PERFUME BASE COMPOSITION

Abstract: The present invention relates to a perfume base composition comprising a carrier and a benzyl-substituted cyclohexanol having formula (1), wherein the dashed line denotes an optional double bond and the benzyl group is in the 2-, 3- or 4-position of the cyclohexanol ring, with the proviso that the benzyl group is in the 4-position when a double bond is present in the cyclohexanol ring. The composition has not only a well-balanced fragrance but also excellent retentivity of fragrance.

Description: DESCRIPTION PERFUME BASE COMPOSITION TECHNICAL FIELD The present invention relates to a perfume base composition which excellently retains its fragrance. Thiε composition can be used for the production of perfume and other products to be scented such as detergents, cosmetics and sprays. BACKGROUND ART A great number of perfume base materialε having a floral fragrance have heretofore been known. Among others, aldehyde type perfume bases are the moεt important perfume baεe materialε. However, εince aldehydes are not always stable in fragrant products having different pHs and product forms, these products often do not smell fresh and natural. Moreover, these products do not retain their fragrance for a very long time, which is disadvantageous. It is accordingly the object of the present invention to provide a perfume base composition which haε a floral fragrance and high stability and can impart excellent retentivity of fragrance to blending systems. DISCLOSURE OF THE INVENTION This object is achieved by the use of specific benzyl-εubstituted cyclohexanolε, which compounds can impart freshness to the perfume base compoεition and the products made therefrom. Due to the use of theεe benzyl- εubstituted cyclohexanolε the articles made from the perfume baεe compoεition additionally have a natural, soft and voluminous feeling. According to the present invention, there is thus provided a perfume base composition comprising a benzyl- εubεtituted cyclohexanol having the following formula (1) : wherein the dashed line denotes an optional double bond and the benzyl group is in the 2-, 3- or 4-position of the cyclohexanol ring, with the proviso that the benzyl group iε in the 4-poεition when a double bond iε present in the cyclohexanol ring. BEST MODE FOR CARRYING OUT THE INVENTION The benzyl-substituted cyclohexanols (1) are known compounds. For example, 2-benzylcyclohexanol is described in Tetrahedron, 4B / 2059 (1992) , Tetrahedron Lett., 3j5, 123 (1994) and J. Chem. Soc, 1809 (1956) ; 3-benzylcyclohexanol is described in J. Chem. Soc, 1809 (1956) ; and 4- . benzylcyclohexanol and 4-benzyl-2-cyclohexen-l-ol are described in Tetrahedron, 48_, 2059 (1992). These documents, however, do not discloεe the uεe of benzylcyclohexanolε as a fragrance. Moreover, the prior art does not suggest to use these compounds to retain the fragrance of perfume base compoεitionε and of the products made therefrom. Examples of the benzyl-substituted cyclohexanols (1) useful in the practice of the present invention include 2- benzylcyclohexanol, 3-benzylcyclohexanol, 4-benzylcyclo- hexanol and 4-benzyl-2-cyclohexen-l-ol. Of these, 2-benzyl- cyclohexanol, 3-benzylcyclohexanol and 4-benzylcyclohexanol are preferred with 3-benzylcyclohexanol being particularly preferred. Cis-trans isomerism exists in the benzyl-substituted cyclohexanols (1) according to the substitution state between the benzyl group and the hydroxyl group on the cyclohexane ring (or cyclohexene ring) . In the present invention both cis- and trans-benzylcyclohexanols and mixtures thereof may be used. Among these isomers, the cis-form is particularly preferred. The benzyl-substituted cyclohexanolε (1) can be prepared in accordance with the processes described in the above literature. For example, 2-benzylcyclohexanol (la) can be prepared by subjecting benzaldehyde (2) and cyclohexanone (3) to aldol condensation and hyάrogenating the resulting enone (4) (see the following reaction scheme] C2> (3) (4) (ia) 3 - B enzylcyclohexanol (lb) can be prepare d b y su b jecting a Grignard reagent (5) prepared from a b enzyl hali d e, and 2-cyclohexen-l-one (6) to 1,4-a d dition an d hy d rogenating the resulting ketone (7) (see the f ollowing reaction scheme) . C5) (6) (7) (lb) 4-Benzylcyclohexanol (lc) and 4-benzyl-2-cyclo h exen- l - ol (id) can be prepared by using an enamine (9) obtaine d b y the dehydration-condensation of 3-phenylpropionaldehyde (8) and morpholine to form 4-benzyl-2-cyclohexen-l-ol (io ) b y Robinson annellation and selectively hydrogenating only the carbonyl of the compound (10) to form 4-benzyl-2-cyclohexen- l-ol (ld) or hydrogenating both olefin and carbonyl o f the compound (10) to form 4-benzylcyclohexanol (lc) (see the following reaction scheme) . 1 d) (1 c) Since most of the benzyl-substituted cyclohexanols (1) obtained in such a manner are mixtures of cis- and trans¬ forms, their isomers have to be separated from each other by column chromatography, recrystallization from a hydrocarbon solvent, superfractionation and/or the like if necessary. The benzyl-substituted cyclohexanols (1) may be used as a deodorant component either singly or in combination with a carrier. Any carrier may be used without any limitation so far as it does not impair the fragrance of the benzyl-substituted cyclohexanols (1) . Examples thereof include gaseous, liquid and solid carriers, which may contain other perfume compounds. The examples of the preferable gaseou carriers include a gas for .propelland agents. The preferable liquid carriers include water, various organic solvents, and volatile oily substances. The preferable solid carriers includ solid oily substances such as various waxes, and polymers. The amount of the benzyl-substituted cyclohexanol (1 ) to be incorpor in tiie perfume base composition according to the present invent varies according to the kind of the formulated oerfume ba=.e use in combination, the kind and inteRit of the intended fragrance and the like, and no particular limitation is imposed on the amount. However, it is generally preferable to use it in a proportion of 0.1-90 wt.%, particularly preferably 0.5-70 wt.% based on the perfume base composition. In addition to the benzyl-substituted cyclohexanol (l) and the carrier, optional components routinely incorporated in perfume base compositions may be incorporated into the perfume base composition according to the present invention within limits not impeding the effect of the present invention. The perfume base composition according to the present invention can be obtained by mixing and stirring the benzyl- εubεtituted cyclohexanol (1) , carrier and optional components in accordance with a method known per se in the art. The perfume baεe compoεition according to the preεent invention may be suitably applied to products required to be scented, such as perfumes, detergents, cosmetics, various sprays and fragrances, in particular, toiletry productε such as soap, shampoos and rinses. The perfume base composition according to the preεent invention has a well-balanced fragrance and is also excellent in retentivity of fragrance. EXAMPLES The preεent invention will hereinafter be deεcribed in more detail by the following examples. Preparation Example 1: A l→liter four-necked flask equipped with a Dean-Stark trap and a thermometer was charged with 71 g of morpholine and 400 ml of toluene, and 100 g of 3-phenylpropionaldehyde were added dropwise thereto while chilling with ice water, followed by azeotropic dehydration for 1 hour. After cooling the reaction mixture, exceεε morpholine waε diεtilled off with toluene. The reεidue waε dissolved in 400 ml of toluene. In a 1-liter four-necked flask equipped with a thermometer and a condenser, 70 g of methyl vinyl ketone were added dropwiεe under reflux to the solution over 1 hour. After aging under reflux for 1 hour, the reaction mixture was cooled, and 10% sulfuric acid was added dropwise to the reaction mixture until the pH of the reaction mixture reached 3. The thus-acidified reaction mixture was then stirred at room temperature for 1.5 hours. After separating the resulting lower water layer, the residual organic layer was neutralized, washed with water, dried and concentrated, thereby obtaining 137 g of a crude product. Dissolved in 500 ml of methanol were 137 g of the crude product, and 4 ml of 4.5 mol/liter aqueous KOH were added dropwise to the solution at room temperature, followed by stirring for 3 hours at the same temperature. After neutralizing the resultant mixture with acetic acid, methanol was distilled off. After the residue was charged into a 1-liter four- necked flask equipped with a Dean-Stark trap and a thermometer to dissolve it in 500 ml of toluene, 2 g of p- toluenesulfonic acid were added to the solution, followed by azeotropic dehydration for 3 hours. After cooling, the residue was neutralized and washed with water, and the resultant organic layer was dried and concentrated, thereby obtaining 119 g of a crude product. Thiε product waε purified by column chromatography to obtain 41 g (yield: 30%) of 4-benzyl-2-cyclohexen-l-one. To a suspension of 3.2 g of lithium aluminum hydride in 500 ml of ether, 30 g of 4-benzyl-2-cyclohexen-l-one were added dropwise at O'C. After stirring the mixture for 2 hours at the same temperature, it was washed with diluted hydrochloric acid and water, and the resultant organic layer was dried and concentrated, thereby obtaining 31 g of a crude product. This product was purified by column chromatography to obtain 30 g (yield: 98%) of 4-benzyl-2- cyclohexen-l-ol. A ratio of a cis-form to a trans-form was found to be 32:68 by 1 H-NMR. 4-Benzyl-2-cyclohexen-l-ol : -H-NMR δ : 1.17-2.77 (8H,m) , 4.10-4.30 (lH,m) , 5.1-5.35 (2H,m) 7.1-7.35(5H,m) . Besideε, 30 g of the above-obtained 4-benzyl-2- cyclohexen-1-one were hydrogenated at room temperature for 6 hours using 5 g of Raney nickel in methanol under hydrogen pressure (3 kg/cm 2 ) until the absorption of hydrogen was stopped. After an organic layer was collected by decantation and concentrated, the residue waε purified by column chromatography, thereby obtaining 13 g of ciε-4- benzylcyclo-hexanol and 14 g of trans-4-benzylcyclohexanol (yield: 90% in total) . Cis-4-benzylcyclohexanol : -•-H-NMR δ: 1.30-1.80(10H,m) , 2.54 (2H, d, J=6.97Hz ) , 3.90-4.01(lH,br) , 7.08-7.32 (5H, m) . Trans-4-benzylcyclohexanol : 1 H-NMR «: 0.87-1.30(4H,m) , 1.35-1.62 (lH,m) , 1.63-1.85 (2H,m) , 1.85-2.03 (3H,m) , 2.47 (2H, d, J=7. IHz) , 3.42-3.62(lH,m) , 7.08-7.35(5H,m) . Preparation Example 2 : A 500-ml four-necked flaεk equipped with a thermometer and a condenser was charged with 2.4 g of a piece of magnesium and 120 ml of absolute ether, to which a part of 17 g of benzyl bromide waε added with heating. After a reaction εtarted, the remaining amount of benzyl bromide waε added dropwise to such a degree that reflux continued. After completion of the drop addition, the resultant mixture was εtirred further for 1 hour at room temperature to obtain a liquid reaction mixture. A 500-ml four-necked flask equipped with a thermometer was charged with a suεpenεion of 1 g of copper iodide in 60 ml of absolute ether, to which the liquid reaction mixture waε added dropwise at -5°C. After stirring the resultant mixture for 1 hour at the same temperature, it was cooled to -20°C. A solution of 8.6 g of 2-cyclohexen-l-one in 10 ml of absolute ether was added dropwise to the mixture, and the temperature of the resulting liquid reaction mixture was then raised to room temperature while stirring for 24 hours. The liquid reaction mixture was washed with water, dried, filtered and concentrated, and 21 g of the resulting crude product were purified by column chromatography, thereby obtaining 9.6 g (yield: 57%) of 3-benzylcyclohexenone. Then, 9.6 g of 3-benzylcyclohexenone were hydrogenated at room temperature using 1 g of Raney nickel in methanol under hydrogen pressure (3 kg/cm 2 ) until the absorption of hydrogen was stopped. After an organic layer was collected by decantation and concentrated, the reεidue waε purified by column chromatography, thereby obtaining 4.5 g of ciε-3- benzylcyclohexanol and 4.5 g of trans-3-benzylcyclohexanol (yield: 92% in total) . Cis-3-benzylcyclohexanol: ^-H-NMR δ : 0.9-1.15(lH,m) , 1.17-1.82 (8H,m) , 1.87-2.15 (lH,m) , 2.55(2H,d), 7.1-7.4(lH,m) , 7.12-7.35 (5H,m) . Trans-3-benzylcyclohexanol: ' - ■■ H-NMR δ : 0.75-1.35(4H,m) , 1.45-1.85 (4H,m) , 1.85-2.03 (2H,m) , 2.24-2.62(2H,m) , 3.42-3.62 (lH,m) , 7.08-7.35(5H,m) . Preparation Example 3: A 500-ml four-necked flask equipped with a thermometer was charged with 53 g of benzaldehyde, 25 ml of water and 1 g of sodium hydroxide, to which 68 g of cyclohexanone were added dropwise at 30°C over 30 minutes. The resultant mixture was stirred for 1 hour at the same temperature. After neutralizing the reaction mixture to separate liquid layers from each other, the resultant reaction product was dissolved in 500 ml of toluene. To the solution, 0.5 g of PTS (p-toluenesulfonic acid) was added to conduct azeotropic dehydration for 3 hours in a 1-liter four-necked flaεk equipped with a Dean-Stark trap and a thermometer. After cooling, the residue was neutralized and washed with water, and the reεultant organic layer was dried and concentrated, thereby obtaining 119 g of a crude product. This product was purified by column chromatography to obtain 24 g (yield: 28%) of 2-benzylidenecyclohexanone. Then, 10 g of 2-benzylidenecyclohexanone were hydrogenated at room temperature using 1 g of Raney nickel in methanol under hydrogen pressure (3 kg/cm 2 ) until the absorption of hydrogen was stopped. After an organic layer was collected by decantation and concentrated, the residue was purified by column chromatography, thereby obtaining 4.6 g of cis-2-benzylcyclohexanol and 4.4 g of trans-2-benzyl- cyclohexanol (yield: 88% in total) . Cis-2-benzylcyclohexanol: 1 H-NMR i: l.l-1.35(lH,m) , 1.35-1.85 (9H,m) , 2.53 (lH,dd,J=7.1 , 13.4Hz) , 2.70(lH,dd,J=9.2,13.3Hz) , 3.75-3.82 (IH,bs) , 7.12-7.35(5H,m) . Trans-2-benzylcyclohexanol : 1 H-NMR δ: 0.8-1.85(9H,m) , 1.91-2.08 ( lH,m) , 2.34(lH,dd, J=9.2, 13.3Hz) , 3.17(lH,dd,J=4.0,13.3Hz) , 3.28-3.4 ( lH,m) , 7.12-7.35(5H,m) . The fragrance of the benzyl-substituted cyclohexanols (1) obtained in the above-described preparation examples are shown in Table 1. 4-benzyl-2-cyclohexen-l-ol, 2-benzyl-cyclohexanol , 3- benzylcyclohexanol and 4-benzylcyclohexanol will ■hereinafter be referred to as "ld", "la", "lb" and "lc", respectively. Nu eralε in ( : ) following each of the symbols indicate the porportionε of the cis-form and the trans-form. For example, lc (0:100) means that the ratio of the ciε-form to the tranε-form in 4-benzylcyclohexanol iε 0:100. Table 1 Compound Odor ld (32:68) Floral-Green-Muguet Roεe-Geraniu lc (100:0) Floral-Roεe-Geranium lc (0:100) Floral-Green-Sweet lb (100:0) Floral-Grapefruit- oody-Vetiver lb (0:100) Floral-Grapefruit-Vetiver la (100:0) Floral-Grapefruit la (0:100) Floral-Grapefruit Example 1: lc (100:0) or the like were added to a roεe base having a composition shown in Table 2 and the effect brought about by the addition was evaluated in accordance with an organoleptic teεt by 5 expert panelistε. Organoleptic evaluation εtandard: 1: The effect of the addition waε recognized to a very deεirable extent; 2: The effect of the addition waε recognized to a desirable extent; 3: The effect of the addition was scarcely recognized; 4: No effect of the addition was recognized, and the balance of fragrance was poor. Table 2 Invention Comparative Comparative product 1 product 1 product 2 Rose base: Geraniol 400 400 400 Phenylethyl alcohol 80 80 80 Geranyl acetate 80 80 80 Geranium oil 50 50 50 Rhodinol 50 50 50 α-Ionone 50 50 50 Diphenyl oxide 40 40 40 Linalol 30 30 30 lc (100:0) 220 - - £-Citronellol - 220 - Dipropylene glycol - - 220 Total (parts by weight) 1000 1000 1000 Organoleptic evaluation 1 2 4 The invention product 1 had a voluminous, well- balanced, rose-like fragrance. The comparative product 1 had a rose-like fragrance, but was lacking in a voluminous feeling. The comparative product 2 had an ill-balanced fragrance not aεsociated with roses. Example 2: A composition having a gorgeous, soft, voluminous, lily of the valley-like fragrance was obtained in accordance with the following formulation. (Components) (parts by weight) Phenylethyl alcohol 250 Hydroxycitronellal 250 Bergamot oil 100 Jasmine oil 100 Heliotropin 100 Linalyl benzoate 50 Phenylethyl acetate 10 Cinnamic alcohol 10 lc (100:0) 130 Total 1000 Example 3: A floral perfume base for soap, which had a soft, sweet fragrance, was obtained in accordance with the following formulation. In particular, voluminous sweetness waε recognized during itε uεe. (Components) (parts by weight) Bois de Rose oil 250 Terpineol 150 Lavender oil 100 Cederwood oil 100 Citronella oil 150 Eugenol 50 Linalyl acetate 50 Diphenyl oxide 30 Pearlide BB (product of Kao Corporation) 70 Styrax resinoid 20 lc (0:100) 80 Total 1000 Example 4 : Added to a grapefruit base having a composition shown in Table 3 were la (50:50) or lb (50:50), thereby obtaining grapefruit type perfume base compositions. These compositions were organoleptically evaluated. Table 3 Invention Invention product 2 product 3 Grapefruit base: Orange oil 718 718 Orange terpenelesε oil 20 20 Fruitate* 1 20 20 ' Pollenal II* 2 20 20 Linalol 10 10 Ethyl octanoate 10 10 2-Methyl-4-propyl-l, 3-oxathiane 2 2 la (50:50) 200 - lb (50:50) - 200 Total (partε by weight) 1000 1000 *1: Kao's specialty chemical; ethyl-bicyclo[5.2.1.0 2 ' 6 ]- decane-2-carboxylate. *2: Kao's εpecialty chemical; 2-cyclohexylpropanal. As a result, the invention product 2 was found to have a grapefruit type natural fragrance with better softneεε. On the other hand, the invention product 3 waε found to have a grapefruit type, natural, fresh, voluminous, and long-lasting fragrance. Of these, the formulated fragrance of the invention product 3, in which lb (50:50) had been incorporated, was very excellent from the viewpoint of freshness. Example 5: la (50:50) or lb (50:50) were added to a citron base having the composition shown in Table 4 to obtain citron type perfume base compositions. These compositions were organoleptically evaluated. Table 4 Invention Invention product 4 product 5 Citron base: Orange oil 298 298 Mandarin oil 150 150 7-Terpinene 100 100 Linalol 200 200 Dihydromyrcenol 50 50 Dimethyloctenone 50 50 Dihydrojasmonate 50 50 2-Methyl-4-propyl-l, 3-oxathiane 2 2 la (50:50) 100 - lb (50:50) - 100 Total (parts by weight) 1000 1000 As a result, the invention product 4 was found to be a citron type natural perfume base composition having better softness. On the other hand, the invention product 5 was found to be a natural, fresh citron type perfume base composition feeling like the rind of a citron. Of these, the formulated fragrance of the invention product 5, in which lb (50:50) had been incorporated, was very excellent from the viewpoint of freshnesε.

Claims: CLAIMS 1. A perfume base composition comprising a carrier and a benzyl-substituted cyclohexanol having the following formula (1) : wherein the dashed line denotes an optional double bond and the benzyl group is in the 2-, 3- or 4-position of the cyclohexanol ring, with the proviso that the benzyl group is in the 4-position when a double bond iε preεent in the cyclohexanol ring. 2. The perfume base composition according to Claim 1, wherein the benzyl-substituted cyclohexanol is a cis- or trans-benzylcyclohexanol or a mixture thereof. 3. The perfume base composition according to Claim 1 or 2, wherein the benzyl-substituted cyclohexanol is a cis- benzylcyclohexanol. 4. The perfume baεe compoεition according to Claim 3, wherein the benzyl-substituted cyclohexanol is 2- benzylcyclohexanol, 3-benzylcyclohexanol or 4-benzyl-2- cyclohexen-1-ol. 5. The perfume baεe composition according to Claim 3, wherein the benzyi-sustituted cyclohexanol is 3- benzylcyclohexanol. 6. The perfume base composition according to any one of Claim, 1, wherein the content of the benz / 1- εubεtituted cyclohexanol is 0.1-90 wt.% based on the perfume base composition. 7. Use of a benzyl-substituted cyclohexanol having the following formula (1): wherein the dashed line denotes an optional double bond and the benzyl group is in the 2-, 3- or 4-position of the cyclohexanol ring, with the proviso that the benzyl group is in the 4-poεition when a double bond iε preεent in the cyclohexanol ring as a fragrance. 8. The use according to Claim 7 for the production of toiletry, perfumes, detergentε, cosmetics and sprays.

Inventors: FUKUDA KAZUYUKI, KOHAMA MAKOTO, KOSHINO JUNJI, TOI NAO, FUKUDA, KAZUYUKI, KOHAMA, MAKOTO, KOSHINO, JUNJI, TOI, NAO
Applicants: FUKUDA KAZUYUKI, KAO CORP, KOHAMA MAKOTO, KOSHINO JUNJI, TOI NAO, FUKUDA, KAZUYUKI, KAO CORPORATION, KOHAMA, MAKOTO, KOSHINO, JUNJI, TOI, NAO
Application year: 1996
Main classification: C11D3
IPC codes: A61K8, A61Q13, C11B9, C11D3