JP3488103B2 - Fragrance composition containing 4-methyl-5-hexene-1-al - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [0001] TECHNICAL FIELD The present invention is useful as a fragrance material
4-Methyl-5-hexene-1-aThePerfume included
Composition. [0002] 2. Description of the Related Art The odor of a compound depends on slight structural differences.
Are completely different and have their properties, for example,
Generally, volatility and the like change. Therefore, various
Synthesizing a compound and examining its odor is a new fragrance
It is extremely important to get Traditionally aliphatic
Aldehydes are useful as fragrance materials, and many aldehydes
Hides are manufactured and actually used (Motoichi Indo
Author, Synthetic perfume (chemical and product knowledge), Chemical Daily 1996
Year). For 4-methyl-5-hexen-1-al
Citronellal, J. Org. Chem. 42, 3622, (1977).
Has been reported, but the number of processes is large.
The cost was high. Also, 4-methyl-5-hexene
There is no description about the odor characteristics of N-1-R. Incense
There have been no reports on the use of
No. Analogous compounds of 4-methyl-5-hexen-1-al
Cis-3-hexenal is very expensive and
Lance-2-hexenal has a strong pungent odor. [0003] SUMMARY OF THE INVENTION Therefore, the present invention
Has no irritating odor and has a mild scentIncenseComposition
The task is to provide things. [0004] Means for Solving the Problems The present inventors have solved the above problems.
In order to resolve this,Fruit Four-Methyl-5-
Hexen-1-RFeelingHighly diffusible and strong fresh
Green fruity scentAndSimilar aromatization
Cis-3-hexenal, trans-2-he
XenalAromaLess irritating odor compared to
Completed the present invention by finding that it is mild in tee
did. That is, the present inventionIs belowGeneral formula (1) Embedded image Contains 4-methyl-5-hexene-1-al represented by
The present invention provides a fragrance composition. [0006] BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail.
Of the present inventionThe above general formula (1), which is an aroma component of the fragrance composition
Represented by Four -Methyl- Five -Hexen-1-al is
The general formula (2) Embedded image (In the formula, a phenyl group having 1 to 12 carbon atoms, a naphthyl group
Is an acyloxy group which may have The wavy line is cis
Shows the mixture of the isomer and trans isomer )A diene compound represented by
It can be produced by hydrolyzing the product.
the aboveGeneral formula (2)Represented byThe diene compound reacts as follows
In the presence of a ruthenium catalyst as shown in formula (I),
Rene (3) and vinyl carboxylate compound (4) (wherein R
Is synonymous with R of the diene compound (2)).
Can be achieved. [0007] Embedded image A vinyl carboxylate compound of the above formula (4)
In (4), R is phenyl having 1 to 12 carbons.
And an acyloxy group which may have a naphthyl group.
You. C 1 to C 12 (having a phenyl group and a naphthyl group
Examples of the acyloxy group include formyl
Oxy, acetoxy, propanoyloxy, butanoyl
Oxy, pivaloyloxy, pentanoyloxy,
Nylacetoxy, acetoacetoxy, benzoyloxy
And naphthoyloxy. Like
Vinegar is a good example of a vinyl carboxylate compound.
Vinyl acid, vinyl butyrate, vinyl pivalate, benzoic acid
Nil and the like. [0009]Represented by the above general formula (2)Diene compounds
In the above, R represents a phenyl group having 1 to 12 carbon atoms,
An acyloxy group which may have a tyl group. Carbon number
1 to 12 (having a phenyl group or a naphthyl group)
Good), examples of acyloxy groups include formyloxy,
Acetoxy, propanoyloxy, butanoyloxy,
Pivaloyloxy, pentanoyloxy, phenylacetate
Toxic, acetoacetoxy, benzoyloxy, naphtho
Iloxy and the like can be exemplified. Preferred examples of the diene compound (2)
4-methyl-1,5-hexadien-1-ylacetate
, 4-methyl-1,5-hexadien-1-ylbutanoate
Ethate, 4-methyl-1,5-hexadiene-1-ylpiva
Rate, 4-methyl-1,5-hexadien-1-ylben
Zoate and the like. The reaction between isoprene and a vinyl carboxylate compound
To synthesize diene compound (2) by co-dimerization reaction
The ruthenium catalyst used for the following general formula
(5) Embedded image (Where R¹, R^Two, R^Three, R^FourAnd R^FiveAre the same
Or different.¹, R^Two,
R^Three, R^FourAnd R^FiveAny two adjacent carbon sources within
Water which may combine to form a 5- or 6-membered ring
A hydrogen atom, a lower alkyl group having 1 to 4 carbon atoms;
Are 1,3-butadiene, isoprene, myrcene, 1,5-
Crooctadiene, norbonadiene, 2,3-dimethyl-1,3
-Butadiene, a halogen atom; X¹Is a halogen field
I am a child. )) Is preferably used. Alternatively, the following general formula (6) Embedded image (Where R⁶, R⁷, R⁸, R⁹, R^TenAnd R¹¹Is the same
May be one or different, and furthermore R⁶,
R⁷, R⁸, R⁹, R^TenAnd R¹¹Any adjacent in
Two carbon atoms combine to form a 5- or 6-membered ring
Hydrogen atom, lower alkyl having 1 to 4 carbon atoms
A group; X¹Is a halogen atom; R¹²And R
¹³Represents a hydrogen atom, a lower alkyl group having 1 to 4 carbon atoms,
A cycloalkyl group having a prime number of 5 to 7, or a carbon number of 1 to 4
May be substituted with a lower alkyl group or a halogen atom
Phenyl group, lower alkyl group having 1 to 4 carbon atoms, halogen
A naphthyl group which may be substituted with
4 may be substituted with a lower alkyl group or a halogen atom
Benzyl group and also R¹²And R¹³And the number of carbons together
3-6 alkylene groups; R¹⁴Is a hydrogen atom, charcoal
A lower alkyl group having 1 to 4 prime numbers, a cycle having 5 to 7 carbon atoms
Loalkyl group, halogenated lower alkyl group, or carbon number
1 to 4 lower alkyl groups or halogen atoms
Phenyl group, lower alkyl having 1 to 4 carbon atoms
Group, a naphthyl group which may be substituted with a halogen atom
N is from 0 to 1. Ruthenium compound represented by)
And the following general formula (7) Embedded image (Where M is an alkali metal, alkaline earth metal, ammonium
, Silver, aluminum, lanthanum, samarium, etc.
Mono, di or trications; X^Two Is Cl
O_Four ^-1, BF_Four ^-1, PF₆ ^-1, BPh_Four ^-1(Ph represents a phenyl group
You. ), CF_ThreeSO_TwoO^-1, CH_ThreeSO_TwoO^-1, C₆H_FiveSO_TwoO^-1, 4-CH_ThreeC₆
H_FourSO_TwoO^-1, 4-ClC₆H_FourSO_TwoO^-1And the like; M
When a is a monocation, a is 1 and M is a dication
When a is 2, a is 2 when M is a trication.
3. ) Formed by mixing with the salt represented by
A ruthenium catalyst is preferred. [0013]Represented by the general formula (5) used in the above reaction
BeRuthenium touchMediumIn addition, one of the ligands is the following general
Equation (8) Embedded image (Where R¹, R^Two, R^Three, R^FourAnd R^FiveAre the same
Or different.¹, R^Two, R^Three,
R^FourAnd R^FiveAny two adjacent carbon atoms in
Hydrogen source that may form a 5- or 6-membered ring
And a lower alkyl group having 1 to 4 carbon atoms. )
Ligand. In the ligand (8), R¹, R^Two,
R^Three, R^FourAnd R^FiveExamples of the hydrogen atom, methyl
, Ethyl, propyl, isopropyl, butyl, isobu
C 1 -C 4 butyl, sec-butyl, tert-butyl, etc.
And lower alkyl groups. As a preferred specific example
Examples of the ligand (8) include cyclopentadienyl,
Tramethylcyclopentadienyl, pentamethylcyclo
Pentadienyl, indenyl and the like can be mentioned. W is 1,3-butadiene, isoprene, mill
Sen, 1,5-cyclooctadiene, norbonadiene, 2,3-
Dimethyl-1,3-butadiene, halogen atom (halogen atom
Examples of fluorine include fluorine, chlorine, bromine, iodine, etc.
You. ). X¹Is a halogen atom,
Examples of fluorine include fluorine, chlorine, bromine, iodine, etc.
You. Specific examples of the ruthenium compound of the general formula (5)
Examples thereof include the following. What
Contact, the following η^mMeans that the number of coordinated electrons is m.
Specifically, η⁶Means that the number of coordinating electrons is 6.
You. (Η^Five-Cyclopentadienyl) lute dichloride
(III), (η^Five-Cyclopentadienyl) dibromide
Tenium (III), (η^Five-Cyclopentadienyl) (η^Four-1,
3-butadiene) ruthenium (II) chloride, (η^Five-Cyclopen
Tadienyl) (η^Four-Isoprene) ruthenium (II) chloride, (
η^Five-Cyclopentadienyl) (η^Four-Myrcene) Ruthene chloride
Um (II), (η^Five-Cyclopentadienyl) (η^Four-1,5-sik
(Roctadiene) ruthenium (II) chloride, (η^Five-Cyclope
Antadienyl) (η^Four-Norbonadiene) ruthenium chloride (I
I), (η^Five-Cyclopentadienyl) (η^Four-2,3-dimethyl-
1,3-butadiene) ruthenium (II) chloride, (η^Five-Penta
Methylcyclopentadienyl) ruthenium (III) dichloride
 , (Η^Five-Pentamethylcyclopentadienyl) dibromide
Ruthenium (III), (η^Five-Pentamethylcyclopentadi
Enil) (η^Four(-1,3-butadiene) ruthenium (II) chloride, (
η^Five-Pentamethylcyclopentadienyl) (η^Four-Isopure
) Ruthenium (II) chloride, (η^Five-Pentamethylcyclope
Antadienyl) (η^Four-Myrcene) ruthenium (II) chloride, (
η^Five-Pentamethylcyclopentadienyl) (η^Four-1,5-sik
(Roctadiene) ruthenium (II) chloride, (η^Five-Pentame
Tylcyclopentadienyl) (η^Four-Norbonadiene) chloride
Ruthenium (II), (η^Five-Pentamethylcyclopentadie
Nil) (η^Four-2,3-dimethyl-1,3-butadiene) rutheni chloride
Umm (II) Preparation of a ruthenium compound of the general formula (5)
For example, see the literature (K. Masuda et al., Organometallics, 1993).
Year, Volume 12, p. 2221, edited by The Chemical Society of Japan
Study Course, Vol. 18, Organometallic Complex, 1991, Maruzen, 269
Page) and its equivalent.
it can. [0019]Represented by the above general formula (6)Ruthenium
CombinationOn thingsWherein one of the ligands is represented by the following general formula (9) Embedded image (Where R⁶, R⁷, R⁸, R⁹, R^TenAnd R¹¹Is the same
May be one or different, and furthermore R⁶, R⁷,
R⁸, R⁹, R^TenAnd R¹¹Any two adjacent in
Even if carbon atoms are bonded to form a 5- or 6-membered ring
A hydrogen atom or a lower alkyl group having 1 to 4 carbon atoms.
You. ). In the ligand (9), R⁶, R⁷,
R⁸, R⁹, R^TenAnd R¹¹As a specific example of
Child, methyl, ethyl, propyl, isopropyl, spot
Butyl, isobutyl, sec-butyl, tert-butyl, etc.
And a rualkyl group. Distribution as a preferred embodiment
Ligand (9) is benzene, p-cymene, mesitylene, hex
Samethylbenzene and the like can be mentioned. In the general formula (6), one of the ligands
One is the following general formula (10) Embedded image (Where R¹²And R¹³Is a hydrogen atom, having 1 to 4 carbon atoms
Lower alkyl groups, cycloalkyl groups having 5 to 7 carbon atoms,
Or a lower alkyl group having 1 to 4 carbon atoms and a halogen atom
Phenyl group which may be substituted, lower having 1 to 4 carbon atoms
Naphthyl optionally substituted with alkyl group and halogen atom
Group, lower alkyl group having 1 to 4 carbon atoms, halogen atom
Is an optionally substituted benzyl group, and further R¹²And R¹³And
R 3 is an alkylene group having 3 to 6 carbon atoms taken together;
¹⁴Represents a hydrogen atom, a lower alkyl group having 1 to 4 carbon atoms,
A cycloalkyl group having a prime number of 5 to 7, a halogenated lower alkyl
A kill group, a lower alkyl group having 1 to 4 carbon atoms,
A phenyl group which may be substituted with
4 may be substituted with a lower alkyl group or a halogen atom
A naphthyl group; n is 0-1. )
Ligand. In the ligand (10), R¹²And R
¹³As a specific example, a hydrogen atom, a lower carbon atom having 1 to 4 carbon atoms
Alkyl groups (eg, methyl, ethyl, propyl, iso
Propyl, butyl, isobutyl, sec-butyl, tert-butyl
Butyl, etc.), a cycloalkyl group having 5 to 7 carbon atoms (eg,
For example, cyclopentyl, cyclohexyl, cycloheptyl
And so on. ) Or a lower alkyl group having 1 to 4 carbon atoms
(Eg, methyl, ethyl, propyl, isopropyl,
Butyl, isobutyl, sec-butyl, tert-butyl, etc.),
A phenyl group optionally substituted by a halogen atom (halogen
Examples of fluorine atoms are fluorine, chlorine, bromine, iodine
Etc.), lower alkyl groups having 1 to 4 carbon atoms, halogen atoms
May be a substituted naphthyl group, having 1 to 4 carbon atoms.
Primary alkyl group, ben optionally substituted by halogen atom
Zyl group, and also R¹²And R¹³Together with 3 or more carbon atoms
6 may form an alkylene group (for example, 1,3-
Propylene, 1,4-butylene, 1,5-pentylene, 1,6-hexene
Selenium, etc.). R¹⁴Specific examples of the hydrogen atom, carbon number
A lower alkyl group having 1 to 4 carbon atoms, a cycloalkyl having 5 to 7 carbon atoms,
Alkyl group, halogenated lower alkyl group (for example,
Loromethyl, trichloromethyl, etc.)
4 may be substituted with a lower alkyl group or a halogen atom
Phenyl group, lower alkyl group having 1 to 4 carbon atoms, halo
A naphthyl group which may be substituted with a gen atom;
You. Specific examples of preferred ligand (10)
Is N-2-aminoethyl-methanesulfonamide, N-2-A
Minoethyl-benzenesulfonamide, N-2-aminoethyl
-P-toluenesulfonamide, N-2-aminoethyl
Trifluoromethanesulfonamide, N-2-aminoethyl-
Trichloromethanesulfonamide, N-3-aminopropyl
-Methanesulfonamide, N-3-aminopropyl-benze
N-sulfonamide, N-3-aminopropyl-p-toluene
Rufonamide, N-3-aminopropyl-trifluorometa
N-sulfonamide, N-3-aminopropyl-trichlorome
Tansulfonamide, N-2-amino-1,2-dimethylethyl
-Methanesulfonamide, N-2-amino-1,2-dimethyl ether
Cyl-benzenesulfonamide, N-2-amino-1,2-dimension
Tylethyl-p-toluenesulfonamide, N-2-amino-
1,2-dimethylethyl-trifluoromethanesulfone
Mido, N-2-amino-1,2-dimethylethyl-trichlorome
Tansulfonamide, N-2-amino-1,2-diphenylethyl
Le-methanesulfonamide, N-2-amino-1,2-diphenyl
Ruethyl-benzenesulfonamide, N-2-amino-1,2-
Diphenylethyl-p-toluenesulfonamide, N-2-A
Mino-1,2-diphenylethyl-trifluoromethanesul
Honamide, N-2-amino-1,2-diphenylethyl-tri
Chloromethanesulfonamide, 2-methanesulfonylamido
No-cyclohexylamine, 2-benzenesulfonylami
No-cyclohexylamine, 2-p-toluenesulfonylua
Mino-cyclohexylamine, 2-trifluoromethanes
Ruphonylamino-cyclohexylamine, 2-trichloro
Methanesulfonylamino-cyclohexylamine
I can do it. In the general formula (7), M is an alkali metal,
Alkaline earth metals, ammonium, silver, aluminum,
Mono-, di- or trications such as lanthanum and samarium
And specific examples are Li⁺, Na⁺, K⁺, Mg²⁺, Ca
²⁺, NH_Four ⁺, Ag⁺, Al³⁺, La³⁺, Sm³⁺And the like.
X^TwoAre anions, and specific examples are ClO_Four ^-1, BF
_Four ^-1, PF₆ ^-1, BPh_Four ^-1(Ph represents a phenyl group), CF_Three
SO_TwoO^-1, CH_ThreeSO_TwoO^-1, C₆H_FiveSO_TwoO^-1, 4-CH_ThreeC₆H_FourSO_TwoO
^-1, 4-ClC₆H_FourSO_TwoO^-1And the like. Specific examples of the ruthenium compound of the general formula (7)
Examples thereof include the following. What
Contact, the following η^mMeans that the number of coordinated electrons is m.
Specifically, η⁶Means that the number of coordinating electrons is 6.
You. (N-2-aminoethyl-p-toluenesulfonamide)
(η⁶-Benzene) ruthenium (II) chloride, (N-2-amino)
Ethyl-p-toluenesulfonamide) (η⁶-p-cymene) salt
Ruthenium (II) chloride, (N-2-aminoethyl-p-toluene
Sulfonamide) (η⁶-Mesitylene) ruthenium chloride (I
I), (N-2-aminoethyl-p-toluenesulfonamide)
(η⁶-Benzene) ruthenium (II) bromide, (N-2-amino)
Ethyl-p-toluenesulfonamide) (η⁶-p-cymene) Odor
Ruthenium (II) chloride, (N-2-aminoethyl-p-toluene
Sulfonamide) (η⁶-Mesitylene) Ruthenium bromide (I
I) Production of a ruthenium compound of the general formula (6)
For example, known methods (eg, WO97 / 20789, etc.)
It is. ) And an equivalent method.
Wear. [0028] Isoprene (3) and vinyl carboxylate compound
As the solvent used for the co-dimerization reaction with the product (4),
Any inert solvent that does not participate in the reaction may be used, for example,
Water, methanol, ethanol, propanol, isopro
Lower alcohols such as panol and butanol, dimethyl
Formamide, dimethylacetamide, dimethylimida
Parents such as amides such as zolidinone and N-methylpyrrolidone
It is preferable to use an aqueous solvent or a mixed solvent thereof.
it can. Preferably, methanol, ethanol, or hydrous
Tanol and the like are exemplified. The amount of solvent used is isoprene
0.1 to 25 times the volume, preferably 0.8 to 1 part by weight
Up to 3 times capacity. In the codimerization reaction, vinyl carboxylate
Compound (4) is generally used in an amount of 0.05 to 1 equivalent of isoprene.
It is 50 equivalents, preferably 0.1 to 10 equivalents. Co-dimerization reaction
In the above, the amount of the ruthenium compound used is
About 0.001 to 50 mol% with respect to
Is about 0.08 to 10 mol%. Furthermore, the reaction is usually 0 to 20
0 ° C, preferably 70-120 ° C
In general, about 1 hour to 72 hours, preferably 5 hours
The reaction is completed in about 24 hours.
These conditions depend on the reactants and ruthenium compounds used.
It can be appropriately changed depending on the amount. This reaction is usually performed with nitrogen gas.
Or under an inert gas atmosphere such as argon gas.
However, the reaction may be performed under a gas atmosphere of a starting material. The diene compound thus obtained
In (2), the double bond is a cis form, a trans form, or
In any case of a mixture of cis form and trans form,
Preferably, it is a cis form. The present inventionIs an aroma component of4-methyl-5-hexyl
Sen-1-al (1) hydrolyzes diene compound (2)
And can be easily obtained. Specific hydrolysis
As a method, diene compound (2) is added to aqueous sulfuric acid, aqueous hydrochloric acid and
Heating and / or stirring in an aqueous acetic acid solution, or
Compound (2) in an aqueous alkali solution such as sodium hydroxide
There is a method of heating as needed. [0032]It is an aroma component of the present invention.4- in general formula (1)
Methyl-5-hexene-1-al is shown in the test examples below.
Fresh green fruity with strong diffusibility
Cis-3-hexyl, which has a similar aroma and is a similar aroma compound
Senal compared to trans-2-hexenal
Because of its low odor, fruity and mild
Ingredients for blending lean apple, kiwi, apple, etc.
It is a fruity type and a floral green type.
It can be used for general purposes and also for accenting the fragrance for fruit
Can be used. Accordingly, the fragrance composition of the present invention containing the same
Is thisToFragrances and various incenses contained as aroma
Can provide cosmetics, health and hygiene materials, etc.
You. That is, fragrances such as deodorants and indoor fragrances;
Cleaning cosmetics such as soaps, shampoos and rinses, hair dyes,
Cosmetics for hair such as hair, cream, lotion, odekoro
Basic cosmetics such as cosmetics and packs, towels, foundations
Make-up cosmetics such as balm, blush, etc., and aromatic makeup such as perfume
Products, suntan, sunscreen cosmetics, lipstick, lip balm
Lip cosmetics, toothpaste, mouthwash, etc.
Various cosmetics such as cosmetics and bath cosmetics; disinfectants, insecticides, etc.
Health and hygiene materials; other bleaches, softeners, dishwashing
The appropriate amount that can give the fragrance to the agent, etc.
Product value can be increased. [0034] 4-Methyl-5-hex to the fragrance composition of the present invention
The amount of sen-1-al can be determined appropriately according to the purpose.
Although it is not particularly limited, it is usually 10 ppm to 10 times
% Is preferred. In addition, the flavor composition of the present invention has
Various perfume and perfume bases can be appropriately compounded according to
Things. [0035] The present invention will now be described with reference to Comparative Examples and Examples.
Although described in detail, the present invention is not limited by these.
And does not depart from the scope of the present invention.
You may make it. In the examples, various measurements were made as follows.
Was. 1. The chemical purity of the product is measured by gas chromatography.
It was performed by the tomography method (GLC). The conditions are described below
That's right. Analyzer used: Hewlett-Packard HP5890 series
II gas chromatograph Column: Neutrabond-1 (0.25mm × 30m) Detector: FID 2. Product identification¹By H-NMR spectrum,
The comparison was made.¹ H-NMR: Varian GEMINI2000 (¹(H, 200MHz) [Reference Example 1]( η ^Five - Pentamethylcyclopentadienyl ) ( η ^Four - Isop
Len ) Ruthenium chloride (II) Synthesis of (Η^Five-Pentamethylcyclopentadienyl) dichloride
Tenium dimer (II) (200mg, 0.65mm as monomer
ol) and zinc dust (42 mg) in 20 ml of methanol.
Cool in an ice bath under Lugon atmosphere. Where isoprene
 Add 2 ml, then add 42 mg of zinc. One reaction mixture
Stir with ice cooling for hours, filter and concentrate to obtain (
η^Five-Pentamethylcyclopentadienyl) (η^Four-Isopure
75 mg of ruthenium (II) chloride (34% yield) was obtained. Various
Spectral data was consistent with literature values. Reference Example 2Four- Methyl -1 , Five- Hexadiene -1- Synthesis of il acetate (Η obtained in Reference Example 1)^Five-Pentamethylcyclopentadieni
Le) (η^Four-Isoprene) ruthenium (II) chloride (6.5 mg, 0.0
2 mmol), isoprene (5 ml, 50 mmol), vinyl acetate (5
 ml, 54 mmol) and methanol (5 ml) in an argon atmosphere
The mixture was heated and stirred at 80 ° C. for 15 hours. Distill the reaction solution
Followed by unreacted isoprene and vinyl acetate, followed by 1.07 g
(Yield: 14% based on isoprene) co-dimer (4-methyl acetate)
Ruhexa-1,5-dien-1-yl). polymer
No distillation residue was seen, and the reaction was selectively proceeding
(Purity 91%, Regioisomer 4%, Cyclic dimer 5 between dienes 5
%). Boiling point: 80-100 ° C./10 mmHg¹ H-NMR (200MHz, CDCl_Three): δ1.01 (3H, d, J = 6.6Hz), 2.
14 (3H, s), 2.0-2.4 (3H, m), 4.8-5.1 (3H, m), 5.7
4 (1H, ddd, J = 6.8, 10.2, 17.2Hz), 7.38 (1H, dm, J =
(6.6Hz) Gas chromatography analysis: Column: NB-1 (GL)
Science Co., Ltd.), measurement temperature; 60 ℃ ~ 250 ℃ (10 ℃ /
Min), retention time = 7.29 min (product), 7.8
4 minutes (isomer), 7.53 (dimer) [Reference Example 3]Four- Methyl -1 , Five- Hexadiene -1- Synthesis of il acetate Obtained in Reference Example 3 of Japanese Patent Application No. 10-240413 (N
-2-aminoethyl-p-toluenesulfonamide) (η⁶-B
Ruthenium (II) chloride (16.5 mg, 0.038 mmol)
Silver triflate (9 mg, 0.035 mmol) in methanol 2.5m
l, isoprene (2 ml, 20 mmol), vinyl acetate (2 ml, 22
 mmol) at 100 ° C for 13 hours under an argon atmosphere.
The mixture was heated and stirred. The reaction solution is poured into water, and the separated organic layer is
Analysis was performed by chromatography. As a result, the organic layer
Is 4-methylhexa-1,5-dien-1-yl acetate 70%, position
The composition is 25% isomer and 5% cyclized dimer between dienes.
Was. [Reference Example 4]Four- Methyl -1 , Five- Hexadiene -1- Synthesis of il acetate Same as used in Reference Example 1 (η^Five-Pentamethylcyclohexene
Sadienyl) (η^Four-Isoprene) ruthenium (II) chloride (11.
8 mg, 0.035 mmol), isoprene (1 ml, 10 mmol),
Vinyl valerate (1 ml, 6.7 mmol) and methanol (2 ml)
The mixture was heated and stirred at 100 ° C. for 12 hours under an argon atmosphere. Anti
The reaction solution is diluted with water, and the organic layer is concentrated and distilled.
The product was obtained in a yield of 1.1 g (84%). Distillation residue such as polymer
No reaction was observed and the reaction proceeded selectively (purity 94.6%
 , Regioisomer 4.7%, diene-cyclized dimer <1%)
 . Boiling point: 110 ° C./10 mmHg¹ H-NMR (200MHz, CDCl_Three): δ1.01 (3H, d, J = 6.4Hz), 1.
25 (9H, s), 2.0-2.4 (3H, m), 4.8-5.0 (1H, m), 4.93
 (1H, dm, J = 10.4 Hz), 4.98 (1H, dm, J = 17.2 Hz), 5.
75 (1H, ddd, J = 6.8, 10.4, 17.2 Hz), 7.04 (1H, dm,
(J = 6.4 Hz) Gas Chromatography Analysis: Column: NB-1 (GL)
(Manufactured by Science Inc.), measurement temperature;
), Retention time = 15.2 min (product), 16.2
Min (isomer) [0043][Reference Example 5] Four- Methyl -Five- Hexene -1- Synthesis of Earl 4-methyl-1,5-hexadiene-1-yl acetate (8.8 g,
 57 mmol) in methanol (50 ml) and 20% sulfuric acid (1
0 ml) and stirred at room temperature for 16 hours. Satiate this one
The mixture was carefully poured into an aqueous solution of sodium bicarbonate and extracted with ether. Extract
Acetic acid aqueous solution (20 ml of water in 10 ml of acetic acid)
), And heat and stir at 100 ° C for 2 hours.
The hydrolysis was completed. The reaction mixture is carefully
Drain into the solution, extract with ether, and wash the ether layer with saturated aqueous sodium bicarbonate.
After washing once with liquid, water, and saturated saline,
Dried with sodium. Concentrate and distill this product
This gave 4.2 g (66%) of the desired product. [0044]¹H-NMR (200MHz, CCl_Four): δ1.02 (3H, d,
J = 6 Hz), 1.10 (s, 9H), 1.5 (2H, m), 2.2 (3H, m),
4.8-5.0 (2H, m), 5.4-5.8 (1H, m), 7.5 (1H, t, J = 4
(Hz) This is highly diffusive, strong fresh green full
It was a colorless and transparent liquid having a tea-like aroma. [0045][Example 1] In the above-mentioned perfume mixture 900 partsReference example 5Manufactured in
To add 100 parts of 4-methyl-5-hexene-1-al
A more fresh green fruity feeling
A pull-type blended fragrance was obtained. 4-Methyl of the compound of the present invention
Le-5-Hexene-1-R 100 partsToInstead, similar incense
Composition using cis-3-hexenal, a gaseous compound
Was prepared. The five panelists
As a result of a palatability test, the results were all unanimous.
-Hexene-1-al is preferred and relatively irritating
With a balance of mild and fruity aroma without odor
Fragrance composition suitable for use in shampoos
Was. [0047][Example 2] To 950 parts of the above blended fragranceReference example 5Manufactured in
By adding 50 parts of 4-methyl-5-hexene-1-al
Herbal green type blended fragrance with a green feeling
was gotten. 4-methyl-5-hexene-1-al
The trans-2-hexenner is a similar odor component
To prepare a fragrance composition. For both,
A taste test was conducted by 10 panelists, and as a result, 9
Mild and herbal green incense with relatively no irritating odor
4-methyl-5-hexene-1-al
Prefer the addition, for a well-balanced male cosmetic
It was evaluated as a suitable fragrance composition. [0049] The present inventionFragrance compositionFour-
Methyl-5-hexene-1-al is highly diffusible and strong new
Has a fresh green fruity-like scent and similar scent
Compounds cis-3-hexenal, trans-2-hexen
Less irritating odor, more fruity compared to Senar
Green apple, kiwi, a
In addition to raw materials for preparation such as
It can be used for general purposes such as a rotary green type, for fruits
Can also be used for fragrance accents. Therefore, this
The fragrance composition of the present invention contains fragrance, various cosmetics, health
It can be used effectively in sanitary materials and other wide fields.
is there.

──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Toshimitsu Hagiwara 1-4-11, Nishi-Hachiman, Hiratsuka-shi, Kanagawa Prefecture Inside the Research Laboratory of Takasago International Inc. (72) Inventor Hisao Iwai 1-4-4, Nishi-Hachiman, Hiratsuka-shi, Kanagawa No. 11 Takasago International Corporation (56) References JP-A-7-330653 (JP, A) Swiss Patent Application No. 586517 (CH, A3) Journal of Organic Chemistry, 1977, Vol. 42, No. 22, 3622-3624 (58) Fields investigated (Int. Cl. ⁷ , DB name) C07C 47/21 C07C 45/42-45/43 C07C 47/42

Claims (1)

(57) [Claims] (Claim 1) The following general formula (1) A fragrance composition containing 4-methyl-5-hexene-1-al represented by the formula: