US20190241833A1 - Perfume composition - Google Patents

Perfume composition Download PDF

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Publication number
US20190241833A1
US20190241833A1 US16/332,316 US201716332316A US2019241833A1 US 20190241833 A1 US20190241833 A1 US 20190241833A1 US 201716332316 A US201716332316 A US 201716332316A US 2019241833 A1 US2019241833 A1 US 2019241833A1
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Prior art keywords
reaction
carboxylic acid
methyl
formula
aroma
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US16/332,316
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Inventor
Mitsuharu Kitamura
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Mitsubishi Gas Chemical Co Inc
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Mitsubishi Gas Chemical Co Inc
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Assigned to MITSUBISHI GAS CHEMICAL COMPANY, INC. reassignment MITSUBISHI GAS CHEMICAL COMPANY, INC. ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: KITAMURA, MITSUHARU
Publication of US20190241833A1 publication Critical patent/US20190241833A1/en
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Classifications

    • 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
    • C11B9/0026—Essential oils; Perfumes compounds containing an alicyclic ring not condensed with another ring
    • C11B9/0038—Essential oils; Perfumes compounds containing an alicyclic ring not condensed with another ring the ring containing more than six carbon atoms
    • 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
    • A—HUMAN NECESSITIES
    • A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23L—FOODS, FOODSTUFFS, OR NON-ALCOHOLIC BEVERAGES, NOT COVERED BY SUBCLASSES A21D OR A23B-A23J; THEIR PREPARATION OR TREATMENT, e.g. COOKING, MODIFICATION OF NUTRITIVE QUALITIES, PHYSICAL TREATMENT; PRESERVATION OF FOODS OR FOODSTUFFS, IN GENERAL
    • A23L2/00—Non-alcoholic beverages; Dry compositions or concentrates therefor; Their preparation
    • A23L2/52—Adding ingredients
    • A23L2/56—Flavouring or bittering agents
    • A—HUMAN NECESSITIES
    • A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23L—FOODS, FOODSTUFFS, OR NON-ALCOHOLIC BEVERAGES, NOT COVERED BY SUBCLASSES A21D OR A23B-A23J; THEIR PREPARATION OR TREATMENT, e.g. COOKING, MODIFICATION OF NUTRITIVE QUALITIES, PHYSICAL TREATMENT; PRESERVATION OF FOODS OR FOODSTUFFS, IN GENERAL
    • A23L27/00—Spices; Flavouring agents or condiments; Artificial sweetening agents; Table salts; Dietetic salt substitutes; Preparation or treatment thereof
    • A23L27/20—Synthetic spices, flavouring agents or condiments
    • A—HUMAN NECESSITIES
    • A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23L—FOODS, FOODSTUFFS, OR NON-ALCOHOLIC BEVERAGES, NOT COVERED BY SUBCLASSES A21D OR A23B-A23J; THEIR PREPARATION OR TREATMENT, e.g. COOKING, MODIFICATION OF NUTRITIVE QUALITIES, PHYSICAL TREATMENT; PRESERVATION OF FOODS OR FOODSTUFFS, IN GENERAL
    • A23L27/00—Spices; Flavouring agents or condiments; Artificial sweetening agents; Table salts; Dietetic salt substitutes; Preparation or treatment thereof
    • A23L27/20—Synthetic spices, flavouring agents or condiments
    • A23L27/203—Alicyclic compounds
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K47/00—Medicinal preparations characterised by the non-active ingredients used, e.g. carriers or inert additives; Targeting or modifying agents chemically bound to the active ingredient
    • A61K47/06—Organic compounds, e.g. natural or synthetic hydrocarbons, polyolefins, mineral oil, petrolatum or ozokerite
    • A61K47/08—Organic compounds, e.g. natural or synthetic hydrocarbons, polyolefins, mineral oil, petrolatum or ozokerite containing oxygen, e.g. ethers, acetals, ketones, quinones, aldehydes, peroxides
    • A61K47/14—Esters of carboxylic acids, e.g. fatty acid monoglycerides, medium-chain triglycerides, parabens or PEG fatty acid esters
    • 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
    • A61K8/37—Esters of carboxylic acids
    • 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
    • C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
    • C07C69/74—Esters of carboxylic acids having an esterified carboxyl group bound to a carbon atom of a ring other than a six-membered aromatic ring
    • C07C69/753—Esters of carboxylic acids having an esterified carboxyl group bound to a carbon atom of a ring other than a six-membered aromatic ring of polycyclic acids
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
    • C07C69/74—Esters of carboxylic acids having an esterified carboxyl group bound to a carbon atom of a ring other than a six-membered aromatic ring
    • C07C69/757—Esters of carboxylic acids having an esterified carboxyl group bound to a carbon atom of a ring other than a six-membered aromatic ring having any of the groups OH, O—metal, —CHO, keto, ether, acyloxy, groups, groups, or in the acid moiety
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
    • C07C69/96—Esters of carbonic or haloformic acids
    • 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
    • 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
    • A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23V—INDEXING SCHEME RELATING TO FOODS, FOODSTUFFS OR NON-ALCOHOLIC BEVERAGES AND LACTIC OR PROPIONIC ACID BACTERIA USED IN FOODSTUFFS OR FOOD PREPARATION
    • A23V2002/00—Food compositions, function of food ingredients or processes for food or foodstuffs
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2602/00—Systems containing two condensed rings
    • C07C2602/36—Systems containing two condensed rings the rings having more than two atoms in common
    • C07C2602/42—Systems containing two condensed rings the rings having more than two atoms in common the bicyclo ring system containing seven carbon atoms

Definitions

  • the present invention relates to a perfume composition.
  • Non Patent Literature 1 states that geranyl acetate having a rose-like aroma, methyl jasmonate having a jasmine-like sweet aroma, fruitate having a fruity aroma, methyl benzoate having an intense dry fruity aroma and the like are useful as compound perfume materials.
  • An object of the present invention is to provide a perfume composition useful as a compound perfume material and having an excellent aroma and aroma persistence.
  • the present inventor took an interest in a fact that many compounds having a polycyclic structure among terpenes have excellent aromas, and synthesized various compounds having a polycyclic structure to evaluate their aromas, resulting in finding that norbornane-2-carboxylic acid ester compounds have excellent aromas and are excellent as compound perfumes, and thus, the present invention was accomplished.
  • the present invention provides the following:
  • a perfume composition comprising a compound represented by the following formula (1):
  • R 1 , R 2 and R 3 are independently hydrogen or a methyl group
  • X is an alkyl group having 1 to 4 carbon atoms
  • R 4 and R 5 are independently hydrogen or a —CHO group
  • R 1 , R 2 and R 3 are independently hydrogen or a methyl group
  • X is an alkyl group having 1 to 4 carbon atoms
  • R 1 , R 2 and R 3 are independently hydrogen or a methyl group
  • X is an alkyl group having 1 to 4 carbon atoms
  • R 1 , R 2 and R 3 are independently hydrogen or a methyl group
  • X is an alkyl group having 1 to 4 carbon atoms
  • either one of R 4 and R 5 is hydrogen and the other is a —CHO group.
  • a perfumery and cosmetics product, a health and hygiene material, a miscellaneous good, a drink, a food, a quasi-drug or a pharmaceutical comprising the perfume composition according to [1] or [2].
  • a perfume composition of the present invention comprising a norbornane-2-carbyxlic acid ester compound has an excellent aroma and excellent aroma persistence, and hence is useful as a perfuming ingredient for a variety of products including toiletries, soap and laundry detergents.
  • a perfume composition of the present embodiment comprises a norbornane-2-carboxylic acid ester compound, namely, a compound represented by formula (1).
  • the perfume composition of the present embodiment may be a perfume composition comprising, as a principal component, single one or two or more compounds represented by formula (1), or may be a perfume composition comprising single one or two or more of compounds represented by formula (1) in combination with another perfume component or a compound perfume having a desired composition usually used.
  • compositions represented by formula (1) refers to that compounds represented by formula (1) are comprised in an amount of usually 85% by mass or more, preferably 90% by mass or more, more preferably 96% by mass or more, and further preferably 98% by mass or more with respect to a total amount of the perfume composition.
  • R 1 , R 2 and R 3 are independently hydrogen or a methyl group
  • X is an alkyl group having 1 to 4 carbon atoms
  • R 4 and R 5 are independently hydrogen or a —CHO group
  • the compounds represented by formula (1) of the present embodiment are preferably compounds represented by the following formulas (1-1) to (1-3).
  • the compounds represented by formulas (1-1) to (1-3) may be used singly or in combinations of two or more.
  • R 1 , R 2 , R 3 and X have the same meaning as R 1 , R 2 , R 3 and X in formula (1).
  • R 1 , R 2 and R 3 are independently hydrogen or a methyl group
  • X is an alkyl group having 1 to 4 carbon atoms.
  • R 1 , R 2 , R 3 and X have the same meaning as R 1 , R 2 , R 3 and X in formula (1).
  • R 1 , R 2 and R 3 are independently hydrogen or a methyl group
  • X is an alkyl group having 1 to 4 carbon atoms.
  • R 1 , R 2 , R 3 and X have the same meaning as R 1 , R 2 , R 3 and X in formula (1).
  • R 1 , R 2 and R 3 are independently hydrogen or a methyl group
  • X is an alkyl group having 1 to 4 carbon atoms.
  • R 4 and R 5 are hydrogen, and the other is a —CHO group.
  • R 1 , R 2 and R 3 are independently hydrogen or a methyl group.
  • R 2 and R 3 are preferably hydrogen.
  • X is an alkyl group having 1 to 4 carbon atoms.
  • the alkyl group having 1 to 4 carbon atoms include a methyl group, an ethyl group, an n-propyl group, an iso-propyl group, an n-butyl group, an iso-butyl group and a tert-butyl group.
  • X is preferably a methyl group or an ethyl group.
  • the compound represented by any of formula (1) and formulas (1-1) to (1-3) may be any single substance out of optical isomers based on asymmetric carbon whose configuration is not shown, or may be a mixture of any of these in an arbitrary ratio.
  • the compound represented by formula (1-1) is preferably any one of norbornene-2-carboxylic acid methyl ester, norbornene-2-carboxylic acid ethyl ester, norbornene-2-methyl-2-carboxylic acid methyl ester and norbornene-2-methyl-2-carboxylic acid ethyl ester, and more preferably any one of norbornene-2-carboxylic acid methyl ester and norbornene-2-methyl-2-carboxylic acid methyl ester.
  • the compound represented by formula (1-1) of the present embodiment has an aroma including both an intense ripe banana and melon-like fruity note and an ozone-like marine note, or an aroma including both a fresh floral green note and a fruity note, and is also excellent in persistence.
  • the compound represented by formula (1-2) is preferably any one of norbornane-2-carboxylic acid methyl ester, norbornane-2-carboxylic acid ethyl ester, norbornane-2-methyl-2-carboxylic acid methyl ester and norbornane-2-methyl-2-carboxylic acid ethyl ester, and more preferably any one of norbornane-2-carboxylic acid methyl ester and norbornane-2-methyl-2-carboxylic acid methyl ester.
  • the compound represented by formula (1-2) of the present embodiment has a herbal green-like aroma with a fruity note, and is also excellent in persistence.
  • the compound represented by formula (1-3) is preferably any one of formylnorbornane-2-carboxylic acid methyl ester, formylnorbornane-2-carboxylic acid ethyl ester, formylnorbornane-2-methyl-2-carboxylic acid methyl ester and formylnorbornane-2-methyl-2-carboxylic acid ethyl ester, and more preferably any one of formylnorbornane-2-carboxylic acid methyl ester and formylnorbornane-2-methyl-2-carboxylic acid methyl ester.
  • the compound represented by formula (1-3) of the present embodiment has a novel aroma including all of an intense melon or kiwi-like fruity note, a fresh marine note and a rose-like floral note, and is also excellent in persistence.
  • the compound represented by formula (1) has an excellent aroma with a fruity note and the like and is also excellent in persistence, and hence can be used, singly or in combination with another component, as an aroma component for various products such as perfumery and cosmetics products, health and hygiene materials, miscellaneous goods, drinks, foods, quasi-drugs and pharmaceuticals.
  • the compound can be used as a perfuming ingredient of soap, a shampoo, a rinse, a detergent, cosmetics, a spray product, an aromatic, a perfume or a bath additive.
  • the compound represented by formula (1) of the present embodiment can be produced by, for example, a synthesis method including, as a key step, a Diels-Alder reaction for heat-reacting an olefin and dicyclopentadiene.
  • the compound represented by formula (1-1) can be produced by a Diels-Alder reaction for heat-reacting an olefin and dicyclopentadiene as follows:
  • R 1 , R 2 , R 3 and X have the same meaning as R 1 , R 2 , R 3 and X in formula (1).
  • R 1 , R 2 and R 3 are independently hydrogen or a methyl group
  • X is an alkyl group having 1 to 4 carbon atoms.
  • Examples of the olefin include methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, methyl crotonate, ethyl crotonate, propyl crotonate, butyl crotonate, methyl 3-methylcrotonate, ethyl 3-methylcrotonate, propyl 3-methylcrotonate and butyl 3-methylcrotonate.
  • methyl acrylate, ethyl acrylate, methyl methacrylate, ethyl methacrylate, methyl crotonate, ethyl crotonate, methyl 3-methylcrotonate and ethyl 3-methylcrotonate are preferred, and methyl acrylate, ethyl acrylate, methyl methacrylate and ethyl methacrylate are more preferred.
  • the dicyclopentadiene preferably has a higher purity, and it is desirable to avoid containment of butadiene, isoprene and the like therein as far as possible.
  • the purity of the dicyclopentadiene is preferably 90% or more, and more preferably 95% or more. Since dicyclopentadiene is known to be changed into cyclopentadiene through depolymerization under heating conditions, cyclopentadiene may be used instead of dicyclopentadiene.
  • the reaction temperature is preferably 100° C. or more, more preferably 120° C. or more, and further preferably 130° C. or more.
  • the reaction temperature is preferably 250° C. or less.
  • a hydrocarbon, an alcohol, an ester or the like can be used as a reaction solvent, and an aliphatic hydrocarbon having 6 or more carbon atoms, and specifically, cyclohexane, toluene, xylene, ethylbenzene, mesitylene, propanol, butanol or the like is suitably used.
  • any of various reaction methods such as a batch method using a tank reactor or the like, a semi-batch method in which a substrate or a substrate solution is supplied to a tank reactor under reaction conditions, and a continuous flow method in which a substrate is allowed to flow to a tubular reactor under reaction conditions, can be employed.
  • a product obtained through the above-described reaction may be used as a perfume composition comprising the compound represented by formula (1), may be used as a starting material for a next reaction, or may be used as a perfume composition or a starting material for a next reaction after purification by distillation, extraction, crystallization or the like.
  • the thus obtained product namely, the compound represented by formula (1-1), can be used as a starting material for a next reaction, and can be used as a starting material for synthesizing the compound represented by formula (1-2) or the compound represented by formula (1-3).
  • the compound represented by formula (1-2) can be produced as follows by subjecting the compound represented by formula (1-1) to a hydrogenation reaction in the presence of a catalyst.
  • R 1 , R 2 , R 3 and X have the same meaning as R 1 , R 2 , R 3 and X in formula (1).
  • R 1 , R 2 and R 3 are independently hydrogen or a methyl group
  • X is an alkyl group having 1 to 4 carbon atoms.
  • the catalyst to be used in the hydrogenation reaction is not especially limited as long as it is a catalyst usually used for hydrogenation of an unsaturated bond, and is preferably a catalyst containing at least one selected from the group 8 to 11 metals of the periodic table.
  • a specific example includes a catalyst containing at least one of iron, cobalt, nickel, copper, ruthenium, rhodium, palladium, silver, osmium, iridium, platinum and gold.
  • the hydrogenation catalyst may be a solid catalyst or a homogeneous catalyst, and from the viewpoint of releasability from a reaction product, is preferably a solid catalyst.
  • the solid catalyst include a non-supported metal catalyst and a supported metal catalyst.
  • the non-supported metal catalyst can be preferably a Raney catalyst such as Raney nickel, Raney cobalt or Raney copper; an oxide of platinum, palladium, rhodium or ruthenium; or a colloidal catalyst.
  • a Raney catalyst such as Raney nickel, Raney cobalt or Raney copper
  • an oxide of platinum, palladium, rhodium or ruthenium or a colloidal catalyst.
  • the supported metal catalyst is a catalyst in which at least one of, for example, iron, cobalt, nickel, copper, ruthenium, rhodium, palladium, silver, osmium, iridium, copper and gold is supported on or mixed with a support of magnesia, zirconia, ceria, diatomaceous earth, activated carbon, alumina, silica, zeolite, titania or the like.
  • the supported metal catalyst suitably include supported copper catalysts in which a copper catalyst, such as a copper-chromium catalyst (Adkins catalyst), a copper-zinc catalyst or a copper-iron catalyst, is supported on a support, supported platinum catalysts of Pt/C and Pt/alumina, supported palladium catalysts of Pd/C and Pd/alumina, supported ruthenium catalysts of Ru/C and Ru/alumina, and supported rhodium catalysts of Rh/C and Rh/alumina.
  • a copper catalyst such as a copper-chromium catalyst (Adkins catalyst), a copper-zinc catalyst or a copper-iron catalyst
  • supported platinum catalysts of Pt/C and Pt/alumina supported palladium catalysts of Pd/C and Pd/alumina
  • supported ruthenium catalysts of Ru/C and Ru/alumina supported rhodium catalysts of Rh/C and Rh/alumina.
  • a catalyst containing copper is more preferred from the viewpoints of reaction activity and selectivity.
  • a use amount of the hydrogenation catalyst may be appropriately adjusted depending on the type of the catalyst, and is 0.001 to 100% by mass, preferably 0.01 to 30% by mass, and further preferably 0.1 to 20% by mass with respect to the norbornene-2-carboxylic acid ester compound used as the starting material.
  • a hydrogen pressure to be employed in the hydrogenation reaction may be either of normal pressure or increased pressure, and is usually normal pressure to 4.0 MPa, preferably 0.1 to 3.0 MPa, and more preferably 0.1 to 2.0 MPa.
  • the hydrogenation reaction may be performed in the absence of a solvent or with a solvent used.
  • the solvent examples include water, organic acids such as formic acid and acetic acid; esters such as ethyl acetate and butyl acetate; aromatic compounds such as benzene, o-dichlorobenzene, toluene and xylene; hydrocarbons such as hexane, heptane and cyclohexane; alcohols such as methanol, ethanol, isopropyl alcohol, t-butyl alcohol, ethylene glycol and diethylene glycol; ethers such as dioxane, tetrahydrofuran, dimethoxyethane and diglyme; and a mixture of any of these.
  • organic acids such as formic acid and acetic acid
  • esters such as ethyl acetate and butyl acetate
  • aromatic compounds such as benzene, o-dichlorobenzene, toluene and xylene
  • hydrocarbons such as hexane, h
  • An amount of the solvent when used in the hydrogenation reaction is usually 0.1 to 30 mass times, and preferably 0.2 to 20 mass times the amount of the norbornene-2-carboxylic acid ester compound used as the starting material.
  • a reaction temperature of the hydrogenation reaction can be usually ⁇ 90° C. to 200° C.
  • the reaction temperature is preferably 20° C. to 150° C., and more preferably 50° C. to 120° C.
  • the type of the hydrogenation reaction is not especially limited as long as a catalytic hydrogenation reaction can be performed, and any of usually employed known types may be employed.
  • Examples of the type of the hydrogenation reaction include a type using a slurry bed reactor in which the catalytic hydrogenation reaction is performed with a catalyst allowed to flow in the form of a fluid, and a type using a fixed bed reactor in which the catalytic hydrogenation reaction is performed with a catalyst filled/fixed and with a fluid supplied.
  • a reaction product obtained through the hydrogenation reaction can be rectified with a distillation column after removing a low boiling point substance and the like therefrom with an evaporator or the like, and thus, the resultant can be used as the perfume composition comprising the compound represented by formula (1-2).
  • the compound represented by formula (1-3) can be synthesized from the compound represented by formula (1-1) as follows by performing a hydroformylation reaction of carbon monoxide and hydrogen gas in the presence of a rhodium compound and an organophosphorus compound.
  • R 1 , R 2 , R 3 and X have the same meaning as R 1 , R 2 , R 3 and X in formula (1).
  • R 1 , R 2 and R 3 are independently hydrogen or a methyl group
  • X is an alkyl group having 1 to 4 carbon atoms.
  • Either one of R 4 and R 5 is hydrogen, and the other is a —CHO group.
  • the rhodium compound used in the hydroformylation reaction is not limited in the form of a precursor thereof as long as it is a compound forming a complex together with the organophosphorus compound and exhibiting hydroformylation activity in the presence of carbon monoxide and hydrogen.
  • a catalyst precursor such as rhodium acetylacetonate dicarbonyl (hereinafter referred to as Rh(acac) (CO) 2 ), Rh 2 O 3 , Rh 4 (CO) 12 , Rh 6 (CO) 16 or Rh(NO 3 ) 3 may be introduced into a reaction mixture together with the organophosphorus compound to form a rhodium metal hydridocarbonyl phosphorus complex having catalytic activity in a reaction vessel, or a rhodium metal hydridocarbonyl phosphorus complex may be precedently prepared to be supplied into a reactor.
  • a method in which Rh(acac) (CO) 2 is reacted with the organophosphorus compound in the presence of a solvent, and the resultant is introduced into a reactor together with an excessive amount of the organophosphorus compound to obtain a rhodium-organophosphorus complex having catalytic activity may be employed.
  • An amount of the rhodium compound used in the hydroformylation reaction is preferably 0.1 to 30 micromoles, more preferably 0.2 to 20 micromoles, and further preferably 0.5 to 10 micromoles per mole of an olefin used as a substrate of the hydroformylation reaction.
  • the amount of the rhodium compound used is smaller than 30 micromoles per mole of the olefin, there is no need to provide recovery recycling equipment for a rhodium complex, and hence cost of the rhodium catalyst can be reduced, and thus, economic burden related to the recovery recycling equipment can be reduced.
  • the amount of the rhodium compound used is larger than 0.1 micromoles per mole of the olefin, a hydroformylation reaction product can be obtained in a high yield.
  • organophosphorus compound used in the hydroformylation reaction for forming, together with the rhodium compound, the catalyst of the hydroformylation reaction examples include a phosphine represented by general formula P(—R 6 )(—R 7 )(—R 8 ) and a phosphite represented by general formula P(—OR 6 )(—OR 7 )(—OR 8 ).
  • R 6 , R 7 and R 8 include an aryl group that may be substituted with an alkyl group having 1 to 4 carbon atoms or an alkoxy group having 1 to 4 carbon atoms, and an alicyclic alkyl group that may be substituted with an alkyl group having 1 to 4 carbon atoms or an alkoxy group having 1 to 4 carbon atoms.
  • triphenylphosphine or triphenylphosphite is suitably used as the organophosphorus compound.
  • An amount of the organophosphorus compound used is preferably 500 times mole to 10000 times mole, more preferably 700 times mole to 5000 times mole, and further preferably 900 times mole to 2000 times mole of the rhodium metal.
  • the amount of the organophosphorus compound used is smaller than 500 times mole of the rhodium metal, the stability of the rhodium metal hydridocarbonyl phosphorus complex working as the catalyst active material is spoiled, and hence, the progress of the reaction tends to be slowed.
  • the amount of the organophosphorus compound used is larger than 10000 times mole of the rhodium metal, cost related to the organophosphorus compound tends to be increased.
  • the hydroformylation reaction can be performed without using a solvent, and when a solvent inert to the reaction is used, the reaction can be more suitably performed.
  • the solvent is not especially limited as long as it dissolves an olefin, dicyclopentadiene or cyclopentadiene, and the rhodium compound and the organophosphorus compound.
  • the solvent include hydrocarbons such as aliphatic hydrocarbons, alicyclic hydrocarbons and aromatic hydrocarbons; esters such as aliphatic esters, alicyclic esters and aromatic esters; alcohols such as aliphatic alcohols and alicyclic alcohols; and aromatic halides.
  • hydrocarbons such as aliphatic hydrocarbons, alicyclic hydrocarbons and aromatic hydrocarbons
  • esters such as aliphatic esters, alicyclic esters and aromatic esters
  • alcohols such as aliphatic alcohols and alicyclic alcohols
  • aromatic halides aromatic halides.
  • a hydrocarbon is preferred, and an alicyclic hydrocarbon or an aromatic hydrocarbon is more preferred.
  • a temperature in performing the hydroformylation reaction is preferably 40° C. to 160° C., and more preferably 80° C. to 140° C.
  • the reaction temperature is 40° C. or more, a sufficient reaction rate can be obtained, and hence remaining of the olefin used as the starting material can be inhibited.
  • the reaction temperature is 160° C. or less, generation of byproducts derived from the olefin of the starting material and the reaction product is inhibited to prevent degradation of a reaction result.
  • the reaction For performing the hydroformylation reaction, the reaction needs to be performed under pressure of carbon monoxide (CO) and hydrogen (H 2 ) gas.
  • the CO and the H 2 gas can be each independently introduced into the reaction system or can be introduced into the reaction system in the form of a mixed gas precedently prepared.
  • a molar ratio between the CO and the H 2 gas ( ⁇ CO/H 2 ) to be introduced into the reaction system is preferably 0.2 to 5, more preferably 0.5 to 2, and further preferably 0.8 to 1.2. If the molar ratio between the CO and the H 2 gas is out of this range, the reaction activity of the hydroformylation reaction and selectivity of a target aldehyde may be lowered in some cases. Since the CO and the H 2 gas introduced into the reaction system are reduced in accordance with the progress of the reaction, the reaction may be easily controlled in some cases by utilizing a precedently prepared mixed gas of CO and H 2 .
  • a reaction pressure employed in the hydroformylation reaction is preferably 1 to 12 MPa, more preferably 1.2 to 9 MPa, and further preferably 1.5 to 5 MPa.
  • the reaction pressure is 1 MPa or more, a sufficient reaction rate can be obtained, and hence the olefin used as a starting material can be inhibited from remaining.
  • the reaction pressure is 12 MPa or less, it is economically advantageous because there is no need to use expensive equipment excellent in pressure resistance performance.
  • it is necessary to discharge the CO and the H 2 gas and to reduce the pressure after completing the reaction and therefore, loss of the CO and the H 2 gas is reduced as the pressure is lower, which is economically advantageous.
  • a batch reaction or a semi-batch reaction is suitably employed as a reaction method for performing the hydroformylation reaction.
  • the semi-batch reaction can be performed by adding the rhodium compound, the organophosphorus compound, and the solvent to the reactor, applying a pressure with a CO/H 2 gas and increasing a temperature to obtain the above-described reaction conditions, and then, supplying an olefin used as the starting material or a solution thereof to the reactor.
  • a reaction product obtained through the hydroformylation reaction can be rectified with a distillation column after removing a low boiling point substance and the like therefrom with an evaporator or the like, and thus, the resultant can be used as the perfume composition comprising the compound represented by formula (1-3).
  • another perfume component and/or a compound perfume having a desired composition may be mixed with a single one or two or more of the compounds represented by formula (1) to be blended therein.
  • An amount of the compound represented by formula (1) blended in the perfume composition of the present embodiment may be appropriately adjusted in accordance with the type of the compound perfume, the type and the intensity of a desired aroma and the like, and the compound is added to a compound perfume in an amount of preferably 0.01 to 90% by mass, and more preferably 0.1 to 50% by mass.
  • perfume component usable in the perfume composition of the present embodiment in combination with the compound represented by formula (1) include, but are not limited to, surfactants such as polyoxyethylene lauryl ether sulfate; solvents such as dipropylene glycol, diethyl phthalate, ethylene glycol, propylene glycol, methyl myristate and triethyl citrate; hydrocarbons such as limonene, ⁇ -pinene, ⁇ -pinene, terpinene, cedrene, longifolene and valencene; alcohols such as linalool, citronellol, geraniol, nerol, terpineol, dihydromyrcenol, ethyl linalool, farnesol, nerolidol, cis-3-hexenol, cedrol, menthol, borneol, ⁇ -phenylethyl alcohol, benzyl alcohol, phenyl alcohol,
  • the perfume composition comprising the compound represented by formula (1) can be used as an aroma component, used for purposes of imparting an aroma or improving an aroma of a target to be blended with, of various products such as perfumery and cosmetics products, health and hygiene materials, miscellaneous goods, drinks, foods, quasi-drugs and pharmaceuticals.
  • the perfume composition comprising the compound represented by formula (1) can be used as an aroma component of, for example, fragrance products such as a perfume and colognes; hair cosmetics such as a shampoo, a rinse, a hair tonic, a hair cream, a hair mousse, a hair gel, a pomade and a hair spray; skin cosmetics such as a skin lotion, an essence, a cream, a milky lotion, a face mask, a foundation, a face powder, a lipstick and various make-ups; a dishwashing detergent, a laundry detergent, a softener, a disinfection detergent, a deodorant detergent, an environmental fragrance, a furniture care agent, a glass cleaner, a furniture cleaner, a floor cleaner, a disinfectant, an insecticide, a bleaching agent and other detergents for various health and hygiene applications; quasi-drugs such as a dentifrice, a mouthwash, a bath additive, an antiperspirant product and a perm solution; miscellaneous goods such as toilet paper
  • An amount of the perfume or perfume composition of the present embodiment blended in each of the above-described products is, in terms of an amount of a formylnorbornane-2-carboxylic acid ester compound represented by formula (1), preferably 0.001 to 50% by mass, and more preferably 0.01 to 20% by mass with respect to the total amount of the product.
  • Synthesis was performed by using a stainless steel autoclave having an internal volume of 500 ml and equipped with a magnetic induction stirrer and three inlet nozzles disposed in an upper portion.
  • the autoclave was charged with 101.2 g of n-dodecane (special grade reagent, manufactured by Tokyo Chemical Industry Co., Ltd.), and after nitrogen gas replacement, the resultant was heated to a liquid temperature of 195° C.
  • n-dodecane special grade reagent, manufactured by Tokyo Chemical Industry Co., Ltd.
  • the thus obtained liquid was rectified by using a distillation column having 20 theoretical plates (distillation temperature: 88° C., degree of vacuum: 2.7 kPa), and a main distillate portion having 98.5 GC % by the gas chromatography analysis was obtained in an amount of 120.5 g (distillation yield: 90.5% by mol).
  • the resultant fraction was analyzed by the GC-MS, resulting in finding a molecular weight of 152 of the target.
  • the thus obtained fraction had a novel aroma including both a ripe banana and melon-like fruity note and an ozone-like marine note differently from known fruitate having a fruity aroma alone or known geranyl acetate having a rose-like aroma alone, and was characterized by excellent aroma persistence superior to the other known esters or geranyl acetate.
  • a perfume composition (a control) having a composition listed in Table 1 was produced.
  • 10 parts by mass of the norbornene-2-carboxylic acid methyl ester prepared as described above was added to 90 parts by mass of the control to prepare a perfume composition.
  • the thus obtained perfume composition was verified, through aroma evaluation by a perfumer, to have an apricot-like fruity scent having a gorgeous gardenia-like floral note.
  • the thus obtained liquid was rectified by using a spinning band distillation column having 40 theoretical plates (distillation temperature: 90° C., degree of vacuum: 2.7 kPa), and a main distillate portion having 98.5 GC % by the gas chromatography analysis was obtained in an amount of 127.5 g (distillation yield: 91.1% by mol).
  • the resultant fraction was analyzed by the GC-MS, resulting in finding a molecular weight of 166 of the target.
  • the thus obtained fraction had a novel aroma including both a fresh floral green note and a fruity note differently from known fruitate having a fruity aroma alone or known geranyl acetate having a rose-like aroma alone, and was characterized by excellent aroma persistence superior to the other known esters or geranyl acetate.
  • a perfume composition (a control) having a composition listed in Table 2 was produced.
  • 10 parts by mass of the norbornene-2-methyl-2-carboxylic acid methyl ester prepared as described above was added to 90 parts by mass of the control to prepare a perfume composition.
  • the thus obtained perfume composition was verified, through aroma evaluation by a perfumer, to have a fruity scent like a fresh pear.
  • a hydrogenation reaction was performed by using a stainless steel autoclave having an internal volume of 500 ml and equipped with a magnetic induction stirrer and three inlet nozzles disposed in an upper portion.
  • the autoclave was charged with 6.0 g of a Cu—Cr catalyst (N-203S manufactured by JGC Corporation) and 120.0 g of isopropyl alcohol (special grade reagent, manufactured by Wako Pure Chemical Industries Ltd.), and activation was performed at 170° C. and a hydrogen pressure of 2 MPa for 1 hour.
  • 60.0 g of the norbornene-2-carboxylic acid methyl ester prepared as described above was charged, and a reduction reaction was performed at 120° C. and a hydrogen pressure of 2 MPa for 3 hours under stirring.
  • reaction solution was filtered to remove the catalyst, and thus, 173.9 g of a reaction solution containing 57.6 g of norbornane-2-carboxylic acid methyl ester was obtained (conversion rate:100%, yield: 96.2%).
  • conversion rate:100%, yield: 96.2% As a result in terms of the norbornene-2-carboxylic acid methyl ester, the yield was 96.2% by mol, and the selectivity was 100% by mol.
  • the thus obtained liquid was rectified by using a spinning band distillation column having 40 theoretical plates (distillation temperature: 89° C., degree of vacuum: 2.7 kPa), and a main distillate portion having 98.5 GC % by the gas chromatography analysis was obtained in an amount of 53.5 g (distillation yield: 91.5% by mol).
  • the resultant fraction was analyzed by the GC-MS, resulting in finding a molecular weight of 154 of the target.
  • the thus obtained fraction had a herbal green-like novel aroma having an intense fruity note differently from known fruitate having a fruity aroma alone or known geranyl acetate having a rose-like aroma alone, and was characterized by excellent aroma persistence superior to the other known esters or geranyl acetate.
  • a perfume composition (a control) having a composition listed in Table 3 was produced.
  • 10 parts by mass of the norbornane-2-carboxylic acid methyl ester prepared as described above was added to 90 parts by mass of the control to prepare a perfume composition.
  • the thus obtained perfume composition was verified, through aroma evaluation by a perfumer, to have a fruity scent with green apple freshness.
  • a hydroformylation reaction was performed by using a stainless steel autoclave having an internal volume of 500 ml and equipped with a magnetic induction stirrer and three inlet nozzles disposed in an upper portion.
  • the resultant reaction solution was subjected to the gas chromatography analysis to obtain 186.9 g of the reaction solution containing 69.0 g of formylnorbornane-2-carboxylic acid methyl ester (a mixture of 5-formylnorbornane-2-carboxylic acid methyl ester and 6-formylnorbornane-2-carboxylic acid methyl ester).
  • formylnorbornane-2-carboxylic acid methyl ester a mixture of 5-formylnorbornane-2-carboxylic acid methyl ester and 6-formylnorbornane-2-carboxylic acid methyl ester.
  • the thus obtained liquid was rectified by using a spinning band distillation column having 40 theoretical plates (distillation temperature: 112° C., degree of vacuum: 0.19 kPa), and a main distillate portion having 98.4 GC % by the gas chromatography analysis was obtained in an amount of 63.5 g (distillation yield: 90.7% by mol).
  • the resultant fraction was analyzed by the GC-MS, resulting in finding a molecular weight of 182 of the target.
  • the thus obtained fraction had a novel aroma having all of an intense melon or kiwi-like fruity note, a fresh marine note and a rose-like floral note differently from known fruitate having a fruity aroma alone or known geranyl acetate having a rose-like aroma alone, and was characterized by excellent aroma persistence superior to the other known esters or geranyl acetate.
  • a perfume composition (a control) having a composition listed in Table 4 was produced.
  • 10 parts by mass of the formylnorbornane-2-carboxylic acid methyl ester prepared as described above was added to 90 parts by mass of the control to prepare a perfume composition.
  • the thus obtained perfume composition was verified, through aroma evaluation by a perfumer, to have a fruity scent with a sweet and beautiful gardenia-like floral note.
  • a carboxylic acid ester compound having a norbornane skeleton of the present invention has a fruity aroma and excellent aroma persistence, and therefore is useful as a perfuming ingredient for a variety of products including toiletries, soap and laundry detergents.

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WO2021146495A1 (en) * 2020-01-15 2021-07-22 Promerus, Llc Fragrance compositions containing norbornene derivatives for personal care products
US11725161B2 (en) 2018-11-16 2023-08-15 Mitsubishi Gas Chemical Company, Inc. Carboxylic acid ester compound, production method thereof, and fragrance composition

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KR102052857B1 (ko) * 2019-07-03 2019-12-05 오태성 방향제 장치 및 그의 제조방법
JP7343373B2 (ja) * 2019-12-02 2023-09-12 花王株式会社 香料組成物
WO2021146494A1 (en) * 2020-01-15 2021-07-22 Promerus, Llc Fine fragrance compositions containing norbornene ester derivatives

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