JP6137681B2 - Nitrile compounds - Google Patents

Description

  The present invention relates to a novel nitrile compound and a fragrance composition containing the same.

  The scent is an important factor that produces a taste of products, a sense of luxury, a sense of security, and a sense of expectation for effects. Furthermore, the characteristic fragrance gives product identification effect and customer suction. On the other hand, in order to control fragrance balance and sustainability, it is common to use a fragrance composition in which a plurality of fragrance materials are mixed. The fragrance material constituting the fragrance composition is required to have good harmony with other fragrance materials.

  As a fragrance material that is a nitrile compound having an alicyclic structure, 2-cyclohexylidene-2-phenylacetonitrile, Peonyl (Givaudan), is known to have a fresh, grapefruit, geranium, rose floral-like aroma. (Non-Patent Document 1).

  In addition, in Patent Document 1, unsaturated derivatives of 2,6,6-trimethylcyclohexane-1-acetonitrile such as 2,6,6-trimethyl-1-cyclohexene-1-acetonitrile are patchouli odor substances. It is described.

  Patent Document 2 describes that specific cyclohexanenitriles are useful as intermediates for the production of Irons, and are also useful as a lasting fragrance imparting or modulating agent.

  Patent Document 3 discloses a process for producing 2-methyl-3- (2,2-dimethyl-3-alkyl-6-methylenecyclohexyl) acrylonitrile, which is a synthetic intermediate such as ionone and Iron useful as a perfume substance. ing.

  Also, Cetonal (Givaudan), which is trimethylcyclohexene methylbutanal, has a strong Oris-like woody odor, 2-methyl-4- (2,6,6-trimethyl-1 (2) -cyclohexenyl) butene- 1-al, Ional, Veltonal (Bedukian) has a sweet fruity, woody fig-like aroma, 2-methyl-4- (2,6,6-trimethyl-1 (2) -cyclohexenyl) butene It is known that Boronal (Symrise), which is -2-al, has a floral fragrance reminiscent of Boronia with violet accents (Non-Patent Documents 1 and 2).

  Roughly speaking, a fragrance material has a similar fragrance tone if the structure is similar, but there are many exceptions, especially when changing the combination of multiple substituents, how the fragrance tone changes. It is difficult to predict whether it will go, and it is difficult to predict the harmony with other fragrance materials.

Motoichi Intoh Synthetic fragrance Chemistry and product knowledge Supplement revised edition 2005, 199 pages, 200 pages and 702 pages Kurt Bauer, Dorothea Garbe Common Fragrance and Flavor Materials 1985, pp. 79 and 80

Special table 2010-522797 JP-A-2-160755 JP-A-61-97251

  The object of the present invention is to enhance the floral fragrance by blending with other fragrances, having a woody-floral fragrance with a rich Oris-like sweetness useful as a fragrance. It is in providing the fragrance | flavor composition containing the compound which can be used, and the compound.

  The nitrile compound having a specific structure has a woody-floral fragrance having a rich Oris-like sweetness, is highly durable, and is blended with other fragrances. The present inventors have found that it is possible to emphasize the floral sweetness and completed the present invention.

  That is, the present invention is a nitrile compound represented by the formula (I).

In the above formula,
One of the bonds between C-3 ′ and C-2 ′ and C-2 ′ and C-1 ′ represents a double bond with a dotted line;
One of the bonds between C-4 and C-3, and C-3 and C-2 represents a double bond with a dotted line, or C-4 and C-3, and C-3 And the bond between C-2 represents a single bond.

  Moreover, this invention is a fragrance | flavor composition containing the nitrile compound represented by said Formula (I).

  The nitrile compound represented by the formula (I) of the present invention has a woody-floral fragrance having a rich Oris-like sweetness useful as a fragrance and has a high durability. Moreover, the nitrile compound represented by the formula (I) of the present invention can emphasize floral sweetness by blending with other fragrances.

  The present invention is a nitrile compound represented by the formula (I).

In the above formula,
One of the bonds between C-3 ′ and C-2 ′ and C-2 ′ and C-1 ′ represents a double bond with a dotted line;
One of the bonds between C-4 and C-3, and C-3 and C-2 represents a double bond with a dotted line, or C-4 and C-3, and C-3 And the bond between C-2 represents a single bond.

  The nitrile compound represented by the formula (I) is specifically as follows.

From the viewpoint that the nitrile compound represented by the formula (I) has a woody-floral fragrance having a rich Oris-like sweetness useful as a fragrance,
The bond between C-3 ′ and C-2 ′ represents a double bond with a dotted line, and both the bonds between C-4 and C-3 and C-3 and C-2 are single bonds. Representing a bond (nitrile compound represented by formula (I-1)) or
The bond between C-2 ′ and C-1 ′ represents a double bond with a dotted line, and both the bonds between C-4 and C-3 and C-3 and C-2 are single bonds. Representing a bond (nitrile compound represented by formula (I-2)),
The bond between C-2 ′ and C-1 ′ represents a double bond together with the dotted line, and the bond between C-3 and C-2 represents a double bond together with the dotted line (formula (I− Nitrile compound represented by 3))
Or
The bond between C-3 ′ and C-2 ′ represents a double bond together with the dotted line, and the bond between C-3 and C-2 represents a double bond together with the dotted line (formula (I− Nitrile compounds represented by 5) are preferred.

  From the viewpoint of having a woody-floral fragrance having a rich Oris-like sweetness useful as a fragrance, the nitrile compound represented by the formula (I) is represented by C-3 ′ and C— in the formula (I). 2 ′ and one of the bonds between C-2 ′ and C-1 ′ represents a double bond with a dotted line, the bond between C-4 and C-3 represents a single bond, The bond between 3 and C-2 represents a double bond with a dotted line, or both the bonds between C-4 and C-3 and C-3 and C-2 represent a single bond Nitrile compounds are preferred, and in formula (I), one of the bonds between C-3 ′ and C-2 ′ and C-2 ′ and C-1 ′ represents a double bond together with a dotted line, and C More preferred are nitrile compounds in which both the bonds between -4 and C-3 and between C-3 and C-2 are single bonds. That is, in the nitrile compound represented by the formula (I), the bond between C-3 ′ and C-2 ′ represents a double bond together with a dotted line, and C-4, C-3, and C -3 and C-2 both represent a single bond (nitrile compound represented by formula (I-1)), or the bond between C-2 ′ and C-1 ′ is a dotted line And a bond between C-4 and C-3, and a bond between C-3 and C-2 both represent a single bond (nitrile compound represented by formula (I-2) Or more preferred.

[Method for producing nitrile compound represented by formula (I)]
The nitrile compound represented by the formula (I) of the present invention can be synthesized using a general organic chemical reaction, and the production method is not limited. The method for producing the nitrile compound represented by the formula (I) of the present invention includes, for example, a dehydration step of dehydrating the oxime compound represented by the formula (II) to obtain the nitrile compound represented by the formula (I). The method of having is preferable.

In the formulas (I) and (II),
One of the bonds between C-3 ′ and C-2 ′ and C-2 ′ and C-1 ′ represents a double bond with a dotted line;
One of the bonds between C-4 and C-3, and C-3 and C-2 represents a double bond with a dotted line, or C-4 and C-3, and C-3 And the bond between C-2 represents a single bond.

  The oxime compound represented by the formula (II) can be produced by, for example, a step of obtaining a compound represented by the formula (II) by oximation of an aldehyde compound represented by the formula (III). preferable.

In the formulas (II) and (III),
One of the bonds between C-3 ′ and C-2 ′ and C-2 ′ and C-1 ′ represents a double bond with a dotted line;
One of the bonds between C-4 and C-3, and C-3 and C-2 represents a double bond with a dotted line, or C-4 and C-3, and C-3 And the bond between C-2 represents a single bond.

<Dehydration process>
As described above, the production method of the present invention includes a step of dehydrating the oxime compound represented by the formula (II) to obtain the nitrile compound represented by the formula (I).

In the formulas (I) and (II),
One of the bonds between C-3 ′ and C-2 ′ and C-2 ′ and C-1 ′ represents a double bond with a dotted line;
One of the bonds between C-4 and C-3, and C-3 and C-2 represents a double bond with a dotted line, or C-4 and C-3, and C-3 And the bond between C-2 represents a single bond.

  In this step, an acetic anhydride method using acetic anhydride, an alkali catalyst method using alkali, and the like are preferable, and an alkali catalyst method is more preferable from the viewpoint of increasing the yield and purity of the obtained product.

[Acetic anhydride method]
The acetic anhydride method has a step of obtaining a nitrile compound represented by the formula (I) by dehydrating the oxime compound represented by the formula (II) by heating in the presence of acetic anhydride.

  In the acetic anhydride method, the amount of acetic anhydride used is preferably 1.0 to 10 moles compared to the oxime compound represented by the formula (II) from the viewpoint of high yield and ease of post-reaction treatment. 1.0-5 mol times is more preferable, 1.0-3 mol times is further more preferable, and 1.3-2.0 mol times is further more preferable.

  From the viewpoint of efficiently completing the reaction, the reaction temperature is preferably 120 to 200 ° C, more preferably 120 to 180 ° C, and more preferably 120 to 160 ° C where unreacted acetic anhydride and by-produced acetic acid are sufficiently refluxed. preferable.

  Although the reaction can be carried out without solvent, it can also be carried out under reflux using an appropriate amount of a solvent having a boiling point near the preferred reaction temperature from the viewpoint of slow heating.

  The reaction product nitrile compound represented by formula (I) and excess acetic anhydride or by-produced acetic acid are converted into acetate by distillation or neutralization with alkaline water after the reaction, and together with the aqueous layer It can be separated by the removal method.

[Alkaline catalyst method]
The alkali catalyst method has a step of obtaining a nitrile compound represented by the formula (I) by dehydrating the oxime compound represented by the formula (II) by heating in the presence of the alkali catalyst.

  In the alkali catalyst method, an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide is preferably used as the alkali catalyst.

  The amount of the alkali catalyst used is preferably 0.1 to 20% by mass with respect to the oxime compound represented by the formula (II) from the viewpoint of increasing the yield, and 1 to 15% by mass from the viewpoint of reaction operability. More preferred.

  In the alkali catalyst method, it is preferable to carry out the reaction while removing by-product water out of the system. Examples include an azeotropic dehydration method under reflux of the solvent and a continuous dehydration method in which the product is also removed from the reaction system. Among them, from the viewpoint of suppressing thermal decomposition and thermal polymerization of the nitrile compound represented by the formula (I) obtained as a product, the nitrile compound represented by the formula (I) is similarly removed from the reaction system. The method is preferred.

  The reaction temperature in the alkali catalyst method is 80 from the viewpoint of efficiently completing the reaction and suppressing thermal decomposition and thermal polymerization of the oxime compound represented by formula (II) and the nitrile compound represented by formula (I). -250 degreeC is preferable and 120-200 degreeC is more preferable from a viewpoint of a high yield. In this case, it is preferable to carry out under reduced pressure from the viewpoint of efficiently distilling the nitrile compound represented by the formula (I) under a preferable temperature range and suppressing thermal decomposition and thermal polymerization of the product. More preferably.

  Further, from the viewpoint of shortening the residence time of the oxime compound represented by the formula (II) and suppressing side reactions, a method of continuously dropping the oxime compound represented by the formula (II) into the reaction system is preferable. .

  The nitrile compound represented by the formula (I) obtained by any of the methods is preferably further subjected to distillation or silica gel column chromatography purification from the viewpoint of improving the quality more preferable as a perfume material.

  The following is an illustration of a production method for obtaining the oxime compound represented by the formula (II) in the production method of the present invention.

<Oximation process>
For example, an oxime reaction can be performed using an aldehyde compound represented by the formula (III) and hydroxylamine to obtain an oxime compound represented by the formula (II).

In the formulas (II) and (III),
One of the bonds between C-3 ′ and C-2 ′ and C-2 ′ and C-1 ′ represents a double bond with a dotted line;
One of the bonds between C-4 and C-3, and C-3 and C-2 represents a double bond with a dotted line, or C-4 and C-3, and C-3 And the bond between C-2 represents a single bond.

  As a suitable method in this step, a method in which a hydroxylamine aqueous solution is added dropwise to an aldehyde compound represented by formula (III), an aqueous solution of an aldehyde compound represented by formula (III) and an inorganic acid salt of hydroxylamine is mixed. However, there is a method of dropping a base, and among them, a method of dropping a base is preferable when an aldehyde compound represented by the formula (III) and an aqueous solution of an inorganic acid salt of hydroxylamine are mixed. According to this method, there is an advantage that hydroxylamine can be generated in the reaction system by dropping the base, side reactions can be suppressed, and the reaction can be performed safely.

  As an inorganic acid salt of hydroxylamine used in this step, it is preferable to use hydroxylamine sulfate from the viewpoints of suppressing side reactions and economy.

  The use amount of hydroxylamine or its inorganic acid salt is 1.0 to 3.0 mol times with respect to the aldehyde compound represented by the formula (III) in terms of hydroxylamine from the viewpoint of simplicity of post-reaction treatment and economy. Is preferable, 1.0-2.0 mol times is more preferable, and 1.0-1.5 mol times is further more preferable.

  As a base used in a suitable method for dropping the base, a base that is stronger than hydroxylamine is used, and in particular, it is preferably water-soluble. From the economical viewpoint, alkali metal hydroxides such as sodium hydroxide and potassium hydroxide are preferred. From the viewpoint of operability and work efficiency, it is preferable to use a 20 to 40% by mass aqueous solution of an alkali metal hydroxide.

  Although the reaction may be carried out without a solvent, it is preferable to use a solvent from the viewpoint of suppressing the increase in viscosity of the reaction solution accompanying the slow heating and the progress of the reaction. As the solvent, an aldehyde intermediate as a raw material and an aliphatic alcohol that easily dissolves hydroxylamine, water, and the like are preferable. As said aliphatic alcohol, a C1-C3 aliphatic alcohol is preferable and ethanol, isopropyl alcohol, etc. are more preferable. As the solvent, a mixture of an aliphatic alcohol and water is more preferable.

  The reaction temperature is preferably maintained at 30 to 50 ° C. from the viewpoint of efficiently completing the reaction and suppressing exothermic decomposition of hydroxylamine.

  The oxime compound represented by the formula (II), which is a reaction product, can be used in the next reaction as it is after separating the aqueous layer, but the solvent and high-boiling by-products are removed by distillation purification or the like. Is preferably used.

[Perfume composition]
The fragrance composition of the present invention contains a nitrile compound represented by the formula (I). The content of the nitrile compound represented by the formula (I) is preferably 0.01 to 99% by mass, more preferably 0.1 to 15% by mass, and still more preferably 0.3 to 3% by mass in the fragrance composition. %. By containing 0.01 to 99% by mass of the nitrile compound represented by the formula (I), it is possible to impart a woody-floral fragrance having a rich Oris-like sweetness useful as a fragrance to the fragrance composition. it can.

  Since the fragrance composition of the present invention contains the nitrile compound represented by the formula (I), it has a woody-floral fragrance having a rich Oris-like sweetness useful as a fragrance, and other fragrances. It is possible to emphasize floral sweetness. In addition to the nitrile compound represented by the formula (I), the fragrance composition of the present invention contains other commonly used fragrance components and blended fragrances having a desired composition as other fragrances. Aromas such as floral tone, fruity tone, herbal tone, spicy tone, green tone, woody tone, and balsam aroma can be imparted. Therefore, the fragrance composition of the present invention preferably further contains a fragrance other than the nitrile compound represented by the formula (I).

  Examples of other fragrances that can be used in combination with the nitrile compound represented by the formula (I) in the fragrance composition of the present invention include hydrocarbons, alcohols, phenols, aldehydes, ketones, acetals, One or more of ethers, esters, carbonates, lactones, oximes, nitriles, Schiff bases, nitrogen-containing compounds, sulfur-containing compounds, natural essential oils and natural extracts are preferred, among which alcohols, aldehydes From the point of view of emphasizing the floral sweetness of one or more selected from flavours, ketones, ethers, esters, lactones, nitrogen-containing compounds, natural essential oils, and natural extracts by blending with other fragrances. preferable.

  In the present specification, the “class” of each fragrance means a single compound or a mixture of two or more compounds.

  Examples of hydrocarbons include limonene, α-pinene, β-pinene, terpinene, p-cymene, cedrene, longifolene, valencene, camphene and myrcene.

  Examples of alcohols include aliphatic alcohols, terpene alcohols, and aromatic alcohols.

  Examples of the aliphatic alcohol include prenol, trans-2-hexenol, cis-3-hexenol, 2,6-dimethylheptanol, 1-octen-3-ol, 3,6-nonadien-1-ol, 3,6- Nonadieol, Undecabertool (trade name, 4-methyl-3-decen-5-ol), 2,4-dimethyl-3-cyclohexene-1-methanol, isocyclogeraniol, 2-tert-butylcyclohexanol , 4-tert-butylcyclohexanol, Mayol (trade name of Firmenich, 4- (1-methylethyl) -cyclohexanemethanol), Ambercore (trade name of Kao Corporation), Timberol (trade name of Simrise Inc., 1- (2 , 2,6-Trimethylcyclohexyl) hexane-3-ol) Sandal Mysole Core (trade name of Kao Corporation, 2-methyl-4- (2,2,3-trimethyl-3-cyclopenten-1-yl) -2-buten-1-ol), Bacdanol (trade name of IFF, 2-ethyl-4- (2,2,3-trimethyl-3-cyclopenten-1-yl) -2-buten-1-ol), Florosa (trade name of dibodan, 4-methyl-2- (2-methyl) Propyl) tetrahydro-2H-4-pyranol), bacdanol (trade name of IFF, 2-ethyl-4- (2,2,3-trimethylcyclopent-1-yl) -2-buten-1-ol), etc. Can be mentioned. Among these, cis-3-hexenol or florosa is preferable from the viewpoint of enhancing floral sweetness by blending with other fragrances.

  Terpene alcohols include citronellol, hydroxycitronellol, linalool, dihydrolinalol, tetrahydrolinalol, ethyl linalool, geraniol, nerol, tetrahydrogeraniol, myrsenol, dihydromyrcenol, tetrahydromyrsenol, osmenol, terpineol, menthol, borneol, phen Examples include kill alcohol, farnesol, nerolidol, cedrol, and terpineol. Of these, citronellol, linalool or geraniol is preferred from the viewpoint of enhancing floral sweetness by blending with other fragrances.

  Aromatic alcohols include benzyl alcohol, styryl alcohol, phenethyl alcohol, cumin alcohol, dimethylphenyl ethyl carbinol, cinnamic alcohol, phenyl hexanol (trade name of Kao Corporation), Pample Fleur (trade name of IFF, 4-phenyl) Pentanol), magentol (trade name of Simrise Co., Ltd., 2,2-dimethyl-3- (3-methylphenyl) propanol) and the like. Among them, phenethyl alcohol or cinnamic alcohol is preferable from the viewpoint of enhancing floral sweetness by blending with other fragrances.

  Examples of phenols include anethole, guaiacol, eugenol, isoeugenol, and moth synth.

  Examples of the aldehydes include aliphatic aldehydes, terpene aldehydes, aromatic aldehydes and the like, as in the case of the alcohols described above, and all aldehydes obtained by converting only functional groups of the alcohol fragrance components are listed as fragrance components.

  Other aldehydes include aldehyde C-6 (trade name, Kao Corporation, 1-hexanal), aldehyde C-8 (trade name, Kao Corporation, 1-octanal), aldehyde C-9 (trade name, Kao Corporation), 1-nonanal), aldehyde C-10 (trade name of Kao Corporation, 1-decanal), aldehyde C-11 UNDECYL (trade name of Kao Corporation, undecinal), aldehyde C-111 LEN (trade name of Kao Corporation, 10- Undecenal), aldehyde C-12 LAURYL (trade name, 1-dodecanal), aldehyde C-12MNA (trade name, 2-methylundecanal), cis-4-decenal, trans-4-decenal, Floral Super (trade name of IFF, 4,8-dimethyl- 4,9-Decadienal), Polenal II (Kao Corporation trade name, 2-cyclohexylpropanal), Mylacaldehyde (IFF trade name, 4 (3)-(4-methyl-3-penten-1-yl) -3-cyclohexene-1-carboxaldehyde), Lilal (trade name of IFF, 4 (3)-(4-hydroxy-4-methylpentyl) -3-cyclohexene-1-carboxaldehyde), Setonal (trade name of Givadan) , Trimethylcyclohexene methylbutanal), Bernaldehyde (trade name of dibodan, 1-methyl-4- (4-methylpentyl) -3-cyclohexene carboxaldehyde), merozone (trade name of IFF, octahydro-4,7-methano) Indene carboxaldehyde), centenal (Filmenich company) Name, methoxydicyclopentadienecarboxaldehyde), Dupicar (trade name of dibodan, 4-tricyclodecylidenebutanal), Bergamar (trade name of IFF, 3,7-dimethyl-2-methylene-6-octenal), Kanho Renaldehyde, burgeonal (trade name of dibodan, 3- (4-tert-butylphenyl) propanal), cyclamenaldehyde (trade name of dibodan, 3- (4-isopropylphenyl) -2-methylpropionaldehyde), florarozone ( Product name of IFF, 3- (4-ethylphenyl) -2,2-dimethylpropionaldehyde), Szalal (trade name of Takasago International Corporation, 3- (4-isobutylphenyl) -2-methylpropionaldehyde), Lilyal (Gibodan product name, 3- ( -T-butylphenyl) -2-methylpropionaldehyde), amylcinnamic aldehyde (trade name of Kao Corporation), hexylcinnamic aldehyde (trade name of Kao Corporation, 2-n-hexyl-3-phenyl-2-propenal) ), Cantoxal (trade name of IFF, 2-methyl-3- (4-methoxyphenyl) propanal), vanillin, ethyl vanillin, heliotropin (trade name of Takasago International Corporation, 3,4-methylenedioxybenzaldehyde), Helional (trade name of IFF, α-methyl-1,3 benzodioxole-5-propanal), tripral (trade name of IFF, 2,4-dimethyl-3-cyclohexane-1-carboxaldehyde), 2, Examples include 6-nonadienal and 2,6-nonadienol. Among these, heliotropin is preferable from the viewpoint of enhancing floral sweetness by blending with other fragrances.

  As ketones, methyl heptenone, dimethyl octenone, 3-octanone, hexylcyclopentanone, dihydrojasmon, Belton (trade name of Firmenich, 2,2,5-trimethyl-5-pentylcyclopentanone), nectaryl (Dibodan) Trade name, 2- (2- (4-methyl-3-cyclohexen-1-yl) propyl) cyclopentanone), ionone, methylionone, γ-methylionone, damascon, α-damascon, β-damascon, δ-damascon, Isodamascon (trade name of Simrise Co., Ltd., 1- (2,4,4-trimethyl-2-cyclohexyl) -trans-2-butanone), damacenone, Dynascon (trade name of Firmenich, 1- (5,5-dimethyl-1- Cyclohexen-1-yl) -4-pentene-1 ON), Iron, Kashmeran (trade name of IFF, 1,2,3,5,6,7-hexahydro-1,1,2,3,3-pentamethyl-4H-inden-4-one), Iso-E・ Super (trade name of IFF, 1- (1,2,3,4,5,6,7,8-octahydro-2,3,8,8-tetramethyl-2-naphthalenyl) -ethane-1-one ), Karon (trade name of Firmenich, 7-methyl-3,5-dihydro-2H-benzodioxepin-3-one), carvone, menthone, acetyl cedrene, isolongifolanone, nootkatone, benzylacetone, raspberry ketone , Benzophenone, tonalide (trade name of PFW, 6-acetyl-1,1,2,4,4,7-hexamethyltetrahydronaphthalene), β-methylnaphthyl ketone, ethyl Rutor, camphor, muscone, musenone (Firmmenich product, 3-methyl-5-cyclopentadecene-1-one), civeton, globanone (Simrise Corp. trade name, 8-cyclohexadecenone), methylnonyl ketone, cis-jasmon Etc. Of these, ionone, damacenone, iso-e super, or γ-methylionone is preferred from the viewpoint of enhancing floral sweetness by blending with other fragrances.

  Examples of acetals include anthoxan (trade name of Kao Corporation), Boazin Brenforte (trade name of Kao Corporation), Troenan (trade name of Kao Corporation), methylpample mousse (trade name of Givaudan, 1,1-dimethoxy- 2,2,5-trimethyl-4-hexene), acetaldehyde ethyl linalyl acetal, citral dimethyl acetal, hydratropaldehyde dimethyl acetal, verdoxan (trade name, Kao Corporation), fluoropearl (trade name, Simrise Corporation, 2, 4, 6-trimethyl-2-phenyl-1,3-dioxane) and the like.

  Examples of ethers include Herbaval (trade name of Kao Corporation, 3,3,5-trimethylcyclohexyl ethyl ether), Cedryl methyl ether, Ambroxan (trade name of Kao Corporation, [3aR- (3a.α, 5a.β). , 9a.α, 9b.β)] dodecahydro-3a, 6,6,9a-tetramethylnaphtho [2,1-b] furan), Ambrotech (trade name of Kao Corporation, dodecahydro-3a, 6,6, 9a-tetramethylnaphtho [2,1-b] furan), methyl isoeugenol, citronellyl ethyl ether, geranyl ethyl ether, 1,8-cineole, rose oxide, dihydrorose oxide, linalool oxide, estragole, anethole, hinokitiol , Diphenyl oxide, β-naphthol methyl ether, β Naphthol ethyl ether, galaxolide (trade name of IFF, 1,3,4,6,7,8-hexahydro-4,6,6,7,8,8-hexamethylcyclopenta-γ-2-benzopyran) and the like Can be mentioned. Of these, methylisoeugenol is preferred from the viewpoint of enhancing floral sweetness by blending with other fragrances.

  Examples of the esters used as the perfume material include aliphatic carboxylic acid esters, aromatic carboxylic acid esters, and other carboxylic acid esters.

  Examples of the aliphatic carboxylic acid forming the aliphatic carboxylic acid ester include linear and branched carboxylic acids having 1 to 18 carbon atoms, and among them, carboxylic acids having 1 to 6 carbon atoms such as formic acid, acetic acid, propionic acid and the like. Especially, acetic acid is important. Examples of the aromatic carboxylic acid that forms the aromatic carboxylic acid ester include benzoic acid, anisic acid, phenylacetic acid, cinnamic acid, salicylic acid, and anthranilic acid. Examples of alcohols that form aliphatic and aromatic esters include linear and branched aliphatic alcohols having 1 to 5 carbon atoms and the above-described perfume component alcohols.

Examples of other carboxylic acid esters include ethyl safranate (trade name of dibodan, ethyl dihydrocyclogelatin), poilenate (trade name of Kao Corporation, ethyl-2-cyclohexylpropionate), flutate (trade name of Kao Corporation, Ethyltricyclo [5.2.1.0 ^2.6 ] decane-2-carboxylate), methyl jasmonate, MDJ (trade name, methyl dihydrojasmonate, methyl (2-pentyl-3-oxocyclopentyl) acetate) ), Cyclohexyl salicylate (trade name of Kao Corporation) and the like.

  Examples of carbonates include rifarom (trade name of IFF, cis-3-hexenylmethyl carbonate), jasma cyclat (trade name of Kao Corporation), Floramat (trade name of Kao Corporation), and the like.

  Examples of lactones include γ-nonalactone, γ-decalactone, δ-decalactone, jasmolactone (trade name of Firmenich, tetrahydro-6- (3-hexenyl) -2H-pyran-2-one), γ-undecalactone. , Coumarin, Octahydrocoumarin, Florex (Filmenich company name, 6-ethylideneoctahydro-5,8-methano-2H-1-benzopyran-2-one), Cyclopentadecanolide, Habanolide (Filmenig company name 12 (11) -oxacyclohexadecene-2-one), ambretlide (trade name of IFF, 10-octacycloheptadecen-2-one), ethylene brushate, and the like. Among these, cyclopentadecanolide is preferable from the viewpoint of enhancing floral sweetness by blending with other fragrances.

  Examples of the oximes include buccoxime (trade name of Simrise Co., Ltd., 1,5-dimethyl-bicyclo [3,2,1] octane-8-one oxime), rabioxime (trade name of Dibodan Co., 2,4,4,7-tetramethyl). -6,8-nonadiene-3-one oxime), 5-methyl-3-heptanone oxime and the like.

  Examples of nitriles include dodecane nitrile, citronellyl nitrile, cuminyl nitrile, cinnamyl nitrile, pionyl (trade name of dibodan, 2-cyclohexylidene-2-phenylacetonitrile), and the like.

  Schiff bases include auranthiol (trade name of dibodan, N- (3,7-dimethyl-7-hydroxyoctylidene) -methyl anthranilate), ligantoral (trade name of dibodan, 3,5-dimethyl-3). -Methyl cyclohexen-1-yl-methylene anthranilate), methyl 2-[(2-methylundecylidene) amino] benzoate, and the like.

  Examples of the nitrogen-containing compound include amides, pyrroles, indoles, and thiazoles. Of these, indoles are preferred from the viewpoint of enhancing floral sweetness by blending with other fragrances.

  Examples of amides include garamide (trade name of dibodan, N, 2-dimethyl-N-phenylbutyramide), paradiseamide (trade name of dibodan, 2-ethyl-N-methyl-N- (3-methylphenyl) butanamide. ) And the like.

  Examples of the sulfur-containing compound include thiols, sulfides, thiophenes, and thiocarboxylic acids.

  Natural essential oils and extracts include orange, lemon, lime, bergamot, pettigren, vanilla, mandarin, peppermint, spearmint, lavender, camomil, rosemary, eucalyptus, sage, basil, rose, rock rose, geranium, jasmine, iran Iran, anise, clove, ginger, nutmeg, cardamom, cedar, cypress, vetiver, patchouli, lemongrass, lovedanum, galvanum, olivenum and the like. Among them, ylang ylang is preferred from the viewpoint of emphasizing the floral sweetness by blending with other fragrances.

  The content of these other fragrances can be appropriately selected depending on the kind of the blended fragrance, the type of the target fragrance, the intensity of the fragrance, and the like, and preferably 0.0001 to 99.99 in the fragrance composition. It is 99 mass%, More preferably, it is 0.001-80 mass%, Preferably it is 5-99.99 mass% in total in a fragrance | flavor composition, More preferably, it is 50-99.9 mass%.

  The fragrance composition of the present invention can contain an oil agent that does not have an odor as a base for containing the nitrile compound represented by the formula (I) of the present invention and other fragrance materials. Such an oil agent can mix a fragrance | flavor component uniformly, is easy to mix | blend with a product, and can make it easy to perfume the intensity | strength of moderate intensity | strength. Examples of the oil include polyhydric alcohols such as ethylene glycol, propylene glycol, butylene glycol and dipropylene glycol, esters such as isopropyl myristate, dibutyl adipate and diethyl sebacate, hydrocarbons such as liquid paraffin and squalane, poly Surfactants such as oxyethylene alkyl ether and sorbitan fatty acid ester can be used.

  Among these, from the viewpoint of solubility of all the perfume ingredients, the oil agent is preferably a polyhydric alcohol and an ester, and more preferably dipropylene glycol and isopropyl myristate. The content of the oil is preferably 0.01 to 95% by mass, more preferably 1 to 90% by mass, and further preferably 5 to 80% by mass in the fragrance composition.

  In addition to the odor of the nitrile compound represented by the formula (I), the fragrance composition of the present invention is mixed with another fragrance to give a woody-floral fragrance having a rich Oris-like sweetness. There is also an effect that it can be done. Such a fragrance composition can be suitably used, for example, for perfume such as a detergent composition, a fiber treatment composition, and a cosmetic.

[Use as perfuming ingredients]
The fragrance composition containing the nitrile compound represented by the formula (I) of the present invention is given a woody-floral fragrance having an Oris-like rich sweetness, and is further blended with other fragrances, It can be used as a flavoring ingredient in various products as a blended fragrance having a preferable fragrance that can emphasize sweetness. Therefore, the present invention provides a method of using a nitrile compound represented by the formula (I) as a fragrance component, preferably a nitrile compound represented by the formula (I) as a fragrance composition, a detergent composition, and a cosmetic. Or it is the method of using as a fragrance | flavor component of a fiber treatment composition. The compound is used alone or in combination with other ingredients in the base of toiletries such as soaps, cosmetics, hair cosmetics, detergents, softeners, spray products, fragrances, perfumes, bathing agents, etc. be able to.

  Among them, the nitrile compound represented by the formula (I) of the present invention has a high persistence, and by blending with other fragrances, it has a woody-floral fragrance with a rich Oris-like sweetness. Since it is the use which can be provided, it is more preferable to use it for a cleaning composition, cosmetics, and a fiber treatment composition as a fragrance | flavor component, and it is still more preferable to use for a cleaning composition.

Therefore, this invention also provides the detergent composition containing the fragrance composition of this invention, the cosmetics containing the fragrance composition of this invention, and the fiber treatment composition containing the fragrance composition of this invention.
As the cleaning composition of the present invention, a body cleaning composition, a clothing cleaning composition, and a hard surface cleaning composition are preferable, and a body cleaning composition and a clothing cleaning composition are more preferable. Further, a cleaning composition for clothing is more preferable.

  Examples of the body cleaning composition include a skin cleaning composition, a hair cleaning composition, and a soap composition, and a skin cleaning composition is preferred.

  Examples of the hard surface cleaner composition include an all-purpose cleaner and a dish cleaner composition.

  As the fiber treatment composition of the present invention, a softener composition is preferable.

  A perfume is preferable as the cosmetic of the present invention.

  In addition to the fragrance composition containing the nitrile compound represented by the formula (I) of the present invention, the cleaning composition of the present invention preferably contains an anionic surfactant, and further a nonionic surfactant. , PH adjusting agents, viscosity adjusting agents, solvents, oil agents, preservatives, water and the like can be blended.

  The fiber treatment composition of the present invention preferably contains a cationic surfactant in addition to the fragrance composition containing the nitrile compound represented by the formula (I) of the present invention. Oils, preservatives, water and the like can be blended.

  In addition to the fragrance composition containing the nitrile compound represented by the formula (I) of the present invention, the perfume of the present invention can be mixed with a solvent, water and the like.

  As described above, the nitrile compound represented by the formula (I) has a woody-floral fragrance with a rich Oris-like sweetness, and is further blended with other fragrances to give a floral sweetness. Can be emphasized. Therefore, this invention is a method of using the nitrile compound represented by Formula (I) as a fragrance | flavor component of a fragrance | flavor composition, a cleaning composition, cosmetics, or a fiber treatment composition as mentioned above. As the cleaning composition, a body cleaning composition, a clothing cleaning composition, and a hard surface cleaning composition are preferable, a body cleaning composition and a clothing cleaning composition are more preferable, and clothing. More preferred is a detergent composition. Examples of the body cleaning composition include a skin cleaning composition, a hair cleaning composition, and a soap composition, and a skin cleaning composition is preferred. Examples of the hard surface cleaner composition include a multipurpose cleaner and a dish cleaner composition. As the cosmetic, perfume is preferable. As the fiber treatment composition, a softener composition is preferable.

  In the method to be used, the nitrile compound represented by the formula (I) is preferably 0.01 to 99% by mass, more preferably 0.1 to 50% by mass, and still more preferably, with respect to the entire fragrance composition. Used in an amount of 0.3 to 25% by mass. By using the nitrile compound represented by the formula (I) in an amount of 0.01 to 99% by mass, it is possible to impart a woody-floral fragrance having a rich Oris-like sweetness to the fragrance composition. it can.

  In the method to be used, the nitrile compound represented by the formula (I) is preferably 0.01 to 99% by mass, more preferably 0.1% with respect to the cleaning composition, cosmetic or softener composition. It is used in an amount of ˜50 mass%, more preferably 0.3 to 25 mass%. By using the nitrile compound represented by the formula (I) in an amount of 0.01 to 99% by mass, a woody composition having a rich Oris-like sweetness to a detergent composition, a cosmetic or a softener composition A floral fragrance can be imparted.

  In the method to be used, the fragrance composition using the nitrile compound represented by the formula (I) as a fragrance component may contain an oil agent that does not itself have an odor. About the said oil agent, it is the same as that of what was demonstrated in the said fragrance | flavor composition. Moreover, in the said method to be used, the fragrance | flavor composition which uses the nitrile compound represented by Formula (I) as a fragrance | flavor component normally uses as other fragrance | flavors other than the nitrile compound represented by Formula (I). It may also contain other perfume ingredients that are prepared and blended perfumes of the desired composition. Such other fragrances are the same as those described in the fragrance composition.

  In the method used, the cleaning composition, cosmetic or softener composition using the nitrile compound represented by formula (I) as a perfuming component may contain an oil agent that does not have an odor itself. Good. About the said oil agent, it is the same as that of what was demonstrated in the said fragrance | flavor composition. In the method used, the cleaning composition, cosmetic or softener composition using the nitrile compound represented by the formula (I) as a perfuming component, other than the nitrile compound represented by the formula (I) In addition, as other fragrances, other commonly used fragrance components and blended fragrances having a desired composition may be included. Such other fragrances are the same as those described in the fragrance composition.

  In relation to the above-described embodiment, the present invention further discloses a nitrile compound represented by the formula (I) and a method for producing the nitrile compound represented by the formula (I).

<1> A nitrile compound represented by the formula (I).

[In the above formula,
One of the bonds between C-3 ′ and C-2 ′ and C-2 ′ and C-1 ′ represents a double bond with a dotted line;
One of the bonds between C-4 and C-3, and C-3 and C-2 represents a double bond with a dotted line, or C-4 and C-3, and C-3 And the bond between C-2 represents a single bond. ]

<2> In formula (I), one of the bonds between C-3 ′ and C-2 ′ and C-2 ′ and C-1 ′ represents a double bond together with a dotted line,
The bond between C-4 and C-3 represents a single bond, and the bond between C-3 and C-2 represents a double bond with a dotted line, or C-4 and C-3, and The nitrile compound according to <1>, wherein both of the bonds between C-3 and C-2 represent a single bond.

<3> In formula (I), one of the bonds between C-3 ′ and C-2 ′ and C-2 ′ and C-1 ′ represents a double bond together with a dotted line,
The nitrile compound according to <1> or <2>, wherein both of the bonds between C-4 and C-3 and C-3 and C-2 represent a single bond.

  <4> A fragrance composition containing the nitrile compound according to any one of <1> to <3>.

  <5> The content of the nitrile compound represented by the formula (I) is 0.01 to 99% by mass, preferably 0.1 to 15% by mass, more preferably 0.3 to 3% by mass in the fragrance composition. % Of the fragrance composition according to <4>.

  <6> The fragrance composition according to <4> or <5>, further containing a fragrance other than the nitrile compound according to any one of <1> to <3>.

  <7> Perfumes other than the nitrile compounds are hydrocarbons, alcohols, phenols, aldehydes, ketones, acetals, ethers, esters, carbonates, lactones, oximes, nitriles, Schiff bases <6> The fragrance composition according to <6>, which contains at least one selected from the group consisting of nitrogen, a nitrogen-containing compound, a sulfur-containing compound, a natural essential oil, and a natural extract.

  <8> A cleaning composition containing the fragrance composition according to any one of <4> to <7>.

  <9> Cosmetics containing the fragrance composition according to any one of <4> to <7>.

  <10> A fiber treatment composition containing the fragrance composition according to any one of <4> to <7>.

  <11> A method of using the nitrile compound according to any one of <1> to <3> as a flavoring component.

  <12> A method of using the nitrile compound represented by the formula (I) as a fragrance component of a fragrance composition, a detergent composition, a cosmetic or a fiber treatment composition.

  <13> The nitrile compound represented by the formula (I) is preferably 0.01 to 99% by mass, more preferably, relative to the entire fragrance composition, cleaning composition, cosmetic or fiber treatment composition. The method according to <12>, which is used in an amount of 0.1 to 50% by mass, more preferably 0.3 to 25% by mass.

  <14> A method for producing a nitrile compound represented by formula (I), comprising a dehydration step of dehydrating an oxime compound represented by formula (II) to obtain a nitrile compound represented by formula (I).

[In the above formulas (I) and (II),
One of the bonds between C-3 ′ and C-2 ′ and C-2 ′ and C-1 ′ represents a double bond with a dotted line;
One of the bonds between C-4 and C-3, and C-3 and C-2 represents a double bond with a dotted line, or C-4 and C-3, and C-3 And the bond between C-2 represents a single bond. ]

  <15> The production method according to <14>, wherein the dehydration step is performed by an acetic anhydride method using acetic anhydride or an alkali catalyst method using an alkali.

  <16> The method according to <15>, wherein the acetic anhydride method includes a step of dehydrating the oxime compound represented by the formula (II) by heating in the presence of acetic anhydride to obtain a nitrile compound represented by the formula (I). Manufacturing method.

  <17> The amount of acetic anhydride used is preferably 1.0 to 10 moles, more preferably 1.0 to 5 moles, and even more preferably 1.0 to the oxime compound represented by the formula (II). The production method according to <16>, which is ˜3 mol times, more preferably 1.3 to 2.0 mol times.

  <18> The oxime compound represented by formula (II) is obtained by performing an oximation reaction using an aldehyde compound represented by formula (III) and hydroxylamine. The manufacturing method in any one.

In the formulas (II) and (III),
One of the bonds between C-3 ′ and C-2 ′ and C-2 ′ and C-1 ′ represents a double bond with a dotted line;
One of the bonds between C-4 and C-3, and C-3 and C-2 represents a double bond with a dotted line, or C-4 and C-3, and C-3 And the bond between C-2 represents a single bond.

  <19> A method in which the oximation is a method in which a hydroxylamine aqueous solution is dropped into an aldehyde compound represented by formula (III), or an inorganic acid salt of aldehyde compound and hydroxylamine represented by formula (III) (preferably hydroxylamine) The production method according to <18>, which is performed by a method in which a base (preferably an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide) is added dropwise to an aqueous solution of sulfate.

  <20> The amount of hydroxylamine or its inorganic acid salt used is preferably 1.0 to 3.0 moles, more preferably 1. mol times relative to the aldehyde compound represented by formula (III) in terms of hydroxylamine. The production method according to <19>, which is 0 to 2.0 mol times, more preferably 1.0 to 1.5 mol times.

  Details of the measurement methods performed in the following Examples and Comparative Examples are summarized below.

Details of the measurement methods performed in the following production examples are summarized below.
[Conversion rate and reaction yield]
The conversion rates and reaction yields shown in the following production examples were determined by internal standard method gas chromatography (GC) quantitative analysis.
<Gas chromatography apparatus and analysis conditions>
GC device: manufactured by HEWLWTT PACKARD, model: HP6850
Column: J & W, DB-1 (inner diameter 0.25 mm, length 30 m, film thickness 0.25 μm)
Carrier gas: He, 1.5 mL / min
Injection conditions: 280 ° C., split ratio 1/100
Detection condition: FID method, 280 ° C
Column temperature condition: 100 ° C. → 6 ° C./min temperature rise → 300 ° C. 10 min hold Internal standard compound: n-dodecane

[Identification of compounds]
Each compound obtained in the following production examples includes a Fourier transform infrared spectrophotometer (manufactured by Horiba, Ltd., model: FT-710), and a gas chromatograph mass (GC-MS) analyzer (manufactured by Shimadzu, model). : GC-2010). Measurement conditions and the like are described in each measurement result.

[Odor evaluation]
The incense tone and strength were determined by the odor paper method by two skilled workers who have experience in fragrance and fragrance evaluation work for 5 years or more and less than 10 years and 3 skilled workers for 25 years or more. About 5 mm of the tip of odor paper (fragrance test paper having a width of 6 mm and a length of 150 mm) was immersed in the sample and evaluated.

  As for aroma, the scents (main fragrances) that are mainly felt are listed in order from those that are felt more strongly, and the scents (secondary aromas) that are secondarily felt are added.

  The odor intensity was expressed as a relative evaluation with 0 being odorless and 5 being very strong.

  [Production Example 1] (Production of 2-methyl-4- (2,6,6-trimethyl-2 (1) -cyclohexen-1-yl) butanal oxime)

  In a 200 mL flask, 39 g of 2-methyl-4- (2,6,6-trimethyl-2 (1) -cyclohexen-1-yl) butanal (trade name Setonal, dibodan, pure content 37 g, 0.18 mol), isopropyl 30 g of alcohol, 20 g of hydroxylamine sulfate (0.12 mol, 0.67 mol times relative to aldehyde, 1.34 mol times in terms of hydroxylamine) and 40 g of ion-exchanged water were added in this order, and the mixture was stirred at 45 ° C. under a nitrogen atmosphere. Heated. While maintaining the reaction temperature at 40 to 50 ° C., 32 g (0.24 mol) of 30% by mass aqueous sodium hydroxide solution was added dropwise over 30 minutes, and heating and stirring were continued for 1 hour. After cooling the reaction solution to room temperature, the aqueous layer was extracted with a stationary layer, the organic layer was washed with a 10% by mass sodium sulfate aqueous solution, and isopropyl alcohol was distilled off to obtain 43 g of a yellow liquid crude product. As a result of gas chromatography quantitative analysis of the crude product, the conversion of 2-methyl-4- (2,6,6-trimethyl-2 (1) -cyclohexen-1-yl) butanal was 100%, and 2-methyl- The purity of 4- (2,6,6-trimethyl-2 (1) -cyclohexen-1-yl) butanal oxime was 83%, and the crude yield was 90%.

  Note that 2-methyl-4- (2,6,6-trimethyl-2 (1) -cyclohexen-1-yl) butanal is 2-methyl-4- (2,6,6-trimethyl-2-cyclohexene- 1-yl) butanal and 2-methyl-4- (2,6,6-trimethyl-1-cyclohexen-1-yl) butanal, a mixture of 2-methyl-4- (2,6,6-trimethyl- 2 (1) -Cyclohexen-1-yl) butanal oxime is composed of 2-methyl-4- (2,6,6-trimethyl-2-cyclohexen-1-yl) butanal oxime and 2-methyl-4- ( 2,6,6-trimethyl-1-cyclohexen-1-yl) butanal oxime.

30 g of this crude product was purified by distillation under reduced pressure to obtain a colorless liquid distilled at 96-100 ° C./27 Pa. The purity of 4,8-dimethyl-4,9-decadienal oxime was 95%.
GC-MS analysis of this distillate fraction revealed that 2-methyl-4- (2,6,6-trimethyl-2 (1) -cyclohexen-1-yl) butanal oxime was a mixture of four diastereomers. It was confirmed that.

The measurement results of each spectrum analysis and aroma evaluation are shown below.
(1) MS (EI method); m / z: 223 (M ⁺ ), 206, 190, 177, 162, 149, 134, 121, 107, 95, 81, 55, 41.
(2) FT-IR (neat); cm ⁻¹ : 3226 (br), 2960, 2913, 2868, 2364, 2330, 1657, 1454, 1377, 939.
(3) Fragrance: (Main fragrance) Woody, (Sub fragrance) Camphor, Floral.
(4) Odor intensity: 3.

  [Example 1] (Production of 2-methyl-4- (2,6,6-trimethyl-2 (1) -cyclohexen-1-yl) butanenitrile)

  In a 200 mL flask, 30 g of 2-methyl-4- (2,6,6-trimethyl-2 (1) -cyclohexen-1-yl) butanal oxime (crude product of Production Example 1, pure content 25 g, 0.11 Mol), 75 g of toluene and 17 g of acetic anhydride (0.17 mol, 1.55 mol times the oxime compound) were added and stirred, and the mixture was refluxed for 2 hours under a nitrogen atmosphere. Subsequently, a mixture of toluene, acetic anhydride and acetic acid was distilled off, and the reaction solution was cooled to room temperature and then neutralized with a dilute aqueous sodium hydroxide solution. After adding 30 g of ethyl acetate, the aqueous layer was extracted with a stationary layer, and the organic layer was further washed twice with a 10% by mass aqueous sodium sulfate solution. The ethyl acetate was distilled off to obtain 29 g of a colorless liquid crude product. As a result of quantitative gas chromatographic analysis of the crude product, conversion of 2-methyl-4- (2,6,6-trimethyl-2 (1) -cyclohexen-1-yl) butanal oxime was 100%, The purity of methyl-4- (2,6,6-trimethyl-2 (1) -cyclohexen-1-yl) butanenitrile was 76%, and the crude yield was 96%.

  Note that 2-methyl-4- (2,6,6-trimethyl-2 (1) -cyclohexen-1-yl) butanal oxime is 2-methyl-4- (2,6,6-trimethyl-2- A mixture of cyclohexen-1-yl) butanal oxime and 2-methyl-4- (2,6,6-trimethyl-1-cyclohexen-1-yl) butanal oxime, 2-methyl-4- (2, 6,6-Trimethyl-2 (1) -cyclohexen-1-yl) butanenitrile is composed of 2-methyl-4- (2,6,6-trimethyl-2-cyclohexen-1-yl) butanenitrile and 2-methyl It is a mixture of -4- (2,6,6-trimethyl-1-cyclohexen-1-yl) butanenitrile.

  25 g of this crude product was purified by distillation under reduced pressure to obtain a colorless liquid distilled at 82 ° C./40 Pa. The purity of 2-methyl-4- (2,6,6-trimethyl-2 (1) -cyclohexen-1-yl) butanenitrile was 98%. GC-MS analysis of this distillation fraction showed that 2-methyl-4- (2,6,6-trimethyl-2 (1) -cyclohexen-1-yl) butanenitrile was a mixture of two diastereomers. I confirmed that there was.

The measurement results of each spectrum analysis are shown below.
(1) MS (EI method); m / z: 205 (M ⁺ ), 190, 177, 162, 149, 134, 121, 107, 95, 81, 67, 55, 41.
(2) FT-IR (neat); cm ⁻¹ : 2954, 2868, 2362, 2339, 2239, 1664, 1454, 1383, 818.

  [Production Example 2] (Production of 2-methyl-4- (2,6,6-trimethylcyclohexen-1-yl) -2-butenal oxime)

  To a 500 mL flask, 65 g of 2-methyl-4- (2,6,6-trimethylcyclohexen-1-yl) -2-butenal (trade name Boronal, Simrise Co., Ltd., 62 g, 0.30 mol), 65 g of isopropyl alcohol, 27 g of hydroxylamine sulfate (0.16 mol, 0.55 mol times the aldehyde, 1.1 mol times in terms of hydroxylamine) and 50 g of ion-exchanged water were added in that order, and the mixture was heated to 45 ° C. with stirring under a nitrogen atmosphere. . While maintaining the reaction temperature at 40 to 50 ° C., 46 g (0.35 mol) of a 30% by mass aqueous sodium hydroxide solution was added dropwise over 1 hour, and the stirring was continued for 1 hour. After cooling the reaction solution to room temperature, the aqueous layer was extracted with a stationary layer, the organic layer was washed with a 10 mass% aqueous sodium sulfate solution, and isopropyl alcohol was distilled off to obtain 71 g of a crude product as a yellow liquid. As a result of gas chromatography quantitative analysis of the crude product, the conversion of 2-methyl-4- (2,6,6-trimethylcyclohexen-1-yl) -2-butenal was 100%, and 2-methyl-4- ( The purity of 2,6,6-trimethylcyclohexen-1-yl) -2-butenal oxime was 89%, and the crude yield was 95%.

The measurement results of each spectrum analysis are shown below.
(1) MS (EI method); m / z: 221 (M ⁺ ), 204, 188, 173, 161, 146, 123, 98, 81, 67, 55, 41.
(2) FT-IR (neat); cm ⁻¹ : 3290 (br), 2925, 2866, 2364, 1633, 1468, 1360, 947.

  [Example 2] (Production of 2-methyl-4- (2,6,6-trimethylcyclohexen-1-yl) -2-butenenitrile)

  In a 500 mL flask, 60 g of 2-methyl-4- (2,6,6-trimethylcyclohexen-1-yl) -2-butenal oxime (crude product of Production Example 1, pure content 53 g, 0.24 mol) Toluene 140 g was added and stirred under a nitrogen atmosphere. The acetic anhydride 28g (0.27 mol, 1.13 mol times with respect to an oxime compound) was dripped here over 15 minutes, and also it was made to recirculate | reflux for 1 hour. Subsequently, a mixture of toluene, acetic anhydride and acetic acid was distilled off, and the reaction solution was cooled to room temperature and then neutralized with a dilute aqueous sodium hydroxide solution. After adding 50 g of ethyl acetate, the aqueous layer was extracted with a stationary layer, and the organic layer was further washed twice with a 10% by mass aqueous sodium sulfate solution. Ethyl acetate was distilled off to obtain 60 g of a red liquid crude product. As a result of gas chromatography quantitative analysis of the crude product, the conversion of 2-methyl-4- (2,6,6-trimethylcyclohexen-1-yl) -2-butenal oxime was 100%, and 2-methyl- The purity of 4- (2,6,6-trimethylcyclohexen-1-yl) -2-butenenitrile was 69%, and the crude yield was 84%.

  50 g of this crude product was purified by distillation under reduced pressure to obtain a pale yellow liquid distilled at 129 to 131 ° C./133 Pa. The purity of 2-methyl-4- (2,6,6-trimethylcyclohexen-1-yl) -2-butenenitrile was 90%.

The measurement results of each spectrum analysis are shown below.
(1) MS (EI method); m / z: 203 (M ⁺ ), 188, 173, 160, 146, 123, 108, 93, 81, 67, 53, 41.
(2) FT-IR (neat); cm ⁻¹ : 2927, 2866, 2364, 2215, 1768, 1629, 1468, 1362, 1201, 935.

[Aroma evaluation result of fragrance composition containing nitrile compound and setneral or boronal obtained in Examples 1 and 2]
The nitrile compound obtained in Example 1 was dissolved in dipropylene glycol at a concentration of 90% by mass to prepare a fragrance composition, and then fragrance evaluation was performed by the fragrance evaluation method. Instead of the nitrile compound obtained in Example 1, each composition was obtained using the nitrile compound obtained in Example 2, Setonal (manufactured by Givaudan) or boronal (manufactured by Simrise). Aroma evaluation was performed on each of the obtained compositions. The obtained results are shown in Table 1.

  The fragrance composition containing the nitrile compound of the formula (I) of the present invention was different in sweetness from the fragrance compositions containing other compounds of Comparative Examples 1 and 2, and had a rich sweetness.

[Examples 3 and 4 and Comparative Example 3] (Perfume composition for body cleaner)
2-methyl-4- (2,6,6-trimethyl-2 (1) -cyclohexen-1-yl) butanenitrile obtained in Example 1 and 2-methyl-4-obtained in Example 2 Using (2,6,6-trimethylcyclohexen-1-yl) -2-butenenitrile, a fragrance was prepared so as to have the composition shown in Table 2, and a fragrance composition was obtained.

In the table,
Florosa is a product name of Dibodan, 4-methyl-2- (2-methylpropyl) tetrahydro-2H-4-pyranol,
Heliotropin is a trade name of Takasago International Corporation, 3,4-methylenedioxybenzaldehyde,
MDJ is a trade name of Kao Corporation, methyl dihydrojasmonate, methyl (2-pentyl-3-oxocyclopentyl) acetate.

The evaluation was performed in the same manner as the fragrance evaluation. Compared with the fragrance composition of Comparative Example 3, the fragrance composition of Example 3 had a stronger floral-green fragrance and a more violet-like fragrance.
The fragrance composition of Example 4 was stronger in floral aroma and violet-like sweetness than the fragrance composition of Comparative Example 3.

[Example 5 and Comparative Examples 4 and 5] (Perfume composition for soap)
Using 2-methyl-4- (2,6,6-trimethylcyclohexen-1-yl) -2-butenenitrile obtained in Example 2, the fragrance was added so as to have the composition shown in Table 3. A fragrance composition was obtained by blending.

In the table,
Vaccanol is a trade name of IFF, 2-ethyl-4- (2,2,3-trimethylcyclopent-1-yl) -2-buten-1-ol,
Florosa is a product name of Dibodan, 4-methyl-2- (2-methylpropyl) tetrahydro-2H-4-pyranol,
Heliotropin is a trade name of Takasago International Corporation, 3,4-methylenedioxybenzaldehyde,
Iso-Esuper is a trade name of IFF, 1- (1,2,3,4,5,6,7,8-octahydro-2,3,8,8-tetramethyl-2-naphthalenyl) -ethane- 1-on,
MDJ is a trade name of Kao Corporation, methyl dihydrojasmonate, methyl (2-pentyl-3-oxocyclopentyl) acetate.

  The evaluation was performed in the same manner as the fragrance evaluation. Compared with the fragrance composition of Comparative Example 4, the fragrance composition of Example 5 was enhanced in sweetness and powdery feeling of a rose-like floral fragrance and at the same time added a volume to the scent. Compared with the fragrance composition of Comparative Example 4, the fragrance composition of Comparative Example 5 had a rose-like floral fragrance and a fruit-like fragrance.

  Since the nitrile compound of the present invention has a woody-floral fragrance having a rich Oris-like sweetness useful as a fragrance, it can be used as a fragrance material. Furthermore, it is highly sustainable. Moreover, the nitrile compound of this invention can also emphasize floral sweetness by mix | blending with another fragrance | flavor. From the above, the fragrance composition containing the nitrile compound of the present invention can be used as a fragrance component.

Claims (10)

A nitrile compound represented by the formula (I).

[In the above formula,
One of the bonds between C-3 ′ and C-2 ′ and C-2 ′ and C-1 ′ represents a double bond with a dotted line;
The bond between C-4 and C-3 represents a single bond, and the bond between C-3 and C-2 represents a double bond with a dotted line, or C-4 and C-3, and Both bonds between C-3 and C-2 represent a single bond . ] In formula (I), one of the bonds between C-3 ′ and C-2 ′ and C-2 ′ and C-1 ′ represents a double bond together with a dotted line,
The nitrile compound according to claim 1 , wherein both the bond between C-4 and C-3, and C-3 and C-2 represent a single bond. A fragrance composition containing the nitrile compound according to claim 1 . The fragrance | flavor composition of Claim 3 which further contains fragrance | flavors other than the nitrile compound of Claim 1 or 2 . Perfumes other than the nitrile compounds include hydrocarbons, alcohols, phenols, aldehydes, ketones, acetals, ethers, esters, carbonates, lactones, oximes, nitriles, Schiff bases, The fragrance | flavor composition of Claim 4 containing 1 or more types among a nitrogen compound, a sulfur-containing compound, natural essential oil, and a natural extract. A cleaning composition containing the fragrance composition according to claim 3 . Cosmetics containing the fragrance composition according to any one of claims 3 to 5 . The fiber processing composition containing the fragrance | flavor composition in any one of Claims 3-5 . A method of using the nitrile compound according to claim 1 as a perfuming component. A method for producing a nitrile compound represented by formula (I), comprising a dehydration step of dehydrating an oxime compound represented by formula (II) to obtain a nitrile compound represented by formula (I).

[In the above formulas (I) and (II),
One of the bonds between C-3 ′ and C-2 ′ and C-2 ′ and C-1 ′ represents a double bond with a dotted line;
The bond between C-4 and C-3 represents a single bond, and the bond between C-3 and C-2 represents a double bond with a dotted line, or C-4 and C-3, and Both bonds between C-3 and C-2 represent a single bond. ]