JPS6039344B2 - Method for producing 6- or 7-alkyne-11-one - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a novel method for producing an intermediate for producing an unsaturated ketone, which is a sex pheromone component of certain moths and is useful as a repellent.

Formula C ratio (CH2)4CH niCH(CH2)3C.

Cis-6-hendicosene-11-one, represented by (CH2)9CH3, is a species of moth (Douglasfirth order sock moth) that damages coniferous trees in western North America.
cis-7-nonadecen-11-one, represented by the formula CH3(CH2)5CH=CH(CQ)2C0(CH2)7CH3;
2) 5CH=CH(CH2)2C.

Cis-7-eicosen-11-one, represented by (CH2)8CH3, is a sex pheromone component of the Japanese peach moth, which causes great damage by feeding on fruits such as peaches, apples, and pears in Japan. It is used to exterminate pests. The methods for producing these compounds include:
Several methods have been known so far, but since all of these compounds have a cis-type double bond, first an acetylenic ketone with the corresponding triple bond is produced, and then the triple bond is reduced to produce a double bond. The method of forming double bonds is industrially advantageous.

However, all of the known methods for producing acetylenic ketones, which are intermediates for producing the above compounds, have drawbacks such as difficulty in obtaining raw materials, complicated reaction operations, and low yields. However, it was not satisfactory for industrial implementation.

The present inventors have conducted intensive research to develop an industrially practicable method for efficiently producing acetylene ketones, which are intermediates for producing the pheromone component described above. They discovered that the object could be achieved by reacting -nonine or 1-halogen-3-nonine with 3-oxocarboxylic acid ester and decarboxylating the reaction product at the same time as hydrolyzing it, leading to the present invention. Ta.

That is, the present invention relates to a compound having the general formula CH3(CH2)mC3C(CH2)6-mX .
．． ．． (1) (in the formula, X is a halogen atom, m is an integer of 4 or 5) and a halogenated alkyne with the general formula CH3(CH2)nCOCQC02R...
・After reacting with a 3-oxocarboxylic acid ester represented by (0) (in the formula, R is a lower alkyl group and n is an integer of 7 to 9) in the presence of a base, the reaction is performed with an acid or alkali aqueous solution. General formula CH3(CH2)mC...C(C-wide)7-mC○(CH2)nCH3...(
m) (wherein m and n have the same meanings as above) provides a method for producing 6-1 or 7-alkyne-11-one.

The compound of formula (1) used in the production method of the present invention is 1
-halogen-2-nonine, 1-halogen-3-nonine, etc., and chlorine or bromine is particularly advantageously used as the halogen.

Further, the compound represented by the above formula (b) is a lower alkyl ester of 3-oxocarboxylic acid, a lower alkyl ester of 3-oxotridecanoate, or a lower alkyl ester of 3-oxotetradecanoate, and a lower alkyl ester of the ester The alkyl group is selected from methyl, ethyl, propyl and butyl groups having up to 4 carbon atoms, with methyl being particularly preferred. The compounds represented by formulas (1) and (0) above are usually reacted in a solvent.

Such a solvent is not particularly limited as long as it dissolves both of these reaction components and does not react with both components, but
For example, aromatic hydrocarbons such as benzene and toluene; aliphatic hydrocarbons such as pentane and hexane; ether,
Preferred examples include solvents such as tetrahydrofuran; aprotic polar solvents such as dimethylformamide and dimethyl sulfoxide. These may be used alone or in combination of two or more. Furthermore, it is necessary to have a base present in the reaction system.

Examples of such bases include highly preferred ones such as sodium alcoholate, sodium hydride, sodium metal, and sodium amide, but any base that can form a phenolate of 3-ketester can be used. These bases may be used alone or in combination of two or more.
Extremely low or high temperatures are not preferred for the reaction temperature, and a temperature at which the commonly used solvent refluxes relatively slowly is preferred. Although the reaction time varies depending on the base used, the type and amount of the solvent, etc., it generally takes from one European hour to several days. Furthermore, since this reaction is significantly inhibited by the presence of moisture in the reaction system, it is important to block moisture. After the reaction is completed in this manner, the solvent used is distilled off and the remaining reaction product is subjected to hydrolysis and decarboxylation treatment.

This treatment is performed under acidic or alkaline conditions. Acidic conditions are preferably applied with aqueous solutions of mineral acids, and alkaline conditions are conveniently applied with aqueous solutions of alkali metal oxides such as sodium hydroxide, potassium hydroxide. Acidic conditions can also be used, but in that case it is desirable to use them in combination with mineral acids. It is not preferable for these acids or alkalis to be too concentrated, and an aqueous solution of about 1 to 25% by weight is usually advantageously used. During this hydrolysis and decarboxylation treatment, the reaction product from which the solvent has been removed may be purified, but it is extremely advantageous because it can be directly subjected to the next hydrolysis and decarboxylation reaction without being purified. . The hydrolytic decarboxylation reaction is usually carried out under heating, and a temperature at which the reaction solution to which an acid or alkali aqueous solution is added is gently refluxed is advantageously employed in practice.

The reaction time varies depending on the type and concentration of the acid or alkali used and the temperature, but is usually in the range of several hours to several feeding hours. After the reaction is completed, the target compound can be taken out by a conventional method.

For example, the reaction solution is cooled to room temperature, and when the reaction is carried out in an acidic environment, it is poured into ice water and added with salt to saturate it, and when the reaction is carried out in an alkaline environment, it is poured into ice water containing hydrochloric acid and the solution is poured into ice water. Mix to saturate with salt. Next, this is extracted with a water-immiscible solvent such as enamel, and the enamel layer is sequentially washed with an aqueous solution of sodium bicarbonate and brine, dried, and then the solvent is distilled off to obtain the target product. can. In order to obtain a highly pure target product, commonly known methods such as purification means such as distillation and chromatography can be used. According to the method of the present invention, 6-alkyne-11-one and 7-alxo-11-one, which could only be produced by completely different methods in the past, can be produced in the same reaction process, and furthermore, the method of the present invention Since the method can produce the desired product much more easily and with a higher yield than conventional methods, it is extremely advantageous industrially and has excellent practicality.

Next, the present invention will be explained in more detail with reference to Examples.

Example 1 Into a three-neck flask equipped with a cooling tube with a calcium chloride tube at the top and a dropping funnel, 100 g of dry toluene was added, and 10 g of dry dimethylformamide and 2.45 g of sodium hydride were added. and stirred.

Seal the third spout, add a mixture of 24.2 g of methyl 3-oxotetradecanoate and 150 g of dry toluene to the dropping funnel, and stir the inside of the flask using a magnetic stirrer.
The mixture was slowly added dropwise through the funnel while stirring.
Dripping was controlled so that the inside of the flask was maintained at 25° C. or lower, and a water bath was used for cooling from time to time. After the dropwise addition was completed, the mixture was further stirred at room temperature for 11 hours. During this time, the viscosity of the liquid in the flask became somewhat high, so a small amount of dry toluene was added. Dry sodium iodide powder was then added through the third neck, while 1-chloro-
3 and 18 minutes were added to the flask little by little.

The flask was then heated using a heating mantle, and the contents were kept under reflux conditions for 20 hours to react. After the reaction was completed, toluene was removed under reduced pressure, 300 g of 10% aqueous sodium hydroxide solution was added to the residue, the flask was heated again, and reflux was continued for 2 hours.

The resulting reaction solution was transferred to two beakers, and while cooling with ice water, concentrated hydrochloric acid was added to adjust the pH to slightly acidic.
This was extracted twice with 400 μl of ether, and the combined ether layers were washed with 100 μl of 10% sodium bicarbonate solution, twice with saturated saline solution, and then dried over anhydrous magnesium sulfate.

Next, this was distilled to remove ether, and the residue was distilled under reduced pressure to give 25.2 hours of 6-heneikosyn-11-one (
A yield of 82%) was obtained. The boiling point of this thing is 162-165
℃ (0.01 tom), and when left in a cold place, it solidifies into a waxy state, but does not show a clear melting point. NMR spectrum (6) 2.00-2.33 (4-day multiplet, C3C-CH
2) 2.26 to 2.60 (4-day multiplet, C&C=○) Example 2 Same conditions as Example 1 using methyl 3-oxotridecanoate 22.8 days and 1-chloro-2-nonine 18 days 24.6% of 7-eicosyn-11-one was obtained (yield: 84%).

Its boiling point is 152-155 qo (0.7 torr),
When left undisturbed, it becomes a wax-like solid, but it does not show a clear melting point. NMR spectrum (6) 1.90-2.23 (4
Daily multiplet C-C group) 2.26-2.60 (4-day multiplet, CH curve C=0) Example 3 Methyl 3-oxododecanoate 21.6% and 1-chloro2nonine as reaction components 23.7 days of 7-nonadecin-11-one was obtained in the same manner as in Example 1 using 18 days of use (yield: 85%). Its boiling point is 143 to 14,600 (0.7 torr), and when left to stand, it becomes a waxy solid, but it does not show a clear melting point. NMR spectrum (6) 1.72-2.22 (4-day multiplet C3CCH2) 2.26-2.62 (4-day multiplet CH2C〇).

Claims (1)

[Claims] 1 General formula CH_3(CH_2)_mC■C(CH_2)_6_-
_mX (in the formula, X is a halogen atom, m is an integer of 4 or 5) and a halogenated alkyne represented by the general formula C
After reacting with a 3-oxocarboxylic acid ester represented by H_3(CH_2)_nCOCH_2CO_2R (in the formula, R is a lower alkyl group and n is an integer of 7 to 9) in the presence of a base, the reaction product is General formula CH_3(CH_2)_mC ■C(CH_2)_7_-_mCO(CH_2)_nC characterized by hydrolysis and decarboxylation by heating with acid or alkaline aqueous solution
A method for producing 6- or 7-alkyne-11-one represented by H_3 (m and n in the formula have the same meanings as above). 2. The manufacturing method according to claim 1, wherein m in the general formula is 4 and n is 9. 3. The manufacturing method according to claim 1, wherein m in the general formula is 5 and n is 7 or 8.