11-Halo-1,1-dialkoxy-7-undecene compounds, and processes for producing 11,11-dialkoxy-4-undecenyltriarylphosphonium halide compounds, trienal compounds and dienal compounds therefrom

Abstract

To provide a method capable of efficiently producing each of two sex pheromone constituents of Citrus, and leafminer from a common synthetic intermediate by a short process.SOLUTION: A method of producing a (4Z)-11,11-dialkoxy-4-undecenyltriarylphosphonium=halide compound (3-Z) includes: at least a process of obtaining a (4Z)-11,11-dialkoxy-4-undecenyltriarylphosphonium=halide compound represented by the following general formula (3-Z) by phosphonium salt-forming reaction of a (7Z)-11-halo-1,1-dialkoxy-7-undecene compound represented by the following general formula (1-Z) and a phosphine compound represented by the following general formula (2).SELECTED DRAWING: None

Description

Technical Field

[0001] The present invention relates to an 11-halo-1,1-dialkoxy-7-undecene compound, and a method for producing an 11,11-dialkoxy-4-undecenyltriarylphosphonium halide compound, a trienal compound, and a dienal compound therefrom.

[0002] The present invention also relates to an 11,11-dialkoxy-4-undecenyltriarylphosphonium halide compound, and a method for producing a trienal compound and a dienal compound therefrom.

Background Art

[0003] Citrus leafminer( Phyllocnistis citrella ) is an important pest of citrus widely distributed in North, Central and South America such as the United States, Brazil and Argentina, the Mediterranean coast such as Spain and Italy, Asia such as Japan, Taiwan, Indonesia, the Philippines and India, Oceania such as Australia, Middle Eastern countries such as Saudi Arabia, and Africa such as Tunisia and South Africa. Since Citrus leafminer parasitizes and damages leaves, it has a great impact on the growth of young trees and seedlings. In addition, its feeding damage marks promote the occurrence of citrus canker, so control is important. Furthermore, since Citrus leafminer penetrates into the mesophyll, it is difficult to control because pesticides do not reach the inside with ordinary pesticide spraying. Also, due to concerns about residual pesticides, biological control methods are being focused on, and the use of sex pheromone substances is expected as one of them.

[0004] The sex pheromone composition of Citrus leafminer is an aldehyde having 16 carbon atoms, and in regions except Japan, it is a 3:1 mixture of (7Z,11Z,13E)-7,11,13-hexadecatrienal and (7Z,11Z)-7,11-hexadecadienal (Non-Patent Documents 1 and 2 below), and in Japan only, it is reported to be (7Z,11Z)-7,11-hexadecadienal alone (Non-Patent Document 3 below).

[0005] (7Z,11Z,13E)-7,11,13-Hexadecatrienal can be produced, for example, using 2-(5-bromopentyl)-1,3-dioxane as a starting material. The 2-(5-bromopentyl)-1,3-dioxane is iodinated with sodium iodide in acetone to synthesize 2-(5-iodopentyl)-1,3-dioxane. Next, the obtained 2-(5-iodopentyl)-1,3-dioxane is subjected to a coupling reaction with (5-chloro-1-pentin-1-yl)lithium in hexamethylphosphoric triamide (HMPA) and tetrahydrofuran (THF) to synthesize 2-(10-chloro-6-decyl-1-yl)-1,3-dioxane. Next, the obtained 2-(10-chloro-6-decyl-1-yl)-1,3-dioxane is reacted with potassium acetate in HMPA to synthesize 10-(1,3-dioxan-2-yl)-4-decynyl acetate. Subsequently, the obtained 10-(1,3-dioxan-2-yl)-4-decynyl acetate is subjected to a hydrogenation reaction using 5% palladium-on-barium sulfate as a catalyst and quinoline as a catalyst poison to reduce the carbon-carbon triple bond to a carbon-carbon double bond, thereby synthesizing (4Z)-10-(1,3-dioxan-2-yl)-4-decenyl acetate. Next, the obtained (4Z)-10-(1,3-dioxan-2-yl)-4-decenyl acetate is subjected to a hydrolysis reaction with an aqueous potassium hydroxide solution in methanol to synthesize (4Z)-10-(1,3-dioxan-2-yl)-4-decen-1-ol. The obtained (4Z)-10-(1,3-dioxan-2-yl)-4-decen-1-ol is oxidized with pyridinium dichromate (PDC) in dichloromethane to oxidize the hydroxyl group, thereby synthesizing (4Z)-10-(1,3-dioxan-2-yl)-4-decenal. The obtained (4Z)-10-(1,3-dioxan-2-yl)-4-decenal is subjected to a Wittig reaction with triphenylphosphonium=(2E)-2-pentenylide prepared separately in THF and HMPA to synthesize 2-(6Z,10Z,12E)-6,10,12-pentadecatrien-1-yl-1,3-dioxane.Subsequently, the obtained 2-(6Z,10Z,12E)-6,10,12-pentadecatrien-1-yl-1,3-dioxane is reacted with methanol in the presence of p-toluenesulfonic acid to synthesize (3E,5Z,9Z)-16,16-dimethoxy-3,5,9-hexadecatriene. Finally, a method of hydrolyzing the obtained (3E,5Z,9Z)-16,16-dimethoxy-3,5,9-hexadecatriene with hydrochloric acid in THF has been reported (Non-Patent Document 1 below).

[0006] Also, as another production method of (7Z,11Z,13E)-7,11,13-hexadecatrienal, 3-bromo-1-propanol is used as a starting material, and 1-bromo-3-(tert-butyldimethylsilyloxy)propane is synthesized by protecting the hydroxyl group in the 3-bromo-1-propanol. Next, separately synthesized tetrahydro-2-(7-octyn-1-yloxy)- 2H -pyran is reacted with n-butyllithium in THF, and subsequently THF, N , N’React with 1-bromo-3-(tert-butyldimethylsilyloxy)propane in a mixed solution of N,N'-dimethylpropyleneurea (DMPU) to synthesize 1-(tert-butyldimethylsilyloxy)-11-(tetrahydropyranyloxy)-4-undecyne. Remove the tert-butyldimethylsilyl group of the obtained 1-(tert-butyldimethylsilyloxy)-11-(tetrahydropyranyloxy)-4-undecyne with tetra-n-butylammonium fluoride (TBAF) in THF, and use nickel boride (P-2Ni) as a catalyst to reduce the carbon-carbon triple bond to a carbon-carbon double bond by hydrogenation reaction to synthesize (4Z)-11-(tetrahydropyranyloxy)-4-undecen-1-ol. Iodinate the hydroxyl group of the obtained (4Z)-11-(tetrahydropyranyloxy)-4-undecen-1-ol with iodine in the presence of imidazole and triphenylphosphine (TPP) in THF, and then react with TPP in toluene to synthesize (4Z)-11-(tetrahydropyranyloxy)-4-undecenyltriphenylphosphonium iodide. React the obtained (4Z)-11-(tetrahydropyranyloxy)-4-undecenyltriphenylphosphonium iodide with n-butyllithium in DMPU, and then perform a Wittig reaction with (2E)-2-pentenal to synthesize (7Z,11Z,13E)-1-(tetrahydropyranyloxy)-hexadecatriene. React the obtained (7Z,11Z,13E)-1-(tetrahydropyranyloxy)-hexadecatriene with methanol in the presence of p-toluenesulfonic acid to synthesize (7Z,11Z,13E)-7,11,13-hexadecatrienol. Finally, a method of oxidizing the hydroxyl group of the obtained (7Z,11Z,13E)-7,11,13-hexadecatrienol with pyridinium chlorochromate (PCC) has been reported (Non-Patent Document 2 below).

[0007] Next, as a method for producing (7Z,11Z)-7,11-hexadecadienal, for example, using 1,3-dibromopropane as a starting material, the 1,3-dibromopropane is subjected to a coupling reaction with [2-(1,3-dioxan-2-yl)ethyl]magnesium bromide in THF to synthesize 2-(5-bromopentyl)-1,3-dioxane. Next, the obtained 2-(5-bromopentyl)-1,3-dioxane is reacted with lithium acetylide in HMPA and THF to synthesize 2-(6-heptin-1-yl)-1,3-dioxane. Next, the obtained 2-(6-heptin-1-yl)-1,3-dioxane is reacted with n-butyllithium in THF, and then subjected to a coupling reaction with (3Z)-1-bromo-3-octene in HMPA to synthesize 2-[(11Z)-11-hexadecen-7-yloxy]tetrahydro- 2H -pyran. Subsequently, the obtained 2-[(11Z)-11-hexadecen-7-yloxy]tetrahydro- 2H -pyran is reduced with a hydrogenation reaction to convert the carbon-carbon triple bond to a carbon-carbon double bond using 5% palladium-on-barium sulfate as a catalyst and quinoline as a catalyst poison to synthesize 2-[(7Z,11Z)-7,11-hexadecadien-1-yloxy]tetrahydro- 2H -pyran. The obtained 2-[(7Z,11Z)-7,11-hexadecadien-1-yloxy]tetrahydro- 2H -pyran is reacted with methanol in the presence of p-toluenesulfonic acid to synthesize (5Z,9Z)-16,16-dimethoxy-5,9-hexadecadiene. Finally, a method of hydrolyzing the obtained (5Z,9Z)-16,16-dimethoxy-5,9-hexadecadiene with hydrochloric acid in THF has been reported (Non-Patent Document 1 below).

[0008] Also, as another production method of (7Z,11Z)-7,11-hexadecadienal different from the above, using tetrahydro-2-(7-octyn-1-yloxy)- 2H -pyran as a starting material, the tetrahydro-2-(7-octyn-1-yloxy)- 2H-Pyran is reacted with n-butyllithium in THF and then with 1-chloro-3-iodopropane to give 2-[(11-chloro-7-undecyn-1-yl)oxy]tetrahydro- 2H -pyran. The obtained 2-[(11-chloro-7-undecyn-1-yl)oxy]tetrahydro- 2H -pyran is iodinated with sodium iodide in acetone to give 2-[(11-iodo-7-undecyn-1-yl)oxy]tetrahydro- 2H -pyran. Subsequently, the obtained 2-[(11-iodo-7-undecyn-1-yl)oxy]tetrahydro- 2H -pyran is reacted with TPP in toluene to synthesize 11-(tetrahydropyranyloxy)-4-undecynyltriphenylphosphonium iodide. Next, the obtained 11-(tetrahydropyranyloxy)-4-undecynyltriphenylphosphonium iodide is reacted with n-butyllithium in DMPU and then undergoes a Wittig reaction with pentanal to synthesize (11Z)-1-(tetrahydropyranyloxy)-hexadec-7-en-1-yne. The obtained (11Z)-1-(tetrahydropyranyloxy)-hexadec-7-en-1-yne is reacted with methanol in the presence of p-toluenesulfonic acid to synthesize (11Z)-11-hexadec-7-en-1-yn-1-ol. The carbon-carbon triple bond in the obtained (11Z)-11-hexadec-7-en-1-yn-1-ol is reduced to a carbon-carbon double bond by a hydrogenation reaction in the presence of nickel boride (P-2Ni) as a catalyst to synthesize (7Z,11Z)-7,11-hexadecadienol. Finally, a method for oxidizing the hydroxyl group of the obtained (7Z,11Z)-7,11-hexadecadienol with pyridinium chlorochromate (PCC) in dichloromethane has been reported (Non-Patent Document 2 below).

Prior Art Documents

Non-Patent Documents

[0009]

Non-Patent Document 1

Non-Patent Document 2

Non-Patent Document 3

Summary of the Invention

Problems to be Solved by the Invention

[0010] However, in any of the production methods of (7Z,11Z,13E)-7,11,13-hexadecatrienal and (7Z,11Z)-7,11-hexadecadienal reported in Non-Patent Document 1, hexamethylphosphoric triamide, which is a carcinogenic substance, is used in a large amount as a solvent, making industrialization difficult. In addition, n-butyllithium used in Non-Patent Document 1 is sensitive to air or water and may catch fire when exposed to air, making it difficult to handle. Furthermore, since a hydrogenation reaction using an expensive palladium catalyst is carried out, it is not economically advantageous. In addition, quinoline used as a catalyst poison is considered a chemical substance that has an impact on the human body in recent years, making industrial use difficult. In addition, in the production method of (7Z,11Z,13E)-7,11,13-hexadecatrienal, an oxidation reaction using PDC, which is a chromium compound with an extremely large environmental load, is used, and the oxidation reaction often involves the risk of explosion, making it difficult to carry out on an industrial scale. Furthermore, the overall yield of this synthesis method is extremely low at 14%, and the number of steps is as long as 9 steps. Also, in the production method of (7Z,11Z)-7,11-hexadecadienal, the overall yield is extremely low at 15%, and the number of steps is long at 6 steps.

[0011] In any of the production methods of (7Z,11Z,13E)-7,11,13-hexadecatrienal and (7Z,11Z)-7,11-hexadecadienal reported in Non-Patent Document 2, n-butyllithium, which is sensitive to air or water and may catch fire when exposed to air and is difficult to handle, is used. An oxidation reaction using PCC, which is a chromium compound with an extremely large environmental load, is used. Furthermore, since the oxidation reaction often involves the risk of explosion, it is difficult to carry out on an industrial scale. In addition, since dichloromethane with a large environmental load is used as a solvent, it is not desirable from an environmental perspective. Also, in the production method of (7Z,11Z,13E)-7,11,13-hexadecatrienal, the total yield is extremely low at 7% and the number of steps is as long as 9 steps. Also, in the production method of (7Z,11Z)-7,11-hexadecadienal, the total yield is low at 22% and the number of steps is long at 7 steps.

[0012] In addition, in any of the production methods of (7Z,11Z,13E)-7,11,13-hexadecatrienal and (7Z,11Z)-7,11-hexadecadienal reported in Non-Patent Documents 1 and 2, there is no common synthetic intermediate, and each compound has to be synthesized separately, so it is not desirable from the perspective of economically producing the two components of the sex pheromone of Citrus leafminer.

[0013] The present invention has been made in view of the above circumstances, and an object thereof is to provide a method capable of efficiently producing each of the two components of the sex pheromone of Citrus leafminer from a common synthetic intermediate in a short process.

Means for Solving the Problems

[0014] As a result of intensive studies to solve the above problems, the present inventors have found that the (4Z)-11,11-dialkoxy-4-undecenyltriarylphosphonium halide compound is a common synthetic intermediate useful in the production of (7Z,11Z,13E)-7,11,13-hexadecatrienal and (7Z,11Z)-7,11-hexadecadienal, which are the two components of the sex pheromone of Citrus leafminer. And they have found that (7Z,11Z,13E)-7,11,13-hexadecatrienal and (7Z,11Z)-7,11-hexadecadienal can be produced in good yield in a short process from the (4Z)-11,11-dialkoxy-4-undecenyltriarylphosphonium halide compound, thus arriving at the present invention.

[0015] The present inventors have also further found that the (7Z)-11-halo-1,1-dialkoxy-7-undecene compound is a useful synthetic intermediate in the production of the (4Z)-11,11-dialkoxy-4-undecenyltriarylphosphonium halide compound, which is a common synthetic intermediate for the above two components of the sex pheromone, thus arriving at the present invention.

[0016] According to the first aspect of the present invention, the following general formula (1-Z):

Chemical formula

[0017] According to a second aspect of the present invention, (4Z)-11,11-dialkoxy-4-undecenyltriarylphosphonium halide compound (3-Z) is deprotonated in the presence of a base to obtain a reaction product mixture, wherein the (4Z)-11,11-dialkoxy-4-undecenyltriarylphosphonium halide compound (3-Z) may be produced according to the production method according to the above first aspect for the (4Z)-11,11-dialkoxy-4-undecenyltriarylphosphonium halide compound (3-Z), or may be produced by another production method, The reaction product mixture and the following formula (5): [Chemical formula] are subjected to Wittig reaction conditions with (2E)-2-pentenal represented by the following general formula (6): [Chemical formula] (In the formula, R 1 and R 2 are as defined above.) Step of obtaining a (3E,5Z,9Z)-16,16-dialkoxy-3,5,9-hexadecatriene compound represented by A method for producing a (3E,5Z,9Z)-16,16-dialkoxy-3,5,9-hexadecatriene compound (6) containing at least

[0018] According to a third aspect of the present invention, the above production method of the above (3E,5Z,9Z)-16,16-dialkoxy-3,5,9-hexadecatriene compound (6), and by the hydrolysis reaction of the (3E,5Z,9Z)-16,16-dialkoxy-3,5,9-hexadecatriene compound (6), the following formula (7):

Chemical formula

[0019] According to a fourth aspect of the present invention, (4Z)-11,11-dialkoxy-4-undecenyltriarylphosphonium halide compound (3-Z) is subjected to a deprotonation reaction in the presence of a base to obtain a reaction product mixture, where the (4Z)-11,11-dialkoxy-4-undecenyltriarylphosphonium halide compound (3-Z) may be produced according to the production method according to the above first aspect for the (4Z)-11,11-dialkoxy-4-undecenyltriarylphosphonium halide compound (3-Z), or may be produced by another production method. The reaction product mixture and the following formula (8): CH 3 (CH 2 ) 3 CHO (8) represented by pentanal are subjected to Wittig reaction conditions to obtain the following general formula (9):

Chemical formula

[0020] According to a fifth aspect of the present invention, the above-described method for producing the above (5Z,9Z)-16,16-dialkoxy-5,9-hexadecadiene compound (9), and by a hydrolysis reaction of the (5Z,9Z)-16,16-dialkoxy-5,9-hexadecadiene compound (9), the following formula (10):

Chemical formula

[0021] According to a sixth aspect of the present invention, (4Z)-11,11-dialkoxy-4-undecenyltriarylphosphonium = halide compound (3-Z) is deprotonated in the presence of a base to obtain a reaction product mixture, wherein the (4Z)-11,11-dialkoxy-4-undecenyltriarylphosphonium = halide compound (3-Z) may be produced according to the production method according to the above-described first aspect for the (4Z)-11,11-dialkoxy-4-undecenyltriarylphosphonium = halide compound (3-Z), or may be produced by another production method, the reaction product mixture and the following formula (5):

Chemical formula

[0022] According to the seventh aspect of the present invention, the above-described method for producing a mixture containing the above (3E,5Z,9Z)-16,16-dialkoxy-3,5,9-hexadecatriene compound (6) and (5Z,9Z)-16,16-dialkoxy-5,9-hexadiene compound (9), and subjecting the mixture containing the (3E,5Z,9Z)-16,16-dialkoxy-3,5,9-hexadecatriene compound (6) and (5Z,9Z)-16,16-dialkoxy-5,9-hexadiene compound (9) to hydrolysis reaction conditions to obtain, respectively, the following formula (7): [Chemical formula] (7Z,11Z,13E)-7,11,13-Hexadecatrienal represented by the following formula and the following formula (10): [Chemical formula] A step of obtaining a mixture containing (7Z,11Z)-7,11-hexadecadienal represented by the following formula: A method for producing a mixture containing (7Z,11Z,13E)-7,11,13-hexadecatrienal (7) and (7Z,11Z)-7,11-hexadecadienal (10), which includes at least the following:

[0023] According to the eighth aspect of the present invention, the following general formula (A): L(CH 2 ) 3 CH=CH(CH 2 ) 5 CH(OR 1 )(OR 2 ) (A) (In the formula, R 1 and R 2 are each independently a monovalent hydrocarbon group having 1 to 15 carbon atoms, or R 1 and R 2 are bonded to each other to form R 1 -R 2 representing a divalent hydrocarbon group having 2 to 10 carbon atoms, and L represents X 1 or Y - Ar 3 P + ; X 1 and Y represent halogen atoms, and Ar represents aryl groups which may be the same or different from each other.) A compound represented by the following formula is provided. Here, when L is X 1 , the following general formula (1): X 1 (CH 2 ) 3 CH=CH(CH 2 ) 5 CH(OR 1 )(OR 2 ) (1) is an 11-halo-1,1-dialkoxy-7-undecene compound, and when L is Y - Ar 3 P + in the case of, the following general formula (3): Y - Ar 3 P + (CH 2 ) 3 CH=CH(CH 2 ) 5 CH(OR 1 )(OR 2 ) (3) is an 11,11-dialkoxy-4-undecenyltriarylphosphonium halide compound represented by

Advantages of the Invention

[0024] According to the present invention, (7Z,11Z,13E)-7,11,13-hexadecatrienal (7), (7Z,11Z)-7,11-hexadecadienal (10), or a mixture thereof can be produced in a short process with good yield. Further, according to the present invention, an 11-halo-1,1-dialkoxy-7-undecene compound (1) and an 11,11-dialkoxy-4-undecenyltriarylphosphonium halide compound (3), which are useful synthetic intermediates in the production of (7Z,11Z,13E)-7,11,13-hexadecatrienal (7) and (7Z,11Z)-7,11-hexadecadienal (10), can also be provided.

Modes for Carrying Out the Invention

[0025] A. Regarding the compound represented by the general formula (A) The following general formula (A): L(CH 2 ) 3 CH=CH(CH 2 ) 5 CH(OR 1 )(OR 2 ) (A) The compound represented by will be described below. In the above general formula (A), R 1 and R2 is each independently a monovalent hydrocarbon group having 1 to 15 carbon atoms, or R 1 and R 2 in which R 1 -R 2 represents a divalent hydrocarbon group having 2 to 10 carbon atoms, and L represents X 1 or Y - Ar 3 P + wherein X 1 and Y represent halogen atoms, and Ar represents an aryl group which may be the same or different from each other. In the compound (A), when L is X 1 , the compound (A) is an 11-halo-1,1-dialkoxy-7-undecene compound represented by the following general formula (1). X 1 (CH 2 ) 3 CH=CH(CH 2 ) 5 CH(OR 1 )(OR 2 ) (1) In the compound (A), when L is Y - Ar 3 P + , the compound (A) is an 11,11-dialkoxy-4-undecenyltriarylphosphonium halide compound represented by the following general formula (3). Y - Ar 3 P + (CH 2 ) 3 CH=CH(CH 2 ) 5 CH(OR 1 )(OR 2 ) (3)

[0026] (A-1). About the 11-halo-1,1-dialkoxy-7-undecene compound (1) and its production method First, the 11-halo-1,1-dialkoxy-7-undecene compound (1) will be described. X 1 (CH 2 ) 3 CH=CH(CH2 ) 5 CH(OR 1 )(OR 2 ) (1) X 1 represents a halogen atom as defined by the general formula (A) above. Specifically, the halogen atom X 1 includes a chlorine atom, a bromine atom, and an iodine atom, and a chlorine atom and a bromine atom are preferred from the viewpoint of handling.

[0027] In the general formula (1), R 1 and R 2 each independently represent a monovalent hydrocarbon group having 1 to 15 carbon atoms, preferably 1 to 10 carbon atoms, more preferably 1 to 4 carbon atoms, or R 1 and R 2 are bonded to each other to form a divalent hydrocarbon group having 2 to 10 carbon atoms, preferably 2 to 4 carbon atoms, represented by R 1 -R 2 .

[0028] Examples of the monovalent hydrocarbon group include linear saturated hydrocarbon groups such as methyl group, ethyl group, n-propyl group, n-butyl group, n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, n-nonyl group, n-decyl group, n-undecyl group, and n-dodecyl group; branched saturated hydrocarbon groups such as isopropyl group, 2-isobutyl group, and 2-methylbutyl group; linear unsaturated hydrocarbon groups such as 2-propenyl group; branched unsaturated hydrocarbon groups such as 2-methyl-2-propenyl group; and cyclic saturated hydrocarbon groups such as cyclopropyl group, and hydrocarbon groups that are isomers thereof may also be used. Further, a part of the hydrogen atoms of these hydrocarbon groups may be substituted with a methyl group or an ethyl group. From the viewpoint of handling, the monovalent hydrocarbon group is preferably a methyl group, an ethyl group, an n-propyl group, or an n-butyl group.

[0029] Examples of the divalent hydrocarbon group include linear saturated hydrocarbon groups such as an ethylene group, a 1,3-propylene group, and a 1,4-butylene group; branched saturated hydrocarbon groups such as a 1,2-propylene group, a 2,2-dimethyl-1,3-propylene group, a 1,2-butylene group, a 1,3-butylene group, a 2,3-butylene group, and a 2,3-dimethyl-2,3-butylene group; linear unsaturated hydrocarbon groups such as a 1-vinylethylene group; branched unsaturated hydrocarbon groups such as a 2-methylene-1,3-propylene group; and cyclic hydrocarbon groups such as a 1,2-cyclopropylene group and a 1,2-cyclobutylene group. Hydrocarbon groups that are isomers of these may also be used. Further, a part of the hydrogen atoms of these hydrocarbon groups may be substituted with a methyl group, an ethyl group, or the like. As the divalent hydrocarbon group, in consideration of the reactivity in deprotection, ease of purification, or ease of availability, a lower (preferably having 2 to 4 carbon atoms) hydrocarbon group having high reactivity and by-products generated by deprotection that can be easily removed by washing with water or concentration is preferred. Considering these, particularly preferred examples of the divalent hydrocarbon group include an ethylene group, a 1,3-propylene group, a 1,2-propylene group, a 1,2-butylene group, a 1,3-butylene group, and a 2,3-dimethyl-2,3-butylene group.

[0030] The 11-halo-1,1-dialkoxy-7-undecene compound (1) includes a (7Z)-11-halo-1,1-dialkoxy-7-undecene compound represented by the general formula (1-Z) and a (7E)-11-halo-1,1-dialkoxy-7-undecene compound represented by the general formula (1-E).

[0031] Specific examples of the (7Z)-11-halo-1,1-dialkoxy-7-undecene compound (1-Z) include the following compounds: (7Z)-11-chloro-1,1-dimethoxy-7-undecene, (7Z)-11-chloro-1,1-diethoxy-7-undecene, (7Z)-11-chloro-1,1-dipropyloxy-7-undecene, (7Z)-11-chloro-1,1-dibutyloxy-7-undecene, (7Z)-11-chloro-1,1-dipentyloxy-7-undecene, (7Z)-11-chloro-1,1-dihexyloxy-7-undecene, (7Z)-11-chloro-1,1-diheptyloxy-7-undecene, (7Z)-11-chloro-1,1-dioctyloxy-7-undecene, (7Z)-11-chloro-1,1-dinonyloxy-7-undecene, and (7Z)-11-chloro-1,1-didecyloxy-7-undecene and other (7Z)-11-chloro-1,1-dialkoxy-7-undecene compounds (1-Z:X 1 =Cl); (7Z)-11-bromo-1,1-dimethoxy-7-undecene, (7Z)-11-bromo-1,1-diethoxy-7-undecene, (7Z)-11-bromo-1,1-dipropyloxy-7-undecene, (7Z)-11-bromo-1,1-dibutyloxy-7-undecene, (7Z)-11-bromo-1,1-dipentyloxy-7-undecene, (7Z)-11-bromo-1,1-dihexyloxy-7-undecene, (7Z)-11-bromo-1,1-diheptyloxy-7-undecene, (7Z)-11-bromo-1,1-dioctyloxy-7-undecene, (7Z)-11-bromo-1,1-dinonyloxy-7-undecene, and (7Z)-11-bromo-1,1-didecyloxy-7-undecene and other (7Z)-11-bromo-1,1-dialkoxy-7-undecene compounds (1-Z:X 1 =Br); and, (7Z)-11-Iodo-1,1-dimethoxy-7-undecene, (7Z)-11-iodo-1,1-diethoxy-7-undecene, (7Z)-11-iodo-1,1-dipropyloxy-7-undecene, (7Z)-11-iodo-1,1-dibutyloxy-7-undecene, (7Z)-11-iodo-1,1-dipentyloxy-7-undecene, (7Z)-11-iodo-1,1-dihexyloxy-7-undecene, (7Z)-11-iodo-1,1-diheptyloxy-7-undecene, (7Z)-11-iodo-1,1-dioctyloxy-7-undecene, (7Z)-11-iodo-1,1-dinonyloxy-7-undecene, and (7Z)-11-iodo-1,1-didecyloxy-7-undecene and other (7Z)-11-iodo-1,1-dialkoxy-7-undecene compounds (1-Z:X 1 =I).

[0032] Specific examples of the (7E)-11-halo-1,1-dialkoxy-7-undecene compound (1-E) include the following compounds: (7E)-11-Chloro-1,1-dimethoxy-7-undecene, (7E)-11-chloro-1,1-diethoxy-7-undecene, (7E)-11-chloro-1,1-dipropyloxy-7-undecene, (7E)-11-chloro-1,1-dibutyloxy-7-undecene, (7E)-11-chloro-1,1-dipentyloxy-7-undecene, (7E)-11-chloro-1,1-dihexyloxy-7-undecene, (7E)-11-chloro-1,1-diheptyloxy-7-undecene, (7E)-11-chloro-1,1-dioctyloxy-7-undecene, (7E)-11-chloro-1,1-dinonyloxy-7-undecene, and (7E)-11-chloro-1,1-didecyloxy-7-undecene and other (7E)-11-chloro-1,1-dialkoxy-7-undecene compounds (1-E:X 1 =Cl); (7E)-11-bromo-1,1-dimethoxy-7-undecene, (7E)-11-bromo-1,1-diethoxy-7-undecene, (7E)-11-bromo-1,1-dipropyloxy-7-undecene, (7E)-11-bromo-1,1-dibutyloxy-7-undecene, (7E)-11-bromo-1,1-dipentyloxy-7-undecene, (7E)-11-bromo-1,1-dihexyloxy-7-undecene, (7E)-11-bromo-1,1-diheptyloxy-7-undecene, (7E)-11-bromo-1,1-dioctyloxy-7-undecene, (7E)-11-bromo-1,1-dinonyloxy-7-undecene and (7E)-11-bromo-1,1-didecyloxy-7-undecene and other (7E)-11-bromo-1,1-dialkoxy-7-undecene compounds (1-E:X 1 =Br); and, (7E)-11-iodo-1,1-dimethoxy-7-undecene, (7E)-11-iodo-1,1-diethoxy-7-undecene, (7E)-11-iodo-1,1-dipropyloxy-7-undecene, (7E)-11-iodo-1,1-dibutyloxy-7-undecene, (7E)-11-iodo-1,1-dipentyloxy-7-undecene, (7E)-11-iodo-1,1-dihexyloxy-7-undecene, (7E)-11-iodo-1,1-diheptyloxy-7-undecene, (7E)-11-iodo-1,1-dioctyloxy-7-undecene, (7E)-11-iodo-1,1-dinonyloxy-7-undecene and (7E)-11-iodo-1,1-didecyloxy-7-undecene and other (7E)-11-iodo-1,1-dialkoxy-7-undecene compounds (1-E:X 1 =I).

[0033] From the viewpoint of producing the sex pheromone of Citrus leafminer, as the 11-halo-1,1-dialkoxy-7-undecene compound (1), the (7Z)-11-halo-1,1-dialkoxy-7-undecene compound (1-Z) is preferred, and particularly the (7Z)-11-chloro-1,1-dialkoxy-7-undecene compound (1-Z:X 1=(Cl), (7Z)-11-bromo-1,1-dialkoxy-7-undecene compound (1-Z:X 1 =Br) and (7Z)-11-iodo-1,1-dialkoxy-7-undecene compound (1-Z:X 1 =I) are preferred.

[0034] Hereinafter, in this specification, the production method thereof will be described using the (7Z)-11-halo-1,1-dialkoxy-7-undecene compound (1-Z). However, the reaction also proceeds in the (7E)-11-halo-1,1-dialkoxy-7-undecene compound (1-E) in the same manner as in the (7Z)-11-halo-1,1-dialkoxy-7-undecene compound (1-Z), and the corresponding compound can be produced.

[0035] (7Z)-11-Halo-1,1-dialkoxy-7-undecene compound (1-Z) can be synthesized, for example, according to the reaction formula including at least the following three steps.

Chemical formula

[0036] In the formula of the above reaction formula, R 1 , R 2 and X 1 are as defined in the above general formula (1), and X 2 and X 3 represent halogen atoms. Further, M represents Li or MgZ, and Z represents a halogen atom or a 6,6-dialkoxyhexyl group.

[0037] First, a 6,6-dialkoxyhexyl nucleophile represented by the general formula (15) is prepared by reacting a 6-halo-1,1-dialkoxyhexane compound represented by the general formula (14) with magnesium or lithium in a solvent (the first step). Then, the obtained 6,6-dialkoxyhexyl nucleophile (15) is subjected to a coupling reaction with a 1-halo-5-halo-1-pentyne compound represented by the general formula (16) in the presence of a catalyst as needed to prepare an 11-halo-1,1-dialkoxy-7-undecyne compound represented by the general formula (17) (the second step). Then, the carbon-carbon triple bond of the obtained 11-halo-1,1-dialkoxy-7-undecyne compound (17) is reduced to obtain the target (7Z)-11-halo-1,1-dialkoxy-7-undecene compound (1-Z) (the third step). The above synthetic method of the (7Z)-11-halo-1,1-dialkoxy-7-undecene compound (1-Z) will be described in more detail below.

[0038] The 6-halo-1,1-dialkoxyhexane compound (14) will be described below. R in the above general formula (14) 1 and R 2 are as defined in the above general formula (1). X in the above general formula (14) 3 represents a halogen atom. Specifically, examples of the halogen atom X 3 include a chlorine atom, a bromine atom, and an iodine atom, and a chlorine atom and a bromine atom are preferred from the viewpoint of reactivity. Specific examples of the 6-halo-1,1-dialkoxyhexane compound (14) include the following compounds: 6-chloro-1,1-dimethoxyhexane, 6-chloro-1,1-diethoxyhexane, 6-chloro-1,1-dipropyloxy-hexane, 6-chloro-1,1-dibutyloxy-hexane, 6-chloro-1,1-dipentyloxy-hexane, 6-chloro-1,1-dihexyloxy-hexane, 6-chloro-1,1-diheptyloxy-hexane, 6-chloro-1,1-dioctyloxy-hexane, 6-chloro-1,1-dinonyloxy-hexane and 6-chloro-1,1-didecyloxy-hexane and other 6-chloro-1,1-dialkoxyhexane compounds (14:X 3 =Cl); 6-bromo-1,1-dimethoxyhexane, 6-bromo-1,1-diethoxyhexane, 6-bromo-1,1-dipropyloxy-hexane, 6-bromo-1,1-dibutyloxy-hexane, 6-bromo-1,1-dipentyloxy-hexane, 6-bromo-1,1-dihexyloxy-hexane, 6-bromo-1,1-diheptyloxy-hexane, 6-bromo-1,1-dioctyloxy-hexane, 6-bromo-1,1-dinonyloxy-hexane and 6-bromo-1,1-didecyloxy-hexane and other 6-bromo-1,1-dialkoxyhexane compounds (14:X 3 =Br); and 6-iodo-1,1-dimethoxyhexane, 6-iodo-1,1-diethoxyhexane, 6-iodo-1,1-dipropyloxy-hexane, 6-iodo-1,1-dibutyloxy-hexane, 6-iodo-1,1-dipentyloxy-hexane, 6-iodo-1,1-dihexyloxy-hexane, 6-iodo-1,1-diheptyloxy-hexane, 6-iodo-1,1-dioctyloxy-hexane, 6-iodo-1,1-dinonyloxy-hexane and 6-iodo-1,1-didecyloxy-hexane and other 6-iodo-1,1-dialkoxyhexane compounds (14:X 3 =I). As the 6-halo-1,1-dialkoxyhexane compound (14), from the viewpoint of reactivity, the 6-chloro-1,1-dialkoxyhexane compound (14:X 3 =Cl) and the 6-bromo-1,1-dialkoxyhexane compound (14:X 3=Br) is preferred.

[0039] (The first step) As one method for synthesizing the 6,6-dialkoxyhexyl nucleophilic reagent (15), for example, as shown in the following chemical reaction formula, by reacting a 6-halo-1,1-dialkoxyhexane compound (14) with magnesium in a solvent, a method for obtaining a 6,6-dialkoxyhexyl nucleophilic reagent (15: M = MgZ) as a Grignard reagent can be mentioned (hereinafter, also referred to as the "Grignard reagent preparation reaction"). [Chemical formula]

[0040] The amount of magnesium used in the Grignard reagent preparation reaction is preferably 1.0 to 2.0 gram atoms per 1 mol of the 6-halo-1,1-dialkoxyhexane compound (14) from the viewpoint of complete reaction. Examples of the solvent used in the Grignard reagent preparation reaction include ethers such as tetrahydrofuran, 2-methyltetrahydrofuran (2-MeTHF), diethyl ether, and 4-methyltetrahydropyran; hydrocarbons such as toluene, xylene, and hexane. From the viewpoint of the reaction rate of Grignard reagent formation, ethers such as tetrahydrofuran, 2-methyltetrahydrofuran, diethyl ether, and 4-methyltetrahydropyran are preferred, and tetrahydrofuran and 2-methyltetrahydrofuran are more preferred. One type of the solvent or, if necessary, two or more types may be used. Also, a commercially available solvent can be used. The amount of the solvent used is preferably 30 to 5000 g, more preferably 50 g to 3000 g, per 1 mol of the 6-halo-1,1-dialkoxyhexane compound (14) from the viewpoint of reactivity.

[0041] The reaction temperature in the Grignard reagent preparation reaction varies depending on the solvent used, but is preferably 0 to 120°C from the viewpoint of reactivity. The reaction time in the Grignard reagent preparation reaction varies depending on the solvent used and / or the reaction scale, but from the perspective of reactivity, it is preferably 0.5 to 100 hours.

[0042] As another method for synthesizing the 6,6-dialkoxyhexyl nucleophile (15), for example, as shown in the following chemical reaction formula, a 6-halo-1,1-dialkoxyhexane compound (14) is reacted with lithium in a solvent to obtain a 6,6-dialkoxyhexyl nucleophile (15: M = Li) as an organolithium reagent (hereinafter, also referred to as "lithium reagent preparation reaction").

Chemical formula

[0043] From the perspective of the completion of the reaction, the amount of lithium used in the lithium reagent preparation reaction is preferably 1.0 to 2.0 gram atoms per 1 mol of the 6-halo-1,1-dialkoxyhexane compound (14). Examples of the solvent used in the lithium reagent preparation reaction include ethers such as tetrahydrofuran, 2-methyltetrahydrofuran, diethyl ether, and 4-methyltetrahydropyran; hydrocarbons such as toluene, xylene, and hexane, etc. From the perspective of the reaction rate of lithium reagent generation, ethers such as tetrahydrofuran, 2-methyltetrahydrofuran, diethyl ether, and 4-methyltetrahydropyran; and hydrocarbons such as toluene, xylene, and hexane are preferred, and tetrahydrofuran, 2-methyltetrahydrofuran, toluene, and hexane are more preferred. One type of the solvent or, if necessary, two or more types may be used. Also, a commercially available solvent can be used. From the perspective of reactivity, the amount of the solvent used is preferably 30 to 5000 g, more preferably 50 g to 3000 g, per 1 mol of the 6-halo-1,1-dialkoxyhexane compound (14).

[0044] The reaction temperature in the lithium reagent preparation reaction varies depending on the solvent used, but from the perspective of reactivity, it is preferably -40 to 120 °C. The reaction time in the lithium reagent preparation reaction varies depending on the solvent and / or reaction scale used, but from the perspective of reactivity, it is preferably 0.5 to 100 hours.

[0045] The 6,6-dialkoxyhexyl nucleophilic reagent (15) will be described below. R in the above general formula (15) 1 and R 2 are as defined in the above general formula (1). M in the above general formula (15) represents Li or MgZ, and Z represents a halogen atom or a 6,6-dialkoxyhexyl group. Specifically, examples of the halogen atom Z include a chlorine atom, a bromine atom, and an iodine atom, etc. From the perspective of reactivity, a chlorine atom and a bromine atom are preferred, and a chlorine atom is more preferred.

[0046] The 6,6-dialkoxyhexyl nucleophilic reagent (15) includes a 6,6-dialkoxyhexylmagnesium halide compound (15: M = MgZ, Z = halogen atom) and a bis(6,6-dialkoxyhexyl)magnesium compound (15: M = MgZ, Z = 6,6-dialkoxyhexyl group). Specific examples of the 6,6-dialkoxyhexylmagnesium halide compound (15: M = MgZ, Z = halogen atom) include the following compounds: 6,6-dialkoxyhexyl lithium compounds (15: M = Li) such as 6,6-dimethoxyhexyl lithium, 6,6-diethoxyhexyl lithium, 6,6-dipropyloxy-hexyl lithium, 6,6-dibutyloxy-hexyl lithium, 6,6-dipentyloxy-hexyl lithium, 6,6-dihexyloxy-hexyl lithium, 6,6-diheptyloxy-hexyl lithium, 6,6-dioctyloxy-hexyl lithium, 6,6-dinonyloxy-hexyl lithium, and 6,6-didecyloxy-hexyl lithium; 6,6-dimethoxyhexylmagnesium chloride, 6,6-diethoxyhexylmagnesium chloride, 6,6-dipropyloxyhexylmagnesium chloride, 6,6-dibutyloxyhexylmagnesium chloride, 6,6-dipentyloxyhexylmagnesium chloride, 6,6-dihexyloxyhexylmagnesium chloride, 6,6-diheptyloxyhexylmagnesium chloride, 6,6-dioctyloxyhexylmagnesium chloride, 6,6-dinonyloxyhexylmagnesium chloride, and 6,6-didecyloxyhexylmagnesium chloride, etc. 6,6-dialkoxyhexylmagnesium chloride compounds (15:M = MgZ, Z = chlorine atom); 6,6-dimethoxyhexylmagnesium bromide, 6,6-diethoxyhexylmagnesium bromide, 6,6-dipropyloxyhexylmagnesium bromide, 6,6-dibutyloxyhexylmagnesium bromide, 6,6-dipentyloxyhexylmagnesium bromide, 6,6-dihexyloxyhexylmagnesium bromide, 6,6-diheptyloxyhexylmagnesium bromide, 6,6-dioctyloxyhexylmagnesium bromide, 6,6-dinonyloxyhexylmagnesium bromide, and 6,6-didecyloxyhexylmagnesium bromide, etc. 6,6-dialkoxyhexylmagnesium bromide compounds (15:M = MgZ, Z = bromine atom); 6,6-dimethoxyhexylmagnesium iodide, 6,6-diethoxyhexylmagnesium iodide, 6,6-dipropyloxyhexylmagnesium iodide, 6,6-dibutyloxyhexylmagnesium iodide, 6,6-dipentyloxyhexylmagnesium iodide, 6,6-dihexyloxyhexylmagnesium iodide, 6,6-diheptyloxyhexylmagnesium iodide, 6,6-dioctyloxyhexylmagnesium iodide, 6,6-dinonyloxyhexylmagnesium iodide, and 6,6-didecyloxyhexylmagnesium iodide, etc. 6,6-dialkoxyhexylmagnesium iodide compounds (15:M = MgZ, Z = iodine atom). Specific examples of the bis(6,6-dialkoxyhexyl)magnesium compound (15: M = MgZ, Z = 6,6-dialkoxyhexyl group) include compounds such as bis(6,6-dimethoxyhexyl)magnesium, bis(6,6-diethoxyhexyl)magnesium, bis(6,6-dipropoxyhexyl)magnesium, bis(6,6-dibutyloxyhexyl)magnesium, bis(6,6-dipentyloxyhexyl)magnesium, bis(6,6-dihexyloxyhexyl)magnesium, bis(6,6-diheptyloxyhexyl)magnesium, bis(6,6-dioctyloxyhexyl)magnesium, bis(6,6-dinonyloxyhexyl)magnesium, and bis(6,6-didecyloxyhexyl)magnesium. As the 6,6-dialkoxyhexyl nucleophile (15), from the viewpoint of ease of preparation, 6,6-dialkoxyhexyl magnesium = halide compounds (15: M = MgZ, Z = halogen atom) such as 6,6-dialkoxyhexyl magnesium = chloride compound (15: M = MgZ, Z = chlorine atom) are preferred.

[0047] The 6,6-dialkoxyhexyl nucleophile (15) may be used alone or, if necessary, two or more kinds thereof may be used. The 6,6-dialkoxyhexyl nucleophile (15) may be commercially available or may be synthesized independently.

[0048] The 1-halo-5-halo-1-pentyne compound (16) will be described below. X in the general formula (16) above 1 is as defined in the general formula (1). X 2 is a halogen atom. Specifically, examples of the halogen atom X 2 include a chlorine atom, a bromine atom, and an iodine atom, etc., and from the viewpoint of reactivity, a bromine atom and an iodine atom are preferred.

[0049] Specific examples of the 1-halo-5-halo-1-pentyne compound (16) include the following compounds, etc.: 1-chloro-5-chloro-1-pentyne, 1-chloro-5-bromo-1-pentyne, 1-chloro-5-iodo-1-pentyne and other 1-chloro-5-halo-1-pentyne compounds (16:X 2 = chlorine atom); 1-bromo-5-chloro-1-pentyne, 1-bromo-5-bromo-1-pentyne, 1-bromo-5-iodo-1-pentyne and other 1-bromo-5-halo-1-pentyne compounds (16:X 2 = bromine atom); 1-iodo-5-chloro-1-pentyne, 1-iodo-5-bromo-1-pentyne, 1-iodo-5-iodo-1-pentyne and other 1-iodo-5-halo-1-pentyne compounds (16:X 2 = iodine atom). As the 1-halo-5-halo-1-pentyne compound (16), from the viewpoint of ease of preparation, 1-bromo-5-halo-1-pentyne compounds such as 1-bromo-5-chloro-1-pentyne (16:X 2 = bromine atom) are preferred.

[0050] The 1-halo-5-halo-1-pentyne compound (16) may be used singly or, if necessary, two or more kinds may be used. The 1-halo-5-halo-1-pentyne compound (16) may be commercially available or may be synthesized independently.

[0051] For the coupling reaction, a solvent may be used if necessary. Examples of the solvent include general solvents such as ethers such as diethyl ether, dibutyl ether, 4-methyltetrahydropyran, tetrahydrofuran (THF), 2-methyltetrahydrofuran, cyclopentylmethyl ether and 1,4-dioxane; hydrocarbons such as hexane, heptane, benzene, toluene, xylene and cumene; chlorinated solvents such as trichloroethylene, dichloromethane and chloroform; dimethyl sulfoxide, γ-butyrolactone (GBL), N-methylpyrrolidone (NMP), N , N -dimethylformamide (DMF), N , NAprotic polar solvents such as N,N-dimethylacetamide (DMAC) and hexamethylphosphoric triamide (HMPA); and nitriles such as acetonitrile and propionitrile can be mentioned. From the viewpoint of reactivity, toluene, xylene, tetrahydrofuran, 2-methyltetrahydrofuran, 4-methyltetrahydropyran and acetonitrile are preferred, and tetrahydrofuran and 2-methyltetrahydrofuran are more preferred. One type of the solvent or, if necessary, two or more types may be used. Further, a commercially available solvent can be used. From the viewpoint of reactivity, the amount of the solvent used is preferably 30 to 8000 g, more preferably 50 to 5000 g, per 1 mol of the 1-halo-5-halo-1-pentyne compound (16).

[0052] (Second step) In order to cause a coupling reaction between the 6,6-dialkoxyhexyl nucleophile (15) and the 1-halo-5-halo-1-pentyne compound (16), a catalyst may be used if necessary. Examples of the catalyst include copper compounds such as cuprous chloride, cuprous bromide, and cuprous iodide, and divalent copper halides such as cupric chloride, cupric bromide, and cupric iodide; iron compounds such as iron(II) chloride, iron(III) chloride, iron(II) bromide, iron(III) bromide, iron(II) iodide, iron(III) iodide, and iron(III) acetylacetonate; silver compounds such as silver chloride, silver nitrate, and silver acetate; titanium compounds such as titanium tetrachloride, titanium tetrabromide, titanium(IV)=methoxide, titanium(IV)=ethoxide, titanium(IV)=isopropoxide, and titanium(IV) oxide; palladium(II) compounds such as dichlorobis(triphenylphosphine)palladium and dichloro[1,1'-bis(diphenylphosphino)ferrocene]palladium; and nickel compounds such as nickel chloride, dichloro[1,2-bis(diphenylphosphino)ethane]nickel(II), and dichlorobis(triphenylphosphine)nickel(II). When the 6,6-dialkoxyhexyl nucleophile (15) is a Grignard reagent, that is, a 6,6-dialkoxyhexylmagnesium=halide compound (15:M = MgZ), from the viewpoints of reactivity and / or economy, a copper compound is preferred, and cupric halides such as cupric chloride, cupric bromide, and cupric iodide are more preferred. One type of the catalyst or, if necessary, two or more types may be used. Also, a commercially available catalyst can be used. The amount of the catalyst used is preferably 0.0003 to 0.500 mol, more preferably 0.003 to 0.200 mol, per 1 mol of the 1-halo-5-halo-1-pentyne compound (16) from the viewpoints of reaction rate and post-treatment.

[0053] When a catalyst is used in the coupling reaction, a cocatalyst may be used as necessary. Examples of the cocatalyst include trialkyl phosphite compounds having 3 to 9 carbon atoms such as triethyl phosphite; and aryl phosphine compounds having 18 to 44 carbon atoms such as triphenylphosphine, tritolylphosphine, and 2,2'-bis(diphenylphosphino)-1,1'-binaphthyl (BINAP). From the viewpoint of reactivity, trialkyl phosphite is preferred, and triethyl phosphite is particularly preferred. The cocatalyst may be used singly or, if necessary, in combination of two or more. Also, commercially available cocatalysts can be used. The amount of the cocatalyst used is preferably 0.0001 to 1.00 mol, more preferably 0.001 to 0.300 mol, per 1 mol of the 1-halo-5-halo-1-pentyne compound (16). When an organolithium reagent is used in the coupling reaction, if necessary N , N , N’ , N’ -tetramethylethylenediamine (TMEDA), hexamethylphosphoric triamide (HMPA), or N , N’ -dimethylpropyleneurea (DMPU) or the like may be added to improve the reaction rate.

[0054] When a catalyst is used in the coupling reaction, a lithium salt may be added as necessary. Examples of the lithium salt include lithium halides such as lithium chloride, lithium bromide, and lithium iodide, lithium nitrate, lithium carbonate, etc. From the viewpoint of reactivity, lithium halides such as lithium chloride and lithium nitrate are preferred. The lithium salt may be used singly or, if necessary, in combination of two or more. Also, commercially available lithium salts can be used. The amount of the lithium salt used in the coupling reaction is preferably 0.0001 to 1.00 mol, more preferably 0.001 to 0.300 mol, per 1 mol of the 1-halo-5-halo-1-pentyne compound (16) from the viewpoint of reactivity.

[0055] The reaction temperature in the coupling reaction varies depending on the 6,6-dialkoxyhexyl nucleophile (15) used, but from the perspective of reactivity, it is preferably -78 to 100 °C, more preferably -25 to 60 °C. The reaction time in the coupling reaction varies depending on the solvent used and / or the reaction scale, but from the perspective of reactivity, it is preferably 0.5 to 100 hours.

[0056] The 11-halo-1,1-dialkoxy-7-undecyne compound (17) will be described below. X in the general formula (17) above 1 , R 1 and R 2 are as defined in the general formula (1).

[0057] Specific examples of the 11-halo-1,1-dialkoxy-7-undecyne compound (17) include the following compounds: 11-chloro-1,1-dimethoxy-7-undecyne, 11-chloro-1,1-diethoxy-7-undecyne, 11-chloro-1,1-dipropyloxy-7-undecyne, 11-chloro-1,1-dibutyloxy-7-undecyne, 11-chloro-1,1-dipentyloxy-7-undecyne, 11-chloro-1,1-dihexyloxy-7-undecyne, 11-chloro-1,1-diheptyloxy-7-undecyne, 11-chloro-1,1-dioctyloxy-7-undecyne, 11-chloro-1,1-dinonyloxy-7-undecyne, and 11-chloro-1,1-didecyloxy-7-undecyne, etc. 11-chloro-1,1-dialkoxy-7-undecyne compounds (17: X 1 = chlorine atom); 11-bromo-1,1-dimethoxy-7-undecyne, 11-bromo-1,1-diethoxy-7-undecyne, 11-bromo-1,1-dipropyloxy-7-undecyne, 11-bromo-1,1-dibutyloxy-7-undecyne, 11-bromo-1,1-dipentyloxy-7-undecyne, 11-bromo-1,1-dihexyloxy-7-undecyne, 11-bromo-1,1-diheptyloxy-7-undecyne, 11-bromo-1,1-dioctyloxy-7-undecyne, 11-bromo-1,1-dinonyloxy-7-undecyne, and 11-bromo-1,1-didecyloxy-7-undecyne and other 11-bromo-1,1-dialkoxy-7-undecyne compounds (17:X 1 = bromine atom); 11-iodo-1,1-dimethoxy-7-undecyne, 11-iodo-1,1-diethoxy-7-undecyne, 11-iodo-1,1-dipropyloxy-7-undecyne, 11-iodo-1,1-dibutyloxy-7-undecyne, 11-iodo-1,1-dipentyloxy-7-undecyne, 11-iodo-1,1-dihexyloxy-7-undecyne, 11-iodo-1,1-diheptyloxy-7-undecyne, 11-iodo-1,1-dioctyloxy-7-undecyne, 11-iodo-1,1-dinonyloxy-7-undecyne, and 11-iodo-1,1-didecyloxy-7-undecyne and other 11-iodo-1,1-dialkoxy-7-undecyne compounds (17:X 1 = iodine atom).

[0058] (The third step) As the reduction reaction for reducing the carbon-carbon triple bond of the 11-halo-1,1-dialkoxy-7-undecyne compound (17) to synthesize the (7Z)-11-halo-1,1-dialkoxy-7-undecene compound (1-Z), there are (i) a catalytic hydrogenation reaction, (ii) a reduction reaction using zinc in an alcohol solvent, (iii) a reduction reaction by hydroboration using a dialkylborane followed by protonation, (iv) in the presence of a palladium catalyst such as palladium acetate, potassium hydroxide and N , N- Reduction reaction using dimethylformamide (DMF), (v) hydrosilylation to obtain vinylsilane, followed by a reduction reaction of desilylation, (vi) Birch reduction, (vii) ammonia-free Birch reduction, and (viii) Benkeser reduction, etc. can be mentioned. From the viewpoints of selectivity and productivity, the catalytic reduction reaction of (i) above, the reduction reaction using zinc of (ii) above, and the reduction reaction by hydroboration of (iii) above followed by protonation are preferred, and the catalytic reduction reaction of (i) is more preferred. In addition, as the reduction reaction for reducing the carbon-carbon triple bond of the 11-halo-1,1-dialkoxy-7-undecyne compound (17) to synthesize the (7E)-11-halo-1,1-dialkoxy-7-undecene compound (1-E), among the reduction reactions of (i) to (viii) above, (vi) Birch reduction, (vii) ammonia-free Birch reduction, and (viii) Benkeser reduction are preferred, and (viii) Benkeser reduction is most preferred from the viewpoint of production.

[0059] (i) Contact reduction reaction The catalytic reduction reaction is carried out by adding hydrogen gas in the presence of a metal catalyst. Examples of the metal catalyst used in the catalytic reduction reaction include nickel boride catalyst, nickel(0) nanoparticles (Fransisco Alonso et al, Tetrahedron, 2007, 63, 93-102), and nickel catalysts such as U-Ni-A and U-Ni-B; and Lindlar catalyst, Palladium on carbon, Pd / CaCO 3 、Pd / BaSO 4 、Pd / Al 2 O 3 、Pd / SiO doped with Hg 2, Pd / McM-41, Pd nanoparticles in hydrotalcite, Pd / Zn alloy, and Pd-PEI (where Pd-PEI is palladium carbon poisoned with polyethyleneimine polymer (PEI)) and palladium catalysts such as Pd-PEI poisoned with polyethyleneimine polymer (PEI) and palladium carbon, etc. can be mentioned, but are not limited thereto. Examples of the above nickel boride catalysts include, for example, P-1 nickel boride catalyst and P-2 nickel boride catalyst (Thomas J. Caggiano et al. Encyclopedia of Reagents for Organic Synthesis: 3694-3699.) (hereinafter, also referred to as "P-2Ni catalyst"); and nickel dispersed on graphite (for example, Ni-Gr1 and Ni-Gr2), Caubere catalyst (Nic), and nickel in hydrogenated boron exchange resin (Ni 2 B-BER) (Laurence Balas, HAL, 2021; https: / / hal.archives-ouvertes.fr / hal-00801666), etc. can be mentioned, but are not limited thereto. From the perspective of economy, Lindlar catalyst and nickel catalyst are preferred. The amount of the metal catalyst used varies depending on the catalyst used. From the perspective of reactivity, when the catalyst is solid like Lindlar catalyst, etc., 0.01-50 g is preferred per 1 mol of 11-halo-1,1-dialkoxy-7-undecyne compound (17). Also, the P-2Ni catalyst is preferably used such that the equivalent amount as a nickel compound is 0.0001-2.0 mol per 1 mol of 11-halo-1,1-dialkoxy-7-undecyne compound (17). In addition, the solid catalyst may be used after being dispersed in a solvent.

[0060] When the activity of the metal catalyst is high, a catalyst poison may be used as necessary. Examples of the catalyst poison include amine compounds such as pyridine, quinoline and ethylenediamine; phosphine compounds such as triphenylphosphine, tritolylphosphine and triethyl phosphite; and sulfur compounds such as benzenethiol, diphenyl sulfide, dimethyl sulfide and dimethyl sulfoxide. The amount of the catalyst poison used varies greatly depending on the catalyst poison used. From the viewpoints of reaction rate and geometric selectivity, it is preferably 0.0001 to 20.0 mol, more preferably 0.001 to 2.0 mol, per 1 mol of the 11-halo-1,1-dialkoxy-7-undecyne compound (17).

[0061] Examples of the solvent used in the catalytic reduction reaction include hydrocarbons such as hexane, heptane, benzene, toluene, xylene and cumene; nitriles such as acetonitrile and propionitrile; esters such as methyl acetate, ethyl acetate, n-propyl acetate and n-butyl acetate; and alcohols such as methanol, ethanol, propanol, butanol, pentanol, hexanol, 2-propanol, 2-butanol and cyclohexanol. One type of the solvent may be used, or two or more types may be used as necessary. Also, commercially available solvents can be used.

[0062] When using Lindlar catalyst, from the viewpoint of reactivity, hydrocarbons such as hexane, heptane, toluene and xylene are preferred as the solvent. When using nickel catalyst, from the viewpoint of reactivity, alcohols such as methanol, ethanol, propanol, butanol and 2-propanol are preferred as the solvent. When using palladium catalyst such as palladium on carbon, from the viewpoint of reactivity, esters such as methyl acetate and ethyl acetate are preferred as the solvent. The amount of the solvent used varies depending on the catalyst and / or solvent used. From the viewpoint of reactivity, it is preferably 0 to 1000 g per 1 mol of the 11-halo-1,1-dialkoxy-7-undecyne compound (17).

[0063] The reaction temperature of the catalytic reduction reaction varies depending on the type of catalyst and / or solvent used. From the perspective of geometric selectivity, it is preferably 0 to 160 °C, more preferably 20 to 100 °C. The reaction time of the catalytic reduction reaction is preferably 0.5 to 100 hours from the perspective of yield.

[0064] (ii) Reduction reaction using zinc in an alcohol solvent The reduction reaction is carried out using zinc in an alcohol solvent. The number of carbon atoms of the alcohol used as the solvent is preferably 1 to 10, more preferably 1 to 5. Examples of the alcohol used as the solvent include linear alcohol compounds such as methanol, ethanol, propanol, butanol, pentanol, hexanol, heptanol, octanol, nonanol, and decanol; branched alcohol compounds such as 2-propanol and 2-butanol; and cyclic alcohol compounds such as cyclohexanol. From the perspective of reactivity, alcohol compounds with 1 to 5 carbon atoms such as methanol, ethanol, propanol, butanol, pentanol, and 2-propanol are preferred. From the perspective of reactivity, the amount of the alcohol used is preferably 46 to 1000 g per 1 mol of the 11-halo-1,1-dialkoxy-7-undecyne compound (17). From the perspective of reactivity, the amount of zinc used is preferably 1.0 to 1000 mol, more preferably 1.0 to 200 mol per 1 mol of the 11-halo-1,1-dialkoxy-7-undecyne compound (17).

[0065] Due to the low reactivity of zinc, the reaction time of the reduction reaction may be long. Therefore, if necessary, an activator for activating zinc may be added, or pre-prepared activated zinc may be used. Examples of the activator include 1,2-dibromoethane, cuprous chloride, cuprous bromide, cuprous iodide, lithium bromide, iodine, and chlorotrimethylsilane. One type of the activator or, if necessary, two or more types may be used. From the perspective of reactivity, the amount of the activator used is preferably 0.01 to 10.0 mol per 1 mol of the 11-halo-1,1-dialkoxy-7-undecyne compound (17). Activated zinc can be prepared, for example, by treating metallic zinc with an acid such as hydrochloric acid, or by reducing zinc chloride with metallic lithium in tetrahydrofuran or 2-methyltetrahydrofuran, or by reacting metallic zinc with 1,2-dibromoethane and lithium dibromocuprate in tetrahydrofuran or 2-methyltetrahydrofuran.

[0066] The reaction temperature of the reduction reaction varies depending on the solvent used, but from the perspective of reactivity, it is preferably 20 to 180 °C. From the perspective of the completion of the reaction, the reaction time of the reduction reaction is preferably 0.5 to 150 hours.

[0067] (iii) Hydroboration using dialkylborane and subsequent reduction reaction by protonation In the reduction reaction, first, hydroboration is carried out using a dialkylborane in a solvent. The number of carbon atoms of the dialkylborane used for hydroboration is preferably 4 to 18, more preferably 6 to 12. Examples of the dialkylborane include dicyclohexylborane, diisopentylborane, dicyamylborane, 9-borabicyclo[3.3.1]nonane (9-BBN), diisopinocampheylborane, catecholborane, and pinacolborane. From the perspective of reactivity, dicyclohexylborane and diisopentylborane are preferred. From the perspective of reactivity, the amount of the dialkylborane used is preferably 1.0 to 4.0 mol per 1 mol of the 11-halo-1,1-dialkoxy-7-undecyne compound (17).

[0068] Examples of the solvent used for the hydroboration include ethers such as tetrahydrofuran, 2-methyltetrahydrofuran, diethyl ether, dibutyl ether, 4-methyltetrahydropyran, cyclopentyl methyl ether, 1,4-dioxane, and diethylene glycol dimethyl ether; and hydrocarbons such as hexane, heptane, benzene, toluene, xylene, and cumene. From the perspective of reactivity, ethers such as tetrahydrofuran, 2-methyltetrahydrofuran, 4-methyltetrahydropyran, and diethylene glycol dimethyl ether are more preferred. One type of the solvent or two or more types thereof may be used as necessary. Further, a commercially available solvent can be used. From the perspective of reactivity, the amount of the solvent used is preferably 100 to 3000 g per 1 mol of the 11-halo-1,1-dialkoxy-7-undecyne compound (17).

[0069] From the perspective of geometric selectivity, the reaction temperature of the hydroboration is preferably -20°C to 50°C. The reaction time of the hydroboration varies depending on the reaction temperature and / or the scale of the reaction. From the perspective of reactivity, it is preferably 0.5 to 100 hours.

[0070] In the above reduction reaction, protonation is carried out using an acid in a solvent following the hydroboration. Examples of the acid used for protonation following the hydroboration include carboxylic acids such as acetic acid, propionic acid, butyric acid, pentanoic acid, pivalic acid, heptanoic acid, trifluoroacetic acid, chloroacetic acid, formic acid, and oxalic acid; sulfonic acids such as p-toluenesulfonic acid; and mineral acids such as sulfuric acid, hydrochloric acid, nitric acid, and phosphoric acid. From the perspective of reactivity, carboxylic acids such as acetic acid and propionic acid are preferred. From the perspective of reactivity, the amount of the acid used is preferably 2.0 to 20.0 mol per 1 mol of the 11-halo-1,1-dialkoxy-7-undecyne compound (17). The solvent used for the protonation and its amount used are the same as those used for the hydroboration because the protonation is carried out in the same reaction system following the hydroboration.

[0071] The reaction temperature of the protonation varies depending on the reagent used, but from the viewpoint of the reaction rate, it is preferably 0 °C to 150 °C. The reaction time of the protonation varies depending on the reaction temperature and / or the scale of the reaction, but from the viewpoint of reactivity, it is preferably 1 to 70 hours.

[0072] (iv) Reduction reaction using potassium hydroxide and N,N-dimethylformamide (DMF) in the presence of a palladium catalyst such as palladium acetate The reduction reaction is carried out in the presence of a palladium catalyst such as palladium acetate, potassium hydroxide, and N , N -dimethylformamide (DMF), preferably at 100 to 180 °C for 0.5 to 100 hours.

[0073] (v) Hydrosilylation to obtain vinylsilane, followed by desilylation reduction reaction The hydrosilylation is carried out using a metal catalyst such as Wilkinson catalyst and Trost catalyst, and a trialkylsilane. From the viewpoint of reactivity, the amount of the metal catalyst used is preferably 0.0001 to 4.0 mol, more preferably 0.001 to 1.0 mol, per 1 mol of the 11-halo-1,1-dialkoxy-7-undecyne compound (17). The hydrosilylation is preferably carried out at 5 to 100 °C for 0.5 to 100 hours. The desilylation after the hydrosilylation is preferably carried out using at least one of acids such as sulfuric acid and hydrochloric acid, hydrogen iodide, acetyl chloride, titanium tetrachloride, and iodine at 5 °C to 80 °C for 0.5 to 100 hours.

[0074] (vi) Birch reduction The Birch reduction is carried out using a metal in ammonia. From the perspective of reactivity, the amount of ammonia used is preferably 1.0 to 10,000 mol, more preferably 10 to 3,000 mol, per 1 mol of the 11-halo-1,1-dialkoxy-7-undecyne compound (17).

[0075] Examples of the metal include alkali metals such as potassium, sodium, and lithium; and alkaline earth metals such as calcium and magnesium. From the perspective of reactivity, the amount of the metal used is preferably 1.0 to 1,000 mol, more preferably 1.0 to 100 mol, per 1 mol of the 11-halo-1,1-dialkoxy-7-undecyne compound (17).

[0076] In the Birch reduction, it is preferable to add a proton source in addition to ammonia. Examples of the proton source include alcohols such as methanol, ethanol, n-propanol, 2-propanol, and 2-methyl-2-propanol; and tetrahydrofuran (THF) and 2-methyltetrahydrofuran. One type of the proton source or two or more types thereof may be used as necessary. Also, commercially available proton sources can be used. From the perspective of reactivity, the amount of the proton source used is preferably 1.0 to 10,000 mol, more preferably 1.0 to 3,000 mol, per 1 mol of the 11-halo-1,1-dialkoxy-7-undecyne compound (17).

[0077] From the perspective of reactivity, the reaction temperature in the Birch reduction is preferably -78 to 0 °C, more preferably -78 to -33 °C. The reaction time in the Birch reduction varies depending on the reaction scale, but from the perspective of reactivity, it is preferably 0.5 to 100 hours.

[0078] (vii) Ammonia-free Birch reduction The ammonia-free Birch reduction is carried out using a metal in a crown ether. Examples of the crown ether include 12-crown-4, 15-crown-5, 18-crown-6, dibenzo-18-crown-6, diaza-18-crown-6, and the like. One type of the crown ether or two or more types thereof may be used as needed. Further, a commercially available crown ether can be used. From the viewpoint of reactivity, the amount of the crown ether used is preferably 1.0 to 100.0 mol, more preferably 1.0 to 20.0 mol, per 1 mol of the 11-halo-1,1-dialkoxy-7-undecyne compound (17).

[0079] Examples of the metal include alkali metals such as potassium, sodium, and lithium; and alkaline earth metals such as calcium and magnesium. From the viewpoint of reactivity, the amount of the metal used is preferably 1.0 to 100.0 mol, more preferably 1.0 to 20.0 mol, per 1 mol of the 11-halo-1,1-dialkoxy-7-undecyne compound (17).

[0080] In the ammonia-free Birch reduction, it is preferable to add a proton source in addition to the crown ether. Examples of the proton source include alcohols such as methanol, ethanol, n-propanol, 2-propanol, and 2-methyl-2-propanol; and tetrahydrofuran (THF), 2-methyltetrahydrofuran, and the like. One type of the proton source or two or more types thereof may be used as needed. Further, a commercially available proton source can be used. From the viewpoint of reactivity, the amount of the proton source used is preferably 1.0 to 100.0 mol, more preferably 1.0 to 20.0 mol, per 1 mol of the 11-halo-1,1-dialkoxy-7-undecyne compound (17).

[0081] The reaction temperature in the ammonia-free Benkeser reduction varies depending on the metal and / or crown ether used, but from the perspective of reactivity, it is preferably -78 to 100 °C, more preferably -40 to 40 °C. The reaction time in the ammonia-free Benkeser reduction varies depending on the metal, crown ether, and / or reaction scale used, but from the perspective of reactivity, it is preferably 0.1 to 100 hours, more preferably 0.1 to 5 hours.

[0082] (viii) Benkeser reduction The Benkeser reduction is carried out using a metal in an alkylamine. Examples of the alkylamine include lower amines such as methylamine, ethylamine, propylamine, and 1,3-propanediamine. From the perspective of reactivity, the amount of the alkylamine used is preferably 1.0 to 5000 mol, more preferably 1.0 to 1000 mol, per 1 mol of the 11-halo-1,1-dialkoxy-7-undecyne compound (17).

[0083] Examples of the metal include alkali metals such as potassium, sodium, and lithium; and alkaline earth metals such as calcium and magnesium. From the perspective of reactivity, the amount of the metal used is preferably 1.0 to 1000 mol, more preferably 1.0 to 100 mol, per 1 mol of the 11-halo-1,1-dialkoxy-7-undecyne compound (17).

[0084] From the perspective of reactivity, the reaction temperature in the Benkeser reduction is preferably -78 to 100 °C, more preferably -78 to 60 °C. The reaction time in the Benkeser reduction varies depending on the reaction scale, but from the perspective of reactivity, it is preferably 0.5 to 100 hours.

[0085] Note that the 11-halo-1,1-dialkoxy-7-undecene compound (1) is Coniesa ignefusalis (7E)-7-dodecenal, which is the sex pheromone of Spaelotis clandestinaIt is useful for the production of synthetic intermediates such as (7Z)-7-tetradecenal, which is the sex pheromone of Helicoverpa armigera and (7Z)-7-hexadecenal, which is the sex pheromone of

[0086] (A-2). Regarding the 11,11-dialkoxy-4-undecenyltriarylphosphonium halide compound (3) Next, the 11,11-dialkoxy-4-undecenyltriarylphosphonium halide compound (3) will be described. Y - Ar 3 P + (CH 2 ) 3 CH=CH(CH 2 ) 5 CH(OR 1 )(OR 2 ) (3) As defined in the above general formula (A), Y represents a halogen atom. Specifically, examples of the halogen atom Y include a chlorine atom, a bromine atom, and an iodine atom, and a bromine atom and an iodine atom are preferred from the viewpoint of reactivity. In the above general formula (3), R 1 and R 2 are as defined in the above general formula (1). In the above general formula (3), Ar represents an aryl group which may be the same or different from each other. The number of carbon atoms of the aryl group is preferably 6 to 24, more preferably 6 to 12, and still more preferably 6 to 7. Examples of the aryl group include a phenyl group (Ph group), a tolyl group, a naphthyl group, and an anthracenyl group. From the viewpoint of ease of synthesis, a phenyl group is preferred, and it is more preferred that all three aryl groups are phenyl groups.

[0087] The 11,11-dialkoxy-4-undecenyltriarylphosphonium halide compound (3) includes a (4Z)-11,11-dialkoxy-4-undecenyltriarylphosphonium halide compound represented by the general formula (3-Z) and a (4E)-11,11-dialkoxy-4-undecenyltriarylphosphonium halide compound represented by the general formula (3-E).

[0088] Specific examples of the (4Z)-11,11-dialkoxy-4-undecenyltriarylphosphonium halide compound (3-Z) include the following compounds: (4Z)-11,11-dimethoxy-4-undecenyltriphenylphosphonium chloride, (4Z)-11,11-diethoxy-4-undecenyltriphenylphosphonium chloride, (4Z)-11,11-dipropyloxy-4-undecenyltriphenylphosphonium chloride, (4Z)-11,11-dibutyloxy-4-undecenyltriphenylphosphonium chloride, (4Z)-11,11-dipentyloxy-4-undecenyltriphenylphosphonium chloride, (4Z)-11,11-dihexyloxy-4-undecenyltriphenylphosphonium chloride, (4Z)-11,11-diheptyloxy-4-undecenyltriphenylphosphonium chloride, (4Z)-11,11-dioctyloxy-4-undecenyltriphenylphosphonium chloride, (4Z)-11,11-dinonyloxy-4-undecenyltriphenylphosphonium chloride, and (4Z)-11,11-didecyloxy-4-undecenyltriphenylphosphonium chloride and other (4Z)-11,11-dialkoxy-4-undecenyltriphenylphosphonium chloride compounds (3-Z: Y = chlorine atom, Ar = phenyl group); (4Z)-11,11-Dimethoxy-4-undecenyltritolylphosphonium chloride, (4Z)-11,11-diethoxy-4-undecenyltritolylphosphonium chloride, (4Z)-11,11-dipropyloxy-4-undecenyltritolylphosphonium chloride, (4Z)-11,11-dibutyloxy-4-undecenyltritolylphosphonium chloride, (4Z)-11,11-dipentyloxy-4-undecenyltritolylphosphonium chloride, (4Z)-11,11-dihexyloxy-4-undecenyltritolylphosphonium chloride, (4Z)-11,11-diheptyloxy-4-undecenyltritolylphosphonium chloride, (4Z)-11,11-dioctyloxy-4-undecenyltritolylphosphonium chloride, (4Z)-11,11-dinonyloxy-4-undecenyltritolylphosphonium chloride and (4Z)-11,11-didecyloxy-4-undecenyltritolylphosphonium chloride and other (4Z)-11,11-dialkoxy-4-undecenyltritolylphosphonium chloride compounds (3-Z: Y = chlorine atom, Ar = tolyl group); (4Z)-11,11-Dimethoxy-4-undecenyltriphenylphosphonium bromide, (4Z)-11,11-diethoxy-4-undecenyltriphenylphosphonium bromide, (4Z)-11,11-dipropyloxy-4-undecenyltriphenylphosphonium bromide, (4Z)-11,11-dibutyloxy-4-undecenyltriphenylphosphonium bromide, (4Z)-11,11-dipentyloxy-4-undecenyltriphenylphosphonium bromide, (4Z)-11,11-dihexyloxy-4-undecenyltriphenylphosphonium bromide, (4Z)-11,11-diheptyloxy-4-undecenyltriphenylphosphonium bromide, (4Z)-11,11-dioctyloxy-4-undecenyltriphenylphosphonium bromide, (4Z)-11,11-dinonyloxy-4-undecenyltriphenylphosphonium bromide, and (4Z)-11,11-didecyloxy-4-undecenyltriphenylphosphonium bromide, etc., (4Z)-11,11-dialkoxy-4-undecenyltriphenylphosphonium bromide compounds (3-Z: Y = bromine atom, Ar = phenyl group); (4Z)-11,11-dimethoxy-4-undecenyltritolylphosphonium bromide, (4Z)-11,11-diethoxy-4-undecenyltritolylphosphonium bromide, (4Z)-11,11-dipropyloxy-4-undecenyltritolylphosphonium bromide, (4Z)-11,11-dibutyloxy-4-undecenyltritolylphosphonium bromide, (4Z)-11,11-dipentyloxy-4-undecenyltritolylphosphonium bromide, (4Z)-11,11-dihexyloxy-4-undecenyltritolylphosphonium bromide, (4Z)-11,11-diheptyloxy-4-undecenyltritolylphosphonium bromide, (4Z)-11,11-dioctyloxy-4-undecenyltritolylphosphonium bromide, (4Z)-11,11-dinonyloxy-4-undecenyltritolylphosphonium bromide, and (4Z)-11,11-didecyloxy-4-undecenyltritolylphosphonium bromide, etc., (4Z)-11,11-dialkoxy-4-undecenyltritolylphosphonium bromide compounds (3-Z: Y = bromine atom, Ar = tolyl group); (4Z)-11,11-Dimethoxy-4-undecenyltriphenylphosphonium iodide, (4Z)-11,11-diethoxy-4-undecenyltriphenylphosphonium iodide, (4Z)-11,11-dipropyloxy-4-undecenyltriphenylphosphonium iodide, (4Z)-11,11-dibutyloxy-4-undecenyltriphenylphosphonium iodide, (4Z)-11,11-dipentyloxy-4-undecenyltriphenylphosphonium iodide, (4Z)-11,11-dihexyloxy-4-undecenyltriphenylphosphonium iodide, (4Z)-11,11-diheptyloxy-4-undecenyltriphenylphosphonium iodide, (4Z)-11,11-dioctyloxy-4-undecenyltriphenylphosphonium iodide, (4Z)-11,11-dinonyloxy-4-undecenyltriphenylphosphonium iodide and (4Z)-11,11-didecyloxy-4-undecenyltriphenylphosphonium iodide and other (4Z)-11,11-dialkoxy-4-undecenyltriphenylphosphonium iodide compounds (3-Z: Y = iodine atom, Ar = phenyl group); and, (4Z)-11,11-Dimethoxy-4-undecenyltritolylphosphonium iodide, (4Z)-11,11-diethoxy-4-undecenyltritolylphosphonium iodide, (4Z)-11,11-dipropyloxy-4-undecenyltritolylphosphonium iodide, (4Z)-11,11-dibutyloxy-4-undecenyltritolylphosphonium iodide, (4Z)-11,11-dipentyloxy-4-undecenyltritolylphosphonium iodide, (4Z)-11,11-dihexyloxy-4-undecenyltritolylphosphonium iodide, (4Z)-11,11-diheptyloxy-4-undecenyltritolylphosphonium iodide, (4Z)-11,11-dioctyloxy-4-undecenyltritolylphosphonium iodide, (4Z)-11,11-dinonyloxy-4-undecenyltritolylphosphonium iodide, and (4Z)-11,11-didecyloxy-4-undecenyltritolylphosphonium iodide, etc., (4Z)-11,11-dialkoxy-4-undecenyltritolylphosphonium iodide compounds (3-Z: Y = iodine atom, Ar = tolyl group). As the (4Z)-11,11-dialkoxy-4-undecenyltriarylphosphonium halide compound (3-Z), from the viewpoint of ease of preparation, (4Z)-11,11-dialkoxy-4-undecenyltriphenylphosphonium chloride compound (3-Z: Y = chlorine atom, Ar = phenyl group), (4Z)-11,11-dialkoxy-4-undecenyltriphenylphosphonium bromide compound (3-Z: Y = bromine atom, Ar = phenyl group), and (4Z)-11,11-dialkoxy-4-undecenyltriphenylphosphonium iodide compound (3-Z: Y = iodine atom, Ar = phenyl group) are preferred.

[0089] Specific examples of the (4E)-11,11-dialkoxy-4-undecenyltriarylphosphonium halide compound (3-E) include the following compounds: (4E)-11,11-dimethoxy-4-undecenyltriphenylphosphonium chloride, (4E)-11,11-diethoxy-4-undecenyltriphenylphosphonium chloride, (4E)-11,11-dipropyloxy-4-undecenyltriphenylphosphonium chloride, (4E)-11,11-dibutyloxy-4-undecenyltriphenylphosphonium chloride, (4E)-11,11-dipentyloxy-4-undecenyltriphenylphosphonium chloride, (4E)-11,11-dihexyloxy-4-undecenyltriphenylphosphonium chloride, (4E)-11,11-diheptyloxy-4-undecenyltriphenylphosphonium chloride, (4E)-11,11-dioctyloxy-4-undecenyltriphenylphosphonium chloride, (4E)-11,11-dinonyloxy-4-undecenyltriphenylphosphonium chloride, and (4E)-11,11-didecyloxy-4-undecenyltriphenylphosphonium chloride and other (4E)-11,11-dialkoxy-4-undecenyltriphenylphosphonium chloride compounds (3-E: Y = chlorine atom, Ar = phenyl group); (4E)-11,11-dimethoxy-4-undecenyltritolylphosphonium chloride, (4E)-11,11-diethoxy-4-undecenyltritolylphosphonium chloride, (4E)-11,11-dipropyloxy-4-undecenyltritolylphosphonium chloride, (4E)-11,11-dibutyloxy-4-undecenyltritolylphosphonium chloride, (4E)-11,11-dipentyloxy-4-undecenyltritolylphosphonium chloride, (4E)-11,11-dihexyloxy-4-undecenyltritolylphosphonium chloride, (4E)-11,11-diheptyloxy-4-undecenyltritolylphosphonium chloride, (4E)-11,11-dioctyloxy-4-undecenyltritolylphosphonium chloride, (4E)-11,11-dinonyloxy-4-undecenyltritolylphosphonium chloride and (4E)-11,11-didecyloxy-4-undecenyltritolylphosphonium chloride and other (4E)-11,11-dialkoxy-4-undecenyltritolylphosphonium chloride compounds (3-E: Y = chlorine atom, Ar = tolyl group); (4E)-11,11-dimethoxy-4-undecenyltriphenylphosphonium bromide, (4E)-11,11-diethoxy-4-undecenyltriphenylphosphonium bromide, (4E)-11,11-dipropyloxy-4-undecenyltriphenylphosphonium bromide, (4E)-11,11-dibutyloxy-4-undecenyltriphenylphosphonium bromide, (4E)-11,11-dipentyloxy-4-undecenyltriphenylphosphonium bromide, (4E)-11,11-dihexyloxy-4-undecenyltriphenylphosphonium bromide, (4E)-11,11-diheptyloxy-4-undecenyltriphenylphosphonium bromide, (4E)-11,11-dioctyloxy-4-undecenyltriphenylphosphonium bromide, (4E)-11,11-dinonyloxy-4-undecenyltriphenylphosphonium bromide, and (4E)-11,11-didecyloxy-4-undecenyltriphenylphosphonium bromide and other (4E)-11,11-dialkoxy-4-undecenyltriphenylphosphonium bromide compounds (3-E: Y = bromine atom, Ar = phenyl group); (4E)-11,11-dimethoxy-4-undecenyltritolylphosphonium bromide, (4E)-11,11-diethoxy-4-undecenyltritolylphosphonium bromide, (4E)-11,11-dipropyloxy-4-undecenyltritolylphosphonium bromide, (4E)-11,11-dibutyloxy-4-undecenyltritolylphosphonium bromide, (4E)-11,11-dipentyloxy-4-undecenyltritolylphosphonium bromide, (4E)-11,11-dihexyloxy-4-undecenyltritolylphosphonium bromide, (4E)-11,11-diheptyloxy-4-undecenyltritolylphosphonium bromide, (4E)-11,11-dioctyloxy-4-undecenyltritolylphosphonium bromide, (4E)-11,11-dinonyloxy-4-undecenyltritolylphosphonium bromide, and (4E)-11,11-didecyloxy-4-undecenyltritolylphosphonium bromide and other (4E)-11,11-dialkoxy-4-undecenyltritolylphosphonium bromide compounds (3-E: Y = bromine atom, Ar = tolyl group); (4E)-11,11-dimethoxy-4-undecenyltriphenylphosphonium iodide, (4E)-11,11-diethoxy-4-undecenyltriphenylphosphonium iodide, (4E)-11,11-dipropyloxy-4-undecenyltriphenylphosphonium iodide, (4E)-11,11-dibutyloxy-4-undecenyltriphenylphosphonium iodide, (4E)-11,11-dipentyloxy-4-undecenyltriphenylphosphonium iodide, (4E)-11,11-dihexyloxy-4-undecenyltriphenylphosphonium iodide, (4E)-11,11-diheptyloxy-4-undecenyltriphenylphosphonium iodide, (4E)-11,11-dioctyloxy-4-undecenyltriphenylphosphonium iodide, (4E)-11,11-dinonyloxy-4-undecenyltriphenylphosphonium iodide and (4E)-11,11-didecyloxy-4-undecenyltriphenylphosphonium iodide and other (4E)-11,11-dialkoxy-4-undecenyltriphenylphosphonium iodide compounds (3-E: Y = iodine atom, Ar = phenyl group); and, (4E)-11,11-Dimethoxy-4-undecenyltritolylphosphonium iodide, (4E)-11,11-diethoxy-4-undecenyltritolylphosphonium iodide, (4E)-11,11-dipropyloxy-4-undecenyltritolylphosphonium iodide, (4E)-11,11-dibutyloxy-4-undecenyltritolylphosphonium iodide, (4E)-11,11-dipentyloxy-4-undecenyltritolylphosphonium iodide, (4E)-11,11-dihexyloxy-4-undecenyltritolylphosphonium iodide, (4E)-11,11-diheptyloxy-4-undecenyltritolylphosphonium iodide, (4E)-11,11-dioctyloxy-4-undecenyltritolylphosphonium iodide, (4E)-11,11-dinonyloxy-4-undecenyltritolylphosphonium iodide, and (4E)-11,11-didecyloxy-4-undecenyltritolylphosphonium iodide and other (4E)-11,11-dialkoxy-4-undecenyltritolylphosphonium iodide compounds (3-E: Y = iodine atom, Ar = tolyl group). As the (4E)-11,11-dialkoxy-4-undecenyltriarylphosphonium halide compound (3-E), from the viewpoint of ease of preparation, (4E)-11,11-dialkoxy-4-undecenyltriphenylphosphonium chloride compound (3-E: Y = chlorine atom, Ar = phenyl group), (4E)-11,11-dialkoxy-4-undecenyltriphenylphosphonium bromide compound (3-E: Y = bromine atom, Ar = phenyl group), and (4E)-11,11-dialkoxy-4-undecenyltriphenylphosphonium iodide compound (3-E: Y = iodine atom, Ar = phenyl group) are preferred.

[0090] (4Z)-11,11-Dialkoxy-4-undecenyltriarylphosphonium halide compound (3-Z) can be used as a common synthetic intermediate in the production of (7Z,11Z,13E)-7,11,13-hexadecatrienal (7) and the production of (7Z,11Z)-7,11-hexadecadienal (10) as described below.

[0091] (4Z)-11,11-dialkoxy-4-undecenyltriarylphosphonium halide compound (3-Z) and (4E)-11,11-dialkoxy-4-undecenyltriarylphosphonium halide compound (3-E) will be described in the following section B.

[0092] B. Method for producing 11,11-dialkoxy-4-undecenyltriarylphosphonium halide compound (3) Hereinafter, in this specification, the production method will be described using the (4Z)-11,11-dialkoxy-4-undecenyltriarylphosphonium halide compound (3-Z). However, in the case of the (4E)-11,11-dialkoxy-4-undecenyltriarylphosphonium halide compound (3-E), the reaction proceeds in the same manner as that of the (4Z)-11,11-dialkoxy-4-undecenyltriarylphosphonium halide compound (3-Z), and the corresponding compound can be produced.

[0093] (4Z)-11,11-dialkoxy-4-undecenyltriarylphosphonium halide compound (3-Z) can be prepared, for example, by a phosphonium salt formation reaction between the above (7Z)-11-halo-1,1-dialkoxy-7-undecene compound (1-Z) and a phosphine compound represented by the following general formula (2), as shown in the following chemical reaction formula.

[0094]

Chemical formula

[0095] Examples of the phosphine compound (2) include triarylphosphine compounds such as triphenylphosphine, tritolylphosphine, trinaphthylphosphine, and trianthracenylphosphine. From the viewpoint of reactivity, triphenylphosphine is preferred. From the perspective of reactivity, the amount of the phosphine compound (2) used is preferably 0.8 to 5.0 mol per 1 mol of the (7Z)-11-halo-1,1-dialkoxy-7-undecene compound (1-Z).

[0096] <Regarding the phosphonium salt formation reaction> For the preparation of the (4Z)-11,11-dialkoxy-4-undecenyltriarylphosphonium = halide compound (3-Z), a halide may be used as necessary. Examples of the halide include iodides such as sodium iodide and potassium iodide; and bromides such as sodium bromide and potassium bromide. From the perspective of reactivity, iodides such as sodium iodide and potassium iodide are preferred. When no halide is used in the above preparation of the (4Z)-11,11-dialkoxy-4-undecenyltriarylphosphonium = halide compound (3-Z), Y in the general formula (3-Z) is the same halogen atom as X in the general formula (1-Z). 1 On the other hand, when an iodide is used as the halide in the preparation, Y in the general formula (3-Z) is the same halogen atom as X in the general formula (1-Z) for the (7Z)-11-halo-1,1-dialkoxy-7-undecene compound (1-Z) 1 or an iodine atom. The halide may be used alone or, if necessary, two or more kinds may be used. Also, commercially available halides can be used. From the perspective of reactivity, the amount of the halide used is preferably 0.1 to 10.0 mol, more preferably 0.8 to 4.0 mol, per 1 mol of the (7Z)-11-halo-1,1-dialkoxy-7-undecene compound (1-Z).

[0097] For the preparation of the (4Z)-11,11-dialkoxy-4-undecenyltriarylphosphonium = halide compound (3-Z), a base may be added as necessary. Examples of the base include alkali metal carbonates such as potassium carbonate and sodium carbonate; alkaline earth metal carbonates such as calcium carbonate and magnesium carbonate; and amines such as triethylamine, tripropylamine, triisopropylamine, tributylamine, N , N -diethylaniline and pyridine. From the perspective of handling, alkali metal carbonates are preferred. One type of the base or two or more types may be used as necessary. In addition, commercially available bases can be used. From the perspective of reactivity, the amount of the base used is preferably 0.001 to 1.0 mol relative to 1 mol of the (7Z)-11-halo-1,1-dialkoxy-7-undecene compound (1-Z).

[0098] (4Z)-11,11-Dialkoxy-4-undecenyltriarylphosphonium = halide compound (3-Z) may be prepared using a solvent as necessary. Examples of the solvent include ether solvents such as tetrahydrofuran, 2-methyltetrahydrofuran, diethyl ether, dibutyl ether, 4-methyltetrahydropyran, cyclopentylmethyl ether and 1,4-dioxane; hydrocarbon solvents such as hexane, heptane, benzene, toluene, xylene and cumene; and N , N -dimethylformamide, N , N -dimethylacetamide, N-methylpyrrolidone, dimethyl sulfoxide, γ-butyrolactone, acetonitrile, dichloromethane and chloroform and other polar solvents. From the perspective of reactivity, ether solvents such as tetrahydrofuran, 2-methyltetrahydrofuran and 4-methyltetrahydropyran and N , N -dimethylformamide and N , N polar solvents such as -dimethylacetamide are preferred. The solvent may be one type or, if necessary, two or more types may be used. Also, a commercially available solvent can be used. From the viewpoint of reactivity, the amount of the solvent used is preferably 50 to 7000 g with respect to the (7Z)-11-halo-1,1-dialkoxy-7-undecene compound (1-Z).

[0099] In the preparation of the (4Z)-11,11-dialkoxy-4-undecenyltriarylphosphonium halide compound (3-Z), the reaction temperature varies depending on the solvent used, but is preferably 30 to 180°C, more preferably 50 to 150°C. In the preparation of the (4Z)-11,11-dialkoxy-4-undecenyltriarylphosphonium halide compound (3-Z), the reaction time varies depending on the solvent used and / or the reaction scale, but is preferably 0.5 to 100 hours.

[0100] C. Regarding the (3E,5Z,9Z)-16,16-dialkoxy-3,5,9-hexadecatriene compound (6) and the (5Z,9Z)-16,16-dialkoxy-5,9-hexadecadiene compound (9), and their production methods

[0101] (C-1). The (3E,5Z,9Z)-16,16-dialkoxy-3,5,9-hexadecatriene compound (6) and its production method will be described below. (3E,5Z,9Z)-16,16-Dialkoxy-3,5,9-hexadecatriene compound (6) can be produced according to the following chemical reaction formula. First, (4Z)-11,11-dialkoxy-4-undecenyltriarylphosphonium = halide compound (3-Z) is deprotonated in the presence of a base to obtain a reaction product mixture. The mixture obtained by the deprotonation reaction is presumed to contain triarylphosphonium = (4Z)-11,11-dialkoxy-4-undecenylide compound (4) as a reaction product (hereinafter, the reaction product will be described as triarylphosphonium = (4Z)-11,11-dialkoxy-4-undecenylide compound (4)). Then, next, the reaction product mixture and (2E)-2-pentenal represented by the following formula (5) are subjected to Wittig reaction conditions, for example, in situ, whereby (3E,5Z,9Z)-16,16-dialkoxy-3,5,9-hexadecatriene compound (6) can be produced.

[0102]

Chemical formula

[0103] First, the reaction product mixture, triarylphosphonium = (4Z)-11,11-dialkoxy-4-undecenylide compound (4), will be described. In the above general formula (4), R 1 and R 2 are as defined in the above general formula (1), and Ar is as defined in the above general formula (3).

[0104] Specific examples of triarylphosphonium = (4Z)-11,11-dialkoxy-4-undecenylide compound (4) include the following compounds: Triphenylphosphonium=(4Z)-11,11-dimethoxy-4-undecenylide, triphenylphosphonium=(4Z)-11,11-diethoxy-4-undecenylide, triphenylphosphonium=(4Z)-11,11-dipropyloxy-4-undecenylide, triphenylphosphonium=(4Z)-11,11-dibutyloxy-4-undecenylide, triphenylphosphonium=(4Z)-11,11-dipentyloxy-4-undecenylide, triphenylphosphonium=(4Z)-11,11-dihexyloxy-4-undecenylide, triphenylphosphonium=(4Z)-11,11-diheptyloxy-4-undecenylide, triphenylphosphonium=(4Z)-11,11-dioctyloxy-4-undecenylide, triphenylphosphonium=(4Z)-11,11-dinonyloxy-4-undecenylide and triphenylphosphonium=(4Z)-11,11-didecyloxy-4-undecenylide and other triphenylphosphonium=(4Z)-11,11-dialkoxy-4-undecenylide compounds (4: Ar = phenyl group); Tritolylphosphonium=(4Z)-11,11-dimethoxy-4-undecenylide, tritolylphosphonium=(4Z)-11,11-diethoxy-4-undecenylide, tritolylphosphonium=(4Z)-11,11-dipropyloxy-4-undecenylide, tritolylphosphonium=(4Z)-11,11-dibutyloxy-4-undecenylide, tritolylphosphonium=(4Z)-11,11-dipentyloxy-4-undecenylide, tritolylphosphonium=(4Z)-11,11-dihexyloxy-4-undecenylide, tritolylphosphonium=(4Z)-11,11-diheptyloxy-4-undecenylide, tritolylphosphonium=(4Z)-11,11-dioctyloxy-4-undecenylide, tritolylphosphonium=(4Z)-11,11-dinonyloxy-4-undecenylide and tritolylphosphonium=(4Z)-11,11-didecyloxy-4-undecenylide and other tritolylphosphonium=(4Z)-11,11-dialkoxy-4-undecenylide compounds (4: Ar = tolyl group). As the triarylphosphonium=(4Z)-11,11-dialkoxy-4-undecenylide compound (4), from the viewpoint of ease of preparation, triphenylphosphonium=(4Z)-11,11-dialkoxy-4-undecenylide compound (4: Ar = phenyl group) is preferred.

[0105] <Regarding the deprotonation reaction> For the above reaction product mixture, a base may be added to the reaction system after preparing the (4Z)-11,11-dialkoxy-4-undecenyltriarylphosphonium=halide compound (3-Z) to directly lead to the triarylphosphonium=(4Z)-11,11-dialkoxy-4-undecenylide compound (4), or the (4Z)-11,11-dialkoxy-4-undecenyltriarylphosphonium=halide compound (3-Z) may be purified and then reacted with a base to lead to the triarylphosphonium=(4Z)-11,11-dialkoxy-4-undecenylide compound (4). Examples of the base used for preparing the above reaction product mixture include alkyllithiums such as n-butyllithium and tert-butyllithium; organometallic reagents such as methylmagnesium=chloride, methylmagnesium=bromide, sodium=acetylide and potassium=acetylide; metal alkoxides such as potassium=tert-butoxide, sodium=tert-butoxide, potassium=methoxide, sodium=methoxide and potassium=ethoxide, sodium=ethoxide; and metal amides such as lithium=diisopropylamide, sodium=bis(trimethylsilyl)amide, etc. From the viewpoint of reactivity, metal alkoxides are preferred, and potassium=tert-butoxide, sodium=methoxide and sodium=ethoxide are more preferred. From the viewpoint of reactivity, the amount of the base used is preferably 0.7 to 5.0 mol per 1 mol of the (7Z)-11-halo-1,1-dialkoxy-7-undecene compound (1-Z) or the (4Z)-11,11-dialkoxy-4-undecenyltriarylphosphonium=halide compound (3-Z).

[0106] (4Z)-11,11-Dialkoxy-4-undecenyltriarylphosphonium halide compound (3-Z) and triarylphosphonium=(4Z)-11,11-dialkoxy-4-undecenylide compound (4) may be prepared using a solvent as required. Examples of the solvent include ether solvents such as tetrahydrofuran, 2-methyltetrahydrofuran, diethyl ether, dibutyl ether, 4-methyltetrahydropyran, cyclopentylmethyl ether, and 1,4-dioxane; hydrocarbon solvents such as hexane, heptane, benzene, toluene, xylene, and cumene; and N , N N,N-dimethylformamide, N , N N,N-dimethylacetamide, N-methylpyrrolidone, dimethyl sulfoxide, γ-butyrolactone, acetonitrile, dichloromethane, chloroform, and other polar solvents. From the perspective of reactivity, ether solvents such as tetrahydrofuran, 2-methyltetrahydrofuran, and 4-methyltetrahydropyran and N , N N,N-dimethylformamide and N , N N,N-dimethylacetamide and other polar solvents are preferred. One type of the solvent or two or more types may be used as required. Also, commercially available solvents can be used. From the perspective of reactivity, the amount of the solvent used is preferably 50 to 7000 g per 1 mol of the (7Z)-11-halo-1,1-dialkoxy-7-undecene compound (1-Z) or the (4Z)-11,11-dialkoxy-4-undecenyltriarylphosphonium halide compound (3-Z).

[0107] The reaction temperature in the preparation of the above reaction product mixture varies depending on the solvent and / or base used, but is preferably -78 to 70 °C. For example, when a metal alkoxide is used as the base, the optimum temperature is -78 to 25 °C. The reaction time in the preparation of the above reaction product mixture varies depending on the solvent used and / or the reaction scale, but is preferably 0.5 to 100 hours.

[0108] Next, the (3E,5Z,9Z)-16,16-dialkoxy-3,5,9-hexadecatriene compound (6) will be described below.

[0109]

Chemical formula

[0110] R in the above general formula (6) 1 and R 2 are as defined in the above general formula (1).

[0111] Specific examples of the (3E,5Z,9Z)-16,16-dialkoxy-3,5,9-hexadecatriene compound (6) include the following compounds: (3E,5Z,9Z)-16,16-dimethoxy-3,5,9-hexadecatriene, (3E,5Z,9Z)-16,16-diethoxy-3,5,9-hexadecatriene, (3E,5Z,9Z)-16,16-dipropyloxy-3,5,9-hexadecatriene, (3E,5Z,9Z)-16,16-dibutyloxy-3,5,9-hexadecatriene, (3E,5Z,9Z)-16,16-dipentyloxy-3,5,9-hexadecatriene, (3E,5Z,9Z)-16,16-dihexyloxy-3,5,9-hexadecatriene, (3E,5Z,9Z)-16,16-diheptyloxy-3,5,9-hexadecatriene, (3E,5Z,9Z)-16,16-dioctyloxy-3,5,9-hexadecatriene, (3E,5Z,9Z)-16,16-dinonyloxy-3,5,9-hexadecatriene, and (3E,5Z,9Z)-16,16-didecyloxy-3,5,9-hexadecatriene. (3E,5Z,9Z)-16,16-Dialkoxy-3,5,9-hexadecatriene compound (6), from the viewpoint of economy, (3E,5Z,9Z)-16,16-dimethoxy-3,5,9-hexadecatriene and (3E,5Z,9Z)-16,16-diethoxy-3,5,9-hexadecatriene are preferred.

[0112] <Regarding the Wittig reaction> The usage amount of triarylphosphonium=(4Z)-11,11-dialkoxy-4-undecenylide compound (4) is preferably 1.0 to 4.0 mol, more preferably 1.0 to 2.0 mol, per 1 mol of (2E)-2-pentenal (5) from the viewpoint of reactivity. Also, triarylphosphonium=(4Z)-11,11-dialkoxy-4-undecenylide compound (4) may be used alone or, if necessary, two or more kinds may be used. (2E)-2-Pentenal (5) may be commercially available or, for example, may be synthesized independently by oxidation of (2E)-2-penten-1-ol or hydrolysis reaction of (2E)-1,1-dialkoxy-2-pentene.

[0113] For the Wittig reaction, a solvent may be used if necessary. Examples of the solvent include ether solvents such as tetrahydrofuran, 2-methyltetrahydrofuran, diethyl ether, dibutyl ether, 4-methyltetrahydropyran, cyclopentyl methyl ether, and 1,4-dioxane; hydrocarbon solvents such as hexane, heptane, benzene, toluene, xylene, and cumene; and polar solvents such as N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone, dimethyl sulfoxide, γ-butyrolactone, acetonitrile, dichloromethane, and chloroform. From the viewpoint of reactivity, ether solvents such as tetrahydrofuran, 2-methyltetrahydrofuran, and 4-methyltetrahydropyran; and polar solvents such as acetonitrile, N,N-dimethylformamide, and N,N-dimethylacetamide are preferred. The solvent may be one type or, if necessary, two or more types may be used. Also, commercially available solvents can be used. From the perspective of reactivity, the amount of the solvent used is preferably 50 to 7000 g per 1 mol of (2E)-2-pentenal (5).

[0114] In the Wittig reaction, the optimal temperature varies depending on the solvent used, but it is preferably -78 to 80°C. To perform the Wittig reaction in a Z-selective manner, it is more preferable to carry out the reaction at -78 to 30°C. After performing the Wittig reaction at -78 to -40°C, the reaction can also be carried out selectively in the E-form by reacting the resulting synthetic intermediate under conditions such as the Schlosser modification method by treatment with a strong base such as phenyllithium. Also, the reaction can be carried out selectively in the E-form by adding lithium halide under normal Wittig reaction conditions. In the Wittig reaction, the reaction time varies depending on the reaction scale, but it is preferably 0.5 to 100 hours.

[0115] (C-2). The (5Z,9Z)-16,16-dialkoxy-5,9-hexadecadiene compound (9) and its production method will be described below. (5Z,9Z)-16,16-Dialkoxy-5,9-hexadecadiene compound (9) can be produced according to the following chemical reaction formula. First, (4Z)-11,11-dialkoxy-4-undecenyltriarylphosphonium halide compound (3-Z) is deprotonated in the presence of a base to obtain a reaction product mixture. The mixture obtained by the deprotonation reaction is presumed to contain triarylphosphonium=(4Z)-11,11-dialkoxy-4-undecenylide compound (4) as a reaction product (hereinafter, the reaction product will be described as triarylphosphonium=(4Z)-11,11-dialkoxy-4-undecenylide compound (4)). Then, next, the reaction product mixture and pentanal represented by the following formula (8) are subjected to a Wittig reaction, for example, in situ, to produce (5Z,9Z)-16,16-dialkoxy-5,9-hexadecadiene compound (9).

[0116] [Chemical formula]

[0117] (4Z)-11,11-Dialkoxy-4-undecenyltriarylphosphonium halide compound (3-Z) and an example of its production method are as described in the above items (A-2) and (B). Triarylphosphonium=(4Z)-11,11-dialkoxy-4-undecenylide compound (4) contained in the reaction product mixture and its production method are as described in the above item (C-1).

[0118] Next, (5Z,9Z)-16,16-dialkoxy-5,9-hexadecadiene compound (9) will be described below.

[0119] [Chemical formula]

[0120] R in the general formula (9) above 1 and R 2 are as defined in the general formula (1).

[0121] Specific examples of the (5Z,9Z)-16,16-dialkoxy-5,9-hexadecadiene compound (9) include the following compounds: (5Z,9Z)-16,16-dimethoxy-5,9-hexadecadiene, (5Z,9Z)-16,16-diethoxy-5,9-hexadecadiene, (5Z,9Z)-16,16-dipropyloxy-5,9-hexadecadiene, (5Z,9Z)-16,16-dibutyloxy-5,9-hexadecadiene, (5Z,9Z)-16,16-dipentyloxy-5,9-hexadecadiene, (5Z,9Z)-16,16-dihexyloxy-5,9-hexadecadiene, (5Z,9Z)-16,16-diheptyloxy-5,9-hexadecadiene, (5Z,9Z)-16,16-dioctyloxy-5,9-hexadecadiene, (5Z,9Z)-16,16-dinonyloxy-5,9-hexadecadiene, (5Z,9Z)-16,16-didecyloxy-5,9-hexadecadiene. From the perspective of economy, (5Z,9Z)-16,16-dimethoxy-5,9-hexadecadiene and (5Z,9Z)-16,16-diethoxy-5,9-hexadecadiene are preferred as the (5Z,9Z)-16,16-dialkoxy-5,9-hexadecadiene compound (9).

[0122] <Regarding the Wittig reaction> From the perspective of reactivity, the amount of use of the triarylphosphonium=(4Z)-11,11-dialkoxy-4-undecenylide compound (4) is preferably 1.0 to 4.0 mol, more preferably 1.0 to 2.0 mol, per 1 mol of pentanal (8). Also, the triarylphosphonium=(4Z)-11,11-dialkoxy-4-undecenylide compound (4) may be used alone or, if necessary, two or more kinds may be used. Pentanal (8) may be commercially available. When a solvent is used in the Wittig reaction, the amount of the solvent used is preferably 50 to 7000 g per 1 mol of pentanal (8) from the viewpoint of reactivity. Other conditions of the Wittig reaction are as described in the above item (C-1).

[0123] (C-3) A method for producing a mixture containing a (3E,5Z,9Z)-16,16-dialkoxy-3,5,9-hexadecatriene compound (6) and a (5Z,9Z)-16,16-dialkoxy-5,9-hexadecadiene compound (9) will be described below. The (5Z,9Z)-16,16-dialkoxy-5,9-hexadecadiene compound (9) can be produced according to the following chemical reaction formula. First, a (4Z)-11,11-dialkoxy-4-undecenyltriarylphosphonium halide compound (3-Z) is deprotonated in the presence of a base to obtain a reaction product mixture. The mixture obtained by the deprotonation reaction is presumed to contain a triarylphosphonium-(4Z)-11,11-dialkoxy-4-undecenylide compound (4) as a reaction product (hereinafter, the reaction product will be described as the triarylphosphonium-(4Z)-11,11-dialkoxy-4-undecenylide compound (4)). Then, next, the reaction product mixture, (2E)-2-pentanal (5), and pentanal (8) are subjected to Wittig reaction conditions, for example, in situ, to produce a mixture containing a (3E,5Z,9Z)-16,16-dialkoxy-3,5,9-hexadecatriene compound (6) and a (5Z,9Z)-16,16-dialkoxy-5,9-hexadecadiene compound (9), respectively.

[0124] [Chemical formula]

[0125] The triarylphosphonium=(4Z)-11,11-dialkoxy-4-undecenylide compound (4) contained in the reaction product mixture and its production method are as described in the above item (C-1). The (3E,5Z,9Z)-16,16-dialkoxy-3,5,9-hexadecatriene compound (6) produced from the reaction product mixture and (2E)-2-pentenal (5), and the (5Z,9Z)-16,16-dialkoxy-5,9-hexadiene compound (9) produced from the reaction product mixture and pentanal (8) are also as described in the above items (C-1) and (C-2), respectively.

[0126] In the production of a mixture containing the (3E,5Z,9Z)-16,16-dialkoxy-3,5,9-hexadecatriene compound (6) and the (5Z,9Z)-16,16-dialkoxy-5,9-hexadiene compound (9), the ratio of the (3E,5Z,9Z)-16,16-dialkoxy-3,5,9-hexadecatriene compound (6) to the (5Z,9Z)-16,16-dialkoxy-5,9-hexadiene compound (9) can be adjusted by arbitrarily adjusting the ratio of (2E)-2-pentenal (5) to pentanal (8).

[0127] (2E)-2-Pentenal (5) and pentanal (8) may be used as a mixture, or (2E)-2-pentenal (5) and pentanal (8) may be added sequentially.

[0128] D. (7Z,11Z,13E)-7,11,13-Hexadecatrienal (7) and (7Z,11Z)-7,11-hexadienal (10), and their production methods

[0129] (D-1). The (7Z,11Z,13E)-7,11,13-hexadecatrienal (7) and its production method will be described below. (7Z,11Z,13E)-7,11,13-Hexadecatrienal, which is the sex pheromone substance of the citrus leafminer, can be produced by the hydrolysis reaction of the above-mentioned (3E,5Z,9Z)-16,16-dialkoxy-3,5,9-hexadecatriene compound (6) as shown in the following chemical reaction formula.

[0130] [Chemical formula]

[0131] (3E,5Z,9Z)-16,16-Dialkoxy-3,5,9-hexadecatriene compound (6) and its production method are as described in the above item (C-1).

[0132] [Regarding the hydrolysis reaction] In the above hydrolysis reaction, the (3E,5Z,9Z)-16,16-dialkoxy-3,5,9-hexadecatriene compound (6) may be used alone or, if necessary, two or more kinds may be used.

[0133] The hydrolysis reaction can be carried out, for example, using an acid and water. Examples of the above-mentioned acid include inorganic acids such as hydrochloric acid and hydrobromic acid, p-toluenesulfonic acid, benzenesulfonic acid, trifluoroacetic acid, acetic acid, formic acid, oxalic acid, iodotrimethylsilane, and titanium tetrachloride. From the perspective of reactivity, acetic acid, formic acid, and oxalic acid are preferred. The acid may be used alone or, if necessary, two or more kinds may be used. Also, commercially available acids can be used. The amount of the acid used is preferably 0.01 to 10.0 mol per 1 mol of the (3E,5Z,9Z)-16,16-dialkoxy-3,5,9-hexadecatriene compound (6). The amount of the above-mentioned water used is preferably 18 to 7000 g, more preferably 18 to 3000 g per 1 mol of the (3E,5Z,9Z)-16,16-dialkoxy-3,5,9-hexadecatriene compound (6) from the perspective of reactivity.

[0134] For this hydrolysis reaction, a solvent may be further used as necessary together with the aforementioned acid or water. Examples of the solvent include hydrocarbon solvents such as toluene, xylene, hexane, heptane, benzene, and cumene; ether solvents such as tetrahydrofuran, 2-methyltetrahydrofuran, diethyl ether, dibutyl ether, 4-methyltetrahydropyran, cyclopentyl methyl ether, and 1,4-dioxane; polar solvents such as N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone, dimethyl sulfoxide, acetonitrile, acetone, γ-butyrolactone, dichloromethane, and chloroform; and alcohol solvents such as methanol and ethanol. The solvent may be used singly or, if necessary, in combination of two or more. Also, commercially available solvents can be used. Although the optimal solvent varies depending on the acid used, for example, when oxalic acid is used as the acid, from the viewpoint of reactivity, tetrahydrofuran, 2-methyltetrahydrofuran, acetone, and γ-butyrolactone are preferred. From the viewpoint of reactivity, the amount of the solvent used is preferably 0 to 7000 g, more preferably 18 to 3000 g, per 1 mol of the total of the (3E,5Z,9Z)-16,16-dialkoxy-3,5,9-hexadecatriene compound (6) or the (5Z,9Z)-16,16-dialkoxy-5,9-hexadecadiene compound (9) or the mixture of the (3E,5Z,9Z)-16,16-dialkoxy-3,5,9-hexadecatriene compound (6) and the (5Z,9Z)-16,16-dialkoxy-5,9-hexadecadiene compound (9) (see the mixture (12) described in Example 12).

[0135] The reaction temperature in the hydrolysis reaction varies depending on the acid and / or solvent used, but from the viewpoint of reactivity, it is preferably 5 to 180°C. The reaction time in the hydrolysis reaction varies depending on the acid and / or solvent and / or reaction scale used, but from the perspective of reactivity, it is preferably 0.5 to 100 hours.

[0136] (D-2). (7Z,11Z)-7,11-Hexadecadienal (10) and its production method will be described below. (7Z,11Z)-7,11-Hexadecadienal (10), which is a sex pheromone substance of Citrus leafminer, can be produced by the hydrolysis reaction of the above-mentioned (5Z,9Z)-16,16-dialkoxy-5,9-hexadecadiene compound (9) as shown in the following chemical reaction formula.

[0137] [Chemical formula]

[0138] (5Z,9Z)-16,16-Dialkoxy-5,9-hexadecadiene compound (9) and its production method are as described in the above item (C-2).

[0139] <Regarding the hydrolysis reaction> In the above hydrolysis reaction, the (5Z,9Z)-16,16-dialkoxy-5,9-hexadecadiene compound (9) may be used alone or, if necessary, two or more kinds may be used.

[0140] This hydrolysis reaction can be carried out, for example, using an acid and water. The above-mentioned acid is as described in the above item (D-1). The amount of the acid used is preferably 0.01 to 10.0 mol per 1 mol of the (5Z,9Z)-16,16-dialkoxy-5,9-hexadecadiene compound (9). The amount of the above-mentioned water used is preferably 18 to 7000 g, more preferably 18 to 3000 g per 1 mol of the (5Z,9Z)-16,16-dialkoxy-5,9-hexadecadiene compound (9) from the perspective of reactivity.

[0141] For this hydrolysis reaction, a solvent may be further used as necessary together with the above-mentioned acid or water. The above-mentioned solvent is as described in item (D-1) above. From the viewpoint of reactivity, the amount of the solvent used is preferably 0 to 7000 g, more preferably 18 to 3000 g, per 1 mol of the (5Z,9Z)-16,16-dialkoxy-5,9-hexadecadiene compound (9).

[0142] Other conditions of this hydrolysis reaction are as described in item (D-1) above.

[0143] (D-3). A method for producing a mixture containing (7Z,11Z,13E)-7,11,13-hexadecatrienal (7) and (7Z,11Z)-7,11-hexadecadienal (10) will be described below. By subjecting a mixture containing a (3E,5Z,9Z)-16,16-dialkoxy-3,5,9-hexadecatriene compound (6) and a (5Z,9Z)-16,16-dialkoxy-5,9-hexadecadiene compound (9) to hydrolysis reaction conditions, a mixture containing (7Z,11Z,13E)-7,11,13-hexadecatrienal (7) and (7Z,11Z)-7,11-hexadecadienal (10) can be produced, respectively.

[0144] [Chemical formula]

[0145] The method for producing a mixture containing a (3E,5Z,9Z)-16,16-dialkoxy-3,5,9-hexadecatriene compound (6) and a (5Z,9Z)-16,16-dialkoxy-5,9-hexadecadiene compound (9) is as described in item (C-3) above.

[0146] In the production of a mixture containing a (3E,5Z,9Z)-16,16-dialkoxy-3,5,9-hexadecatriene compound (6) and a (5Z,9Z)-16,16-dialkoxy-5,9-hexadecadiene compound (9), depending on the ratio of the (3E,5Z,9Z)-16,16-dialkoxy-3,5,9-hexadecatriene compound (6) to the (5Z,9Z)-16,16-dialkoxy-5,9-hexadecadiene compound (9) in the mixture containing the (3E,5Z,9Z)-16,16-dialkoxy-3,5,9-hexadecatriene compound (6) and the (5Z,9Z)-16,16-dialkoxy-5,9-hexadecadiene compound (9), it is possible to prepare the ratio of the (3E,5Z,9Z)-16,16-dialkoxy-3,5,9-hexadecatriene compound (6) to the (5Z,9Z)-16,16-dialkoxy-5,9-hexadecadiene compound (9). Therefore, for example, it is also possible to produce at once a mixture in which the ratio of (7Z,11Z,13E)-7,11,13-hexadecatrienal (7), which is the sex pheromone composition of Citrus leafminer, to (7Z,11Z)-7,11-hexadecadienal (10) is 3:1.

[0147] <Regarding the hydrolysis reaction>

[0148] The hydrolysis reaction can be carried out, for example, using an acid and water. The above-mentioned acid is as described in the above item (D-1). The amount of the acid used is preferably 0.01 to 10.0 mol per 1 mol of the mixture containing the (3E,5Z,9Z)-16,16-dialkoxy-3,5,9-hexadecatriene compound (6) and the (5Z,9Z)-16,16-dialkoxy-5,9-hexadecadiene compound (9). The amount of the above-mentioned water used is preferably 18 to 7000 g, more preferably 18 to 3000 g per 1 mol of the mixture containing the (3E,5Z,9Z)-16,16-dialkoxy-3,5,9-hexadecatriene compound (6) and the (5Z,9Z)-16,16-dialkoxy-5,9-hexadecadiene compound (9) from the viewpoint of reactivity.

[0149] For this hydrolysis reaction, a solvent may be further used as needed together with the above-mentioned acid or water. The above-mentioned solvent is as described in item (D-1) above. The amount of the solvent used is preferably 0 to 7000 g, more preferably 18 to 3000 g, from the viewpoint of reactivity, per 1 mol of the mixture containing the (3E,5Z,9Z)-16,16-dialkoxy-3,5,9-hexadecatriene compound (6) and the (5Z,9Z)-16,16-dialkoxy-5,9-hexadecadiene compound (9).

[0150] Other conditions of this hydrolysis reaction are as described in item (D-1) above.

Examples

[0151] Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not limited to the following examples. In the following, unless otherwise specified, "purity" refers to the area percentage obtained by gas chromatography (GC) analysis, "formation ratio" refers to the relative ratio of the area percentages obtained by GC analysis. Also, "yield" refers to the yield calculated based on the area percentage obtained by GC analysis. In each example, the reaction was monitored and the yield was calculated according to the following GC conditions. GC conditions: GC: Shimadzu Corporation Capillary Gas Chromatograph GC-2014, column: DB-WAX (DB-5), 0.25 μm x 0.25 mm φ x 30 m, carrier gas: He (1.55 mL / min), detector: FID, column temperature: 150 °C rising at 5 °C / min to 230 °C. The yield was calculated according to the following formula considering the purity (%GC) of the raw materials and products. Yield (%) = {[(weight of the product obtained by the reaction × %GC) / molecular weight of the product] ÷[(weight of the starting material in the reaction × %GC) / molecular weight of the starting material]} × 100 Note that THF is tetrahydrofuran, P-2Ni is P-2 type nickel boride, EDA is ethylenediamine, Me is methyl group, Et is ethyl group, t Bu represents tert-butyl group and Ph represents phenyl group.

[0152] Example 1 <(7Z)-11-chloro-1,1-dimethoxy-7-undecyne (17:X 1 =Cl,R 1 =R 2 =Me) Production>

[0153]

Chemical formula

[0154] At room temperature, magnesium (51.64 g, 2.13 gram atoms) and tetrahydrofuran (607.20 g) were added to the reactor and stirred at 60 - 65 °C for 31 minutes. After completion of stirring, 6-chloro-1,1-dimethoxyhexane (14:X 1 =Cl,R 1 =R 2 =Me) (367.17 g, 2.02 mol, purity 99.59%) was added dropwise at 60 - 75 °C. After completion of the dropwise addition, stirring was carried out at 75 - 80 °C for 2 hours to prepare 6,6-dimethoxyhexylmagnesium chloride (15:M = MgCl,R 1 =R 2 =Me). Subsequently, cupric chloride (3.24 g, 0.024 mol), lithium chloride (2.04 g, 0.048 mol), triethyl phosphite (16.11 g, 0.097 mol), tetrahydrofuran (306.53 g) and 1-bromo-5-chloro-1-pentyne (16:X 1 =Cl,X 2 =Br) (340.14 g, 1.86 mol, purity 99.34%) were added to another reactor, and 6,6-dimethoxyhexylmagnesium chloride (15:M = MgCl,R 1 =R 2=Me) was added dropwise at 15 - 30 °C. After the addition was completed, the mixture was stirred at 25 - 35 °C for 1.5 hours. Next, an aqueous acetic acid solution (acetic acid (253.00 g) and water (759.00 g)) was added to the reaction solution, and liquid separation was carried out, and the aqueous layer was removed. The obtained organic layer was washed with an aqueous sodium hydroxide solution (520.00 g, 3.25 mol as sodium hydroxide), and then concentrated under reduced pressure, and the residue was distilled under reduced pressure to obtain (7Z)-11-chloro-1,1-dimethoxy-7-undecyne (17:X 1 =Cl,R 1 =R 2 =Me) (425.97 g, 1.64 mol, purity 95.12%, b.p. = 123.0 - 131.1 °C / 0.40 kPa (3.0 mmHg)) in a yield of 88.18%.

[0155] The spectral data of the (7Z)-11-chloro-1,1-dimethoxy-7-undecyne (17:X 1 =Cl,R 1 =R 2 =Me) obtained above are shown below. 〔Nuclear Magnetic Resonance Spectrum〕 1 H-NMR(500MHz,CDCl 3 ):δ=1.30‐1.42(4H,m),1.47(2H,quin-like,J=7.3Hz),1.59(2H,dt,J=9.2Hz,5.7Hz),1.91(2H,tt,J=6.5Hz,6.5Hz),2.13(2H,tt,J=7.3Hz,2.3Hz),2.32(2H,tt,J=6.9Hz,2.3Hz),3.30(6H,s),3.63(2H,t,J=6.5Hz),4.34(1H,t,J=6.1Hz); 13 C-NMR(500MHz,CDCl 3 ):δ=16.16,18.58,24.10,28.62,28.88,31.74,32.37,43.75,52.60,78.10,81.19,104.45 〔Mass Spectrum〕EI-Mass Spectrum (70eV): m / z 245(M + -1),215,185,137,119,105,91,75 〔Infrared Absorption Spectrum〕(D-ATR): νmax = 2938, 2860, 1457, 1437, 1386, 1291, 1192, 1127, 1076, 1053, 969, 910, 652

[0156] Example 2 <(7Z)-11-chloro-1,1-diethoxy-7-undecene (17:X 1 = Cl, R 1 = R 2 = Et) Production

[0157]

Chemical Structure

[0158] At room temperature, magnesium (89.30 g, 3.67 gram atoms) and tetrahydrofuran (1050.00 g) were added to the reactor and stirred at 60 - 65 °C for 17 minutes. After the stirring was completed, 6-chloro-1,1-diethoxyhexane (14:X 1 = Cl, R 1 = R 2 = Et) (744.93 g, 3.50 mol, purity 98.08%) was added dropwise at 60 - 75 °C. After the dropwise addition was completed, the mixture was stirred at 75 - 80 °C for 2 hours to prepare 6,6-diethoxyhexylmagnesium chloride (15:M = MgCl, R 1 = R 2 = Et). Subsequently, cupric chloride (5.60 g, 0.042 mol), lithium chloride (3.54 g, 0.084 mol), triethyl phosphite (27.86 g, 0.17 mol), tetrahydrofuran (530.08 g), and 1-bromo-5-chloropent-1-yne (16:X 1 = Cl, X 2 = Br) (584.30 g, 3.22 mol, purity 100%) were added to another reactor, and the 6,6-diethoxyhexylmagnesium chloride (15:M = MgCl, R 1 = R 2=Et) was added dropwise at 15 - 30 °C. After the addition was completed, the mixture was stirred at 25 - 35 °C for 1.5 hours. Next, an aqueous acetic acid solution (acetic acid (437.50 g) and water (1312.50 g)) was added to the reaction solution, followed by liquid separation, and the aqueous layer was removed. The obtained organic layer was washed with an aqueous sodium hydroxide solution (900.00 g, 5.63 mol as sodium hydroxide), and then concentrated under reduced pressure. The residue was subjected to vacuum distillation to obtain (7Z)-11-chloro-1,1-diethoxy-7-undecyne (17:X 1 =Cl,R 1 =R 2 =Et) (798.79 g, 2.71 mol, purity 93.24%, b.p. = 148.1 - 154.2 °C / 0.40 kPa (3.0 mmHg)) in a yield of 84.25%.

[0159] The spectral data of the (7Z)-11-chloro-1,1-diethoxy-7-undecyne (17:X 1 =Cl,R 1 =R 2 =Et) obtained above are shown below. 〔Nuclear Magnetic Resonance Spectrum〕 1 H-NMR(500MHz,CDCl 3 ): δ = 1.19(6H,t,J = 7.3Hz), 1.29 - 1.42(2H,m), 1.47(2H,quin-like,J = 7.3Hz), 1.60(2H,dt,J = 9.2Hz,5.8Hz), 1.91(2H,tt,J = 6.5Hz), 2.13(2H,tt,J = 6.5Hz), 2.13(2H,tt,J = 7.3Hz,2.3Hz), 2.32(2H,tt,J = 6.9Hz,2.3Hz), 3.47(2H,tt,J = 8.2Hz,6.9Hz), 3.59 - 3.66(4H,m), 4.46(1H,t,J = 5.8Hz); 13 C-NMR(500MHz,CDCl 3 ): δ = 15.32, 16.16, 18.58, 24.25, 28.64, 28.90, 31.72, 33.47, 43.76, 60.84, 78.05, 81.23, 102.82 〔Mass Spectrum〕EI - Mass Spectrum (70eV): m / z 273(M +-1), 229, 183, 165, 151, 137, 123, 103, 57 〔Infrared Absorption Spectrum〕(D-ATR): νmax = 2974, 2932, 2862, 1442, 1374, 1345, 1291, 1128, 1061, 1001, 653

[0160] Example 3 <11-Chloro-1,1-dimethoxy-7-undecene (1-Z:X 1 = Cl, R 1 = R 2 = Me) Production>

[0161]

Chemical Formula

[0162] At room temperature, (7Z)-11-chloro-1,1-methoxy-7-undecene (17:X 1 = Cl, R 1 = R 2 = Me) (788.66 g, 3.04 mol, purity 95.12%), P-2Ni catalyst (381.12 g, 0.096 mol as Ni), and EDA (8.32 g) were added to the reactor, and hydrogen was added while stirring at 45 - 55 °C for 11.5 hours. The reaction rate was confirmed to be 100% by GC. Then, water (132.98 g) was added to the reaction solution for liquid separation, and the aqueous layer was removed to obtain an organic layer. The obtained organic layer was concentrated under reduced pressure, and the residue was subjected to vacuum distillation to obtain 11-chloro-1,1-dimethoxy-7-undecene (1-Z:X 1 = Cl, R 1 = R 2 = Me) (785.92 g, 2.88 mol, purity 91.17%, b.p. = 123.1 - 142.1 °C / 0.40 kPa (3.0 mmHg)) in a yield of 94.74%.

[0163] The spectral data of 11-chloro-1,1-dimethoxy-7-undecene (1-Z:X 1 = Cl, R 1 = R 2 = Me) obtained above are shown below. 〔Nuclear Magnetic Resonance Spectrum〕 1 H-NMR(500MHz,CDCl 3 ):δ = 1.24 - 1.39(6H,m), 1.55 - 1.61(2H,m), 1.81(2H,dt,J = 6.9Hz, 6.9Hz), 2.04(2H,q-like,J = 6.9Hz), 2.18(2H,dt,J = 7.3Hz, 7.3Hz), 3.30(6H,s), 3.52(2H,t,J = 6.5Hz), 4.35(1H,t,J = 5.7Hz), 5.30(1H,dtt,J = 10.7Hz, 7.3Hz, 1.5Hz), 5.42(1H,dtt,J = 10.7Hz, 7.3Hz, 1.5HZ); 13 C-NMR(500MHz,CDCl 3 ):δ = 24.33, 24.44, 27.08, 29.06, 29.54, 32.41, 32.43, 44.46, 52.55, 104.47, 127.63, 131.45 〔Mass Spectrum〕EI - Mass Spectrum(70eV): m / z 247(M + - 1), 217, 184, 158, 134, 121, 97, 75, 55, 41 〔Infrared Absorption Spectrum〕(D - ATR): νmax = 2932, 2857, 1457, 1444, 1127, 1074, 1055, 965, 912, 726, 653

[0164] Example 4 <11 - Chloro - 1,1 - diethoxy - 7 - undecene(1 - Z:X 1 = Cl, R 1 = R 2 = Et) Production>

[0165]

Chemical Structure

[0166] At room temperature, in a reactor, (7Z) - 11 - chloro - 1,1 - ethoxy - 7 - undecyne obtained in Example 2(17:X 1 = Cl, R 1 = R 2=(Et)(798.79 g, 2.71 mol, purity 93.24%) and P-2Ni catalyst (339.53 g, 0.10 mol as Ni) and EDA (7.43 g) were added, and hydrogen was added while stirring at 45 - 55 °C for 10 hours. The reaction rate of 100% was confirmed by GC. Then, water (118.46 g) was added to the reaction solution and separated by liquid separation, and the aqueous layer was removed to obtain an organic layer. The obtained organic layer was concentrated under reduced pressure, and the residue was distilled under reduced pressure to obtain 11-chloro-1,1-diethoxy-7-undecene (1-Z:X 1 =Cl,R 1 =R 2 =Et)(781.02 g, 2.49 mol, purity 88.26%, b.p. = 150.0 - 165.0 °C / 0.40 kPa (3.0 mmHg)) was obtained in a yield of 91.79%. During the distillation, (7Z)-11-chloro-1,1-ethoxy-7-undecyne (17:X 1 =Cl,R 1 =R 2 =Et) was contaminated with 1-ethoxy-11-chloro-1,7-undecadiene in which the ethoxy moiety was eliminated as ethanol as an impurity (0.061 mol, content rate 1.8%).

[0167] The spectral data of the 11-chloro-1,1-diethoxy-7-undecene (1-Z:X 1 =Cl,R 1 =R 2 =Et) obtained above are shown below. 〔Nuclear Magnetic Resonance Spectrum〕 1 H-NMR(500MHz,CDCl 3): δ = 1.19 (6H, t, J = 6.9 Hz), 1.26 - 1.39 (6H, m), 1.56 - 1.64 (2H, m), 1.81 (2H, tt, J = 6.9 Hz, 6.9 Hz), 2.03 (2H, q - like, J = 6.9 Hz), 2.18 (2H, dt, J = 7.1 Hz, 7.1 Hz), 3.48 (2H, dt, J = 9.4 Hz, 7.3 Hz), 3.52 (2H, t, J = 6.9 Hz), 3.62 (2H, dq, J = 9.4 Hz, 7.3 Hz), 4.46 (1H, t, J = 5.7 Hz), 5.29 (1H, dtt, J = 10.7 Hz, 7.3 Hz, 1.5 Hz), 5.41 (1H, dtt, J = 10.7 Hz, 7.3 Hz, 1.5 Hz); 13 C - NMR (500 MHz, CDCl 3 ): δ = 15.32, 24.31, 24.59, 27.10, 29.07, 29.55, 32.42, 33.51, 44.46, 60.78, 102.86, 127.58, 131.49 〔Mass Spectrum〕EI - mass spectrum (70 eV): m / z 275 (M + - 1), 231, 185, 148, 103, 85, 57, 41 〔Infrared Absorption Spectrum〕(D - ATR): νmax = 2975, 2930, 2858, 1444, 1373, 1344, 1128, 1062, 1001, 727, 653

[0168] Example 5 <(3E,5Z,9Z) - 16,16 - dimethoxy - 3,5,9 - hexadecatriene (6:R 1 = R 2 = Me) Preparation>

[0169]

Chem.

[0170] At room temperature, in a reactor, 11 - chloro - 1,1 - dimethoxy - 7 - undecene (1 - Z:X 1 = Cl, R 1 = R 2=Me)(261.97 g, 0.96 mol, purity 91.17%), triphenylphosphine (2:Ar = Ph)(252.40 g, 0.96 mol), sodium iodide (155.89 g, 1.04 mol), potassium carbonate (7.74 g, 0.056 mol) and acetonitrile (360.00 g) were added, and the mixture was stirred at 75 - 85 °C for 16 hours to prepare (4Z)-11,11-dimethoxy-4-undecenyltriphenylphosphonium = iodide (3:Y = I, Ar = Ph, R 1 =R 2 =Me).

[0171] Next, tetrahydrofuran (640.00 g) was added dropwise to the reactor at 30 - 40 °C. After the addition was complete, the reaction solution was cooled to 0 - -15 °C. Subsequently, potassium = tert-butoxide (103.23 g, 0.92 mol) was added, and then the mixture was stirred for 1 hour to obtain a reaction product mixture. The reaction product mixture is presumed to contain triphenylphosphonium = (4Z)-11,11-dimethoxy-4-undecenylide (4:Ar = Ph, R 1 =R 2 =Me) as the reaction product.

[0172] Thereafter, (2E)-2-pentenal (5)(68.09 g, 0.80 mol, purity 98.84%, 2E:2Z = 98.7:1.3) was added dropwise to the above reactor at -70 - -60 °C. After the addition was complete, the mixture was stirred at 20 - 30 °C for 12 hours. Thereafter, brine (sodium chloride (121.26 g) and water (1212.40 g)) was added to the reaction solution and separated by liquid separation to remove the aqueous layer and obtain an organic layer. Then, the organic layer was concentrated under reduced pressure to obtain a crude product of (3E,5Z,9Z)-16,16-dimethoxy-3,5,9-hexadecatriene (6:R 1 =R 2 =Me) (228.31 g, 0.77 mol, purity 94.02%, 3E5Z9Z:3E5E9Z = 92.2:7.8) with a crude yield of 95.68%.

[0173] (4Z)-11,11-dimethoxy-4-undecenyltriphenylphosphonium iodide (3: Y = I, Ar = Ph, R 1 =R 2 =Me) obtained above is shown below in terms of spectral data. [Nuclear magnetic resonance spectrum] 1 H-NMR (500 MHz, CDCl 3 ): δ = 1.22 - 1.34 (6H, m), 1.45 - 1.54 (2H, m), 1.64 (2H, sext-like, J = 7.6 Hz), 1.99 (2H, dt, J = 6.9 Hz, 6.9 Hz), 2.24 (2H, dt, J = 7.3 Hz, 7.3 Hz), 3.23 (6H, s), 3.20 - 3.28 (2H, m), 4.29 (1H, t, J = 5.7 Hz), 5.31 (1H, dtt, J = 10.7 Hz, 7.3 Hz, 1.5 Hz), 5.45 (1H, dtt, J = 10.7 Hz, 7.3 Hz, 1.2 Hz), 7.68 - 7.75 (12H, m), 7.83 - 7.89 (3H, m); 13 C-NMR (500 MHz, CDCl 3 ): δ = 0.80, 0.76, 1.13, 1.30, 1.47, 1.63, 1.80, 105.42, 118.87, 119.56, 131.12, 131.22, 134.54, 134.62, 136.00, 136.03 [Infrared absorption spectrum] (D-ATR): νmax = 2930, 2856, 1438, 1161, 1113, 1055, 996, 736, 723, 691, 531, 509

[0174] (3E,5Z,9Z)-16,16-dimethoxy-3,5,9-hexadecatriene (6: R 1 =R 2 =Me) obtained above is shown below in terms of spectral data. [Nuclear magnetic resonance spectrum] 1 H-NMR (500 MHz, CDCl 3): δ = 1.01 (3H, t, J = 7.3 Hz), 1.24 - 1.39 (6H, m), 1.55 - 1.61 (2H, m), 2.03 (2H, q - like, J = 6.9 Hz), 2.12 (4H, quin - like, J = 7.3 Hz), 2.21 (2H, dt, J = 7.7 Hz, 7.7 Hz), 3.30 (6H, s), 4.35 (1H, t, J = 5.7 Hz), 5.30 (1H, dt, J = 10.7 Hz, 7.3 Hz), 5.33 - 5.41 (2H, m), 5.70 (1H, dt, J = 14.9 Hz, 6.5 Hz), 5.96 (1H, dd, J = 11.1 Hz, 11.1 Hz), 6.29 (1H, dddt, J = 14.9 Hz, 11.1 Hz, 1.5 Hz, 1.5 Hz); 13 C - NMR (500 MHz, CDCl 3 ): δ = 13.59, 24.47, 25.85, 27.14, 27.32, 27.80, 29.10, 29.59, 32.42, 52.53, 104.47, 124.59, 128.93, 129.02, 129.22, 130.33, 136.38 〔Mass Spectrum〕EI - mass spectrum (70 eV): m / z 280 (M + - 1), 248, 217, 166, 121, 94, 75 〔Infrared Absorption Spectrum〕(D - ATR): νmax = 2932, 2856, 1460, 1385, 1127, 1077, 1056, 982, 947, 737

[0175] Example 6 <(3E,5Z,9Z)-16,16 - Diethoxy - 3,5,9 - hexadecatriene (6:R 1 =R 2 =Et) Production>

[0176]

Chem.

[0177] At room temperature, in a reactor, 11 - chloro - 1,1 - diethoxy - 7 - undecene (1 - Z:X) containing 1 - ethoxy - 11 - chloro - 1,7 - undecadiene (0.034 mol, purity 1.8%) obtained in Example 4 1= Cl, R 1 = R 2 = Et)(436.61 g, 1.39 mol, purity 88.26%) triphenylphosphine (2: Ar = Ph)(374.92 g, 1.46 mol), sodium iodide (232.33 g, 1.55 mol), potassium carbonate (12.00 g, 0.087 mol), and acetonitrile (558.00 g) were added, and the mixture was stirred at 75 - 85 °C for 15.5 hours to prepare (4Z)-11,11 - diethoxy - 4 - undecenyltriphenylphosphonium = iodide (3: Y = I; Ar = PhR 1 = R 2 = Et).

[0178] Next, tetrahydrofuran (992.00 g) was added dropwise to the reactor at 30 - 40 °C. After the addition was complete, the reaction solution was cooled to 5 - -10 °C. Subsequently, potassium = tert - butoxide (153.05 g, 1.36 mol) was added, and then the mixture was stirred for 1 hour to obtain a reaction product mixture. The reaction product mixture is presumed to contain triphenylphosphonium = (4Z)-11,11 - diethoxy - 4 - undecenylide (4: Ar = Ph, R 1 = R 2 = Et) as the reaction product.

[0179] Thereafter, (2E)-2 - pentenal (5)(106.27 g, 1.24 mol, purity 98.15%, 2E:2Z = 98.7:1.3) was added dropwise to the above reactor at -10 - 5 °C. After the addition was complete, the mixture was stirred at 15 - 25 °C for 2 hours. Then, brine (sodium chloride (187.95 g) and water (1879.22 g)) was added to the reaction solution and separated by liquid - liquid extraction to remove the aqueous layer and obtain an organic layer. And the organic layer was concentrated under reduced pressure to obtain (3E,5Z,9Z)-16,16 - dimethoxy - 3,5,9 - hexadecatriene (6: R 1 = R 2The crude product of (375.58 g, 0.91 mol, purity 74.36%, 3E5Z9Z:3E5E9Z = 87.4:12.6) of =Et) was obtained with a crude yield of 73.01%. Incidentally, (7Z,11Z,13E)-1-ethoxy-1,7,11,13-hexadecatetraene derived from 1-ethoxy-11-chloro-1,7-undecadiene as an impurity was mixed in (0.037 mol, purity 2.6%).

[0180] The spectral data of the (4Z)-11,11-diethoxy-4-undecenyltriphenylphosphonium = iodide (3:Y = I, Ar = Ph, R 1 =R 2 =Et) obtained above are shown below. [Nuclear magnetic resonance spectrum] 1 H-NMR(500MHz,CDCl 3 ): δ = 1.11(6H,t,J = 7.3Hz), 1.21 - 1.36(6H,m), 1.48(2H,dt,J = 8.8Hz,5.7Hz), 1.65(2H,sext-like,J = 7.7Hz), 1.99(2H,dt,J = 7.3Hz,7.3Hz), 2.24(2H,dt,J = 7.3Hz,7.3Hz), 3.20 - 3.28(2H,m), 3.42(2H,dq,J = 7.3Hz,9.6Hz), 3.57(2H,dq,J = 6.9Hz,9.6Hz), 4.41(1H,t,J = 5.8Hz), 5.31(1H,dtt,J = 10.7Hz,7.3Hz,1.5Hz), 5.45(1H,dtt,J = 11.1Hz,7.3Hz,1.5Hz), 7.68 - 7.75(12H,m), 7.83 - 7.88(3H,m); 13 C-NMR(500MHz,CDCl 3 ): δ = 0.80, 0.97, 1.14, 1.30, 1.46, 1.63, 1.80, 15.68, 29.73, 34.48, 103.70, 118.87, 119.56, 131.12, 131.22, 134.54, 134.2 [Infrared absorption spectrum](D-ATR): νmax = 2973, 2927, 2858, 1587, 1438, 1373, 1113, 1060, 996, 737, 723, 691, 530, 509

[0181] (3E,5Z,9Z)-16,16-Diethoxy-3,5,9-hexadecatriene (6:R obtained above 1 =R 2 =Et) has the spectral data shown below. [Nuclear magnetic resonance spectrum] 1 H-NMR (500 MHz, CDCl 3 ): δ = 1.01 (3H, t, J = 7.3 Hz), 1.20 (6H, t, J = 7.3 Hz), 1.29 - 1.39 (6H, m), 1.57 - 1.63 (2H, m), 2.02 (2H, q-like, J = 6.5 Hz), 2.12 (4H, tt, J = 7.7 Hz, 7.7 Hz), 2.21 (2H, dt, J = 7.3 Hz, 7.3 Hz), 3.48 (2H, dq, J = 9.4 Hz, 7.3 Hz), 3.63 (2H, dq, J = 9.4 Hz, 7.3HZ), 4.47 (1H, t, J = 5.7 Hz), 5.30 (1H, dt, J = 10.7 Hz, 7.3 Hz), 5.37 (2H, dt, J = 5.8 Hz, 3.5 Hz), 5.70 (1H, dt, J = 14.9 Hz, 6.9 Hz), 5.96 (1H, dd, J = 11.1 Hz, 11.1 Hz), 6.29 (1H, dddt, J = 14.9 Hz, 11.1 Hz, 1.5 Hz, 1.5 Hz); 13 C-NMR (500 MHz, CDCl 3 ): δ = 13.59, 15.33, 24.63, 25.85, 27.15, 27.31, 27.79, 29.10, 29.59, 33.51, 60.76, 102.87, 124.58, 128.91, 128.97, 129.23, 130.37, 136.38 [Mass spectrum] EI - mass spectrum (70 eV): m / z 307 (M + -1), 262, 217, 121, 95, 67, 41 [Infrared absorption spectrum] (D-ATR): νmax = 2973, 2930, 2857, 1457, 1443, 1373, 1344, 1128, 1062, 983, 946, 737

[0182] Example 7 <(5Z,9Z)-16,16-Dimethoxy-5,9-hexadecadiene (9:R 1 =R2 = Manufacture of Me)

[0183]

Chemical formula

[0184] At room temperature, 11-chloro-1,1-dimethoxy-7-undecene (1-Z:X 1 = Cl, R 1 = R 2 = Me) (130.99 g, 0.48 mol, purity 91.17%) obtained in Example 3, triphenylphosphine (2:Ar = Ph) (126.20 g, 0.48 mol), sodium iodide (77.94 g, 0.52 mol), potassium carbonate (3.87 g, 0.028 mol) and acetonitrile (180.00 g) were added, and the mixture was stirred at 75 - 85 °C for 17 hours to prepare (4Z)-11,11-dimethoxy-4-undecenyltriphenylphosphonium = iodide (3:Y = I, Ar = Ph, R 1 = R 2 = Me).

[0185] Next, tetrahydrofuran (320.00 g) was added dropwise to the reactor at 30 - 40 °C. After the addition was completed, the reaction solution was cooled to 0 - -15 °C. Subsequently, potassium tert-butoxide (51.62 g, 0.46 mol) was added, and then the mixture was stirred for 1 hour to obtain a reaction product mixture. The reaction product mixture is presumed to contain triphenylphosphonium = (4Z)-11,11-dimethoxy-4-undecenylide (4:Ar = Ph, R 1 = R 2 = Me) as a reaction product.

[0186] Subsequently, pentanal (8) (36.27 g, 0.40 mol, purity 95.00%) was added dropwise to the above reactor at -70 to -60 °C. After completion of the dropwise addition, the mixture was stirred at 20 to 30 °C for 12 hours. Thereafter, brine (sodium chloride (60.63 g) and water (606.20 g)) was added to the reaction solution and separated by liquid separation to remove the aqueous layer and obtain an organic layer. Then, the organic layer was concentrated under reduced pressure to obtain a crude product of (5Z,9Z)-16,16-dimethoxy-5,9-hexadecadiene (9:R 1 =R 2 =Me) (117.29 g, 0.38 mol, purity 90.59%, the 5Z9Z isomer and the 5E9Z isomer could not be separated by GC) in a crude yield of 94.04%.

[0187] The spectral data of the (5Z,9Z)-16,16-dimethoxy-5,9-hexadecadiene (9:R 1 =R 2 =Me) obtained above are shown below. [Nuclear Magnetic Resonance Spectrum] 1 H-NMR (500 MHz, CDCl 3 ): δ = 0.89 (3H, t, J = 7.3 Hz), 1.24 - 1.39 (10H, m), 1.55 - 1.62 (2H, m), 1.99 - 2.05 (4H, m), 2.05 - 2.09 (4H, m), 3.30 (6H, s), 4.35 (1H, t, J = 6.1 Hz), 5.32 - 5.42 (4H, m); 13 C-NMR (500 MHz, CDCl 3 ): δ = 13.97, 22.32, 24.48, 26.93, 27.13, 27.36, 27.40, 29.11, 29.61, 31.90, 32.43, 52.53, 104.48, 129.09, 129.28, 130.12, 130.31 [Mass Spectrum] EI - mass spectrum (70 eV): m / z 281 (M + -1), 250, 219, 149, 136, 121, 108, 93, 75, 55, 41 [Infrared Absorption Spectrum] (D-ATR): νmax = 2928, 2857, 1463, 1385, 1128, 1078, 1056, 966, 728

[0188] Example 8 <Production of a mixture (12) of <(3E,5Z,9Z)-16,16-dimethoxy-3,5,9-hexadecatriene (6:R 1 =R 2 =Me) and (5Z,9Z)-16,16-dimethoxy-5,9-hexadecadiene (9:R 1 =R 2 =Me)>

[0189]

Chemical formula

[0190] At room temperature, 11-chloro-1,1-dimethoxy-7-undecene (1-Z:X 1 =Cl, R 1 =R 2 =Me) (44.75 g, 0.16 mol, purity 91.17%) obtained in Example 3, triphenylphosphine (2:Ar = Ph) (43.13 g, 0.16 mol), sodium iodide (26.64 g, 0.18 mol), potassium carbonate (1.32 g, 0.0096 mol) and acetonitrile (61.52 g) were added, and the mixture was stirred at 75 - 85 °C for 15.5 hours to prepare (4Z)-11,11-dimethoxy-4-undecenyltriphenylphosphonium = iodide (3:Y = I, Ar = Ph, R 1 =R 2 =Me).

[0191] Next, tetrahydrofuran (109.36 g) was added dropwise to the reactor at 30 - 40 °C. After completion of the dropwise addition, the reaction solution was cooled to 0 - -15 °C. Subsequently, potassium = t-butoxide (17.64 g, 0.16 mol) was added, and the mixture was stirred for 1 hour to obtain a reaction product mixture. The reaction product mixture is presumed to contain triphenylphosphonium = (4Z)-11,11-dimethoxy-4-undecenylide (4:Ar = Ph, R 1 =R 2 =Me) as a reaction product.

[0192] Subsequently, a mixture (11) of (2E)-2-pentenal (5) (8.72 g, 0.10 mol, purity 98.84%) and pentanal (8) (3.10 g, 0.034 mol, purity 95.00%) was added dropwise to the above reactor at -70 to -60 °C. After completion of the dropwise addition, the mixture was stirred at 20 to 30 °C for 12 hours. Thereafter, brine (sodium chloride (20.72 g) and water (207.17 g)) was added to the reaction solution and separated by liquid separation to remove the aqueous layer, thereby obtaining an organic layer. Then, by concentrating the organic layer under reduced pressure, (3E,5Z,9Z)-16,16-dimethoxy-3,5,9-hexadecatriene (6:R 1 =R 2 =Me) (40.84 g, 0.092 mol, content in the mixture 63.06%, 3E5Z9Z:3E5E9Z = 90.9:9.1) and (5Z,9Z)-16,16-dimethoxy-5,9-hexadecadiene (9:R 1 =R 2 =Me) (40.84 g, 0.30 mol, content in the mixture 20.59%, the 5Z9Z isomer and the 5E9Z isomer could not be separated by GC) of a mixture (12) were obtained in a crude yield of 88.97%.

[0193] The spectral data of (3E,5Z,9Z)-16,16-dimethoxy-3,5,9-hexadecatriene (6:R 1 =R 1 =Me) and (5Z,9Z)-16,16-dimethoxy-5,9-hexadecadiene (9:R 1 =R 1 =Me) obtained above were the same as the spectral data obtained in Example 5 and Example 7, respectively.

[0194] Example 9 <Production of (7Z,11Z,13E)-7,11,13-hexadecatrienal (7)>

[0195]

Chemical formula

[0196] Into the reactor, the crude product of (3E,5Z,9Z)-16,16-dimethoxy-3,5,9-hexadecatriene (6:R 1 =R 2 =Me) obtained in Example 5 above (228.31 g, 0.77 mol, purity 94.02%, 3E5Z9Z:3E5E9Z = 92.2:7.8), oxalic acid dihydrate (289.48 g, 2.30 mol), tetrahydrofuran (765.40 g) and pure water (765.40 g) were added, and the mixture was stirred at 60 - 65 °C for 3.5 hours. Then, the reaction solution was cooled to 50 °C, hexane (225.10 g) was added, and the mixture was stirred for 30 minutes. After completion of stirring, the reaction solution was allowed to stand and separated into layers, and the aqueous layer was removed to obtain an organic layer. Then, the organic layer was concentrated under reduced pressure, and the residue was subjected to vacuum distillation (125.0 - 134.5 °C / 0.40 kPa (3.0 mmHg)) to obtain (7Z,11Z,13E)-7,11,13-hexadecatrienal (7) (159.21 g, 0.64 mol, purity 94.47%, 7Z11Z13E:7Z11E13E = 91.6:8.4) in a yield of 80.21% as the total yield of the two steps of Example 5 and Example 9. The starting material 1-bromo-5-chloro-1-pentyne (16:X 1 =Cl, X 2 =Br) gave (7Z,11Z,13E)-7,11,13-hexadecatrienal (7) in a total yield of 67.01% as the total yield of all four steps of Example 1, 3, 5 and 9.

[0197] The spectral data of the (7Z,11Z,13E)-7,11,13-hexadecatrienal (7) obtained above are shown below. 〔Nuclear Magnetic Resonance Spectrum〕 1 H-NMR(500MHz,CDCl 3): δ = 1.01 (3H, t, J = 7.3 Hz), 1.29 - 1.41 (4H, m), 1.63 (2H, quin - like, J = 7.3 Hz), 2.04 (2H, q - like, J = 6.9 Hz), 2.08 - 2.15 (4H, m), 2.21 (2H, dt, J = 7.3 Hz, 7.3 Hz), 2.41 (2H, dt, J = 1.9 Hz, 7.3 Hz), 5.29 (1H, dt, J = 11.1 Hz, 7.3 Hz), 5.33 - 5.41 (2H, m), 5.70 (1H, dt, J = 14.9 Hz, 6.5 Hz), 5.96 (1H, dd, J = 11.1 Hz, 11.1 Hz), 6.29 (1H, dddt, J = 15.0 Hz, 11.1 Hz, 1.5 Hz, 1.5 Hz), 9.75 (1H, t, J = 1.9 Hz); 13 C - NMR (500 MHz, CDCl 3 ): δ = 13.58, 21.94, 25.84, 26.98, 27.31, 27.75, 28.74, 29.36, 43.83, 124.55, 128.96, 129.14, 129.25, 129.99, 136.41, 202.72 〔Mass Spectrum〕EI - mass spectrum (70 eV): m / z 234 (M + ), 149, 135, 122, 107, 95, 79, 67, 55, 41 〔Infrared Absorption Spectrum〕(D - ATR): νmax = 2962, 2931, 2856, 1727, 1460, 983, 947, 739

[0198] Example 10 <Production of (7Z,11Z,13E) - 7,11,13 - hexadecatrienal (7)>

[0199]

Chem.

[0200] Into the reactor, (3E,5Z,9Z) - 16,16 - diethoxy - 3,5,9 - hexadecatriene (6: R 1 = R 1=(Et)(375.58 g, 0.91 mol, purity 74.36%, 3E5Z9Z:3E5E9Z = 87.4:12.6) (however, (7Z,11Z,13E)-1-ethoxy-1,7,11,13-hexadecatetraene (0.037 mol, purity 2.6%) is included as an impurity), oxalic acid dihydrate (356.53 g, 2.83 mol), tetrahydrofuran (942.67 g) and pure water (942.67 g) were added, and the mixture was stirred at 60 - 65 °C for 2 hours. Then, the reaction solution was cooled to 50 °C, hexane (277.24 g) was added, and the mixture was stirred for 30 minutes. After completion of stirring, the reaction solution was allowed to stand and separated, and the aqueous layer was removed to obtain an organic layer. Then, the organic layer was concentrated under reduced pressure, and the residue was subjected to vacuum distillation (125.0 - 134.5 °C / 0.40 kPa (3.0 mmHg)) to obtain (7Z,11Z,13E)-7,11,13-hexadecatrienal (7) (221.37 g, 0.90 mol, purity 94.79%, 7Z11Z13E:7Z11E13E = 86.6:13.4) in a yield of 72.20% as the total yield of the two steps of Examples 6 and 10. Incidentally, (7Z,11Z,13E)-1-ethoxy-1,7,11,13-hexadecatetraene was also hydrolyzed and converged to (7Z,11Z,13E)-7,11,13-hexadecatrienal (7). Starting material 1-bromo-5-chloro-1-pentyne (16:X 1 =Cl,X 2 =Br) gave (7Z,11Z,13E)-7,11,13-hexadecatrienal (7) in a total yield of 55.83% as the total yield of all four steps of Examples 2, 4, 6 and 10.

[0201] The spectral data of the (7Z,11Z,13E)-7,11,13-hexadecatrienal (7) obtained above was the same as the spectral data obtained in Example 9.

[0202] Example 11 <Production of (7Z,11Z)-7,11-hexadecadienal (10)>

[0203]

Chemical formula

[0204] To the reactor, the crude product of (5Z,9Z)-16,16-dimethoxy-5,9-hexadecadiene (9:R 1 =R 2 =Me) obtained in Example 7 above (117.29 g, 0.38 mol, purity 90.59%, the 5Z9Z isomer and the 5E9Z isomer were not separated by GC), oxalic acid dihydrate (150.19 g, 1.19 mol), tetrahydrofuran (397.10 g) and pure water (397.10 g) were added, and the mixture was stirred at 60-65 °C for 3 hours. Then, the reaction solution was cooled to 50 °C, hexane (116.79 g) was added, and the mixture was stirred for 30 minutes. After completion of stirring, the reaction solution was allowed to stand for liquid separation, and the aqueous layer was removed to obtain an organic layer. Then, the organic layer was concentrated under reduced pressure, and the residue was subjected to vacuum distillation (110.4-130.6 °C / 0.40 kPa (3.0 mmHg)) to obtain (7Z,11Z)-7,11-hexadecadienal (10) (87.73 g, 0.35 mol, purity 93.90%, 7Z11Z:7Z11E = 94.7:5.3) in a total yield of 87.13% for the two steps of Examples 7 and 10. Starting from 1-bromo-5-chloro-1-pentyne (16:X 1 =Cl, X 2 =Br), (7Z,11Z)-7,11-hexadecadienal (10) was obtained in a total yield of 72.79% for all four steps of Examples 1, 3, 7 and 11.

[0205] The spectral data of the (7Z,11Z)-7,11-hexadecadienal (10) obtained above are shown below. 〔Nuclear magnetic resonance spectrum〕 1 H-NMR (500 MHz, CDCl 3 ): δ = 0.89 (3H, t, J = 7.3 Hz), 1.25-1.39 (8H, m), 1.63 (2H, tt, J = 7.3 Hz, 7.3 Hz), 2.02 (4H, quin-like, J = 6.2 Hz), 2.07 (4H, t, J = 2.7 Hz), 2.41 (2H, dt, J = 1.9 Hz, 7.3 Hz), 5.31-5.41 (4H, m), 9.76 (1H, t J = 1.9 Hz); 13 C-NMR (500 MHz, CDCl3 ): δ = 13.96, 21.95, 22.31, 26.92, 26.96, 27.31, 27.39, 28.75, 29.38, 31.88, 43.84, 129.02, 129.51, 129.79, 130.35, 202.74 〔Mass Spectrum〕EI - Mass Spectrum (70 eV): m / z 236 (M + ), 218, 193, 137, 123, 109, 95, 81, 67, 55, 41 〔Infrared Absorption Spectrum〕(D - ATR): νmax = 2928, 2857, 2715, 1728, 1458, 727

[0206] Example 12 <Production of a mixture (13) of (7Z,11Z,13E) - 7,11,13 - hexadecatrienal (7) and (7Z,11Z) - 7,11 - hexadecadienal (10)>

[0207]

Chem.

[0208] Into the reactor, (3E,5Z,9Z) - 16,16 - dimethoxy - 3,5,9 - hexadecatriene (6:R 1 = R 2 = Me) (40.84 g, 0.092 mol, content in the mixture 63.06%, 3E5Z9Z:3E5E9Z = 90.9:9.1) and (5Z,9Z) - 16,16 - dimethoxy - 5,9 - hexadecadiene (9:R 1 = R 2=Me)(40.84 g, 0.30 mol, content rate in the mixture 20.59%, the 5Z9Z isomer and the 5E9Z isomer could not be separated by GC) and the mixture (12), oxalic acid dihydrate (45.99 g, 0.36 mol), tetrahydrofuran (121.60 g) and pure water (121.60 g) were added, and the mixture was stirred at 60 to 65 °C for 3 hours. Then, the reaction solution was cooled to 50 °C, hexane (35.76 g) was added, and the mixture was stirred for 30 minutes. After completion of stirring, the reaction solution was allowed to stand and separated into layers, and the aqueous layer was removed to obtain an organic layer. Then, the organic layer was concentrated under reduced pressure, and the residue was subjected to vacuum distillation (110.4 to 123.0 °C / 0.40 kPa (3.0 mmHg)) to obtain a mixture (13) of (7Z,11Z,13E)-7,11,13-hexadecatrienal (7) (24.42 g, 0.078 mol, content rate in the mixture 75.23%, 7Z11Z13E:7Z11E13E = 90.6:9.4) and (7Z,11Z)-7,11-hexadecadienal (10) (24.42 g, 0.023 mol, content rate in the mixture 21.83%, 7Z11Z:7Z11E = 94.3:5.7) in a total yield of 75.37% as the total yield of the two steps of Examples 8 and 12.

[0209] The spectral data of the (7Z,11Z,13E)-7,11,13-hexadecatrienal (7) and (7Z,11Z)-7,11-hexadecadienal (10) obtained above were the same as the spectral data obtained in Example 9 and Example 11, respectively.

Claims

1. The following general formula (1-Z): 【Chemical 1】 (wherein X １ represents a halogen atom, R １ and R ２ each independently represents a monovalent hydrocarbon group having 1 to 15 carbon atoms, or R １ and R ２ are bonded to each other to form R １ -R ２ represents a divalent hydrocarbon group having 2 to 10 carbon atoms.) A (7Z)-11-halo-1,1-dialkoxy-7-undecene compound represented by the formula, and the following general formula (2): PAR ３ (2) (In the formula, Ar represents an aryl group which may be the same or different from each other.) By a phosphonium salt formation reaction with a phosphine compound represented by the formula, the following general formula (3-Z): 【Chemical 2】 (In the formula, Y represents a halogen atom, and Ar, R １ and R ２ are as defined above.) A step of obtaining a (4Z)-11,11-dialkoxy-4-undecenyltriarylphosphonium = halide compound represented by the formula A process for producing a (4Z)-11,11-dialkoxy-4-undecenyltriarylphosphonium = halide compound (3-Z), which comprises at least the above step.

2. The method for producing a (4Z)-11,11-dialkoxy-4-undecenyltriarylphosphonium = halide compound (3-Z) according to claim 1, and A step of subjecting the (4Z)-11,11-dialkoxy-4-undecenyltriarylphosphonium = halide compound (3-Z) to a deprotonation reaction in the presence of a base to obtain a reaction product mixture, and The reaction product mixture and the following formula (5): 【Chemical Formula 3】 Subjecting (2E)-2-pentenal represented by the formula to Wittig reaction conditions to obtain the following general formula (6): [Chemical Formula 4] (wherein R １ and R ２ are as defined above.) A step of obtaining a (3E,5Z,9Z)-16,16-dialkoxy-3,5,9-hexadecatriene compound represented by the formula A process for producing a (3E,5Z,9Z)-16,16-dialkoxy-3,5,9-hexadecatriene compound (6), which comprises at least the above steps.

3. The method for producing a (3E,5Z,9Z)-16,16-dialkoxy-3,5,9-hexadecatriene compound (6) according to claim 2, and By a hydrolysis reaction of the (3E,5Z,9Z)-16,16-dialkoxy-3,5,9-hexadecatriene compound (6), the following formula (7): [Chemical Formula 5] A step of obtaining a (7Z,11Z,13E)-7,11,13-hexadecatrienal represented by the formula A process for producing a (7Z,11Z,13E)-7,11,13-hexadecatrienal (7), which comprises at least the above step.

4. The method for producing a (4Z)-11,11-dialkoxy-4-undecenyltriarylphosphonium = halide compound (3-Z) according to claim 1, and A step of subjecting the (4Z)-11,11-dialkoxy-4-undecenyltriarylphosphonium = halide compound (3-Z) to a deprotonation reaction in the presence of a base to obtain a reaction product mixture, and The reaction product mixture and pentanal represented by the following formula (8): CH ３ (CH ２ ) ３ CHO (8) are subjected to Wittig reaction conditions to obtain a (5Z,9Z)-16,16-dialkoxy-5,9-hexadecadiene compound represented by the following general formula (9): 【Chemical Formula 6】 (wherein R １ and R ２ are as defined above.) and a step of obtaining a (5Z,9Z)-16,16-dialkoxy-5,9-hexadecadiene compound (9), which comprises at least the above step A method for producing a (5Z,9Z)-16,16-dialkoxy-5,9-hexadecadiene compound (9), which comprises at least the above step

5. The method for producing a (5Z,9Z)-16,16-dialkoxy-5,9-hexadecadiene compound (9) according to claim 4, and by hydrolysis of the (5Z,9Z)-16,16-dialkoxy-5,9-hexadecadiene compound (9), a step of obtaining (7Z,11Z)-7,11-hexadecadienal represented by the following formula (10): 【Chemical 7】 and a step of obtaining a (7Z,11Z)-7,11-hexadecadienal (10), which comprises at least the above step A method for producing a (7Z,11Z)-7,11-hexadecadienal (10), which comprises at least the above step

6. The method for producing a (4Z)-11,11-dialkoxy-4-undecenyltriarylphosphonium = halide compound (3-Z) according to claim 1, and a step of subjecting the (4Z)-11,11-dialkoxy-4-undecenyltriarylphosphonium = halide compound (3-Z) to a deprotonation reaction in the presence of a base to obtain a reaction product mixture, and the reaction product mixture and (2E)-2-pentanal represented by the following formula (5): 【Chemical 8】 and pentanal represented by the following formula (8): CH ３ (CH ２ ) ３ CHO (8) are subjected to Wittig reaction conditions to obtain a mixture containing a (3E,5Z,9Z)-16,16-dialkoxy-3,5,9-hexadecatriene compound represented by the following general formula (6) and a (5Z,9Z)-16,16-dialkoxy-5,9-hexadecadiene compound represented by the following general formula (9), respectively 【Chemical Formula 9】 (wherein, R １ and R ２ are as defined above.) and a step of obtaining a mixture containing a (3E,5Z,9Z)-16,16-dialkoxy-3,5,9-hexadecatriene compound (6) and a (5Z,9Z)-16,16-dialkoxy-5,9-hexadecadiene compound (9), which comprises at least the above step 【Chemical 10】 (wherein, R １ and R ２ are as defined above.) A method for producing a mixture containing a (3E,5Z,9Z)-16,16-dialkoxy-3,5,9-hexadecatriene compound (6) and a (5Z,9Z)-16,16-dialkoxy-5,9-hexadecadiene compound (9), which comprises at least the above step

7. The method for producing a mixture containing a (3E,5Z,9Z)-16,16-dialkoxy-3,5,9-hexadecatriene compound (6) and a (5Z,9Z)-16,16-dialkoxy-5,9-hexadecadiene compound (9) according to claim 6, and ​ Subjecting a mixture containing the (3E,5Z,9Z)-16,16-dialkoxy-3,5,9-hexadecatriene compound (6) and the (5Z,9Z)-16,16-dialkoxy-5,9-hexadecadiene compound (9) to hydrolysis reaction conditions to obtain a mixture containing, respectively, the (7Z,11Z,13E)-7,11,13-hexadecatrienal represented by the following formula (7): 【Chemical 11】 and the (7Z,11Z)-7,11-hexadecadienal represented by the following formula (10): 【Chemical Formula 12】 A step of obtaining a mixture containing (7Z,11Z,13E)-7,11,13-hexadecatrienal and (7Z,11Z)-7,11-hexadecadienal, which step comprises at least A method for producing a mixture containing (7Z,11Z,13E)-7,11,13-hexadecatrienal (7) and (7Z,11Z)-7,11-hexadecadienal (10), which method comprises at least

8. Subjecting the (4Z)-11,11-dialkoxy-4-undecenyltriarylphosphonium = halide compound (3-Z) represented by the following general formula (3-Z): 【Chemical 13】 (wherein Y represents a halogen atom, Ar represents an aryl group which may be the same or different from each other, and R １ and R ２ each independently represents a monovalent hydrocarbon group having 1 to 15 carbon atoms, or R １ and R ２ are bonded to each other to form R １ -R ２ which represents a divalent hydrocarbon group having 2 to 10 carbon atoms) to a deprotonation reaction in the presence of a base to obtain a reaction product mixture, and Subjecting the reaction product mixture and the (2E)-2-pentenal represented by the following formula (5): 【Chemical Formula 14】 to Wittig reaction conditions to obtain the (3E,5Z,9Z)-16,16-dialkoxy-3,5,9-hexadecatriene compound represented by the following general formula (6): 【Chemical Formula 15】 (wherein, R １ and R ２ are as defined above.) A method for producing a (3E,5Z,9Z)-16,16-dialkoxy-3,5,9-hexadecatriene compound (6), which method comprises at least A method for producing a (3E,5Z,9Z)-16,16-dialkoxy-3,5,9-hexadecatriene compound (6), which method comprises at least

9. The method for producing a (3E,5Z,9Z)-16,16-dialkoxy-3,5,9-hexadecatriene compound (6) according to Claim 8, and A step of obtaining the (7Z,11Z,13E)-7,11,13-hexadecatrienal represented by the following formula (7) by hydrolysis reaction of the (3E,5Z,9Z)-16,16-dialkoxy-3,5,9-hexadecatriene compound (6): 【Chemical 16】 A method for producing a (7Z,11Z,13E)-7,11,13-hexadecatrienal (7), which method comprises at least A method for producing a (7Z,11Z,13E)-7,11,13-hexadecatrienal (7), which method comprises at least

10. Subjecting the (4Z)-11,11-dialkoxy-4-undecenyltriarylphosphonium = halide compound (3-Z) represented by the following general formula (3-Z): 【Chemical 17】 (wherein Y represents a halogen atom, Ar represents an aryl group which may be the same or different from each other, and R １ and R ２ each independently represents a monovalent hydrocarbon group having 1 to 15 carbon atoms, or R １ and R ２ are bonded to each other to form R １ -R ２ represents a divalent hydrocarbon group having 2 to 10 carbon atoms) to a deprotonation reaction in the presence of a base to obtain a reaction product mixture, and Subjecting the reaction product mixture and the pentanal represented by the following formula (8): CH ３ (CH ２ ) ３ CHO (8) to Wittig reaction conditions to obtain the following general formula (9): 【Chemical Formula 18】 (wherein, R １ and R ２ are as defined above.) A step of obtaining a (5Z,9Z)-16,16-dialkoxy-5,9-hexadecadiene compound represented by and A method for producing a (5Z,9Z)-16,16-dialkoxy-5,9-hexadecadiene compound (9) comprising at least **Claim 11** The method for producing a (5Z,9Z)-16,16-dialkoxy-5,9-hexadecadiene compound (9) according to claim 10, and By the hydrolysis reaction of the (5Z,9Z)-16,16-dialkoxy-5,9-hexadecadiene compound (9), the following formula (10): 【Chemical Formula 19】 A step of obtaining a (7Z,11Z)-7,11-hexadecadienal represented by and A method for producing a (7Z,11Z)-7,11-hexadecadienal (10) comprising at least **Claim 12** The following general formula (3-Z): 【Chemical 20】 (wherein Y represents a halogen atom, Ar represents an aryl group which may be the same or different from each other, and R １ and R ２ each independently represents a monovalent hydrocarbon group having 1 to 15 carbon atoms, or R １ and R ２ are bonded to each other to form R １ -R ２ which represents a divalent hydrocarbon group having 2 to 10 carbon atoms) A step of subjecting a (4Z)-11,11-dialkoxy-4-undecenyltriarylphosphonium halide compound (3-Z) represented by to a deprotonation reaction in the presence of a base to obtain a reaction product mixture, and The reaction product mixture and the following formula (5): 【Chemical 21】 (2E)-2-pentenal represented by and the following formula (8): CH ３ (CH ２ ) ３ CHO (8) Pentanal represented by are subjected to Wittig reaction conditions to obtain a mixture containing, respectively, the following general formula (6): 【Chemical 22】 (wherein R １ and R ２ are as defined above.) A (3E,5Z,9Z)-16,16-dialkoxy-3,5,9-hexadecatriene compound represented by and the following general formula (9): 【Chemical 23】 (wherein R １ and R ２ are as defined above.) A step of obtaining a mixture containing a (5Z,9Z)-16,16-dialkoxy-5,9-hexadecadiene compound represented by and A method for producing a mixture containing a (3E,5Z,9Z)-16,16-dialkoxy-3,5,9-hexadecatriene compound (6) and a (5Z,9Z)-16,16-dialkoxy-5,9-hexadecadiene compound (9) comprising at least **Claim 13** The method for producing a mixture containing a (3E,5Z,9Z)-16,16-dialkoxy-3,5,9-hexadecatriene compound (6) and a (5Z,9Z)-16,16-dialkoxy-5,9-hexadecadiene compound (9) according to claim 12, and The mixture containing the (3E,5Z,9Z)-16,16-dialkoxy-3,5,9-hexadecatriene compound (6) and the (5Z,9Z)-16,16-dialkoxy-5,9-hexadecadiene compound (9) is subjected to hydrolysis reaction conditions to obtain, respectively, the following formula (7): 【Chemical Formula 24】 The (7Z,11Z,13E)-7,11,13-hexadecatrienal represented by the following formula and the following formula (10): 【Chemical 25】 The step of obtaining a mixture containing the (7Z,11Z)-7,11-hexadecadienal represented by the following formula and A method for producing a mixture containing (7Z,11Z,13E)-7,11,13-hexadecatrienal (7) and (7Z,11Z)-7,11-hexadecadienal (10), which at least includes

14. The following general formula (A): L(CH ２ ) ３ CH=CH(CH ２ ) ５ CH(OR １ )(OR ２ ) (A) (wherein R １ and R ２ are each independently a monovalent hydrocarbon group having 1 to 15 carbon atoms, or R １ and R ２ are bonded to each other to form R １ -R ２ which represents a divalent hydrocarbon group having 2 to 10 carbon atoms, and L represents X １ or Y － Ar ３ P ＋ ; X １ and Y represent halogen atoms, and Ar represents an aryl group which may be the same or different from each other.) A compound represented by the following formula

15. The compound according to claim 14, which is the following general formula (1): X １ (CH ２ ) ３ CH=CH(CH ２ ) ５ CH(OR １ )(OR ２ ) (1) An 11-halo-1,1-dialkoxy-7-undecene compound represented by the following formula

16. The compound according to claim 14, which is the following general formula (3): Y － Ar ３ P ＋ (CH ２ ) ３ CH=CH(CH ２ ) ５ CH(OR １ )(OR ２ ) (3) An 11,11-dialkoxy-4-undecenyltriarylphosphonium halide compound represented by the following formula

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