(4Z,6E)-4,6-undecadienyl trimethyl acetate and method for producing (5Z,7E)-5,7-dodecadienyl compound therefrom

Abstract

To provide (4Z,6E)-4,6-undecadienyl=trimethylacetate, which is a synthetic precursor for industrially preparing (5Z,7E)-5,7-dodecadiene compound.SOLUTION: A production process includes subjecting [4-(trimethylacetyloxy)butyl]triarylphosphonium=halide compound (4) to a deprotonation reaction in the presence of a base, and then subjecting the reaction product to a Wittig reaction with (2E)-2-heptenal (5) to obtain a precursor compound (1).SELECTED DRAWING: None

Description

[Technical field]

[0001] The present invention relates to (4Z,6E)-4,6-undecadienyl trimethyl acetate and Dendrolimus The present invention relates to a method for producing a (5Z,7E)-5,7-dodecadiene compound, which is a sex pheromone substance of Bombyx mori spp. [Background technology]

[0002] Living all over the world Dendrolimus spp. are forest pests mainly on conifers, for example, the Siberian moth (scientific name: Dendrolimus Superans sibiricus ), Pine-tree lappet moth (scientific name: Dendrolimus pini ) and the Shimano pine caterpillar moth (scientific name: Dendrolimus kikuchii) For example, the Siberian moth (scientific name: Dendrolimus Superans sibiricus It has been reported that the larvae of the Pine-tree lappet moth (scientific name: Dendrolimus pini ) is known as a forest pest in Northern Europe, causing serious damage in Scotland. The conventional control method of spraying insecticides over vast forests is undesirable from an environmental perspective, so attempts are being made to grasp the pest occurrence status using sex pheromone lures and spray insecticides only when necessary, as well as biological control methods that minimize the use of insecticides. Among the biological control methods, mating disruption using sex pheromones is one that is expected to be a promising method (Non-Patent Document 1 below).

[0003] Dendrolimus It has been revealed that the sex pheromone substance of spp. is a (5Z,7E)-5,7-dodecadiene compound. For example, D. Superans sibiricus and D. pini It has been reported that the sex pheromone substance of the Simono pine caterpillar moth (scientific name: Dendrolimus kikuchii) It has been reported that the sex pheromone substance of this insect is a mixture of (5Z,7E)-5,7-dodecadienyl acetate, (5Z,7E)-5,7-dodecadien-1-ol and (5Z)-5-dodecenyl acetate (Non-Patent Document 3 listed below).

[0004] As a method for synthesizing (5Z,7E)-5,7-dodecadienal, for example, 2-hexyn-1-ol is subjected to a zipper reaction in the presence of metallic lithium and 1,3-diaminopropane to synthesize 5-hexyn-1-ol, and the hydroxyl group of the obtained 5-hexyn-1-ol is converted to 3,4-dihydro-2-(3,4-dihydro-1,3,5-trimethylsilyl)-2-(2,4-diphenyl-1,5-trimethylsilyl)-2-(1,3-diphenyl-1 ... H -pyran with THP protection to give 2-(5-hexyne-1-yloxy)tetrahydro-2 H -pyran is synthesized. Then, the obtained 2-(5-hexyne-1-yloxy)tetrahydro-2 H -pyran was reacted with trans-1,2-dichloroethylene in the presence of cuprous iodide and bis(triphenylphosphine)palladium(II) dichloride to give 2-[[(7E)-8-chloro-7-octen-5-yn-1-yl]oxy]tetrahydro-2-(2-phenylpropane)-1,2-dichloroethylene. H -pyran is then synthesized. The resulting 2-[[(7E)-8-chloro-7-octen-5-yn-1-yl]oxy]tetrahydro-2 H 2-[(7E)-7-dodecen-5-yn-1-yloxy]tetrahydro-2-pyran was subjected to a coupling reaction with butylmagnesium bromide in the presence of iron(III) acetylacetonate catalyst to give 2-[(7E)-7-dodecen-5-yn-1-yloxy]tetrahydro-2-pyran. H Next, the obtained 2-[(7E)-7-dodecen-5-yn-1-yloxy]tetrahydro-2-pyran is synthesized. H-Pyran was reduced with zinc to give 2-[(5Z,7E)-5,7-dodecadien-1-yloxy]tetrahydro-2 H -pyran is synthesized. The obtained 2-[(5Z,7E)-5,7-dodecadien-1-yloxy]tetrahydro-2 H In the present invention, tetrahydropyran is deprotected in the presence of camphorsulfonic acid as an acid catalyst in methanol to synthesize (5Z,7E)-5,7-dodecadien-1-ol. The hydroxyl group of the obtained (5Z,7E)-5,7-dodecadien-1-ol is then oxidized with pyridinium chlorochromate (PCC) in dichloromethane to produce (5Z,7E)-5,7-dodecadienal in a total of 7 steps with a yield of 43.5% (Patent Document 1 below).

[0005] Another method for synthesizing (5Z,7E)-5,7-dodecadienal is, for example, PCC oxidation of 5-hexyn-1-ol, followed by acetalization of the formyl group with ethyl orthoformate, followed by deprotonation of the alkyne end to obtain (6,6-diethoxy-1-hexyn-1-yl)magnesium bromide. Separately, 1-hexyne is reacted with diisobutylaluminum hydride, and then reacted with iodine to obtain (1E)-1-iodo-1-hexene. Next, in the presence of a tetrakis(triphenylphosphine)palladium(0) catalyst, the above-obtained (6,6-diethoxy-1-hexyn-1-yl)magnesium bromide and (1E)-1-iodo-1-hexene are subjected to a coupling reaction to synthesize (5E)-12,12-diethoxy-5-dodecene-7-yne. The resulting (5E)-12,12-diethoxy-5-dodecen-7-yne is then reduced with zinc to synthesize (5Z,7E)-1,1-diethoxy-5,7-dodecadiene. The resulting (5Z,7E)-1,1-diethoxy-5,7-dodecadiene is then hydrolyzed with 10% by mass sulfuric acid in acetone to produce (5Z,7E)-5,7-dodecadienal in a total of four steps with a yield of 52.3% (Patent Document 2 below). [Prior art documents] [Non-patent literature]

[0006] [Non-Patent Document 1] Ashot Khrimian et al.,J.Agric.Food Chem.,2002,50,6366-6370. [Non-Patent Document 2] BG Kovalev et al.,Chem. Nat. Comp.,1993,29,135-136. [Non-Patent Document 3] Xiang-Bo Kong et al.,J.Chem.Ecol.,2011,37,412-419. [Patent documents]

[0007] [Patent Document 1] China Patent Publication No. 102613177 [Patent Document 2] Polish Patent Invention No. 215367 Summary of the Invention [Problem to be solved by the invention]

[0008] However, the synthesis methods of (5Z,7E)-5,7-dodecadienal in Patent Documents 1 and 2 are undesirable from the viewpoint of green chemistry because they use PCC and dichloromethane, which are highly environmentally toxic. Furthermore, both synthesis methods use an expensive palladium catalyst and zinc reduction, which requires the use of a large amount of solvent, making them uneconomical and unproductive. For example, in Patent Document 1, the reaction is carried out in a 0.1M aqueous methanol solution, and 1m 3 In addition, both production methods use an oxidation reaction using PCC, which often poses the risk of explosion, making it difficult to carry out on an industrial scale.

[0009] The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a novel compound that is a synthetic precursor for industrially producing a (5Z,7E)-5,7-dodecadiene compound, and a method for producing the novel compound. [Means for solving the problem]

[0010] As a result of intensive research conducted by the present inventors to solve the above problems, it was found that (4Z,6E)-4,6-undecadienyl trimethyl acetate is a novel compound and that the (4Z,6E)-4,6-undecadienyl trimethyl acetate is a useful intermediate in the production of a (5Z,7E)-5,7-dodecadienyl compound. Dendrolimus The present inventors have found that the (5Z,7E)-5,7-dodecadiene compound, which is the sex pheromone of Bombyx mori spp., can be industrially produced in a short process, which has led to the completion of the present invention.

[0011] According to a first aspect of the present invention, a compound represented by the following formula (1): [ka] The compound represented by the formula: (4Z,6E)-4,6-undecadienyl trimethyl acetate is provided.

[0012] According to a second aspect of the present invention, a compound represented by the following general formula (2): [ka] (In the formula, X 1 represents a halogen atom.) and a 4-halobutyl trimethyl acetate compound represented by the following general formula (3): PAr3(3) (In the formula, Ar represents an aryl group which may be the same or different.) By a phosphonium salt formation reaction with a phosphine compound represented by the following general formula (4): [ka] (In the formula, Y represents a halogen atom, and Ar is as defined above.) obtaining a [4-(trimethylacetyloxy)butyl]triarylphosphonium halide compound represented by the formula: a step of deprotonating the [4-(trimethylacetyloxy)butyl]triarylphosphonium halide compound (4) in the presence of a base to obtain a reaction product mixture; and reacting the reaction product mixture with a compound represented by the following formula (5): [ka] and (2E)-2-heptenal represented by the following general formula (1): [ka] and obtaining (4Z,6E)-4,6-undecadienyl trimethyl acetate represented by the formula: The present invention provides a method for producing (4Z,6E)-4,6-undecadienyl trimethyl acetate (1), comprising at least

[0013] According to a third aspect of the present invention, there is provided a compound represented by the following general formula (1): [ka] (4Z,6E)-4,6-undecadienyl trimethyl acetate represented by the following formula (6): [ka] obtaining (4Z,6E)-4,6-undecadien-1-ol represented by the formula: The (4Z,6E)-4,6-undecadien-1-ol (6) is halogenated to obtain a compound represented by the following general formula (7): [ka] (In the formula, X2 represents a halogen atom.) and obtaining a (4Z,6E)-1-halo-4,6-undecadiene compound represented by the formula: The present invention provides a method for producing a (4Z,6E)-1-halo-4,6-undecadiene compound (7), comprising at least

[0014] According to a fourth aspect of the present invention, The above-mentioned method for producing the (4Z,6E)-1-halo-4,6-undecadiene compound (7), The (4Z,6E)-1-halo-4,6-undecadiene compound (7) is reacted with a compound represented by the following general formula (15): [ka] (Wherein, M is Li or MgZ 1 represents Z 1 represents a halogen atom or a (4Z,6E)-4,6-undecadienyl group. and converting the (4Z,6E)-4,6-undecadienyl nucleophile represented by the formula: The (4Z,6E)-4,6-undecadienyl nucleophile (15) is reacted with a compound represented by the following general formula (8): [ka] (In the formula, R may be the same or different and represents an alkyl group having 1 to 6 carbon atoms.) By a nucleophilic substitution reaction with an orthoformate compound (8) represented by the following general formula (9): [ka] (In the formula, R may be the same or different and represents an alkyl group having 1 to 6 carbon atoms.) obtaining a (5Z,7E)-1,1-dialkoxy-5,7-dodecadiene compound represented by the formula: The (5Z,7E)-1,1-dialkoxy-5,7-dodecadiene compound (9) is hydrolyzed to give a compound of the following general formula (10): [ka] and obtaining (5Z,7E)-5,7-dodecadienal represented by the formula: The present invention provides a method for producing (5Z,7E)-5,7-dodecadienal (10), comprising at least

[0015] According to a fifth aspect of the present invention, The above-mentioned method for producing the (5Z,7E)-5,7-dodecadienal (10), The (5Z,7E)-5,7-dodecadienal (10) is subjected to a reduction reaction to obtain a compound represented by the following formula (11): [ka] and obtaining (5Z,7E)-5,7-dodecadien-1-ol represented by the formula: The present invention provides a method for producing (5Z,7E)-5,7-dodecadien-1-ol (11), comprising at least

[0016] According to a sixth aspect of the present invention, The above-mentioned method for producing (5Z,7E)-5,7-dodecadien-1-ol (11), The (5Z,7E)-5,7-dodecadien-1-ol (11) is acetylated to give the compound of the following formula (12): [ka] and obtaining (5Z,7E)-5,7-dodecadienyl acetate represented by the formula: The present invention provides a method for producing (5Z,7E)-5,7-dodecadienyl acetate (12), comprising at least Effect of the Invention

[0017] According to the present invention, it is possible to industrially produce a (5Z,7E)-5,7-dodecadiene compound in a short process without using expensive raw materials, and it is also possible to provide a synthetic intermediate useful for producing the (5Z,7E)-5,7-dodecadiene compound. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0018] A. (4Z,6E)-4,6-undecadienyl trimethyl acetate represented by the following formula (1) [ka]

[0019] (4Z,6E)-4,6-Undecadienyl trimethyl acetate (1) can be produced, for example, according to the chemical reaction scheme shown below.

[0020] [ka]

[0021] First, a [4-(trimethylacetyloxy)butyl]triarylphosphonium halide compound (4) 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 4-(trimethylacetyloxy)butylide compound (13) as a reaction product (hereinafter, the reaction product will be described as a triarylphosphonium 4-(trimethylacetyloxy)butylide compound (13)). Next, the reaction product mixture and above (2E)-2-heptenal represented by the formula (5) can be subjected to a Wittig reaction, for example, in situ, to produce (4Z,6E)-4,6-undecadienyl trimethyl acetate (1).

[0022] Next, in the following section B, the [4-(trimethylacetyloxy)butyl]triarylphosphonium halide compound (4), which is a useful intermediate for the production of (4Z,6E)-4,6-undecadienyl trimethyl acetate (1), will be described.

[0023] B. [4-(Trimethylacetyloxy)butyl]triarylphosphonium halide compound (4)

[0024] [ka] (In the formula, Y represents a halogen atom, and Ar represents an aryl group which may be the same or different from each other.)

[0025] Specifically, examples of the halogen atom Y include a chlorine atom, a bromine atom, and an iodine atom, with a bromine atom and an iodine atom being preferred from the viewpoint of reactivity. In the above general formula (4), 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 further 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, the phenyl group is preferred, and it is more preferred that all three aryl groups are phenyl groups.

[0026] Specific examples of the [4-(trimethylacetyloxy)butyl]triarylphosphonium halide compound (4) include the following compounds: [4-(trimethylacetyloxy)butyl]triphenylphosphonium halide compounds such as [4-(trimethylacetyloxy)butyl]triphenylphosphonium chloride, [4-(trimethylacetyloxy)butyl]triphenylphosphonium bromide, and [4-(trimethylacetyloxy)butyl]triphenylphosphonium iodide; [4-(trimethylacetyloxy)butyl]tritolylphosphonium halide compounds such as [4-(trimethylacetyloxy)butyl]tritolylphosphonium chloride, [4-(trimethylacetyloxy)butyl]tritolylphosphonium bromide, and [4-(trimethylacetyloxy)butyl]tritolylphosphonium iodide. As the [4-(trimethylacetyloxy)butyl]triarylphosphonium halide compound (4), from the viewpoint of ease of synthesis, a [4-(trimethylacetyloxy)butyl]triphenylphosphonium halide compound such as [4-(trimethylacetyloxy)butyl]triphenylphosphonium bromide or [4-(trimethylacetyloxy)butyl]triphenylphosphonium iodide is preferred.

[0027] The [4-(trimethylacetyloxy)butyl]triarylphosphonium halide compound (4) can be used as a synthetic intermediate in the preparation of the (4Z,6E)-4,6-undecadienyl trimethylacetate (1) and (5Z,7E)-5,7-dodecadiene compounds, as described below.

[0028] Next, in the following section C., a method for producing the [4-(trimethylacetyloxy)butyl]triarylphosphonium halide compound (4) will be described.

[0029] C. Method for producing [4-(trimethylacetyloxy)butyl]triarylphosphonium halide compound (4) The [4-(trimethylacetyloxy)butyl]triarylphosphonium halide compound (4) can be produced, for example, by a phosphonium salt-forming reaction between the above-mentioned 4-halobutyl trimethylacetate compound (2) and a phosphine compound represented by the following general formula (3), as shown in the following chemical reaction formula.

[0030] [ka]

[0031] X in general formula (2) 1 represents a halogen atom. Specifically, the halogen atom X 1 Examples of the alkyl group include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Examples of the 4-halobutyl trimethyl acetate compound (2) include 4-chlorobutyl trimethyl acetate, 4-bromobutyl trimethyl acetate, and 4-iodobutyl trimethyl acetate. From the viewpoint of ease of preparation, 4-chlorobutyl trimethyl acetate is preferred.

[0032] Ar in the general formula (3) is as defined in the above general formula (4). Examples of the phosphine compound (3) include triarylphosphine compounds such as triphenylphosphine, tritolylphosphine, trinaphthylphosphine and trianthracenylphosphine, and from the viewpoint of reactivity, triphenylphosphine is preferred. The amount of the phosphine compound (3) used is preferably 0.8 to 5.0 mol per 1 mol of the 4-halobutyl trimethyl acetate compound (2) from the viewpoint of reactivity.

[0033] In preparing the [4-(trimethylacetyloxy)butyl]triarylphosphonium halide compound (4), a halide may be used, if 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 viewpoint of reactivity, iodides such as sodium iodide and potassium iodide are preferred. In the case where no halide is used in the above preparation of the [4-(trimethylacetyloxy)butyl]triarylphosphonium halide compound (4), Y in the above general formula (4) is X in the above general formula (2). 1 On the other hand, when an iodide is used as the halide in the preparation, Y in the above general formula (4) is X in the general formula (2) for the 4-halobutyl trimethyl acetate compound (2). 1 is the same halogen atom or iodine atom as in The halide may be used alone or in combination of two or more kinds, if necessary. The halide may be commercially available. 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 4-halobutyl trimethyl acetate compound (2) from the viewpoint of reactivity.

[0034] In the preparation of the [4-(trimethylacetyloxy)butyl]triarylphosphonium halide compound (4), a base may be added, if 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 triethylamine, tripropylamine, triisopropylamine, tributylamine, N , N Examples of the organic solvent include amines such as diethylaniline and pyridine, and from the viewpoint of handling, alkali metal carbonates are preferred. The base may be used alone or in combination with two or more kinds, if necessary. In addition, commercially available bases may be used. The amount of the base used is preferably 0 to 4.0 mol, more preferably 0.001 to 1.0 mol, per 1 mol of the 4-halobutyl trimethyl acetate compound (2), from the viewpoint of reactivity.

[0035] In preparing the [4-(trimethylacetyloxy)butyl]triarylphosphonium halide compound (4), 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 N , N -dimethylformamide, N , NFrom the viewpoint of reactivity, examples of suitable solvents include ether solvents such as tetrahydrofuran, 2-methyltetrahydrofuran, and 4-methyltetrahydropyran, and acetonitrile. N , N -Dimethylformamide and N , N Polar solvents such as dimethylacetamide are preferred. The solvent may be used alone or in combination with two or more solvents as required. In addition, commercially available solvents may be used. From the viewpoint of reactivity, the amount of the solvent used is preferably 50 to 7000 g per 1 mol of the 4-halobutyl trimethyl acetate compound (2).

[0036] The optimum reaction temperature in the preparation of the [4-(trimethylacetyloxy)butyl]triarylphosphonium halide compound (4) varies depending on the solvent used, but is preferably 30 to 180°C, more preferably 50 to 150°C. The reaction time in the preparation of the [4-(trimethylacetyloxy)butyl]triarylphosphonium halide compound (4) varies depending on the solvent used and / or the reaction scale, but is preferably 0.5 to 100 hours.

[0037] Next, the reaction product mixture, triarylphosphonium 4-(trimethylacetyloxy)butylide compound (13), will be described. [ka] In the above general formula (13), Ar is as defined in the above general formula (4).

[0038] Specific examples of the triarylphosphonium 4-(trimethylacetyloxy)butylide compound (13) include triphenylphosphonium 4-(trimethylacetyloxy)butylide and tritolylphosphonium 4-(trimethylacetyloxy)butylide. As the triarylphosphonium 4-(trimethylacetyloxy)butylide compound (13), a triphenylphosphonium 4-(trimethylacetyloxy)butylide compound (13: Ar=phenyl group) is preferred from the viewpoint of economy.

[0039] <Deprotonation reaction> As a method for obtaining the reaction product mixture, a base may be added to the reaction system after preparation of the [4-(trimethylacetyloxy)butyl]triarylphosphonium halide compound (4) to directly convert it into the triarylphosphonium 4-(trimethylacetyloxy)butylide compound (13), or the [4-(trimethylacetyloxy)butyl]triarylphosphonium halide compound (4) may be purified and then reacted with a base to convert it into the triarylphosphonium 4-(trimethylacetyloxy)butylide compound (13). Examples of the base used in preparing the reaction product mixture include alkyl lithiums 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, potassium ethoxide and sodium ethoxide; and metal amides such as lithium diisopropylamide and sodium bis(trimethylsilyl)amide. From the viewpoint of reactivity, metal alkoxides are preferred, and potassium tert-butoxide, sodium methoxide and sodium ethoxide are more preferred. The amount of the base used is preferably 0.7 to 5.0 mol per mol of the 4-halobutyl trimethylacetate compound (2) or the [4-(trimethylacetyloxy)butyl]triarylphosphonium halide compound (4) from the viewpoint of reactivity.

[0040] In preparing the [4-(trimethylacetyloxy)butyl]triarylphosphonium halide compound (4) and the triarylphosphonium 4-(trimethylacetyloxy)butylide compound (13), 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 N , N -dimethylformamide, N , N From the viewpoint of reactivity, examples of suitable solvents include ether solvents such as tetrahydrofuran, 2-methyltetrahydrofuran, and 4-methyltetrahydropyran, and acetonitrile. N , N -Dimethylformamide and N , N Polar solvents such as dimethylacetamide are preferred. The solvent may be used alone or in combination with two or more solvents as required. In addition, commercially available solvents may be used. From the viewpoint of reactivity, the amount of the solvent used is preferably 50 to 7000 g per 1 mol of the 4-halobutyl trimethylacetate compound (2) or the [4-(trimethylacetyloxy)butyl]triarylphosphonium halide compound (4).

[0041] The optimum reaction temperature in preparing the reaction product mixture varies depending on the solvent and / or base used, but is preferably −78 to 70° C. For example, the optimum temperature when a metal alkoxide is used as the base is −78 to 25° C. The reaction time in preparing the reaction product mixture varies depending on the solvent used and / or the reaction scale, but is preferably 0.5 to 100 hours.

[0042] <About the Wittig reaction> The amount of the triarylphosphonium 4-(trimethylacetyloxy)butylide compound (13) used is preferably 0.8 to 4.0 mol, more preferably 1.0 to 2.0 mol, per 1 mol of the (2E)-2-heptenal (5) from the viewpoint of reactivity. The triarylphosphonium 4-(trimethylacetyloxy)butylide compound (13) may be used alone or in combination of two or more, as necessary. (2E)-2-heptenal (5) can be commercially available or can be independently synthesized, for example, by oxidation of (2E)-2-hepten-1-ol or by hydrolysis of (2E)-1,1-dialkoxy-2-heptene.

[0043] In 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 N , N -dimethylformamide, N , NFrom the viewpoint of reactivity, examples of the solvents include ether solvents such as tetrahydrofuran, 2-methyltetrahydrofuran, and 4-methyltetrahydropyran; and acetonitrile, N , N -Dimethylformamide and N , N Polar solvents such as dimethylacetamide are preferred. The solvent may be used alone or in combination with two or more solvents as required. In addition, commercially available solvents may be used. From the viewpoint of reactivity, the amount of the solvent used is preferably 50 to 7000 g per 1 mol of the (2E)-2-heptenal (5).

[0044] The optimum reaction temperature in the Wittig reaction varies depending on the solvent used, but is preferably -78 to 80°C. In order to carry out the Wittig reaction Z-selectively, it is more preferable to carry out the reaction at -78 to 30°C, and taking into consideration economics and / or the environment, -20 to 25°C is the most preferable. After carrying out the Wittig reaction at -78 to -40°C, the resulting synthetic intermediate is reacted under conditions such as the Schlosser modification method, which involves treating with a strong base such as phenyllithium, to carry out the reaction E-selectively. In addition, the reaction can also be carried out E-selectively by adding lithium halide under normal Wittig reaction conditions. The reaction time in the Wittig reaction varies depending on the solvent used and / or the reaction scale, but is preferably 0.5 to 100 hours.

[0045] It is expected that the Wittig reaction can be carried out using ylide in which the hydroxyl group is protected with an acyl-based protecting group such as an acetyl group or a benzoyl group, in addition to the triarylphosphonium 4-(trimethylacetyloxy)butylide compound (13). However, contrary to expectations, when the hydroxyl group is protected with an acyl group other than the trimethylacetyl group, the yield of this Wittig reaction is poor. For example, when a triarylphosphonium 4-(acetyloxy)butylide compound is used as the ylide, the acetyl group is deprotected during the reaction at a certain temperature or higher, resulting in a poor yield. In addition, for example, when a triarylphosphonium 4-(benzoyloxy)butylide compound is used as the ylide, the precursor [4-(benzoyloxy)butyl]triarylphosphonium halide compound solidifies even in the solvent at around 10°C, so that the triarylphosphonium 4-(benzoyloxy)butylide compound cannot be prepared at low temperatures. It is possible to prepare a triarylphosphonium 4-(benzoyloxy)butylide compound by raising the temperature, but the ylide will decompose quickly, resulting in a poor yield in the Wittig reaction. Therefore, it is important to use a triarylphosphonium 4-(trimethylacetyloxy)butylide compound (13) in which the hydroxyl group is protected with trimethylacetyl, which does not crystallize the phosphonium salt in solution and does not deprotect the acyl group even under basic conditions, in order to perform the Wittig reaction in a good yield. The triarylphosphonium 4-(trimethylacetyloxy)butylide compound (13) is derived from the [4-(trimethylacetyloxy)butyl]triarylphosphonium halide compound (4), in other words, it is important to use the [4-(trimethylacetyloxy)butyl]triarylphosphonium halide compound (4) in the above-mentioned deprotonation reaction, which is the previous step.

[0046] D. (4Z,6E)-4,6-undecadien-1-ol represented by the following formula (6) and its production method As shown in the following chemical reaction formula, (4Z,6E)-4,6-undecadien-1-ol (6) can be produced by de-trimethylacetylating the above-mentioned (4Z,6E)-4,6-undecadienyl trimethyl acetate (1).

[0047] [ka]

[0048] The detrimethylacetylation reaction of (4Z,6E)-4,6-undecadienyl trimethyl acetate (1) can be carried out, for example, using a base. EscapeExamples of the base used in the trimethylacetylation reaction include alkyl lithiums such as n-butyllithium and tert-butyllithium; organometallic reagents such as methylmagnesium chloride, methylmagnesium bromide, sodium acetylide and potassium acetylide; organoaluminum compounds such as diisobutylaluminum hydride (DIBAL), sodium bis(2-methoxyethoxy)aluminum hydride (Red-Al) and lithium aluminum hydride (LAH); metal alkoxides such as potassium tert-butoxide, sodium tert-butoxide, potassium methoxide, sodium methoxide, potassium ethoxide and sodium ethoxide; and alkali metal hydrates such as potassium hydroxide and sodium hydroxide. Examples of the metal amides include oxides; alkali metal carbonates such as potassium carbonate and sodium carbonate; alkaline earth metal carbonates such as calcium carbonate and magnesium carbonate; and metal amides such as lithium diisopropylamide and sodium bis(trimethylsilyl)amide. From the viewpoint of reactivity, preferred are metal alkoxides such as potassium tert-butoxide, sodium methoxide, and sodium ethoxide; organometallic reagents such as methylmagnesium chloride, methylmagnesium bromide, sodium acetylide, and potassium acetylide; alkali metal hydroxides such as potassium hydroxide and sodium hydroxide; and alkali metal carbonates such as potassium carbonate and sodium carbonate, with organometallic reagents and alkali metal carbonates being more preferred. The base may be used alone or in combination with two or more kinds, if necessary. In addition, commercially available bases may be used. The amount of the base used is preferably 0.01 to 30.0 mol, more preferably 0.1 to 15.0 mol, per mol of (4Z,6E)-4,6-undecadienyl trimethyl acetate (1) from the viewpoint of completing the reaction.

[0049] In the detrimethylacetylation 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 N , N -dimethylformamide, N , N polar solvents such as dimethylacetamide, N-methylpyrrolidone, dimethyl sulfoxide, γ-butyrolactone, acetonitrile, dichloromethane, and chloroform; linear alcohols such as methanol, ethanol, n-propanol, n-butanol, n-pentanol, n-hexanol, n-heptanol, n-octanol, n-nonanol, n-decanol, n-undecanol, n-dodecanol, n-tridecanol, n-tetradecanol, and n-pentadecanol; branched alcohols such as isopropanol and 2-butanol; and water. In terms of reactivity, when an organometallic reagent is used as the base, ether solvents such as tetrahydrofuran, 2-methyltetrahydrofuran, and 4-methyltetrahydropyran are preferred. When an alkali metal hydroxide and an alkali metal carbonate are used as the base, linear alcohols such as methanol and ethanol; branched alcohols such as isopropanol and 2-butanol; and water are preferred. The solvent may be used alone or in combination with two or more solvents as required. In addition, commercially available solvents may be used. The amount of the solvent used varies depending on the base used, but from the viewpoint of reactivity, it is preferably 0 to 8000 g, more preferably 0 to 3000 g, per 1 mol of the (4Z,6E)-4,6-undecadienyl trimethyl acetate (1).

[0050] The reaction temperature in the detrimethylacetylation reaction varies depending on the base used, but is preferably 0 to 150°C, more preferably 30 to 100°C, from the viewpoint of completing the reaction. The reaction time in the detrimethylacetylation reaction varies depending on the base used and / or the reaction scale, but is preferably 0.5 to 100 hours from the viewpoint of reactivity.

[0051] E. A (4Z,6E)-1-halo-4,6-undecadiene compound represented by the following general formula (7) and a method for producing the same The (4Z,6E)-1-halo-4,6-undecadiene compound (7) can be produced by halogenating the above-mentioned (4Z,6E)-4,6-undecadiene-1-ol (6), as shown in the following chemical reaction formula.

[0052] [ka]

[0053] The halogenation reaction can be carried out, for example, by a method in which the hydroxyl group is tosylated using a p-toluenesulfonyl halide compound and then halogenated using a lithium halide compound, or by a method in which the hydroxyl group is directly halogenated using a halogenating agent. Examples of the halogenating agent include halogens such as chlorine, bromine, and iodine; hydrogen halide compounds such as hydrogen chloride, hydrogen bromide, and hydrogen iodide; methanesulfonyl halide compounds such as methanesulfonyl chloride, methanesulfonyl bromide, and methanesulfonyl iodide; benzenesulfonyl halide compounds such as benzenesulfonyl chloride, benzenesulfonyl bromide, and benzenesulfonyl iodide; p-toluenesulfonyl halide compounds such as p-toluenesulfonyl chloride, p-toluenesulfonyl bromide, and p-toluenesulfonyl iodide; thionyl halide compounds such as thionyl chloride, thionyl bromide, and thionyl iodide; phosphorus halide compounds such as phosphorus trichloride, phosphorus pentachloride, and phosphorus tribromide; carbon tetrahalide compounds such as carbon tetrachloride, carbon tetrabromide, and carbon tetraiodide; trimethylsilyl chloride, trimethylsilyl bromide, trimethylsilyl iodide, triethylsilyl chloride, triethylsilyl iodide ... Examples of the alkylsilyl halide compounds include ethylsilyl bromide, triethylsilyl iodide, triisopropylsilyl chloride, triisopropylsilyl bromide, triisopropylsilyl iodide, tert-butyldimethylsilyl chloride, tert-butyldimethylsilyl bromide, and tert-butyldimethylsilyl iodide; oxalyl halide compounds such as oxalyl chloride, oxalyl bromide, and oxalyl iodide; and N-halosuccinimide compounds such as N-chlorosuccinimide, N-bromosuccinimide, and N-iodosuccinimide. From the viewpoint of suppressing side reactions, however, preferred are methanesulfonyl halide compounds, benzenesulfonyl halide compounds, p-toluenesulfonyl halide compounds, and thionyl halide compounds, and more preferred are methanesulfonyl halide compounds, benzenesulfonyl halide compounds, and thionyl halide compounds. The halogenating agent may be used alone or in combination of two or more kinds, if necessary. The halogenating agent may be a commercially available product. The amount of the halogenating agent used is preferably 0.8 to 5.0 mol, and more preferably 1.0 to 2.5 mol, per mol of (4Z,6E)-4,6-undecadien-1-ol (6), from the viewpoint of reactivity.

[0054] In the halogenation reaction, a base may be used, if necessary. Examples of the base include hydroxides such as sodium hydroxide, potassium hydroxide, calcium hydroxide, and magnesium hydroxide; carbonates such as sodium carbonate, potassium carbonate, calcium carbonate, and magnesium carbonate; and triethylamine, N , N -Diisopropylethylamine, piperidine, pyrrolidine, pyridine, lutidine, 4-dimethylaminopyridine, N , N -dimethylaniline, N , N -diethylaniline and amines such as 1,8-diazabicyclo[5.4.0]-7-undecene (DBU). When a methanesulfonyl halide compound, a benzenesulfonyl halide compound, a p-toluenesulfonyl halide compound or the like is used as the halogenating agent, it is preferable to use an amine as the base, and it is more preferable to use a pyridine such as pyridine, lutidine or 4-dimethylaminopyridine. When a thionyl halide compound is used as the halogenating agent, it is preferable to use an amine as the base, and it is more preferable to use a trialkylamine such as triethylamine. The base may be used alone or in combination with two or more kinds, if necessary. In addition, commercially available bases may be used. The amount of the base used is preferably 0 to 8.0 mol, more preferably 0 to 3.0 mol, per mol of (4Z,6E)-4,6-undecadien-1-ol (6), from the viewpoint of yield and / or economic efficiency.

[0055] In the halogenation reaction, a metal salt may be added, if necessary. Examples of the metal salt include lithium salts such as lithium chloride, lithium bromide, and lithium iodide; sodium salts such as sodium chloride, sodium bromide, and sodium iodide; potassium salts such as potassium chloride, potassium bromide, and potassium iodide; calcium salts such as calcium chloride, calcium bromide, and calcium iodide; and magnesium salts such as magnesium chloride, magnesium bromide, and magnesium iodide. The metal salt may be used alone or in combination with two or more kinds, if necessary. In addition, commercially available metal salts may be used. The amount of the metal salt used is preferably 0 to 30.0 mol, more preferably 0 to 5.0 mol, per mol of (4Z,6E)-4,6-undecadien-1-ol (6), from the viewpoint of reactivity. By adding the metal salt, the halide concentration in the reaction system can be increased, thereby increasing the reactivity. However, taking into account economic and / or environmental considerations, it is preferable to carry out the reaction without using a metal salt.

[0056] The halogenation reaction may be carried out in the presence of a solvent, 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; N , N -dimethylformamide, N , N polar solvents such as dimethylacetamide, N-methylpyrrolidone, dimethyl sulfoxide, γ-butyrolactone, acetonitrile, dichloromethane, and chloroform; and ester solvents such as methyl acetate, ethyl acetate, n-propyl acetate, and n-butyl acetate. From the viewpoint of reactivity, 2-methyltetrahydrofuran, 4-methyltetrahydropyran, dichloromethane, chloroform, γ-butyrolactone, N-methylpyrrolidone, N , N -dimethylformamide, N ,N -Dimethylacetamide and acetonitrile are preferred, and from the viewpoint of safety, 2-methyltetrahydrofuran, γ-butyrolactone and acetonitrile are particularly preferred. The solvent may be used alone or in combination with two or more solvents as required. In addition, commercially available solvents may be used. The amount of the solvent used in the halogenation reaction is preferably 0 to 3000 g, more preferably 0 to 800 g, relative to 1 mol of (4Z,6E)-4,6-undecadien-1-ol (6). Since the use of such a solvent reduces the amount of the reaction mixture and decreases the productivity, the reaction may be carried out using a base as a solvent without using the above-mentioned solvent.

[0057] The reaction temperature in the halogenation reaction varies depending on the halogenating agent used, but is preferably 5 to 180° C., more preferably 20 to 120° C., from the viewpoint of reactivity. The reaction time in the halogenation reaction varies depending on the halogenating agent used and / or the reaction scale, but is preferably 0.5 to 100 hours from the viewpoint of reactivity.

[0058] The (4Z,6E)-1-halo-4,6-undecadiene compound (7) will be described below. In the above general formula (7), X 2 represents a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom or an iodine atom.

[0059] Specific examples of the (4Z,6E)-1-halo-4,6-undecadiene compound (7) include (4Z,6E)-1-chloro-4,6-undecadiene, (4Z,6E)-1-bromo-4,6-undecadiene, and (4Z,6E)-1-iodo-4,6-undecadiene.

[0060] F. A (5Z,7E)-1,1-dialkoxy-5,7-dodecadiene compound represented by the following general formula (9) and a method for producing the same As shown in the chemical reaction formula below, the (5Z,7E)-1,1-dialkoxy-5,7-dodecadiene compound (9) can be produced by converting the above-mentioned (4Z,6E)-1-halo-4,6-undecadiene compound (7) into a (4Z,6E)-4,6-undecadienyl nucleophile represented by the following general formula (15), and subjecting the (4Z,6E)-4,6-undecadienyl nucleophile (15) to a nucleophilic substitution reaction with an orthoformate compound represented by the following general formula (8).

[0061] [ka]

[0062] The (4Z,6E)-4,6-undecadienyl nucleophile is represented by the above general formula (15). In general formula (15), M is Li or MgZ. 1 represents Z 1 represents a halogen atom or a (4Z,6E)-4,6-undecadienyl group. 1 Examples of the aryl group include a chlorine atom, a bromine atom, and an iodine atom. Specific examples of the (4Z,6E)-4,6-undecadienyl nucleophilic reagent (15) include (4Z,6E)-4,6-undecadienyllithium; and (4Z,6E)-4,6-undecadienylmagnesium halide reagents (Grignard reagents) such as (4Z,6E)-4,6-undecadienylmagnesium chloride, (4Z,6E)-4,6-undecadienylmagnesium bromide, and (4Z,6E)-4,6-undecadienylmagnesium iodide. From the viewpoint of versatility, the (4Z,6E)-4,6-undecadienylmagnesium halide reagent is preferred. The (4Z,6E)-4,6-undecadienyl nucleophile (15) may be used alone or in combination with two or more other compounds as required. The (4Z,6E)-4,6-undecadienyl nucleophile (15) may be commercially available or may be synthesized independently. The (4Z,6E)-4,6-undecadienyl nucleophile (15) can be prepared by the above-mentioned process for preparing the (4Z,6E)-4,6-undecadienyl nucleophile (15) from the (4Z,6E)-1-halo-4,6-undecadienyl compound (7). For example, (4Z,6E)-4,6-undecadienyl Nucleophiles (15) (4Z,6E)-4,6-Undecadienylmagnesium halide reagent (15:M=MgZ 1 ) can be obtained by reacting a (4Z,6E)-1-halo-4,6-undecadienyl magnesium halide reagent (15: M=MgZ) with magnesium in a solvent, as shown in the following chemical reaction formula. 1 ) (preparation of Grignard reagent).

[0063] [ka]

[0064] The (4Z,6E)-1-halo-4,6-undecadiene compound (7) may be used alone or in combination, as necessary. The (4Z,6E)-1-halo-4,6-undecadiene compound (7) may be a commercially available product or may be independently synthesized. (4Z,6E)-1-halo-4,6-undecadienyl magnesium halide reagent (15: M=MgZ 1 The amount of magnesium used in preparing the (4Z,6E)-1-halo-4,6-undecadiene compound (7) is preferably 1.0 to 2.0 gram atoms per mol of the (4Z,6E)-1-halo-4,6-undecadiene compound (7) from the viewpoint of completing the reaction. Examples of the solvent in the preparation of the Grignard reagent include ether-based solvents such as tetrahydrofuran, 2-methyltetrahydrofuran, diethyl ether, dibutyl ether, 4-methyltetrahydropyran, cyclopentyl methyl ether, and 1,4-dioxane; and hydrocarbon-based solvents such as hexane, heptane, benzene, toluene, xylene, and cumene. From the viewpoint of reactivity, ether-based solvents such as tetrahydrofuran, 2-methyltetrahydrofuran, 4-methyltetrahydropyran, and diethyl ether; and hydrocarbon-based solvents such as toluene and xylene are preferred, and ether-based solvents are more preferred. The solvent may be used alone or in combination with two or more solvents as required. In addition, commercially available solvents may be used. The amount of the solvent used is preferably 100 to 2000 g per 1 mol of the (4Z,6E)-1-halo-4,6-undecadiene compound (7) from the viewpoint of reactivity.

[0065] (4Z,6E)-1-halo-4,6-undecadienyl magnesium halide reagent (15: M=MgZ 1 The reaction temperature when preparing ) varies depending on the solvent used, but is preferably 30 to 120° C. from the viewpoint of reactivity. (4Z,6E)-1-halo-4,6-undecadienyl magnesium halide reagent (15: M=MgZ 1 The reaction time in preparing ) varies depending on the solvent used and / or the reaction scale, but is preferably 0.5 to 100 hours from the viewpoint of reactivity.

[0066] (4Z,6E)-4,6-Undecadienylmagnesium halide reagent (15 :M=MgZ 1 From the viewpoint of economy, the amount of the compound (8) used is preferably 0.3 to 1.5 mol per mol of the orthoformate compound (8).

[0067] The orthoformate compound is represented by the above general formula (8). In general formula (8), the three R's may be the same or different and represent alkyl groups having 1 to 6 carbon atoms, preferably 1 to 3 carbon atoms. Examples of the alkyl group having 1 to 6 carbon atoms include linear alkyl groups such as a methyl group, an ethyl group, an n-propyl group, an n-butyl group, an n-pentyl group, and an n-hexyl group; and branched alkyl groups such as an isopropyl group and a 2-methylpropyl group. Specific examples of the orthoformate compound (8) include methyl orthoformate, ethyl orthoformate, propyl orthoformate, butyl orthoformate, pentyl orthoformate, and hexyl orthoformate. From the viewpoint of availability, methyl orthoformate and ethyl orthoformate are preferred. The orthoformate compound (8) may be used alone or in combination with two or more compounds as required. The orthoformate compound (8) may be a commercially available compound.

[0068] Examples of the solvent used in the above nucleophilic substitution reaction include ether solvents such as tetrahydrofuran, 2-methyltetrahydrofuran, diethyl ether, dibutyl ether, 4-methyltetrahydropyran, cyclopentyl methyl ether, and 1,4-dioxane; and hydrocarbon solvents such as hexane, heptane, benzene, toluene, xylene, and cumene. From the viewpoint of reactivity, ether solvents such as tetrahydrofuran, 2-methyltetrahydrofuran, and 4-methyltetrahydropyran; hydrocarbon solvents such as toluene and xylene; and mixtures of the above ether solvents and hydrocarbon solvents are preferred. The solvent may be used alone or in combination with two or more solvents as required. In addition, commercially available solvents may be used. When the (4Z,6E)-4,6-undecadienyl nucleophile (15) is diluted with a solvent or when a solvent is used in preparing the (4Z,6E)-4,6-undecadienyl nucleophile (15), the solvent and the solvent used in the nucleophilic substitution reaction may be the same or different. If the solvent is different, it may be substituted with a solvent that increases the reactivity of the nucleophilic substitution reaction. For example, in the case where tetrahydrofuran is used as a solvent in preparing the (4Z,6E)-4,6-undecadienyl nucleophile (15) and toluene is selected as a solvent for use in the nucleophilic substitution reaction, the (4Z,6E)-4,6-undecadienyl nucleophile (15) containing tetrahydrofuran may be added to a reactor containing an orthoformate compound and toluene, and then the tetrahydrofuran may be distilled off during the process of increasing the reaction temperature, thereby replacing the solvent in the reaction system with toluene. From the viewpoint of reactivity, the amount of the solvent used is preferably 100 to 6,000 g per 1 mol of the orthoformate compound (8).

[0069] The reaction temperature in the nucleophilic substitution reaction is preferably 75 to 150° C. from the viewpoints of smoothly progressing the reaction and preventing evaporation of the solvent. The reaction time in the nucleophilic substitution reaction varies depending on the solvent used and / or the reaction scale, but is preferably 0.5 to 100 hours.

[0070] The (5Z,7E)-1,1-dialkoxy-5,7-dodecadiene compound is represented by the above general formula (9). In the general formula (9), R is as defined in the above general formula (8). Specific examples of the (5Z,7E)-1,1-dialkoxy-5,7-dodecadiene compound (9) include (5Z,7E)-1,1-dimethoxy-5,7-dodecadiene, (5Z,7E)-5,7-1,1-diethoxy-dodecadiene, (5Z,7E)-1,1-dipropyloxy-5,7-dodecadiene, (5Z,7E)-1,1-dibutyloxy-5,7-dodecadiene, (5Z,7E)-1,1-dipentyloxy-5,7-dodecadiene, and (5Z,7E)-1,1-dihexyloxy-5,7-dodecadiene.

[0071] G. (5Z,7E)-5,7-dodecadienal represented by the following general formula (10) and its production method DendrolimusThe sex pheromone substance of Bombyx mori, (5Z,7E)-5,7-dodecadienal (10), can be produced by hydrolysis of the above-mentioned (5Z,7E)-1,1-dialkoxy-5,7-dodecadienal compound (9), as shown in the following chemical reaction formula.

[0072] [ka]

[0073] <Hydrolysis reaction> In the above hydrolysis reaction, the (5Z,7E)-1,1-dialkoxy-5,7-dodecadiene compound (9) may be used alone or in combination with two or more kinds, if necessary.

[0074] The hydrolysis reaction can be carried out, for example, using an acid and water. Examples of the acid include inorganic acids such as hydrochloric acid and hydrobromic acid; as well as p-toluenesulfonic acid, benzenesulfonic acid, trifluoroacetic acid, acetic acid, formic acid, oxalic acid, iodotrimethylsilane, and titanium tetrachloride. From the viewpoint of reactivity, however, acetic acid, formic acid, and oxalic acid are preferred. The acid may be used alone or in combination with two or more acids as required. In addition, commercially available acids may be used. The amount of the acid used is preferably 0.01 to 10.0 mol per 1 mol of the (5Z,7E)-1,1-dialkoxy-5,7-dodecadiene compound (9). The amount of the water used is preferably 18 to 7000 g, and more preferably 18 to 3000 g, per mol of the (5Z,7E)-1,1-dialkoxy-5,7-dodecadiene compound (9) from the viewpoint of reactivity.

[0075] In the hydrolysis reaction, a solvent may be further used, if necessary, in addition to the above-mentioned acid or water. Examples of the solvent include hydrocarbon solvents such as toluene, xylene, hexane, heptane, benzene, and cumene; tetrahydrofuran, 2-methyltetrahydrofuran, and diethyl ether.、 Ether solvents such as dibutyl ether, 4-methyltetrahydropyran, cyclopentyl methyl ether, and 1,4-dioxane; N , N -dimethylformamide, N , N polar solvents such as γ-dimethylacetamide, N-methylpyrrolidone, dimethyl sulfoxide, acetonitrile, acetone, γ-butyrolactone, dichloromethane, and chloroform; and alcoholic solvents such as methanol and ethanol. The solvent may be used alone or in combination with two or more solvents as required. In addition, commercially available solvents may be used. The optimum solvent varies depending on the acid used. For example, when oxalic acid is used as the acid, 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, and more preferably 18 to 3000 g, per mol of the (5Z,7E)-1,1-dialkoxy-5,7-dodecadiene compound (9) from the viewpoint of reactivity.

[0076] The reaction temperature in the hydrolysis reaction varies depending on the acid and / or solvent used, but is preferably −15 to 180° C. from the viewpoint of reactivity, and more preferably −5 to 70° C., and even more preferably 0 to 30° C. from the viewpoint of stability of (5Z,7E)-5,7-dodecadienal (10). The reaction time in the hydrolysis reaction varies depending on the acid used, the solvent used, and / or the reaction scale. From the viewpoint of stability of (5Z,7E)-5,7-dodecadienal (10), for example, when the reaction temperature is 0 to 30°C, the reaction time is preferably 0.5 to 100 hours, more preferably 0.5 to 30 hours, and when the reaction temperature is a relatively high temperature of more than 30°C to 70°C, for example, 60 to 70°C, the reaction time is preferably 0.1 to 100 hours, more preferably 0.1 to 30 hours, and even more preferably 0.1 to 5 hours.

[0077] H. (5Z,7E)-5,7-dodecadien-1-ol represented by the following general formula (11) and its production method Dendrolimus (5Z,7E)-5,7-dodecadien-1-ol (11), which is a sex pheromone substance of Bombyx mori spp., can be produced by subjecting the above-mentioned (5Z,7E)-5,7-dodecadienal (10) to a reduction reaction, as shown in the following chemical reaction formula.

[0078] [ka]

[0079] <Reduction reaction> The reduction reaction can be carried out using a reducing agent. Examples of the reducing agent include metal borohydride compounds such as sodium borohydride, sodium triacetoxyborohydride, lithium triethylborohydride, magnesium borohydride, aluminum borohydride, calcium borohydride, zinc borohydride, sodium cyanoborohydride, and lithium borohydride; organoaluminum compounds such as diisobutylaluminum hydride (DIBAL), sodium bis(2-methoxyethoxy)aluminum hydride (Red-Al), and lithium aluminum hydride (LAH); alkyltin hydride compounds such as tributyltin hydride; and trialkylsilane compounds such as triethylsilane. From the viewpoint of economy, however, metal borohydride compounds such as sodium borohydride, zinc borohydride, and magnesium borohydride; and organoaluminum compounds such as DIBAL and Red-Al are preferred, with metal borohydride compounds being more preferred. The amount of the reducing agent used varies depending on the reducing agent used, but is preferably 0.15 to 10.0 mol, more preferably 0.25 to 5.0 mol, per 1 mol of (5Z,7E)-5,7-dodecadienal (10) from the viewpoints of reactivity and / or economy.

[0080] In the reduction reaction, a base may be used, if necessary. The base includes trimethylamine, triethylamine, and N , N -Trialkylamine compounds such as diisopropylethylamine; cyclic amine compounds such as piperidine, pyrrolidine, 1,8-diazabicyclo[5.4.0]-7-undecene (DBU); pyridine, lutidine, N , N -dimethylaniline, N , N -diethylaniline, N , N aromatic amine compounds such as 4-dibutylaniline and 4-dimethylaminopyridine; alkali metal hydroxides such as potassium hydroxide and sodium hydroxide; and metal alkoxides such as sodium methoxide, sodium ethoxide, sodium t-butoxide, sodium t-amyloxide, lithium methoxide, lithium ethoxide, lithium t-butoxide, lithium t-amyloxide, potassium methoxide, potassium ethoxide, potassium t-butoxide, and potassium t-amyloxide. The base may be used alone or in combination of two or more types, if necessary. The amount of the base used is preferably 0 to 10.0 mol, more preferably 0 to 5.0 mol, per mol of the (5Z,7E)-5,7-dodecadienal (10), from the viewpoint of reactivity.

[0081] The reduction reaction may be carried out in the presence of a solvent, if necessary. The solvent varies depending on the reducing agent used, but may be a hydrocarbon solvent such as toluene, xylene, hexane, heptane, benzene, or cumene; tetrahydrofuran, 2-methyltetrahydrofuran, or diethyl ether. 、 Ether solvents such as dibutyl ether, 4-methyltetrahydropyran, cyclopentyl methyl ether, and 1,4-dioxane; N , N -dimethylformamide, N , NExamples of the solvent include polar solvents such as dimethylacetamide, N-methylpyrrolidone, dimethyl sulfoxide, acetonitrile, acetone, γ-butyrolactone, dichloromethane, and chloroform; alcoholic solvents such as methanol and ethanol; and water. The reduction reaction may be carried out using a two-layer system of water and another solvent as the solvent. The solvent may be used alone or in combination with two or more solvents as required. In addition, commercially available solvents may be used. The amount of the solvent used in the reduction reaction is preferably 0 to 5000 g, more preferably 0 to 2000 g, relative to 1 mol of the (5Z,7E)-5,7-dodecadienal (10).

[0082] The reaction temperature in the reduction reaction varies depending on the reducing agent and / or solvent used, but is preferably −78 to 80° C., more preferably −20 to 40° C., from the viewpoint of the reactivity and / or thermal stability of (5Z,7E)-5,7-dodecadienal (10). The reaction time in the reduction reaction is preferably 0.5 to 100 hours from the viewpoint of reactivity.

[0083] I. (5Z,7E)-5,7-dodecadienyl acetate represented by the following general formula (12) and its production method Dendrolimus The sex pheromone substance of Bombyx mori, (5Z,7E)-5,7-dodecadienyl acetate (12), can be produced by acetylation of the above-mentioned (5Z,7E)-5,7-dodecadien-1-ol (11), as shown in the following chemical reaction formula.

[0084] [ka]

[0085] <About the acetylation reaction> The acetylation can be carried out using an acetylating agent. Examples of the acetylating agent include acid anhydrides such as acetic acid and acetic anhydride; acetyl halide compounds such as acetyl chloride, acetyl bromide, and acetyl iodide; and acetate compounds such as methyl acetate and ethyl acetate. From the viewpoint of versatility, however, acetic anhydride and acetyl halide compounds are preferred. The amount of the acetylating agent used is preferably 1.0 to 10.0 mol, and more preferably 1.0 to 5.0 mol, per mol of (5Z,7E)-5,7-dodecadien-1-ol (11), from the viewpoints of reactivity and economic efficiency.

[0086] The acetylation may be carried out using an acid or a base, if necessary. Examples of the acid include mineral acids such as hydrochloric acid, sulfuric acid, and nitric acid; aromatic sulfonic acids such as benzenesulfonic acid and p-toluenesulfonic acid; and Lewis acids such as aluminum trichloride, aluminum ethoxide, aluminum isopropoxide, aluminum oxide, boron trifluoride, boron trichloride, boron tribromide, magnesium chloride, magnesium bromide, magnesium iodide, zinc chloride, zinc bromide, zinc iodide, tin tetrachloride, tin tetrabromide, dibutyltin dichloride, dibutyltin dimethoxide, dibutyltin oxide, magnesium chloride, magnesium bromide, titanium tetrachloride, titanium tetrabromide, titanium(IV) methoxide, titanium(IV) ethoxide, titanium(IV) isopropoxide, and titanium(IV) oxide. The acid may be used alone or in combination of two or more kinds, if necessary. The amount of the acid used is preferably 0.001 to 3.00 mol, and more preferably 0.01 to 1.50 mol, per mol of (5Z,7E)-5,7-dodecadien-1-ol (11), from the viewpoints of reactivity and economic efficiency.

[0087] The base includes trimethylamine, triethylamine, and N , N -Trialkylamine compounds such as diisopropylethylamine; cyclic amine compounds such as piperidine, pyrrolidine, 1,8-diazabicyclo[5.4.0]-7-undecene (DBU); pyridine, lutidine,N , N -dimethylaniline, N , N -diethylaniline, N , N aromatic amine compounds such as -dibutylaniline and 4-dimethylaminopyridine; and metal alkoxides such as sodium methoxide, sodium ethoxide, sodium t-butoxide, sodium t-amyloxide, lithium methoxide, lithium ethoxide, lithium t-butoxide, lithium t-amyloxide, potassium methoxide, potassium ethoxide, potassium t-butoxide, and potassium t-amyloxide. The base may be used alone or in combination of two or more types, if necessary. The amount of the base used is preferably 0.010 to 10.0 mol, and more preferably 0.001 to 5.0 mol, per mol of (5Z,7E)-5,7-dodecadien-1-ol (11), from the viewpoints of reactivity and economic efficiency.

[0088] The acetylation may be carried out in the presence of a solvent, 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 N , N -dimethylformamide, N , N Examples of the polar solvent include polar solvents such as dimethylacetamide, N-methylpyrrolidone, dimethyl sulfoxide, γ-butyrolactone, acetonitrile, dichloromethane, chloroform, and hexamethylphosphoric triamide (HMPA). From the viewpoint of reactivity, ether solvents such as tetrahydrofuran, 2-methyltetrahydrofuran, and 4-methyltetrahydropyran; and hydrocarbon solvents such as toluene and xylene are preferred. The solvent may be used alone or in combination with two or more solvents as required. In addition, commercially available solvents may be used. The acetylation may be carried out in the presence of a solvent, if necessary, but the reaction may also be carried out without a solvent. The amount of the solvent used in the acetylation is preferably 0 to 5000 g, more preferably 0 to 2000 g, relative to 1 mol of the (5Z,7E)-5,7-dodecadien-1-ol (11).

[0089] The reaction temperature in the acetylation varies depending on the acetylating agent and / or solvent used, but is preferably −40 to 100° C., more preferably −20 to 80° C., and even more preferably 0 to 40° C., from the viewpoint of the reactivity and / or the thermal stability of (5Z,7E)-5,7-dodecadienyl acetate (12). The reaction time for the acetylation is preferably 0.5 to 100 hours from the viewpoint of reactivity.

[0090] In this manner, (5Z,7E)-5,7-dodecadienal (10), (5Z,7E)-5,7-dodecadien-1-ol (11), and (5Z,7E)-5,7-dodecadienyl acetate (12) can be efficiently produced from the synthetic intermediate (4Z,6E)-4,6-undecadienyl trimethyl acetate (1) in a short number of steps.

[0091] [Example] The present invention will be described in detail below 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, "production ratio" refers to the relative ratio of the area percentage obtained by GC analysis, and "yield" was calculated based on the area percentage obtained by GC analysis. In each example, reaction monitoring and yield calculation were performed according to the following GC conditions. GC conditions: GC: Shimadzu Corporation capillary gas chromatograph GC-2014, column: 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, 5°C / min heating to 230°C. The yield was calculated according to the following formula, taking into account the purity (%GC) of the raw materials and the product. Yield (%) = {[(weight of product obtained by reaction × %GC) / molecular weight of product] ÷[(weight of starting material in reaction × %GC) / molecular weight of starting material]} × 100 In addition, THF is tetrahydrofuran, GBL is γ-butyrolactone, Et is ethyl group, Ph is phenyl group, Ac is acetyl group, and t Bu represents a tert-butyl group.

[0092] Example 1 <4-Chlorobutyl trimethyl acetate (2:X 1 =Cl)

[0093] [ka]

[0094] Tetrahydrofuran (774.32 g, 10.74 mol, purity 100%) and zinc chloride (11.26 g, 0.083 mol) were added to a reactor at room temperature, and the temperature was raised to 50°C. Then, trimethylacetyl chloride (996.00 g, 8.26 mol) was added dropwise at an internal temperature of 50 to 60°C. After completion of the dropwise addition, the mixture was stirred at 60 to 65°C for 14 hours. Thereafter, water (826.00 g) and hexane (327.60 g) were added to the reaction liquid, and the liquid was separated. The aqueous layer was removed to obtain an organic layer. The obtained organic layer was then distilled under reduced pressure (bp = 94.5 to 100.0°C / 0.40 kPa (3.0 mmHg)) to obtain 4-chlorobutyl trimethylacetate (2:X). 1 =Cl) (1491.64 g, 7.74 mol, 99.98% purity) was obtained in 93.66% yield.

[0095] The 4-chlorobutyl trimethyl acetate obtained above (2:X 1 The spectral data for (=Cl) is shown below. [Nuclear Magnetic Resonance Spectrum] 1 H-NMR (500MHz, CDCl3): δ=1.19(9H,s),1.75-1.88(4H,m),3.56(2H,t,J=6.5Hz),4.08(2H,t,J=6.5Hz); 13 C-NMR(500MHz,CDCl3):δ=26.06,27.15,29.17,38.71,44.45,63.43,178.47 [Mass spectrum] EI-mass spectrum (70 eV): m / z 193 (M + +1), 157, 129, 115, 103, 85, 57, 41, 29 [Infrared absorption spectrum] (D-ATR): νmax = 2962, 1729, 1481, 1285, 1155

[0096] Example 2 <Production of (4Z,6E)-4,6-undecadienyl trimethyl acetate (1)>

[0097] [ka]

[0098] At room temperature, the reactor was charged with 4-chlorobutyl trimethyl acetate (2:X) obtained in Example 1. 1 =Cl) (23.13g, 0.12mol, purity 99.98%), triphenylphosphine (PPh3) (3:Ar=Ph) (31.55g, 0.12mol), sodium iodide (NaI) (19.49g, 0.13mol), potassium carbonate (K2CO3) (0.97 g , 0.007 mol) and acetonitrile (CH3CN) (45.00 g) were added thereto, and the mixture was stirred at 75 to 85°C for 17 hours to prepare [4-(trimethylacetyloxy)butyl]triphenylphosphonium iodide (4: Y = I, Ar = Ph).

[0099] Next, tetrahydrofuran (THF) (80.00 g) was added dropwise to the reactor at 30 to 40° C. After the dropwise addition was completed, the reaction solution was cooled to −10 to 5° C. Then, potassium tert-butoxide ( t BuOK) (12.90 g, 0.12 mol) was added at -10 to 5°C, and then the mixture was stirred at -10 to 5°C for 1 hour to obtain a reaction product mixture. The reaction product mixture is presumed to contain a triphenylphosphonium 4-(trimethylacetyloxy)butylide compound (13:Ar=Ph) as a reaction product.

[0100] Then, (2E)-2-heptenal (5) (11.41 g, 0.10 mol, purity 98.28%) was added dropwise to the reactor at -5 to 5°C. After the dropwise addition was completed, the mixture was stirred for 3 hours at 20 to 30°C. Then, the reaction liquid was separated by adding saline (salt (15.16 g) and water (151.57 g)), 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 (bp = 102.1 to 113.4 °C / 0.40 kPa (3.0 mmHg)) to obtain (4Z,6E)-4,6-undecadienyl trimethyl acetate (1) (19.49 g, 0.076 mol, purity 98.44%, 4Z6E:4Z6Z:4E6E = 88.4:0.7:10.9) in a yield of 76.17%.

[0101] The spectral data of [4-(trimethylacetyloxy)butyl]triphenylphosphonium iodide (4: Y=I, Ar=Ph) is shown below. [Nuclear Magnetic Resonance Spectrum] 1 H-NMR (500MHz, CDCl3): δ=1.05(9H,s),1.63-1.73(2H,m),1.80-1.88(2H,m), 3.27-3.35(2H,m)4.04(2H,t,J=6.1Hz),7.68-7.77(12H,m),7.83-7.88(3H,m) [Mass spectrum] ESI, N2gas: 12L / min, 241.32kPa( 35psi ) ,250℃ Vcap:4000V):m / z 419.21(M + )

[0102] The spectral data of the (4Z,6E)-4,6-undecadienyl trimethyl acetate (1) obtained above is shown below. [Nuclear Magnetic Resonance Spectrum] 1 H-NMR (500MHz, CDCl3): δ=0.89(3H,t,J=7.3Hz),1.20(9H,s),1.27-1.41(4H,m), 1.71(2H,tt,J=7.3Hz,7.3Hz),2.09(2H,dt,J=6.9Hz,6.9Hz),2.24(2H,dt,J=7.9H z,7.9Hz),4.06(2H,t,J=6.1Hz),5.27(1H,dt,J=10.7Hz,7.7Hz),5.67(1H,dt,J= 7.3Hz,7.3Hz),5.98(1H,dd,J=11.1Hz,11.1Hz),6.27(1H,dd,J=15.0Hz,11.1Hz); 13 C-NMR(500MHz,CDCl3):δ=13.89,22.25,24.00,27.19,28.66,31.47,32.53,38.71,63.63,125.20,128.00,129.67,135.36,178.50 [Mass spectrum] EI-mass spectrum (70 eV): m / z 252 (M + ), 237, 223, 167, 150, 135, 121, 107, 93, 79, 57, 41 [Infrared absorption spectrum] (D-ATR): νmax = 2958, 2929, 2873, 1731, 1480, 1460, 1284, 1156, 984, 948

[0103] Comparative Example 1 <Production of (4Z,6E)-4,6-undecadienyl acetate>

[0104] [ka] 4-Chlorobutyl trimethyl acetate (2:X 1The experiment was carried out under the same conditions as in Example 2, except that (4Z,6E)-4,6-undecadienyl acetate (yield 22.45%) and (4Z,6E)-4,6-undecadienyl acetate (yield 22.45%) were obtained. En The yield was very low, being a mixture of 1- and 2-ols (yield 12.38%).

[0105] The spectral data of the (4Z,6E)-4,6-undecadienyl acetate obtained above is shown below. [Nuclear Magnetic Resonance Spectrum] 1 H-NMR (500MHz, CDCl3): δ=0.89(3H,t,J=7.3Hz),1.27-1.43(4H,m),1.71(2H,tt,J=6.9 Hz,6.9Hz),2.04(3H,s),2.09(2H,dt,J=7.7Hz,7.7Hz),2.23(2H,ddt,J=1.5Hz,7.5Hz,7 .5Hz),4.06(2H,t,J=6.9Hz),5.25(1H,dt,J=11.1Hz,7.7Hz),5.67(1H,dt,J=7.3Hz,7.3 Hz),5.98(1H,dd,J=10.7Hz,10.7Hz),6.26(1H,dddt,J=14.9Hz,11.1Hz,1.5Hz,1.5Hz); 13 C-NMR (500MHz, CDCl3): δ=13.90,20.95,22.25,23.96,28.50,31.46,32.55,63.84,125.17,127.86,129.71,135.42,171.10 [Mass spectrum] EI-mass spectrum (70 eV): m / z 210 (M + ), 167, 150, 135, 121, 107, 93, 79, 67, 55, 43, 29 [Infrared absorption spectrum] (D-ATR): νmax = 2957, 2928, 1743, 1366, 1240, 1041, 984, 949

[0106] Comparative Example 2 <Production of (4Z,6E)-4,6-undecadienyl acetate>

[0107] [ka]

[0108] 4-Chlorobutyl trimethyl acetate (2:X 1 =Cl) was replaced with 4-chlorobutyl acetate (18.10 g, 0.12 mol, purity 99.83%), and the temperature at which potassium tert-butoxide and (2E)-2-heptenal (5) were added to the reactor was changed to -70 to -60 ° C., and the experiment was carried out under the same conditions as in Example 2. As a result, (4Z,6E)-4,6-undecadienyl acetate (12.62 g, 0.071 mol, purity 94.61%, 4Z6E:4Z6Z:4E6E=92.8:0:7.2) was obtained in a yield of 70.94%. Unlike Comparative Example 1, no significant reduction in the deprotection of the acetyl group or in the yield was observed at a low temperature of -60 ° C. or lower, but the yield was lower than that of Example 2. In addition, when performing a low-temperature reaction at -60 ° C. or lower industrially, it is necessary to introduce a special reaction apparatus, and a large amount of electricity is used for cooling, which is very disadvantageous from the viewpoint of economy.

[0109] Comparative Example 3 <Production of (4Z,6E)-4,6-undecadienyl benzoate>

[0110] [ka]

[0111] At room temperature, 4-chlorobutyl benzoate (26.55 g, 0.12 mol, purity 96.12%), triphenylphosphine (3:Ar=Ph) (31.55 g, 0.12 mol), sodium iodide (19.49 g, 0.13 mol), potassium carbonate (0.97 g , 0.007 mol) and acetonitrile (45.00 g) were added thereto, and the mixture was stirred at 75 to 85° C. for 17 hours to prepare [4-(benzoyloxy)butyl]triphenylphosphonium iodide.

[0112] Next, tetrahydrofuran (80.00 g) was added dropwise to the reactor at 30 to 40° C. After the addition was completed, the reaction solution was -10~5 The mixture was cooled to ℃, but solidified and could not be stirred, so tetrahydrofuran (160g) was added. However, since there was a lot of solid and stirring was difficult at -10 to 5℃, [4-(benzoyloxy)butyl]triphenylphosphonium=iodide was dissolved at 5 to 10℃, and then potassium=tert-butoxide (12.90g, 0.12mol) was added. The mixture was then stirred at -5 to 5℃ for 1 hour to obtain a reaction product mixture. It is estimated that the reaction product mixture contains triphenylphosphonium=4-(benzoyloxy)butylide as a reaction product. However, the color of the ylide gradually faded during the 1-hour stirring.

[0113] Then, (2E)-2-heptenal (5) (11.41 g, 0.10 mol, purity 98.28%) was added dropwise to the reactor at -5 to 5°C. After the completion of the dropwise addition, the mixture was stirred at 20 to 30°C for 3 hours. Then, the reaction solution was added with saline (salt (15.16 g) and water (151.57 g)) to separate the liquid, 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, but no (4Z,6E)-4,6-undecadienyl benzoate was obtained. It is presumed that this is due to the decomposition of triphenylphosphonium 4-(benzoyloxy)butylide.

[0114] Example 3 <Production of (4Z,6E)-4,6-undecadien-1-ol (6)>

[0115] [ka]

[0116] At room temperature, (4Z,6E)-4,6-undecadienyl trimethyl acetate (1) (142.69 g, 0.55 mol, purity 97.07%, 4Z6E:4Z6Z:4E6E=87.8:0.7:11.5) obtained by the same production method as in Example 2 was added to a reactor, and the temperature was raised to 50°C. Then, a tetrahydrofuran solution of methylmagnesium chloride (CH3MgCl) (1699.08 g, 4.39 mol as methylmagnesium chloride) was added dropwise at 50-60°C. After the dropwise addition was completed, the mixture was stirred at 60-65°C for 2 hours. Then, 20% by mass hydrochloric acid (900.42 g) was added to the reaction liquid, and the liquid was separated, 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 (bp = 88.1 to 105.0 ° C. / 0.40 kPa (3.0 mmHg)) to obtain (4Z,6E)-4,6-undecadien-1-ol (6) (98.68 g, 0.55 mol, purity 93.79%, 4Z6E:4Z6Z:4E6E = 86.9:1.4:11.7) in a yield of 99.77%.

[0117] The spectral data of the (4Z,6E)-4,6-undecadien-1-ol (6) obtained above is shown below. [Nuclear Magnetic Resonance Spectrum] 1 H-NMR (500MHz, CDCl3): δ=0.89(3H,t,J=7.3Hz),1.27-1.41(4H,m),1.65(2H,quin-lik e,J=6.5Hz),2.09(2H,dt,J=6.9Hz,6.9Hz),2.25(2H,ddt,J=1.6Hz,7.4Hz,7.4Hz),3.6 5(2H,t,J=6.5Hz),5.29(1H,dt,J=10.7Hz,7.7Hz),5.67(1H,ddt,J=7.3Hz,7.3Hz,7.3H z),5.97(1H,dd,J=11.1Hz,11.1Hz),6.30(1H,dddt,J=15.0Hz,11.1Hz,1.6Hz,1.6Hz); 13 C-NMR (500MHz, CDCl3): δ=13.89,22.23,23.98,31.47,32.48,32.51,62.40,125.24,128.69,129.36,135.31 [Mass spectrum] EI-mass spectrum (70 eV): m / z 168 (M + ), 150, 135, 121, 107, 93, 79, 67, 55, 41 [Infrared absorption spectrum] (D-ATR): νmax = 3333, 2956, 2927, 1456, 1059, 983, 947, 731

[0118] Example 4 <Production of (4Z,6E)-4,6-undecadien-1-ol (6)>

[0119] [ka]

[0120] At room temperature, (4Z,6E)-4,6-undecadienyl trimethyl acetate (1) (186.39 g, 0.73 mol, purity 98.22%, 4Z6E:4Z6Z:4E6E=87.9:0.8:11.3) obtained by the same production method as in Example 2, potassium carbonate (30.08 g, 0.22 mol), and methanol (CHOH) (1394.51 g) were added to a reactor and stirred at 60 to 65° C. for 11 hours. Thereafter, acetic acid (26.14 g) was added to the reaction solution, the reaction solution was concentrated under reduced pressure, and the residue was distilled under reduced pressure (bp = 88.1 to 105.0 ° C. / 0.40 kPa (3.0 mmHg)) to obtain (4Z,6E)-4,6-undecadien-1-ol (6) (124.90 g, 0.71 mol, purity 96.32%, 4Z6E:4Z6Z:4E6E = 87.4:0.8:11.8) in a yield of 98.55%.

[0121] The spectral data of the (4Z,6E)-4,6-undecadien-1-ol (6) obtained above was the same as that in Example 3.

[0122] Example 5 <(4Z,6E)-1-chloro-4,6-undecadiene (7:X 2 =Cl)

[0123] [ka]

[0124] To a reactor, (4Z,6E)-4,6-undecadien-1-ol (6) (124.90 g, 0.71 mol, purity 96.32%, 4Z6E:4Z6Z:4E6E=87.4:0.8:11.8) produced in Example 4, pyridine (84.82 g, 1.07 mol), and GBL (107.24 g) were added, and the mixture was stirred at 40° C. for 14 minutes. Subsequently, methanesulfonyl chloride (CH3SO2Cl) (98.27 g, 0.86 mol) was added dropwise at 40 to 60°C. The mixture was then heated to 60 to 65°C and stirred for 7.5 hours. After stirring, water (178.73 g) and hexane (107.24 g) were added and separated, and the aqueous layer was removed to obtain an organic layer. The obtained organic layer was washed with an aqueous acetic acid solution (acetic acid (7.52 g), water (94.06 g)), and then washed with an aqueous sodium hydrogen carbonate solution (sodium hydrogen carbonate (3.76 g), water (94.06 g)). The obtained organic layer was concentrated under reduced pressure, and the residue was distilled under reduced pressure (bp = 90.0 to 97.0°C / 0.67 kPa (5.0 mmHg)) to obtain (4Z,6E)-1-chloro-4,6-undecadiene (7:X 2 =Cl) (123.75 g, 0.65 mol, purity 98.50%, 4Z6E:4Z6Z:4E6E = 86.4:1.1:12.5) was obtained in a yield of 91.32%.

[0125] The (4Z,6E)-1-chloro-4,6-undecadiene (7:X 2 The spectral data for (=Cl) is shown below. [Nuclear Magnetic Resonance Spectrum] 1H-NMR (500MHz, CDCl3): δ=0.90(3H,t,J=6.9Hz),1.28-1.44(4H,m),1.86(2H,quin -like,J=6.9Hz),2.11(2H,dt,J=6.9Hz,6.9Hz),2.33(2H,dt,J=7.5Hz,7.5Hz),3.5 5(2H,t,J=6.9Hz),5.25(1H,dt,J=10.7Hz,7.7Hz),5.69(1H,dt,J=7.7Hz,7.7Hz), 6.01(1H,dd,J=11.1Hz,11.1Hz),6.31(1H,dddt,J=14.9Hz,11.1Hz,1.5Hz,1.5Hz); 13 C-NMR (500MHz, CDCl3): δ=13.91,22.25,24.81,31.45,32.46,32.53,44.42,125.23,127.26,130.20,135.64 [Mass spectrum] EI-mass spectrum (70 eV): m / z 186 (M + ), 171, 157, 143, 130, 107, 95, 81, 67, 55, 41 [Infrared absorption spectrum] (D-ATR): ν=2957, 2928, 1456, 1443, 984, 948, 730, 655

[0126] Example 6 <Production of (5Z,7E)-1,1-diethoxy-5,7-dodecadiene (9:R=Et)>

[0127] [ka]

[0128] Magnesium (15.84 g, 0.65 mol) and tetrahydrofuran (186.30 g) were added to the reactor at room temperature and stirred at 60 to 65° C. for 16 minutes. After stirring was completed, the reactor was charged with (4Z,6E)-1-chloro-4,6-undecadiene (7:X) prepared in Example 5. 2=Cl) (117.72 g, 0.62 mol, purity 98.50%, 4Z6E:4Z6Z:4E6E = 86.4:1.1:12.5) was added dropwise at 60 to 75 ° C. After completion of the dropwise addition, the mixture was stirred at 75 to 80 ° C. for 3 hours to obtain (4Z,6E)-4,6-undecadienyl Magnesium chloride (15: M=MgCl) was prepared. Subsequently, toluene (288.77 g) and ethyl orthoformate (8:R=Et) (119.64, 0.81 mol) were added dropwise to the reactor at 75 to 85° C. After completion of the dropwise addition, the reaction mixture was stirred at 90 to 100° C. for 15 hours. Thereafter, the reaction mixture was cooled to 30 to 45° C., and an aqueous acetic acid solution (acetic acid (77.63 g) and water (232.88 g)) was added to the reaction mixture to separate the liquids, 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 (bp = 105.1 to 110.5 ° C. / 0.40 kPa (3.0 mmHg)) to obtain (5Z,7E)-1,1-diethoxy-5,7-dodecadiene (9:R = Et) (130.91 g, 0.50 mol, purity 96.76%, 5Z7E:5Z7Z:5E7E = 86.0:1.1:12.9) in a yield of 80.18%.

[0129] The spectral data of the (5Z,7E)-1,1-diethoxy-5,7-dodecadiene (9:R=Et) obtained above is shown below. [Nuclear Magnetic Resonance Spectrum] 1 H-NMR (500MHz, CDCl3): δ=0.89(3H,t,J=6.9Hz),1.20(6H,t,J=6.9Hz),1.27-1.41(4H,m),1.41-1.4 9(2H,m),1.63(2H,dt,J=9.9Hz,5.8Hz),2.09(2H,q-like,J=6.9Hz),2.18(2H,q-like,7.5Hz),3.45- 3.52(2H,m),3.59-3.67(2H,m),4.48(1H,t,J=5.7Hz),5.28(1H,dt,J=10.7Hz,7.7Hz),5.65(1H,dt, J=7.3Hz,7.3Hz),5.95(1H,dd,J=11.1Hz,11.1Hz),6.28(1H,dddt,J=15.0Hz,11.1Hz,1.5Hz,1.5Hz);13 C-NMR (500MHz, CDCl3): δ=13.90,15.31,22.24,24.84,27.38,31.51,32.52,33.09,60.82,102.77,125.48,129.01,129.32,134.89 [Mass spectrum] EI-mass spectrum (70 eV): m / z 254 (M + ), 208, 165, 136, 103, 79, 57, 29 [Infrared absorption spectrum] (D-ATR): ν=2956, 2928, 2873, 1457, 1444, 1374, 1343, 1129, 1064, 984, 94

[0130] Example 7-1 <Production of (5Z,7E)-5,7-dodecadienal (10)>

[0131] [ka]

[0132] Into a reactor, (5Z,7E)-1,1-diethoxy-5,7-dodecadiene (9:R=Et) (10.00g, 0.036mol, purity 90.82%, 5Z7E:5Z7Z:5E7E=84.3:1.3:14.4) obtained by the same production method as in Example 6, oxalic acid dihydrate ((COOH)2) (13.50g, 0.11mol), tetrahydrofuran (35.70g) and water (35.70g) were added, and the mixture was stirred at 15 to 25°C for 13.5 hours. Then, hexane (10.42g) was added, and the mixture was stirred for 30 minutes. After the stirring was completed, the reaction solution was left to stand and separated, and the aqueous layer was removed to obtain an organic layer. The organic layer obtained was concentrated under reduced pressure, and the residue was purified by silica gel column chromatography (hexane:ethyl acetate=50:1) to obtain (5Z,7E)-5,7-dodecadienal (10) (6.28 g, 0.033 mol, purity 93.69%, 5Z7E:5Z7Z:5E7E=83.9:1.5:14.6) in a yield of 91.46%.

[0133] Example 7-2 <Production of (5Z,7E)-5,7-dodecadienal (10)>

[0134] [ka]

[0135] Into a reactor, (5Z,7E)-1,1-diethoxy-5,7-dodecadiene (9:R=Et) (10.00g, 0.036mol, purity 90.82%, 5Z7E:5Z7Z:5E7E=84.3:1.3:14.4) obtained by the same production method as in Example 6, oxalic acid dihydrate ((COOH)2) (13.50g, 0.11mol), tetrahydrofuran (35.70g) and water (35.70g) were added, and the mixture was stirred at 60-65°C for 1.5 hours. Then, hexane (10.42g) was added, and the mixture was stirred for 30 minutes. After the stirring was completed, the reaction solution was left to stand and separated, and the aqueous layer was removed to obtain an organic layer. The organic layer obtained was concentrated under reduced pressure, and the residue was purified by silica gel column chromatography (hexane: ethyl acetate = 50: 1), to obtain (5Z, 7E)-5,7-dodecadienal (10) (6.11 g, 0.030 mol, purity 89.74%, 5Z7E: 5Z7Z: 5E7E = 81.1: 1.8: 17.1) in a yield of 84.51%. It was found that if the hydrolysis reaction is continued at a high temperature, for example, at the above-mentioned 60 to 65 ° C. for a long time, the GC purity of (5Z, 7E)-5,7-dodecadienal (10) gradually decreases, and the yield of (5Z, 7E)-5,7-dodecadienal (10) ultimately decreases. This decrease in yield is believed to be due to the decomposition of (5Z, 7E)-5,7-dodecadienal (10). To prevent this decomposition, the hydrolysis reaction can be stopped at an appropriate time by monitoring the reaction by GC or thin layer chromatography (TLC).

[0136] The various spectral data of the (5Z,7E)-5,7-dodecadienal (10) obtained above were the same as those obtained in Example 7-1.

[0137] Example 7-3 <Production of (5Z,7E)-5,7-dodecadienal (10)>

[0138] [ka]

[0139] Into a reactor, (5Z,7E)-1,1-diethoxy-5,7-dodecadiene (9:R=Et) (10.00g, 0.036mol, purity 90.82%, 5Z7E:5Z7Z:5E7E=84.3:1.3:14.4) obtained by the same production method as in Example 6, oxalic acid dihydrate ((COOH)2) (13.50g, 0.11mol), tetrahydrofuran (35.70g) and water (35.70g) were added, and the mixture was stirred at 60-65°C for 5.5 hours. Then, hexane (10.42g) was added, and the mixture was stirred for 30 minutes. After the stirring was completed, the reaction solution was left to stand and separated, and the aqueous layer was removed to obtain an organic layer. The organic layer obtained was concentrated under reduced pressure, and the residue was purified by silica gel column chromatography (hexane:ethyl acetate=50:1), to obtain (5Z,7E)-5,7-dodecadienal (10) (4.89 g, 0.022 mol, purity 81.31%, 5Z7E:5Z7Z:5E7E=72.2:2.7:25.1) in a yield of 61.22%. It was found that if the hydrolysis reaction is continued for a long time at a high temperature, for example, at the above-mentioned 60 to 65°C, the GC purity of (5Z,7E)-5,7-dodecadienal (10) gradually decreases, and the yield of (5Z,7E)-5,7-dodecadienal (10) ultimately decreases. Therefore, as described in Example 7-2, it is possible to stop the hydrolysis reaction at an appropriate timing by tracking the reaction by GC or thin layer chromatography (TLC).

[0140] The various spectral data of the (5Z,7E)-5,7-dodecadienal (10) obtained above were the same as those obtained in Example 7-1.

[0141] The spectral data of the (5Z,7E)-5,7-dodecadienal (10) obtained above is shown below. [Nuclear Magnetic Resonance Spectrum] 1 H-NMR (500MHz, CDCl3): δ=0.89(3H,t,J=7.3Hz),1.27-1.40(4H,m),1.72(2H,tt,J=7.3H z),2.09(2H,q-like,J=6.9Hz),2.21(2H,ddt,J=1.2Hz,7.4Hz,7.4Hz),2.44(2H,dt,J=1. 6Hz,7.3Hz),5.24(1H,dt,J=10.7Hz,7.7Hz),5.68(1H,dt,J=7.3Hz,7.3Hz),5.99(1H,t-l ike,J=11.1Hz),6.24(1H,dddt,J=14.9Hz,11.1Hz,1.6Hz,1.6Hz),9.77(1H,t,J=1.6Hz); 13 C-NMR (500MHz, CDCl3): δ=13.88,21.97,22.22,26.81,31.44,32.50,43.15,125.16,127.96,129.91,135.58,202.48 [Mass spectrum] EI-mass spectrum (70 eV): m / z 180 (M + ), 162, 151, 136, 123, 79, 67, 55, 29 [Infrared absorption spectrum] (D-ATR): ν=2956, 2928, 1726, 1456, 986, 950

[0142] Example 8 <Production of (5Z,7E)-5,7-dodecadien-1-ol (11)>

[0143] [ka]

[0144] Sodium borohydride (NaBH4) (1.08 g, 0.029 mol), tetrahydrofuran (20.00 g), 25 mass% aqueous sodium hydroxide solution (0.27 g, 0.0017 mol as sodium hydroxide) and water (7.26 g) were added to a reactor and stirred at 0 to 5°C for 1 hour. Next, (5Z,7E)-5,7-dodecadienal (10) (10.61 g, 0.057 mol, purity 97.13%, 5Z7E:5Z7Z:5E7E=83.8:1.5:14.7) obtained by the same production method as in Example 7-1 was added dropwise at −5 to 10° C. Then, the mixture was stirred at 0 to 10° C. for 2 hours. After stirring was completed, an aqueous acetic acid solution (acetic acid (20 g), water (60 g)) and hexane (20 g) were added and the mixture was separated, and the aqueous layer The organic layer was then removed to obtain an organic layer. The obtained organic layer was concentrated under reduced pressure, and the residue was purified by silica gel column chromatography (hexane:ethyl acetate=50:1 to 5:1) to obtain (5Z,7E)-5,7-dodecadien-1-ol (11) (9.78 g, 0.051 mol, purity 94.34%, 5Z7E:5Z7Z:5E7E=82.3:1.5:16.2) in a yield of 88.56%.

[0145] The spectral data of the (5Z,7E)-5,7-dodecadien-1-ol (11) obtained above is shown below. [Nuclear Magnetic Resonance Spectrum] 1 H-NMR (500MHz, CDCl3): δ=0.89(3H,t,J=7.3Hz),1.27-1.41(4H,m),1.45(2H,quin-like,J=7 .3Hz),1.54-1.63(2H,m),2.00(1H,brs),2.09(2H,dt,J=6.9Hz,6.9Hz),2.19(2H,dt,J=1.6H z,7.5Hz,7.5Hz),3.64(2H,t,J=6.5Hz),5.28(1H,dt,J=11.1Hz,7.7Hz),5.66(1H,dt,J=7.3H z,7.3Hz),5.95(1H,dd,J=11.1Hz,11.1Hz),6.28(1H,dddt,J=14.9Hz,11.1Hz,1.6Hz,1.6Hz); 13 C-NMR(500MHz,CDCl3):δ=13.91,22.25,25.79,27.32,31.50,32.23,32.53,62.79,125.41,129.01,129.31,135.00 [Mass spectrum] EI-mass spectrum (70 eV): m / z 182 (M +), 164, 135, 121, 107, 93, 79, 67, 55, 41 [Infrared absorption spectrum] (D-ATR): ν=3326, 2956, 2928, 1457, 1425, 1060, 983, 949, 731

[0146] Example 9 <Production of (5Z,7E)-5,7-dodecadienyl acetate (12)>

[0147] [ka] At room temperature, (5Z,7E)-5,7-dodecadien-1-ol (11) (9.63 g, 0.050 mol, purity 94.34%, 5Z7E:5Z7Z:5E7E=82.3:1.5:16.2) obtained in Example 8, pyridine (6.31 g, 0.080 mol) and tetrahydrofuran (30.00 g) were added to a reactor and stirred at 15 to 25 ° C for 2 minutes. After stirring, acetic anhydride (Ac2O) (6.61 g, 0.065 mol) was added dropwise at 15 to 25 ° C, and the mixture was stirred at 15 to 25 ° C for 6.5 hours. Next, water (20.00 g) and hexane (30.00 g) were added to the reaction liquid and the mixture was separated, and the aqueous layer was removed to obtain an organic layer. The organic layer obtained was concentrated under reduced pressure, and the residue was purified by silica gel column chromatography (hexane:ethyl acetate=30:1) to obtain (5Z,7E)-5,7-dodecadienyl acetate (12) (11.21 g, 0.050 mol, purity 99.70%, 5Z7E:5Z7Z:5E7E=81.9:1.6:16.5) in a 100% yield.

[0148] The spectral data of the (5Z,7E)-5,7-dodecadienyl acetate (12) obtained above is shown below. [Nuclear Magnetic Resonance Spectrum] 1H-NMR (500MHz, CDCl3): δ=0.89(3H,t,J=7.3Hz),1.27-1.40(4H,m),1.44(2H,quin-like,J=7.7 Hz),1.64(2H,quin-like,J=6.9Hz),2.04(3H,s),2.09(2H,dt,J=6.9Hz,6.9Hz),2.19(2H,ddt,J =1.5Hz,7.5Hz,7.5Hz),4.06(2H,t,J=6.5Hz),5.26(1H,dt,J=10.7Hz,7.7Hz),5.66(1H,dt,J=7. 3Hz,7.3Hz),5.96(1H,dd,J=11.1Hz,11.1Hz),6.27(1H,dddt,J=15.0Hz,11.1Hz,1.5Hz,1.5Hz); 13 C-NMR (500MHz, CDCl3): δ=13.90,20.96,22.23,25.97,27.15,28.12,31.48,32.52,64.39,125.35,128.96,129.17,135.13,171.17 〔マススペクトル〕EI-マススペクトル(70eV):m / z 224(M + ),181,164,136,121,107,93,79,67,55,43 [Infrared absorption スペクトル] (D-ATR): ν=2956,2928,1742,1365,1238,1042,985,950

Claims

1. The following formula (1): 【Chemistry 01】 (4Z,6E)-4,6-undecadienyl trimethyl acetate represented by the formula:

2. The following general formula (1): 【Chemistry 02】 (4Z,6E)-4,6-undecadienyl trimethyl acetate represented by the following formula (6): 【Chemistry 03】 and obtaining (4Z,6E)-4,6-undecadien-1-ol represented by the formula: The (4Z,6E)-4,6-undecadien-1-ol (6) is halogenated to obtain a compound represented by the following general formula (7): 【Chemistry 04】 (In the formula, X ２ represents a halogen atom.) and obtaining a (4Z,6E)-1-halo-4,6-undecadiene compound represented by the formula: A method for producing a (4Z,6E)-1-halo-4,6-undecadiene compound (7), comprising at least

3. A method for producing a (4Z,6E)-1-halo-4,6-undecadiene compound (7) according to claim 2; The (4Z,6E)-1-halo-4,6-undecadiene compound (7) is reacted with a compound represented by the following general formula (15): 【Chemistry 05】 (Wherein, M is Li or MgZ １ represents Z １ represents a halogen atom or a (4Z,6E)-4,6-undecadienyl group. and converting the compound into a (4Z,6E)-4,6-undecadienyl nucleophile represented by the formula: The (4Z,6E)-4,6-undecadienyl nucleophile (15) is reacted with a compound represented by the following general formula (8): 【Chemistry 06】 (In the formula, R represents an alkyl group having 1 to 6 carbon atoms, which may be the same or different.) By a nucleophilic substitution reaction with an orthoformate compound (8) represented by the following general formula (9): 【Chemistry 07】 (In the formula, R represents an alkyl group having 1 to 6 carbon atoms, which may be the same or different.) obtaining a (5Z,7E)-1,1-dialkoxy-5,7-dodecadiene compound represented by the formula: By the hydrolysis reaction of the (5Z,7E)-1,1-dialkoxy-5,7-dodecadiene compound (9), a compound represented by the following general formula (10): 【Chemistry 08】 and obtaining (5Z,7E)-5,7-dodecadienal represented by the formula: A method for producing (5Z,7E)-5,7-dodecadienal (10), comprising at least

4. A method for producing (5Z,7E)-5,7-dodecadienal (10) according to claim 3; The (5Z,7E)-5,7-dodecadienal (10) is subjected to a reduction reaction to obtain a compound represented by the following formula (11): 【Chemistry 09】 and obtaining (5Z,7E)-5,7-dodecadien-1-ol represented by the formula: A method for producing (5Z,7E)-5,7-dodecadien-1-ol (11), comprising at least

5. A method for producing (5Z,7E)-5,7-dodecadien-1-ol (11) according to claim 4; The (5Z,7E)-5,7-dodecadien-1-ol (11) is acetylated to give the compound represented by the following formula (12): 【Chemistry 10】 and obtaining (5Z,7E)-5,7-dodecadienyl acetate represented by the formula: A method for producing (5Z,7E)-5,7-dodecadienyl acetate (12), comprising at least

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