JPS6045861B2 - Method for producing 3,5-octadiyn-1-ol - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing known substances 3,5-octadiyn-1-ols useful for producing pheromone synthetic intermediates, apple aroma flavor component synthetic intermediates, and other synthetic derivatives.

3,5-octadiyne-17 represented by the above formula (1)
60 (1965), the silkworm moth [SllkM
oth: BombyxnoriL] and Maimai [Gi
psyMoth:LymantriadisparL)
It has been described that it is an important intermediate of cis-3-5- or trans-3-trans-5-octadien-1-ol, which is an attractant for cis-3-5-octadien-1-ol.

Furthermore, according to JP-A No. 54-24805, it is also described that it is an important intermediate of geometrically 3,5-octadien-1-ol, which is an aromatic flavor component in natural apple essential oil. Conventionally, as a method for producing 3,5-octadiyn-1-ol represented by the above formula (1), the above-mentioned JP-A-54-2
Monatsh, Ch., cited in No. 4805, supra.
em.

, 6) pages 1766 to 1760 is known. According to this method, the following formula, C1-CH2
~C...C-CH2=C1+ CH3CH2ICH3CH
2C...C-C King ℃H Liquid ammonia 1) CH3CH2MgBr CHaCH2C...C-C King CH2CH2OH2) H2C
-CH2\ / It is synthesized from 1,4-dichloro-2-butyne through multiple steps.

This method requires the use of liquid ammonia, which is disadvantageous in terms of operation and equipment, requires the use of Grignard reagent, which is complicated to handle and operate, requires multiple steps, and has the disadvantage of producing by-products. There are many problems and the yield is poor.For example, MOnatshChem. ,raccoon dog(
6) As described in pages 1766 to 1780 (1965), the yield is only about 31% at most. The present inventors have conducted research to develop a method for producing 3,5-octadiyn-1-ol that can overcome many of the deficiencies and difficulties in the above-mentioned conventional methods. As a result, 1-halogeno-1-butyne of formula (2) below, which is easily obtained from 1-butyne, and 3-butyn-1-ol of formula (3), which is easily available on the market and easy to produce, were combined with amine 3,5-octadiyn-1-ol of the following formula (1) can be produced with high purity and high yield, and is industrially advantageous with easy operation, by simply contacting it in the presence of a catalytic amount of cuprous ions. discovered that it could be manufactured. In this way, 3,5-octadiyn-1-ol, which has been synthesized by the disadvantageous conventional method, although it has been attracting attention as a synthetic intermediate for pheromone synthesis, apple aroma and flavor component synthesis, etc., can be provided more cheaply and easily. It was found that this method is useful for the development of these synthetic fields.

Therefore, the object of the present invention is to provide 3,5-octadiyne-1-
An object of the present invention is to provide a method for manufacturing oars industrially and advantageously.

The above objects and advantages of the present invention will become more apparent from the following description. According to the method of the present invention, the following formula (2),
However, in the formula, X represents a halogen atom and 1-halogeno-1-butyne and the following formula (3
), in the presence of amines and a catalytic amount of cuprous ion, to form 3,5-octadiyn-1-ol represented by the following formula (1). It can be advantageously produced industrially by easy means with high purity and high yield.

The reaction can be carried out, for example, by dropping the compound of formula (2) into a solution of 3-butyn-1-ol of formula (3) in water or an appropriate organic solvent in the presence of an appropriate amine and a catalytic amount of cuprous ion. This can be easily carried out by bringing them into contact and causing a condensation reaction.

The dropping and reaction can be carried out at a wide range of temperatures, such as from about -80°C to about 100°C, with a more preferable example of a temperature range from about 0°C to about 50°C. The dropping and reaction time can be changed as appropriate depending on the reaction temperature, etc.
For example, a reaction time of about 1 hour to about 5 hours can be exemplified. The above formula (2) 1-halogeno-1-butyne is described, for example, in Ann. Chim (Paris) [13]
λ852 (1957), 0r″G.syrlth■92
1 (1973), J. Chem. SOc. River race 2295
It can be easily produced from 1-butyne according to the method described in et al.

Moreover, 3-butyn-1-ol of formula (3) is easily available on the market. Examples of amines used in the above reaction are:
Preferred examples include amines selected from the group consisting of 01-C4 alkyl amines, di(C1-C4 alkyl) amines, tri(C1-C4 alkyl) amines, and C1-C6 alkanolamines. . Specific examples of such amines include primary amines such as methylamine, ethylamine, propylamine, isopropylamine, and butylamine; secondary amines such as dimethylamine, diethylamine, dipropylamine, diisopropylamine, diisobutynamine, and dibutynamine; Diamines; tertiary amines such as trimethylamine, triethylamine, triisopropylamine, tripropylamine, and tributinamine; monoethanolamine, nodiethanolamine, triethanolamine; and the like.
These amines can be used alone or in combination of two or more. There is no particular restriction on the amount of these amines to be used, but for example, about 1 mol to about 100 mol is sufficient, more preferably about Amounts of about 1 mole to about 50 moles are often used. 3-butyne-1- used in the above condensation reaction
The amount of ol to be used can be appropriately selected, and for example, about 1 to about 2 mol is often employed per 1 mol of the compound of formula (2) as a raw material.

Further, as the cuprous ion source used in the above condensation reaction, any source that produces cuprous ions within the reaction system may be used.

Specific examples include cuprous chloride, cuprous bromide,
Examples include cuprous iodide, copper cyanide, cuprous sulfate, and the like. The amount of these to be used is, for example, about 0.001 to about 1 mol per 1 mol of the compound of formula (2) as the raw material, and more preferably about 0.01 to 0.05 mol. Often adopted. In addition, in the above condensation reaction,
Even better results can be obtained by adding a small amount of a reagent that is effective in suppressing the by-product of cupric ions, such as hydroxylamine. Furthermore, specific examples of the solvent used in the above condensation reaction include water, alcoholic solvents such as methanol and ethanol; tetrahydrofuran, dioxane,
Examples include organic solvents such as ether solvents such as diethyl ether and diglyme; amide solvents such as dimethylformamide, dimethyl sulfoxide, and hexamethylene phosphorotriamide;

These solvents can be used alone or in combination of two or more. There is no particular restriction on the amount of these solvents used, and the amount used is about 0 to about 10 times the heel volume, more preferably about 2 to about 1 times the volume of the compound of formula (2) as the raw material. can be exemplified. After the completion of the above condensation reaction, for example, the reaction product is injected into water, extracted with a suitable solvent, the solvent layer is washed with water, dried and concentrated to obtain the formula (1).
3,5-octadiyn-1-ol can be produced with high yield and high purity.

If desired, further purification can be carried out by means such as vacuum distillation or column chromatography. The embodiments of the present invention will be explained in more detail with reference to Examples below! Explain in detail.

Reference Example (Synthesis of 1-bromo-1-butyne) A reaction flask was charged with 150 g of caustic soda and 400 g of water and cooled to 00C.

104 g of bromine are added dropwise at 0 to 5°C. After the dropwise addition and stirring, 35 g of 1-butyne was introduced at 0°C. O~
After the introduction at 100C, the reaction is continued for an additional 6 hours. hexane 50
Add 1-bromo-1-butyne and extract 1-bromo-1-butyne.
Obtain a hexane solution of 09.
Yield 59g169% yield, obtained 1
- Promobutin may be used as it is in hexane solution. Example 1 3,5-octadiyn-1-ol Into a reaction flask, add 130 ml of a 33% aqueous ethylamine solution.
, cuprous iodide 1.3g1 hydroxyamine hydrochloride 3-
Charge 31 g of butyn-1-ol.

Contains 59 g of 1-bromo-1-butyne obtained as shown in Reference Example. Hexane solution 109 is added dropwise at 30 to 40° C. over J1 hour. After the dropwise addition, the reaction was continued for another 3 hours. After adding 1 g of sodium cyanide, the hexane layer was separated, washed with water, dried, and the hexane was recovered to obtain 38 g of residual liquid. Distilled under reduced pressure, boiling point 98℃~1000C/27r0
37 g of 3,5-octadiyn-1-ol of nHg was obtained. Example 2 Distilled 1-bromo-1-butyne (boiling point 90-92°C/76011g) using cuprous chloride instead of copper iodide 5
The same reaction operation as in Example 1 was carried out using 9 g, and 3
, 46 g of 5-octadiyn-1-ol were obtained.

Example 3 A reaction was carried out in the same manner as in Example 1 using 1-chloro-1-butyne instead of 1-bromo-1-butyne to obtain 3,5-octadiyn-1-ol with a yield of 82%.

Example 4 A reaction was carried out in the same manner as in Example 1 using 1-iodo-1-butyne instead of 1-bromo-1-butyne and dimethylamine instead of ethylamine to give 3,5 with a yield of 80%.
-octadiyn-1-ol was obtained.

Example 5 A reaction was carried out in the same manner as in Example 1 using tributylamine instead of ethylamine to obtain 3,5-octadiyn-1-ol with a yield of 65%.

Example 6 A reaction was carried out in the same manner as in Example 1 using monoethanolamine instead of ethylamine to give 3 with a yield of 73%.
, 5-octadiyn-1-ol was obtained.

Claims (1)

[Claims] 1 The following formula (2) CH_3CH_2C≡C-X (2) However, in the formula, X represents a halogen atom and 1-halogeno-1-butyne and the following formula (3
), HC≡CCH_2CH_2OH (3) The following formula (1), CH_3CH_2C≡, is characterized by condensing 3-butyn-1-ol represented by: C・C≡
A method for producing 3,5-octadiyn-1-ol represented by CCH_2CH_2OH (1). 2 The amines are C_1-C_4 alkyl amines, di(C_1-C_4 alkyl) amines, tri(C
_1~C_4 alkyl)・amines and C_1~C_6
The method according to claim 1, wherein the amine is selected from the group consisting of alkanolamines.