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    • 专利摘要:
    The nitrile compound according to the following structural formula (I) and a fragrance composition comprising the nitrile compound according to structural formula (I) are described. wherein R represents a hydroxy group or an alkoxy group having 1 to 4 carbon atoms. Furthermore, their production from the corresponding oximes is described by dehydration.
    公开号:CH707393B1
    申请号:CH02061/13
    申请日:2013-12-12
    公开日:2017-08-31
    发明作者:Aoki Takashi；Hirose Takahiro；Tahara Shoichi
    申请人:Kao Corp；
    IPC主号:
    专利说明:

    Description Background of the Invention 1. Field of the Invention The present invention relates to a novel nitrile compound and a fragrance composition containing the same. 2. Background Art Fragrances are important components of products because they not only give preference and high quality, but also a sense of security and can raise certain expectations. Characteristic fragrances can also have the effect of identifying a product or of attracting buyers. It is common that for the perfuming of a product a fragrance composition is used in which several fragrances are mixed together, e.g. to achieve balanced scents and to influence their sustainability. For the individual fragrances in a fragrance composition, it is desirable that they blend well with the other fragrances.
    As fragrance with alicyclic structure and nitrile structure Peonile (the company Givaudan), namely 2-cyclohexyl-2-phenylacetonitrile, known which has a smell of fresh grapefruit, geraniums and rose petals (Motoichi Indou: Gouseikouryou - Kagaku to shouhinchishiki, new and expanded edition, 2005, 702 pages, and (translation of int. Publication) JP 2000-514 104 A).
    Further, Japanese Patent Publication JP S62-501 498 A discloses that certain bizykloheptane nitriles have a vegetable-like flavor.
    For fragrances, quite roughly speaking, they have a similar fragrance, if they have a similar structure, but there are also many exceptions. If the structure of fragrances is altered, and especially if multiple substituents are combined and altered, it is difficult to predict how the fragrance of a fragrance will change. Furthermore, it is difficult to predict to what extent such a fragrance harmonizes with other fragrances. Summary of the Invention It is an object of the invention to provide a compound which (a) has a balsamic aroma similar to coumarin, (b) is stable in an aqueous medium, and (c) freshness by blending with other perfumes gives and at the same time various flavors, such as flowery, fruity and musky aromas, and a fragrance composition comprising such a compound.
    The inventors found that certain nitrile compounds having a tetrahydrodizyclopentadiene structure, namely nitrile compounds of the structural formula (I) having a balsamic flavor similar to coumarin, are stable in an aqueous medium, and blending with other perfumes Give freshness and at the same time various flavors, such as flowery, fruity and musky flavors, can emphasize, and thus have reached the present invention.
    Accordingly, a nitrile compound of the present invention is represented by the following structural formula (I).
    (In this structural formula, R represents a hydroxy group or an alkoxy group having 1 to 4 carbon atoms.) Further, a fragrance composition of the present invention comprises a nitrile compound represented by the structural formula (i).
    Detailed Description of the Invention The nitrile compounds of the structural formula (I) of the present invention have a perfume-useful balsamic flavor similar to coumarin, and are stable in aqueous media. Furthermore, the nitrile compounds according to the invention of the structural formula (I) can give freshness by mixing with other fragrances and at the same time produce various aromas, e.g. flowery, fruity and musky aromas, emphasize.
    A nitrile compound according to the invention is represented by the following structural formula (I):
    (In this structural formula, R represents a hydroxy group or an alkoxy group having 1 to 4 carbon atoms.) Examples of alkoxy groups having 1 to 4 carbon atoms are methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, sec-butoxy t-butoxy and the like. As the nitrile compound represented by Structural Formula (I), octahydro-5-methoxy-4,7-methano-1H-indene-2-carbonitrile (where R = methoxy in Structural Formula (I)) with respect to its balsamic aroma and Stability in aqueous media advantageous.
    [Process for Producing Nitrile Compound] The nitrile compound according to the structural formula (I) of the present invention can be synthesized by ordinary organochemical reactions, and there is no limitation on production processes. A suitable process for the preparation of the nitrile compound according to the structural formula (I) comprises a step of dehydrating e.g. an oxime compound represented by Structural Formula (II) (hereinafter also referred to as an oxime intermediate) to thereby obtain the nitrile compound represented by Structural Formula (I).
    (In this structural formula, R represents a hydroxy group or an alkoxy group of 1 to 4 carbon atoms.) The oxime intermediate can be advantageously prepared by e.g. by a step of oximation of an aldehyde compound of the structural formula (III) (hereinafter also referred to simply as "aldehyde (III)"), the oxime compound of the structural formula (II) (the oxime intermediate) is obtained.
    (In this structural formula, R represents a hydroxy group or an alkoxy group having 1 to 4 carbon atoms.) Here, the aldehyde (III) can be prepared on the basis of known documents. The aldehyde (III) is available on the market and may be e.g. under the trade name Scentenal, manufactured by Firmenich. <Dehydration Step> As explained above, a production method of the present invention comprises a step of dehydrating an oxime compound (an oxime intermediate) of the structural formula (II) to obtain a nitrile compound represented by the structural formula (I).
    (In this structural formula, R represents a hydroxy group or an alkoxy group having 1 to 4 carbon atoms.) In this step, a method using acetic anhydride or a method using an alkali catalyst is advantageous, and in view of For increasing the yield and purity of the obtained product, a method using acetic anhydride is advantageous.
    [Method Using Acetic Anhydride] A method using acetic anhydride comprises a step of obtaining the nitrile compound represented by Structural Formula (I) by reacting the oxime compound (the oxime intermediate) represented by Structural Formula (II). is heated and dehydrated in the presence of acetic anhydride.
    In the method using acetic anhydride, it is advantageous from the viewpoint of increasing the yield and the ease of processing after the reaction when the amount of acetic anhydride used is 1.0-1.5 mol in relation to the oxime intermediate.
    In view of efficiently completing the reaction, it is preferable that the reaction temperature is 120-160 ° C, with the unreacted acetic anhydride and the by-produced acetic acid sufficiently refluxed.
    The reaction can be carried out solvent-free, however, in view of a slow heating, it can also be carried out under reflux using a suitable amount of a solvent having a boiling point in the range of the advantageous reaction temperature.
    The reaction product, ie the nitrile compound according to the structural formula (I) and the excess acetic anhydride and by-produced acetic acid can after the reaction by distillation, by conversion to acetate or by neutralization with alkaline water, and the subsequent removal together with the water layer, to be separated.
    [Method Using Alkali Catalyst] A method using an alkali catalyst comprises a step for obtaining the nitrile compound represented by the structural formula (I) by reacting the oxime compound (oxime intermediate) according to the structural formula (II) is heated and dehydrated in the presence of an alkali catalyst.
    In the method using an alkali catalyst, as the alkali catalyst, there is advantageously used a hydroxide of an alkali metal such as alkali metal hydroxide. Sodium hydroxide or potassium hydroxide.
    In view of an increase in the yield, it is advantageous if the amount of alkali catalyst used is 0.1-20% by weight relative to the oxime intermediate, and with regard to the control of the reaction, 1- 15 wt .-% particularly advantageous.
    In the process using an alkali catalyst, it is preferable that the reaction is carried out while removing the by-produced water from the system. Examples are azeotropic dehydration under reflux of the solvent and continuous dehydration upon removal of the produced product from the reaction system, and with a view to suppressing thermal decomposition or thermal polymerization of the nitrile compound represented by the structural formula (I) obtained as a product. is a continuous dehydration, in which also the nitrile compound according to the structural formula (I) is removed from the reaction system, advantageous.
    In view of efficiently completing the reaction and suppressing thermal decomposition or thermal polymerization of the oxime intermediate and the nitrile compound represented by the structural formula (I), it is preferable that the reaction temperature in the continuous dehydration be 80-250 ° C is, and in view of an increased yield 150-200 ° C are particularly advantageous. In this case, in view of efficiently distilling the nitrile compound represented by the structural formula (I) in the favorable temperature range and suppressing thermal decomposition or thermal polymerization of the product, it is preferable that the reaction is carried out in the negative pressure 10 kPa are particularly advantageous.
    Further, in view of shortening the fate of the oxime intermediate for suppressing side reactions, a method in which the oxime intermediate is continuously dropped into the reaction system is advantageous.
    In order to improve the quality of a nitrile compound according to structural formula (I) obtained as fragrance, it is advantageous if it is further distilled or refined by silica gel chromatography.
    The following are examples of preparation processes with which the oxime intermediate is obtained according to the manufacturing process according to the invention. <Oximation Step> As mentioned above, an oximation reaction using an aldehyde (III) and hydroxilamine can be carried out, and the oxime compound of the structural formula (II) (the oxime intermediate) can be obtained.
    (In this structural formula, R represents a hydroxy group or an alkoxy group having 1 to 4 carbon atoms.) Examples of suitable methods for this step are a method in which an aqueous solution containing hydroxila-min is converted to the aldehyde (III). and a method in which just after mixing the aldehyde (III) with an aqueous solution of an inorganic acid salt of hydroxilamine a base is instilled, and among these, the method is advantageous in that just after mixing the aldehyde ( III) with an aqueous solution of an inorganic acid salt of hydroxilamine a base is instilled. With this method, there is the advantage that by instilling a base in the reaction system, hydroxylamine can be produced, side reactions can be suppressed, and the reaction can be stably carried out.
    As the inorganic acid salt of hydroxilamine used in this step, it is advantageous from the viewpoint of suppressing side reactions and economy to use hydroxylamine sulfate.
    For the amount of hydroxylamine or its inorganic acid salt used, in view of the ease of processing after the reaction and the economy, an amount of 1.0-1.5 moles relative to the aldehyde (III) is converted to Hydroxylamine advantageous.
    As the base used for the aforementioned suitable method of dropping a base, a base which is more basic than hydroxylamine can be used, and among them, water-soluble bases are preferable. In terms of economy, a hydroxide of an alkali metal, such as e.g. Sodium hydroxide or potassium hydroxide, advantageous. From the viewpoint of handleability and efficiency, it is preferable to use an aqueous solution containing 20 to 40% by weight of a hydroxide of an alkali metal.
    The reaction can be carried out without solvent, but in view of slow heating and suppression of the increase in the viscosity of the reaction liquid as the reaction progresses, it is advantageous to use a solvent. As the solvent, water or alcohols having 1 to 3 carbon atoms, e.g. Ethanol or isopropyl alcohol, in which the aldehyde intermediate and the hydroxylamine are readily soluble as the starting material, and a mixture of water and isopropyl alcohol is particularly advantageous.
    In view of an efficient completion of the reaction and a suppression of exothermic decomposition of the hydroxylamine, a reaction temperature of 30-50 ° C is advantageous.
    The oxime intermediate product used as the reaction product may be used immediately after the separation of the water layer for the next reaction, but it is preferable to remove the high boiling point solvent or by-products by distilling refining or the like.
    [Fragrance Composition] The fragrance composition of the present invention contains the nitrile compound represented by the structural formula (I). The proportion of the nitrile compound of the structural formula (I) in the fragrance composition is advantageously 0.01-99% by weight, more preferably 0.1-15% by weight, and more preferably 0.3-3% by weight. %. At a level of 0.01-99% by weight of the nitrile compound represented by Structural Formula (I), the perfume composition may be given freshness, and various kinds of flavor such as e.g. flowery, fruity and musky aromas can be emphasized.
    Since the fragrance composition of the present invention contains the nitrile compound represented by the structural formula (I), it has a balm flavor similar to coumarin, and gives freshness by blending with other fragrances to harmonize with other fragrances and can simultaneously various flavors, such as flowery, fruity and musky aromas, emphasize. Furthermore, the fragrance composition according to the invention can also impart aromas, for example with a citrus-like note, floral note, fruity note, herbaceous note, spicy note, green note or woody note, by using other than the nitrile compound according to the structural formula (I) also usually other Contains fragrance components or fragrance mixtures of desired composition as other fragrances.
    It is advantageous in the fragrance composition according to the invention as other fragrances which can be used in combination with the nitrile compound according to the structural formula (I), at least one substance selected from the groups of hydrocarbons, alcohols, phenols, Aldehydes, ketones, acetals, ethers, esters, carbonates, lac-tone, oximes, nitriles, Schiff bases, natural essential oils and natural extracts. Among them, at least one substance selected from the groups of the alcohols, aldehydes, esters and lactones is particularly advantageous.
    In the present specification, "at least one substance selected from the groups of..." Means that a single compound or even a mixture of two or more compounds can be selected from the respective groups.
    Examples of hydrocarbons are limonene, α-pinene, β-pinene, terpinene, p-cymene, cedrene, longifolene, valencene and the like.
    Examples of alcohols are aliphatic alcohols, terpene alcohols, aromatic alcohols and the like.
    Examples of aliphatic alcohols are prenol, trans-2-hexenol, cis-3-hexenol, 2,6-dimethylheptanol, 1-octen-3-ol, 3,6-nonadien-1-ol, undecavertol (trade name of Givaudan, 4-methyl-3-decene-5-OI), 2,4-dimethyl-3-cyclohexene-1-methanol, isocyclogeraniol, 2-tert-butylcyclohexanol, 4-tert-butylcyclohexanol, Mayol (trade name of Firmenich, 4- (1-methylethyl) -cyclohexanemethanol), Amber Gore (trade name of Kao Corporation), Timberol (trade name of Symrise, 1- (2,2,6-trimethylcyclohexyl) hexane-3-OI), Sandal Mysore Gore (trade name of Kao Corporation), bacdanol (trade name of the company IFF, 2-ethyl-4- (2,2,3-trimethyl-3-cyclopentene-1-ll) -2-butene-1-ol) Florosa (trade name of Givaudan, 4-methyl-2- (2-methylpropyl) -tetrahydro-2H-4-pyranol) and the like.
    Examples of terpene alcohols are citronellol, hydroxycitronellol. Linalool, dihydrolinalool, tetrahydrolinalool, ethyllinalool, geraniol, nerol, tetrahydrogeraniol, myrcenol, dihydromyrcenol, tetrahydromyrcenol, ocimenol, terpeneol, menthol, borneol, fenchol, farnesol, nerolidol, cedrai and the like.
    Examples of aromatic alcohols are benzyl alcohol, Styralylakohol, phenethyl alcohol, Dimethylphenylethylkar-binol, cinnamyl alcohol, phenyl hexanol (trade name of the company Kao Corporation), Pamplefleur (trade name of the company IFF, 4-phenylpentanol), Majantol (trade name of the company Symrise, 2 , 2-Dimethl-3- (3-methylphenyl) -propanol) and the like.
    Examples of phenols are anethole, guaiacol, eugenol, isoeugenol and the like.
    Examples of aldehydes are aliphatic aldehydes, terpene aldehydes and aromatic aldehydes similar to the abovementioned alcohols, and examples of fragrance components are all aldehydes in which the functional group of the alcoholic perfume component has been substituted.
    Examples of other aldehydes are aldehydes C-12 MNA (trade name of Kao Corporation), aldehydes C-12 (trade name of Kao Corporation), Floral Super (trade name of the company IFF, 4,8-dimethyldeka-4,9 -Diethanol), Pollenal II (trade name of Kao Corporation, 2-cyclohexylpropanal), Myrac aldehyde (trade name of the company IFF, 4 (3) - (4-methyl-3-penten-1-OI) -3-ZyHoklexen-1 Carboxyaldehyde), Lyral (trade name of the company IFF, 4 (3) - (4-hydroxy-4-methylpentyl) -3-cyclohexene-1-carboxyaldehyde), Cetonal (trade name of Givaudan, trimethylcyclohexenemethylbutanol), vernaldehyde (trade name the company Givaudan, 1-methyl-4- (4-methylpentyl) -3-cyclohexylcarboxyaldehyde), Melozone (trade name of the company IFF, octahydro-4,7-methanoindencarboxyaldehyde), Scentenal (trade name Firmenich, methoxydizyldopentadiene-carboxaldehyde) , Dupical (trade name of the company Givaudan, 4-tricyclodecilidenebutyl), Bergamal (trade name of the company IFF, 3,7-dimethyl-2-methylene-6-octenal), c ampho-lenic aldehyde, bourgeonal (trade name of Givaudan, 3- (4-tert-butylphenyl) propanal), cyclamen aldehydes (trade name of Givaudan, 3- (4-isopropylipheny)) - 2-methylpropionaldehyde), Floralozone (trade name the company IFF, 3- (4-ethylphenyl) -2,2-dimethylpropionaldehyde), Suzaral (trade name of the company Takasago International Corporation, 3- (4-isobutylphenyl) -2-methylpropionaldehyde), Lilial (trade name of the company Givaudan, 3 (4-t-butylphenyl) -2-methylpropionaldehyde), amyl cinnamic aldehydes (trade name of Kao Corporation), hexyl cinnamic aldehydes (trade name of Kao Corporation), canthoxal (trade name of company IFF 2-methyl-3- (4-) Methoxyphenyl) propanol), vanillin, ethyl vanillin, heliotropins (trade name of Takasago International Corporation, 3,4-methylenedioxybenzaldehyde), Helional (trade name of the company IFF, α-methyl-1,3-benzodioxole-5-propane ]), Triplai (trade name of the company IFF, 2,4'-dimethyl-3-cyclohexane-1-carboxyaldehyde), and the like.
    Examples of ketones are methylheptanone, dimethyloctanone, 3-octanone, hexylcyclopentanone, Dihydrojasmon, Vedutone (trade name Firmenich, 2,2,5-trimethyl-5-Penthylzyklopentanon), Nectaryl (trade name of the company Givaudan, 2- (2 - (4-methyl-3-cyclohexene-1-II) -propyl) -cyclopentanone), ionone, methylionone, γ-methyl-ionone, damascone, δ-damascone, damascenone, dynascone (trade name of Firmenich, l- (5,5 -Dimethyl-1-cyclohexene-1-YI) -4-penten-1-one), Iron, Cashmerane (trade name of the company IFF, 1,2,3,5,6,7-hexahydro-1,1,2, 3,3-pentamethyl-4H-inden-4-one), Iso E Super (trade name of the company IFF, 1- (1,2,3,4,5,6,7,8-octahydro-2,3,8 , 8-tetramethyl-2-naphthalenyl) ethane-1-one), Catone (trade name Firmenich, 7-methyl-3,5-dihydro-2H-benzodioxepin-3-one), carvone, menthone, acetylcedrenes , Isolongifolanone, nootkatone, benzylacetone, raspberry ketone, benzophenone, tonalides (trade name of PFW, 6-acetyl-1,1,2,4,4,7-hexamethyltetrahydronaphthalene), β-methylnaphthyl ketone, Muscon, Mus cenone (trade name of Firmenich, 3-methyl-5-cyclopentadecen-1-one), cibeton, globanone (trade name of Finna Symrise, 8-cyclohexyladecenone), and the like.
    Examples of acetals are Anthoxan (trade name of Kao Corporation), Boisambrene Forte (trade name of Kao Corporation), Troenan (trade name of Kao Corporation), Methyl Pamplemousse (trade name of Givaudan, 1,1-dimethoxy-2 , 2,5-trimethyl-4-hexene), citral dimethyl acetal, hydratropaldehyde dimethyl acetal, Verdoxan (trade name of Kao Corporation), and the like.
    Examples of ethers are Herbavert (trade name of Kao Corporation), cedryl methyl ether, Ambroxane (trade name of Kao Corporation), citronellyl ethyl ether, geranyl ethyl ether, 1,8-cineole, rose oxide, estragole, anethethol, hinokitiol, diphenyloxide, β Naphthol methyl ether, β-naphthol ethyl ether, galaxolide (trade name of the company IFF, 1,3,4,6,7,8-hexahytiro-4,6,6,7,8,8-hexamethylcyclopenta-Y-2-benzopyran), and like.
    Examples of esters used as fragrances are aliphatic carboxylic acid esters, aromatic carboxylic acid esters and other carboxylic acid esters.
    Examples of aliphatic carboxylic acids which form aliphatic carboxylic acid esters are straight-chain and branched carboxylic acids having 1 to 18 carbon atoms, and among these are carboxylic acids having 1 to 6 carbon atoms, e.g. Formic acid, acetic acid and propionic acid, and especially acetic acid important. Examples of aromatic carboxylic acids which form aromatic carboxylic esters are benzoic acid, anisic acid, phenylacetic acid, cinnamic acid, salicylic acid, anthranilic acid, and the like. Examples of alcohols which form aliphatic and aromatic esters are the abovementioned perfume component alcohols and also unbranched and branched aliphatic alcohols having 1 to 5 carbon atoms.
    Other examples of carboxylic acid esters are ethyl saffron (trade name of Givaudan, ethyl dihydrocyclogelanate), Poirenate (trade name of Kao Corporation), Fruitate (trade name of Kao Corporation), methyl jasmonate, MDJ (trade name of Kao Corporation) , and the same.
    Examples of carbonates are Liffarome (trade name of the company IFF, cis-3-hexenylmethyl carbonate), Jasmacyclat (trade name of Kao Corporation), Floramat (trade name of Kao Corporation), and the like.
    Examples of lactones are γ-nonalactone, γ-decalactone, δ-decalactone, jasmolactone (trade name of Firmenich, tetrahydro-6- (3-hexenyl) -2H-pyran-2-one), γ-undecalactone, coumarin , Octahydrocoumarin, Florex (trade name of Firmenich, 6-ethylidene octahydro-5-8-methano-2H-1-benzopyran-2-one), cyclopentadecanolide, habanolide (trade name of Firmenich, 12 (11) -oxazyklohexadecene-2-one ), Ambrettolide (trade name of the company IFF, 10-octacycloheptadecen-2-one), ethylene brasylate, and the like.
    Examples of oximes are buccoximes (trade name of the company Symrise, 1,5-dimethyl-bicyclo [3,2,1] octane-8-ono-xim), labienoxime (trade name of the company Givaudan, 2,4,4, 7-tetramethyl-6,8-nonadiene-3-onoxime), 5-methyl-3-hepta-nonoxime, and the like.
    Examples of nitriles are dodecanenitrile, citronellylnitrile, cuminylnitrile, cinnamylnitrile, peonile (trade name of Givaudan, 2-cyclohexylidene-2-phenylacetonitrile), and the like.
    Examples of Schiff bases are aurantiol (trade name of the company Givaudan, N- (3,7-dimethyl-7-Hydroxyoktyli-den) -Methylanthrranilat), Ligantral (trade name of the company Givaudan, 3,5-dimethyl-3- Cyclohexene-1-YI-methyl-methylene-anthranilate), 2 - [(2-methylundecylidene) -amino] -methylbenzoate, and the like.
    Examples of natural essential oils and natural extracts are orange, lemon, lime, bergamot, vanilla, mandarin, peppermint, spearmint, lavender, chamomile, rosemary, eucalyptus, sage, basil, rose, cistus, geranium, jasmine, ylang -Ylang, anise, clove, ginger, nutmeg, cardamon, cedar, hinoki cypress, vetiver, patchouli, lemongrass, labdanum, and the like.
    The contents of other fragrances may be selected according to need, depending on the kind of the fragrance to be mixed and the kind and strength of the desired flavor. The contents of other fragrances in the fragrance composition are preferably each 0.0001-99.99 wt%, and more preferably 0.001-80 wt%. The content of the other fragrances in the fragrance composition is preferably 5-99.99% by weight in total, and more preferably 50-99.9% by weight in total.
    The fragrance composition according to the invention can contain, with the nitrile compound according to the invention according to the structural formula (I) and other fragrances as base, oily substances which themselves have no odor.
    With such oily substances, the perfume components can be uniformly mixed and dispersed in the product, and perfuming with a fragrance of adequate strength can thus be easily achieved. Examples of such oily substances are polyhydric alcohols, e.g. Ethylene glycol, propylene glycol, butylene glycol and dipropylene glycol; Esters, e.g. Isopropyl myristate, dibutyl adipate, diethyl sebacate, hydrocarbons, e.g. Paraffin oil or squalene; and surfactants, e.g. Polyoxyethylene alkyl ether or sorbitan fatty acid ester, and the like.
    Among them, in view of the solubility of all the fragrance components, polyhydric alcohols and esters are advantageous as the oily substance, and dipropylene glycol and isopropyl myristate are particularly advantageous. It is preferable that the content amount of the oily substances in the fragrance composition is 0.01-95% by weight, more preferably 1-90% by weight, and more preferably 5-80% by weight.
    The fragrance composition of the present invention has the effect of imparting freshness in addition to the flavor of the nitrile compound represented by the structural formula (I), and having various kinds of flavor, such as e.g. flowery, fruity and musky aromas, can emphasize. Such a perfume composition may be used, for example, advantageously as perfuming in a detergent composition or fabric softener composition, or in a cosmetic product.
    [Use as perfuming component] A perfume composition comprising the nitrile compound according to the structural formula (I) of the present invention has a balm flavor similar to coumarin and imparts freshness, and can be used for a fragrance mixture having a pleasant fragrance various flavors, such as flowery, fruity and musky aromas, emphasized to be used as a perfuming component for a wide variety of products. Thus, a method of using the nitrile compound represented by Structural Formula (I) as a scavenging component is preferably a method in which the nitrile compound represented by Structural Formula (I) is used as a perfuming component of a fragrance composition, fabric softening or softening composition, hair care product or a detergent composition is used. As a method of using this compound, the compound may be a care agent such as e.g. a soap, a cosmetic product, a hair care product, a detergent, a fabric softener, a spray product, a fragrance, a perfume or in a bath additive alone or in combination with other components as a base.
    It is advantageous to use the nitrile compound according to the structural formula (I) in a composition for textile treatment or textile care, since it is stable in an aqueous medium and gives a fragrance of freshness by their application. It is particularly advantageous to use them in a detergent composition or a softener, and most preferably it can be used in a detergent composition.
    Accordingly, the present invention provides a detergent composition containing the fragrance composition of the present invention, and a softener composition containing the fragrance composition of the present invention.
    A fabric softener composition according to the invention contains the fragrance composition according to the invention and a tertiary amine which has at least one hydrocarbon group with a total of 14 to 26 carbon atoms, which may also be divided by ester groups, amide groups or ether groups, or else its salt or quaternary product or a cationic plasticizer. The softening composition may further contain a nonionic surfactant, a disinfectant, a viscosity modifier, a pH adjuster, a metal complexing agent, a storage stability agent, a solvent, or the like.
    As the cationic plasticizer, a conventionally known plasticizer can be used. Examples of such cationic softeners are cationic surfactants. Examples of such cationic surfactants are surfactants based on quaternary ammonium salt and / or inorganic salts or organic salts of surfactants based on tertiary amines.
    As examples of nonionic surfactants, alkyl ethoxylates, oleyl ethoxylates, glyceryl ethoxylates, dialkyl diethers, and the like may be mentioned. As examples of alkyl ethoxylates, polyoxyethylene (9) lauryl ether, polyoxyethylene (10) lauryl ether, polyoxyethylene (12) lauryl ether, polyoxyethylene (1,5) lauryl ether, polyoxyethylene (8) lauryl ether, polyoxyethylene (5,5) lauryl ether, polyoxyethylene (20) lauryl ether , and the like can be called.
    As examples of disinfectants, e.g. Alcohols having 1 to 8 carbon atoms, benzoic acids, phenyls, and the like, and more specifically, there may be mentioned ethanol, propylene glycol, benzyl alcohol, salicylic acid, paraoxyphenyl methyl benzoate, and cresol.
    As the viscosity modifier, inorganic or organic salts (excluding quaternary ammonium salt) can be used. Specifically, as examples of viscosity modifiers, there may be mentioned sodium chloride, potassium chloride, calcium chloride, magnesium chloride, aluminum chloride, sodium sulfate, magnesium sulfate, potassium sulfate, sodium nitrate, magnesium nitrate, p-sodium toluene sulfonate, sodium glycolate, sodium acetate, potassium acetate, potassium glycolate, sodium lactate, and the like. It is advantageous if the viscosity modifier is calcium chloride or magnesium chloride.
    As examples of the storage stability-increasing agent, there may be mentioned esters of fatty acids (having 8 to 22 carbon atoms) of polyhydric alcohols having 2 to 6 carbon atoms.
    A softener according to the invention contains water as solvent and normally the remainder of the composition is water. As water, deionized water and distilled water are advantageous. A more advantageous pH of the fabric softener according to the invention is 1.5-5, more preferably 2-4.5.
    Any suitable inorganic or organic acid or base can be used as pH adjuster of the fabric softener according to the invention.
    Examples of metal complexing agents are phosphonic acid and its salts, as well as aminopolyacetates and their salts, and among them, ethane-1-hydroxy-1,1-diphosphonic acid, diethylenetriaminepentaacetic acid, and ethylenediaminetetraacetic acid are advantageous.
    Further, in the fabric softener of the present invention, as any other components other than the above-mentioned components, conventional components which are usually mixed into fabric softeners may also be blended to an extent which does not hinder the effect of the invention. As such remaining components, for example, higher fatty acids such as stearic acid, oleic acid or palmitic acid, or their lower alcohols and esters and the like; nonionic surfactants, e.g. Fatty acid glycerol esters as esters of stearic acid and glycerin or the like; higher alcohols, e.g. Stearyl alcohol, palmityl alcohol, oleyl alcohol, and the like, low temperature stabilizers, e.g. Ethylene glycol or glycerin; Urea, pigments, cellulose derivatives, UV absorbers, fluorescent bleaching agents, and the like can be mixed into the fabric softener according to the invention.
    In addition to the embodiments described above, the following perfume compositions, fabric treatment compositions, methods of use, and methods of making the nitrile compound are disclosed.
    Further, to the above-described embodiments, the following nitrile compound and fragrance composition containing the same are disclosed.
    <1> nitrile compound according to the following structural formula (I)
    (In this structural formula, R represents a hydroxy group or an alkoxy group having 1 to 4 carbon atoms).
    <2> nitrile compound according to <1>, wherein R is a methoxy group.
    <3> perfume composition comprising the nitrile compound according to <1> or <2>.
    <4> perfume composition according to <3>, wherein the content amount of the nitrile compound according to <1> in the perfume composition preferably 0.01-99 wt .-%, particularly preferably 0.1-15 wt. -%, and most preferably 0.3-3 wt .-% is.
    <5> perfume composition according to <3> or <4>, further comprising a further perfume except the nitrile compound according to <1> or <2>.
    <6> perfume composition according to <5>, wherein the further perfume except the nitrile compound at least one substance selected from the groups of hydrocarbons, alcohols, phenols, aldehydes, ketones, acetals, ethers, esters, carbonates, lactones , Oximes, nitriles, Schiff bases, natural essential oils and natural extracts, and advantageously at least one substance selected from the groups of alcohols, aldehydes, esters and lactones.
    <7> A textile treatment composition comprising a fragrance composition according to any one of <3> to <6>.
    <8> Detergent composition comprising a perfume composition according to any one of <3> to <6>.
    <9> Softener composition comprising a fragrance composition according to any one of <3> to <6>.
    <10> A method of using the nitrile compound according to <1> or <2> as a perfuming component for a perfume composition, fabric softener composition, hair care product or detergent composition.
    <11> A process for producing a nitrile compound represented by Structural Formula (I), comprising a dehydration step in which an oxime compound represented by Structural Formula (II) is dehydrated to obtain the nitrile compound represented by Structural Formula (II). I).
    rrrv. ίΐΎΛ-cN
    RiAAANOH (Π) (Ι) (In this structural formula, R represents a hydroxy group or an alkoxy group having 1 to 4 carbon atoms.) <12> A process for producing a nitrile compound represented by Structural Formula (I) according to <11 > wherein the dehydration step is carried out by a method using acetic anhydride or by a method using an alkali catalyst.
    <13> A process for producing a nitrile compound represented by the structural formula (I) according to <11>, wherein the dehydration step is carried out by a process in which an oxime compound of the structural formula (II) is heated in the presence of acetic anhydride and dehydrated to obtain the nitrile compound of the structural formula (I).
    <14> A process for producing a nitrile compound represented by the structural formula (I) according to <13>, wherein the amount of acetic anhydride used is 1.0-1.5 mol in relation to the oxime compound of the structural formula (II) ,
    <15> A process for producing a nitrile compound represented by Structural Formula (I) according to <11>, wherein the dehydration step is carried out by a process using an alkali catalyst in which the oxime compound represented by Structural Formula (II) in the presence of an alkali catalyst (advantageously a hydroxide of an alkali metal such as sodium hydroxide or potassium hydroxide) is dehydrated by heating, and the nitrile compound according to the structural formula (I) is obtained.
    <16> Production method according to <15>, wherein the amount of the alkali catalyst used is preferably 0.1-20 wt .-%, particularly preferably 1-15 wt .-%, relative to the oxime compound according to the Structural formula (II) is.
    <17> Production method according to <15> or <16>. wherein the process is carried out using an alkali catalyst by a reaction upon removal of by-produced water from the system, and preferably by means of azeotropic dehydration with reflux of the solvent or continuous dehydration upon removal of the produced product from the reaction system.
    <18> A process for producing a nitrile compound represented by Structural Formula (I) according to any one of <11> to <17>, wherein the oxime compound represented by Structural Formula (II) is synthesized by oximation of an aldehyde compound represented by Structural Formula (III ).
    (In this structural formula, R represents a hydroxy group or an alkoxy group having 1 to 4 carbon atoms) [Embodiments] Details of the measuring methods performed in the following embodiments and comparative examples are summarized below.
    Details of the measuring methods performed in the following production examples are summarized below.
    [Inversion Rate and Reaction Efficiency] The inversion rate and the reaction yield of the following production processes were determined by quantitative analysis by gas chromatography (GC) with internal standard.
    <Gas Chromatography Apparatus and Analysis Conditions>
    GC Device: Manufactured by Hewlett Packard, Type: HP685Q Columns: Prepared by J & W, DB-1 (inner diameter 0.25 mm, length 30 m, film thickness 0.25 pm)
    Carrier gas: He; 1.5mL / min
    Inlet conditions: 280 ° C; Split ratio 1/100
    Detection conditions: FID, 280 ° C column temperature conditions: temperature increase at a rate of 100 ° C 6 ° C / min 300 ° C;
    then hold for 10 min at 300 ° C
    Internal standard compound: n-dodecane [Identification of Chemical Compounds] The compounds obtained by the following Preparation Examples were analyzed by spectral analysis by means of a Fourier transform infrared spectrometer (manufactured by Horiba, Ltd., type: FT-710) and by means of a Gas chromatograph with a mass spectrometer (GC-MS) (manufactured by Shimadzu Corporation, type: GC-2010) identified. The measurement conditions are indicated in the measurement results.
    [Aroma Evaluation] Fragrance rating and strength were evaluated by means of odor paper strips from two experienced individuals having 5 to 10 years' experience in the field of fragrance mixing and aroma evaluation, and three experienced persons of at least 25 years of age Experience in this field. The 5 mm at the front edge of the odor paper strips (6 mm wide and 150 mm long perfume test strips) were dipped in the samples and evaluated.
    For the flavor, the main-felt fragrances (main fragrances) were listed sequentially from the most felt fragrance, and the secondary-felt fragrances (secondary fragrances) were also noted.
    The odor strength was subjected to a relative assessment, and noted in the case of odorlessness as "0" and with an extremely strong odor as "5".
    [Production Example 1] (Preparation of octahydro-5'-methoxy-4,7-methano-1H-indene-2-carboxaldehyde oxime) Into a 500 ml flask were sequentially added 100 g of octahydro-5-methoxy-4 , 7-Methano-1H-indene-2-carboxaldehyde (trade name "Scentenal" from Firmenich, 0.51 mol), 60 g of isopropyl alcohol, 44 g of hydroxylamine sulfate (0.26 mol, 0.51 mol in relation to the aldehyde , 1.02 mol converted to hydroxylamine), and 80 g of deionized water, and heated in a nitrogen atmosphere with constant stirring to 45 ° C. While maintaining the reaction temperature at 40-50 ° C, 64 g (0.53 mol) of an aqueous solution of 33 wt% sodium hydroxide was dropped into this reaction liquid for 30 minutes. After completion of the instillation, the reaction liquid was kept at 45 ° C for one hour by supplying heat and further stirred. After cooling the reaction liquid to room temperature, the reaction liquid was withdrawn by standing and decanting the water layer. The remaining organic layer was rinsed with an aqueous solution of 10% by weight sodium sulfate. From the organic layer, the isopropyl alcohol was distilled off to obtain 136 g of a crude product of a colorless, viscous liquid. As a result of quantitative analysis by gas chromatography of the crude product, it was found that the inversion rate of octahydro-5-methoxy-4,7-methano-1H-indene-2-carboxaldehyde was 100%, the purity of octahydro-5-methoxy-4, 7-Methano-1H-indene-2-carboxaldehyde oxime 74%, and the crude yield was 94%.
    30 g of this crude product were refined by distillation under reduced pressure, and a colorless, viscous fraction was obtained, which distilled off at 129-133 ° C / 13 Pa. The purity of the octahydro-5-methoxy-4,7-methano-1H-indene-2-carboxaldehyde oxime was 90%.
    By GS-MS analysis of this fraction, it was found that the octahydro-5-methoxy-4,7-methano-1H-indene-2-carboxaldehyde oxime was a mixture of six diastereomers.
    The measurement results of the respective spectral analyzes of the octahydro-5-methoxy-4,7-methano-1H-in-the-2-carboxaldehyde oxime obtained are as follows: (1) MS (El method), m / z: 209 (M +), 192, 178, 159, 144, 131, 117, 106, 91, 79, 56, 41. (2) FT-IR (neat), cir f1: 3303 (br), 2945, 2863, 2819, 2360, 1646 , 1448, 1086, 935.
    [Embodiment 1] (Preparation of octahydro-5-methoxy-4,7-methano-1H-indene-2-carbonitrile) Into a 300 ml flask, was added 93 g of octahydro-5-methoxy-4,7- Methano-1H-indene-2-carboxaldehyde oxime (the crude product of Preparative Example 1, purity 69 g, 0.33 mol) and 70 g toluene were added and stirred in a nitrogen atmosphere. To this was added 39 g of acetic anhydride (0.38 mol, 1.15 mol in relation to the intermediate oxime) over 30 minutes, and then refluxed for two hours (at a temperature of 125 ° C) under reflux of the intermediate acetic acid. Next, a mixture of toluene, acetic anhydride and acetic acid was distilled off from the reaction liquid, and after cooling the remaining reaction liquid to room temperature, it was neutralized with a dilute aqueous solution of sodium hydroxide. After 30 g of ethyl acetate was added, the water layer was removed by standing and decanting. The remaining organic layer was rinsed twice with an aqueous solution of 10% by weight sodium sulfate. From the organic layer, the ethyl acetate was distilled off to obtain 74 g of a crude dark brown liquid product. As a result of a quantitative analysis by gas chromatography of the crude product, it was found that the inversion rate of the olahydro-5-methoxy-4,7-methano-1H-indene-2-carboxaldehyde oxime was 100%, the purity of octahydro-5-methoxy-4, 7-Methano-1H-Inden-2-carbonitrile 80%, and the crude yield was 93%.
    50 g of this crude product were refined by distillation under reduced pressure, and a colorless, liquid fraction was obtained, which distilled off at 134-135 ° C / 133 Pa. The purity of the octahydro-5-methoxy-4,7-methano-1H-indene-2-carbonitrile was 98%.
    By GS-MS analysis of this distilled fraction, it was found that the octahydro-5-methoxy-4,7-methano-1H-indene-2-carbonitrile was a mixture of six diastereomers.
    The measurement results of the respective spectral analyzes and flavor evaluations of the obtained octahydro-5-methoxy-4,7-methano-1H-indene-2-carbonitrile were as follows: (1) MS (El method), m / z: 191 (M +), 176, 159, 114, 311, 117, 106, 91, 79, 58, 41. (2) FT-IR (neat), cm "1: 2965, 2873, 2819, 2235, 1734, 1465, 1092. (3) Aroma: (main flavor) Balsamic flavor similar to coumarin, (subsidiary flavor) anise, Pamplemous se. (4) Odor strength: 3 [Embodiment 2 and Comparative Example I] (fragrance mixture for fabric detergent) Using the method described in US Pat In Example 1 of the obtained 1-octahydro-5-methoxy-4,7-methano-1H-indene-2-carbonitrile, fragrances were mixed with the composition shown in Table 1, and a fragrance mixture for a fabric detergent was prepared.
    The evaluation of the resulting fragrance mixture for a laundry detergent was conducted in the same manner as the above-described flavor evaluation. The fragrance blend for a fabric cleanser according to Embodiment 2 was compared with the fragrance composition of Comparative Example 1 to give a fresh and lasting citrus aroma which enhanced the orange and musk aromas derived from the other fragrances.
    [Embodiment 3 and Comparative Examples 2 and 3] (Detergent Mixture for Textile Cleaner) Using the octahydro-5-methoxy-4,7-methano-1H-inden-2-carbonitrile obtained in Example 1, perfumes were prepared as shown in Table 1 2, and a fragrance mixture for a laundry detergent.
    The evaluation of the resulting fragrance mixture for a laundry detergent was carried out in the same manner as the above-described flavor evaluation. The fragrance mixture for a laundry detergent according to Embodiment 3 enhanced the aromas of citrus, lily-of-the-valley, melon and musk compared to the fragrance compositions according to Comparative Examples 2 and 3, and of a fresh quality without being resinous or cumbersome. In the fragrance composition of Comparative Example 2, in comparison with Comparative Example 3, the sweetness was enhanced, but at the same time, there was a greater resinity. Further, the perfume compositions of both Comparative Example 2 and Comparative Example 3 were more cumbersome.
    [EMBODIMENT 4 AND COMPARATIVE EXAMPLES 4] (Fragrance Blend for Fabric Softener) Using the octahydro-5-methoxy-4,7-methano-1H-inden-2-carbonitrile obtained in the embodiment 1, fragrances having the content shown in Table 3 were obtained Mixed composition, and a fragrance mixture for a fabric softener made.
    The evaluation of the resulting fragrance mixture for a softener was carried out in the same manner as the above-described flavor evaluation. The scent mixture for. A fabric softener of Embodiment 4 enhanced the flavor of melon as compared with Comparative Example 4 and was pleasant in its freshness and clarity.
    [Embodiment 5 and Comparative Example 5] (Fragrance Blend for Fabric Softener) Using the octahydro-5-methoxy-4,7-methano-1H-inden-2-carbonitrile obtained in Example 1, fragrances having the composition shown in Table 4 were obtained Mixed composition, and a fragrance mixture for a fabric softener made.
    Table 4 Unit: parts by weight
    Embodiment 5 Comparative Example 5
    Vanillin 3 3
    Octahydro-5-methoxy-4,7-methano-1H-indene-2-carbonitrile 20 (Compound of Example 1)
    Dipropylene glycol 86.5 106.5
    Total 1000 1000 The evaluation of the resulting fragrance mixture for a softener was carried out in the same manner as the above-described flavor evaluation. The fragrance mixture for a softener according to Embodiment 5 was clearer as compared with Comparative Example 5 and enhanced the flavor of melon.
    [Embodiment 6 and Comparative Examples 6] (Fabric Softening Composition) To an unscented liquid softener having the composition shown in Table 5, 1.0% by weight of the softener composition according to Embodiment 5 or the fragrance composition of Comparative Example 5 was used given, and thus the fabric softener composition according to Embodiment 6 or Comparative Example 6 made.
    1) Trade name of Kao Corporation: Tetranyl L1 / 90S
    Using commercially available slightly alkaline detergent (manufactured by Kao Corporation, trade name "Attack"), 24 cotton towels were washed 5 times with a Hitachi NW-6CY fully automatic washing machine and dried at room temperature to give a pre-treatment Removal of excess chemicals was carried out (the concentration of the detergent was 0.0667 wt .-%, 47 L of tap water were used, at a water temperature of 20 ° C, 10 min washing and rinsing 2 times).
    In an electric bucket (manufactured by National, Type N-BK2-A), 5 liters of tap water was poured, and herein 10 g / 1.0 kg of fabrics of the fabric softening fabrics obtained with Embodiment 6 and Comparative Example 6, respectively, were poured. Composition was dissolved (preparation of a treatment bath), and after one minute, two of the cotton towels pretreated with the method described above were immersed for 5 minutes. Thereafter, these two cotton towels were placed in an electric bucket (manufactured by National, Type NA-35) and dehydrated for 3 minutes. After dehydration, they were dried at about 20 ° C room temperature overnight.
    A bottle mouth of a bottle filled with the liquid rinse aid composition, a cotton hand towel immediately after dehydration, and an overnight dried cotton towel were each evaluated by ten specialists according to the same criteria as in the above-described flavor evaluation for olfactory test odor strength and the average values were determined. The result is shown in Table 6.
    权利要求:
    Claims (10)
    [1]

    As shown in Table 6, in the case of the liquid softener composition of Embodiment 6, the odor at both the bottle opening, immediately after dehydrating and after one day drying is stronger and superior than in the liquid softener composition of Comparative Example 6. [0139] The nitrile compound of the present invention is useful as a fragrance and can be used as a fragrance ingredient to achieve a balsamic flavor similar to coumarin. Furthermore, the nitrile compound according to the invention is stable in aqueous solutions. Further, the nitrile compound of the present invention blended with other fragrances can impart freshness so that it can impart a sense of purity, and it can enhance flowery, fruity and musky aromas. From the foregoing, it can be seen that a fragrance composition can be used with the nitrile compound of the present invention as a perfuming component for a detergent composition, a softener composition or the like. claims
    1. Nitrile compound according to the following structural formula (I)

    wherein R represents a hydroxy group or an alkoxy group having 1 to 4 carbon atoms.
    [2]
    2. A nitrile compound according to claim 1, wherein R is a methoxy group.
    [3]
    3. fragrance composition with the nitrile compound according to claim 1 or 2.
    [4]
    4. perfume composition according to claim 3 with other perfumes in addition to the nitrile compound.
    [5]
    5. perfume composition according to claim 4, wherein the other perfumes in addition to the nitrile compound at least one substance selected from the groups of hydrocarbons, alcohols, phenols, aldehydes, ketones, acetals, ethers, esters, carbonates, lactones, oximes, nitriles, Includes ship bases, natural essential oils and natural extracts.
    [6]
    6. A textile treatment composition comprising a fragrance composition according to any one of claims 3 to 5.
    [7]
    7. A detergent composition with a fragrance composition according to any one of claims 3 to 5.
    [8]
    8. Fabric softener composition with a fragrance composition according to one of claims 3 to 5.
    [9]
    9. Use of the nitrile compound according to claim 1 or 2 as a perfuming component in a hair care product.
    [10]
    A process for producing the nitrile compound represented by the following structural formula (I), from an oxime compound represented by the following structural formula (II), comprising the step of dehydrating said oxime compound,

    wherein R represents a hydroxy group or an alkoxy group having 1 to 4 carbon atoms to obtain the nitrile compound represented by the structural formula (I).
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    同族专利:
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    JP2014118372A|2014-06-30|
    CH707393A2|2014-06-30|
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    法律状态:
    优先权:
    申请号 | 申请日 | 专利标题
    JP2012273361A|JP5930467B2|2012-12-14|2012-12-14|Nitrile compounds|
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