JPS611634A - Preparation of alpha-phenyl-gamma, delta-unsaturated aldehyde - Google Patents

Abstract

PURPOSE:To produce the titled compound useful as a scent component of perfumery, economically in high yield, by using alpha-substituted phenylacetaldehyde and (substituted) allyl halide as raw materials, and reacting the materials in the presence of a caustic alkali, water and a phase-transfer catalyst. CONSTITUTION:The alpha-substituted phenylacetaldehyde of formula I (R<1> is lower alkyl) is made to react with the (substituted) allyl halide of formula II (R<2> and R<3> are H or CH3; X is halogen) at room temperature -10 deg.C in a mixture of an aqueous solution of a caustic alkali, a phase-transfer catalyst, and if necessary a reaction solvent such as benzene. The objective compound of formula III such as 2,5-dimethyl-2-phenyl-4-hexen-1-al, etc. having muge-like fragrance as well as hyacinth-like fragrance can be prepared by this process. The phase-transfer catalyst is e.g. a tertiary amine such as trioctylamine, quaternary ammonium salt such as tetrabutylammonium iodide, or betaine-type quaternary ammonium, etc.

Description

Detailed Description of the Invention [Field of Industrial Application] The present invention relates to a method for producing α-phenyl-γ, δ-unsaturated aldehydes, and more specifically, α-substituted phenylacetaldehydes, optionally substituted allyl halides, and α-substituted phenylacetaldehydes. The present invention relates to a method for producing α-phenyl-γ,δ-unsaturated aldehydes by reacting them in the presence of an aqueous alkaline solution and a phase transfer catalyst.

α-phenyl-γ, δ- produced by the method of the present invention]
Unsaturated aldehydes are compounds useful as aroma components in perfumes.

[Conventional technology]

Conventionally, it has been known that α-phenyl-r,δ-unsaturated aldehyde can be produced by the following method (1)% (2) or (8)).

(Bull, Sac, Chim, France,
2618-2628, 1964) (in the formula, R represents a hydrogen atom or a methyl group).

Tetrahedron Letters No. 15
．． pp. 1421-1423, 1967) (wherein, X represents) a rogene atom. Bull, Soc.
.

Chim, France, 903-910.1969
Reference) [Problems to be Solved by the Invention] In the conventional method (1) above, it is necessary to carry out the reaction at a high temperature of 115 to 135°C, the reaction time is as long as 20 to 30 hours, and the yield may be low. It's as low as 30% at most. Also, conventional method (2)
In (8), the reaction process is long and tends to involve a rearrangement reaction at a high temperature of 170 to 175°C. It is necessary to use it as a raw material. Therefore, these conventional methods all produce α-phenyl-γ
, is not an advantageous method for producing δ-unsaturated aldehydes.

An object of the present invention is to provide a method for producing α-phenyl-γ, δ-unsaturated aldehyde at low cost and in good yield.

[Means for solving problems]

According to the present invention, the above object is achieved by α represented by the general formula % (wherein R represents a lower alkyl group).
-Substituted phenylacetaldehyde and an optionally substituted allyl halide represented by the general formula (wherein R2 and R3 are the same or different, each represents a hydrogen atom or a methyl group, and X represents a halogen atom) and α-phenyl-γ represented by the general formula (wherein R1, R2 and R3 are as defined above) , by providing a method for producing δ-unsaturated aldehydes.

Bl, R2, R3 and X in the above general formula will be explained in detail. R1 represents a lower alkyl group such as a methyl group, an ethyl group, or an n-propyl group. R2 and R3 are the same or different, and each represents a hydrogen atom or a methyl group. X represents a halogen atom such as a chlorine atom, a bromine atom, or an iodine atom.

In the reaction of the α-substituted phenylacetaldehyde represented by the general formula (1'l) with the optionally substituted allyl halide represented by the general formula U according to the present invention, the alkali to be present in the reaction system is water. sodium oxide,
Examples include potassium hydroxide, but good reaction results can be obtained by using inexpensive sodium hydroxide. 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 feed ratio of the alkali and water is adjusted so that the aqueous solution has a concentration of the alkali in the range of about 10 to 70% by weight, preferably in the range of about 15 to 50% by weight. The amount of alkali to be used is about 0.5 to 5 mol, preferably about 1.0 mol, per 1 mol of α-substituted phenylacetaldehyde represented by general formula (1).
~3.0 mol.

Examples of phase transfer catalysts used in the method of the present invention include the following nitrogen basic compounds. (1) Tertiary amines represented by the general formula R4R5R6N and salts thereof. However, in the formula, B4.15 and R6 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. , R6 and R6 are never methyl groups at the same time. Such tertiary amines and their salts include, for example, triethylamine, tripropylamine, tributylamine, triisobutylamine, tripentylamine, trioctylamine, trihebutylamine, trioctylamine, tricetylamine, dimethylglopylamine, dimethylisopropylamine. , dimethyloctadecylamine, methyldiethylamine.

Methyl ethylbutylamine, methylethylbutylamine, methylethylisobutylamine, methylglobildecylamine, methylbutylisobutylamine, diethylhexadecylamine, ethyldipropylamine, triethanolamine, penzyldimethylamine, lauryl jetanolamine and their hydrochlorides.

(!i) A quaternary ammonium salt represented by the general formula R7R8R9RIONY. However, in the formula, R7, R8, Bti and RIO 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 group as a substituent. However, R7H: R11 and BIO are never methyl groups at the same time, and at least one of them represents a group with a prime number of 4 or more. Y is Cl-1Br-
, I, OH-, NOs-, etc. Examples of such quaternary ammonium salts include tetrapentylammonium salts.

Lauryltrimethylammonium salt, lauryldimethylethylammonium salt, lauryldimethylbenzylammonium salt, stearyltritylammonium salt, cetyltrimethylammonium salt, cetyldimethylethylammonium salt, cetyldimethylbenzylammonium!
, hensyltrimethylammonium salt, benzyldimethylethylammonium salt, trilaurylmethylammonium salt, dioctyldimethylammonium salt, didecyldimethylammonium salt 1 ditetradecyldimethylammonium salt, recetyldimethylammonium salt, distearyldimethylammonium- salts, tetradecyltrimethylammonium salt, dodecylbenzyldimelammonium salt, decylbenzyldimethylammonium salt, hexadecylbenzyldimethylammonium salt, and triethylhexylammonium salt.

(111) A quaternary ammonium salt of the general formula RuR12R13Ne-A-Qe. However, R11, R12 and R13 in the formula are alkyl groups, R
11, R12 and BIB are never methyl groups at the same time, and at least one of them represents an alkyl group having 12 or more carbon atoms. A represents an alkylene group, qe
B -8O3e Matabar COOe Ter.

Examples of such betaine type quaternary ammonium salts include compounds having the following structural formula.

In the method of the present invention, each of the phase transfer catalysts cannot be used alone, but two or more types can be used in combination as desired. The phase transfer catalyst usually has a molecular weight of about 0.05 to 0.05 to the optionally substituted allyl halide represented by general formula (II), although it varies depending on the type.
A concentration of 20 molar, preferably about 0.1 to 10 molar, is used.

The α-substituted phenylacetaldehyde represented by the general formula (I) and the optionally substituted allyl halide represented by the general formula (11) are used in a wide range of molar ratios, such as about 10:1 to 1:10. However, it is generally preferred to use a molar ratio of about 2:1 to 1:2.

A solvent may or may not be used in reactions according to the present 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 alkali solution, a phase transfer catalyst and, if necessary, a reaction solvent is prepared, and α-substituted phenylacetaldehyde represented by general formula (1) is added to the mixture. In addition, it is preferable to add an optionally substituted allyl halide represented by general formula (It) to start the reaction.

The reaction is usually carried out until almost the entire amount of either or both of the α-substituted phenylacetaldehyde represented by the general formula (1) and the optionally substituted allyl halide represented by the general formula (■) is consumed. Continued. 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-substituted phenylacetaldehyde represented by general formula (1) may be recovered. This aldehyde can be reused as a raw material. If an alkali metal halide precipitates in the reaction solution after the reaction, add water to the reaction solution to dissolve the precipitated alkali metal halide.

It is better to separate the liquid. 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.

As mentioned above, the α-phenyl-γ,δ-unsaturated aldehyde represented by the general formula (Ill) produced by the method of the present invention is useful as an aroma component of perfumes.

For example, 2,5-dimethyl-2-phenyl-4-hexene-1-alphat has a meage-like and hyacinth-like aroma with a faint fresh green note and fruity note.1fc2-methyl-2-
Phenyl-4-penten-1-al has a green floral fragrance.

2-Ether-2-phenyl-4-penten-1-al gives a pine-woody aroma, and 2-ethyl-5-methyl-2-phenyl-4-hexen-1-al and 5-
Methyl-2-phenyl-2-propyl-4-hexene-
1-R each has a floral aroma. All of these α-phenyl-γ, δ-unsaturated aldehydes have excellent properties that harmonize harmoniously with many floral-like fragrance materials, and therefore can be used as aroma components in various fragrances.

〔Example〕

The present invention will be explained below with reference to one example, but the present invention is not limited to these examples.Example 1 2.5-dimethyl-2-phenyl-4-hexene-1-
Earl's synthesis Sodium hydroxide 121' (2.28 mol) water 39
6d solution, benzene 396d and iodide tetrab fk
2-phenylpropionaldehyde 2019 (1
, 50 mol) and stirred for a while, then l-
Chloro-3-methyl-2-butene 151' (1,50m
ol) was slowly added dropwise. Reaction temperature is 40-45℃
Rise in the casing. After finishing dropping 1.Stir for a while,
After confirming the disappearance of 2-phenylpropionaldehyde, the solution was separated into 1 layer. 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 84-b phenyl-4-
Hexene-1-al 230F (1.14 mol) was obtained. Yield: 76 cm. The physical properties of the product are shown below.

1HN M R, <Heku)/'(90MHz)δ(,
DC4s.

1.17 (s, aH); 1.52.1.59 (eac
h s, 6) 1) ;2.55 (a, J=7Hz,
2H); 4.76~s, o6(m, IH); 7.06~
7.47 (m, 5fi); 9.51 (Il, lH) Ma
as spec) le (m/z): 202 [M”], 134
,91°77.69 Example 2 Sodium hydroxide 62F (1,55 mol) water 264
d solution, 264 ml of benzene, and 5.2 f (0.0i 4 mol) of tetrabutylammonium iodide.

2-phenylpropionaldehyde 134F (1, Om
After stirring for a while, 90.6 f (1,0 mol) of 1.-chloro-2-butene was slowly added dropwise. The reaction temperature rose to about 50°C. After the dropwise addition was completed, the mixture was stirred for a while, and after confirming the disappearance of 2-7 enylbrobionaldehyde, the mixture was separated into one liquid. 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 at 80°C/0.4
2-methyl-2-phenyl- as a fraction of ws HP
4-hexene-1-al 1502 (0.80 mol)
I got it. The physical properties of the product with a yield of 80% are shown below.

CDα3゜lf (NMR spectrum (90MHz) δHMS'L3
3 (B, 3H) + L50 (d; J =
6 Hz, 3 H); 2-51 (d, J = 6
Hz, 2”) + 4-86~5-70 (m
, 2H) ;7.0:3-7.43(m, 5H)
;9.42 (s, IH) IR spectrum kccm-”
): 3060, 3030, 2980°2930, 2
810.2710°1720, 1600.1490°1450, 1370.960.760° MaaIS spectrum (n7z): i88[:M+3.159.13
4.91゜Example 3 Synthesis of 2-mef-2-phenyl-4-penten-1-al Sodium hydroxide 31 f (Q, 75 mol) water 1
A solution of
l) into the mixed solution.

2-phenylpropionaldehyde 67t (0.50m
ol) and 1-chloro-2-poly38.3F (0,
50m01) was added thereto, and the mixture was heated and stirred at 45°C for 4 hours. ”
After confirming the disappearance of 2-phenylpropionaldehyde, the mixture was separated into 1 layer, and the organic layer was washed with saturated saline.

It was dried with anhydrous magnesium sulfate. Then, benzene was distilled off from this organic layer, and the residual liquid was distilled under reduced pressure to obtain 2-methyl-2-phenyl-4-pente7 at 65-68°C/0.5 m Hf01 min. -1-7
-ru 59f (0.34 mol) was obtained. Yield: 68 cm. The physical properties of the product are shown below.

"HNMR spectrum # (9'OMHz) δCDα8
゛1.31 (8,3H); 2.51 (d, J=7Hz,
2H); 4.75-5.06 (m, 2H) i
5.06~5.71 (m, IH); 7-00~7
-43 (m-5f() + 9.43 (s, I
H) IR spectrum (an”): 3080.30
30.2970.2930゜2800.2710,17
20,1600°1490.1445,920,760
゜MJL811/C vector Cm/Z): 174 [M”
), 145, 105, 91° Example 4 A solution of sodium hydroxide A 31 t (0.76 mol) in 132 d of water g, benzene 13211! J and tetrabutylammonium iodide 2.6 f (0,007 mo
l) 2-phenylbuty-7#'74 f
(0.5 Omol) 7 was added, and after stirring for a while, l-chloro-3-methyl-2-butene 52r was added.
(o, 5 omol) was added dropwise. The reaction temperature rose to about 40°C. After dropping, stir for a while and confirm the disappearance of 2-phenylptalal.
The separated 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-ethyl-5-nonal-2-phenyl-4-hexene as a fraction at 85°C/0.2 ran Hy. 1-
Earl 86f (0.40 mol) was obtained. Yield 80
%.

The physical properties of the product are shown below.

'HNMR 7/ ) Le (9Q MHz) δCDα
3f (MS' 0.70 (t, J=7Hz, 3H): 1.50, 1.
57 (each s, 6H); 2.23 (q, J=71
(z, 28): 2.57 (d, J Near H2,2
H): 4.75-5.03 (m, IH:): 7
．． 05~7.50(m, 51():9.51(s,
IH) IR spectrum (m'): 3070, 3030, 299
0,2940°2890,2810.2710. t7
25°1600, 1500.1450.1380°76
0,700 Mass spectrum (rrv'z): 21.6CM"
E, 148.91.69° Example 5 5-Methyl-2-phenyl-2-propyl-4 Example 4
2-phenylbutyral 741t' (0,5o
2-phenylpentanal 81r (mol) instead of 2-phenylpentanal 81r (
The reaction was carried out in the same manner except that 0.50 mol) was used.
Then, one reaction mixture was treated in the same manner, and the resulting residue was distilled under reduced pressure to 98°C/0.
5-methyl-2-phenyl-2-furopyru-4-hexen-1-al 81W (
0,'35 mol) was obtained. Yield: 70 buns. The physical properties of the product are shown below.

'HNMR, x pair/Torr(90M)Lz)δCDC
f! a.

HMS' 0.69~1-29 (m15)i): 1.47,
1.56 (e ach s , 6 H); 1, b
9'1.96 (m92H) + 2.56 (d,
J = 71 (z, 2H); 4.76-5.03
(rn, 1f(); 7.03~7.43(m, 5
H); 9.46 (s, IH) Kon spectrum Ccm-'): 3050, 3020, 29
50,2920°2870.2800,2700,17
20.1600, 1495. 1440. 1375
゜755.695 Mass spectrum (m/z), 2301:M''), 1
88,162,133゜9],,69.41 Example 6 Sodium hydroxide 31' (0.76 mol) water 1
32rnl OJ) M solution, benzene 132M and iodide tetrab5-lua7-E=um2.6? (
After adding 2-phenylbutanal 74y (0.50 mol) to a mixed solution of 0.007 mol) and stirring for a while, 1-chloro-2-
38.32 (0.50 rnol) of propene was slowly added dropwise. After dropping, the temperature was increased to 45°C for 4 hours, and the temperature was further increased to 60°C for 3 hours.
After confirming the disappearance of 02-phenylbutanal after heating for a period of time.

The organic layer was washed with saturated brine and dried over anhydrous magnesium sulfate. Then, 1. benzene is distilled off from this organic layer, and the residue is distilled under reduced pressure.
, so ~ 81℃ 10.3 rm 2- as a fraction of HP
Ethyl-2-phenyl-4-penten-1-al67
? (0,36rnol) was obtained. Yield: 72 articles. The physical properties of the product are shown below.

1HNMR/C petal) (90MHz) δCDC'
af (MS 0.73 (t, J = 7Hz, 3H); 1.91 (q, J
=7Hy, 2K); 2.62(d, J=7Hz, 2
H); 485-5.14 (In, 2H); 5.2
6-5.73 (m, 1.H); 7.04-7.49
<m, 5) f) i9.50 (B, IH) IR spectrum (cm”): 3070, 3030, 29
70,2940°2880, 2B10.2710.17
20°1640, 1600.1490.1440°92
0, 760.700 Mass spectrum (”/Z): 1881:M”], 1
59,117,105゜Example 7 Synthesis of 2-phenyl-2-furopyru-4-benden-l-al In Example 6, 2-phenylbutanal 74t (0
, 50 mol) of 2-phenylpentanal 81
The reaction was carried out in the same manner except that f (0.50 mol) was used, and then the reaction mixture was treated in the same manner, and the resulting residue was distilled under reduced pressure to produce 8.
2-phenyl- as a fraction at 0 °C/0.5 m Ht
2-propyl-4-penten-1-7-ol 63r (0,
31 mol) was obtained. Yield 62%. The physical properties of the product are shown below.

CDα3 1HNMR/(vector (901vIHz) δHMS
0.86 (t, J=7Hz, 3H) i 0.9
7-1.40 (m, 2H); 1.76-2. OO(
m, 2H) i 2.65 (d, J near Hz,
2H) i4.76-5.16(m, 2:E();
5.28-5.76 (m, tH) i7.07-7.
50 (m, 5H): 9.52 (s, 1H)
) IR spectrum ((7)-1)2 3070, 3030
,2960,2950°2870,2800.2710
．． 1720°1640.1600,1490,1450
゜920.740,700 Mass spectrum (mA): zoz [M”: l, 17
3,131,117゜Example 8 In Example 1, 1-bromo-3 was substituted for 156F (1,50 mol)
-Methyl-2-butene 2239 (1,50 mol)
92.5-dimethyl-2-phenyl-4-hexene-1-7-#212
f (1.05 mol) was obtained. Yield 709b.

Examples 9-17 2,5-dimethyl-2-phenyl-4-hexene-1
Synthesis of -R In Example 1, the same reaction was carried out using the phase transfer catalyst shown in Table 1 in place of tetrabutylammonium iodide, and one reaction mixture was treated in the same manner. Obtained 2,
The yield of 5-dimethyl-2-phenyl-4-hexen-1-al is shown in Table 1.

Reference Example 1 Muguet-like fragrance, composition A fragrance composition having a Muguet-like fragrance was obtained according to the following formulation.7'C.

Iris part Hydroxycitronellal 35 Phenethyl alcohol 1O” linalool 1O Geraniol 6 Benzyl acetate 5 Citronellol
5 hexyl cinnamic aldehyde 3 methyl ionone
4 Ylang-ylang oil
2α-terpineol
3 Geranium oil 2 Diasmine essential oil 1 Musk ketone 1 Cipet tincture 3 Othrobin
2 Reference Example 2 Hyacinth-like fragrance composition A fragrance composition having a hyacinth-like fragrance was obtained according to the following formulation.

Parts by weight Phenethyl alcohol 15 Nymph alcohol 15 Phenylacetaldehyde 5 Benzyl propionate 5 Neroli oil
,.

Bergamotu oil 5 Ylang ylang oil 5 Benzylisoeugenol 10 Linalool
5α-ionone
5 diasmine essential oil
20-s essential oil
2 Nayu Bellows Conhound
2 gum banum resin
2 Stirax Resin 2 Reference Example 3 Fancy Bouquet Fragrance Composition
A fragrance composition having a quet-like aroma was obtained.

Parts by weight Coriander oil 3 Orange flower oil 5 Geranium oil 3 Phenethyl alcohol i.

Benzyl acetate 5 Anisaldehyde 5 Citronello AJ5 Aldehyde C-12 (MC-12 (CH 2
Geraniol 5 Methylionone 10 Hydroxycitronella-klO α-cubineol 5 Betheverol 5 Diasmine Compound 8 Musk Ambrette 3 Heliotropin
2 Opobonax resin
2 ethyl vanillin
22.5-Dimethyl-2-phenyl-4-hexen-1-al 1O [Effects of the Invention] The method of the present invention can produce compounds represented by general formula (III) with better yields than are clear from the above examples. α-phenyl-γ
, δ-unsaturated aldehydes can be produced.

Patent ratio [Kuraray Co., Ltd.

Claims (1)

[Scope of Claims] α-Substituted phenylacetaldehyde represented by the general formula ▲ Numerical formulas, chemical formulas, tables, etc. ▼ (In the formula, R^1 represents a lower alkyl group) and the general formula ▲ Numerical formulas, chemical formulas, tables, etc. etc. ▼ (In the formula, R^2 and R^3 are the same or different and each represents a hydrogen atom or a methyl group, and X represents a halogen atom.) There are general formulas, mathematical formulas, chemical formulas, tables, etc., which are characterized by the reaction being carried out in the presence of a neutral alkali, water and a phase transfer catalyst. (In the formula, R^1, R^2 and R^3 are as defined above. ) A method for producing an α-phenyl-γ, δ-unsaturated aldehyde.