JPS6176431A - 2,5-dimethyl-2-(lower alkylphenyl)-4-hexen-1-al, its preparation and perfumery composition containing same - Google Patents

Abstract

NEW MATERIAL:The 2,5-dimethyl-2-(lower alkylphenyl)-4-hexen-1-al of formula I (R is lower alkyl positioned at o-, m- or p-site). EXAMPLE:2,5-Dimethyl-2-(4-methylphenyl)-4-hexen-1-al. USE:Useful as a component of compound perfumery. It has balsam-like floral note as the base note, excellent perfume recalling various other fragrance such as gardenia, hyacinth, opoponax, myrrhe, etc., and strong diffusibility and retainability, and harmonizes well with various perfumery components. PREPARATION:The compound of formula I can be prepared by reacting the alpha-(lower alkylphenyl)propionaldehyde of formula II with the prenyl halide of formula III (X is halogen) in the presence of a caustic alkali, water and a phase- transfer catalyst.

Description

[Detailed Description of the Invention] [Industrial Application Field]' The present invention relates to a compound of the general formula (wherein R represents a lower argyl group and is located at either the 0-position, the m-position or the p-position) 2,5-
The present invention relates to a method for producing dimethyl-2-(lower alkylphenyl)-4-hexene-1-al, and a fragrance composition containing the same.

[Conventional technology]

Conventionally, 2,5-dimethyl-2-phenyl-4-hexene-1-al has been used to produce an aromatic aroma, and our method (1)
It is known that it is manufactured by

(Bull, Soc, Chim, France, 26]
8-2628, 3964) It is known that α-phenyl-γ, δ-unsaturated aldehydes are produced by the following method (2) or (8).

(In the formula, R1 represents a hydrogen atom or a methyl group.

Tetrahedron Letters Al 5
, pp. 1421-1423.

19678) L1- (In the formula, yVi represents a halokene atom. Bull.

Soc, Chim, France, 903-9
10, 1969) [Problems to be solved by the invention] According to the research of the present inventors, the above-mentioned 2,5-dimethyl-2
-Phenyl-4-hexene-1-al was found to have a combination of muguet-like and hyacinth-like aromas with a faint green note and fruity note on top. In addition, various aromatic aldehydes such as phenylacetaldehyde and hydroatrobaraldehyde have been used as fragrance materials for preparations, but it is important to provide a new compound with a different aroma from these compounds. This is desirable in order to bring about change.

1 One of the objects of the present invention is to create a new aromatic aldehyde useful as a material for mixed fragrances, especially a balsam that can evoke a variety of aromas! The object of the present invention is to provide α-substituted phenyl-γ,δ-unsaturated aldehydes having a 1.70-ral note. Another object of the present invention is to provide the use of the α-substituted phenylene, nilu-γ, and δ-unsaturated aldehydes as a blended fragrance material.

In addition, in the conventional method (υ) described above, it is necessary to carry out the reaction at a high temperature of 115 to 135°C, the reaction time is long at 20 to 30 hours, and the yield is low at 20 to 30 hours.
2) and (8), the reaction step is long (,170-175
There is a step of carrying out a rearrangement reaction at a high temperature of .degree. C., and furthermore, in consideration of economic efficiency, it is necessary to recover the by-product amino compound and then introduce an allyl group thereto for use as a raw material. Therefore, none of these conventional methods is an advantageous method for producing α-phenyl-γ, δ-unsaturated aldehydes.

Yet another object of the present invention is to provide a method for producing α-substituted phenyl-γ,δ-unsaturated aldehydes at low cost and in good yields.

[Means for solving problems]

According to the present invention, the above object is achieved by providing 2,5-dimethyl-2-(lower alkylphenyl)-4-hexene-1-al represented by the general formula (1); , 5-dimethyl-2-(lower alkylphenyl)-4-hexen-1-al, and also having the general formula (wherein R is as defined above). α-(lower alkylphenyl)propionaldehyde represented by the formula %(1) (wherein, By providing a method for producing 2,5-dimethyl-2-(lower alkylphenyl)-4-hexen-1-al represented by general formula (1), which is characterized by carrying out the reaction in the presence of a transfer catalyst. achieved.

R and X in the above general formula will be explained in detail. R represents a lower alkyl group such as a methyl group, ethyl group, propyl group, butyl group. X represents a chlorine atom such as a chlorine atom, a bromine atom, or an iodine atom.

α-(lower alkylphenyl)globionaldehyde represented by the general formula (U) according to the present invention
Examples of the alkali to be present in the reaction system in the reaction with the prenyl-lide represented by [l') include sodium hydroxide and potassium hydroxide, but it is preferable to use inexpensive sodium hydroxide. Very good reaction results can be obtained. Although the alkali can be supplied to the reaction system separately from water in the form of a solid having any shape such as pellets, powder, or flakes, it is preferably supplied to the reaction system as an aqueous solution. . The supply ratio of alkali and water is such that the concentration of alkali is about 10 to 70%, preferably about 15 to 50% by weight.
% range of aqueous solution.

The amount of alkali to be used is α-(
About 5-5 mol of lower alkylphenyl) per 1 mol of fropionaldehyde, preferably about 1.0-3.
It is 0 mole.

Examples of the phase transfer catalyst used in the method of the present invention include the following nitrogen basic compounds. (1) A tertiary amine represented by the general formula R"R"R'N and a salt thereof. However, in the formula, R2, R3 and R4 are an alkyl group, a carbon alkyl group, a cycloalkyl group having 6 or more carbon atoms, or an aralkyl group having 7 or more carbon atoms, and these groups can have a hydroxyl group as a substituent. , R3 and R4 are never methyl groups at the same time. Such tertiary amines and their salts include, for example, triethylamine, tripropylamine, tributylamine, triisobutylamine, tripentylamine, trihexylamine, trihebutylamine, trioctylamine, tricetylamine, dimethylpropylamine, dimethylimpropyl. Amine, dimethylophtadecylamine, methyldiethylamine, methylethylpromylamine, methylethylbutylamine, methylethylisobutylamine, methylpropyldecylamine, methylbutylisobutylamine, diethylhexadecylamine, etherdipropylamine, triethanolamine, benzyl Examples include dimethylamine, laurylgetanolamine, and their hydrochlorides.

(11) A quaternary ammonium salt with the general formula R''R6R7R8NZ, where R5, R', R7 and R
8 is an alkyl group, a cycloalkyl group having 6 or more carbon atoms, or an aralkyl group having 7 or more carbon atoms, and these groups can have a hydroxyl group or an alkanamide group as a substituent, but 'R6%' R6, R7 and R8 are never methyl groups at the same time, and at least one of them represents a group having 4 or more carbon atoms. 2 is Cl-1Br
-1■-1OH-1NOs- and other 7-ions are shown. Particular quaternary ammonium salts include, for example, tetrapentylammonium salt, lauryltrimethylammonium salt,
Lauryldimethyl spirit thylammonium salt, lauryldimethylbenzylammonium salt, stearyltrimethylammonium salt, stearyldimethylethylammonium salt, cetyltrimethylammonium salt, cetyldimethylethylammonium salt, cetyldimethylbenzylammonium salt, benzyltrimethylammonium salt, benzyldimethylethylammonium salt, trilaurylmethylammonium salt, dioctyldimethylammonium salt,
didecyl dimenal ammonium salt, ditetradecyl dimethel ammonium salt, diceter dimethyl ammonium salt, distearyl dimethyl ammonium salt, tetradecyl trimethyl ammonium salt, dodecylpenzyl di)f ammonium salt, octylbenzyl dimethyl ammonium salt, decyl These include benzyldimethylammonium salt, hexadecylbenzyldimethylammonium salt and triethylhexylammonium salt.

(ii+) General formula R9HloR11φ-A-Qe
A betaine-type quaternary ammonium salt represented by However, R9゜RIG and R11 in the formula are alkyl groups,
R9, RI O and R11 are never methyl groups at the same time, and at least one of them has a carbon number of 12
0AFi represents an alkylene group showing the above alkyl group,
Qe is -803e or -cooe. Examples of such betaine type quaternary ammonium salts include compounds having the following structural formula.

In the method of the present invention, not only can each phase transfer catalyst be used alone, but also two or more types can be used in combination, if desired. The phase transfer catalyst is usually used at a degree of about 0.05 to 20 mol, preferably about 0.1 to 10 mol, relative to the prenyl/)lide represented by the general formula (Ill), although it varies depending on the type. be done.

The α-(lower alkylphenyl)propionaldehyde represented by the general formula (II) and the prenyl halide represented by the general formula (1) can be used in a wide range of molar ratios, such as from about 10:1 to 10:1. However, it is generally preferred to use molar ratios in the range of about 2:1 to 1:2.

A solvent may or may not be used in the reaction according to the invention. As the solvent, for example, hydrocarbons such as pentane, hexane, benzene, toluene, xylene, and tetrahydronaphthalene, which are immiscible with water and inert to the reaction, can be used. Although the reaction can be carried out within a temperature range of about 0.degree. C. to the boiling point of the reaction mixture, it is preferable to carry out the reaction within a temperature range of room temperature to about 60.degree. C. in order to carry out the reaction efficiently.

In carrying out the method of the present invention, a mixture of an aqueous aqueous alkali solution, a phase transfer catalyst, and optionally a reaction solvent is added to the α-(lower It is preferable to start the reaction by adding (alkylphenyl)propionaldehyde and then adding prenyl halide represented by general formula (II).

The reaction is usually continued until either 10,000 of the charged α-(lower alkylphenyl) fropionaldehyde represented by the general formula (II) and the prenyl halide represented by the general formula (DI) or almost the entire amount of both are consumed. be done. After the reaction, the reaction solution is separated into an organic layer and an aqueous layer, and the organic layer is subjected to a separation operation such as distillation to separate the product.

At this time, unreacted α-(lower alkylphenyl)propionaldehyde represented by the general formula (If) may be recovered, but this aldehyde can be reused as a raw material. If an alkali metal halide precipitates in the reaction solution after the reaction, it is preferable to add water to the reaction solution to dissolve the precipitated alkali metal halide, and then separate the solution. The aqueous layer after separation can be reused in the reaction as it is or after being concentrated and/or supplemented with a strong alkali if necessary.

The α-(lower alkylphenyl)propionaldehyde represented by the general formula (If) used as a raw material is (in the formula,
RFi 'J? of the above definition? It can be easily derived from the ketone represented by (2) by the following method using the DarZenS reaction.

(In the above formula, Rii as defined above and 1LR12 represents a methyl group or an ethyl group) 2,5-dimethyl-2-(lower alkylphenyl)-4-hexene-]- represented by the general formula (I) R is based on a pulsam-like floral note with a green note at the top, which has a 5% different character, and a gardenia (Gardenia).
denia) Incense 1 Hyacinth (Hyacintll)
Incense, Ovobonax (Opoponax) Incense, Medication (
It has a fragrance that brings to mind a variety of aromas such as Myrrhe incense, has strong diffusivity and fragrance retention, and blends well with many fragrance materials, making it useful as a material for mixed fragrances.

The fragrance composition of the present invention has a 2°5-
It contains dimethyl-'2-(low 9 alkylphenyl)-4-hexene-1-al in an amount that allows its aroma to be detected olfactory. 2,5-dimethyl-2-(lower alkylphenyl)-4-hexene-I represented by general formula (1)
The content of -R can vary within a wide range, for example between 0.005 and 95% by weight, depending on the intended use of the perfume composition. The perfume compositions of the invention can be used in a wide variety of ways. For example, it can be used for space spraying, and it can also be used for perfumes such as colognes; soaps, lotions, creams and other cosmetics; bath additives; hair cosmetics such as hair tonics, pomades, hair liquids, hair creams, and ticks; shampoos, conditioners, etc. Can be used in hair washes, detergents, purifying agents, etc. The compositions can also be used to scent substrates such as textiles, fabrics and paper products.

〔Example〕

The present invention will be specifically explained below using examples. Note that the present invention is not limited to these examples.

Example 1 Sodium hydroxide! A solution of 24.4 F (0.61 mOf) in 106 d of water, 10611 Ll of benzene and 2.1 F (5.6 mmol) of tetrabutylammonium iodide
), 59.2 f (0.40 mol) of 2-('4-methylphenyl)propionaldehyde was added, and after stirring for a while, ]-chloro-3-methyl-
741.6 f (0.40 mol) of 2-butylene was added dropwise. The reaction temperature rose to 40-50°C.

After the dropwise addition was completed, the mixture was stirred for a while, and after confirming the disappearance of 2-(4-methylphenyl)propionaldehyde, the mixture was separated. The organic layer was washed with saturated brine and dried over anhydrous magnesium sulfate. Then, benzene was distilled off from this organic layer, and the residue was distilled under reduced pressure to obtain 2.5-dimethyl-2-(4-methylphenyl)- as a fraction at 92°C and 10.2 mHf. 4-hexene-1-al 58.3 F (0.27 mol) was obtained. Revenue 468
% o The physical properties of the product are shown below.

DC1a “HNMRx vector (90MHz) δHMS
"1.35 (s, 3H); 1.s2.1.58(e
ach s, 6H) H2,30(s, 3H);
2.52 (d, J=7Hz, 2H) H4,7
5-5.05 (In'-IH) i 7.14 (8
*4H): 9.47 (8, IH) IR spectrum (m 1), 2980, 2930.27
10+1725, 1520.820 Massx vector (m/Z): 216 (M”
], 187, ] 481119, 91.69,4
] Example 2 Sodium hydroxide 24.4f (0.61m01) of water 1
06 ml of solution, benzene 106 and tetrabutylammonium iodide 2.1 ? (5,6 mmol)
(Add 2-(3-methylphenyl)propio to the D mixture.
7/l/dehyde 59.2 f (0.40 mol
) and stirred for a while, then 1-chloro-3-)
-'f-2-butene 41.6 f (0,40mo
l) was slowly added dropwise. The reaction temperature rose to about 50°C. After completing the dropping, stir for a while, then 2-
After confirming the disappearance of (3-methylphenyl)propionaldehyde, the liquid was separated. The organic layer was washed with saturated brine and dried over anhydrous magnesium sulfate. Then, benzene was distilled off from this organic layer, and the residue was distilled under reduced pressure to obtain 2,5-dimethyl-2-(,3- methylphenyl)-4-hexen-1-al60.5f (0,2
8tnol) was obtained. Yield 70%. The physical properties of the product are shown below.

CDCIs.

IHNM'R spectrum (,90MB2) δHMS
'1.34 (S, 3fl); 1.50.1.58 (e
ach S, 61 (); 2.31 (s, 3H); 2.5
2(d, J=7Hz, 2H); 4.75-5.05 (
m, IH) ; 6.90-7.35 (m, 4H
); 9.48 (8, I H) IR spectrum (cfn-1): 2980.2930.
27] 0°1725,] 605,790,705Ma
ssx vector (m/Z-) $216 (M+), 148
1119°9], 69,4] Example 3 Sodium hydroxide A24.4 F (0.61 mol)
A solution of 106 ytl of water, 106 ytl of benzene and 2.1% nium iodide. (5,6
rnmol) (To the D mixture, add 59.2t of 2-(2-methylphenyl)propionaldehyde (0.40m
After stirring for a while, add 1-trichloro3
-Methyl-2-butene 41.6F (0.40m01) was added dropwise. The reaction temperature rose to about 40°C.

After the dropwise addition was completed, the mixture was stirred for a while, and after confirming the disappearance of 27(2-methylphenyl)propionaldehyde, the mixture was separated. The organic layer was washed with saturated saline and dried over anhydrous magnesium sulfate. Then, the benzene from this organic layer was distilled off, and the residue was distilled under reduced pressure to obtain 2.5-dimethyl-2-(2-methylphenyl)-4 as a fraction 90-b. -hexene-1-al51.8F (0,2
4 mol) was obtained. Yield: 60 cm. The physical properties of the product are shown below.

IHNMRx vector is 90MHz) δCDC/3
゜) INS ' 1.34 (St 3H) i 1.46.1.56 (
each s, 6H); 2.19(s, 3H); 2
．． 57 (d, J=7Hz, 2H); 4.70~
5.00 (m, IH); 7.00-7.35 (m
, 4H); 9.62 (S, 11f) IR spectrum (low'): 2980, 2930, 2
720°] 725. ] 600. ] 495.7
50'11"9, 9], 69 21-Example 4 Sodium hydroxide 24.4F (0.61 mol) O water 1
Solution of 061E/, benzene 106. rttl and tetrabutyla, ammo, nium iodide 2.1F (5,6・m
64.8 f (0.40 mol) of 2-(4-etherphenyl)propionaldehyde was added to the mixture of mα1).
After stirring for a while, 1-chloro-3-methyl-2-butene 4'1.6 f (0,
40, mol) was slowly added dropwise. After the dropwise addition was completed, the mixture was stirred for a while, and after confirming the disappearance of 2-(4-etherphenyl)propionaldehyde, the layers were separated, and the layer was washed with saturated saline and dried over anhydrous magnesium sulfate. . Then, benzene was distilled off from this organic layer, and the residue was distilled under reduced pressure to obtain 110
~b 5-dimethyl-2-(4-ethyl7en'yl)-4-hexen-1-al 64.5 f (0.28 mol)
I got it. Yield 70%. The physical properties of the product are shown below.

1H NMR spectrum” (90M, Hl) Hl, 23(t
, J=7Hz, 3H); 1.37(s, 3f(); 1.
53.1.61 (each s, 6fl); 2
．． 40-2.70 (i'n, 2H); 4.75-5
．． 05(m, I)f) i7.20(8,311);
9.51 (S, IH) IR spectrum (cIn-”)!2960,2920,
27]0.1725°] 520.830 FD-Mass spectrum (m/z): 230 Example 5 1-chloro-3-methyl-2-bufone in Example 1 41.6? (0,40 mol) instead of 1-pu0
%-3-) 5-to-2-butene 59.5 f (0,4
2.5-
63.1 f (0.29 mol) was obtained. Yield 73%.

Examples 6 to 14 Similar reactions were carried out in Example 1 using the phase transfer catalyst shown in Table 1 instead of tetrabutylammonium iodide, and the reaction mixture was treated in the same manner. Obtained 2,
The yield of 5-dimethyl-2-(4-methylphenyl)-4-hexene-1-arno is shown in Table 1.

Table 1 Reference example p-methylacetophenone 5o5r (a, 76m01)
, methyl methyl acetate 6'62 f (6,10 mol
) and benzene (500 m/ml), sodium methoxide 340 F (6,1 Ornol) was slowly added to the mixture while cooling with water. After the addition was completed, the mixture was stirred for 2 hours under water cooling, and then a mixed solution of 61 ell of acetic acid and 500 t7 of water was added, stirred for a while, and then separated. The organic layer was washed with water, dried over anhydrous magnesium sulfate, and the solvent was then distilled off. By distilling the residue, 183v (1.36 mol) of p-methylacetophenone was recovered. The obtained crude methyl p-methylphenylmethylglycidate 4972 (2.41 mol) was mixed with 60.
39 (2.62 mol) and ethanol 90 (it) at room temperature, and after the dropwise addition was completed, the solution was stirred at room temperature for 1 hour. To this reaction mixture was added 60 ml of water.
(5,0 m01) was slowly added at room temperature, stirred at room temperature for 1 hour, and then 271 wl (2,6
A mixture of 0 mol) and 1.3 t of water was added, and the mixture was heated under reflux for 2 hours. This reaction mixture was extracted using benzene, and the penzene layer was washed with water and then dried over anhydrous magnesium sulfate. Then, the solvent was distilled off, and the resulting residue was distilled under reduced pressure, bp, 55°C/0.4 W H
2-(4''-methylphenyl)propionaldehyde 168F (1,13m01) was obtained as the fraction t.

Yield: 47 cm (based on reacted p-methylacetophenone)
. The physical properties of the product are shown below.

1H NMR spectrum (90Ml(Z)δCDQ7s.

hMs' 1.36 (d, J=7Hz, 3H), 2.33 (
s, 3H).

342 (Q, J=7Hz, IH), 7.10 (
S, 4f1).

9.50 (8, IH) Mass spectrum (m/z): 148 [M+],
119゜91.77.65.39 Example 15 Gardenia-like fragrance composition Gardenia a
! A fragrance composition having the following aroma was obtained.

Parts by weight Benzyl acetate 1゜Phenethyl alcohol 1゜Bergamot oil
5 orange flower oil
5 Methylphenylcarbinyl acetate 5 Lemon oil 2 Dimethylbenzylcarbinol 1゜Hydroxycitronellal
15"-5'7 7
Linalool 5 Balsam Toru 3 Heli Otrobin
3 Jiyasmine Synthesis
5 coumarin
3 Vetiver oil 3 Sandalwood oil 2 Vanillin
2 Example 16 Hyacinth (Hyac 1nth) according to the following formulation
A fragrance composition having a color D'71 was obtained.

! Okibe Phenethyl Alcohol 15 Phenylacetaldehyde IO Hexyl Cinnamic Aldehyde 5 Cinnamic Alcohol 15 Linalool
10α-terpineol
Benzyl 5-propionate
5 Ylang Ylang Oil 5 Isoeugenol 3 Diyasmine Synthetic 10 Banum Oil
5 Hydroatrovaldehyde
2 Vanillin 2 Heliotropin 329 Example 17 Fancy Bouquet perfume composition, according to the following formulation:
A fragrance composition having the aroma of uquet) v4 was obtained.

Parts by weight Bergamot oil 10 Methyl phenyl carbinyl acetate 5 Dimethyl benzyl carbinyl acetate 7 Phenethyl alcohol
10 linalool
5 Lilial 10 Methyl dihydro jasmonate 10 Aldehyde C-
12 (MNA) 10chi 3゛Rose essential oil
2 diasmine essential oil
2 Miyuge Synthetique] 0 Civet Tincture 2 Vetiver Oil 5 Sandalwood Oil
5 labdanum oil
2 Ovobonax oil
2 Musk Ambrette 3 [Effects of the Invention] The compound represented by the general formula (1) provided by the present invention 2.5
-Dimethyl-2-(lower alkylphenyl)-4-hexene-]-R has a balsam 70-ral note that is different from conventional aromatic aldehydes and evokes the various aromas mentioned above, and also has the general formula (1). 2,5-
The fragrance composition containing dimethyl-2-(lower alkylphenyl)-4-hexene-1-7-l is the 2,5-dimethyl-2-(lower alkylphenyl)-4-hexene-
It has a luxurious and modern scent that effectively utilizes the aroma of 1-R.

Furthermore, according to the method of the present invention, as is clear from the above examples, 25-dimethyl-2-(lower alkylphenyl)-4 to hexene-1 represented by the general formula (1) can be obtained in good yield.
- Able to produce R.

Claims (1)

[Claims] 1. General formula ▲ Numerical formula, chemical formula, table, etc. ▼ (In the formula, R represents a lower alkyl group and is located at the o-position, m-position or p-position) 2,5-dimethyl-2-(lower alkylphenyl)-4-hexen-1-al. 2. General formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (In the formula, R represents a lower alkyl group and is located at either the o-position, m-position or p-position) (lower alkylphenyl) propionaldehyde and a prenyl halide represented by the general formula ▲Mathematical formula, chemical formula, table, etc.▼ (In the formula, X represents a halogen atom) in the presence of a caustic alkali, water, and a phase transfer catalyst. 2,5-dimethyl-2-(lower alkylphenyl)-4 represented by the general formula ▲Mathematical formula, chemical formula, table, etc.▼ (in the formula, R is as defined above) which is characterized by the reaction. - A method for producing hexene-1-al. 3. General formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (In the formula, R represents a lower alkyl group and is located at either the o-position, m-position or p-position) 2,5 - A fragrance composition containing dimethyl-2-(lower alkylphenyl)-4-hexene-1-al.