JP2000226353A - 4-vinyl-8-methyl-7-nonenal, its production and perfume composition containing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject novel compound that is high diffusive and has a strong aliphatic aldehyde-like smell and is useful as a perfume having both of citrus-like and rose-like smells by catalytically forming a carbon-carbon bond. SOLUTION: This novel compound is 4-vinyl-8-methyl-7-nonenal represented by formula I. The compound of formula I is prepared, for example, by allowing myrcene of formula II to react with a vinyl carboxylate ester of formula III [R is H, a 1-4C alkyl, a (1-4C lower alkyl-substituted) phenyl, or the like] in the presence of a ruthenium catalyst [for example, of formula IV (R1-R5 are each H, a 1-4C lower alkyl, two groups adjacent to R1-R5 bond to each other to form 5-6-membered ring; W is 1,3-butadiene, isoprene, myrcene, norbornadiene or the like; X1 is a halogen) in a hydrophilic solvent and subjecting the resultant 1-acyloxy-4-vinyl-8-methyl-1,7-nonadienyl of formula V to hydrolysis.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to 4-vinyl-8-methyl-7-nonenal useful as a perfume material, a method for producing the same, and a perfume composition containing the same.
4-vinyl-8-methyl-7- provided by the present invention
Nonenal has a strong aliphatic aldehyde-like scent, has a citrus-like or rose-like scent, and can be used for perfuming cosmetics.

[0002]

2. Description of the Related Art Aliphatic aldehydes are useful as a fragrance material, and many aldehydes have been produced and actually used (Motoichi Indo, Synthetic fragrance (chemistry and product knowledge), Chemical Industry). Nipponsha 1996). For example, melonal is widely used as a melon-like green fragrance, citral is a lemon-like fragrance, and citronellal is a hawthorn-like unique fragrance.

[0003] Not only aldehydes, the odor of the compound is completely different due to a slight difference in the structure, and its properties such as retention and volatilization are generally changed. Therefore, synthesizing a large number of compounds and studying their odors are extremely important to obtain new fragrances.

As a method for synthesizing a chain terpene compound such as an aliphatic aldehyde for efficiently producing a carbon-carbon bond from butadiene or substituted butadiene, a Diels-Alder reaction (B. M.
Trost et al., Angew. Chem. Int. Ed.
Engl., 1995, 34, 259) and a triple bond (T. Mitsudo et al., J. Org. Chem.,
1985, 50, 565).

[0005] However, all of these methods have the drawback that activation of a conjugated double bond or the other substrate is necessary, and regioselectivity cannot be controlled. Also,
In these methods, the obtained compound may be cyclic, and in this case, there is a problem that it is disadvantageous from the viewpoint of synthesis of a chain terpene.

On the other hand, in a carbon-carbon bond formation reaction in the synthesis of a chain terpene compound, an organometallic reagent has been widely used, and a desired skeleton has been selectively constructed (Japanese Patent Laid-Open No. 3-148228). . However, this method uses a stoichiometric amount of inconvenient organometallics and requires a leaving group, a functional group that is not involved in the actual structure. Was also disadvantageous. Therefore, development of a novel carbon-carbon bond formation reaction that does not require a leaving group and proceeds catalytically is desired.

[0007]

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to find a novel carbon-carbon bond forming reaction which proceeds catalytically, and by utilizing this, a new and useful compound as a fragrance material and a process for producing the same. And a perfume composition containing the compound.

[0008]

Means for Solving the Problems The inventors of the present invention have conducted intensive studies on a novel carbon-carbon bond forming reaction which proceeds catalytically, and found that the myrcene (3) represented by the following formula (3) is Similarly, when a vinyl carboxylate compound represented by the following general formula (4) is reacted by a low polymerization reaction, that is, a so-called codimerization reaction, 1-acyloxy-4-vinyl-8 represented by the following general formula (2) is obtained. -Methyl-1,7
-Nonadienyl, which can be further hydrolyzed to give the following formula (1)

Embedded image 4-vinyl-8-methyl-7-nonenal represented by the following formula:

Further, the present inventors have found that this is a novel fragrance which is rich in diffusivity, has a strong aliphatic aldehyde-like scent, and has a citrus-like and rose-like scent, and completed the present invention.

That is, the present invention provides 4-vinyl-8-methyl-7-nonenal represented by the above formula (1).

[0011] The present invention also provides a fragrance composition containing 4-vinyl-8-methyl-7-nonenal represented by the above formula (1) as an active ingredient.

Further, the present invention provides the following formula (3)

Embedded image And the following equation (4)

Embedded image Wherein R is a hydrogen atom, a lower alkyl group having 1 to 4 carbon atoms, a phenyl group or a naphthyl group which may have a lower alkyl group having 1 to 4 carbon atoms, and a vinyl carboxylate represented by the formula: Is reacted in a hydrophilic solvent in the presence of a ruthenium compound to obtain a compound represented by the following general formula (2)

Embedded image (Wherein, R is a hydrogen atom, a lower alkyl group having 1 to 4 carbon atoms, a phenyl group which may have a lower alkyl group having 1 to 4 carbon atoms, or a naphthyl group)
Formula (1), which is characterized in that it is converted to acyloxy-4-vinyl-8-methyl-1,7-nonadienyl and then hydrolyzed.

Embedded image And a method for producing 4-vinyl-8-methyl-7-nonenal represented by the formula:

The present invention further relates to a ruthenium compound represented by the following general formula (5):

Embedded image(Where R¹, R², R³, R⁴And R⁵Respectively
Same or different hydrogen atom or 1 to 4 carbon atoms
Represents a lower alkyl group;¹, R², R³, R ⁴as well as
R⁵Two adjacent groups are bonded to form a 5- or 6-membered ring
W is 1,3-butadiene, isoprene,
Lucene, 1,5-cyclooctadiene, norbornadie
2,3-dimethyl-1,3-butadiene or halogen
X represents an atom¹Represents a halogen atom)
4-vinyl-8-methyl using a ruthenium catalyst
Method for producing -7-nonenal (1) and conversion to ruthenium
As a compound, the following general formula (6)

Embedded image(Where R⁶, R⁷, R⁸, R⁹, R¹⁰And R¹¹
Are the same or different and are each a hydrogen atom or carbon
Represents a lower alkyl group of Formulas 1 to 4,⁶, R ⁷, R
⁸, R⁹, R¹⁰And R¹¹Two adjacent groups are bonded
X to form a 5- or 6-membered ring; X¹Is a halogen field
Indicates a child; R¹²And R¹³Are hydrogen atom and charcoal, respectively.
A lower alkyl group having 1 to 4 primes, a cycle having 5 to 7 carbon atoms
A loalkyl group, a lower alkyl group having 1 to 4 carbon atoms or
Is a phenyl group optionally substituted with a halogen atom,
Represents a phenyl group or a benzyl group;¹²And R¹³And
Together form an alkylene group having 3 to 6 carbon atoms;
R¹⁴Is a hydrogen atom, a lower alkyl having 1 to 4 carbon atoms
A cycloalkyl group having 5 to 7 carbon atoms,
Lower alkyl group, lower alkyl group having 1 to 4 carbon atoms or
Is a phenyl group optionally substituted with a halogen atom or
A naphthyl group; n is 0 to 1)
A ruthenium compound and the following general formula (7)

Embedded image ^{M (X 2) a (7} ) [ wherein, M is an alkali metal, alkaline earth metal, ammonium, silver, aluminum, lanthanum, mono samarium, shows a di- or trications acids; ^{X 2} is , ClO
_{^{4 -1, BF 4 -1, PF}} 6 -1, BPh 4 -1 ( where Ph represents a phenyl ^{_{group), CF 3 SO 2 O -1}} , C
_{^{H 3 SO 2 O -1, C}} 4 H 9 SO 2 O -, C 6 H 5 SO
_{^{2 O -1, 4-CH 3}} C 6 H 4 SO 2 O -1, 4-Cl
A represents an anion such as C ₆ H ₄ SO ₂ O- ¹ ;
Is 1 when M is a monocation, 2 when M is a dication, and 3 when M is a trication.] The above-mentioned 4-vinyl-8- using a ruthenium catalyst formed by mixing with a salt represented by the formula: It is intended to provide a method for producing methyl-7-nonenal (1).

[0014]

BEST MODE FOR CARRYING OUT THE INVENTION The 4-vinyl-8-methyl-7-nonenal (1) of the present invention is a novel compound.
Naturally, there is no report on the aroma characteristics of -vinyl-8-methyl-7-nonenal (1), and there is no report on its use as a fragrance composition.

The reaction for producing the 4-vinyl-8-methyl-7-nonenal (1) of the present invention is as follows. That is, according to the following formula, myrcene (3) and a vinyl carboxylate compound of the general formula (4) are subjected to a low polymerization reaction, that is, a so-called codimerization reaction in a hydrophilic solvent in the presence of a ruthenium catalyst, and 1-Acyloxy-4-vinyl-8-methyl-1,7-nonadienyl represented by the formula (2) is then hydrolyzed to give 4-vinyl-8-methyl- represented by the formula (1). Produce 7-nonenal.

[0016]

(Equation 1) (In the formula, R is a hydrogen atom, a lower alkyl group having 1 to 4 carbon atoms, a phenyl group which may have a lower alkyl group having 1 to 4 carbon atoms, or a naphthyl group.)

In the vinyl carboxylate compound of the general formula (4), which is a starting material of the present invention, R has a hydrogen atom, a lower alkyl group having 1 to 4 carbon atoms, and a lower alkyl group having 1 to 4 carbon atoms. And a phenyl or naphthyl group. Among them, specific examples of the lower alkyl group having 1 to 4 carbon atoms include methyl, ethyl, propyl, butyl, isobutyl, sec-butyl, tert-butyl and the like. Examples of the lower alkyl group having 1 to 4 carbon atoms in the phenyl group or naphthyl group which may have a lower alkyl group having 1 to 4 carbon atoms include:
Methyl, ethyl, propyl, butyl, isobutyl, se
Examples thereof include c-butyl, tert-butyl and the like.

Preferred examples of the vinyl carboxylate compound represented by the general formula (4) include vinyl acetate,
Examples include vinyl butyrate, vinyl pivalate, and vinyl benzoate.

Further, 1-acyloxy-4-vinyl-8-methyl- of the general formula (2) obtained as an intermediate of the present invention.
In 1,7-nonadienyl, R is a hydrogen atom, a lower alkyl group having 1 to 4 carbon atoms, a phenyl group which may have a lower alkyl group having 1 to 4 carbon atoms, or a naphthyl group.

As a preferred specific example, 1-acyloxy-4-vinyl-8-methyl- represented by the general formula (2)
As 1,7-nonadienyl, 1-acetoxy-4-
Vinyl-8-methyl-1,7-nonadienyl, 1-propionyloxy-4-vinyl-8-methyl-1,7-nonadienyl, 1-butyryloxy-4-vinyl-8-methyl-1,7-nonadienyl, 1 -Pivaloyloxy-
4-vinyl-8-methyl-1,7-nonadienyl, 1-
Benzoyloxy-4-vinyl-8-methyl-1,7-
Nonadienyl and the like.

The intermediate of the present invention, 1-
Asiloxy-4-vinyl-8-methyl-1,7-nonadienyl is obtained by converting myrcene (3) with a vinyl carboxylate compound of the general formula (4) in the presence of a ruthenium catalyst in the presence of a ruthenium catalyst as described above. It is produced by a co-dimerization reaction in a hydrophilic solvent.

In the production of 1-acyloxy-4-vinyl-8-methyl-1,7-nonadienyl (2), the vinyl carboxylate compound (4) is usually used in an amount of 0.05 to 5 equivalents per equivalent of myrcene (3). 50 equivalents, preferably 0.1 to 10 equivalents may be reacted.

The amount of the ruthenium compound used in this reaction is 0.1 mol per mol of myrcene (3).
About 001 to 50 mol%, preferably 0.8 to 1 mol%.
It is about 0 mol% equivalent.

The above reaction is carried out usually at a temperature of about 0 to 200 ° C., preferably at a temperature of about 70 to 120 ° C., usually for 1 hour.
The reaction is completed in about 72 hours, preferably about 5 hours to 24 hours, but these conditions can be appropriately changed depending on the amounts of the reactants, ruthenium compound, and the like used. In addition, this reaction usually proceeds in an atmosphere of an inert gas such as nitrogen gas or argon gas, but may be performed in a gas atmosphere of a starting material. This reaction can be carried out both in a batch system and in a continuous system.

The hydrophilic solvent used in the above reaction may be any inert solvent which does not participate in the reaction, such as water, lower alcohols such as methanol, ethanol, propanol, isopropanol and butanol, dimethylformamide, and the like. A hydrophilic solvent such as amides such as dimethylacetamide, dimethylimidazolidinone, and N-methylpyrrolidone, or a mixed solvent thereof can be suitably used. Among these, preferred are
Examples include methanol, ethanol, and hydrous ethanol. The amount of the hydrophilic solvent used is usually 0.1 to 25 times the volume, preferably 0.8 to 1 part by weight of myrcene (3).
3 times the capacity.

After completion of the reaction, the reaction mixture is treated in a conventional manner, and the resulting mixture is distilled to obtain 1-acyloxy-4-vinyl-8-methyl-1,7-nonadienyl (2) as an intermediate. I can do it.

The above 1-acyloxy-4-vinyl-
In the method for producing 8-methyl-1,7-nonadienyl (2), a ruthenium compound is used. A preferable example thereof is the following general formula (5)

Embedded image(Where R¹, R², R³, R⁴And R⁵Respectively
Same or different hydrogen atom or 1 to 4 carbon atoms
Represents a lower alkyl group;¹, R², R³, R ⁴as well as
R⁵Two adjacent groups are bonded to form a 5- or 6-membered ring
W is 1,3-butadiene, isoprene,
Lucene, 1,5-cyclooctadiene, norbornadie
2,3-dimethyl-1,3-butadiene or halogen
X represents an atom¹Represents a halogen atom)
Ruthenium catalysts.

Another preferred example of the ruthenium compound is a compound represented by the following general formula (6):

Embedded image(Where R⁶, R⁷, R⁸, R⁹, R¹⁰And R¹¹
Are the same or different and are each a hydrogen atom or carbon
Represents a lower alkyl group of Formulas 1 to 4,⁶, R ⁷, R
⁸, R⁹, R¹⁰And R¹¹Two adjacent groups are bonded
X1 is a halogen atom
Indicates a child; R¹²And R¹³Are hydrogen atom and charcoal, respectively.
A lower alkyl group having 1 to 4 primes, a cycle having 5 to 7 carbon atoms
A loalkyl group, a lower alkyl group having 1 to 4 carbon atoms or
Is a phenyl group optionally substituted with a halogen atom,
Represents a phenyl group or a benzyl group;¹²And R¹³And
Together form an alkylene group having 3 to 6 carbon atoms;
R¹⁴Is a hydrogen atom, a lower alkyl having 1 to 4 carbon atoms
A cycloalkyl group having 5 to 7 carbon atoms,
Lower alkyl group, lower alkyl group having 1 to 4 carbon atoms or
Is a phenyl group optionally substituted with a halogen atom or
A naphthyl group; n is 0 to 1)
A ruthenium compound and the following general formula (7)

Embedded image M (X²) A (7) wherein M is an alkali metal, an alkaline earth metal,
, Silver, aluminum, lanthanum, samarium, etc.
X represents a mono, di or trication;²Is ClO
₄ ^-1, BF₄ ^-1, PF₆ ^-1, BPh₄ ^-1(here
And Ph represents a phenyl group), CF₃SO₂O^-1, C
H₃SO₂O^-1, C₄H₉SO ₂O^-, C₆H₅SO
₂O^-1, 4-CH₃C₆H₄SO₂O^-1, 4-Cl
C ₆H₄SO₂O^-1A represents M;
Is 1 when is a monocation, and when M is a dication
2, when M is a trication, it is 3].
Ruthenium catalyst formed by mixing with salts
You.

Further, the general formula (5) used in the above reaction
In the ruthenium catalyst of the formula, one of the ligands represented by the following general formula (8)

Embedded image (Wherein R ¹ , R ² , R ³ , R ⁴ and R ⁵ have the above-mentioned meanings) of R ¹ , R ² , R ³ ,
Specific examples of R ⁴ and R ⁵ include a hydrogen atom, methyl,
Examples thereof include lower alkyl groups having 1 to 4 carbon atoms such as ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl and tert-butyl.

Preferred specific examples of the ligand (8) include:
Cyclopentadienyl, tetramethylcyclopentadienyl, pentamethylcyclopentadienyl, indenyl and the like can be mentioned.

The group W in the general formula (5) is
1,3-butadiene, isoprene, myrcene, 1,5-cyclooctadiene, norbornadiene, 2,3-dimethyl-1,3-butadiene, a halogen atom (here, examples of the halogen atom include fluorine, chlorine, bromine, And iodine). Further, the group X1 in the general formula (5) is a halogen atom, and examples thereof include fluorine, chlorine, bromine and iodine.

Specific examples of the ruthenium compound of the general formula (5) include the following. Note that “η ^m ” in the following compound names means that the number of coordinating atoms is m. For example, in the case of “η ⁶ ”, the number of coordinating atoms is 6.

[0033] (eta ⁵ - cyclopentadienyl) ruthenium dichloride (III) (η ⁵ - cyclopentadienyl) ruthenium bromide (II
I) (η ⁵ - cyclopentadienyl) (eta ^{4-1,3-butadiene)} ruthenium chloride (II) (η ⁵ - cyclopentadienyl) (eta ⁴ - isoprene)
Ruthenium (II) (eta ⁵ - cyclopentadienyl) (eta ⁴ - myrcene) ruthenium chloride (II) (eta ⁵ - cyclopentadienyl) (eta ^{4-1,5-cyclooctadiene)} ruthenium chloride (II ) (eta ⁵ - cyclopentadienyl) (eta ⁴ - norbornadiene) ruthenium chloride (II) (eta ⁵ - cyclopentadienyl) (eta ^{4-2,3-dimethyl-1,3-butadiene)} ruthenium chloride (II ) (eta ⁵ - pentamethyl cyclopentadienyl) ruthenium chloride (III) (η ⁵ - pentamethylcyclopentadienyl) dibromide ruthenium (III) (η ⁵ - pentamethylcyclopentadienyl) (eta ⁴ −
1,3-butadiene) ruthenium chloride (II) (η ⁵ - pentamethylcyclopentadienyl) (eta ⁴ -
Isoprene) ruthenium (II) (η ⁵ - pentamethylcyclopentadienyl) (eta ⁴ -
Myrcene) ruthenium (II) (η ⁵ - pentamethylcyclopentadienyl) (eta ⁴ -
1,5-cyclooctadiene) ruthenium chloride (II) (η ⁵ - pentamethylcyclopentadienyl) (eta ⁴ -
Norbornadiene) ruthenium (II) (η ⁵ - pentamethylcyclopentadienyl) (eta ⁴ -
2,3-dimethyl-1,3-butadiene) ruthenium (II) chloride

The ruthenium compound of the general formula (5) is described in the literature (K. Masuda et al., Organometa).
llics, 1993, vol. 12, p. 2221, and the Chemical Society of Japan, "4th Ed. Experimental Chemistry Course", vol. 18, organometallic complex, 1991, Maruzen, p. 269) and a method analogous thereto. Can be.

[0035] For example, (eta ⁵ - pentamethylcyclopentadienyl) (eta ⁴ - isoprene) ruthenium chloride (I
I) can be synthesized by the following method. That is, pentamethylcyclopentadienyl ruthenium chloride dimer (III) and 1 equivalent of zinc powder were mixed at 0 ° C. with methanol (100 times the volume of the ruthenium complex).
And add 30 equivalents of isoprene. After the reaction for 15 minutes, the solid matter was filtered off, and the obtained solution was concentrated to obtain a crude product, which was recrystallized from ethanol to give (η
^5- Pentamethylcyclopentadienyl) (η ⁴ -isoprene) ruthenium (II) chloride can be prepared.

[0036] The above method, (eta ⁵ - pentamethylcyclopentadienyl) (eta ⁴ - isoprene) which can be utilized as well in order to obtain a ruthenium compound of the general formula other than ruthenium chloride (II) (5) It is.

In addition, one of the ligands in the ruthenium compound of the general formula (6) used in the present reaction, the following general formula (9)

Embedded image (Wherein, R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ and R ¹¹
Has the meaning described above).
Specific examples of R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ and R ¹¹ include a hydrogen atom, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, te
and lower alkyl groups such as rt-butyl.

Preferred specific examples of the ligand (9) include:
Benzene, p-cymene, mesitylene, hexamethylbenzene and the like can be mentioned.

Further, one of the ligands of the ruthenium compound represented by the general formula (6), the following formula (10)

Embedded image (Wherein, R ¹² , R ¹³ , R ¹⁴ and n have the above-mentioned meanings). Specific examples of the groups R ¹² and R ¹³ include a hydrogen atom, a carbon number of 1 to 4
A lower alkyl group (e.g., methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl and the like), a cycloalkyl group having 5 to 7 carbon atoms (e.g., cyclopentyl, cyclohexyl,
A lower alkyl group having 1 to 4 carbon atoms or a phenyl group which may be substituted with a halogen atom (here, examples of the lower alkyl group having 1 to 4 carbon atoms include methyl, ethyl, propyl, isopropyl) , Butyl, isobutyl, sec-butyl, tert-butyl and the like are examples of halogen atoms such as fluorine, chlorine, bromine,
Iodine and the like), a lower alkyl group having 1 to 4 carbon atoms or a naphthyl group which may be substituted with a halogen atom (here, examples of the lower alkyl group having 1 to 4 carbon atoms and a halogen atom are the same as those described above) ), A benzyl group which may be substituted with a lower alkyl group having 1 to 4 carbon atoms or a halogen atom (here, examples of the lower alkyl group having 1 to 4 carbon atoms and a halogen atom are the same as those described above). R ¹² and R ¹³ may together form an alkylene group having 3 to 6 carbon atoms (here, examples of the alkylene group having 3 to 6 carbon atoms include:
1,3-propylene, 1,4-butylene, 1,5-pentylene, 1,6-hexylene, etc.).

[0040] Specific examples of the group ^{R 14} in the ligand (10) is a hydrogen atom, a lower alkyl group having 1 to 4 carbon atoms (e.g., methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec- butyl , Tert-butyl, etc.), a cycloalkyl group having 5 to 7 carbon atoms (eg, cyclopentyl, cyclohexyl, cycloheptyl, etc.),
A halogenated lower alkyl group (for example, trifluoromethyl, trichloromethyl, etc.), a lower alkyl group having 1 to 4 carbon atoms or a phenyl group optionally substituted with a halogen atom (here, a lower alkyl group having 1 to 4 carbon atoms) Examples of are: methyl, ethyl, propyl, isopropyl,
Butyl, isobutyl, sec-butyl, tert-butyl and the like are examples of the halogen atom such as fluorine, chlorine, bromine and iodine), a lower alkyl group having 1 to 4 carbon atoms or a halogen atom. And a naphthyl group (here, examples of a lower alkyl group having 1 to 4 carbon atoms and a halogen atom are the same as described above).

Specific examples of preferred ligands (10) include N-2-aminoethyl-methanesulfonamide,
-2-aminoethyl-benzenesulfonamide, N-2
-Aminoethyl-p-toluenesulfonamide, N-2
-Aminoethyl-trifluoromethanesulfonamide,
N-2-aminoethyl-trichloromethanesulfonamide, N-3-aminopropyl-methanesulfonamide,
N-3-aminopropyl-benzenesulfonamide, N
-3-aminopropyl-p-toluenesulfonamide,
N-3-aminopropyl-trifluoromethanesulfonamide, N-3-aminopropyl-trichloromethanesulfonamide, N-2-amino-1,2-dimethylethyl-methanesulfonamide, N-2-amino-1,2 −
Dimethylethyl-benzenesulfonamide, N-2-amino-1,2-dimethylethyl-p-toluenesulfonamide, N-2-amino-1,2-dimethylethyl-trifluoromethanesulfonamide, N-2-amino-
1,2-dimethylethyl-trichloromethanesulfonamide, N-2-amino-1,2-diphenylethyl-methanesulfonamide, N-2-amino-1,2-diphenylethyl-benzenesulfonamide, N-2- Amino-1,2-diphenylethyl-p-toluenesulfonamide, N-2-amino-1,2-diphenylethyl-trifluoromethanesulfonamide, N-2-amino-
1,2-diphenylethyl-trichloromethanesulfonamide, 2-methanesulfonylamino-cyclohexylamine, 2-benzenesulfonylamino-cyclohexylamine, 2-p-toluenesulfonylamino-cyclohexylamine, 2-trifluoromethanesulfonylamino-cyclohexylamine , 2-trichloromethanesulfonylamino-cyclohexylamine and the like.

X ¹ in the compound (6) is a halogen atom, and specific examples thereof include fluorine, chlorine, bromine,
Iodine and the like can be mentioned.

Specific examples of the ruthenium compound of the general formula (6) include the following. Note that the following “η ^m ” means that the number of coordinating atoms is m. For example, in the case of “η ⁶ ”, the number of coordinating atoms is 6.

(N-2-aminoethyl-p-toluenesulfonamide) (η ⁶ -benzene) ruthenium chloride (I
I) (N-2-aminoethyl-p-toluenesulfonamide) (η ⁶ -p-cymene) ruthenium chloride (II) (N-2-aminoethyl-p-toluenesulfonamide) (η ⁶ -mesitylene) chloride Ruthenium (II) (N-2-aminoethyl-p-toluenesulfonamide) (η ⁶ -benzene) Ruthenium (II) bromide (N-2-aminoethyl-p-toluenesulfonamide) (η ⁶ -p- (Cymene) ruthenium (II) bromide (N-2-aminoethyl-p-toluenesulfonamide) (η ⁶ -mesitylene) ruthenium (II) bromide

The ruthenium compound of the general formula (6) can be produced by a known method (for example, WO97 / 20789) or a method analogous thereto.

For example, (N-2-aminoethyl-p-toluenesulfonamide) (η ⁶ -benzene) ruthenium (II) chloride can be synthesized by the following method. That is, (η ⁶ -benzene) ruthenium (II) dichloride and 1 equivalent of N-2-aminoethyl-p-toluenesulfonamide are heated and stirred at 80 ° C. with isopropanol, and concentrated and washed with water. , (N-
2-aminoethyl-p-toluenesulfonamide) (η
⁶ -benzene) ruthenium (II) chloride can be prepared.

The above method comprises the steps of (N-2-aminoethyl-
It can be similarly used to obtain a ruthenium compound of the general formula (6) other than (p-toluenesulfonamide) (η6-benzene) ruthenium (II) chloride.

On the other hand, salts represented by the above general formula (7)
Is a ruthenium compound together with a ruthenium compound of the general formula (6)
To form a catalyst. In the general formula (7), M is
Lucari metal, alkaline earth metal, ammonium, silver, aluminum
Luminium, lanthanum, samarium, etc.
Trications, for example, Li⁺, Na
⁺, K⁺, Mg²⁺, Ca²⁺, NH⁴⁺, Ag⁺, A
l³⁺, La³⁺, Sm ³⁺And the like. Also, X
²Are anions, and specific examples thereof include ClO₄
⁻, BF₄ ⁻, PF₆ ⁻, BPh₄ ⁻(Ph is phenyl
Represents a group), CF ₃SO₂O^-, CH₃SO₂O^-, C₄
H₉SO₂O^-, C₆H₅SO₂O^-, 4-CH₃C₆H
₄SO₂O^-, 4-ClC₆H₄SO₂O^-Etc.
Can be.

Specific examples of the salts of the general formula (7) include silver triflate (CF ₃ SO ₂ OAg), potassium nonaflate (C ₄ H ₉ SO ₂ OK), lanthanum triflate [(CF ₃ SO ₂ O ) ₃ La], samarium triflate [(CF ₃ SO ₂ O) ₃ Sm], ammonium triflate (CF ₃ SO ₂ ONH ₄ ), and the like. As the salts (7), commercially available products can be used as they are.

In order to form a ruthenium catalyst from the ruthenium compound represented by the general formula (6) and the salts represented by the general formula (7), these may be mixed in an appropriate reaction system. The amount of the salt represented by the general formula (7) is usually about 0.5 to 10 equivalents, preferably 1.0 to 1.0 equivalent to 1 equivalent of the ruthenium compound represented by the general formula (6). It is about 3.0 equivalents.

In the above-mentioned method for producing 1-acyloxy-4-vinyl-8-methyl-1,7-nonadienyl (2), a ruthenium compound is produced instead of using a ruthenium compound prepared in advance as a catalyst. It is also possible to add the starting materials for the reaction separately to the reaction system and carry out the reaction.

The thus obtained 1-acyloxy-
4-vinyl-8-methyl-1,7-nonadienyl (2)
In the above, the double bond may be any of a cis-form, a trans-form or a mixture of a cis-form and a trans-form, and is preferably a cis-form.

The objective compound of the present invention, 4-vinyl-8
-Methyl-7-nonenal (1) is 1-acyloxy-
4-vinyl-8-methyl-1,7-nonadienyl (2)
Can be easily obtained by hydrolysis. As a specific hydrolysis method, 1-acyloxy-4-vinyl-
8-Methyl-1,7-nonadienyl (2) is heated and stirred in an acidic aqueous solution such as aqueous sulfuric acid, aqueous hydrochloric acid and / or aqueous acetic acid, or 1-acyloxy-4-vinyl-8-methyl-
There is a method of heating 1,7-nonadienyl (2) in an aqueous alkali solution such as sodium hydroxide as needed.

The acidic aqueous solution used in the production of 4-vinyl-8-methyl-7-nonenal (1) includes:
Examples thereof include mineral acids such as sulfuric acid and hydrochloric acid, and organic acids such as acetic acid. These can be used alone or as a mixture of two or more. Examples of the aqueous alkaline solution include sodium hydroxide, potassium hydroxide, barium hydroxide, and the like, and one or more of these can be used as appropriate. The concentration of these acidic and alkaline aqueous solutions can be appropriately adjusted and used depending on the reaction, but preferably 1 to 30 equivalent% for mineral acids, about 1 to 5 equivalents for organic acids, and 1 to 5 equivalents for alkali. It is about equivalent.

The above reaction is carried out usually at a temperature of about 20 to 120 ° C., preferably at a temperature of about 30 to 100 ° C., usually for 1 hour.
The reaction is completed for about 72 to 72 hours, preferably about 5 to 24 hours, but these conditions can be appropriately changed depending on the amount of the reactants used and the aqueous acidic and alkaline solutions. In addition, this reaction usually proceeds in an atmosphere of an inert gas such as nitrogen gas or argon gas, but may be performed in a gas atmosphere of a starting material. This reaction can be carried out both in a batch system and in a continuous system.

The solvent used in the above reaction may be any inert solvent which does not participate in the reaction, for example, water, lower alcohols such as methanol, ethanol, propanol, isopropanol and butanol, tetrahydrofuran, dimethylformamide and dimethylacetamide. ,
Solvents such as amides such as dimethylimidazolidinone and N-methylpyrrolidone or a mixed solvent thereof can be suitably used. Among them, preferable examples include methanol, ethanol, tetrahydrofuran and the like. The amount of the hydrophilic solvent used is usually 0.1 to 25 times the volume, preferably 0.8 to 1 part by weight of 1-acyloxy-4-vinyl-8-methyl-1,7-nonadienyl (2). 3 times the capacity.

After completion of the reaction, the mixture is treated in a conventional manner, and the resulting mixture is distilled to obtain the desired 4-vinyl-8-methyl-7-nonenal (1).

The 4-vinyl-8- of the formula (1) according to the present invention
Methyl-7-nonenal, as shown in the Examples below,
Rich in diffusivity, strong aliphatic aldehyde-like aroma, citrus-like, rose-like. When diluted, it becomes a sweet and milky l-citronellol-like scent, so that it can be used for general purposes such as raw materials for preparation such as melon and cucumber, as well as citrus type and floral green type.

Further, in the present invention, 4-vinyl-8-methyl-7-nonenal (1) alone or a fragrance composition further added with other fragrance components which can be generally used can be used as the fragrance component. Other fragrances that can be added and used include, for example, Arcstander
S., "Perfume and Flavor Che
medicals ", published by the
author, Montclair, NJ (US
A) A wide range of perfume ingredients as described in 1969 can be used. As a typical one,
α-pinene, limonene, cis-3-hexenol, phenylethyl alcohol, styryl acetate, eugenol, rose oxide, linalool, benzaldehyde and the like.

The amount of the 4-vinyl-8-methyl-7-nonenal (1) of the present invention to be added to the fragrance composition may be appropriately determined according to the type and purpose of the prepared fragrance, and is not particularly limited. Usually, 10 ppm to 10% by weight of the whole is preferable. The flavor composition of the present invention can be appropriately blended with various blended flavors and flavoring bases according to the purpose.

The fragrance composition containing 4-vinyl-8-methyl-7-nonenal (1) of the present invention is a fragrance containing the fragrance composition as a fragrance component, various fragrances, cosmetics, health and hygiene materials, etc. Can be provided. That is, air fresheners such as deodorants and indoor air fresheners; cleaning cosmetics such as soaps, shampoos, and rinses; hair cosmetics such as hair dyes and hair nourishes; Makeup cosmetics such as cosmetics, foundations and blushers, aromatic cosmetics such as perfumes, tanning, sunscreen cosmetics, lip cosmetics such as lipsticks, lip balms, oral cosmetics such as toothpaste and mouthwash, various cosmetics such as bath cosmetics; disinfectants Health and hygiene materials such as insecticides; bleaching agents, softeners, dishwashing detergents, etc., by adding an appropriate amount capable of imparting the flavor to enhance their commercial value.

[0062]

The present invention will be described below in detail with reference to comparative examples and examples, but the present invention is not limited to these examples, and may be changed without departing from the scope of the present invention. Good. In addition, the measurement in an Example was performed on the following analytical instruments and conditions unless there is particular limitation.

(Analytical Instruments and Conditions) Gas Chromatography (GLC) Equipment: HP5890 Series II Gas Chromatograph (Hewlett Packard) Column: Neutrabond-1 (0.25 mm × 3)
0 m × 0.4 μm) (manufactured by GL Sciences Inc.) Detector: FID Nuclear magnetic resonance spectrum ( ¹ H-NMR) Equipment: GEMINI 2000 (1H, 200 MH)
z) (Varian) ・ Infrared absorption spectrum (IR) Equipment: FTIR-8200PC (manufactured by JASCO Corporation) Measurement method: film

[0064] Reference Example 1 (eta ⁵ - pentamethylcyclopentadienyl) (η ⁴ -
Synthesis of norbornadiene) ruthenium (II) chloride:
(Eta ⁵ - pentamethyl cyclopentadienyl) ruthenium (II) chloride dimer 270mg of (0.44 mmol as monomer) advance was suspended in ethanol 10 ml, thereto Norubonarujien 3 ml (24.5 mm
ol), heat to 70 ° C. and stir for 1 hour.
After returning the reaction solution to room temperature, it is concentrated under reduced pressure and purified through an alumina column. The yellow band was collected and the solvent was distilled off to give a yellow-yellow solid.

Recrystallization from diethyl ether, - [0065] This chloroform to give a - - (norbornadiene eta ⁴⁾ ruthenium (II) 0.256 g (77% yield) (eta ⁵ pentamethylcyclopentadienyl) . Various spectral data of this substance agreed with the literature values.

Example 1 1-Pivaloyloxy-4-vinyl-8-methyl-1,
Synthesis of 7-nonadienyl: 14.6 mg (0.040) of (η5-pentamethylcyclopentadienyl) (η4-norbornadiene) ruthenium (II) chloride obtained in Reference Example 1
mmol), 1.5 ml of myrcene (78%, 6.9 mmol)
l), 1.5 ml (10 mmol) of vinyl pivalate and 2 ml of methanol at 100 ° C. under an argon atmosphere.
For 15 hours. The reaction solution was diluted with water, the organic layer was separated, concentrated, and distilled to obtain 0.75 g (yield 41%) of the title compound (adduct) as a pure product.

Boiling point: 110 ° C./0.5 mmHg ¹ H-NMR (200 MHz, CDCl ₃ ): δ 1.25 (9H, s), 1.2 to 1.6 (2H, m), 1.58
(3H, s), 1.68 (3H, s), 1.9-2.4 (5H,
m), 4.7-5.2 (4H, m), 5.6 (1H, ddd, J
= 8.0, 11.0, 16.0 Hz), 7.03 (1H, dm,
J = 6.4 Hz) Gas chromatography analysis: Measurement temperature 60 ° C. to 16
0 ° C (heating at 5 ° C / min), then 160 ° C to 250 ° C
(The temperature is raised at a rate of 10 ° C./min.) Retention time = 25.9 minutes (25.9 minutes, 94% purity. Isomer 26.6 minutes)

Example 2 Synthesis of 1-acetoxy-4-vinyl-8-methyl-1,7-nonadienyl: (η ⁵ -pentamethylcyclopentadienyl) (η ⁴ -norbornadiene) obtained in Reference Example 1.
Ruthenium (II) chloride 30 mg (0.079 mmol
l), Milsen 10ml (purity 78%, 46mmo)
l), 10 ml (109 mmol) of vinyl acetate and 15 ml of methanol were heated and stirred at 70 ° C. for 23 hours in an argon atmosphere. The reaction solution was diluted with water, and the organic layer was separated, concentrated and distilled to obtain 4.8 g (yield: 47%) of the title compound (adduct) as a pure product.

Boiling point: 110 ° C./0.5 mmHg ¹ H-NMR (200 MHz, CDCl ₃ ): δ 1,2-1.6 (2H, m), 1.58 (3H, s), 1.68
(3H, s), 1.9 to 2.4 (5H, m), 2.18 (3H,
s), 4.7-5.2 (4H, m), 5.60 (1H, ddd,
J = 8.0, 11.0, 16.0 Hz), 7.03 (1H, d
m, J = 6.4 Hz) Gas chromatography analysis: Measurement temperature 60 ° C. to 16
0 ° C (heating at 5 ° C / min), then 160 ° C to 250 ° C
(The temperature is raised at a rate of 10 ° C./min.) Retention time = 23.1 minutes (23.1 minutes, 96% purity; isomer 23.9 minutes)

Reference Example 2 Synthesis of (N-2-aminomethyl-p-toluenesulfonamide) (η ⁶ -benzene) ruthenium (II) chloride: (η ⁶ -benzene) ruthenium (II) dichloride
5 g (10 mmol) and 2.14 g (10 mmol) of N-2-aminomethyl-p-toluenesulfonamide were heated and stirred at 80 ° C. for 4 hours together with 80 ml of isopropanol. This is concentrated and washed with water to give (N-
2-aminomethyl-p-toluenesulfonamide) (η
4 g of ⁶ -benzene) ruthenium (II) chloride (yield 9
3%). Various spectral data agreed with literature values.

Example 3 1-pivaloyloxy-4-vinyl-8-methyl-1,
Synthesis of 7-nonadienyl: (N-2-a) obtained in Reference Example 2.
Minomethyl-p-toluenesulfonamide) (η ⁶−
Senzen) ruthenium (II) chloride 23.7 mg (0.05
5 mmol) and 17.5 mg (0.06) of silver triflate.
8 mmol) in 2 ml of methanol.
Myrcene 2 ml (purity 78%, 1.25 g, 9.2 mm
ol) and 1.73 g (13 mmol) of vinyl pivalate
Was added and stirred at 70 ° C. for 6 hours. The reaction mixture with water
By diluting and analyzing the organic layer by gas chromatography.
With 17% conversion and 76% purity (26% regioisomer)
The formation of the title compound (adduct) was confirmed.
Was.

Example 4 Synthesis of 4-vinyl-8-methyl-7-nonenal from 1-acetoxy-4-vinyl-8-methyl-1,7-nonadienyl: 1-acetoxy-4 obtained in Example 2 4.8 g of vinyl-8-methyl-1,7-nonadienyl (21.6
mmol) was dissolved in 10 ml of methanol, 2 ml of 20% sulfuric acid was added, and the mixture was stirred at room temperature for 16 hours. This was poured into water and extracted with ether. The extract was washed with a saturated aqueous solution of sodium bicarbonate and a saturated saline solution. This was concentrated, and aqueous acetic acid (a mixture of acetic acid (10 ml), water (20 ml) and tetrahydrofuran (10 ml)) was added thereto, followed by heating and stirring at 100 ° C. for 2 hours to complete the hydrolysis. The reaction mixture was poured into water and extracted with ether.
After washing with water and saturated saline in this order, the extract was dried over anhydrous sodium sulfate. By concentrating and distilling this product, 1.
1 g (yield 28%) of the title compound was obtained.

Boiling point: 120 ° C./5 mmHg IR: 1726 cm ⁻¹ (CHO) ¹ H-NMR (200 MHz, CDCl ₃ ): δ 0.8-2.1 (7H, m), 1.58 (3H, s), 1.66
(3H, s), 2.3-2.5 (2H, m), 4.8-5.2
(3H, m), 5.45 (1H, t, J = 9.7,11.1.1,1
6.6Hz), 9.78 (1H, s)

This was a colorless and transparent liquid which was rich in diffusivity, had a strong aliphatic aldehyde-like aroma, and had a slight citrus-like and rose-like aroma.

Example 5 1-Pivaloyloxy-4-vinyl-8-methyl-1,
Synthesis of 4-vinyl-8-methyl-7-nonenal from 7-nonadienyl: 1 obtained in Example 3 in place of 1-acetoxy-4-vinyl-8-methyl-1,7-nonadienyl in Example 4. -Piparoyloxy-4-vinyl-8-
The target compound, 4-vinyl-8-methyl-7-nonenal, was obtained by hydrolyzing methyl-1,7-nonadienyl under the same conditions as in Example 4.

Example 6 Citrus-type blended fragrance: (weight ratio) 1-decanal 7 citral 20 citronellol 950 10 α-damascon 2 dihydromyrcenol 30 ethyl 2-methylbutyrate 1 grapefruit oil 30 lemon oil 160 lime oil 200 Linalool 30 Orange Oil 490 ───────────────────────────── 980

The compound of the present invention 4-
By adding 20 parts of vinyl-8-methyl-7-nonenal, a citrus-type blended flavor having a fresh green feeling was obtained.

Example 7 Green-type blended fragrance: (weight ratio) 1% solution of 2-trans-6-cisnonadienal in dipropylene glycol 20 benzyl salicylate 80 cis-3-hexenol 0.5 cyclamen aldehil 20 covanol 200 L-laurinal 40 melonal 1.5 methylyonone 20 phenylethyl alcohol 296 hexylcinnamic aldehyde 300 ───────────────────────────── 978

The compound of the present invention 4-
By adding 22 parts of vinyl-8-methyl-7-nonenal, a melon and cucumber type blended flavor having a green feeling was obtained.

[0080]

According to the present invention, 4-vinyl-8 of high purity can be obtained.
-Methyl-7-nonenal (1) can be produced at a low cost by a simple method. This compound is rich in diffusivity and has a strong aliphatic aldehyde-like scent.It is a new fragrance that combines a citrus-like and rose-like scent. Can be used and can also be used for citrus fragrance accents. Therefore, the fragrance composition of the present invention containing the fragrance, various cosmetics, health and hygiene materials,
It can be used effectively in other wide fields. that's all

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) // C07B 61/00 300 C07B 61/00 300 (72) Inventor Mitsuhiko Fujiwara 1-chome Nishi-Hachiman, Hiratsuka-shi, Kanagawa No. 4-11 Takasago International Co., Ltd. (72) Inventor Toshimitsu Hagiwara 1-4-11 Nishihachiman, Hiratsuka-shi, Kanagawa Prefecture Inside Takano-Saka International Co., Ltd. (72) Inventor Hisao Iwai Kanagawa 1-4-11 Nishi-Hachiman, Hiratsuka-shi Takasago International Co., Ltd. F-term (reference) 4G069 AA02 BA21A BA21B BC70A BC70B BD02A BD02B BD11A BD11B BD12A BD12B BE01A BE01B BE13A BE20A BE21A CB35 DA02 4H006 AA01 AC45A BA05 BA06 BA08 BA09 BA23 BA31 BA34 BA36 BA37 BA44 BA47 BB47 4H039 CA20 CF10 4H059 BA19 BB04 BB06 DA09 EA32 EA35

Claims (5)

[Claims] (1) Formula (1) 4-vinyl-8-methyl-7-nonenal represented by the formula: 2. Formula (1) A fragrance composition containing 4-vinyl-8-methyl-7-nonenal represented by the formula: as an active ingredient. (3) Formula (3) And a myrcene represented by the following general formula (4): Wherein R is a hydrogen atom, a lower alkyl group having 1 to 4 carbon atoms, a phenyl group or a naphthyl group which may have a lower alkyl group having 1 to 4 carbon atoms, and a vinyl carboxylate represented by the formula: Is reacted in a hydrophilic solvent in the presence of a ruthenium compound to obtain a compound represented by the following general formula (2): (Wherein, R is a hydrogen atom, a lower alkyl group having 1 to 4 carbon atoms, a phenyl group which may have a lower alkyl group having 1 to 4 carbon atoms, or a naphthyl group)
-Acyloxy-4-vinyl-8-methyl-1,7-nonadienyl, which is then hydrolyzed, characterized by the formula (1) A method for producing 4-vinyl-8-methyl-7-nonenal represented by the formula: 4. A ruthenium compound represented by the following general formula:
(5)(Where R¹, R², R³, R⁴And R⁵Respectively
Same or different hydrogen atom or 1 to 4 carbon atoms
Represents a lower alkyl group;¹, R², R³, R ⁴as well as
R⁵Two adjacent groups are bonded to form a 5- or 6-membered ring
W is 1,3-butadiene, isoprene,
Lucene, 1,5-cyclooctadiene, norbornadie
2,3-dimethyl-1,3-butadiene or halogen
X represents an atom¹Represents a halogen atom)
The 4-vinyl-8 according to claim 3, wherein a ruthenium catalyst is used.
-Method for producing methyl-7-nonenal. 5. The ruthenium compound represented by the following general formula (6): (Wherein, R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ and R ¹¹
Represents a hydrogen atom or a lower alkyl group having 1 to 4 carbon atoms, which are the same or different, or R ⁶ , R ⁷ ,
Two adjacent groups of R ⁸ , R ⁹ , R ¹⁰ and R ¹¹ combine to form a 5- or 6-membered ring; X ¹ represents a halogen atom; R ¹² and R ¹³ each represent a hydrogen atom ,
A lower alkyl group having 1 to 4 carbon atoms, a cycloalkyl group having 5 to 7 carbon atoms, a lower alkyl group having 1 to 4 carbon atoms or a phenyl group which may be substituted with a halogen atom,
Represents a naphthyl group or a benzyl group, or R ¹² and R ¹³ together form an alkylene group having 3 to 6 carbon atoms; R ¹⁴ is a hydrogen atom, a lower alkyl group having 1 to 4 carbon atoms, A cycloalkyl group of the formulas 5 to 7, a halogenated lower alkyl group, a lower alkyl group of 1 to 4 carbon atoms or a phenyl group or a naphthyl group which may be substituted with a halogen atom; n is 0 to 1) And a ruthenium compound represented by the following general formula (7): M (X ² ) a (7) wherein M is an alkali metal, alkaline earth metal, ammonium, silver, aluminum, lanthanum, samarium mono etc., indicate the di- or trications acids; ^{X 2} is, ClO
_{^{4 -1, BF 4 -1, PF}} 6 -1, BPh 4 -1 ( where Ph represents a phenyl ^{_{group), CF 3 SO 2 O -1}} , C
_{^{H 3 SO 2 O -1, C}} 4 H 9 SO 2 O -, C 6 H 5 SO
_{^{2 O -1, 4-CH 3}} C 6 H 4 SO 2 O -1, 4-Cl
A represents an anion such as C ₆ H ₄ SO ₂ O- ¹ ;
Is 1 when M is a monocation, 2 when M is a dication, and 3 when M is a trication.] A ruthenium catalyst formed by mixing with a salt represented by the formula: A method for producing vinyl-8-methyl-7-nonenal.