JPH0514695B2 - - Google Patents

Description

[Detailed description of the invention]

[Industrial Application Field] The present invention relates to a method for producing 2-substituted-5-methyl-4-hexen-1-al, and more specifically, the present invention relates to a method for producing 2-substituted-5-methyl-4-hexen-1-al, in particular, an aldehyde, 1-halogeno-3-methyl-2-butene, a caustic alkali, The present invention relates to a method for producing 2-substituted-5-methyl-4-hexen-1-al by reacting in the presence of water and a phase transfer catalyst, and then treating the resulting reaction mixture with an acid. 2-substituted-5- produced by the method of the invention
Methyl-4-hexen-1-al is a compound useful as an aroma component of perfumes or a raw material for its synthesis [see Oil Chemistry, Vol. 31, pp. 295-299 (1982)]. [Prior art] Conventionally, 2-substituted-5-methyl-4-hexene-
It is known that 1-R is produced by the following method (1), (2), (3) or (4). [See Bull.Soc.Chim.France, 2618 (1964)] [See Tetrahedron Letters, No. 15, 1273 (1973)] [See Tetrahedron Letters, No. 5491 (1978)] [See Oil Chemistry, Vol. 31, p. 295 (1982)] [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 135°C for a long time of 30 hours. Moreover, the yield of the target aldehyde is as low as 23%. In the conventional method (2), 2
A large amount of -ethyl-1-hexenyl 3-methyl-2-butenyl ether is produced as a by-product, and furthermore, it is difficult to separate it from the target aldehyde. Also, conventional method
In (3), the reaction reagents potassium hydride and tetrahydrofuran (THF) are expensive. Furthermore, in the conventional method (4), reaction reagents such as lithium aluminum hydride and pyridinium chlorochromate are expensive, and the reaction process is long. Therefore, none of these conventional methods is an advantageous method for producing 2-substituted-5-methyl-4-hexene-1-al-. An object of the present invention is to provide a method for producing highly pure 2-substituted-5-methyl-4-hexen-1-al at low cost and with a good yield. [Means for Solving the Problems] According to the present invention, the above object is achieved by solving the general formula (In the formula, R ¹ and R ² are the same or different and each represents a lower alkyl group or a lower alkenyl group,
Or R ¹ and R ² together

[Formula] Represents a chain. Here, X ¹ , X ² and X ³ are the same or different and each represents a hydrogen atom or a lower alkyl group, and Y ¹ and Y ² each represent a hydrogen atom or together represent a single bond. ) and 1-halogeno-3-methyl-2-butene in the presence of a caustic alkali, water and a phase transfer catalyst, and then the resulting organic product is treated with an acid. general formula to (In the formula, R ¹ and R ² are as defined above.)
This is achieved by providing a method for producing 2-substituted-5-methyl-4-hexen-1-al represented by: R ¹ and R ² in the above general formula will be explained in detail. R ¹ and R ² are the same or different, each a methyl group,
Ethyl group, n-propyl group, i-propyl group, n
-butyl group, i-butyl group, sec-butyl group, n
-lower alkyl group such as pentyl group, n-hexyl group; or vinyl group, 1-propenyl group, 2
-represents a lower alkenyl group such as a propenyl group, 1-butenyl group, 2-butenyl group, 3-butenyl group, or R ¹ and R ² taken together

〔Example〕

EXAMPLES The present invention will be explained below with reference to Examples, but the present invention is not limited to these Examples. Example 1 2,2,5-trimethyl-5-hexene-1
−Synthesis of R Sodium hydroxide 340g (8.50mol), water 340ml,
In a mixed solution of 400 ml of benzene and 31.4 g (85 mmol) of tetrabutylammonium iodide, 760 g (7.27 mmol) of 1-chloro-3-methyl-2-butene was added.
mol) and isobutyraldehyde 639g (8.86mol)
was added dropwise over 8 hours at a temperature of 60 to 70°C. After the dropwise addition was completed, the mixture was stirred at 70°C for 2 hours. After adding 1.5 g of water to this reaction mixture to dissolve the precipitated common salt, the mixture was separated into an organic layer and an aqueous layer.
The solvent was distilled off from the organic layer, 300 ml of 2N sulfuric acid and 300 ml of tetrahydrofuran were added to the residue, and the mixture was heated under reflux for 90 minutes. The product was extracted from the reaction mixture with diethyl ether. The extract was washed successively with water, an aqueous sodium thiosulfate solution, an aqueous sodium bicarbonate solution, and a saturated saline solution, dried over anhydrous magnesium sulfate, and then the solvent was distilled off. By distilling the residue under reduced pressure, 68
2,2,5-trimethyl-5-hexene-1-al (purity 95%) as a fraction at °C/20 mmHg.
642g (4.58mol) was obtained. Yield 63%. of the product
The NMR spectrum is shown below. ¹ HNMR spectrum (90MHz) δ ^CCl4 _HMS : 0.95 (s,
3H); 1.53, 1.64 (each s, 6H); 2.03 (d, J
=7Hz, 2H); 4.83-5.12 (m, 1H); 9.36 (s,
1H) Example 2 Synthesis of 2-ethyl-2,5-dimethyl-4-hexen-1-al In Example 1, 639 g of isobutyraldehyde
(8.86mol) instead of 2-methylbutanal 763g
The reaction was carried out in the same manner except that (8.86 mol) was used,
The reaction mixture was then treated in the same manner and the resulting residue was distilled under reduced pressure to give 88-
2-ethyl-2,5 as a fraction at 89℃/20mmHg
-dimethyl-4-hexene-1-al (purity 90
%) was obtained (606 g (3.93 mol)). Yield 54%. The NMR spectrum of the product is shown below. ¹ HNMR spectrum (90MHz) δ ^CCl4 _HMS : 0.79 (t, J
=7Hz, 3H); 0.95, (s, 3H); 1.31~1.52
(m, 2H); 1.59, 1.68 (each s, 6H); 2.08
(d, J=7Hz, 2H); 4.85-5.15 (m, 1H);
9.43 (s, 1H) Example 3 Synthesis of 2,5-dimethyl-2-propyl-4-hexen-1-al In Example 1, 639 g of isobutyraldehyde
(8.86mol) instead of 2-methylpentanal728
The reaction was carried out in the same manner except that 2.0 g (7.27 mol) was used, and then the reaction mixture was treated in the same manner, and the resulting residue was distilled under reduced pressure to obtain 2. 820 g (4.87 mol) of 5-dimethyl-2-propyl-4-hexen-1-al (purity 96%) was obtained. Yield 67
%. The NMR spectrum of the product is shown below. ^1HNMR spectrum (90MHz) δ ^CCl4 _HMS : 0.69-1.03
(m, 3H); 0.94 (S, 3H); 1.03~1.53 (m,
4H); 1.57-1.67 (each s, 6H); 2.07 (d, J
=7Hz, 2H); 4.85-5.15 (m, 1H); 9.40 (s,
1H) Example 4 2-butyl-2-ethyl-5-methyl-4-
Synthesis of hexene-1-al In Example 1, 639 g of isobutyraldehyde
(8.86mol) instead of 2-ethylhexanal
The reaction was carried out in the same manner except that 1136 g (8.86 mol) was used, and the reaction mixture was then treated in the same manner, and the resulting residue was distilled under reduced pressure to obtain 2- Butyl-2
-Ethyl-5-methyl-4-hexen-1-al (purity 95%) was obtained in an amount of 742 g (3.78 mol). yield
52%. The NMR spectrum of the product is shown below. ¹ HNMR spectrum (90MHz) δ ^CCl4 _HMS : 1.75 (t, J
=7Hz, 3H); 0.77-1.54, (m, 8H); 1.47
(q, J=7Hz2H); 1.60, 1.67 (each s,
6H); 2.14 (d, J=7Hz, 2H); 4.85-5.10
(m, 1H); 9.40 (s, 1H) Example 5 Synthesis of 1-(3-methyl-2-butenyl)-3-cyclohexenecarbaldehyde In Example 1, 639 g of isobutyraldehyde
The reaction was carried out in the same manner except that 3-975 g (8.86 mol) was used instead of 3-975 g (8.86 mol), and the reaction mixture was then treated in the same manner. /0.9mmHg fraction 1-(3-methyl-2-butenyl)-3-
Cyclohexecanecarbaldehyde (92% purity)
621g (3.49mol) of was obtained. Yield 48%. of the product
The NMR spectrum is shown below. ¹ HNMR spectrum (90MHz) δ ^CCl4 _HMS : 1.57, 1.67
(each s, 6H); 1.59~1.86 (m, 2H); 1.89~
2.30 (m, 6H); 4.89-5.17 (m, 1H); 5.63 (bs,
2H); 9.50 (s, 1H) Example 6 Synthesis of 1-(3-methyl-2-butenyl)cyclohexanecarbaldehyde In Example 1, 639 g of isobutyraldehyde
The reaction was carried out in the same manner except that 994 g (8.86 mol) of cyclohexanecarbaldehyde was used instead of 67 1-(3 as a fraction of °C/0.9mmHg
-Methyl-2-butenyl) cyclohexacarbaldehyde (purity 94%) was obtained in an amount of 680 g (3.78 mol).
Yield 52%. The NMR spectrum of the product is shown below. ^1HNMR spectrum (90MHz) δ ^CCl4 _HMS : 1.31~1.67
(m, 10H); 1.54, 1.66 (each s, 6H); 2.05
(d, J=7Hz, 2H); 4.88-5.15 (m, 1H);
9.48 (s, 1H) Example 7 Synthesis of 1-(3-methyl-2-butenyl)-6-methyl-3-cyclohexenecarbaldehyde In Example 1, 639 g of isobutyraldehyde
The reaction was carried out in the same manner except that 1100 g (8.86 mol) of 6-methyl-3-cyclohexenecarbaldehyde was used instead of 6-methyl-3-cyclohexenecarbaldehyde (8.86 mol), and the reaction mixture was then treated in the same manner. By distillation, 1-(3-methyl-2-butenyl)-6-
685 g (3.56 mol) of methyl-3-cyclohexenecarbaldehyde (purity 93%) was obtained. Yield 49
%. The NMR spectrum of the product is shown below. ¹ HNMR spectrum (90MHz) δ ^CCl4 _HMS : 1.09 (d, J
=7Hz, 3H); 1.55, 1.64 (each s, 6H);
1.88-2.29 (m, 7H); 4.90-5.18 (m, 1H);
5.57 (bs, 2H); 9.50 (s, 1H) Example 8 Synthesis of 1-(3-methyl-2-butenyl)-3-methyl-3-cyclohexenecarbaldehyde In Example 1, 639 g of isobutyraldehyde
The reaction was carried out in the same manner except that 1100 g (8.86 mol) of 3-methyl-3-cyclohexenecarbaldehyde was used instead of 3-methyl-3-cyclohexenecarbaldehyde (8.86 mol), and the reaction mixture was then treated in the same manner. By distillation, 1-(3-methyl-2-butenyl)-3-
495 g (3.92 mol) of methyl-3-cyclohexenecarbaldehyde (purity 95%) was obtained. Yield 54
%. The NMR spectrum of the product is shown below. ¹ HNR spectrum (90MHzσ ^Ccl4 _HMS : 1.40~1.55 (m,
2H); 1.54, 1.63, 1.69 (each s, 9H); 1.87~
2.31 (m, 6H); 4.89-5.20 (m, 1H); 5.49 (bs,
1H); 9.45 (s, 1H) Example 9 1-(3-methyl-2-butenyl)-4-(2-
Synthesis of methylpropyl)-3-cyclohexenecarbaldehyde In Example 1, 639 g of isobutyraldehyde
(8.86mol) instead of 4-(2-methylpropyl)
-3-Cyclohexenecarbaldehyde 1473g
The reaction was carried out in the same manner except that (8.86 mol) was used,
The reaction mixture was then treated in the same manner and the resulting residue was distilled under reduced pressure to give 91-
1-(3-methyl-
2-butenyl)-4-(2-methylpropyl)-3
- Cyclohexenecarbaldehyde (95% purity)
1022g (4.36mol) of was obtained. Yield 60%. of the product
The NMR spectrum is shown below. ¹ HNR spectrum (90MHz) σ ^CCl4 _HMS : 0.98 (d, J
=7Hz, 6H); 1.26-1.53 (m, 3H); 1.55,
1.67 (eachs, 6H); 1.85-2.29 (m, 8H); 4.89
~5.18 (m, 1H); 5.61 (bs, 1H); 9.54 (s,
1H) Examples 10 to 18 The reaction was carried out in the same manner as in Example 1 except that the phase transfer catalyst shown in Table 1 was used instead of tetrabutylammonium iodide, and the reaction mixture was then treated in the same manner. Table 1 shows the purity and yield of the obtained 2,2,5-trimethyl-4-hexen-1-al.

【table】

【table】

[Table] Examples 19-25 The reaction was carried out in the same manner as in Example 1 except that the acids shown in Table 2 were used instead of 300 ml of 2N sulfuric acid, and then the reaction mixture was treated in the same manner. The obtained 2,2,5-trimethyl-4-hexene-
The purity and yield of 1-R are shown in Table 2.

[Table] Comparative Examples 1 to 5 Reactions were carried out in the same manner as in Examples 1 to 5 except that the acid treatment was not performed, and the reaction mixtures were treated in the same manner. The purity and yield of the obtained aldehyde were measured in the third
Shown in the table.

【table】

〔Effect of the invention〕

According to the method of the present invention, as is clear from the above examples, highly purified 2-substituted-5-methyl-4-hexen-1-al represented by the general formula () can be produced at low cost and in a good yield. be able to.

Claims (1)

[Claims] 1 General formula [Formula] (wherein R ¹ and R ² are the same or different and each represents a lower alkyl group or a lower alkenyl group,
Or R ¹ and R ² together represent a chain. Here, X ¹ , X ² and X ³ are the same or different and each represents a hydrogen atom or a lower alkyl group, and Y ¹ and Y ² each represent a hydrogen atom or together represent a single bond. ) and 1-halogeno-3-methyl-2-butene in the presence of a caustic alkali, water and a phase transfer catalyst, and then the resulting organic product is treated with an acid. general formula to (In the formula, R ¹ and R ² are as defined above.)
A method for producing 2-substituted-5-methyl-4-hexen-1-al represented by