JPH04368354A - Production of tridecatrienyl acetate - Google Patents

Abstract

PURPOSE:To obtain the title compound in an industrially advantageous way by reaction of a trans-1,6-dihalo-2-hexene with a Grignard reagent from 1,4- heptadiyne followed by hydrogenation to convert the triple bond to double bond and then reaction of an acetate. CONSTITUTION:Reaction is made between (A) a trans-1,6-dihalo-2-hexene of formula II and (B) a Grignard reagent of formula I easily prepared by reaction of 1,4-heptadiyne with methylmagnesium chloride or ethylmagnesium bromide to alkynylate only the halogen group at 1-site into an enediyne compound of formula III, which is, in turn, put to catalytic reduction to convert the triple bond therein to cis-double bond followed by reaction with an acetate to convert the halogen group into acetyl group, thus obtaining the objective E,Z,Z-4,7,10- tridecatrienyl acetate of formula IV. Use of the above sequence of processes will produce the objective compound at a low cost in high purity without the need for any protective groups or special reaction conditions. The present compound of the formula IV is a sex pheromone component in potato tuberworms.

Description

[Detailed description of the invention]

0001

[Industrial Application Field] In recent years, the application of sex pheromones as a pest control method has attracted attention, and monitoring, mass attraction, communication disruption, etc. are being widely studied. In particular, when sex pheromones are used in the communication disruption method, it is an industrially essential requirement to supply a low-cost, high-purity pheromone substance. The present invention is directed to the potato moth (Phthorimaea), which is a worldwide pest of solanaceous plants.
The present invention relates to a method for producing E,Z,Z-4,7,10-tridecatrienyl acetate, which is useful as a pheromone component of P. perculella, Zeller).

0002

[Prior Art] Up to now, several E, Z, Z-4
, 7,10-tridecatrienyl acetate has been reported. For example, the West German patent by Ferman et al.
In DE2735361, ClCH2CH=CH
It is synthesized using a compound with a protected hydroxyl group represented by (CH2)3OR (R represents a tetrahydropyranyl group) as an intermediate. Also, Yadav (Indian J
Our own of Chemistry, 25B,
1220-1223 (1986)) and Chadha et al.
Indian Journal of Chemistry
y, 26B, 187-188 (1987)) was synthesized using an orthoester Claisen rearrangement reaction. The former uses liquid ammonia, and the latter uses a tetrahydropyranyl group to protect the hydroxyl group.

0003

[Problem to be solved by the invention] Since the above synthetic method uses protecting groups and liquid ammonia,
There were many problems in terms of price and handling in order to carry out the process on an industrial scale. Therefore, an industrial E suitable for large-scale synthesis
, Z, Z-4,7,10-tridecatrienyl acetate has been sought.

0004

[Means for Solving the Problems] The present inventors have conducted intensive studies to solve these problems, and as a result, Trans-1,
When 6-dihalo-2-hexene is reacted with the Grignard reagent of 1,4-heptadiyne, only the halogen group at the 1-position can be converted into an alkynylated enediyne compound, and then the 7- and 10-positions of this compound After catalytically reducing the triple bond at the cis position to form a cis double bond, the halogen group is converted to an acetyl group by reacting with acetate, resulting in E, Z
, Z-4,7,10-tridecatrienyl acetate could be synthesized by using this series of steps without using protecting groups or special reaction conditions.
, 10-tridecatrienyl acetate can be produced at low cost and with high purity, and the present invention has been completed.

The Grignard reagent, which is the starting material of the present invention, can be easily obtained by reacting methylmagnesium chloride, ethylmagnesium bromide, etc. with 1,4-heptadiyne as shown in formula 1 below.

[Chemical 1] The solvent used in this reaction is tetrahydrofuran (hereinafter referred to as
THF), ethers such as ethyl ether and n-butyl ether, and hydrocarbons such as toluene, benzene and xylene may be used alone or in combination of two or more.

This Grignard reagent (1) and trans-
1,6-dihalo-2-hexene (2) from 0.8 to 1
．． Used in an amount of 2 molar, in the presence of a copper catalyst, at a temperature of 20 to 12
If the reaction is carried out at 0°C, preferably 40-80°C, 2-10
The reaction of formula 2 below is completed in a few hours.

[Chemical 2] The copper catalyst used here is copper(I) chloride, copper(I) bromide,
Monovalent copper salts such as copper (I) iodide and copper (I) cyanide,
Mention may be made of divalent copper salts such as copper(II) chloride, copper(II) bromide or copper-lithium catalysts such as lithium tetrachlorocuprate.

Next, the enediyne compound (3) obtained here is hydrogenated (formula 3), and the catalysts used for this reaction are palladium-carbon, palladium-barium sulfate, palladium-alumina. , palladium-
Diatomaceous earth, palladium-calcium carbonate, rhodium-
Carbon, ruthenium-carbon, P-2 nickel, Raney nickel, Lindlar catalyst, etc. may be mentioned. The amount of catalyst used is between 0.001 and 0.00% relative to the reaction substrate.
2 equivalents, and the hydrogen pressure is in the range of normal pressure to 10 kg/cm2, preferably 1 to 5 kg/cm2. The reaction temperature is 0 to 80°C, but since it greatly affects the reaction rate,
The temperature is preferably 0 to 50°C. After the reaction, the catalyst is separated by normal operations and proceeded to the next acetylation step.

[Chemical formula 3]

The above (4) can be easily converted into an acetate by heating in a solvent with at least an equimolar amount, preferably from 1.2 to several times the molar amount, of an acetate of various metals. The solvent used in this reaction includes hydrocarbons such as toluene and xylene, aprotic polar solvents such as acetonitrile, N,N-dimethylformamide, and dimethyl sulfoxide, either alone or in combination. The reaction temperature is usually 80 to 200°C, preferably 12
The temperature is 0 to 150°C. After the reaction, E, Z, and Z are purified by conventional purification operations such as distillation or column chromatography.
-4,7,10-tridecatrienyl acetate (5)
is obtained.

embedded image As described above, according to the present invention, E,Z,Z-4,7,10-tridecatrienyl acetate, which is a sex pheromone of potato moth, can be easily produced with high purity.

[0009]

[Examples] Examples will be shown below, but the present invention is not limited to these descriptions. Example 1: E-1-chloro-
Production of 4-tridecene-7,10-diyne (3) Under a nitrogen atmosphere, 3.52 g of 1,4-heptadiyne was added to a THF solution of 14.3 g (375 g/mol) of methylmagnesium chloride and heated under reflux for 1 hour. Then, magnesium acetylide (1) was prepared. This was mixed with 4.50 g (purity 82.9%) of trans-1,6-dichloro-2-hexene (2), a catalytic amount of copper(I) chloride, and 10 ml of THF.
was added dropwise over 20 minutes. After the reaction mixture was refluxed for 1.5 hours while stirring under a nitrogen stream, an aqueous ammonium chloride solution was added and the mixture was further stirred for 10 minutes. The organic layer was separated, and the aqueous layer was extracted with n-hexane. The combined organic layers were washed with saturated ammonium chloride solution, water, and saturated brine, dried over magnesium sulfate, and concentrated under reduced pressure to obtain 4.58 g of E-1-chloro-4-tridecene-7,
10-diyne (3) was obtained with a purity of 86.8% and a yield from (2) of 78.0%. GC (Shimazu GC-14A, column: DB-WAX30m x 0.25mmφ; 150
°C +5 °C/min, carrier gas: He; 1.0 kg/
cm2, detection: FID): retention time 14.18 minutes.

Example 2: E,Z,Z-1-chloro-4,
Production of 7,10-tridecatriene (4) (3) 2 above
．． 00 g in 10 ml of ethyl acetate solution, 20 each
Add 0mg Lindlar catalyst and quinoline, 2.5k
g/cm2 of hydrogen was added. Follow the reaction with GC (
After confirming the disappearance of the peak 3), the catalyst was filtered off. The filtrate was diluted with n-hexane, washed with dilute hydrochloric acid, saturated sodium carbonate solution, water, and then saturated brine, dried over magnesium sulfate, and concentrated under reduced pressure. The residue was purified by column chromatography using 30 g of silica gel to obtain the target product E,
1.84 g of Z,Z-1-chloro-4,7,10-tridecatriene (4), purity 91.2%, yield 94.8%
I got it from GC (Shimazu GC-14A, column: DB-W
AX30m×0.25mmφ; 150℃+5℃/min,
Carrier gas: He; 1.0kg/cm2, detection:
FID): Retention time 7.31 minutes (intermediate dienein during reduction 9.95, 10.3 minutes, excess reduction product 6
．． 37, 6.44 minutes). Example 3: Preparation of E,Z,Z-4,7,10-tridecadienyl acetate (5) Above (4) 876 mg of D
Add 1.00 g of sodium acetate to 5 ml of MF solution,
The mixture was heated under reflux at 150°C for 4 hours. The reaction mixture was poured into ice water and extracted with n-hexane. n-hexane solution,
It was washed with water and saturated brine, dried over magnesium sulfate, and concentrated under reduced pressure. The residue was purified by column chromatography on 40 g of silica gel to obtain 847 mg of E,Z,Z-4,7,10-tridecadienyl acetate (5) with a purity of 95.2% and a yield of 95.4%. Ta. GC (Shimaz GC
-14A, column: DB-WAX30m x 0.25mm
φ; 150°C + 5°C/min, carrier gas: He;
1.0kg/cm2, detection: FID): retention time 1
0.43 minutes.

[0011]

According to the present invention, the potato moth sex pheromone E,Z,Z-4,7,10-tridecatrienyl acetate can be easily produced with high purity.

Claims (1)

[Claims] Claim 1: After reacting the Grignard reagent of 1,4-heptadiyne with trans-1,6-dihalo-2-hexene, hydrogenation is performed to convert two triple bonds into cis double bonds, and then acetate is added. E, Z characterized by reacting with
, Z-4,7,10-tridecatrienyl acetate manufacturing method.