JPS5946513B2 - 1,2-epoxy derivative - Google Patents

Description

[Detailed description of the invention] The present invention relates to novel 1,2-epoxy derivatives.

The 1,2-epoxy derivative of the present invention is a novel compound that has not been described in any literature, and has the general formula [wherein R represents a group C4H9CΞC- or a group C4H9CH-CH-].

].

The 1,2-epoxy derivative of the present invention is a compound useful as an intermediate for synthesizing Z-11-hexadecenal, which is known as the sex pheromone of the diamondback moth. The 1,2-epoxy derivative of the present invention is, for example, the following reaction scheme-1
It is manufactured as shown in .

Reaction Scheme-1 [In the formula, Ts represents a tosyl group.

] 10-Undecen-1-ol (Compound [3)] is produced by reducing known 10-Undecenoic acid (Compound [2]).

Examples of the reducing agent used include lithium borohydride,
Examples include sodium borohydride aluminum monochloride, lithium aluminum hydride, lithium aluminum hydride aluminum monochloride, alkylamine-borane, and diborane (preferably lithium aluminum hydride). The amount of such reducing agent used is compound [2]
It is usually at least 0.5 times the molar amount, preferably equimolar to 2 times the molar amount. The reaction is generally carried out in an inert solvent. Specific examples of inert solvents include ethers such as dinityl ether, monoglyme, diglyme, dioxane, and tetrahydrofuran, hexane,
Examples include saturated hydrocarbons such as cyclohexane and petroleum ether, and aromatic hydrocarbons (preferably ethers) such as benzene, toluene and xylene. The reaction temperature for this reaction is usually -20 to 50°C, preferably 00C to room temperature, and the reaction is generally completed in about 1 to 5 hours. 1-Tosyloxy-10-undecene (compound [4]) is produced by tosylating compound [3].

Examples of tosylation agents that can be used include p-toluenesulfonyl chloride and p-toluenesulfonyl bromide. The amount of the tosylating agent to be used is usually at least equimolar, preferably 1.5 to 2 times the molar amount of compound [3]. The reaction is generally carried out in the presence of a basic compound in an inert solvent. A wide range of known basic compounds can be used,
Preferred examples include tertiary amines such as pyridine and triethylamine, and carbonates such as sodium hydrogen carbonate and potassium carbonate. Specific examples of inert solvents include tertiary amines such as pyridine and triethylamine, halogenated hydrocarbons such as chloroform, methylene chloride, dichloromethane, and 1,2-dichloroethane, the above-mentioned ethers,
Examples include the aromatic hydrocarbons, dimethyl sulfoxide, dimethyl formamide (preferably tertiary amines and halogenated hydrocarbons). The reaction temperature for this reaction is usually -3°C to room temperature, preferably -10 to 5°C, and the reaction is generally completed in about 1 to 5 hours. 1-brome-1
0-Undecene (compound [5)] is produced by reacting compound [4] with metal bromide.

Examples of the metal bromide used include lithium bromide, sodium bromide, and potassium bromide (preferably lithium bromide).
I can list many things. The amount of metal bromide to be used is usually equimolar to excess, preferably 1.5 to 2 times the molar amount of compound [4]. The reaction is generally carried out in a solvent such as the above-mentioned ethers, the above-mentioned halogenated hydrocarbons, and ketones (preferably ketones) such as acetone, methyl ethyl ketone, and diethyl ketone. The reaction temperature for this reaction is usually room temperature to 150°C, preferably 50°C.
~100°C, and the reaction is generally completed in about 3 to 8 hours. 1-bromo-10,11-epoxyundecene (compound [6]) is produced by reacting compound [5] with a peroxide.

The peroxide to be used is not particularly limited and a wide range of ordinary inorganic or organic peroxides can be used. Examples include perbenzoic acids such as perbenzoic acid and m-chloroperbenzoic acid, performic acid, peracetic acid, and peroxide. Examples include lower fatty acids such as propionic acid, hydrogen peroxide (preferably perbenzoic acids), and the like. The amount of peroxide to be used is usually an equimolar to an excess amount, preferably an equimolar to 1.5 times the molar amount of the compound [5]. The reaction is generally carried out in an inert solvent. Examples of the inert solvent include the above halogenated hydrocarbons, the above saturated hydrocarbons, the above ethers,
The aromatic hydrocarbons, water, dimethyl sulfoxide, dimethyl formamide, hexamethyl phosphoric triamide (
Preferred examples include halogenated hydrocarbons). The reaction temperature for this reaction is usually 13°C to room temperature, preferably 0 to 5°C, and the reaction is completed in about 0.5 to 6 hours.
Compound [1a] is produced by reacting compound [6] with l-hexyne (compound [7]).

The ratio of compound [6] and compound [7] to be used is usually at least equal moles of the latter to the former, preferably 1.
It is preferable to use 5 to 2 times the molar amount. The reaction proceeds advantageously in the presence of a basic compound. Basic compounds include metal amides such as sodium amide, lithium amide, potassium amide, methyllithium, n-butyllithium,
Examples include alkyllithiums (preferably n-butyllithium) such as Sec-butyllithium and t-butyllithium, and the amount of such basic compounds is usually at least equimolar, preferably equimolar to 1, relative to compound [7]. It is preferable to use .5 times the molar amount. The reaction is generally carried out in a solvent such as the ethers, saturated hydrocarbons, aromatic hydrocarbons, liquid ammonia (preferably ethers), or the like. The reaction temperature for this reaction is usually -5°C to room temperature, preferably -30 to 10°C, and the reaction is generally completed in about 1 to 5 hours. 1,2-epoxy-12(Z)-heptadecene (compound [1b] is produced by catalytic reduction of compound [1a]).

Catalytic reduction catalysts used include palladium barium monosulfate, palladium monocalcium carbonate, and P-2 nickel (
Preferred examples include palladium (barium monosulfate) and the like. The reaction is carried out in a solvent such as water, lower alcohols such as methanol, ethanol, and isopropanol, the above-mentioned ethers, and lower fatty acids (preferably lower alcohols) such as acetic acid and propionic acid. The reaction involves pyridine,
It proceeds advantageously in the presence of a base such as quinoline or ethylenediamine. The reaction temperature of this reaction is usually -3°C to 50°C.
The temperature is preferably 0° C. to room temperature, and the reaction is generally completed in about 1 to 5 hours. The compound of the present invention thus obtained (
Compound [1a] and compound [1b)) can be easily isolated and purified by conventional separation means such as solvent extraction, distillation, silica gel column chromatography, etc.

Compound [1b] can be induced to Z-11-hexadecenal (compound [8]), which is a sex pheromone of the diamondback moth, for example, by the method shown in the following reaction scheme-2.

Reaction Scheme-2 Compound [8] is produced by oxidation reaction of compound [1b].

Examples of the oxidizing agent that can be used include periodic acid salts such as periodic acid, sodium periodate, and potassium periodate. It is preferable to use a molar to 1.5 times the molar amount. The reaction involves water, the halogenated hydrocarbons,
The reaction is carried out in a solvent such as the saturated hydrocarbons, ethers, dimethylsulfoxide, dimethylformamide, hexamethylphosphoric triamide (preferably water, ethers, dimethylsulfoxide and dimethylformamide). The reaction temperature is usually -30°C to room temperature, preferably 0 to 10°C, and the reaction is generally completed in about 1 to 3 hours. Compound [2], which is a starting material for synthesizing the compound of the present invention, is a cheap and easily available compound, and the reaction operations for each reaction are simple and the desired product can be obtained in good yield.

Therefore, by combining the above reaction schemes 11 and 2, compound [8], which is a sex pheromone substance for the diamondback moth, can be produced in good yield and at low cost through simple operations. Therefore, it can be said that the compounds of the present invention are extremely useful as intermediates for synthesizing the sex pheromone of the diamondback moth. Examples and reference examples are listed below.

Example (1) 10-undecen-1-ol (compound [3)
Preparation of ) 7.39 g of lithium aluminum hydride are suspended in 100 d of dry ether.

A solution of 10-undecenoic acid 259 in 50 ml of dry ether was added dropwise to this mixture over a period of 1 hour while stirring on ice. Stir overnight at room temperature. The reaction solution was carefully poured into ice water, adjusted to PHL with 5% hydrochloric acid, and extracted with ether. The ether solution is washed with water, saturated aqueous sodium bicarbonate and saturated brine, and dried over potassium carbonate. The ether is distilled off and the residue is distilled under reduced pressure. Yield: 2.29, boiling point: 95-102℃/1.571mHg (
2) l-Tosyloxy-10-undecene (compound [
4) Production of 10-undecen-1-ol 22.29
is dissolved in 100 ml of dry pyridine.

Add p-toluenesulfonyl chloride 2979 while stirring on ice. Stir for 2 hours under ice cooling. Pour the reaction solution into ice water and extract with ether. The ether solution is washed with dilute hydrochloric acid, saturated aqueous sodium bicarbonate and saturated brine, and dried over magnesium sulfate. The ether was distilled off to obtain a crude product, which was used as it was in the next reaction. Yield 359 (3) l-brome-10
-Production of undecene (compound [5]) 1-tosyloxy-10-undecene 35f! Dissolve in 150 ml of acetone.

Lithium bromide 1919 was added to the mixture and the mixture was refluxed for 3 hours with stirring. Acetone was distilled off, water was added to the residue, and the mixture was extracted with n-hexane. The n-hexane solution was washed with saturated brine and dried over magnesium sulfate. The n-hexane is distilled off and the residue is distilled under reduced pressure. Yield 2389, boiling point 95~
98°C/371111Hgn151.4680D° (4) Preparation of 1-bromo-10,11-epoxyundecene 2 (compound [6]) 1-Bromo-10-undecene 2389 was dissolved in 100 ml of methylene chloride.

To this was added dropwise a solution of 24.99 m-chloroperbenzoic acid in 250 ml of methylene chloride while stirring on ice. Stir overnight at room temperature. The reaction solution was washed with saturated aqueous sodium bicarbonate and saturated brine, and then dried over magnesium sulfate. The methylene chloride is distilled off and the residue is distilled under reduced pressure. Yield 20.89, boiling point 123-12
5 n151.4733 D (5) Preparation of 1,2-epoxy-12-heptadecine (compound [1a]) 4.29 ml of 1-hexyne is dissolved in 30 ml of dry tetrahydrofuran.

To this was added n- of 1.6N n-butyllithium under ice-cooling and stirring.
Add 18 drops of 31.5ml of hexane solution and stir for 30 minutes. Then, 10.4 f of 1-bromo-10,11-epoxyundecene was added under ice-cooling and stirring! A solution of 60 ml of dry hexamethylphosphorus triamide was added dropwise and stirred for 2 hours. The reaction solution was poured into ice water and extracted with n-hexane. The n-hexane solution was washed with water and saturated saline, and dried over magnesium sulfate.''The n-hexane was distilled off, and the residue was subjected to silica gel column chromatography (Wakogel C-200, 1).
009). n-hexane ether (20:
1) and distilled under reduced pressure. Yield 8.19, boiling point 13
3-135 (C/1HI11Hgn151.4626D (6) Preparation of 1,2-epoxy-12(2)-heptadecene (compound [1b]) 1,2-epoxy-12-heptadecine 49 is dissolved in 80 ml of ethanol.

To this, 0.59 I) barium palladium monosulfate and 8 drops of quinoline are added, and hydrogen is absorbed at room temperature and normal pressure.
When the theoretical amount of hydrogen has been absorbed, the catalyst is removed and the mother liquor is concentrated under reduced pressure. The residue was dissolved in ether, washed with water and saturated brine, and dried over magnesium sulfate. The ether was distilled off, and the residue was subjected to silica gel column chromatography (
Purify with Kieselgel 6O, 70-230 mesh, 409) manufactured by Talc.

Elute with n-hexane ether (20:1) and distill under reduced pressure. Yield 349, boiling point 122-125℃/0.7m
7! THgnl5l. 4562D Reference Example Z-1 Production of 1-hexadecenal (compound [8]) 1
, 0.69 of 2-epoxy-12(Z)-heptadecene is dissolved in 10 ml of ether.

To this was added dropwise a solution of 06 g of periodic acid in 5 ml of tetrahydrofuran while stirring on ice. Stir at room temperature for 2 hours. Pour the reaction solution into water and extract with ether. The ether solution is washed with saturated aqueous sodium bicarbonate and saturated brine, and then dried over magnesium sulfate. The ether was distilled off, and the residue was subjected to silica gel column chromatography (Kiesel gel 6O manufactured by Talc).
, 209). n-hexane riether (40
:l) and distilled under reduced pressure. Yield 0.39, boiling point 125-13'C/0.157mHgn241.451
2D

Claims (1)

[Claims] 1. General formula▲There are mathematical formulas, chemical formulas, tables, etc.▼ [In the formula, R is a group C_4H_9C≡C- or a group C_4H_
9CH=CH-. ] A 1,2-epoxy derivative represented by: