Classifications

• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
  • C11D3/50—Perfumes
• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
  • A61K8/00—Cosmetics or similar toiletry preparations
  • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
  • A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
  • A61K8/33—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing oxygen
  • A61K8/34—Alcohols
• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
  • A61Q13/00—Formulations or additives for perfume preparations
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11B—PRODUCING, e.g. BY PRESSING RAW MATERIALS OR BY EXTRACTION FROM WASTE MATERIALS, REFINING OR PRESERVING FATS, FATTY SUBSTANCES, e.g. LANOLIN, FATTY OILS OR WAXES; ESSENTIAL OILS; PERFUMES
  • C11B9/00—Essential oils; Perfumes
  • C11B9/0042—Essential oils; Perfumes compounds containing condensed hydrocarbon rings
  • C11B9/0046—Essential oils; Perfumes compounds containing condensed hydrocarbon rings containing only two condensed rings
  • C11B9/0049—Essential oils; Perfumes compounds containing condensed hydrocarbon rings containing only two condensed rings the condensed rings sharing two common C atoms
  • C11B9/0053—Essential oils; Perfumes compounds containing condensed hydrocarbon rings containing only two condensed rings the condensed rings sharing two common C atoms both rings being six-membered
• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11B—PRODUCING, e.g. BY PRESSING RAW MATERIALS OR BY EXTRACTION FROM WASTE MATERIALS, REFINING OR PRESERVING FATS, FATTY SUBSTANCES, e.g. LANOLIN, FATTY OILS OR WAXES; ESSENTIAL OILS; PERFUMES
  • C11B9/00—Essential oils; Perfumes
  • C11B9/0069—Heterocyclic compounds
  • C11B9/0073—Heterocyclic compounds containing only O or S as heteroatoms
  • C11B9/0076—Heterocyclic compounds containing only O or S as heteroatoms the hetero rings containing less than six atoms
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
  • C07B2200/00—Indexing scheme relating to specific properties of organic compounds
  • C07B2200/07—Optical isomers
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C2602/00—Systems containing two condensed rings
  • C07C2602/02—Systems containing two condensed rings the rings having only two atoms in common
  • C07C2602/14—All rings being cycloaliphatic
  • C07C2602/26—All rings being cycloaliphatic the ring system containing ten carbon atoms
  • C07C2602/28—Hydrogenated naphthalenes

Definitions

• the present invention relates to a fragrance composition containing decalin alcohol having a specific structure.
• Woody and amber-like scented fragrances with a polycyclic structure give a scent reminiscent of natural wood and amber grease, and in addition, a variety of objects such as skin, hair and clothing. It is known that it can effectively remain in the market, and has both the taste and functionality.
• Typical examples include acetyl sedrene, isolongifolanone, cedolyl methyl ether, etc., all of which use natural timber as a raw material, and excessive logging has caused various environmental problems such as flooding. There is a growing demand for synthetic fragrances that do not use wood as a raw material.
• 1,2,3,4,4 &, 5,6,7-octahydro-2,5,5-trimethinole has an otatalin skeleton and hydroxyl group similar to the decalin skeleton and is used as a fragrance.
• 2-Naphtalenore has a strong odor and can be effective with a small amount of formulation, but it has the disadvantage that it has an animal-like impression and lacks versatility.
• 7-Terametinolenaphthalene has a harsh and dry odor, but it is difficult to exert its characteristics in perfumes and other perfumes that require high-class feeling and discrimination. There are some drawbacks.
• C. R. Enzell obtains a mixture containing 8-drimanol by bioconversion of (Z) -abienol, but there is no description as a fragrance (Non-patent Document 3).
• Non-Patent Document 1 Croatica Chemica Acta, 58 (4) p.491 (1985)
• Non-Patent Document 2 Acta Chemica Scandinavica B 28 No.3 p.289 (1974)
• Non-Patent Document 3 Acta Chemica Scandinavica 49 p.375 (1995)
• the present invention relates to 0.0005 to 10% by mass of 8-drimanol represented by the formula (la) (component (a)), and ⁇ - ⁇ cetinole 1,2,3,4,5,6,7, 8 -year-old Kutahydro 1,1,6,7 -tetramethinolenaphthalene, l, 2,3,4,4a, 5,6,7 -octahydro-2,5,5-trimethyl-2-naphthalenol, l, 2 , 3,4,4a, 7,8,8a-octahydro-2,4a, 5,8a-tetramethyl-1-naphthylformate, 3a-ethyliddecahydro-6,6,9a-trimethylnaphtho [2 , 1-b] furan and racemic or optically active dodecahydro-3a, 6,6,9a-tetramethyl Naphtho [2, 1-b]
• Franca A fragrance composition containing 90 to 99.9995% by mass of one
• the present invention provides cosmetics, household products, and environmental hygiene products containing a fragrant composition.
• the present invention provides a method for improving the fragrance of a fragrance composition by adding the component (a) to the fragrance composition containing the component (b).
• the present invention further provides a process for producing decalin alcohol (1) by subjecting hemiacetal (2) or aldehyde (3) to a decarbolization reaction.
• the present invention relates to a highly versatile fragrance composition capable of producing a natural Ambergris fragrance and exhibiting an effect of enhancing warmth and texture in a small amount.
• the inventors of the present invention have not yet found use as a fragrance, but the 8-drimanol force represented by the formula (la) itself has a weak woody-amber-like scent. It was found that it has a characteristic of emitting a strong amber scent when heated.
• the present inventors combined 8-dolmanol with a specific polycyclic woody-amber fragrance to enhance the odor and softness and warmth that natural Ambergris has. It has been found that a high effect of improving quality can be exhibited.
• a fragrance composition containing 8-drimanol and a specific woody-amber fragrance compound is used in cosmetic products such as household products, the amber remaining fragrance that is comfortable on the skin and hair after use is obtained. It was found that it has the characteristics to be given.
• the 8-drimanol of the component (a) contained in the fragrance composition of the present invention has a power that only has a weak woody-amber-like scent at room temperature, and the odor intensity suddenly increases by heating, which is comfortable. It is a compound that develops an amber-like odor.
• the (a) component is combined with a fragrance having a specific woody-amber fragrance (component (b)) to enhance the amber feeling and to provide an effect of imparting and promoting a high volume and texture.
• a fragrance composition having the softness and warmth of natural Ambergris can be obtained.
• the aroma of the fragrance composition can be improved by adding the component (a) to the fragrance composition containing the fragrance compound [component (b)] having a specific woody-amber fragrance. .
• Non-patent Document 2 As a method for producing 8-drimanol (la), a method using the above-mentioned dorim-7-en-11-ol as a raw material (Non-patent Document 2) is known, but it is difficult to obtain a compound. Six steps are required to use as a starting material. Therefore, it is preferable to produce the decalin alcohol (1) by the decarbolation reaction of hemiacetal (2) or aldehyde (3) represented by the following reaction formula. According to this method, decalin alcohol (1) can be produced efficiently in a short time.
• Production of decalin alcohol (1) by decarbolation of hemiacetal (2) or aldehyde (3) according to the present invention can be carried out by reacting with a transition metal complex. wear. Either hemiacetal (2) or aldehyde (3) may be used, or a mixture of both may be used.
• the transition metal complex is preferably a rhodium complex, a ruthenium complex, or an iron complex, and particularly preferably a mouthful complex.
• halotris triphenylphosphine
• carbocarbbis triphenylphosphine
• I carbocarbbis
• chlorotris triphenylphosphine
• PPh ruthenium complex
• black carborubbis triphenylphosphine
• the amount of the transition metal complex is preferably 1 to 20 mol, particularly preferably 1 to 2 mol, per 1 mol of the total amount of hemiacetal (2) and aldehyde (3). ! /
• bidentate phosphine ligands include 1,2-bis (diphenylphosphino) ethane, 1,3-bis (diphenylphosphino) propane, 1,4-bis (diphenylphosphino) butane, and the like. 1,3-bis (diphenylphosphino) propane is particularly useful.
• the amount of addition is preferably 1 to 50 mol, particularly 1 to 4 mol, per 1 mol of the rhodium complex.
• the rhodium complex amount is 0.00001 to 1 mol, especially 0.001 to 0.05 mol from the viewpoint of economy and productivity, with respect to 1 mol of the total amount of hemiacetal (2) and aldehyde (3). is there.
• the rhodium complex and the bidentate phosphine ligand may be intermittently calcined as the reaction proceeds.
• the rhodium complex and the bidentate phosphine ligand can be added separately V, or the rhodium complex can be coordinated with the ligand!
• the reaction solvent is preferably a halogen-based or aromatic solvent, such as dichloromethane, benzene, toluene, xylene, or the like.
• xylene is particularly useful because it allows reaction at high temperatures.
• the amount of solvent is preferably 1 to 100 mL with respect to the total amount lg of hemiacetal (2) and aldehyde (3), and about 1 to 10 mL from the viewpoint of productivity.
• the atmosphere when the transition metal complex is allowed to act on the hemiacetal (2) or the aldehyde (3) it is preferable to use an inert gas such as nitrogen gas or argon gas.
• the reaction temperature is Usually, 20 to 120 ° C is preferable as long as it is not extremely high.
• the reaction temperature is the boiling point of the solvent. It is desirable to be in the vicinity.
• the end point of this reaction can be the time when hemiacetal (2) and aldehyde (3) disappear by gas chromatography, thin layer liquid chromatography, etc., and the reaction time is usually 1-24. It's time.
• the hemiacetal (2) and aldehyde (3) used in the reaction can be produced by reducing the sclareolides (4).
• the reducing agent metal hydrides are preferred, and alumino and idride are particularly preferred.
• the amount of the reducing agent is preferably from 0.1 to 5 mol, particularly preferably from 0.5 to 2 mol, per 1 mol of sclareolides (4).
• a solvent having a low freezing point is preferable.
• dichloromethane, hexane, toluene and the like are preferable.
• An anhydrous solvent is particularly preferable.
• the atmosphere when the reducing agent is allowed to act on the sclareolides (4) is preferably a water-free condition under an inert gas atmosphere such as nitrogen gas or argon gas.
• the reaction temperature is preferably a low temperature, particularly 78 ° C to 140 ° C.
• the end point of this reaction can be the time when the sclareolide (4) disappears by gas chromatography, thin layer liquid chromatography or the like, and the reaction time is usually 30 minutes to 2 hours.
• the sclareolide (4) is an extract of natural clarisage.
• (+)-sclareolide (4a) obtained by acidifying (-)-sclareol is used
• 8-drimanol (la) is obtained as decalin alcohol (1).
• this 8-drimanol (la) has not been known for its use as a fragrance, it is a weak amber fragrance at room temperature, but it is characterized by a strong and remarkable amber fragrance when heated from body temperature to 50 ° C. .
• homophalnesyl acid isotonicity was also obtained by a known method using a mixture as sclareolides (4) (Japanese Patent Publication No. Hei 8-506 103).-From sclareolide (4ab), 8 -A mixture containing drimanol (la) can be produced at a lower cost.
• the component (b) is a fragrance compound having a decalin or otatalin skeleton or a decahydronaphtholane skeleton similar to the component (a), and the component (b)
• the effect of enhancing the texture of the odor of woody-amber can be achieved without detracting from the characteristics of.
• the fragrance composition of the present invention contains (a) component 0.0005 to 10% by mass and (b) component 90 to 99.9995% by mass.
• Preferred content is (a) component 0.001-10 mass% and (b) component 90-99.999 mass%, more preferred content is (a) component 0.005-10 mass% and (b) component 90-99.995 mass%, More preferable contents are (a) component 0.01 to 10% by mass and (b) component 90 to 99.99% by mass.
• the fragrance composition containing the component (a) and the component (b) of the present invention includes at least one of the following: It can be used in combination with a perfume material.
• Hydrocarbons such as limonene, ⁇ -pinene, j8-pinene, tenolepinene, cedrene, longifolene, and norencens.
• Phenols such as eugenol, thymol and vanillin.
• Acetals such as acetaldehyde ethylpropylpropylacetal, citral jetylacetal, phenolacetylglycerol glycerol acetal, ethyl acetate acetate ethylene glycol ketal, etc. Ketals.
• Ethers such as vanetol, j8-naphthylmethyl ether, j8-naphthylethyl ether, limonene oxide, rose oxide, 1,8-cineole; and-such as geranyl nitrile and citronellyl-tolyl Toryls.
• the perfume composition of the present invention can be formulated or applied to various forms of aromatic products.
• Examples of the application field include cosmetics, household products, and environmental hygiene products.
• Cosmetics is a product for making a person's appearance clean or beautiful. Specifically, sarcophagus, body cleaning agents, hair cleaning agents, hair cosmetics, cosmetics (for example, Skin cosmetics
• Finishing cosmetics perfumes, colons, antiperspirants, deodorants, bath preparations and the like.
• a "household product” is a product for maintaining the function or cleanliness of various articles such as dwellings and household products necessary for home life. Specifically, it is a detergent for clothing and for clothing. Examples include softeners, garment pastes, residential detergents, bath detergents, dish detergents, bleaches, mold removers, and floor coverings.
• Environmental hygiene product is a product for adjusting the environment to a predetermined state or atmosphere, and in particular, as a product capable of adjusting the fragrance drifting in the environment by applying a perfume composition, Physically, a fragrance, a deodorant, a musk, an incense stick, a candle, etc. are mentioned.
• the component (a) exhibits a pleasant amber-like odor due to a sudden increase in odor intensity due to heating above body temperature, which is a weak woody amber-like scent at room temperature. Therefore, the fragrance composition of the present invention has a product form that is applied directly to the skin and hair, such as perfume colon, skin care products and cosmetics, hair care products for beautifying and styling hair, etc. Product forms involved, for example, bathing agents used in the heated state, hair care products such as shampoos and conditioners heated in the hair dryer after use, clothing finishes and softeners heated in the dryer or iron after use This product is highly olfactory and effective.
• the (a) component has a scent persistence behavior similar to that of the (b) component, the natural ambergris can be combined with the (b) component without changing the scent. High incense tone and texture can be maintained. Therefore, it is possible to maintain a soft and soft smell on the skin and hair by direct application. Also, household detergents such as laundry detergents and clothing softeners In products, it is possible to leave a fragrance on clothes effectively during washing and processing. It is also easy to harmonize with fragrances used in environmental sanitary products such as fragrances, deodorants, incense sticks, and candles.
• fragrance composition of the present invention There are various methods of using the product to which the fragrance composition of the present invention is applied. For example, a method of generating odor by actively applying to a predetermined site such as perfume and cosmetics, and a cleaning agent. Soot! / How to leave odors in the application site after burning, how to make odors drift by volatilizing in the space like a fragrance, how to smell like incense and candles, There are ways to make it drift.
• component (a) 0.005% by mass of component (a) is added to component (b), and a fragrance composition containing 20% by mass of this is added to 0.5% by mass of hair cleanser.
• a fragrance composition containing 20% by mass of this is added to 0.5% by mass of hair cleanser.
• Room temperature Has a weak woody odor.
• Fragrance compositions A, B, C and D were prepared at a mass ratio shown in Table 1, and dissolved in a commercial liquid paraffin so as to have a concentration of 1% by mass.
• a fragrance composition prepared under the same conditions and not containing component (a) Using the liquid paraffin solution of substance E as a reference, the odor was compared and evaluated by the consensus of four expert panelists. As a result, as shown below, a high effect of component (a) was recognized.
• Fragrance composition A Warmth was added with amber feeling.
• Fragrance composition B Amber feeling and warmth were strengthened, and an effect of bringing volume and cleanliness was recognized.
• Fragrance composition C Amber warmth and volume power were further strengthened. Fragrance composition D: Cosmetics with strong warmth and softness.
• Ambroxan (trade name of Kao Co., Ltd.) derived from natural raw material sclareol is reused in ethanol
• Fragrance compositions F and G were prepared, and the odor was compared and evaluated in the same manner as in Example 1 using the fragrance H as a reference by the consultation of four professional panelists. As a result, as shown below, a high effect of component (a) was recognized.
• Fragrance composition F Woody and fruity fragrance of the racemic body was modulated, and the effect of increasing the amber warmth was recognized.
• Fragrance composition G Amber warmth and volume power were further strengthened.
• component (a) By adding 0.001 parts by mass of component (a) to 99.999 parts by mass of the fragrance composition having the composition shown in Table 3, an amber-type scent having characteristics of sweetness and natural Ambergris was obtained.
• Perfume composition for perfume having the composition shown in Table 4 of Example 8 was added to 99.5 parts by mass of Perfume Composition E of Comparative Example 1 (Table 1). There was a warm scent of smell V.
• Fragrance composition for detergents for clothes that gives a sweet and soft scent by adding 5.5 parts by mass of the woody-amber fragrance composition I shown in Table 6 to 94.5 parts by mass of the fragrance composition having the composition shown in Table 5.
• Ambroxan (trade name of Kao Corporation) derived from natural raw material sclareol to ethanol
• Ambroxan (trade name of Kao Corporation) derived from natural raw material sclareol to ethanol
• Example 10 Detergent composition for clothing
• Example 9 Spray 9 parts by mass of the detergent composition for detergents obtained in Example 9 (Table 5 + Table 6) 0.49 parts by mass into 99.6 parts by mass of the powder detergent composition having the composition described in Table 8 , and weigh 20 g of this. And dissolved in 30 L of 3.5 ° DH hard water. Put 2 kg of a commercially available cotton towel in this aqueous solution and stir for 5 minutes. After rinsing for 1 minute, it was dehydrated. When the smell of this cotton towel was evaluated, a soft and clean scent was felt, and the effect of component (a) was confirmed.
• the woody-amber fragrance composition of Comparative Example 4 (Table 5 + Table 7) was used in place of the fragrance composition for detergents for clothing (Table 5 + Table 6) obtained in Example 10 used in Example 10.
• the odor of cotton towels was evaluated in the same manner as in Example 10, the hard woody odor increased, and the warmth and volume of natural Ambergris with poor lances were not recognized.
• Racemic Getalox (trade name of FirmeniGh) was used.
• Fragrance composition A of Example 1 (Table 9) was added to 99.5 parts by mass of the fragrance composition having the composition shown in Table 11.
• the softener composition having the composition shown in Table 12 was added to 99.5 parts by mass of the fragrance obtained in Example 12.
• the composition (Example 11 in Table 11 + Table 1) was mixed with 0.5 part by mass, 3 g of this was weighed and dissolved in 30 L of water.
• 2 kg of a commercially available cotton towel was added and stirred at 25 ° C. for 1 minute. After dehydration, it was dried at room temperature, and the smell of cotton towel the next day was evaluated. The aroma of musk, sandals, and floral as well as the rich amber scent was felt on the dry cloth. The result that it is sustained was obtained.
• Fragrance composition C of Example 3 (Table 9) was added to 99.7 parts by mass of the fragrance composition having the composition shown in Table 14.
• a fragrance composition for a liquid body cleanser characterized by a soft, warm and sweet scented skin residue could be obtained.

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• Chemical & Material Sciences (AREA)
• Life Sciences & Earth Sciences (AREA)
• Organic Chemistry (AREA)
• Health & Medical Sciences (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Wood Science & Technology (AREA)
• Oil, Petroleum & Natural Gas (AREA)
• Engineering & Computer Science (AREA)
• Veterinary Medicine (AREA)
• Public Health (AREA)
• General Health & Medical Sciences (AREA)
• Animal Behavior & Ethology (AREA)
• Emergency Medicine (AREA)
• Birds (AREA)
• Epidemiology (AREA)
• Fats And Perfumes (AREA)
• Cosmetics (AREA)
• Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
• Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
• Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
• Detergent Compositions (AREA)

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