 O.2O O.20 O.2O O.20 O.2O Methyl p-oxybenzoate O.10 O.10 O.10 O.10 O.10 O.10 O.10 O.10 Fragrance composition containing 1.00 1.OO 1.00 1.OO 1.00 1.OO 1.00 1.OO the sensory stimulation agent comprising the following components Citrus-herbal mixed fragrance (0.65) (0.65) (0.65) (0.65) (0.65) (0.65) (0.65) (0.65) Compound 1 (0.25) Compound 2 (0.25) Compound 3 (0.25) Compound 4 (0.25) Compound 5 (0.25) Compound 6 (0.25) Compound 7 (0.25) Compound 8 (0.25) Mixture containing equal weight (0.10) (0.10) (0.10) (0.10) amount of Compounds 2, 3 and 8 Mixture containing equal weight (0.10) (0.10) (0.10) (0.10) amount of Compounds 1 to 4 Purified water (balance) Total 100.00 1OOOO 100.00 1OOOO 100.00 1OOOO 100.00 1OOOO

Example 21 Cooling Sensation Agent Composition 0112 Seven kinds of cooling sensation agent composi tions 1 to 7 were prepared according to the following pre Scription (addition amount is based on parts by mass) by mixing the compound of the invention that was obtained from the Synthetic examples above.

TABLE 4 Amount compounded Cooling Cooling Cooling Cooling Cooling Cooling Cooling sensation sensation sensation sensation sensation sensation sensation Ingredients composition 1 Composition 2 Composition 3 Composition 4 Composition 5 Composition 6 Composition 7

1-Isopulegol 15 7.5 7.5 7.5 7.5 7.5 1-Menthoxy- 35 17.5 17.5 17.5 17.5 17.5 propanediol 1-Menthol 30 2O 2O 2O 2O 19.995 p-Menthane- 2O 5 5 5 5 5 3,8-diol Vanillyl O.OOOS butyl ether Compound 1 10 10 2O 10 Compound 2 10 10 10 10 Compound 3 10 10 10 10 US 2011/008 1393 A1 Apr. 7, 2011 15

TABLE 4-continued Amount compounded Cooling Cooling Cooling Cooling Cooling Cooling Cooling sensation sensation sensation sensation sensation sensation sensation Ingredients composition 1 Composition 2 Composition 3 Composition 4 Composition 5 Composition 6 Composition 7 Compound 4 10 12.5 10 Compound 5 10 12.5 10 Compound 6 10 12.5 10 Compound 7 10 12.5 10 Compound 8 30 2O 2O 2O

Total 1OO 100 100 1OO 1OO 100 100

Example 22 by 1 g to a pure cotton hand towel (white plain towel made in Japan, 20 cmx20 cm, degrease-finished). Those which were Lotion with Cooling Sensation Effect air-dried for 3 hours or 8 hours were brought into contact with the inside of upper parts of arms, and the cooling action of the 0113. Seven kinds oflotions A to G with cooling sensation towel was determined organoleptically. Results are shown in effect were prepared according to the following prescription Table 5. The lotions prepared by using the cooling sensation (addition amount is based on parts by mass) by using the agent compositions 2 to 7 showed better lasting cooling sen seven cooling sensation agent compositions that were sation effect compared to the lotion prepared by using the obtained from Example 21. Each of the lotions was sprayed cooling sensation agent composition 1.

TABLE 5

Prescription oflotion with cooling sensation effect

Amount compounded

Ingredients C D E

95% ethanol 50 50 50 50 50 50 50 Coo ing sensation composition 1 O.S Coo ing sensation composition 2 O.S Coo ing sensation composition 3 O.S Coo ing sensation composition 4 O.S Coo ing sensation composition 5 O.S Coo ing sensation composition 6 O.S Coo ing sensation composition 7 O.S Purified water balance balance balance balance balance balance balance

Tota 1OO 100 100 1OO 100 1OO 100 Cooling sensation effect O O O O O A O (after 3 hours) Cooling sensation effect X A A O A A O (after 8 hours) O: Strong cooling sensation effect was recognized. A: Gentle cooling sensation effect was recognized, X: Almost no cooling sensation effect was recognized.

Example 23 Deodorant 0114 Six kinds of deodorant spray agents A to F with a cooling sensation effect were prepared according to the fol lowing prescription (addition amount is based on parts by mass) by using the cooling sensation agent compositions 2 to 7 that are obtained from Example 21. The deodorants pre pared by using the cooling sensation agent compositions 2 to 7 had an excellent lasting cooling sensation effect. US 2011/008 1393 A1 Apr. 7, 2011

TABLE 6 Prescription of deodorant Amounts compounded

Ingredients A. B C D E F Dipropylene glycol O.O2 O.O2 O.O2 O.O2 O.O2 O.O2 Phenoxy ethanol O.OS O.OS O.OS O.OS O.OS O.OS Anise aldehyde O.OOO3 O.OOO3 O.OOO3 O.OOO3 O.OOO3 O.OOO3 Linalool O.O1 O.O1 O.O1 O.O1 O.O1 O.O1 MuskT (manufactured by Takasago O.OO1 O.OOO1 O.OOO1 O.OOO1 O.OOO1 O.OOO1 International Corporation) Heliotropin O.OOO1 O.OOO1 O.OOO1 O.OOO1 O.OOO1 O.OOO1 Tesalon O.2 O.2 O.2 O.2 O.2 O.2 Green tea extract O.3 O.3 O.3 O.3 O.3 O.3 95% Ethanol 10 10 10 1O 10 10 Dipotassium hydrogen phosphate O.S O.S O.S O.S O.S O.S Cooling sensation composition 2 O.S Cooling sensation composition 3 O.S Cooling sensation composition 4 O.S Cooling sensation composition 5 O.S Cooling sensation composition 6 O.S Cooling sensation composition 7 O.S Purified water balance balance balance balance balance balance

Total 1OO 100 1OO 100 100

What is claimed is: 6. The cooling sensation agent composition according to 1. A cooling sensation agent composition which contains at claim 1, which further comprises at least one kind of cooling least one of diester compounds of dicarboxylic acid repre sensation Substances other than the compounds correspond sented by the formula (1): ing to the formula (1). 7. The cooling sensation agent composition according to claim 6, wherein the cooling sensation Substances other than (1) the compounds corresponding to the formula (1) are menthol, O O menthone, camphor, pulegol, isopulegol, cineole, mint oil, peppermint oil, spearmint oil, eucalyptus oil, 3-(1-menthoxy) propane-1,2-diol. N-alkyl-p-menthane-3-carboxamide, 1. 2-methyl-3-(1-menthoxy)propane-1,2-diol, p-menthane-3.8- diol. 2-(1-menthoxy)ethan-1-ol. 3-(1-menthoxy)propan-1-ol. wherein. A represents CH or CH=CH, in represents an inte 4-(1-menthoxy)butan-1-ol, menthyl 3-hydroxybutanoate, ger of 0 to 4 when A is CH, or 1 when A is CH=CH, B is an menthyl lactate, menthone glycerin ketal, N-methyl-2.2-iso alcohol residue having 10 to 18 carbon atoms and containing propylmethyl-3-methylbutane amide and menthyl glyoxy a para-menthane skeleton, which may have a Substituent, and late. 8. A sensory stimulation agent composition which contains C is an alcohol residue having 6 to 18 carbon atoms, which the cooling sensation agent composition according to claim 1. may have a Substituent. 9. The sensory stimulation agent composition according to 2. The cooling sensation agent composition according to claim8, which further comprises at least one kind of warming claim 1, wherein C in the formula (1) is an alcohol residue and pungent Substances. having a para-menthane skeleton, which may have a substitu 10. The sensory stimulation agent composition according ent. to claim 9, wherein the warming and pungent Substances are 3. The cooling sensation agent composition according to vanillyl ethyl ether, vanillyl propyl ether, vanillin propylene claim 2, wherein Band C in the formula (1) are not the same glycol acetal, ethylvanillin propylene glycol acetal, capsai residue. cin, gingerol, Vanillyl butyl ether, 4-(1-menthoxymethyl)-2- 4. The cooling sensation agent composition according to (3'-methoxy-4'-hydroxy-phenyl)-1,3-dioxolane, pepper oil, claim 1, wherein the alcohol residue for B or B and C in the pepper oleoresin, ginger oleoresin, nonylic acid Vanillyla formula (1) having a para-menthane skeleton, which may mide, jamboo oleoresin, Zanthoxylum Piperitum Peel have a substituent, is one selected from alcohol residues of Extract, Sanshool-I, Sanshool-II, Sanshoamide, black pepper 1-menthol, l-isopulegol, 3-(1-menthoxy)propane-1,2-diol. extract, chavicine, piperine and spilanthol. 2-(1-menthoxy)ethan-1-ol. 3-(1-menthoxy)propan-1-ol. 11. A flavor or fragrance composition, a beverage, a food 2-methyl-3-(1-menthoxy)propane-1,2-diol and para-men product, a perfume or cosmetic product, a toiletry product, thane-3,8-diol. daily utensil products or groceries, a fiber, a fiber product, 5. The cooling sensation agent composition according to clothes, clothing or a medicine, which comprises the cooling claim 1, wherein the diester compounds of dicarboxylic acid sensation agent composition according to claim 1. represented by the formula (1) have ClogP of 3.0 or more and 12. A flavor or fragrance composition, a beverage, a food the molecular weight of 250 to 600. product, a perfume or cosmetic product, a toiletry product, US 2011/008 1393 A1 Apr. 7, 2011 daily utensil products or groceries, a fiber, a fiber product, tion according to claim 1 with a beverage, a food product, a clothes, clothing or a medicine, which comprises the sensory perfume or cosmetic product, a toiletry product, daily utensil stimulation agent composition according to claim 7. products or groceries, a fiber, a fiber product, clothes, clothing 13. A method for providing a long-lasting cooling sensa or a medicine. tion effect which comprises applying directly any one of 22. A method for producing a flavor or fragrance compo products according to claim 11 onto a skin or a scalp, admin sition, a beverage, a food product, a perfume or cosmetic istering any one of them into an oral cavity, or applying any product, a toiletry product, daily utensil products or groceries, one of them to a fiber, a fiber product, clothes or clothing. a fiber, a fiber product, clothes, clothing or a medicine, which 14. A method for providing a long-lasting cooling sensa comprises compounding the sensory stimulation agent com tion effect which comprises applying directly any one of position according to claim 7 with a beverage, a food product, products according to claim 12 onto a skin or a scalp, admin a perfume or cosmetic product, a toiletry product, daily uten istering any one of them into an oral cavity, or applying any sil products or groceries, a fiber, a fiber product, clothes, one of them to a fiber, a fiber product, clothes or clothing. clothing or a medicine. 15. A flavor or fragrance composition according to claim 23. Diester compounds ofdicarboxylic acid represented by 11, wherein the content of the cooling sensation agent com the formula (1"): position is 0.0001 to 90% by mass. 16. A flavor or fragrance composition according to claim 12, wherein the content of the sensory stimulation agent (1") composition is 0.0001 to 90% by mass. 17. A beverage, a food product, a perfume or cosmetic product, a toiletry product, daily utensil products or groceries, ---, a fiber, a fiber product, clothes, clothing or a medicine accord ing to claim 11, wherein the content of the cooling sensation wherein. A represents CH2, n represents an integer of 0 to 4. agent composition is 1x107 to 20% by mass. B is an alcohol residue of an alcohol having 10 to 18 carbon 18. A beverage, a food product, a perfume or cosmetic atoms and containing a para-menthane skeleton, which may product, a toiletry product, daily utensil products or groceries, have a Substituent, and C is an alcohol residue of an alcohol a fiber, a fiber product, clothes, clothing or a medicine accord having 6 to 18 carbon atoms, which may have a Substituent, ing to claim 12, wherein the content of the sensory stimula however when B or C is an alcohol residue of menthol, tion agent composition is 1x107 to 20% by mass. another is not a residue of menthol. 19. A cool refreshment processing method of a fiber, a fiber 24. The diester compounds of dicarboxylic acid according product, clothes or clothing, which comprises compounding to 23, wherein C in the formula (1") is an alcohol residue of the cooling sensation agent composition according to claim 1 an alcohol having a para-menthane skeleton, which may have with a fiber, a fiber product, clothes or clothing or processing a Substituent. a fiber, a fiber product, clothes or clothing with the cooling 25. The diester compounds of dicarboxylic acid according sensation agent composition according to claim 1. to claim 23, wherein B and C in the formula (1") are not the 20. A cool refreshment processing method of a fiber, a fiber same residue. product, clothes or clothing, which comprises compounding 26. The diester compounds of dicarboxylic acid according the sensory stimulation agent composition according to claim to claim 23, wherein the alcohol residue for B or B and C 7 with a fiber, a fiber product, clothes or clothing, or process in the formula (1) having a para-menthane skeleton, which ing a fiber, a fiber product, clothes or clothing with the sensory may have a substituent, is any one selected from alcohol stimulation agent composition according to 7. residues of 1-menthol, l-isopulegol, 3-(1-menthoxy)propane 21. A method for producing a flavor or fragrance compo 1.2-diol. 2-(1-menthoxy)ethan-1-ol. 3-(1-menthoxy)propan sition, a beverage or a food product, a perfume or cosmetic 1-ol. 2-methyl-3-(1-menthoxy)propane-1,2-diol and product, a toiletry product, daily utensil products or groceries, para-menthane-3,8-diol. a fiber, a fiber product, clothes, clothing or a medicine, which comprises compounding a cooling sensation agent composi c c c c c