JPH0451533B2 - - Google Patents

Description

[Detailed description of the invention]

[Industrial Field of Application] The present invention is based on the general formula (In the formula, R represents a lower alkyl group, o-
2,5-dimethyl-2-(lower alkylphenyl)-4-hexen-1-al represented by The present invention relates to fragrance compositions. [Prior art] Conventionally, 2,5-dimethyl-2-phenyl-4-
It is known that hexene-1-al has an aroma and can be produced by the following method (1). (See Bull.Soc.Chim.France, 2618-2628, 1964) It is also known that α-phenyl-γ,δ-unsaturated aldehyde can be produced by the following method (2) or (3). . (In the formula, R ¹ represents a hydrogen atom or a methyl group.
Tetrahedron Letters No.15, pp.1421−1423,
(see 1967) (In the formula, Y represents a halogen atom.Bull.
(See Soc. Chim. France, 903-910, 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- Earl was found to have a combination of miyuge-like and hyacinth-like aromas with a faintly fresh green note and fruity note at the 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. One of the objects of the present invention is to develop aromatic aldehydes which are novel and useful as raw materials for blended fragrances, particularly α-substituted phenyl-γ,δ-unsaturated aldehydes having a balsam-like floral note that evokes a variety of aromas. It is on offer. Another object of the present invention is to provide the use of the α-substituted phenyl-γ,δ-unsaturated aldehyde as a blended fragrance material. Furthermore, in the above conventional method (1), it is necessary to carry out the reaction at a high temperature of 115 to 135°C, the reaction time is long, 20 to 30 hours, and the yield is low, at most 30%. In addition, in conventional methods (2) and (3), the reaction process is long and includes a step of performing a rearrangement reaction at a high temperature of 170 to 175°C. It is necessary to introduce an allyl group into this and use it 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 the Problems] According to the present invention, the above object is achieved by solving 2,5-dimethyl-2-(lower alkylphenyl)-4-hexene-1- represented by the general formula (). 2,5-dimethyl-2-(lower alkylphenyl)-4-hexene-1-al, Furthermore, the general formula (In the formula, R is as defined above) and α-(lower alkylphenyl)propionaldehyde represented by the general formula (In the formula, X represents a halogen atom) and the prenyl halide represented by
Provided is a method for producing 2,5-dimethyl-2-(lower alkylphenyl)-4-hexen-1-al represented by the general formula (), which is characterized by carrying out the reaction in the presence of water and a phase transfer catalyst. This is achieved by doing. 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 halogen atom such as a chlorine atom, a bromine atom, or an iodine atom. In the reaction of α-(lower alkyl phenyl) propionaldehyde represented by the general formula () and prenyl halide represented by the general formula () according to the present invention, the caustic alkali to be present in the reaction system includes sodium hydroxide, Examples include potassium hydroxide, but good reaction results can be obtained by using inexpensive sodium hydroxide.
Although the caustic 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 preferable to supply this to the reaction system as an aqueous solution. .
The supply ratio of caustic alkali and water is such that the concentration of caustic alkali ranges from about 10 to 70% by weight, preferably about 15% by weight.
Adjust to an aqueous solution in the range of ~50% by weight. The amount of caustic alkali used is about 0.5 to 5 mol, preferably about 1.0 to 3.0 mol, per 1 mol of α-(lower alkylphenyl)propionaldehyde represented by the general formula (). Examples of the phase transfer catalyst used in the method of the present invention include the following nitrogen basic compounds. () A tertiary amine represented by the general formula R ² R ³ R ⁴ N and its salt. However, in the formula, R ² , R ³ and R ⁴ are 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 as a substituent. , R ² , R ³ and R ⁴ are never methyl groups at the same time. Such tertiary amines and their salts include, for example, triethylamine, tripropylamine, tributylamine, triisobutylamine, tripentylamine, trihexylamine, triheptylamine, trioctylamine, tricetylamine, dimethylpropylamine, dimethylisopropylamine. , dimethyloctadecylamine, methyldiethylamine, methylethylpropylamine, methylethylbutylamine, methylethylisobutylamine, methylpropyldecylamine, methylbutylisobutylamine, diethylhexadecylamine, ethyldipropylamine, triethanolamine, benzyldimethylamine, Examples include lauryl diethanolamine and their hydrochlorides. () A quaternary ammonium salt represented by the general formula R ⁵ R ⁶ R ⁷ R ⁸ NZ. However, in the formula, R ⁵ , R ⁶ , R ⁷ and R ⁸ are 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 have a hydroxyl group or an alkanamide as a substituent. can have a group,
R ⁵ , R ⁶ , R ⁷ and R ⁸ are never methyl groups at the same time, and at least one of them represents a group having 4 or more carbon atoms. Z is Cl ^- , Br ^- , I ^- ,
Indicates anions such as OH ^- and NO ₃ ^- . Examples of such quaternary ammonium salts include tetrabentylammonium salt, lauryltrimethylammonium salt, lauryldimethylethylammonium salt, lauryldimethylpendylammonium salt, stearyltrimethylammonium salt, stearyldimethylethylammonium salt, cetyltrimethylammonium salt, and cetyldimethyl. Ethylammonium salt, cetyldimethylbenzylammonium salt, benzyltrimethylammonium salt, benzyldimethylethylammonium salt, trilaurylmethylammonium salt, dioctyldimethylammonium salt, didecyldimethylammonium salt, ditetradecyldimethylammonium salt, dicetyldimethylammonium salt , distearyldimethylammonium salt, tetradecyltrimethylammonium salt,
These include dodecylbenzyldimethylammonium salt, octylbenzyldimethylammonium salt, decylbenzyldimethylammonium salt, hexadecylbenzyldimethylammonium salt, and triethylhexylammonium salt. () A betaine-type quaternary ammonium salt represented by the general formula R ⁹ R ¹⁰ R ¹¹ N-A-Q. However, R ⁹ , R ¹⁰ , and R ¹¹ in the formula are alkyl groups, and R ⁹ , R ¹⁰ , and R ¹¹ are never methyl groups at the same time, and at least one of them is not a methyl group.
1 indicates an alkyl group having 12 or more carbon atoms. A represents an alkylene group, Q is -SO ₃ or -COO
It is. 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.
Although the phase transfer catalyst varies depending on its type, it usually contains about 0.05 to 20 mol%, preferably about
Used in concentrations of 0.1-10 mol%. The molar ratio of α-(lower alkylphenyl)propionaldehyde represented by the general formula () and prenyl halide represented by the general formula () is approximately
Generally, the molar ratio is about 2:1 to 1:2, although a wide range can be used, such as from 10:1 to 1:10.
It is suitable to use within the range of . 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°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°C in order to carry out the reaction efficiently. In carrying out the method of the present invention, a mixture of an aqueous caustic alkali solution, a phase transfer catalyst, and, if necessary, a reaction solvent is prepared, and a mixture of α-(lower alkyl phenyl )
It is preferable to start the reaction by adding propionaldehyde and then adding prenyl halide represented by the general formula (). The reaction is usually continued until almost the entire amount of either or both of the charged α-(lower alkylphenyl)propionaldehyde represented by the general formula () and the prenyl halide represented by the general formula () is consumed. 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 products. At this time, unreacted α-(lower alkylphenyl)propionaldehyde represented by the general formula () 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 caustic alkali if necessary. α shown by the general formula () used as a raw material
-(Lower alkyl phenyl)propionaldehyde is, for example, a compound of the general formula (wherein R is as defined above) It can be easily derived from the ketone represented by the following by the following method using Darzens reaction. (In the above formula, R is as defined above,
R ¹² represents a methyl group or an ethyl group) 2,5-dimethyl- represented by the general formula ()
2-(lower alkylphenyl)-4-hexene-
1-R is based on a unique balsam-like floral note with a green note at the top, and a variety of incense such as Gardenia incense, Hyacinth incense, Opoponax incense, Myrrh incense, etc. It is useful as a material for mixed fragrances because it has a fragrance that evokes scents, has strong diffusivity and fragrance retention, and blends well with many fragrance materials. The fragrance composition of the present invention contains 2,5-dimethyl-2-(lower alkyl phenyl)-4-hexene-1-al represented by the general formula () in an amount that allows its aroma to be sensed olfactorily. It becomes. 2,5-dimethyl-2- represented by the general formula ()
(lower alkyl phenyl)-4-hexene-1-
The content of Earl 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 spatial spraying; perfumes; colognes; cosmetics such as soaps, lotions, and creams; bath agents; hair cosmetics such as hair tonics, pomades, hair liquids, hair creams, and hair; hair washes such as shampoos and conditioners; detergents; ;
It can be used as a purifying agent. 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 2,5-dimethyl-2-(4-methylphenyl)
-Synthesis of 4-hexene-1-al 24.4g (0.61mol) of sodium hydroxide in 106ml of water
, 106 ml of benzene, and 2.1 g (5.6 mmol) of tetrabutylammonium iodide.
-(4-methylphenyl)propionaldehyde
After adding 59.2g (0.40mol) and stirring for a while, 41.6g of 1-chloro-3-methyl-2-butene
(0.40 mol) was slowly added dropwise. The reaction temperature is 40
The temperature rose to ~50℃. 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-
58.3 g (0.27 mol) of dimethyl-2-(4-methylphenyl)-4-hexene-1-al was obtained. Yield 68%. The physical properties of the product are shown below. ^1H NMR spectrum (90MHz) δ ^CDCl3 _HMS : 1.35 (s, 3H); 1.52, 1.58 (each s,
6H); 2.30 (s, 3H); 2.52 (d, J=7Hz,
2H); 4.75-5.05 (m, 1H); 7.14 (s, 4H); 9.47 (s, 1H) IR spectrum (cm ^-1 ): 2980, 2930, 2710,
1725, 1520, 820 Mass spectrum (m/z): 216 [M ⁺ ], 187,
148,119,91,69,41 Example 2 2,5-dimethyl-2-(3-methylphenyl)
-Synthesis of 4-hexene-1-al 24.4g (0.61mol) of sodium hydroxide in 106ml of water
, 106 ml of benzene, and 2.1 g (5.6 mmol) of tetrabutylammonium iodide.
-(3-methylphenyl)propionaldehyde
After adding 59.2g (0.40mol) and stirring for a while, 41.6g of 1-chloro-3-methyl-2-butene
(0.40 mol) was slowly added dropwise. The reaction temperature is approx.
The temperature rose to 50℃. After the dropwise addition was completed, the mixture was stirred for a while, and after confirming the disappearance of 2-(3-methylphenyl)propionaldehyde, the mixture was separated.
The organic layer was washed with saturated brine and dried over anhydrous magnesium sulfate. Next, benzene is distilled off from this organic layer, and the residue is distilled under reduced pressure to obtain a fraction of 100-102°C/0.5mmHg.
60.5 g (0.28 mol) of -dimethyl-2-(3-methylphenyl)-4-hexene-1-al was obtained.
Yield 70%. The physical properties of the product are shown below. ^1H NMR spectrum (90MHz) δ ^CDCl3 _HMS : 1.34 (s, 3H); 1.50, 1.58 (each s,
6H); 2.31 (s, 3H); 2.52 (d, J=7Hz,
2H); 4.75-5.05 (m, 1H); 6.90-7.35 (m,
4H); 9.48 (s, 1H) IR spectrum (cm ^-1 ): 2980, 2930, 2710,
1725, 1605, 790, 705 Mass spectrum (m/z): 216 [M ⁺ ], 148,
119,91,69,41 Example 3 2,5-dimethyl-2-(2-methylphenyl)
-Synthesis of 4-hexene-1-al 24.4g (0.61mol) of sodium hydroxide in 106ml of water
, 106 ml of benzene, and 2.1 g (5.6 mmol) of tetrabutylammonium iodide.
-(2-methylphenyl)propionaldehyde
After adding 59.2g (0.40mol) and stirring for a while, 41.6g of 1-chloro-3-methyl-2-butene
(0.40 mol) was slowly added dropwise. The reaction temperature is approx.
The temperature rose to 40℃. After the dropwise addition was completed, the mixture was stirred for a while, and after confirming the disappearance of 2-(2-methylphenyl)propionaldehyde, the mixture was separated.
The organic layer was washed with saturated brine and dried over anhydrous magnesium sulfate. Then, benzene is distilled off from this organic layer, and the residue is distilled under reduced pressure to obtain 2,5-
51.8 g (0.24 mol) of dimethyl-2-(2-methylphenyl)-4-hexene-1-al was obtained. Yield 60%. The physical properties of the product are shown below. ^1H NMR spectrum (90MHz) δ ^CDCl3 _HMS : 1.34 (s, 3H); 1.46, 1.56 (each s,
6H); 2.19 (s, 3H); 2.57 (d, J=7Hz,
2H); 4.70-5.00 (m, 1H); 7.00-7.35 (m,
4H); 9.62 (s, 1H) IR spectrum (cm ^-1 ): 2980, 2930, 2720,
1725, 1600, 1495, 790 Mass spectrum (m/z): 216 [M ⁺ ], 148,
119,91,69 Example 4 2,5-dimethyl-2-(4-ethylphenyl)
-Synthesis of 4-hexene-1-al 24.4g (0.61mol) of sodium hydroxide in 106ml of water
, 106 ml of benzene, and 2.1 g (5.6 mmol) of tetrabutylammonium iodide.
-(4-ethylphenyl)propionaldehyde
After adding 64.8g (0.40mol) and stirring for a while, 1-chloro-3-methyl-2-
41.6 g (0.40 mol) of butene was slowly added dropwise.
After dropping, stir for a while and add 2-(4
After confirming the disappearance of -ethyl phenyl) propionaldehyde, the layers were separated, and 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 110-113
2,5-dimethyl-2 as a fraction at °C/0.3 mmHg
64.5 g (0.28 mol) of -(4-ethylphenyl)-4-hexene-1-al was obtained. Yield 70%. The physical properties of the product are shown below. ^1H NMR spectrum (90MHz): 1.23 (t, J = 7Hz, 3H); 1.37 (s,
3H); 1.53, 1.61 (each s, 6H); 2.40-2.70
(m, 2H); 4.75-5.05 (m, 1H); 7.20
(s, 3H); 9.51 (s, 1H) IR spectrum (cm ^-1 ): 2960, 2920, 2710,
1725, 1520, 830 D-Mass spectrum (m/z): 230 Example 5 2,5-dimethyl-2-(4-methylphenyl)
-Synthesis of 4-hexene-1-al In Example 1, 1-chloro-3-methyl-2
- React in the same manner, except that 59.5 g (0.40 mol) of 1-bromo-3-methyl-2-butene is used instead of 41.6 g (0.40 mol) of butene, and then treat the reaction mixture in the same manner. 2,5-
63.1 g (0.29 mol) of dimethyl-2-(4-methylphenyl)-4-hexene-1-al was obtained. Yield 73%. Examples 6 to 14 The same reaction as in Example 1 was carried out using the phase transfer catalyst shown in Table 1 instead of tetrabutylammonium iodide, and the reaction mixture was treated in the same manner. The obtained 2,5-dimethyl-2-(4-
The yield of methylphenyl)-4-hexen-1-al is shown in Table 1.

〔Effect of the invention〕

2,5-dimethyl-2-(lower alkyl phenyl)-4-hexene-1-al represented by the general formula () provided by the present invention combines the various aromas mentioned above, which are different from conventional aromatic aldehydes. It has a balsam-like floral note reminiscent of 2,5-dimethyl-2 represented by the general formula ().
-(lower alkyl phenyl)-4-hexene-1-
A fragrance composition containing Al has a high-grade, modern fragrance tone that effectively utilizes the aroma of 2,5-dimethyl-2-(lower alkyl phenyl)-4-hexene-1-al. Furthermore, according to the method of the present invention, as is clear from the above examples, 2,5-dimethyl-2-(lower alkyl phenyl) represented by the general formula () can be produced in good yield.
-4-hexene-1-al can be produced.

Claims (1)

[Claims] 1. General formula (In the formula, R represents a lower alkyl group, o-
2,5-dimethyl-2-(lower alkylphenyl)-4-hexen-1-al, which is located at either the m-position, the m-position or the p-position. 2 General formula (In the formula, R represents a lower alkyl group, o-
α-(lower alkylphenyl)propionaldehyde represented by (In the formula, X represents a halogen atom) and a prenyl halide represented by a caustic alkali,
General formula characterized by reaction in the presence of water and a phase transfer catalyst (In the formula, R is as defined above.) A method for producing 2,5-dimethyl-2-(lower alkylphenyl)-4-hexen-1-al. 3 General formula (In the formula, R represents a lower alkyl group, o-
A fragrance composition containing 2,5-dimethyl-2-(lower alkyl phenyl)-4-hexen-1-al, which is represented by the following formula: