JP2815072B2 - Method for producing tridecatrienyl acetate - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

2. Description of the Related Art In recent years, application of sex pheromones as a method for controlling pests has attracted attention, and monitoring, mass attraction, and disturbance of communication have been widely studied.
In particular, when a sex pheromone is used for the communication disruption method, it is an essential industrial condition to supply a low-cost, high-purity pheromone substance. The present invention relates to a potato moth (Phthorimaea operculell), a worldwide pest of solanaceous plants.
a, Zeller) useful as pheromone components of E, Z, Z
The present invention relates to a method for producing -4,7,10-tridecatrienyl acetate.

[0002]

2. Description of the Related Art Heretofore, several E, Z, Z-
A method for synthesizing 4,7,10-tridecatrienyl acetate has been reported. For example, the German patent D by Ferman et al.
In the specification of E2735361, a compound having a protected hydroxyl group represented by ClCH ₂ CH = CH (CH ₂ ) ₃ OR (R represents a tetrahydropyranyl group) is used as an intermediate. Also, Yadaf (Indian Journal of Chemistry, 25B, 1220-1223 (1
986)) and Chada et al. (Indian Journal of Chemistry, 26B,
187-188 (1987)) are synthesized utilizing an orthoester Claisen rearrangement reaction. The former uses liquid ammonia, and the latter uses a tetrahydropyranyl group to protect the hydroxyl group.

[0003]

In the above synthesis method, since a protecting group or liquid ammonia is used,
There were many problems such as price and handling in performing on an industrial scale. Therefore, there is a need for an industrial method for synthesizing E, Z, Z-4,7,10-tridecatrienyl acetate suitable for large-scale synthesis.

[0004]

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

The Grignard reagent as a starting material of the present invention can be easily obtained by reacting 1,4-heptadiyne with methylmagnesium chloride, ethylmagnesium bromide or the like as shown in the following formula.

Embedded image 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 are used alone or in combination of two or more.

The Grignard reagent (1) and trans-
If 1,6-dihalo-2-hexene (2) is used at 0.8 to 1.2 mol in the presence of a copper catalyst and reacted at a temperature of 20 to 120 ° C, preferably 40 to 80 ° C, the following reaction takes 2 to 10 hours. The reaction of Chemical Formula 2 is completed.

Embedded image The copper catalyst used here is copper (I) chloride, copper (I) bromide,
Monovalent copper salts such as copper (I) iodide, copper (I) cyanide,
Examples thereof include divalent copper salts such as copper (II) chloride and copper (II) bromide and copper-lithium catalysts such as lithium tetrachlorocuprate.

Next, the enediyne compound (3) thus obtained is subjected to hydrogenation (formula 3). The catalyst used in this reaction is palladium-carbon, palladium-barium sulfate, palladium-alumina. , Palladium-
Diatomaceous earth, palladium-calcium carbonate, rhodium-
Examples thereof include carbon, ruthenium-carbon, P-2 nickel, Raney nickel, and Lindlar catalyst. The amount of the catalyst used is 0.001 to 0.2 equivalent to the reaction substrate, and the hydrogen pressure is in the range of normal pressure to 10 kg / cm ² , preferably 1 to
5 kg / cm ² . The reaction temperature is from 0 to 80 ° C, but is preferably from 20 to 50 ° C because it greatly affects the reaction rate. After the reaction, the catalyst is separated by a usual operation and the process proceeds to the next acetylation step.

Embedded image

The above (4) can be easily converted to acetate by heating in at least equimolar amount, preferably 1.2 to several times molar amount of various metal acetates and a solvent. As the solvent used in this reaction, hydrocarbons such as toluene and xylene, and aprotic polar solvents such as acetonitrile, N, N-dimethylformamide and dimethylsulfoxide are used alone or as a mixture. The reaction temperature is usually from 80 to 200 ° C, preferably from 120 to 150 ° C. After the reaction, E, Z, Z-4,7,10-tridecatrienyl acetate (5) is obtained by ordinary purification operations such as distillation or column chromatography.

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]

The present invention is not limited to the following examples, but the present invention is limited to these examples. Example 1: E-1-chloro-
Preparation of 4-Tridecene-7,10-diyne (3) Under a nitrogen stream, 3.52 g of 1,4-heptadiyne was added to a THF solution of 14.3 g (375 g / mol) of methylmagnesium chloride, and the mixture was heated under reflux for 1 hour. Magnesium acetylide (1)
Was prepared. This was added dropwise over 20 minutes to a mixture of 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. . Stir the reaction mixture under a stream of nitrogen for 1.5
After refluxing for an hour, aqueous ammonium chloride solution was added
Stir for 10 minutes. The organic layer was separated, and the aqueous layer was extracted with n-hexane. The combined organic layers were washed with a saturated ammonium chloride solution, water and saturated saline, dried over magnesium sulfate, concentrated under reduced pressure, and 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): 78.0%. GC (Shimadzu GC-14A, Column: DB-WAX30m × 0.25mmφ; 150 ℃ + 5 ℃ / min, carrier gas: He; 1.0kg / cm ^2, Detection: FID): retention time 1
4.18 minutes.

Example 2: E, Z, Z-1-chloro-4,
Production of 7,10-tridecatriene (4) To each of 2.00 g of ethyl acetate solution (10 ml) described in (3) above, 2
00 mg of Lindlar catalyst and quinoline were added, and 2.5 kg / cm ² of hydrogen was added. The reaction was followed by GC to confirm the disappearance of the peak of (3), and the catalyst was separated by filtration. The filtrate was diluted with n-hexane, washed with dilute hydrochloric acid, saturated sodium carbonate solution, water, and then with saturated saline, dried over magnesium sulfate, and concentrated under reduced pressure. The residue was purified by column chromatography on 30 g of silica gel to give 1.84 g of the desired product, E, Z, Z-1-chloro-4,7,10-tridecatriene (4).
It was obtained with a purity of 91.2% and a yield of 94.8%. GC (Shimazu GC-14A,
Column: DB-WAX 30 m × 0.25 mmφ; 150 ° C. + 5 ° C./min, carrier gas: He; 1.0 kg / cm ² , detection: FID): retention time 7.31 minutes (intermediate diene in 9.95, 10.3 during reduction)
Min, excess reduction product 6.37, 6.44 min). Example 3: Preparation of E, Z, Z-4,7,10-tridecadienyl acetate (5) 1.00 g of sodium acetate was added to 5 ml of 876 mg of DMF and heated at 150 ° C. for 4 hours. Refluxed. The reaction mixture was poured into ice water and extracted with n-hexane. The n-hexane solution was washed with water and saturated saline, dried over magnesium sulfate, and concentrated under reduced pressure. The residue
Purification by column chromatography on 40 g of silica gel gave 847 mg of E, Z, Z-4,7,10-tridecadienenyl acetate (5) in 95.2% purity and 95.4% yield. G
C (Shimazu GC-14A, column: DB-WAX30m x 0.25mmφ; 1
50 ° C. + 5 ° C./min, carrier gas: He; 1.0 kg / cm ² , detection: FID): retention time 10.43 minutes.

[0011]

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

──────────────────────────────────────────────────続 き Continuation of the front page (56) References JP-A-4-368355 (JP, A) JP-A-63-227546 (JP, A) JP-A-2-117629 (JP, A) JP-A 63-227546 39837 (JP, A) JP-A-2-101028 (JP, A) JP-A-53-37612 (JP, A) JP-A-3-240752 (JP, A) JP-A-53-34926 (JP, A) JP-B-36-23021 (JP, B1) (58) Fields investigated (Int. Cl. ⁶ , DB name) C07C 69/07 B01J 27/122 C07C 67/00 C07C 67/10 BEILSTEIN (STN) CA (STN ) REGISTRY (STN) WPIDS (STN)

Claims (1)

(57) [Claims] 1. A reaction between a Grignard reagent of 1,4-heptadiyne and trans-1,6-dihalo-2-hexene, followed by hydrogenation to convert two triple bonds into a cis double bond, E characterized by reacting with
A method for producing Z, Z-4,7,10-tridecatrienyl acetate.