Methods for producing organic halogen compounds having conjugated double bonds, their acetate compounds and alcohol compounds, and compounds used for synthesizing said organic halogen compounds.

Abstract

To provide (4E,6E,10Z)-4,6,10-hexadecatrienyl halide, which is a synthetic intermediate of the sex pheromone of the cocoa pod borer, and an industrial and economic process for preparing the same.SOLUTION: The present invention provides a process for preparing an organohalogen compound (5), the process at least comprising a step of subjecting an (ω-halo-2-alkenyl)triphenylphosphonium halide compound represented by the general formula (1) in the figure to a phosphorus ylide preparation reaction with an alkali metal alkoxide represented by the general formula (3) in the figure in the presence of a lithium halide represented by the general formula (2) in the figure, and then subjecting the reaction product to a Wittig reaction with an aldehyde compound represented by the general formula (4) in the figure so as to obtain the organohalogen compound represented by the general formula (5) in the figure.SELECTED DRAWING: None

Description

[Technical Field]

[0001] This invention relates to organic halogen compounds having conjugated double bonds, and to methods for producing acetate and alcohol compounds thereof. Furthermore, this invention provides (ω-halo-2-alkenyl)triphenylphosphonium halide compounds, which are compounds used for synthesizing the above-mentioned organic halogen compounds. [Background technology]

[0002] The cocoa pod borer (scientific name: Cocoa pod borer), belonging to the family Gracilidae in the order Lepidoptera. Conopomorpha cramerella Cacao (scientific name: Cacao) is cultivated in Southeast Asia. Theobroma cacao It is known as a major pest of cocoa. The cocoa pod borer lays its eggs on the surface of the cocoa pod, and the hatched larvae penetrate the inside of the pod and feed on the pulp, causing a major problem of reduced cocoa bean yield and quality.

[0003] While insecticides are commonly used to control the cocoa pod borer, their effectiveness is limited because the larvae enter the pod immediately after hatching.

[0004] Furthermore, in recent years, due to the adverse environmental and human health effects of pesticide use, there has been a demand for the development of new pest control technologies that have less environmental impact and are highly safe, such as mating disruption and mass trapping using insect sex pheromone substances. To develop these pest control technologies, it is necessary to manufacture sex pheromone substances industrially, inexpensively, and in large quantities.

[0005] The sex pheromone substance of Cocoa-Pod-Boller is a mixture of (4E,6E,10Z)-4,6,10-hexadecatrienyl acetate, (4E,6Z,10Z)-4,6,10-hexadecatrienyl acetate, (4E,6E,10Z)-4,6,10-hexadecatrienyl alcohol, (4E,6Z,10Z)-4,6,10-hexadecatrienyl alcohol, and n-hexadecyl alcohol, with the component ratio of the sex pheromone substance reported to be 60:40:6:4:10 (see Non-Patent Literature 1 below).

[0006] Among these sex pheromone substances, the acetate compounds, namely (4E,6E,10Z)-4,6,10-hexadecatrienyl acetate and (4E,6Z,10Z)-4,6,10-hexadecatrienyl acetate, are generally known to be synthesized by constructing the double bond at position 6 using the Wittig reaction. Furthermore, (4E,6E,10Z)-4,6,10-hexadecatrienyl alcohol and (4E,6Z,10Z)-4,6,10-hexadecatrienyl alcohol can be synthesized by hydrolysis of the acetate compounds obtained above.

[0007] For example, Non-Patent Document 1 below reports a method for preparing a phosphorus ylide by reacting (4Z)-4-decenyltriphenylphosphonium bromide with potassium t-butoxide as a base, and then synthesizing (4E,6Z,10Z)-4,6,10-hexadecatrienyl acetate by Wittig reaction of the phosphorus ylide with (2E)-6-[(tetrahydropyranyl)oxy]-2-hexenal. Furthermore, Non-Patent Document 1 reports a method for synthesizing (4E,6E,10Z)-4,6,10-hexadecatrienyl acetate by isomerizing the geometric structure of the double bond of the obtained (4E,6E,10Z)-4,6,10-hexadecatrienyl acetate using iodine as a catalyst under sunlight, and then separating and purifying the mixture of isomers using liquid chromatography or a cheletropic reaction with liquid sulfur dioxide.

[0008] Furthermore, Non-Patent Document 2 below reports a method for synthesizing (4E,6Z,10Z)-4,6,10-hexadecatrienyl acetate, similar to that described in Non-Patent Document 1, and a method for synthesizing (4E,6E,10Z)-4,6,10-hexadecatrienyl acetate by reacting (2E)-6-[(tetrahydropyranyl)oxy]-2-hexenyltriphenylphosphonium bromide with n-butyllithium as a base to prepare an ylide, and then reacting the ylide with (4Z)-4-decenal in a Wittig reaction. [Prior art documents] [Non-patent literature]

[0009] [Non-Patent Document 1] PS Beevor et al., J. Chem. Ecol, 12, 1986, 1-23. [Non-Patent Document 2] Yao-Pin Yen et al.,Synth.Commun.,22,1992,1567-1581. [Overview of the project] [Problems that the invention aims to solve]

[0010] However, the synthesis methods for (4E,6Z,10Z)-4,6,10-hexadecatrienyl acetate described in Non-Patent Documents 1 and 2 yield geometric isomers with a double bond structure of (4E,6Z,10Z) as the main product. Therefore, in order to obtain the geometric isomer ratio of the cocoa-pod-bohler sex pheromone substance, it was necessary to synthesize (4E,6E,10Z)-4,6,10-hexadecatrienyl acetate separately and mix them to obtain the desired geometric isomer ratio.

[0011] Furthermore, the synthesis method for (4E,6E,10Z)-4,6,10-hexadecatrienyl acetate described in Non-Patent Literature 1 had several problems, including extremely low yields in the separation and purification method using liquid chromatography from the isomer mixture obtained from the isomerization reaction of (4E,6Z,10Z)-4,6,10-hexadecatrienyl acetate, and the high toxicity of sulfur dioxide and the inability of the reaction to proceed when scaled up in the separation and purification method using the chelatepy reaction with liquid sulfur dioxide.

[0012] Furthermore, the synthesis method for (4E,6E,10Z)-4,6,10-hexadecatrienyl acetate described in Non-Patent Literature 2 had several problems, including the need to use a flammable organolithium compound and the requirement of a reaction at an extremely low temperature of -78°C.

[0013] Thus, with conventional technology, industrial and economical mass production was impossible.

[0014] This invention has been made in view of the above circumstances, and aims to solve the problems of the prior art and provide an industrial and economical method for producing (4E,6E,10Z)-4,6,10-hexadecatrienyl halide and (4E,6Z,10Z)-4,6,10-hexadecatrienyl halide, which are synthetic intermediates for cocoa-pod-borer sex pheromone substances.

[0015] Furthermore, the present invention aims to provide an industrial and economical method for producing (4E,6E,10Z)-4,6,10-hexadecatrienyl acetate and (4E,6Z,10Z)-4,6,10-hexadecatrienyl acetate, as well as (4E,6E,10Z)-4,6,10-hexadecatrienyl alcohol and (4E,6Z,10Z)-4,6,10-hexadecatrienyl alcohol, which are sex pheromone substances of cocoa pod borer, using the above-mentioned organic halogen compound as an intermediate. [Means for solving the problem]

[0016] As a result of diligent research, the present inventors have found that a novel compound, the (ω-halo-2-alkenyl)triphenylphosphonium=halide compound, can be prepared by reacting the (ω-halo-2-alkenyl)triphenylphosphonium=halide compound with an alkali metal alkoxide as a base in the presence of lithium halide to obtain a reaction product mixture, and by subjecting this reaction product mixture and an aldehyde compound to a Wittig reaction, an organic halogen compound having a conjugated double bond can be produced in high yield, without using toxic and flammable raw materials, and within a reaction temperature range that is easily applicable industrially. This has led to the present invention.

[0017] Furthermore, the present inventors have discovered that by subjecting the obtained organic halogen compound to an acetoxylation reaction, an acetate compound having a conjugated double bond can be efficiently and industrially produced in a short number of steps, thus concluding the present invention.

[0018] Furthermore, the inventors have discovered that by subjecting the acetate compound to a hydrolysis reaction, an alcohol compound having a conjugated double bond can be efficiently and industrially produced in a short number of steps, thus leading to the present invention.

[0019] One aspect of the present invention is the following general formula (1): [ka] (In the formula, n represents the number of methylene groups from 1 to 10, X 1 and X 2 (The '' represents halogen atoms that may be the same or different from each other, and 'Ph' represents a phenyl group.) (ω-halo-2-alkenyl)triphenylphosphonium halide compounds represented by The following general formula (2): [ka] (In the formula, X 3 (This represents a halogen atom.) In the presence of lithium halide represented by the following general formula (3): [ka] (In the formula, R 1 (where represents a linear or branched alkyl group having 1 to 6 carbon atoms, and M represents an alkali metal atom.) An alkali metal alkosyl represented by the following general formula (4) is subjected to a phosphorus ylide preparation reaction to obtain a reaction product mixture, and then the reaction product mixture is mixed with the following general formula (4): [ka] (In the formula, R 2 (This represents a monovalent hydrocarbon group having 1 to 10 carbon atoms, which can be linear, branched, or aromatic.) When an aldehyde compound represented by is subjected to the Wittig reaction, the following general formula (5): [ka] (In the formula, R 2 In the above general formula (4), n and X 2 This is defined as in the general formula (1) above. The present invention provides a method for producing an organic halogen compound (5), which includes at least a step of obtaining an organic halogen compound represented by [the given formula].

[0020] Also, as another aspect of the present invention, the method for producing the organic halogen compound (5) described above, and subjecting the organic halogen compound (5) to an acetoxylation reaction to obtain an acetate compound having a conjugated double bond represented by the following general formula (6):

Chemical formula

[0021] Also, as yet another aspect of the present invention, the method for producing the acetate compound (6) described above, and subjecting the acetate compound (6) to a hydrolysis reaction to obtain an alcohol compound having a conjugated double bond represented by the following general formula (7):

Chemical formula

[0022] Furthermore, as another aspect of the present invention, the following general formula (8):

Chemical formula

Chemical formula

[0023] Furthermore, one aspect of the present invention is the following general formula (1): [ka] (In the formula, n represents the number of methylene groups from 1 to 10, X 1 and X 2 (The '' represents halogen atoms that may be the same or different from each other, and 'Ph' represents a phenyl group.) The present invention provides (ω-halo-2-alkenyl)triphenylphosphonium halide compound (1) represented by [formula]. [Effects of the Invention]

[0024] According to the present invention, organic halogen compounds having conjugated double bonds can be produced in high yield within an industrially applicable reaction temperature range without using toxic and flammable raw materials. Furthermore, according to the present invention, acetate compounds having conjugated double bonds can be produced efficiently and industrially in a short number of steps by subjecting the obtained organic halogen compounds to an acetoxylation reaction. Moreover, according to the present invention, alcohol compounds having conjugated double bonds can be produced efficiently and industrially in a short number of steps by subjecting the obtained acetate compounds to a hydrolysis reaction.

[0025] Furthermore, the novel compound (ω-halo-2-alkenyl)triphenylphosphonium halide compound (1) is found in the Western avocado leafroller, a species of tortricidal moth (Tortricidae family). Amorbia cuneata A mixture of (10E,12E)-10,12-tetradecadienyl acetate and (10E,12Z)-10,12-tetradecadienyl acetate, which are sex pheromone substances of Tortricidae insects (scientific name: Eucosma abandoned It is also effective as a synthetic intermediate for a mixture of (7E,9E)-7,9-decadienyl acetate and (7E,9Z)-7,9-decadienyl acetate, which are attractants of ). [Modes for carrying out the invention]

[0026] The following describes in detail embodiments for carrying out the present invention, but the present invention is not limited thereto.

[0027] A. The novel compound (ω-halo-2-alkenyl)triphenylphosphonium halide, represented by the general formula (1) below, will be explained below. [ka]

[0028] In the above general formula (1), n ​​represents the number of methylene groups from 1 to 10, and X 1 and X 2 represents halogen atoms that may be the same or different from each other, and Ph represents a phenyl group.

[0029] When n in the above general formula (1) is 1, 2, 3, 4, 5, 6, 7, 8, 9 and 10, the compounds are (6-halo-2-hexenyl)triphenylphosphonium halide (n=1), (7-halo-2-heptenyl)triphenylphosphonium halide (n=2), (8-halo-2-octenyl)triphenylphosphonium halide (n=3), (9-halo-2-nonenyl)triphenylphosphonium halide (n=4), (10-halo-2-decenyl)triphenylphosphonium halide (n=5), (11-halo Examples include (2-undecenyl)triphenylphosphonium halide (n=6), (12-halo-2-dodecenyl)triphenylphosphonium halide (n=7), (13-halo-2-tridecenyl)triphenylphosphonium halide (n=8), (14-halo-2-tetradecenyl)triphenylphosphonium halide (n=9), and (15-halo-2-pentadecenyl)triphenylphosphonium halide (n=10). From the viewpoint of the structural effectiveness of the obtained product, n is preferably 1 to 8, and more preferably 1 to 4.

[0030] Furthermore, in the above general formula (1), X 1 and X 2 The terms represent halogen atoms that may be the same or different from each other, and examples of such halogen atoms include chlorine atoms, bromine atoms, and iodine atoms.

[0031] In the above general formula (1), X 1 and X 2 The combination of halogen atoms may be the same or different, and as a compound, (ω-chloro-2-alkenyl)triphenylphosphonium=chloride (X 1 =Cl,X 2 =Cl), (ω-bromo-2-alkenyl)triphenylphosphonium chloride (X 1 =Cl,X 2 =Br) and (ω-iodo-2-alkenyl)triphenylphosphonium chloride (X 1 =Cl,X 2(ω-halo-2-alkenyl)triphenylphosphonium chloride compounds such as (I) and (ω-chloro-2-alkenyl)triphenylphosphonium bromide (X 1 =Br,X 2 =Cl), (ω-bromo-2-alkenyl)triphenylphosphonium=bromide(X 1 =Br,X 2 =Br) and (ω-iodo-2-alkenyl)triphenylphosphonium=bromide(X 1 =Br,X 2 (ω-halo-2-alkenyl)triphenylphosphonium=bromide compounds such as (I); and (ω-chloro-2-alkenyl)triphenylphosphonium=iodide (X 1 =I,X 2 =Cl), (ω-bromo-2-alkenyl)triphenylphosphonium=iodide(X 1 =I,X 2 =Br) and (ω-iodine-2-alkenyl)triphenylphosphonium=iodide(X 1 =I,X 2 Examples include (ω-halo-2-alkenyl)triphenylphosphonium=iodide compounds such as (I), and from the viewpoint of reactivity and / or selectivity, (ω-chloro-2-alkenyl)triphenylphosphonium=chloride (X 1 =Cl,X 2 =Cl), (ω-chloro-2-alkenyl)triphenylphosphonium=bromide(X 1 =Br,X 2 =Cl), (ω-bromo-2-alkenyl)triphenylphosphonium=bromide(X 1 =Br,X 2 =Br), (ω-chloro-2-alkenyl)triphenylphosphonium=iodide(X 1 =I,X 2 =Cl), (ω-bromo-2-alkenyl)triphenylphosphonium=iodide(X 1 =I,X 2 =Br), and (ω-iodo-2-alkenyl)triphenylphosphonium=iodide(X 1 =I,X 2 =I) Preferred.

[0032] Examples of the above (ω-halo-2-alkenyl)triphenylphosphonium halide compounds (1) include the following compounds: (ω-chloro-2-alkenyl)triphenylphosphonium chloride compounds such as (6-chloro-2-hexenyl)triphenylphosphonium chloride, (7-chloro-2-heptenyl)triphenylphosphonium chloride, (8-chloro-2-octenyl)triphenylphosphonium chloride, (9-chloro-2-nonenyl)triphenylphosphonium chloride, (10-chloro-2-decenyl)triphenylphosphonium chloride, (11-chloro-2-undecenyl)triphenylphosphonium chloride, (12-chloro-2-dodecenyl)triphenylphosphonium chloride, (13-chloro-2-tridecenyl)triphenylphosphonium chloride, (14-chloro-2-tetradecenyl)triphenylphosphonium chloride, and (15-chloro-2-pentadecenyl)triphenylphosphonium chloride; (6-bromo-2-hexenyl)triphenylphosphonium chloride, (7-bromo-2-heptenyl)triphenylphosphonium chloride, (8-bromo-2-octenyl)triphenylphosphonium chloride, (9-bromo-2-nonenyl)triphenylphosphonium chloride, (10-bromo-2-decenyl)triphenylphosphonium chloride, (11-bromo-2-undecenyl)triphenylphosphonium chloride (ω-bromo-2-alkenyl)triphenylphosphonium chloride compounds such as phonium chloride, (12-bromo-2-dodecenyl)triphenylphosphonium chloride, (13-bromo-2-tridecenyl)triphenylphosphonium chloride, (14-bromo-2-tetradecenyl)triphenylphosphonium chloride, and (15-bromo-2-pentadecenyl)triphenylphosphonium chloride; (6-iodo-2-hexenyl)triphenylphosphonium chloride, (7-iodo-2-heptenyl)triphenylphosphonium chloride, (8-iodo-2-octenyl)triphenylphosphonium chloride, (9-iodo-2-nonenyl)triphenylphosphonium chloride, (10-iodo-2-decenyl)triphenylphosphonium chloride, (11-iodo-2-undecenyl)triphenylphosphonium chloride (ω-iodo-2-alkenyl)triphenylphosphonium chloride compounds such as phonium chloride, (12-iodo-2-dodecenyl)triphenylphosphonium chloride, (13-iodo-2-tridecenyl)triphenylphosphonium chloride, (14-iodo-2-tetradecenyl)triphenylphosphonium chloride, and (15-iodo-2-pentadecenyl)triphenylphosphonium chloride; (ω-chloro-2-alkenyl)triphenylphosphonium=bromide compounds such as (6-chloro-2-hexenyl)triphenylphosphonium=bromide, (7-chloro-2-heptenyl)triphenylphosphonium=bromide, (8-chloro-2-octenyl)triphenylphosphonium=bromide, (9-chloro-2-nonenyl)triphenylphosphonium=bromide, (10-chloro-2-decenyl)triphenylphosphonium=bromide, (11-chloro-2-undecenyl)triphenylphosphonium=bromide, (12-chloro-2-dodecenyl)triphenylphosphonium=bromide, (13-chloro-2-tridecenyl)triphenylphosphonium=bromide, (14-chloro-2-tetradecenyl)triphenylphosphonium=bromide, and (15-chloro-2-pentadecenyl)triphenylphosphonium=bromide; (6-bromo-2-hexenyl)triphenylphosphonium=bromide, (7-bromo-2-heptenyl)triphenylphosphonium=bromide, (8-bromo-2-octenyl)triphenylphosphonium=bromide, (9-bromo-2-nonenyl)triphenylphosphonium=bromide, (10-bromo-2-decenyl)triphenylphosphonium=bromide, (11-bromo-2-undecenyl)triphenylphosphonium=bromide (ω-bromo-2-alkenyl)triphenylphosphonium bromide compounds such as honium bromide, (12-bromo-2-dodecenyl)triphenylphosphonium bromide, (13-bromo-2-tridecenyl)triphenylphosphonium bromide, (14-bromo-2-tetradecenyl)triphenylphosphonium bromide, and (15-bromo-2-pentadecenyl)triphenylphosphonium bromide; (6-iodo-2-hexenyl)triphenylphosphonium=bromide, (7-iodo-2-heptenyl)triphenylphosphonium=bromide, (8-iodo-2-octenyl)triphenylphosphonium=bromide, (9-iodo-2-nonenyl)triphenylphosphonium=bromide, (10-iodo-2-decenyl)triphenylphosphonium=bromide, (11-iodo-2-undecenyl)triphenylphosphonium=bromide (ω-iodo-2-alkenyl)triphenylphosphonium bromide compounds such as honium bromide, (12-iodo-2-dodecenyl)triphenylphosphonium bromide, (13-iodo-2-tridecenyl)triphenylphosphonium bromide, (14-iodo-2-tetradecenyl)triphenylphosphonium bromide, and (15-iodo-2-pentadecenyl)triphenylphosphonium bromide; (ω-chloro-2-alkenyl)triphenylphosphonium=iodide compounds such as (6-chloro-2-hexenyl)triphenylphosphonium=iodide, (7-chloro-2-heptenyl)triphenylphosphonium=iodide, (8-chloro-2-octenyl)triphenylphosphonium=iodide, (9-chloro-2-nonenyl)triphenylphosphonium=iodide, (10-chloro-2-decenyl)triphenylphosphonium=iodide, (11-chloro-2-undecenyl)triphenylphosphonium=iodide, (12-chloro-2-dodecenyl)triphenylphosphonium=iodide, (13-chloro-2-tridecenyl)triphenylphosphonium=iodide, (14-chloro-2-tetradecenyl)triphenylphosphonium=iodide, and (15-chloro-2-pentadecenyl)triphenylphosphonium=iodide; (6-bromo-2-hexenyl)triphenylphosphonium=iodide, (7-bromo-2-heptenyl)triphenylphosphonium=iodide, (8-bromo-2-octenyl)triphenylphosphonium=iodide, (9-bromo-2-nonenyl)triphenylphosphonium=iodide, (10-bromo-2-decenyl)triphenylphosphonium=iodide, (11-bromo-2-undecenyl)triphenylphosphonium=iodide (ω-bromo-2-alkenyl)triphenylphosphonium=iodide compounds such as ω-bromo-2-alkenyl)triphenylphosphonium=iodide, (13-bromo-2-tridecenyl)triphenylphosphonium=iodide, (14-bromo-2-tetradecenyl)triphenylphosphonium=iodide and (15-bromo-2-pentadecenyl)triphenylphosphonium=iodide; and, (6-iodo-2-hexenyl)triphenylphosphonium=iodide, (7-iodo-2-heptenyl)triphenylphosphonium=iodide, (8-iodo-2-octenyl)triphenylphosphonium=iodide, (9-iodo-2-nonenyl)triphenylphosphonium=iodide, (10-iodo-2-decenyl)triphenylphosphonium=iodide, (11-iodo-2-undecenyl)triphenylphosphonium (ω-iodo-2-alkenyl)triphenylphosphonium=iodide compounds such as honium=iodide, (12-iodo-2-dodecenyl)triphenylphosphonium=iodide, (13-iodo-2-tridecenyl)triphenylphosphonium=iodide, (14-iodo-2-tetradecenyl)triphenylphosphonium=iodide, and (15-iodo-2-pentadecenyl)triphenylphosphonium=iodide.

[0033] Furthermore, examples of the above (ω-halo-2-alkenyl)triphenylphosphonium halide compound (1) include mixtures of cis-trans isomers of the double bond portion.

[0034] Next, the method for producing the above (ω-halo-2-alkenyl)triphenylphosphonium=halide compound (1) will be described below.

[0035] The (ω-halo-2-alkenyl)triphenylphosphonium halide compound (1) can be obtained, for example, by subjecting an ω-halo-2-alkenyl halide compound represented by the following general formula (8) to a substitution reaction with triphenylphosphine, as shown in the reaction equation below.

[0036] [ka]

[0037] The above-mentioned synthesis method for the (ω-halo-2-alkenyl)triphenylphosphonium halide compound (1) will be described in more detail below.

[0038] The above ω-halo-2-alkenyl halide compound (8) as the starting material will be described below.

[0039] In the above general formula (8), n, X 1 and X 2 are as defined in the above general formula (1).

[0040] When n in the above general formula (8) is 1, 2, 3, 4, 5, 6, 7, 8, 9, and 10, examples of the compound include 6-halo-2-hexenyl halide (n = 1), 7-halo-2-heptenyl halide (n = 2), 8-halo-2-octenyl halide (n = 3), 9-halo-2-nonenyl halide (n = 4), 10-halo-2-decenyl halide (n = 5), 11-halo-2-undecenyl halide (n = 6), 12-halo-2-dodecenyl halide (n = 7), 13-halo-2-tridecenyl halide (n = 8), 14-halo-2-tetradecenyl halide (n = 9), and 15-halo-2-pentadecenyl halide (n = 10), etc.

[0041] In the above general formula (8), X 1 and X 2 The combination of halogen atoms may be the same as or different from each other. Examples of the compound include ω-chloro-2-alkenyl chloride (X 1 = Cl, X 2 = Cl), ω-bromo-2-alkenyl chloride (X 1 = Cl, X 2 = Br), and ω-iodo-2-alkenyl chloride (X 1 = Cl, X 2 = I), etc. of ω-halo-2-alkenyl chloride compounds; ω-chloro-2-alkenyl bromide (X 1 = Br, X 2 = Cl), ω-bromo-2-alkenyl bromide (X 1 = Br, X 2 = Br), and ω-iodo-2-alkenyl bromide (X 1 = Br, X 2ω-halo-2-alkenyl bromide compounds such as (I); and ω-chloro-2-alkenyl iodide (X 1 =I,X 2 =Cl), ω-bromo-2-alkenyl=iodide(X 1 =I,X 2 =Br) and ω-iodine-2-alkenyl=iodide(X 1 =I,X 2 Examples include ω-halo-2-alkenyl iodide compounds such as (I), and from the viewpoint of reactivity and / or selectivity, ω-chloro-2-alkenyl chloride (X 1 =Cl,X 2 =Cl), ω-chloro-2-alkenyl=bromide(X 1 =Br,X 2 =Cl), ω-bromo-2-alkenyl=bromide(X 1 =Br,X 2 =Br), ω-chloro-2-alkenyl=iodide(X 1 =I,X 2 =Cl), ω-bromo-2-alkenyl=iodide(X 1 =I,X 2 =Br) and ω-iodine-2-alkenyl=iodide(X 1 =I,X 2 =I) Preferred.

[0042] Examples of the above ω-halo-2-alkenyl halide compounds (8) include the following compounds: ω-chloro-2-alkenyl chloride compounds such as 6-chloro-2-hexenyl chloride, 7-chloro-2-heptenyl chloride, 8-chloro-2-octenyl chloride, 9-chloro-2-nonenyl chloride, 10-chloro-2-decenyl chloride, 11-chloro-2-undecenyl chloride, 12-chloro-2-dodecenyl chloride, 13-chloro-2-tridecenyl chloride, 14-chloro-2-tetradecenyl chloride, and 15-chloro-2-pentadecenyl chloride; ω-bromo-2-alkenyl chloride compounds such as 6-bromo-2-hexenyl chloride, 7-bromo-2-heptenyl chloride, 8-bromo-2-octenyl chloride, 9-bromo-2-nonenyl chloride, 10-bromo-2-decenyl chloride, 11-bromo-2-undecenyl chloride, 12-bromo-2-dodecenyl chloride, 13-bromo-2-tridecenyl chloride, 14-bromo-2-tetradecenyl chloride, and 15-bromo-2-pentadecenyl chloride; ω-iodo-2-alkenyl chloride compounds such as 6-iodo-2-hexenyl chloride, 7-iodo-2-heptenyl chloride, 8-iodo-2-octenyl chloride, 9-iodo-2-nonenyl chloride, 10-iodo-2-decenyl chloride, 11-iodo-2-undecenyl chloride, 12-iodo-2-dodecenyl chloride, 13-iodo-2-tridecenyl chloride, 14-iodo-2-tetradecenyl chloride, and 15-iodo-2-pentadecenyl chloride; ω-chloro-2-alkenyl bromide compounds such as 6-chloro-2-hexenyl bromide, 7-chloro-2-heptenyl bromide, 8-chloro-2-octenyl bromide, 9-chloro-2-nonenyl bromide, 10-chloro-2-decenyl bromide, 11-chloro-2-undecenyl bromide, 12-chloro-2-dodecenyl bromide, 13-chloro-2-tridecenyl bromide, 14-chloro-2-tetradecenyl bromide, and 15-chloro-2-pentadecenyl bromide; ω-bromo-2-alkenyl bromide compounds such as 6-bromo-2-hexenyl bromide, 7-bromo-2-heptenyl bromide, 8-bromo-2-octenyl bromide, 9-bromo-2-nonenyl bromide, 10-bromo-2-decenyl bromide, 11-bromo-2-undecenyl bromide, 12-bromo-2-dodecenyl bromide, 13-bromo-2-tridecenyl bromide, 14-bromo-2-tetradecenyl bromide, and 15-bromo-2-pentadecenyl bromide; ω-iodo-2-alkenyl bromide compounds such as 6-iodo-2-hexenyl bromide, 7-iodo-2-heptenyl bromide, 8-iodo-2-octenyl bromide, 9-iodo-2-nonenyl bromide, 10-iodo-2-decenyl bromide, 11-iodo-2-undecenyl bromide, 12-iodo-2-dodecenyl bromide, 13-iodo-2-tridecenyl bromide, 14-iodo-2-tetradecenyl bromide, and 15-iodo-2-pentadecenyl bromide; ω-chloro-2-alkenyl iodide compounds such as 6-chloro-2-hexenyl iodide, 7-chloro-2-heptenyl iodide, 8-chloro-2-octenyl iodide, 9-chloro-2-nonenyl iodide, 10-chloro-2-decenyl iodide, 11-chloro-2-undecenyl iodide, 12-chloro-2-dodecenyl iodide, 13-chloro-2-tridecenyl iodide, 14-chloro-2-tetradecenyl iodide, and 15-chloro-2-pentadecenyl iodide; ω-bromo-2-alkenyl iodide compounds such as 6-bromo-2-hexenyl iodide, 7-bromo-2-heptenyl iodide, 8-bromo-2-octenyl iodide, 9-bromo-2-nonenyl iodide, 10-bromo-2-decenyl iodide, 11-bromo-2-undecenyl iodide, 12-bromo-2-dodecenyl iodide, 13-bromo-2-tridecenyl iodide, 14-bromo-2-tetradecenyl iodide and 15-bromo-2-pentadecenyl iodide; and, ω-iodo-2-alkenyl=iodide compounds such as 6-iodo-2-hexenyl=iodide, 7-iodo-2-heptenyl=iodide, 8-iodo-2-octenyl=iodide, 9-iodo-2-nonenyl=iodide, 10-iodo-2-decenyl=iodide, 11-iodo-2-undecenyl=iodide, 12-iodo-2-dodecenyl=iodide, 13-iodo-2-tridecenyl=iodide, 14-iodo-2-tetradecenyl=iodide, and 15-iodo-2-pentadecenyl=iodide.

[0043] Furthermore, examples of the above-mentioned ω-halo-2-alkenyl halide compound (8) include mixtures of cis-trans isomers of the double bond portion.

[0044] Furthermore, the above-mentioned ω-halo-2-alkenyl halide compound (8) may be a commercially available product or may be independently synthesized.

[0045] The substitution reaction between the above ω-halo-2-alkenyl halide compound (8) and triphenylphosphine can be carried out under heating or cooling as necessary.

[0046] The triphenylphosphine used in the substitution reaction may be commercially available, either purified or unpurified.

[0047] The amount of triphenylphosphine used in the substitution reaction is preferably 0.2 to 5.0 moles per mole of the above ω-halo-2-alkenyl halide compound (8), more preferably 0.5 to 3.0 moles, and even more preferably 0.8 to 2.0 moles, from the viewpoint of yield and / or reactivity.

[0048] Any solvent that does not adversely affect the substitution reaction can be used as the solvent for the substitution reaction. For example, halogenated solvents such as methylene chloride, chloroform, carbon tetrachloride, and 1,2-dichloroethane; ether solvents such as diethyl ether, di-n-butyl ether, di-t-butyl ether, tetrahydrofuran, 2-methyltetrahydrofuran, 4-methyltetrahydropyran, 1,4-dioxane, and diethylene glycol-dimethyl ether; hydrocarbon solvents such as hexane, heptane, benzene, toluene, and xylene; ketone solvents such as acetone, methyl ethyl ketone, isobutyl methyl ketone, and cyclohexanone; methyl alcohol, ethyl alcohol, n-butyl methyl ketone, etc. Examples of solvents include alcoholic solvents such as propyl alcohol, isopropyl alcohol, isobutyl alcohol, ethylene glycol, propylene glycol, and benzyl alcohol; esteric solvents such as ethyl acetate, n-propyl acetate, n-butyl acetate, and isobutyl acetate; nitrile solvents such as acetonitrile; and aprotic polar solvents such as N,N-dimethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide, and hexamethylphosphoric triamide. From the viewpoint of reactivity, etheric solvents, hydrocarbon solvents, nitrile solvents, and aprotic polar solvents are preferred.

[0049] The solvent may be one type or, if necessary, two or more types, and can be arbitrarily selected considering the reactivity and / or selectivity of the ω-halo-2-alkenyl halide compound (8). A commercially available solvent may be used after purification or in its unpurified state.

[0050] The amount of solvent used in the substitution reaction can be arbitrarily selected considering the reactivity of the ω-halo-2-alkenyl=halide compound (8). For example, 100g to 10000g is preferred per mole of the ω-halo-2-alkenyl=halide compound (8), more preferably 200g to 5000g, and even more preferably 300g to 2000g from the viewpoint of reactivity and / or economy.

[0051] The reaction temperature for the substitution reaction can be arbitrarily selected considering the reactivity and / or yield of the ω-halo-2-alkenyl halide compound (8). For example, -30°C to 200°C is preferred, 0°C to 150°C is more preferred from the viewpoint of reactivity and / or impurity formation, and 20°C to 100°C is even more preferred.

[0052] The reaction time for the substitution reaction is preferably optimized by tracking the progress of the reaction using gas chromatography and / or thin-layer chromatography and / or nuclear magnetic resonance spectroscopy to confirm the disappearance of the ω-halo-2-alkenyl=halide compound (8) and / or triphenylphosphine, and by monitoring the reaction progress using gas chromatography and / or thin-layer chromatography and / or nuclear magnetic resonance spectroscopy, etc., depending on the reactivity of the ω-halo-2-alkenyl=halide compound (8). For example, 0.5 to 72 hours is usually preferred, 0.5 to 24 hours is more preferred from the viewpoint of yield and / or impurity generation, and 0.5 to 12 hours is even more preferred.

[0053] The isolation and / or purification of the (ω-halo-2-alkenyl)triphenylphosphonium=halide compound (1) obtained by the substitution reaction can be appropriately selected from conventional purification methods in organic synthesis, such as vacuum distillation and / or recrystallization and / or various types of chromatography. However, recrystallization is preferred from the viewpoint of the physical properties of the (ω-halo-2-alkenyl)triphenylphosphonium=halide compound (1) and / or industrial economics. Furthermore, if the (ω-halo-2-alkenyl)triphenylphosphonium=halide compound (1) obtained by the substitution reaction has sufficient purity, the crude product may be used directly in the next step without isolation and purification. For example, after the substitution reaction, the solution and / or suspension, which are the reaction product mixture, may be used directly in the next step.

[0054] B. Next, the method for producing organic halogen compounds represented by the following general formula (5) will be described below.

[0055] The organic halogen compound (5) is obtained by subjecting the (ω-halo-2-alkenyl) triphenylphosphonium halide compound (1) to a phosphorus ylide preparation reaction by reacting it with an alkali metal alkoxide represented by the following general formula (3) in the presence of lithium halide represented by the following general formula (2) to obtain a reaction product mixture, and then subjecting the reaction product mixture and an aldehyde compound represented by the following general formula (4) to a Wittig reaction, as shown in the following reaction formula.

[0056]

Chemical formula

[0057] The starting material, the (ω-halo-2-alkenyl) triphenylphosphonium halide compound (1), is as described above.

[0058] Next, the organic halogen compound (5) obtained by the above phosphorus ylide preparation reaction and subsequent Wittig reaction will be described below.

[0059] In the above general formula (5), R 2 represents a linear, branched or aromatic monovalent hydrocarbon group having 1 to 10 carbon atoms, and n and X 2 are as defined in the above general formula (1).

[0060] In the above general formula (5), R 2 Examples of R include linear saturated monovalent hydrocarbon groups such as methyl group, ethyl group, n-propyl group, n-butyl group, n-pentyl group, n-heptyl group and n-nonyl group; linear unsaturated monovalent hydrocarbon groups such as vinyl group, 1-propenyl group, 1-butenyl group, 5-hexenyl group and (3Z)-3-nonenyl group; branched saturated monovalent hydrocarbon groups such as 2-methylpropyl group, 2-methyl-2-propyl group, 2-pentyl group and 3-methylheptyl group; branched unsaturated monovalent hydrocarbon groups such as 2-methyl-1-propenyl group and 3-methyl-3-butenyl group; and aromatic monovalent hydrocarbon groups such as phenyl group.

[0061] When the organic halogen compound (5) is synthesized from the (ω-halo-2-alkenyl)triphenylphosphonium halide compound (1), n and X in the general formula (5) 2 are respectively the n and X selected in the general formula (1), 2 and when synthesized from the aldehyde compound (4), R in the general formula (5) 2 is the R selected in the general formula (4) 2 and remains unchanged.

[0062] Examples of the organic halogen compound (5) include the following compounds: (10Z)-4,6,10-hexadecatrienyl chloride, 4,6-hexadecadienyl chloride, 7,9-tetradecadienyl chloride, 7,9-dodecadienyl chloride, (11E)-7,9,11-tridecatrienyl chloride, 11,13-hexadecadienyl chloride and other linear organic chlorine compounds; 10-methyl-4,6,10-undecatrienyl chloride, 8,8-dimethyl-4,6-nonadienyl chloride, 11-methyl-7,9-tetradecadienyl chloride, 12-methyl-7,9,11-tridecatrienyl chloride, 14-methyl-9,11,13-pentadecatrienyl chloride and other branched organic chlorine compounds; 7-phenyl-4,6-heptadienyl chloride, 10-phenyl-7,9-decadienyl chloride and other aromatic organic chlorine compounds; (10Z)-4,6,10-hexadecatrienyl bromide, 4,6-hexadecadienyl bromide, 7,9-tetradecadienyl bromide, 7,9-dodecadienyl bromide, (11E)-7,9,11-tridecatrienyl bromide, 11,13-hexadecadienyl bromide and other linear organic bromine compounds; Branched organobromine compounds such as 10-methyl-4,6,10-undecatrienyle=bromide, 8,8-dimethyl-4,6-nonadienyl=bromide, 11-methyl-7,9-tetradecadienyl=bromide, 12-methyl-7,9,11-tridecatrienyle=bromide, and 14-methyl-9,11,13-pentadecatrienyle=bromide; Aromatic organobromine compounds such as 7-phenyl-4,6-heptadienyl bromide and 10-phenyl-7,9-decadienyl bromide; Linear organiodine compounds such as (10Z)-4,6,10-hexadecadiennyl=iodide, 4,6-hexadecadiennyl=iodide, 7,9-tetradecadienyl=iodide, 7,9-dodecadiennyl=iodide, (11E)-7,9,11-tridecatriennyl=iodide, and 11,13-hexadecadiennyl=iodide; Branched organioid compounds such as 10-methyl-4,6,10-undecatrienylon=iodide, 8,8-dimethyl-4,6-nonadienyl=iodide, 11-methyl-7,9-tetradecadienyl=iodide, 12-methyl-7,9,11-tridecatrienylon=iodide and 14-methyl-9,11,13-pentadecatrienylon=iodide; and, Aromatic organioidone compounds such as 7-phenyl-4,6-heptadienyl iodide and 10-phenyl-7,9-decadienyl iodide.

[0063] Furthermore, examples of the above-mentioned organic halogen compound (5) include enantiomers, diastereomers, and mixtures of equal and non-equal amounts of these stereoisomers.

[0064] The above phosphorus ylide preparation reaction can be carried out using an alkali metal alkosoxide (3) in the presence of lithium halide (2), and can be carried out under heating or cooling as necessary.

[0065] X in the above general formula (2) 3 The symbol represents a halogen atom, and examples of halogen atoms include chlorine atoms, bromine atoms, and iodine atoms.

[0066] Examples of lithium halide (2) include lithium chloride, lithium bromide, and lithium iodide, with lithium chloride and lithium bromide being preferred from the viewpoint of reactivity and / or economics. One type of lithium halide (2) or two or more types may be used as needed, and commercially available products may be used after purification or in their unpurified state.

[0067] The amount of lithium halide (2) used varies depending on the reactivity of the starting material, (ω-halo-2-alkenyl)triphenylphosphonium=halide compound (1). However, 0.1 to 5.0 moles are preferred per mole of (ω-halo-2-alkenyl)triphenylphosphonium=halide compound (1), more preferably 0.5 to 3.0 moles, and even more preferably 0.8 to 2.0 moles from an economic standpoint.

[0068] In the above general formula (3), R 1 represents a linear or branched alkyl group having 1 to 6 carbon atoms, and M represents an alkali metal atom. In the above general formula (3), R 1 From the viewpoint of availability and / or ease of preparation, preferred examples include linear alkyl groups such as methyl and ethyl groups, and branched alkyl groups such as t-butyl, 2-methyl-2-butyl, and cyclohexyl groups.

[0069] Examples of alkali metal atoms include lithium atoms, sodium atoms, and potassium atoms.

[0070] Examples of the alkali metal alkoxide (3) include lithium alkoxides such as lithium methoxide, lithium ethoxide, lithium t-butoxide, lithium 2-methyl-2-butoxide, and lithium cyclohexanoxide; sodium alkoxides such as sodium methoxide, sodium ethoxide, sodium t-butoxide, sodium 2-methyl-2-butoxide, and sodium cyclohexanoxide; and potassium alkoxides such as potassium methoxide, potassium ethoxide, potassium t-butoxide, potassium 2-methyl-2-butoxide, and potassium cyclohexanoxide. From the viewpoint of reactivity and / or yield, sodium t-butoxide and potassium t-butoxide are more preferred.

[0071] The alkali metal alkosoxide (3) may be one type or, if necessary, two or more types, and may be a commercially available product, either purified or unpurified.

[0072] The alkali metal alkosoxide (3) can be used in solution, which is obtained by dissolving it in a solvent or the like.

[0073] Examples of the above solvents include alcoholic solvents such as methyl alcohol, ethyl alcohol, t-butyl alcohol, 2-methyl-2-butyl alcohol, and cyclohexyl alcohol; etheric solvents such as diethyl ether, di-n-butyl ether, di-t-butyl ether, tetrahydrofuran, 2-methyltetrahydrofuran, 4-methyltetrahydropyran, 1,4-dioxane, and diethylene glycol dimethyl ether; and aromatic hydrocarbon solvents such as benzene, toluene, and xylene. One or more types may be used as needed.

[0074] The amount of alkali metal alkosoxide (3) used in the phosphorus ylide preparation reaction varies depending on the reactivity of the starting material, (ω-halo-2-alkenyl)triphenylphosphonium=halide compound (1). However, 0.1 to 5.0 moles are preferred per mole of (ω-halo-2-alkenyl)triphenylphosphonium=halide compound (1), more preferably 0.5 to 3.0 moles, and even more preferably 0.8 to 2.0 moles from an economic standpoint.

[0075] Any solvent can be used as the solvent for the phosphorus ylide preparation reaction, as long as it does not adversely affect the reaction. Examples include ether-based solvents such as diethyl ether, di-n-butyl ether, di-t-butyl ether, tetrahydrofuran, 2-methyltetrahydrofuran, 4-methyltetrahydropyran, 1,4-dioxane, and diethylene glycol dimethyl ether; hydrocarbon-based solvents such as hexane, heptane, benzene, toluene, and xylene; alcohol-based solvents such as methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, isobutyl alcohol, t-butyl alcohol, 2-methyl-2-butyl alcohol, cyclohexyl alcohol, ethylene glycol, propylene glycol, and benzyl alcohol; ester-based solvents such as ethyl acetate, n-propyl acetate, n-butyl acetate, and isobutyl acetate; nitrile-based solvents such as acetonitrile; and aprotic polar solvents such as N,N-dimethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide, and hexamethylphosphoric triamide. From the viewpoint of reactivity, ether-based solvents, hydrocarbon-based solvents, alcohol-based solvents, and aprotic polar solvents are preferred.

[0076] The solvent may be one type or, if necessary, two or more types, and can be arbitrarily selected considering the reactivity and / or yield of the (ω-halo-2-alkenyl)triphenylphosphonium=halide compound (1) above, and may be a commercially available solvent, either purified or unpurified.

[0077] Furthermore, when the above-mentioned (ω-halo-2-alkenyl)triphenylphosphonium=halide compound (1) is used directly in the phosphorus ylide preparation reaction without isolation and purification, the solvent used in the substitution reaction can be used as is. In addition, to improve reactivity and / or adjust the concentration, a solvent different from the one used in the substitution reaction or the solvent used in the substitution reaction can be newly added to the phosphorus ylide preparation reaction.

[0078] The amount of solvent used in the phosphorus ylide preparation reaction can be arbitrarily selected considering the reactivity of the (ω-halo-2-alkenyl)triphenylphosphonium=halide compound (1). For example, 100g to 10000g is preferred per mole of the (ω-halo-2-alkenyl)triphenylphosphonium=halide compound (1), more preferably 500g to 5000g, and even more preferably 800g to 3000g from the viewpoint of reactivity and / or economy.

[0079] The reaction temperature for the phosphorus ylide preparation reaction can be arbitrarily selected considering the reactivity and / or yield of the (ω-halo-2-alkenyl)triphenylphosphonium=halide compound (1). For example, -35°C to 80°C is preferred, -20°C to 50°C is more preferred from the viewpoint of yield and / or impurity generation, and -10°C to 20°C is even more preferred.

[0080] The reaction time for the phosphorus ylide preparation reaction is preferably optimized by tracking the progress of the reaction using gas chromatography and / or thin-layer chromatography and / or nuclear magnetic resonance spectroscopy to confirm the disappearance of the (ω-halo-2-alkenyl)triphenylphosphonium=halide compound (1), and by the reactivity of the (ω-halo-2-alkenyl)triphenylphosphonium=halide compound (1). For example, 0.5 to 24 hours is usually preferred, 0.5 to 12 hours is more preferred from the viewpoint of yield and / or impurity generation, and 0.5 to 6 hours is even more preferred.

[0081] The phosphorus ylide preparation reaction yields a reaction product mixture. It is believed that a phosphorus ylide compound represented by the following general formula (9) is generated within the reaction system, forming the reaction product mixture.

[0082] [ka]

[0083] In the above general formula (9), n, X 2 And Ph are as defined in the general formula (1) above.

[0084] The above-mentioned phosphorus ylide compounds can be appropriately isolated and / or purified by conventional organic synthesis purification methods such as vacuum distillation and / or recrystallization and / or various types of chromatography, and then used in the subsequent Wittig reaction. If isolation and / or purification is difficult due to the properties of the phosphorus ylide compound, it is preferable to use it directly in the subsequent Wittig reaction.

[0085] The resulting reaction product mixture is considered to contain at least a phosphorus ylide compound (9), and the reaction product mixture may optionally contain at least one of the starting materials for the phosphorus ylide preparation reaction: the (ω-halo-2-alkenyl)triphenylphosphonium halide compound (1), lithium halide (2), and alkali metal alkosoxide (3). The reaction product mixture may be used as is in the next step; for example, it may be used as is in the next step after the phosphorus ylide preparation reaction, or it may be purified before being used in the next step. In this specification, unless otherwise specified, the term "reaction product mixture" includes both purified and unpurified solutions or suspensions after the reaction.

[0086] The Wittig reaction described above is carried out using the phosphorus ylide compound (9) and aldehyde compound (4) obtained from the phosphorus ylide preparation reaction, and can be carried out under heating or cooling as necessary.

[0087] R in the general formula (4) above 2 is as defined in the general formula (5).

[0088] Examples of the aldehyde compound (4) include linear saturated aldehyde compounds such as acetaldehyde, n-propanal, n-butanol, n-pentanal, n-octanal, and n-decanal; linear unsaturated aldehyde compounds such as acrolein, (2E)-2-butenal, (2E)-2-pentenal, 6-heptenal, and (4Z)-4-decenal; branched saturated aldehyde compounds such as 3-methylbutanal, 2,2-dimethylpropanal, 2-methylpentanal, and 4-methyloctanal; branched unsaturated aldehyde compounds such as 3-methyl-2-butenal and 4-methyl-4-pentenal; and aromatic aldehyde compounds such as benzaldehyde.

[0089] The amount of the aldehyde compound (4) used in the Wittig reaction varies depending on the reactivity of the phosphonium ylide compound (9) and / or the aldehyde compound (4). However, 0.1 mol to 5.0 mol, more preferably 0.5 mol to 3.0 mol, and even more preferably 0.8 mol to 2.0 mol, are preferred per 1 mol of the (ω-halo-2-alkenyl)triphenylphosphonium halide compound (1) or the phosphonium ylide compound (9), from the viewpoints of yield and / or economy.

[0090] Any solvent that does not adversely affect the Wittig reaction can be used as the solvent for the Wittig reaction. Examples include ether-based solvents such as diethyl ether, di-n-butyl ether, di-t-butyl ether, tetrahydrofuran, 2-methyltetrahydrofuran, 4-methyltetrahydropyran, 1,4-dioxane, and diethylene glycol dimethyl ether; hydrocarbon-based solvents such as hexane, heptane, benzene, toluene, and xylene; alcohol-based solvents such as methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, isobutyl alcohol, t-butyl alcohol, 2-methyl-2-butyl alcohol, cyclohexyl alcohol, ethylene glycol, propylene glycol, and benzyl alcohol; ester-based solvents such as ethyl acetate, n-propyl acetate, n-butyl acetate, and isobutyl acetate; nitrile-based solvents such as acetonitrile; and aprotic polar solvents such as N,N-dimethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide, and hexamethylphosphoric triamide. From the viewpoint of reactivity, ether-based solvents, hydrocarbon-based solvents, alcohol-based solvents, and aprotic polar solvents are preferred.

[0091] The solvent may be one type or, if necessary, two or more types, and can be arbitrarily selected considering the reactivity and / or yield of the phosphorus ylide compound (9) and / or aldehyde compound (4). A commercially available solvent may be used after purification or in its unpurified state.

[0092] Furthermore, if the phosphorus ylide compound (9) is used directly in the Wittig reaction without isolation and purification, the solvent used in the phosphorus ylide preparation reaction can be used as is. In addition, to improve reactivity and / or adjust the concentration, a different solvent from the one used in the phosphorus ylide preparation reaction can be newly added to the Wittig reaction.

[0093] The amount of solvent used in the Wittig reaction can be arbitrarily selected considering the reactivity of the phosphorus ylide compound (9) and / or aldehyde compound (4). For example, 100g to 10000g is preferred per mole of the (ω-halo-2-alkenyl)triphenylphosphonium=halide compound (1) or the phosphorus ylide compound (9), more preferably 300g to 5000g, and even more preferably 500g to 3000g from the viewpoint of reactivity and / or economy.

[0094] The reaction temperature for the Wittig reaction can be arbitrarily selected considering the reactivity and / or yield of the phosphorus ylide compound (9) and / or aldehyde compound (4). For example, -35°C to 80°C is preferred, -20°C to 50°C is more preferred from the viewpoint of yield and / or impurity formation, and -10°C to 30°C is even more preferred.

[0095] The reaction time for the Wittig reaction is preferably optimized by tracking the progress of the reaction using gas chromatography and / or thin-layer chromatography and / or nuclear magnetic resonance spectroscopy to confirm the disappearance of the phosphorus ylide compound (9) and / or aldehyde compound (4), and by considering the reactivity of the phosphorus ylide compound (9) and / or aldehyde compound (4). For example, 0.5 to 24 hours is usually preferred, 0.5 to 12 hours is more preferred from the viewpoint of yield and / or impurity generation, and 0.5 to 6 hours is even more preferred.

[0096] The isolation and / or purification of the organic halogen compound (5) obtained by the above phosphorus ylide preparation reaction and subsequent Wittig reaction can be appropriately selected from conventional purification methods in organic synthesis, such as vacuum distillation and / or various types of chromatography, but vacuum distillation is preferred from the viewpoint of industrial economics. Furthermore, if the organic halogen compound (5) has sufficient purity, the crude product may be used directly in the next step without isolation and purification.

[0097] C. Next, the method for producing the acetate compound represented by the following general formula (6) will be described below.

[0098] The acetate compound (6) is obtained by subjecting the above organic halogen compound (5) to an acetoxylation reaction, as shown in the reaction formula below.

[0099] [ka]

[0100] The starting material, the organic halogen compound (5), is as described above.

[0101] Next, the acetate compound (6) obtained from the above acetoxylation reaction will be described below.

[0102] In the above general formula (6), n is as defined in the above general formula (1), and R 2 R is defined as in the general formula (5) above, and Ac represents an acetyl group. When the acetate compound (6) is synthesized from the organic halogen compound (5), R in the general formula (6) 2 and n are R selected in the general formula (5), respectively. 2 And n remains unchanged.

[0103] The acetate compound (6) includes linear acetate compounds such as (10Z)-4,6,10-hexadecatrienyle=acetate, 4,6-hexadecatrienyle=acetate, 7,9-tetradecadienyl=acetate, 7,9-dodecadienyl=acetate, (11E)-7,9,11-tridecatrienyle=acetate and 11,13-hexadecatrienyle=acetate; 10-methyl-4,6,10-undecatrienyle=acetate, 8 Examples include branched acetate compounds such as ,8-dimethyl-4,6-nonadienyl acetate, 11-methyl-7,9-tetradecadienyl acetate, 12-methyl-7,9,11-tridecatrienylate acetate, and 14-methyl-9,11,13-pentadecatrienylate acetate; and aromatic acetate compounds such as 7-phenyl-4,6-heptadienyl acetate and 10-phenyl-7,9-decadienyl acetate.

[0104] Furthermore, examples of the acetate compound (6) include enantiomers, diastereomers, and mixtures of equal and non-equal amounts of these stereoisomers.

[0105] The above acetoxylation reaction can be carried out using a known acetoxyling agent and may be performed under heating or cooling conditions as necessary.

[0106] Examples of acetoxyling agents used in this acetoxylation reaction include acetic acid or acetate salts. When acetic acid is used as the acetoxyling agent, the reaction can be carried out in the presence of a base.

[0107] Examples of acetate salts used as acetoxyling agents include metal acetate salts such as sodium acetate, lithium acetate, potassium acetate, silver(I) acetate, copper(I) acetate, lead(II) acetate, and tri-n-butyltin acetate; and ammonium acetate salts such as tetramethylammonium acetate, tetraethylammonium acetate, tetra-n-butylammonium acetate, and 1-ethyl-3-methylimidazolium acetate. From the viewpoint of yield and / or economy, sodium acetate and potassium acetate are preferred, and one type or two or more types may be used as needed.

[0108] The amount of acetoxyling agent used is preferably 0.1 moles to 30.0 moles per mole of organic halogen compound (5), more preferably 0.5 moles to 10.0 moles from an economic standpoint, and even more preferably 1.0 moles to 5.0 moles.

[0109] When acetic acid is used as the acetoxyling agent, suitable bases include alkali metal hydroxides such as sodium hydroxide, lithium hydroxide, and potassium hydroxide; alkali metal carbonates such as sodium carbonate, lithium carbonate, and potassium carbonate; and amines such as triethylamine and diisopropylethylamine. From the viewpoint of reactivity and / or yield, sodium hydroxide, potassium hydroxide, and potassium carbonate are preferred.

[0110] The base may be one type or, if necessary, two or more types, and can be arbitrarily selected considering the type and / or reactivity of the organic halogen compound (5). The amount of base used is preferably 0.1 to 50.0 moles per mole of organic halogen compound (5), more preferably 0.5 to 30.0 moles from an economic standpoint, and even more preferably 1.0 to 10 moles.

[0111] The acetoxylation reaction can be carried out by adding a metal halide compound to improve its reactivity. Examples of metal halide compounds include metal iodides such as sodium iodide, lithium iodide, and potassium iodide; and metal bromides such as sodium bromide, lithium bromide, and potassium bromide. From the viewpoint of reactivity and / or economy, sodium iodide, potassium iodide, sodium bromide, and potassium bromide are preferred.

[0112] The amount of the above-mentioned metal halide compound used is preferably 0.01 moles to 1.0 mole per mole of the organic halogen compound (5), more preferably 0.03 to 0.5 moles from an economic standpoint, and even more preferably 0.05 to 0.3 moles.

[0113] Any solvent that does not adversely affect the acetoxylation reaction can be used as the solvent for the acetoxylation reaction. For example, water; halogenated solvents such as methylene chloride, chloroform, carbon tetrachloride, and 1,2-dichloroethane; ether solvents such as diethyl ether, di-n-butyl ether, di-t-butyl ether, tetrahydrofuran, 2-methyltetrahydrofuran, 4-methyltetrahydropyran, 1,4-dioxane, and diethylene glycol dimethyl ether; hydrocarbon solvents such as hexane, heptane, benzene, toluene, and xylene; ketone solvents such as acetone, methyl ethyl ketone, isobutyl methyl ketone, and cyclohexanone; methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl Examples of solvents include alcoholic solvents such as =alcohol, isobutyl=alcohol, ethylene glycol, propylene glycol, and benzyl=alcohol; esteric solvents such as ethyl acetate, n-propyl acetate, n-butyl acetate, and isobutyl acetate; nitrile solvents such as acetonitrile; and aprotic polar solvents such as N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, dimethyl sulfoxide, and hexamethylphosphoric triamide. From the viewpoint of reactivity, etheric solvents, hydrocarbon solvents, nitrile solvents, and aprotic polar solvents are preferred.

[0114] The solvent may be one type or, if necessary, two or more types, and can be arbitrarily selected considering the reactivity and / or economics of the organic halogen compound (5). A commercially available solvent may be used, either after purification or in its unpurified state.

[0115] The amount of solvent used in the acetoxylation reaction can be arbitrarily selected considering the reactivity of the organic halogen compound (5). For example, 50 g to 5000 g is preferred per mole of the organic halogen compound (5), 100 g to 2000 g is more preferred from the viewpoint of reactivity and / or the formation of impurities as by-products, and 200 g to 1000 g is even more preferred.

[0116] The reaction temperature for the acetoxylation reaction can be arbitrarily selected considering the reactivity and / or yield of the organic halogen compound (5). For example, 0°C to 200°C is preferred, 25°C to 180°C is more preferred from the viewpoint of reactivity and / or impurity formation, and 50°C to 150°C is even more preferred.

[0117] The reaction time for the acetoxylation reaction is preferably optimized by tracking the progress of the reaction using gas chromatography and / or thin-layer chromatography and / or nuclear magnetic resonance spectroscopy to confirm the disappearance of the organic halogen compound (5), and by considering the reactivity of the organic halogen compound (5). For example, 0.5 to 72 hours is usually preferred, 0.5 to 24 hours is more preferred from the viewpoint of yield and / or impurity generation, and 0.5 to 12 hours is even more preferred.

[0118] The acetate compound (6) obtained by the acetoxylation reaction can be isolated and / or purified using any of the usual purification methods in organic synthesis, such as vacuum distillation and / or various types of chromatography, but vacuum distillation is preferred from the viewpoint of industrial economics. Furthermore, if the acetate compound (6) obtained by the acetoxylation reaction has sufficient purity, the crude product may be used as is without isolation and purification.

[0119] D. Next, the method for producing the alcohol compound represented by the following general formula (7) will be described below.

[0120] The alcohol compound (7) is obtained by subjecting the acetate compound (6) to a hydrolysis reaction, as shown in the reaction formula below.

[0121] [ka]

[0122] The starting material, acetate compound (6), is as described above.

[0123] Next, the alcohol compound (7) obtained from the above hydrolysis reaction will be described below.

[0124] In the above general formula (7), n is as defined in the above general formula (1), and R 2 This is as defined in the general formula (6) above. When the alcohol compound (7) is synthesized from the acetate compound (6), the R in the general formula (7) 2 and n are R selected in the general formula (6), respectively. 2 And n remains unchanged.

[0125] The alcohol compound (7) includes linear alcohol compounds such as (10Z)-4,6,10-hexadecadienyl=alcohol, 4,6-hexadecadienyl=alcohol, 7,9-tetradecadienyl=alcohol, 7,9-dodecadienyl=alcohol, (11E)-7,9,11-tridecatriennyl=alcohol and 11,13-hexadecadienyl=alcohol; 10-methyl-4,6,10-undecatriennyl=alcohol, 8 Examples include branched alcohol compounds such as ,8-dimethyl-4,6-nonadienyl=alcohol, 11-methyl-7,9-tetradecadienyl=alcohol, 12-methyl-7,9,11-tridecatrienylon=alcohol and 14-methyl-9,11,13-pentadecatrienylon=alcohol, as well as aromatic alcohol compounds such as 7-phenyl-4,6-heptadienyl=alcohol and 10-phenyl-7,9-decadienyl=alcohol.

[0126] Furthermore, examples of the alcohol compound (7) include enantiomers, diastereomers, and mixtures of equal and non-equal amounts of these stereoisomers.

[0127] The above hydrolysis reaction can be carried out using known hydrolysis reactions and can be performed under heating or cooling conditions as necessary.

[0128] The hydrolysis reaction can be carried out, for example, under basic conditions using a base, under acidic conditions using an acid, or under neutral conditions using salts or silane halides.

[0129] Examples of bases used for hydrolysis under basic conditions include hydroxide salts such as sodium hydroxide, lithium hydroxide, potassium hydroxide, and barium hydroxide; carbonates or bicarbonates such as sodium carbonate, potassium carbonate, sodium bicarbonate, and potassium bicarbonate; and metal alkoxides such as sodium methoxide, sodium ethoxide, sodium t-butoxide, lithium methoxide, lithium ethoxide, lithium t-butoxide, potassium methoxide, potassium ethoxide, and potassium t-butoxide.

[0130] The base may be one type or, if necessary, two or more types, and can be arbitrarily selected considering the reactivity and / or yield of the acetate compound (6). A commercially available base may be used, either purified or unpurified.

[0131] Examples of acids used for hydrolysis under acidic conditions include inorganic acids such as hydrochloric acid, hydrobromic acid, sulfuric acid, and nitric acid; organic acids such as acetic acid, formic acid, oxalic acid, trifluoroacetic acid, methanesulfonic acid, benzenesulfonic acid, and p-toluenesulfonic acid; and Lewis acids such as aluminum trichloride, aluminum ethoxide, aluminum isopropoxide, boron trifluoride, boron trichloride, boron tribromide, tin tetrachloride, tin tetrabromide, dibutyltin dichloride, dibutyltin dimethoxide, dibutyltin oxide, titanium tetrachloride, titanium tetrabromide, titanium(IV) methoxide, titanium(IV) ethoxide, and titanium(IV) isopropoxide.

[0132] The acid may be one type or, if necessary, two or more types, and can be arbitrarily selected considering the reactivity and / or yield of the acetate compound (6). A commercially available acid may be used, either purified or unpurified.

[0133] Examples of salts used for hydrolysis under neutral conditions include lithium iodide, lithium bromide, sodium cyanide, potassium cyanide, lithium methanethiolate, and sodium benzenethiolate.

[0134] Examples of halogenated silanes used for hydrolysis under neutral conditions include trimethylsilane iodide and trimethylsilane bromide.

[0135] The salts or silane halogens may be one type, or, as necessary, two or more types of salts, two or more types of silane halogens, or two or more combinations of salts and silane halogens, and can be arbitrarily selected considering the reactivity and / or yield of the acetate compound (6), and commercially available products may be used after purification or in their unpurified state.

[0136] The hydrolysis reaction is preferably carried out under basic conditions, and hydrolysis using hydroxide salts, carbonates, or bicarbonates is more preferable from the viewpoint of yield and / or impurity generation.

[0137] The amount of base, acid, or salt or halogenated silane used in the hydrolysis reaction can be arbitrarily set from a very small amount to a large excess amount depending on the reactivity of the acetate compound (6). For example, 0.1 to 50 moles per mole of acetate compound (6) is preferred, 0.3 to 30 moles is more preferred from the viewpoint of reaction time and / or yield, and 0.5 to 10 moles is even more preferred.

[0138] The solvent used in the hydrolysis reaction can be any solvent that does not adversely affect the reaction, such as water; halogenated solvents such as methylene chloride, chloroform, carbon tetrachloride, and 1,2-dichloroethane; ether solvents such as diethyl ether, di-n-butyl ether, di-t-butyl ether, tetrahydrofuran, 2-methyltetrahydrofuran, 4-methyltetrahydropyran, 1,4-dioxane, and diethylene glycol dimethyl ether; hydrocarbon solvents such as hexane, heptane, benzene, toluene, and xylene; acetone, methyl ethyl ketone, and isobutyl methyl ketone. Examples of solvents include ketone solvents such as cyclohexanone; alcoholic solvents such as methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, isobutyl alcohol, ethylene glycol, propylene glycol, and benzyl alcohol; nitrile solvents such as acetonitrile; and aprotic polar solvents such as N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, dimethyl sulfoxide, and hexamethylphosphoric triamide. From the viewpoint of reactivity, water, ether-based solvents, and alcohol-based solvents are preferred.

[0139] The solvent may be one type or, if necessary, two or more types, and can be arbitrarily selected considering the reactivity and / or yield of the acetate compound (6). A commercially available solvent may be used, either after purification or in its unpurified state.

[0140] The amount of solvent used can be arbitrarily selected considering the reactivity and / or solubility of the acetate compound (6). For example, 30 g to 10,000 g is preferred per mole of acetate compound (6), 50 g to 5,000 g is more preferred from the viewpoint of reactivity and / or economy, and 100 g to 1,000 g is even more preferred.

[0141] The reaction temperature for the hydrolysis reaction can be arbitrarily selected considering the reactivity of the acetate compound (6) and / or the formation of impurities. For example, -30°C to 250°C is preferred, 0°C to 150°C is more preferred from the viewpoint of reactivity and / or the formation of impurities, and 25°C to 100°C is even more preferred.

[0142] The reaction time for the hydrolysis reaction is preferably optimized by tracking the progress of the reaction using gas chromatography and / or thin-layer chromatography and / or nuclear magnetic resonance spectroscopy to confirm the disappearance of the acetate compound (6), which is the substrate, and by considering the reactivity of the acetate compound (6). For example, 1 to 72 hours is usually preferred, 1 to 24 hours is more preferred from the viewpoint of yield and / or impurity generation, and 1 to 12 hours is even more preferred.

[0143] The isolation and / or purification of the alcohol compound (7) obtained from the hydrolysis reaction can be appropriately selected from conventional purification methods in organic synthesis, such as vacuum distillation and / or various types of chromatography, but vacuum distillation is preferred from the viewpoint of industrial economics. Furthermore, if the target alcohol compound (7) has sufficient purity, the crude product may be used as is without purification.

[0144] As described above, an (ω-halo-2-alkenyl)triphenylphosphonium halide compound (1) is subjected to a phosphorus ylide preparation reaction with an alkali metal alkosyl (3) in the presence of lithium halide (2) to obtain a reaction product mixture. Subsequently, this reaction product mixture and an aldehyde compound (4) are subjected to a Wittig reaction, thereby enabling the industrial production of an organic halogen compound (5) in a short number of steps and in high yield within an industrially applicable reaction temperature range, without using toxic and flammable raw materials. Furthermore, an acetate compound (6) can be produced from the organic halogen compound (5), and an alcohol compound (7) can be produced from the acetate compound (6) in high yield and in a short number of steps. [Examples]

[0145] The present invention will be specifically described below with reference to examples and comparative examples, but the present invention is not limited to the following examples.

[0146] In the following, unless otherwise specified, "purity" refers to the area percentage obtained by gas chromatography (hereinafter also referred to as "GC") analysis, and "production ratio" refers to the relative ratio of the area percentages obtained by GC analysis. Furthermore, "Yield" refers to the yield calculated based on the area percentage obtained by GC analysis. The yield was calculated according to the following formula, taking into account the purity (%GC) of the starting 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 The conditions for GC analysis are as follows: GC conditions for measuring "purity" and "production ratio": GC: Shimadzu Corporation capillary gas chromatograph GC-2010plus, Column: DB-WAX, 0.25 μm × 0.25 mmφ × 30 m, Carrier gas: He (1.55 mL / min), Detector: FID, Column temperature: 150°C, held for 3 minutes, then increased temperature by 5°C / min to 230°C.

[0147] Example 1 Examples 1-1 to 1-3 below describe the production of (ω-halo-2-alkenyl)triphenylphosphonium halide compounds represented by the following general formula (1), as shown in the reaction equation below.

[0148] [ka]

[0149] Example 1-1 (2E)-(6-chloro-2-hexenyl)triphenylphosphonium=bromide(1:X 1 =Br,X 2 Manufacturing of Cl, n=1)

[0150] [ka]

[0151] The reactor, equipped with a stirrer, condenser, and thermometer, was purged with nitrogen, and triphenylphosphine (PPh3) (275.40 g: 1.05 mol) and acetonitrile (CH3CN) (850.0 g) were added to the reactor to adjust the liquid temperature to 25°C to 28°C. (2E)-6-chloro-2-hexenyl bromide (8:X 1 =Br,X 2 (=Cl,n=1) (197.50g:1.00 mol, purity 96.7%) was added dropwise over 2 hours at a liquid temperature of 28°C to 30°C. After the addition was complete, the reaction mixture was stirred at a liquid temperature of 30°C to 35°C for 7 hours. After stirring, the solvent was removed from the reaction mixture under reduced pressure, and toluene (700.0g) followed by n-hexane (700.0g) was added to precipitate the crystals. This suspension was stirred at a liquid temperature of 20°C to 25°C for 1 hour, after which the crystals were filtered off and washed with n-hexane (30.0g).

[0152] Subsequently, the crystalline material is dried under reduced pressure to obtain (2E)-(6-chloro-2-hexenyl)triphenylphosphonium=bromide (1:X 1 =Br,X 2 =Cl,n=1) (460.25g:0.98 mol, yield 98.3%, purity 98.2%) was obtained. The above yield and purity are for 1,4-bis(trimethylsilyl)benzene- d4 This was used as the internal standard. 1 This was determined by 1H-NMR.

[0153] The (2E)-(6-chloro-2-hexenyl)triphenylphosphonium bromide (1:X) obtained above 1 =Br,X 2 The spectral data for (=Cl, n=1) are shown below. (Nuclear magnetic resonance spectrum) 1H-NMR(500MHz, CDCl3):δ 1.63(2H,quin,J=6.8Hz),2.19(2H,dt,J=12.5,6.1Hz),3.24(2H,t,J=6.5Hz),4.69(2H.q,J=7.4Hz), 5.31(1H,dt,J=21.6,6.2Hz),5.96(1H,dt,J=21.7,6.3Hz),7.63-7.67(6H,m),7.73-7.81(9H,m)ppm. 13 C-NMR(126MHz,CDCl3):δ 27.48,27.87,29.60,29.62,30.83,30.86,43.95,115.34,115.42,117.54,1 18.23,130.18,130.29,133.75,133.83,134.92,134.94,140.70,140.80ppm. (Mass Spectrum) ESI (Positive): m / z 382.2, 380.2, 379.1 (M + ). (Infrared absorption spectrum) (ATR method): ν (cm) -1 )493,500,545,692,718,749,843,994,1114,1161,1268,1403,1435,1485,1587,2782,2853,2879,2960,2989,3006,305.

[0154] Examples 1-2 (2E)-(9-chloro-2-nonenyl)triphenylphosphonium=bromide(1:X 1 =Br,X 2 Manufacturing of (=Cl,n=4)

[0155] [ka]

[0156] (2E)-6-chloro-2-hexenyl=bromide (8:X) as a raw material 1 =Br,X 2 Instead of (=Cl,n=1), use (2E)-9-chloro-2-nonenyl=bromide(1:X 1 =Br,X 2The same procedure as in Example 1-1 was followed, except that (2E)-(9-chloro-2-nonenyl)triphenylphosphonium=bromide(1:X 1 =Br,X 2 =Cl,n=4) (497.84g:0.99 mol, yield 99.0%, purity 99.8%) was obtained. The above yield and purity are for 1,4-bis(trimethylsilyl)benzene- d4 This was used as the internal standard. 1 This was determined by 1H-NMR.

[0157] The (2E)-(9-chloro-2-nonenyl)triphenylphosphonium bromide (1:X) obtained above 1 =Br,X 2 The spectral data for (=Cl,n=4) are shown below. (Nuclear magnetic resonance spectrum) 1 H-NMR(500MHz,CD3CN):δ 1.08(2H,quin,J=7.6Hz),1.19(2H,quin,J=7.5Hz),1.29(2H,quin,J=7.6Hz),1.64(2H.q,J=7.1Hz),1.96(2H,q,J=6.1Hz),3.52( 2H,t,J=6.7Hz),4.26(2H,q,J=7.4Hz),5.31-5.26(1H,m),5.76(1H,dt,J=21.0,6.9Hz),7.68-7.76(12H,m),7.83-7.87(3H,m)ppm. 13 C-NMR(126MHz,CD3CN):δ 27.11,27.61,28.01,28.69,29.09,29.11,32.96,32.99,33.13,46.17,115.40 ,118.79,119.48,130.98,131.09,134.94,135.97,136.00,143.01,143.11ppm. (Mass Spectrum) ESI (Positive): m / z 424.2, 422.2, 421.2 (M + ). (Infrared absorption spectrum) (ATR method): ν (cm) -1)502,512,538,645,692,722,742,754,850,980,995,1112,1163,1184,1437,1485,1587,2777,2866,2932,2986,3003,3041.

[0158] Examples 1-3 (2E)-(13-chloro-2-tridecenyl)triphenylphosphonium=bromide(1:X 1 =Br,X 2 Manufacturing of (=Cl,n=8)

[0159] [ka]

[0160] (2E)-6-chloro-2-hexenyl=bromide (8:X) as a raw material 1 =Br,X 2 Instead of (=Cl,n=1), use (2E)-13-chloro-2-tridecenyl=bromide(1:X 1 =Br,X 2 The same procedure as in Example 1-1 was followed, except that (2E)-(13-chloro-2-tridecenyl)triphenylphosphonium=bromide(1:X 1 =Br,X 2 =Cl,n=8) (497.84g:0.99 mol, yield 98.8%, purity 96.6%) was obtained. The above yield and purity are for 1,4-bis(trimethylsilyl)benzene- d4 This was used as the internal standard. 1 This was determined by 1H-NMR.

[0161] The (2E)-(13-chloro-2-tridecenyl)triphenylphosphonium bromide (1:X) obtained above 1 =Br,X 2 The spectral data for (=Cl, n=8) are shown below. (Nuclear magnetic resonance spectrum) 1H-NMR(500MHz,CD3CN):δ 1.02-1.08(2H,m),1.14-1.30(10H,m),1.38(2H,quin,J=7.4Hz),1.72(2H.quin,J=7.2Hz),1.96(2H,q,J=6.3Hz),3.56(2H,t,J=6. 7Hz),4.22(2H,q,J=7.5Hz),5.33(1H,dt,J=21.3,6.5Hz),5.76(1H,dt,J=20.0,5.6Hz),7.67-7.76(12H,m),7.83-7.87(3H,m)ppm. 13 C-NMR(126MHz,CD3CN):δ 27.44,27.59,27.99,29.27,29.30,29.45,29.49,29.92,30.05,33.08,33.10,33.28,46. 25,115.25,115.33,118.78,119.47,134.86,134.93,135.97,136.00,143.18,143.29ppm. (Mass Spectrum) ESI (Positive): m / z 480.2, 478.2, 477.2 (M + ). (Infrared absorption spectrum) (ATR method): ν (cm) -1 )490,506,544,692,723,739,753,844,996,1113,1161,1436,1485,1588,2778,2852,2923,2987,3055.

[0162] Example 2 Examples 2-1 to 2-17 below describe the production of an organic halogen compound represented by the following general formula (5), as shown in the reaction equation below.

[0163] [ka]

[0164] Example 2-1 (4E,10Z)-4,6,10-Hexadecatrienyl Chloride(5:X 2 =Cl,n=1,R 2Production of (3Z)-3-nonenyl group

[0165] [ka]

[0166] The reactor, equipped with a stirrer, condenser, and thermometer, was purged with nitrogen, and the reactor was then filled with (2E)-(6-chloro-2-hexenyl)triphenylphosphonium bromide (1:X) obtained according to Example 1-1. 1 =Br,X 2 =Cl,n=1)(505.77g:1.10 mol, purity 98.2%), lithium bromide (LiBr)(2:X 3 Potassium t-butoxide (t-BuOK) (3:R) (104.21 g, 1.20 mol) and tetrahydrofuran (THF) (1800.0 g) were added, and the solution temperature was cooled to -10°C to -5°C. Potassium t-butoxide (t-BuOK) (3:R) was added to this mixture. 1 (t-Bu group, M=potassium) (122.31g: 1.09 mol) was added over 10 minutes at a liquid temperature of -5°C to 0°C, and after the addition was complete, the mixture was reacted at a liquid temperature of -5°C to 0°C for 1.5 hours.

[0167] After the reaction is complete, stabilize the reaction mixture temperature at -5°C and (4Z)-4-decenal (4:R 2 (3Z)-3-nonenyl group (154.25g, 1.00 mol, purity 97.5%) was added over 2 hours at a liquid temperature of -5°C to 0°C.

[0168] The reaction mixture was stirred at a liquid temperature of 0°C to 10°C for 1 hour. After stirring, water (600.0 g) was added to the reactor to stop the reaction, and the mixture was separated into an organic layer and an aqueous layer. The solvent was removed from the obtained organic layer under reduced pressure, and then n-hexane (1500.0 g) was added. The precipitated triphenylphosphine oxide was separated from the filtrate by filtration. The filtrate was washed sequentially with 5% by weight sodium bicarbonate aqueous solution (800.0 g), followed by 15% by weight sodium chloride aqueous solution (800.0 g), and then the solvent was removed from the organic layer under reduced pressure.

[0169] The crude product obtained was purified by vacuum distillation to obtain (4E,10Z)-4,6,10-hexadecatrienyl chloride (5:X 2 =Cl,n=1,R 2 =(3Z)-3-nonenyl group) (224.26 g: 0.88 mol, yield 87.9%, purity 93.1%) was obtained.

[0170] The (4E,10Z)-4,6,10-hexadecatrienyl chloride (5:X) obtained above 2 =Cl,n=1,R 2 Analysis by gas chromatography revealed that the (3Z)-3-nonenyl group produced two cis-trans isomers at retention times of 14.78 min and 15.61 min [isomer formation ratio = 39.9 (GC retention time 14.78 min): 60.1 (GC retention time 15.61 min)]. The above (4E,10Z)-4,6,10-hexadecatrienyl chloride (5:X 2 =Cl,n=1,R 2 The above yields and quantities of (3Z)-3-nonenyl group are described as a mixture of the two cis-trans isomers.

[0171] Also, the above (4E,10Z)-4,6,10-hexadecatrienyl chloride (5:X 2 =Cl,n=1,R 2 To determine the stereochemistry of the two cis-trans isomers of the (3Z)-3-nonenyl group, 1 H-NMR and 2D NMR 13 The spin coupling constant between double-bonded hydrogen nuclei was confirmed from 13C non-irradiated HSQC slice data. As a result, it was considered that the cis-trans isomer detected at GC retention time 14.78 minutes was (4E,6Z,10Z)-4,6,10-hexadecatrienyl chloride, and the cis-trans isomer detected at GC retention time 15.61 minutes was also (4E,6E,10Z)-4,6,10-hexadecatrienyl chloride.

[0172] The (4E,10Z)-4,6,10-hexadecatrienyl chloride (5:X) obtained above 2 =Cl,n=1,R2 =(3Z)-3-ノネニルbase) various kinds of スペクトルデータを are shown below. (Nuclear Magnetic Resonance System) 1 H-NMR (600MHz, CDCl3): δ 0.89(3H,t,J=7.2Hz),1.24-1.37(6H,m),1.83-1.90(2H,m),2.02(2H.quin,J=7 .1Hz),2.11-2.14(3H,m),2.22(2H,q,J=7.4Hz),2.26(1H,q,J=7.2Hz),3.52-3.5 6(2H,m),5.33-5.42(2.4H,m),5.52(0.6H,dt,J=18.4,7.2Hz),5.59-5.64(1H,m ),5.96(0.4H,t,J=11.1Hz),5.99-6.07(1.2H,m),6.36(0.4H,dd,J=15.0Hz)ppm. 13 C-NMR (126MHz, CDCl3): δ 14.22,22.72,27.20,27.38,27.43,28.02,29.51,29.53,29.76,30.04,31.66,32.25,32.29,32.86,4 4.52,127.13,128.69,128.91,130.14,130.33,130.38,130.72,130.84,131.84,132.38,132.78ppm. 1 H-NMR and 2D NMR 13 C non-irradiation HSQC スライスデータより Find the binding definite number between double-bound hydrogen nuclei (4E, 6Z, 10Z): J 4,5 =15.2Hz (4-5 bits), J 6,7 =10.8Hz (6-7 bits), J 10,11 =11.1Hz (10-11 bits); (4E, 6E, 10Z) Volume: J 4,5 =14.9Hz (4-5 bits), J 6,7 =14.9Hz (6-7 bits), J 10,11 =11.1Hz (10-11 bits). (Masterpiece) EI (70eV) (GC retention time = 14.78 min) (4E, 6Z, 10Z) Volume: m / z 254 (M +),197,183,163,143,107,93,79,67,55,41,21;(GC retention time=15.61 min)(4E,6E,10Z):Body m / z 254(M + ),197,183,163,143,107,93,79,67,55,41,27. (Infrared absorption spectrum) (ATR method): ν (cm) -1 )656,727,947,987,1308,1442,2855,2927,2956,3007.

[0173] Example 2-2 (4E,10Z)-4,6,10-Hexadecatrienyl Chloride(5:X 2 =Cl,n=1,R 2 Production of (3Z)-3-nonenyl group Lithium bromide (LiBr)(2:X) was used as lithium halide (2) in Example 2-1. 3 The same procedure as in Example 2-1 was followed, except that the amount of (Br) used was (138.94 g, 1.60 mol). As a result, (4E,10Z)-4,6,10-hexadecatrienyl chloride (5:X 2 =Cl,n=1,R 2 =(3Z)-3-nonenyl group) (214.83g: 0.84 mol, yield 84.3%, purity 94.0%) was obtained.

[0174] The (4E,10Z)-4,6,10-hexadecatrienyl chloride (5:X) obtained above 2 =Cl,n=1,R 2 The (3Z)-3-nonenyl group was identified by gas chromatography as two cis-trans isomers of (4E,6Z,10Z)-4,6,10-hexadecatrienyl chloride at a retention time of 14.78 min and at 15.61 min [isomer formation ratio = 39.9 (GC retention time 14.78 min): 60.1 (GC retention time 15.61 min)]. The above (4E,10Z)-4,6,10-hexadecatrienyl chloride (5:X 2 =Cl,n=1,R 2The above yields and quantities of (3Z)-3-nonenyl group are described as a mixture of the two cis-trans isomers.

[0175] (4E,10Z)-4,6,10-Hexadecatrienyl Chloride(5:X 2 =Cl,n=1,R 2 The spectral data for the (3Z)-3-nonenyl group were the same as those obtained in Example 2-1.

[0176] Examples 2-3 (4E,10Z)-4,6,10-Hexadecatrienyl Chloride(5:X 2 =Cl,n=1,R 2 Production of (3Z)-3-nonenyl group Lithium bromide (LiBr)(2:X) was used as lithium halide (2) in Example 2-1. 3 The same procedure as in Example 2-1 was followed, except that the amount of Br used was (52.10 g, 0.6 moles). As a result, (4E,10Z)-4,6,10-hexadecatrienyl chloride (5:X 2 =Cl,n=1,R 2 =(3Z)-3-nonenyl group) (193.68g: 0.76 mol, yield 76.1%, purity 94.9%) was obtained.

[0177] The (4E,10Z)-4,6,10-hexadecatrienyl chloride (5:X) obtained above 2 =Cl,n=1,R 2 The (3Z)-3-nonyl group was identified by gas chromatography as two cis-trans isomers of (4E,6Z,10Z)-4,6,10-hexadecatrienyl chloride at a retention time of 14.78 min and at 15.61 min [isomer formation ratio = 46.0 (GC retention time 14.78 min): 54.0 (GC retention time 15.61 min)]. The above (4E,10Z)-4,6,10-hexadecatrienyl chloride (5:X 2 =Cl,n=1,R 2The above yields and quantities of (3Z)-3-nonenyl group are described as a mixture of the two cis-trans isomers.

[0178] (4E,10Z)-4,6,10-Hexadecatrienyl Chloride(5:X 2 =Cl,n=1,R 2 The spectral data for the (3Z)-3-nonenyl group were the same as those obtained in Example 2-1.

[0179] Examples 2-4 (4E,10Z)-4,6,10-Hexadecatrienyl Chloride(5:X 2 =Cl,n=1,R 2 Production of (3Z)-3-nonenyl group In Example 2-1, (4Z)-4-decenal (4:R) was used as the aldehyde compound (4). 2 The same procedure as in Example 2-1 was followed, except that the (3Z)-3-nonenyl group was added at a liquid temperature of -25°C to -20°C instead of at a liquid temperature of -5°C to 0°C. As a result, (4E,10Z)-4,6,10-hexadecatrienyl chloride (5:X 2 =Cl,n=1,R 2 =(3Z)-3-nonenyl group) (163.10 g: 0.64 mol, yield 64.0%, purity 92.5%) was obtained.

[0180] The (4E,10Z)-4,6,10-hexadecatrienyl chloride (5:X) obtained above 2 =Cl,n=1,R 2 The (3Z)-3-nonenyl group was identified by gas chromatography as two cis-trans isomers of (4E,6Z,10Z)-4,6,10-hexadecatrienyl chloride at a retention time of 14.78 min and at 15.61 min [isomer formation ratio = 39.0 (GC retention time 14.78 min): 61.0 (GC retention time 15.61 min)]. The above (4E,10Z)-4,6,10-hexadecatrienyl chloride (5:X 2 =Cl,n=1,R2 The above yields and quantities of (3Z)-3-nonenyl group are described as a mixture of the two cis-trans isomers.

[0181] (4E,10Z)-4,6,10-Hexadecatrienyl Chloride(5:X 2 =Cl,n=1,R 2 The spectral data for the (3Z)-3-nonenyl group were the same as those obtained in Example 2-1.

[0182] Examples 2-5 (4E,10Z)-4,6,10-Hexadecatrienyl Chloride(5:X 2 =Cl,n=1,R 2 Production of (3Z)-3-nonenyl group In Example 2-1, (4Z)-4-decenal (4:R) was used as the aldehyde compound (4). 2 The same procedure as in Example 2-1 was followed, except that the (3Z)-3-nonenyl group was added at a liquid temperature of 30°C to 35°C instead of at a liquid temperature of -5°C to 0°C. As a result, (4E,10Z)-4,6,10-hexadecatrienyl chloride (5:X 2 =Cl,n=1,R 2 =(3Z)-3-nonenyl group) (226.81g: 0.89 mol, yield 88.6%, purity 87.3%) was obtained.

[0183] The (4E,10Z)-4,6,10-hexadecatrienyl chloride (5:X) obtained above 2 =Cl,n=1,R 2 The (3Z)-3-nonenyl group was identified by gas chromatography as two cis-trans isomers of (4E,6Z,10Z)-4,6,10-hexadecatrienyl chloride at a retention time of 14.78 min and at 15.61 min [isomer formation ratio = 43.8 (GC retention time 14.78 min): 56.2 (GC retention time 15.61 min)]. The above (4E,10Z)-4,6,10-hexadecatrienyl chloride (5:X 2=Cl,n=1,R 2 The above yields and quantities of (3Z)-3-nonenyl group are described as a mixture of the two cis-trans isomers.

[0184] (4E,10Z)-4,6,10-Hexadecatrienyl Chloride(5:X 2 =Cl,n=1,R 2 The spectral data for the (3Z)-3-nonenyl group were the same as those obtained in Example 2-1.

[0185] Examples 2-6 (4E,10Z)-4,6,10-Hexadecatrienyl Chloride(5:X 2 =Cl,n=1,R 2 Production of (3Z)-3-nonenyl group The same procedure as in Example 2-1 was followed, except that acetonitrile (CH3CN) (1800.0 g) was used as the solvent instead of tetrahydrofuran (THF) as in Example 2-1. As a result, (4E,10Z)-4,6,10-hexadecatrienyl chloride (5:X 2 =Cl,n=1,R 2 =(3Z)-3-nonenyl group) (145.26 g: 0.57 mol, yield 56.8%, purity 92.8%) was obtained.

[0186] The (4E,10Z)-4,6,10-hexadecatrienyl chloride (5:X) obtained above 2 =Cl,n=1,R 2 The (3Z)-3-nonenyl group was identified by gas chromatography as two cis-trans isomers of (4E,6Z,10Z)-4,6,10-hexadecatrienyl chloride at a retention time of 14.78 min and at 15.61 min [isomer formation ratio = 52.6 (GC retention time 14.78 min): 47.4 (GC retention time 15.61 min)]. The above (4E,10Z)-4,6,10-hexadecatrienyl chloride (5:X 2 =Cl,n=1,R 2The above yields and quantities of (3Z)-3-nonenyl group are described as a mixture of the two cis-trans isomers.

[0187] (4E,10Z)-4,6,10-Hexadecatrienyl Chloride(5:X 2 =Cl,n=1,R 2 The spectral data for the (3Z)-3-nonenyl group were the same as those obtained in Example 2-1.

[0188] Example 2-7 (4E,10Z)-4,6,10-Hexadecatrienyl Chloride(5:X 2 =Cl,n=1,R 2 Production of (3Z)-3-nonenyl group

[0189] [ka]

[0190] Potassium t-butoxide (t-BuOK) (3:R) was used as the alkali metal alkoxide (3) in Example 2-1. 1 Instead of (=t-Bu group, M=potassium), use sodium = t-butoxide (t-BuONa) (3:R 1 The same procedure as in Example 2-1 was followed, except that (t-Bu group, M=sodium) (104.75g:1.09 mol) was used. As a result, (4E,10Z)-4,6,10-hexadecatrienyl chloride (5:X 2 =Cl,n=1,R 2 =(3Z)-3-nonenyl group) (211.51 g: 0.83 mol, yield 83.1%, purity 96.1%) was obtained.

[0191] The (4E,10Z)-4,6,10-hexadecatrienyl chloride (5:X) obtained above 2 =Cl,n=1,R 2The (3Z)-3-nonenyl group was identified by gas chromatography as two cis-trans isomers of (4E,6Z,10Z)-4,6,10-hexadecatrienyl chloride at a retention time of 14.78 min and at 15.61 min [isomer formation ratio = 40.7 (GC retention time 14.78 min): 59.3 (GC retention time 15.61 min)]. The above (4E,10Z)-4,6,10-hexadecatrienyl chloride (5:X 2 =Cl,n=1,R 2 The above yields and quantities of (3Z)-3-nonenyl group are described as a mixture of the two cis-trans isomers.

[0192] (4E,10Z)-4,6,10-Hexadecatrienyl Chloride(5:X 2 =Cl,n=1,R 2 The spectral data for the (3Z)-3-nonenyl group were the same as those obtained in Example 2-1.

[0193] Example 2-8 (4E,10Z)-4,6,10-Hexadecatrienyl Chloride(5:X 2 =Cl,n=1,R 2 Production of (3Z)-3-nonenyl group

[0194] [ka]

[0195] In Example 2-1, lithium bromide (LiBr) (2:X) was used as lithium halide (2). 3 Instead of =Br)(104.21g, 1.20mol), use lithium chloride (LiCl)(2:X 3 The same procedure as in Example 2-1 was followed, except that (4E,10Z)-4,6,10-hexadecatrienyl chloride (5:X 2 =Cl,n=1,R 2=(3Z)-3-nonenyl group) (187.97g: 0.74 mol, yield 73.6%, purity 94.6%) was obtained.

[0196] The (4E,10Z)-4,6,10-hexadecatrienyl chloride (5:X) obtained above 2 =Cl,n=1,R 2 The (3Z)-3-nonenyl group was identified by gas chromatography as two cis-trans isomers of (4E,6Z,10Z)-4,6,10-hexadecatrienyl chloride at a retention time of 14.78 min and at 15.61 min [isomer formation ratio = 38.7 (GC retention time 14.78 min): 61.3 (GC retention time 15.61 min)]. The above (4E,10Z)-4,6,10-hexadecatrienyl chloride (5:X 2 =Cl,n=1,R 2 The above yields and quantities of (3Z)-3-nonenyl group are described as a mixture of the two cis-trans isomers.

[0197] (4E,10Z)-4,6,10-Hexadecatrienyl Chloride(5:X 2 =Cl,n=1,R 2 The spectral data for the (3Z)-3-nonenyl group were the same as those obtained in Example 2-1.

[0198] Examples 2-9 (4E,10Z)-4,6,10-Hexadecatrienyl Chloride(5:X 2 =Cl,n=1,R 2 Production of (3Z)-3-nonenyl group

[0199] [ka]

[0200] In Example 2-1, lithium bromide (LiBr) (2:X) was used as lithium halide (2). 3Instead of =Br)(104.21g, 1.20mol), use lithium iodide (LiI)(2:X 3 The same procedure as in Example 2-1 was followed, except that =I) (160.62g, 1.20 mol) was used. As a result, (4E,10Z)-4,6,10-hexadecatrienyl chloride (5:X 2 =Cl,n=1,R 2 =(3Z)-3-nonenyl group) (187.97g: 0.71 mol, yield 71.3%, purity 95.2%) was obtained.

[0201] The (4E,10Z)-4,6,10-hexadecatrienyl chloride (5:X) obtained above 2 =Cl,n=1,R 2 The (3Z)-3-nonenyl group was identified by gas chromatography as two cis-trans isomers of (4E,6Z,10Z)-4,6,10-hexadecatrienyl chloride at a retention time of 14.78 min and at 15.61 min [isomer formation ratio = 46.1 (GC retention time 14.78 min): 53.9 (GC retention time 15.61 min)]. The above (4E,10Z)-4,6,10-hexadecatrienyl chloride (5:X 2 =Cl,n=1,R 2 The above yields and quantities of (3Z)-3-nonenyl group are described as a mixture of the two cis-trans isomers.

[0202] (4E,10Z)-4,6,10-Hexadecatrienyl Chloride(5:X 2 =Cl,n=1,R 2 The spectral data for the (3Z)-3-nonenyl group were the same as those obtained in Example 2-1.

[0203] Example 2-10 (4E,10Z)-4,6,10-Hexadecatrienyl Chloride(5:X 2 =Cl,n=1,R 2 Production of (3Z)-3-nonenyl group

[0204] [ka]

[0205] The same procedure as in Example 1-1 was followed, except that tetrahydrofuran (THF) (500.0 g) was used as the solvent instead of acetonitrile (CH3CN) as in Example 1-1. The resulting (2E)-(6-chloro-2-hexenyl)triphenylphosphonium bromide (1:X 1 =Br,X 2 The reaction solution of (=Cl,n=1) was not isolated or purified, but was used directly in the production of the organic halogen compound (5) described in Example 2.

[0206] The amount of tetrahydrofuran (THF) used as the solvent in Example 2-1 was set to (600.0 g), and the above (2E)-(6-chloro-2-hexenyl)triphenylphosphonium=bromide (1:X 1 =Br,X 2 To the reaction solution of =Cl,n=1, lithium bromide (LiBr) (2:X) is added as lithium halide. 3 The same procedure as in Example 2-1 was followed, except that (4E,10Z)-4,6,10-hexadecatrienyl chloride (5:X 2 =Cl,n=1,R 2 =(3Z)-3-nonenyl group) (221.71 g: 0.87 mol, yield 87.0%, purity 95.6%) was obtained.

[0207] The (4E,10Z)-4,6,10-hexadecatrienyl chloride (5:X) obtained above 2 =Cl,n=1,R 2The (3Z)-3-nonenyl group was identified by gas chromatography as two cis-trans isomers of (4E,6Z,10Z)-4,6,10-hexadecatrienyl chloride at a retention time of 14.78 min and at 15.61 min [isomer formation ratio = 40.9 (GC retention time 14.78 min): 59.1 (GC retention time 15.61 min)]. The above (4E,10Z)-4,6,10-hexadecatrienyl chloride (5:X 2 =Cl,n=1,R 2 The above yields and quantities of (3Z)-3-nonenyl group are described as a mixture of the two cis-trans isomers.

[0208] (4E,10Z)-4,6,10-Hexadecatrienyl Chloride(5:X 2 =Cl,n=1,R 2 The spectral data for the (3Z)-3-nonenyl group were the same as those obtained in Example 2-1.

[0209] Example 2-11 (4E)-4,6-Hexadecadienyl Chloride (5:X 2 =Cl,n=1,R 2 Production of n-nonenyl group

[0210] [ka]

[0211] (4Z)-4-decenal (4:R) as the aldehyde compound (4) used in Example 2-1 2 Instead of (3Z)-3-nonenyl group, use n-decanal (4:R 2 The same procedure as in Example 2-1 was followed, except that (4E)-4,6-hexadecadienyl chloride (5:X 2 =Cl,n=1,R 2=n-nonyl group) (228.61g: 0.89 mol, yield 88.8%, purity 94.1%) was obtained.

[0212] The (4E)-4,6-hexadecadienyl chloride (5:X) obtained above 2 =Cl,n=1,R 2 Analysis by gas chromatography revealed that the (n-nonyl group) produced two cis-trans isomers at retention times of 13.98 min and 14.89 min [isomer formation ratio = 41.4 (GC retention time 13.98 min): 58.6 (GC retention time 14.89 min)]. The above (4E)-4,6-hexadecadienyl chloride (5:X 2 =Cl,n=1,R 2 The above yields and quantities of the (n-nonyl group) are described as a mixture of the two cis-trans isomers.

[0213] Also, the above (4E)-4,6-hexadecadienyl chloride (5:X 2 =Cl,n=1,R 2 To determine the stereochemistry of the two cis-trans isomers of the n-nonyl group, 1 H-NMR and 2D NMR 13 The spin coupling constant between double-bonded hydrogen nuclei was confirmed from 13C non-irradiated HSQC slice data. As a result, it was considered that the cis-trans isomer detected at GC retention time 13.98 minutes was (4E,6Z)-4,6-hexadecadienyl chloride, and the cis-trans isomer detected at GC retention time 14.89 minutes was also (4E,6E)-4,6-hexadecadienyl chloride.

[0214] The (4E)-4,6-hexadecadienyl chloride (5:X) obtained above 2 =Cl,n=1,R 2 The spectral data for various groups (=n-nonyl group) are shown below. (Nuclear magnetic resonance spectrum) 1H-NMR (500MHz, CDCl3): δ 0.88(3H,t,J=7.1Hz),1.27-1.39(14H,m),1.83-1.91(2H,m),2.05(2H.q,J=7.1Hz),2.16( 0.8H,q,J=7.3Hz),2.23(1.2H,q,J=7.9Hz),2.28(0.8H,q,J=6.7Hz),3.52-3.56(2H,m),5. 35(0.4H,dt,J=11.0,7.5Hz),5.51(0.6H,dt,J=14.6,7.2Hz),5.60(1H,dt,J=14.5,7.2Hz) ,5.95(0.6H,dd,J=15.7,11.2Hz),5.99-6.08(1H,m),6.36(0.4H,dd,J=15.1,11.0Hz)ppm. 13 C-NMR (126MHz, CDCl3): δ 14.09,22.67,27.71,29.21,29.25,29.31,29.35,29.51,29.56,29.58,29.60,29.68,29.89,31 .89,32.13,32.16,32.58,127.03,128.14,129.61,129.87,131.05,131.81,131.88,133.44ppm. 1 H-NMR and 2D NMR 13 C non-irradiation HSQC スライスデータよりFind the めたdouble bound hydrogen internuclear のスピン binding definite number (4E, 6Z) body: J 4,5 =15.1Hz (4-5 bits), J 6,7 =11.0Hz (6-7 bits); (4E, 6E) volume: J 4,5 =15.1Hz (4-5 bits), J 6,7 =14.7Hz (6-7 bits). (Mascuit)EI (70eV) (GC retention time = 13.98 minutes) (4E, 6Z) body: m / z 256 (M + ), 158, 144, 130, 109, 95, 81, 67, 54, 41, 27; (GC retention time = 14.89 minutes) (4E, 6E) volume: m / z 256 (M + ),158,144,130,109,95,81,67,54,41,27. (Infrared ray absorption radiation) (ATR method): ν (cm -1)656,723,948,987,1442,1458,2854,2924,2956,3016.

[0215] Example 2-12 (4E)-7-phenyl-4,6-heptadienyl chloride (5:X 2 =Cl,n=1,R 2 Production of phenyl group

[0216] [ka]

[0217] (4Z)-4-decenal (4:R) as the aldehyde compound (4) used in Example 2-1 2 Instead of (3Z)-3-nonenyl group, use benzaldehyde (4:R 2 The same procedure as in Example 2-1 was followed, except that (4E)-7-phenyl-4,6-heptadienyl chloride (5:X) was used (106.12g, 1.00 mol, purity 98.0%). As a result, (4E)-7-phenyl-4,6-heptadienyl chloride (5:X) was obtained. 2 =Cl,n=1,R 2 =phenyl group) (190.17g: 0.92 mol, yield 91.8%, purity 96.2%) was obtained.

[0218] The (4E)-7-phenyl-4,6-heptadienyl chloride (5:X) obtained above 2 =Cl,n=1,R 2 Analysis by gas chromatography revealed that the (4E)-7-phenyl-4,6-heptadienyl chloride (5:X) exhibits two cis-trans isomers at retention times of 13.44 min and 16.80 min [isomer formation ratio = 38.6 (GC retention time 13.44 min): 61.4 (GC retention time 16.80 min)]. 2 =Cl,n=1,R 2 The above yields and quantities of the phenyl group are described as a mixture of the two cis-trans isomers.

[0219] Also, the above (4E)-7-phenyl-4,6-heptadienyl chloride (5:X 2 =Cl,n=1,R 2 To determine the stereochemistry of the two cis-trans isomers of the phenyl group, 1 H-NMR and 2D NMR 13 The spin coupling constant between double-bonded hydrogen nuclei was confirmed from 13C non-irradiated HSQC slice data. As a result, it was considered that the cis-trans isomer detected at GC retention time 13.44 minutes was (4E,6Z)-7-phenyl-4,6-heptadienyl chloride, and the cis-trans isomer detected at GC retention time 16.80 minutes was (4E,6E)-7-phenyl-4,6-heptadienyl chloride.

[0220] The (4E)-7-phenyl-4,6-heptadienyl chloride (5:X) obtained above 2 =Cl,n=1,R 2 The spectral data for various phenyl groups are shown below. (Nuclear magnetic resonance spectrum) 1 H-NMR(600MHz, CDCl3):δ 1.91(2H,sep,J=7.1Hz),2.31(2H,sext,J=7.3Hz),3.56(1.2H,t,6.6Hz),3.57(0.8 Ht,J=6.5Hz),5.75-5.86(1H,m),6.22(0.6H,t,J=11.4Hz),6.27(0.4H,dd,J=15.1, 8.7Hz),6.37(0.4H,d,J=11.5Hz),6.48(0.6H,d,J=15.6Hz),6.66(0.4H,dd,J=15.0 ,11.0Hz),6.76(0.6H,dd,J=15.7,8.7Hz),7.21-7.26(1H,m),7.30-7.39(4H,m)ppm. 13 C-NMR(150MHz, CDCl3):δ 29.99,30.08,32.11,32.16,44.47,126.33,126.95,127.41,127.98,128.38,128.54, 128.71,129.02,129.06,130.17,130.94,131.99,133.30,135.51,137.57,137.74ppm. 1 H-NMR and 2D NMR 13 Spin coupling constants (4E,6Z) between double-bonded hydrogen nuclei determined from non-irradiated HSQC slice data: J 4,5 =14.4Hz(4th-5th place),J 6,7 =11.0Hz(6-7th place);(4E,6E) body:J 4,5 =15.1Hz(4th-5th place),J 6,7 =15.6Hz(6th-7th place). (Mass spectrum) EI (70 eV) (GC retention time = 13.44 mins) (4E, 6Z) Body: m / z 206 (M + ),143,129,115,91,77,65,51,39,27;(GC retention time = 16.80 min) (4E,6E) body: m / z 208(M + ),143,129,115,91,77,65,51,39,27. (Infrared absorption spectrum) (ATR method): ν (cm) -1 )508,652,692,701,746,771,916,949,989,1028,1072,1295,1446,1492,1596,1643,2841,2936,2955,3022,3057,3078.

[0221] Example 2-13 (7E)-7,9-tetradecadienyl chloride (5:X 2 =Cl,n=4,R 2 Production of n-butyl group

[0222] [ka]

[0223] (2E)-(6-chloro-2-hexenyl)triphenylphosphonium bromide (1:X) as the (ω-halo-2-alkenyl)triphenylphosphonium=halide compound (1) used in Example 2-1. 1 =Br,X 2Instead of (=Cl,n=1), use (2E)-(9-chloro-2-nonenyl)triphenylphosphonium bromide (1:X) obtained according to Example 1-2. 1 =Br,X 2 =Cl,n=4) (552.06g, 1.10 mol, purity 99.8%), and (4Z)-4-decenal (4:R) as the aldehyde compound (4). 2 Instead of (3Z)-3-nonenyl group, use n-pentanal (4:R 2 The same procedure as in Example 2-1 was followed, except that (7E)-7,9-tetradecadienyl chloride (5:X 2 =Cl,n=4,R 2 =n-butyl group) (205.92g:0.90 mol, yield 90.5%, purity 95.5%) was obtained.

[0224] The (7E)-7,9-tetradecadienyl chloride (5:X) obtained above 2 =Cl,n=4,R 2 Analysis by gas chromatography revealed that the (7E)-7,9-tetradecadienyl chloride (5:X) produced two cis-trans isomers at retention times of 10.43 min and 11.06 min [isomer formation ratio = 41.9 (GC retention time 10.43 min): 58.1 (GC retention time 11.06 min)]. 2 =Cl,n=4,R 2 The above yields and quantities of the n-butyl group are described as a mixture of the two cis-trans isomers.

[0225] Also, the above (7E)-7,9-tetradecadienyl chloride (5:X 2 =Cl,n=4,R 2 To determine the stereochemistry of the two cis-trans isomers of the n-butyl group, 1 H-NMR and 2D NMR 13The spin coupling constant between double-bonded hydrogen nuclei was confirmed from 13C non-irradiated HSQC slice data. As a result, it was considered that the cis-trans isomer detected at GC retention time 10.43 mins was (7E,9Z)-7,9-tetradecadienyl chloride, and the cis-trans isomer detected at GC retention time 11.06 mins was also (7E,9E)-7,9-tetradecadienyl chloride.

[0226] The (7E)-7,9-tetradecadienyl chloride (5:X) obtained above 2 =Cl,n=4,R 2 The spectral data for the n-butyl group are shown below. (Nuclear magnetic resonance spectrum) 1 H-NMR(600MHz, CDCl3):δ 0.88-0.92(3H,m),1.28-1.46(10H,m),1.74-1.80(2H,m),2.06(2.4Hq,J=7.0Hz),2.10( 0.8H,q,J=7.2Hz),2.16(0.8H,q,J=7.2Hz),3.53(1.2H,t,J=6.8Hz),3.53(0.8H,t,J=6. 8Hz),5.31(0.4H,dt,J=10.7,7.6Hz),5.51-5.60(1.2H,m),5.64(0.4H,dt,J=14.4,7.3H z),5.94(0.4H,t,J=11.0Hz),5.97-6.02(1.2H,m),6.30(0.4H,dd,J=15.1,11.0Hz)ppm. 13 C-NMR(150MHz, CDCl3):δ 14.08,14.11,22.39,22.46,26.87,26.88,27.54,28.55,29.33,29.34,31.71,32.04,32.41,32 .58,32.72,32.86,45.27,125.98,128.64,130.38,130.40,130.70,132.11,132.73,134.37ppm. 1 H-NMR and 2D NMR 13 Spin coupling constants (7E,9Z) between double-bonded hydrogen nuclei determined from non-irradiated HSQC slice data: J 7,8 =14.4Hz(7th-8th place),J9,10 =10.8Hz(9-10th place);(7E,9E) body:J 7,8 =15.2Hz(7th-8th place),J 9,10 =15.5Hz(9-10th place). (Mass spectrum) EI (70 eV) (GC retention time = 10.43 mins) (7E, 9Z) Body: m / z 228 (M + ),185,171,157,144,123,109,95,81,67,54,41;(GC retention time=11.06 min)(7E,9E) body: m / z 228(M + ),185,171,157,144,123,109,95,81,67,54,41. (Infrared absorption spectrum) (ATR method): ν (cm) -1 )653,729,949,987,1464,2856,2928,2956,3015.

[0227] Example 2-14 (7E)-7,9-Dodecadienyl Chloride (5:X 2 =Cl,n=4,R 2 Production of ethyl group

[0228] [ka]

[0229] n-pentanal (4:R) as the aldehyde compound (4) used in Example 2-13 2 Instead of the n-butyl group, use propanal (4:R 2 The same procedure as in Example 2-13 was followed, except that (7E)-7,9-dodecadienyl chloride (5:X) was used. As a result, (7E)-7,9-dodecadienyl chloride (5:X) was obtained. 2 =Cl,n=4,R 2 (=ethyl group) (194.73g: 0.97 mol, yield 96.7%, purity 93.4%) was obtained.

[0230] The (7E)-7,9-dodecadienyl chloride (5:X) obtained above 2 =Cl,n=4,R2 Analysis by gas chromatography revealed that the (7E)-7,9-dodecadienyl chloride (5:X) produced two cis-trans isomers at retention times of 12.98 min and 13.35 min [isomer formation ratio = 44.8 (GC retention time 12.98 min): 55.2 (GC retention time 13.35 min)]. 2 =Cl,n=4,R 2 The above yields and quantities of (ethyl group) are described as a mixture of the two cis-trans isomers.

[0231] Also, the above (7E)-7,9-dodecadienyl chloride (5:X 2 =Cl,n=4,R 2 To determine the stereochemistry of the two cis-trans isomers of the ethyl group, 1 H-NMR and 2D NMR 13 The spin coupling constant between double-bonded hydrogen nuclei was confirmed from 13C non-irradiated HSQC slice data. As a result, it was considered that the cis-trans isomer detected at GC retention time 12.98 minutes was (7E,9Z)-7,9-dodecadienyl chloride, and the cis-trans isomer detected at GC retention time 13.35 minutes was also (7E,9E)-7,9-dodecadienyl chloride.

[0232] The (7E)-7,9-dodecadienyl chloride (5:X) obtained above 2 =Cl,n=4,R 2 The spectral data for various groups (=ethyl group) are shown below. (Nuclear magnetic resonance spectrum) 1H-NMR (600MHz, CDCl3): δ 0.99(1.2H,t,J=7.5Hz),1.00(1.8H,t,J=7.4Hz),1.31-1.47(6H,m),1.74-1.79(2H.m), 2.04-2.13(3.2H,m),2.17(0.8H,quin,J=7.4Hz),3.52(1.2H,t,J=6.8Hz),3.53(0.8H,t, J=6.8Hz),5.31(0.4H,dt,J=10.7,7.5Hz),5.56(0.6H,dt,J=14.1,7.0Hz),5.60-5.67(1H ,m),5.91(0.4H,t,J=10.9Hz),5.97-6.03(1.2H,m),6.30(0.4H,dd,J=15.1,11.0Hz)ppm. 13 C-NMR (150MHz, CDCl3): δ 13.77,14.46,21.15,25.72,26.86,26.87,28.54,28.57,29.32,29.35,32.58,32.71 ,32.85,45.26,125.84,128.07,129.44,130.68,131.96,132.19,134.19,134.44ppm. 1 H-NMR and 2D NMR 13 C non-irradiation HSQC スライスデータよりFind the めたdouble bound hydrogen internuclear のスピン binding definite number (7E, 9Z) body: J 7,8 =15.2Hz (7-8 bits), J 9,10 =10.8Hz (9-10 bits); (7E, 9E) volume: J 7,8 =14.8Hz (7-8 bits), J 9,10 =14.9Hz (9-10 bits). (Mascuit)EI (70eV) (GC retention time = 12.98 minutes) (7E, 9Z) body: m / z 200 (M + ), 171, 157, 144, 123, 109, 95, 82, 67, 55, 41, 27; (GC retention time = 13.35 minutes) (7E, 9E) volume: m / z 200 (M + ),171,157,144,123,109,95,82,67,55,41,27. (Infrared ray absorption radiation) (ATR method): ν (cm -1)542,652,725,947,987,1120,1309,1438,1461,2855,2931,2962,3016.

[0233] Example 2-15 (7E)-11-methyl-7,9-tetradecadienyl chloride (5:X 2 =Cl,n=4,R 2 Production of (2-pentyl group)

[0234] [ka]

[0235] n-pentanal (4:R) as the aldehyde compound (4) used in Example 2-13 2 Instead of the n-butyl group, use 2-methylpentanal (4:R 2 The same procedure as in Example 2-13 was followed, except that (7E)-11-methyl-7,9-tetradecadienyl chloride (5:X 2 =Cl,n=4,R 2 A solution containing 2-pentyl groups was obtained (218.55 g: 0.90 mol, yield 90.3%, purity 96.9%).

[0236] The (7E)-11-methyl-7,9-tetradecadienyl chloride obtained above (5:X 2 =Cl,n=4,R 2 Analysis by gas chromatography revealed two cis-trans isomers of the (7E)-11-methyl-7,9-tetradecadienyl chloride (5:X) at retention times of 10.21 min and 11.43 min [isomer formation ratio = 51.3 (GC retention time 10.21 min): 48.7 (GC retention time 11.43 min)]. 2 =Cl,n=4,R 2 The above yields and quantities of the 2-pentyl group are described as a mixture of the two cis-trans isomers.

[0237] Also, the above (7E)-11-methyl-7,9-tetradecadienyl chloride (5:X 2 =Cl,n=4,R 2 To determine the stereochemistry of the two cis-trans isomers of the 2-pentyl group, 1 H-NMR and 2D NMR 13 The spin coupling constant between double-bonded hydrogen nuclei was confirmed from 13C non-irradiated HSQC slice data. As a result, it was considered that the cis-trans isomer detected at GC retention time 10.21 minutes is (7E,9Z)-11-methyl-7,9-dodecadienyl chloride, and the cis-trans isomer detected at GC retention time 11.43 minutes is (7E,9E)-11-methyl-7,9-tetradecadienyl chloride.

[0238] The (7E)-11-methyl-7,9-tetradecadienyl chloride obtained above (5:X 2 =Cl,n=4,R 2 The spectral data for the 2-pentyl group are shown below. (Nuclear magnetic resonance spectrum) 1 H-NMR(600MHz, CDCl3):δ 0.87(1.5H,t,J=7.0Hz),0.88(1.5H,t,J=7.1Hz),0.96(1.5H,d,J=6.7Hz),0.98(1.5Hd,J=6.7Hz),1.26-1.36(6H,m),1.37 -1.46(4H,m),1.74-1.80(2H,m),2.06(1H,q,J=7.4Hz),2.10(1H,q,J=7.2Hz),2.12-2.19(0.5H,m),2.56-2.64(0.5H,m),3. 53(1H,t,J=6.8Hz),3.54(1H,t,J=6.8Hz),5.07(0.5H,t,J=10.4Hz),5.45(0.5H,dd,J=14.4,7.9Hz),5.56(0.5H,dt,J=14.3 ,7.1Hz),5.63(0.5H,dt,J=14.7,7.3Hz),5.89(0.5H,t,J=10.9Hz),5.93-6.02(1H,m),6.28(0.5H,dd,J=15.0,10.9Hz)ppm. 13C-NMR(150MHz, CDCl3):δ 14.31,14.35,20.58,20.70,20.72,21.43,26.86,26.88,28.55,28.58,29.30,29.36,32.06,32.61,32.72 ,32.83,36.57,39.50,39.98,45.26,126.20,127.30,128.51,130.81,132.16,134.31,136.85,138.75ppm. 1 H-NMR and 2D NMR 13 Spin coupling constants (7E,9Z) between double-bonded hydrogen nuclei determined from non-irradiated HSQC slice data: J 7,8 =14.7Hz(7th-8th place),J 9,10 =10.7Hz(9-10th place);(7E,9E) body:J 7,8 =14.3Hz(7th-8th place),J 9,10 =14.4Hz(9-10th place). (Mass spectrum) EI (70 eV) (GC retention time = 10.21 mins) (7E, 9Z) Body: m / z 242 (M + ),199,171,158,143,123,109,95,81,67,55,41;(GC retention time=11.43 min)(7E,9E) body: m / z 242(M + ),199,171,158,143,123,109,95,81,67,55,41. (Infrared absorption spectrum) (ATR method): ν (cm) -1 )654,720,949,987,1376,1456,2858,2927,2956,3016.

[0239] Example 2-16 (7E,11E)-7,9,11-tridecatrienyl chloride (5:X 2 =Cl,n=4,R 2 Production of (1-propenyl group)

[0240] [ka]

[0241] n-pentanal (4:R) as the aldehyde compound (4) used in Example 2-13 2 Instead of the n-butyl group, (2E)-2-butenal (4:R 2 The same procedure as in Example 2-13 was followed, except that (7E,11E)-7,9,11-tridecatrienyl chloride (5:X 2 =Cl,n=4,R 2 =1-propenyl group) (195.74g: 0.92 mol, yield 91.9%, purity 96.9%) was obtained.

[0242] The (7E,11E)-7,9,11-tridecatrienyl chloride (5:X) obtained above 2 =Cl,n=4,R 2 Analysis by gas chromatography revealed that the (1-propenyl group) produced two cis-trans isomers at retention times of 10.62 min and 10.96 min [isomer formation ratio = 53.0 (GC retention time 10.62 min): 47.0 (GC retention time 10.96 min)]. The above (7E,11E)-7,9,11-tridecatrienyl chloride (5:X 2 =Cl,n=4,R 2 The above yields and quantities of the 1-propenyl group are described as a mixture of the two cis-trans isomers.

[0243] Also, the above (7E,11E)-7,9,11-tridecatrienyl chloride (5:X 2 =Cl,n=4,R 2 To determine the stereochemistry of the two cis-trans isomers of the 1-propenyl group, 1 H-NMR and 2D NMR 13 The spin coupling constant between double-bonded hydrogen nuclei was confirmed from 13C non-irradiated HSQC slice data. As a result, it was considered that the cis-trans isomer detected at GC retention time 10.62 minutes is (7E,9Z,11E)-7,9,11-tridecatriennyl chloride, and the cis-trans isomer detected at GC retention time 10.96 minutes is (7E,9E,11E)-7,9,11-tridecatriennyl chloride.

[0244] The (7E,11E)-7,9,11-tridecatrienyl chloride (5:X) obtained above 2 =Cl,n=4,R 2 The spectral data for the 1-propenyl group are shown below. (Nuclear magnetic resonance spectrum) 1 H-NMR(600MHz, CDCl3):δ 1.24-1.37(2H,m),1.38-1.48(4H,m),1.74-1.78(3.5H,m),1.80(1.5H,d,J=6.8Hz),2.09(1H,q,J=7.7Hz),2.13(1H,q,J=7.4Hz ),3.52(1H,t,J=6.7Hz),3.53(1H,t,J=6.8Hz),5.62-5.73(2H,m),5.81-5.87(1H,m),6.01-6.09(2H,m),6.45-6.53(1H,m)ppm. 13 C-NMR(150MHz, CDCl3):δ 18.41,18.53,26.86,28.52,28.56,29.27,32.70,32.77,32.92,45.26,126.08,127.29 ,127.46,127.75,129.02,130.04,130.63,130.76,130.99,131.89,134.17,135.18ppm. 1 H-NMR and 2D NMR 13 Spin coupling constants (7E, 9Z, 11E) between double-bonded hydrogen nuclei, obtained from non-irradiated HSQC slice data: J 7,8 =15.1Hz(7th-8th place),J 9,10 =11.4Hz(9-10th place),J 11,12 =14.8Hz(11-12th place);(7E,9E,11E) body:J 7,8 =14.6Hz(7th-8th place),J 9,10 =14.5Hz(9-10th place),J 11,12 =14.7Hz(11th-12th place). (Mass spectrum) EI (70 eV) (GC retention time = 10.62 mins) (7E, 9Z, 11E) Body: m / z 212 (M +),144,121,107,93,79,67,55,41;(GC retention time = 10.96 min) (7E,9E,11E) body: m / z 212(M + ),144,121,107,93,79,67,55,41. (Infrared absorption spectrum) (ATR method): ν (cm) -1 )542,651,724,925,963,996,1308,1376,1446,2855,2930,3012.

[0245] Example 2-17 (11E)-11,13-Hexadecadienyl Chloride (5:X 2 =Cl,n=8,R 2 Production of ethyl group

[0246] [ka]

[0247] (2E)-(6-chloro-2-hexenyl)triphenylphosphonium bromide (1:X) as the (ω-halo-2-alkenyl)triphenylphosphonium=halide compound (1) used in Example 2-1. 1 =Br,X 2 Instead of (=Cl,n=1), use (2E)-(13-chloro-2-tridecenyl)triphenylphosphonium bromide (1:X) obtained according to Examples 1-3. 1 =Br,X 2 =Cl,n=8) (613.78g, 1.10 mol, purity 96.6%), and (4Z)-4-decenal (4:R) as the aldehyde compound (4). 2 Instead of (3Z)-3-nonenyl group, use propanal (4:R 2 The same procedure as in Example 2-1 was followed, except that (11E)-11,13-hexadecadienyl chloride (5:X 2 =Cl,n=8,R 2 (=ethyl group) (249.15 g: 0.97 mol, yield 96.6%, purity 88.5%) was obtained.

[0248] The (11E)-11,13-hexadecadienyl chloride (5:X) obtained above 2 =Cl,n=8,R 2 Analysis by gas chromatography revealed two cis-trans isomers of (11E)-11,13-hexadecadienyl chloride (5:X) at retention times of 15.38 min and 15.77 min [isomer formation ratio = 44.4 (GC retention time 15.38 min): 55.6 (GC retention time 15.77 min)]. 2 =Cl,n=8,R 2 The above yields and quantities of (ethyl group) are described as a mixture of the two cis-trans isomers.

[0249] Also, the above (11E)-11,13-hexadecadienyl chloride (5:X 2 =Cl,n=8,R 2 To determine the stereochemistry of the two cis-trans isomers of the ethyl group, 1 H-NMR and 2D NMR 13 The spin coupling constant between double-bonded hydrogen nuclei was confirmed from 13C non-irradiated HSQC slice data. As a result, it was considered that the cis-trans isomer detected at GC retention time 15.38 minutes is (11E,13Z)-11,13-hexadecadienyl chloride, and the cis-trans isomer detected at GC retention time 15.77 minutes is (11E,13E)-11,13-hexadecadienyl chloride.

[0250] The (11E)-11,13-hexadecadienyl chloride (5:X) obtained above 2 =Cl,n=8,R 2 The spectral data for various groups (=ethyl group) are shown below. (Nuclear magnetic resonance spectrum) 1H-NMR (600MHz, CDCl3): δ 0.99(1.3H,t,J=7.5Hz),1.00(1.7H,t,J=7.5Hz),1.24-1.44(14H,m),1.76(2H.quin ,J=7.2Hz),2.02-2.11(3.1H,m),2.18(0.9H,quin,J=7.4Hz),3.53(2H,t,J=6.9Hz), 5.30(0.4H,dt,J=10.8,7.2Hz),5.54-5.63(1.2H,m),5.66(0.4H,dt,J=14.7,7.3Hz) ,5.92(0.4H,t,J=10.8Hz),5.97-6.03(1.2H,m),6.30(0.4H,dd,J=15.1,10.8Hz)ppm. 13 C-NMR (150MHz, CDCl3): δ 13.79,14.47,21.15,25.73,27.02,29.02,29.32,29.35,29.53,29.57,29.58,29.59,29.61,32 .74,32.80,33.01,45.33,125.63,128.17,129.53,130.46,131.78,132.60,134.00,134.84ppm. 1 H-NMR and 2D NMR 13 C non-irradiation HSQC スライスデータより Find the binding definite number between double-bound hydrogen nuclei (11E, 13Z): J 11,12 =14.9Hz (11-12 bits), J 13,14 =10.8Hz (13-14 bits); (11E, 13E) volume: J 11,12 =14.3Hz (11-12 bits), J 13,14 =15.3Hz (13-14 bits). (Mascuit)EI (70eV) (GC retention time = 15.38 minutes) (11E, 13Z) body: m / z 256 (M + ),200,172,137,123,109,96,82,64,57,41;(GC retention time = 15.77 minutes)(11E,13E) volume: m / z 256 (M + ),200,172,137,123,109,96,82,64,57,41.

[0251] Example 3 Examples 3-1 to 3-8 below describe the production of acetate compounds represented by the following general formula (6), as shown in the reaction equation below.

[0252] [ka]

[0253] Example 3-1 (4E,10Z)-4,6,10-Hexadecatrienyl=acetate(6:n=1,R 2 Production of (3Z)-3-nonenyl group

[0254] [ka]

[0255] The reactor, equipped with a stirrer, condenser, and thermometer, was purged with nitrogen, and the (4E,10Z)-4,6,10-hexadecatrienyl chloride (5:X) obtained according to Example 2-1 was added to the reactor. 2 =Cl,n=1,R 2 (3Z)-3-nonenyl group (254.84 g: 1.00 mol, purity 93.1%), sodium acetate (AcONa) (98.41 g, 1.20 mol), sodium iodide (NaI) (8.99 g, 0.06 mol), and N-methyl-2-pyrrolidone (NMP) (300.0 g) were added. The reaction mixture was allowed to react at a liquid temperature of 120°C to 130°C for 1.5 hours.

[0256] After the reaction was complete, water (360.0 g) was added to the reactor to stop the reaction, and then n-hexane (200.0 g) was added to separate the organic layer from the aqueous layer. The resulting organic layer was washed sequentially with 10 wt% sodium chloride aqueous solution (280.0 g), followed by 8 wt% sodium bicarbonate aqueous solution (250.0 g), and then the solvent was removed from the organic layer under reduced pressure.

[0257] The crude product obtained is purified by vacuum distillation to obtain (4E,10Z)-4,6,10-hexadecatrienyl acetate (6:n=1,R 2 =(3Z)-3-nonenyl group) (256.16 g: 0.92 mol, yield 92.3%, purity 97.3%) was obtained.

[0258] The (4E,10Z)-4,6,10-hexadecatrienyl acetate obtained above (6:n=1,R 2 Analysis by gas chromatography revealed that the (3Z)-3-nonenyl group produced two cis-trans isomers at retention times of 18.68 min and 19.69 min [isomer formation ratio = 40.7 (GC retention time 18.68 min): 59.3 (GC retention time 19.69 min)]. The above (4E,10Z)-4,6,10-hexadecatrienyl acetate (6:n=1,R 2 The above yields and quantities of (3Z)-3-nonenyl group are described as a mixture of the two cis-trans isomers.

[0259] Also, the above (4E,10Z)-4,6,10-hexadecatrienyl=acetate(6:n=1,R 2 To determine the stereochemistry of the two cis-trans isomers of the (3Z)-3-nonenyl group, 1 H-NMR and 2D NMR 13 The spin coupling constant between double-bonded hydrogen nuclei was confirmed from 13C non-irradiated HSQC slice data. As a result, it was considered that the cis-trans isomer detected at GC retention time 18.68 minutes is (4E,6Z,10Z)-4,6,10-hexadecatrienyl acetate, and the cis-trans isomer detected at GC retention time 19.69 minutes is (4E,6E,10Z)-4,6,10-hexadecatrienyl acetate.

[0260] The (4E,10Z)-4,6,10-hexadecatrienyl acetate obtained above (6:n=1,R 2 The spectral data for the (3Z)-3-nonenyl group are shown below. (Nuclear magnetic resonance spectrum) 1H-NMR (500MHz, CDCl3): δ 0.88(3H,t,J=7.7Hz),1.23-1.36(6H,m),1.68-1.76(2H,m),2.03(2H.quin,J= 6.6Hz),2.04(1.8H,s),2.05(1.2H,s),2.10-2.28(6H,m),4.06(1.2H,t,J=6.1 Hz),4.07(0.8H,t,J=5.0Hz),5.31-5.45(2.5H,m),5.50-5.71(1.5H,m),5.95( 0.4H,t,J=11.1Hz),5.98-6.04(1.2H,m),6.32(0.4H,dd,J=14.8,11.5Hz)ppm. 13 C-NMR (126MHz, CDCl3): δ 14.05,20.95,22.56,27.04,27.20,27.27,27.84,28.26,28.87,29.17,29.34,29.36,31.48,32.68, 63.92,63.94,126.43,128.58,128.76,129.95,130.28,130.51,130.58,131.19,132.39,132.89ppm. 1 H-NMR and 2D NMR 13 C non-irradiation HSQC スライスデータより Find the binding definite number between double-bound hydrogen nuclei (4E, 6Z, 10Z): J 4,5 =15.1Hz (4-5 bits), J 6,7 =10.6Hz (6-7 bits), J 10,11 =10.3Hz (10-11 bits); (4E, 6E, 10Z) Volume: J 4,5 =15.1Hz (4-5 bits), J 6,7 =14.7Hz (6-7 bits), J 10,11 =10.9Hz (10-11 bits). (Mascuit)EI (70eV) (GC retention time = 18.68 minutes) (4E, 6Z, 10Z) body: m / z 278 (M + ),218,190,175,161,147,133,119,107,93,79,65,55,43,29;(GC retention time = 19.69 minutes)(4E,6E,10Z) volume: m / z 278 (M +),218,177,161,150,133,107,93,79,65,55,43,29. (Infrared absorption spectrum) (ATR method): ν (cm) -1 )732,947,988,1042,1239,1365,1386,1449,1742,2855,2926,2956,3008.

[0261] Example 3-2 (4E)-4,6-Hexadecadienyl=acetate(6:n=1,R 2 Production of (n-nonyl group)

[0262] [ka]

[0263] (4E,10Z)-4,6,10-hexadecatrienyl chloride (5:X) used in Example 3-1 as the organic halogen compound (5) 2 =Cl,n=1,R 2 Instead of the (3Z)-3-nonenyl group, use (4E)-4,6-hexadecadienyl chloride (5:X) obtained according to Example 2-11. 2 =Cl,n=1,R 2 The same procedure as in Example 3-1 was followed, except that (4E)-4,6-hexadecadienyl acetate (6:n=1,R 2 =n-nonyl group) (249.15g: 0.92 mol, yield 92.2%, purity 97.1%) was obtained.

[0264] The (4E)-4,6-hexadecadienyl acetate obtained above (6:n=1,R 2 Analysis by gas chromatography revealed two cis-trans isomers of the (n-nonyl group) at retention times of 17.64 min and 18.77 min [isomer formation ratio = 42.7 (GC retention time 17.64 min): 57.3 (GC retention time 18.77 min)]. The above (4E)-4,6-hexadecadienyl acetate (6:n=1,R 2The above yields and quantities of the (n-nonyl group) are described as a mixture of the two cis-trans isomers.

[0265] Also, the above (4E)-4,6-hexadecadienyl acetate (6:n=1,R 2 To determine the stereochemistry of the two cis-trans isomers of the n-nonyl group, 1 H-NMR and 2D NMR 13 The spin coupling constant between double-bonded hydrogen nuclei was confirmed from 13C non-irradiated HSQC slice data. As a result, it was considered that the cis-trans isomer detected at GC retention time 17.64 minutes was (4E,6Z)-4,6-hexadecadienyl acetate, and the cis-trans isomer detected at GC retention time 18.77 minutes was also (4E,6E)-4,6-hexadecadienyl acetate.

[0266] The (4E)-4,6-hexadecadienyl acetate obtained above (6:n=1,R 2 The spectral data for various groups (=n-nonyl group) are shown below. (Nuclear magnetic resonance spectrum) 1 H-NMR(500MHz, CDCl3):δ 0.88(3H,t,J=6.9Hz),1.27-1.36(14H,m),1.68-1.76(2H,m),2.03(1.8Hs),2.04(1.2H,s),2.09-2.21(4H,q,m),4.06(1.2H,t,J=6.5Hz) ,4.07(0.8H,t,J=6.5Hz),5.32(0.4H,dt,J=14.7,5.5Hz),5.50-5.65(1.6H,m),5.91-6.04(1.6H,m),6.32(0.4H,dd,J=15.0,11.0Hz)ppm. 13C-NMR(126MHz,CDCl3):δ 14.09,20.94,22.65,27.70,28.30,28.87,29.17,29.19,29.26,29.31,29.36,29.50,29.56,29. 68,31.87,32.57,126.50,128.20,129.94,130.26,130.83,131.30,132.56,133.21,171.11ppm. 1 H-NMR and 2D NMR 13 The spin coupling constants between double-bonded hydrogen nuclei, determined from non-irradiated HSQC slice data, are as follows: (4E,6Z) form: J4,5 = 15.1 Hz (4-5 sq.), J6,7 = 11.0 Hz (6-7 sq.); (4E,6E) form: J4,5 = 15.0 Hz (4-5 sq.), J6,7 = 14.7 Hz (6-7 sq.). (Mass Spectrum) EI (70 eV) (GC retention time = 17.64 mins) (4E, 6Z) Body: m / z 280 (M + ),220,149,135,121,107,93,79,57,43,28;(GC retention time = 18.77 minutes) (4E,6E) body: m / z 280(M + ),220,149,135,121,107,93,79,57,43,29. (Infrared absorption spectrum) (ATR method): ν (cm) -1 )606,948,987,1042,1239,1365,1387,1466,1743,2854,2924,2955,3017.

[0267] Example 3-3 (4E)-7-phenyl-4,6-heptadienyl acetate (6:n=1,R 2 Production of phenyl group

[0268] [ka]

[0269] (4E,10Z)-4,6,10-hexadecatrienyl chloride (5:X) used in Example 3-1 as the organic halogen compound (5) 2=Cl,n=1,R 2 Instead of the (3Z)-3-nonenyl group, use (4E)-7-phenyl-4,6-heptadienyl chloride (5:X) obtained according to Example 2-12. 2 =Cl,n=1,R 2 The same procedure as in Example 3-1 was followed, except that (4E)-7-phenyl-4,6-heptadienyl acetate (6:n=1,R 2 (=phenyl group) (211.88g: 0.92 mol, yield 91.8%, purity 98.0%) was obtained.

[0270] The (4E)-7-phenyl-4,6-heptadienyl acetate obtained above (6:n=1,R 2 Analysis by gas chromatography revealed two cis-trans isomers of the phenyl group at retention times of 17.03 min and 21.59 min [isomer formation ratio = 57.3 (GC retention time 17.03 min): 42.7 (GC retention time 21.59 min)]. The above (4E)-7-phenyl-4,6-heptadienyl acetate (6:n=1,R 2 The above yields and quantities of the phenyl group are described as a mixture of the two cis-trans isomers.

[0271] Also, the above (4E)-7-phenyl-4,6-heptadienyl acetate (6:n=1,R 2 To determine the stereochemistry of the two cis-trans isomers of the phenyl group, 1 H-NMR and 2D NMR 13 The spin coupling constant between double-bonded hydrogen nuclei was confirmed from 13C non-irradiated HSQC slice data. As a result, it was considered that the cis-trans isomer detected at GC retention time 17.03 minutes was (4E,6Z)-7-phenyl-4,6-heptadienyl acetate, and the cis-trans isomer detected at GC retention time 21.59 minutes was also (4E,6E)-7-phenyl-4,6-heptadienyl acetate.

[0272] The (4E)-7-phenyl-4,6-heptadienyl acetate obtained above (6:n=1,R 2 The spectral data for various phenyl groups are shown below. (Nuclear magnetic resonance spectrum) 1 H-NMR(500MHz, CDCl3):δ 1.76(2H,sep,J=6.9Hz),2.04(1.8H,s),2.06(1.2H,s),2.21(2H.sext,J=6.7Hz),4.08(1.2H,t, J=6.7Hz),4.10(0.8H,t,J=6.5Hz),5.77-5.87(1H,dd,J=15.1,8.7Hz),6.37(0.4H,d,J=11.5Hz), 6.48(0.6H,m),6.18-6.26(1H,m),6.34(0.6H,d,J=11.5Hz),6.46(0.4H,d,J=15.7Hz),6.62(0.6H ,dd,J=15.2,11.2Hz),6.74(0.4H,dd,J=15.7,10.3Hz),7.18-7.25(1H,m),7.28-7.39(4H,m)ppm. 13 C-NMR(125MHz, CDCl3):δ 20.93,20.95,28.13,28.19,29.14,29.18,63.81,63.85,126.13,126.72,127.18,127.32,128.17,128.1 9,128.52,128.84,128.97,130.11,130.58,131.33,133.81,136.00,137.42,137.63,171.09,171.11ppm. 1 H-NMR and 2D NMR 13 Spin coupling constants (4E,6Z) between double-bonded hydrogen nuclei determined from non-irradiated HSQC slice data: J 4,5 =15.2Hz(4th-5th place),J 6,7 =11.5Hz(6-7th place);(4E,6E) body:J 4,5 =15.1Hz(4th-5th place),J 6,7 =15.7Hz(6th-7th place). (Mass Spectrum) EI (70 eV) (GC retention time = 17.03 mins) (4E, 6Z) Body: m / z 230 (M +),170,155,141,128,115,103,91,78,65,43;(GC retention time = 21.59 minutes) (4E,6E) body: m / z 230(M + ),170,155,141,128,115,103,91,79,65,43. (Infrared absorption spectrum) (ATR method): ν (cm) -1 )606,701,748,771,950,990,1042,1241,1366,1387,1447,1492,1596,1644,1739,2954,3022.

[0273] Examples 3-4 (7E)-7,9-tetradecadienyl acetate (6:n=4,R 2 Production of n-butyl group

[0274] [ka]

[0275] (4E,10Z)-4,6,10-hexadecatrienyl chloride (5:X) used in Example 3-1 as the organic halogen compound (5) 2 =Cl,n=1,R 2 Instead of the (3Z)-3-nonenyl group, use (7E)-7,9-tetradecadienyl chloride (5:X) obtained according to Example 2-13. 2 =Cl,n=4,R 2 The same procedure as in Example 3-1 was followed, except that (7E)-7,9-tetradecadienyl acetate (6:n=4,R 2 =n-butyl group) (234.72g: 0.93 mol, yield 93.8%, purity 97.1%) was obtained.

[0276] The (7E)-7,9-tetradecadienyl acetate obtained above (6:n=4,R 2Analysis by gas chromatography revealed two cis-trans isomers of the (7E)-7,9-tetradecadienyl acetate (6:n=4,R) at retention times of 14.30 min and 14.48 min [isomer formation ratio = 41.1 (GC retention time 14.30 min): 58.9 (GC retention time 14.48 min)]. 2 The above yields and quantities of the n-butyl group are described as a mixture of the two cis-trans isomers.

[0277] Also, the above (7E)-7,9-tetradecadienyl acetate (6:n=4,R 2 To determine the stereochemistry of the two cis-trans isomers of the n-butyl group, 1 H-NMR and 2D NMR 13 The spin coupling constant between double-bonded hydrogen nuclei was confirmed from 13C non-irradiated HSQC slice data. As a result, it was considered that the cis-trans isomer detected at GC retention time 14.30 minutes was (7E,9Z)-7,9-tetradecadienyl acetate, and the cis-trans isomer detected at GC retention time 14.48 minutes was also (7E,9E)-7,9-tetradecadienyl acetate.

[0278] The (7E)-7,9-tetradecadienyl acetate obtained above (6:n=4,R 2 The spectral data for the n-butyl group are shown below. (Nuclear magnetic resonance spectrum) 1H-NMR (600MHz, CDCl3): δ 0.89(1.8H,t,J=7.7Hz),0.90(1.2H,t,J=7.7Hz),1.28-1.43(10H,m),1.59-1.64(2H.m),2.13- 2.07(5.4H,m),2.09(0.8H,q,J=7.1Hz),2.16(0.8H,q,J=6.8Hz),4.04(1.2H,t,J=6.8Hz),4.05 (0.8H,t,J=6.8Hz),5.30(0.4H,dt,J=10.7,7.6Hz),5.51-5.60(1.2H,m),5.64(0.4H,dt,J=14. 8,7.3Hz),5.93(0.4H,t,J=10.9Hz),5.97-6.02(1.2H,m),6.30(0.4H,dd,J=15.1,10.9Hz)ppm. 13 C-NMR (150MHz, CDCl3): δ 14.08,14.10,21.15,22.38,22.46,25.93,27.53,28.68,28.69,28.92,28.95,29.40,31.71,32.03,32. 40,32.60,32.89,64.74,125.92,128.65,130.36,130.38,130.65,132.18,132.69,134.45,171.37ppm. 1 H-NMR and 2D NMR 13 C non-irradiation HSQC スライスデータよりFind the めたdouble bound hydrogen internuclear のスピン binding definite number (7E, 9Z) body: J 7,8 =15.0Hz (7-8 bits), J 9,10 =10.8Hz (9-10 bits); (7E, 9E) volume: J 7,8 =14.5Hz (7-8 bits), J 9,10 =15.0Hz (9-10 bits). (Mascuit)EI (70eV) (GC retention time = 14.30 minutes) (7E, 9Z) body: m / z 252 (M + ),192,163,149,135,121,95,81,67,43;(GC retention time = 14.48 minutes)(7E,9E) volume: m / z 252 (M + ),192,163,149,135,121,95,81,67,43. (Infrared absorption spectrum) (ATR method): ν (cm) -1 )606,728,948,987,1038,1239,1365,1465,1741,2857,2928,2955,3015.

[0279] Examples 3-5 (7E)-7,9-Dodecadienyl acetate (6:n=4,R 2 Production of ethyl group

[0280] [ka]

[0281] (4E,10Z)-4,6,10-hexadecatrienyl chloride (5:X) used in Example 3-1 as the organic halogen compound (5) 2 =Cl,n=1,R 2 Instead of the (3Z)-3-nonenyl group, use (7E)-7,9-dodecadienyl chloride (5:X) obtained according to Example 2-14. 2 =Cl,n=4,R 2 The same procedure as in Example 3-1 was followed, except that (7E)-7,9-dodecadienyl acetate (6:n=4,R 2 (=ethyl group) (188.45g: 0.84 mol, yield 83.5%, purity 97.9%) was obtained.

[0282] The (7E)-7,9-dodecadienyl acetate obtained above (6:n=4,R 2 Analysis by gas chromatography revealed two cis-trans isomers of the (7E)-7,9-dodecadienyl acetate (6:n=4,R) at retention times of 17.53 min and 17.98 min [isomer formation ratio = 44.9 (GC retention time 17.53 min): 55.1 (GC retention time 17.98 min)]. 2 The above yields and quantities of (ethyl group) are described as a mixture of the two cis-trans isomers.

[0283] Also, the above (7E)-7,9-dodecadienyl acetate (6:n=4,R 2 To determine the stereochemistry of the two cis-trans isomers of the ethyl group, 1 H-NMR and 2D NMR 13 The spin coupling constant between double-bonded hydrogen nuclei was confirmed from 13C non-irradiated HSQC slice data. As a result, it was considered that the cis-trans isomer detected at GC retention time 17.53 minutes was (7E,9Z)-7,9-dodecadienyl acetate, and the cis-trans isomer detected at GC retention time 17.98 minutes was also (7E,9E)-7,9-dodecadienyl acetate.

[0284] The (7E)-7,9-dodecadienyl acetate obtained above (6:n=4,R 2 The spectral data for various groups (=ethyl group) are shown below. (Nuclear magnetic resonance spectrum) 1 H-NMR(600MHz, CDCl3):δ 0.99(1.2H,t,J=7.5Hz),1.00(1.8H,t,J=7.4Hz),1.30-1.43(6H,m),1.59-1.64( 2H.m),2.03-2.11(6.2H,m),2.17(0.8H,quin,J=7.5Hz),4.03(1.2H,t,J=6.8Hz), 4.05(0.8H,t,J=6.8Hz),5.30(0.4H,dt,J=10.7,7.6Hz),5.53-5.66(1.6H,m),5. 91(0.4H,t,J=10.9Hz),5.97-6.02(1.2H,m),6.29(0.4H,dd,J=15.1,11.1Hz)ppm. 13 C-NMR(150MHz, CDCl3):δ 13.76,14.44,21.14,25.71,25.92,28.67,28.90,28.94,29.37,29.40,32.59,32.87, 64.73,125.78,128.08,129.45,130.63,131.92,132.25,134.14,134.50,171.36ppm. 1 H-NMR and 2D NMR 13Spin coupling constants between double-bonded hydrogen nuclei determined from 13C non-irradiated HSQC slice data (7E,9Z)body:J 7,8 =15.1Hz(7th-8th place),J 9,10 =10.8Hz (9-10th place; (7E,9E) body: J 7,8 =14.8Hz(7th-8th place),J 9,10 =15.3Hz(9-10th place). (Mass spectrum) EI (70 eV) (GC retention time = 17.53 mins) (7E, 9Z) Body: m / z 224 (M + ),164,135,121,107,95,79,67,55,43;(GC retention time = 17.98 min) (7E,9E) body: m / z 224(M + ),164,135,121,107,95,79,67,55,43. (Infrared absorption spectrum) (ATR method): ν (cm) -1 )606,728,948,987,1038,1239,1365,1387,1462,1742,2856,2931,2962,3016.

[0285] Examples 3-6 (7E)-11-methyl-7,9-tetradecadienyl acetate (6:n=4,R 2 Production of (2-pentyl group)

[0286] [ka]

[0287] (4E,10Z)-4,6,10-hexadecatrienyl chloride (5:X) used in Example 3-1 as the organic halogen compound (5) 2 =Cl,n=1,R 2 Instead of the (3Z)-3-nonenyl group, use (7E)-11-methyl-7,9-tetradecadienyl chloride (5:X) obtained according to Example 2-15. 2 =Cl,n=4,R 2The same procedure as in Example 3-1 was followed, except that (7E)-11-methyl-7,9-tetradecadienyl acetate (6:n=4,R 2 =2-pentyl group) (245.11 g: 0.92 mol, yield 91.9%, purity 97.2%) was obtained.

[0288] The (7E)-11-methyl-7,9-tetradecadienyl acetate obtained above (6:n=4,R 2 Analysis by gas chromatography revealed two cis-trans isomers of the (7E)-11-methyl-7,9-tetradecadienyl acetate (6:n=4,R) at retention times of 14.06 min and 15.36 min [isomer formation ratio = 52.1 (GC retention time 14.06 min): 47.9 (GC retention time 15.36 min)]. 2 The above yields and quantities of the 2-pentyl group are described as a mixture of the two cis-trans isomers.

[0289] Also, the above (7E)-11-methyl-7,9-tetradecadienyl acetate (6:n=4,R 2 To determine the stereochemistry of the two cis-trans isomers of the 2-pentyl group, 1 H-NMR and 2D NMR 13 The spin coupling constant between double-bonded hydrogen nuclei was confirmed from 13C non-irradiated HSQC slice data. As a result, it was considered that the cis-trans isomer detected at GC retention time 14.06 minutes was (7E,9Z)-11-methyl-7,9-tetradecadienyl acetate, and the cis-trans isomer detected at GC retention time 15.36 minutes was (7E,9E)-11-methyl-7,9-tetradecadienyl acetate.

[0290] The (7E)-11-methyl-7,9-tetradecadienyl acetate obtained above (6:n=4,R 2 The spectral data for the 2-pentyl group are shown below. (Nuclear magnetic resonance spectrum) 1H-NMR (600MHz, CDCl3): δ 0.87(1.5H,t,J=7.0Hz),0.88(1.5H,t,J=7.1Hz),0.95(1.5H,d,J=6.7Hz),0.97(1.5Hd,J=6.7Hz),1.18-1.43(10H,m) ,1.59-1.64(2H,m),2.03-2.06(4H,m),2.08(1H,q,J=7.6Hz),2.11-2.16(0.5H,m),2.55-2.63(0.5H,m),4.05(1H,t,J =6.8Hz),4.06(1H,t,J=6.8Hz),5.07(0.5H,t,J=10.4Hz),5.44(0.5H,dd,J=14.5,7.9Hz),5.56(0.5H,dt,J=14.3,7.1 Hz),5.63(0.5H,dt,J=14.7,7.3Hz),5.89(0.5H,t,J=10.9Hz),5.93-6.01(1H,m),6.27(0.5H,dd,J=15.0,11.0Hz)ppm. 13 C-NMR (150MHz, CDCl3): δ 14.30,14.34,20.57,20.69,20.71,21.15,21.42,25.93,28.68,28.70,28.94,29.36,29.41,32.05,32.63,32. 87,36.56,39.49,39.98,64.74,126.14,127.31,128.52,130.75,132.23,134.39,136.81,138.71,171.37ppm. 1 H-NMR and 2D NMR 13 C non-irradiation HSQC スライスデータよりFind the めたdouble bound hydrogen internuclear のスピン binding definite number (7E, 9Z) body: J 7,8 =14.9Hz (7-8 bits), J 9,10 =10.7Hz (9-10 bits); (7E, 9E) volume: J 7,8 =14.3Hz (7-8 bits), J 9,10 =14.5Hz (9-10 bits). (Mascuit)EI (70eV) (GC retention time = 14.06 minutes) (7E, 9Z) body: m / z 266 (M +),223,177,163,149,135,121,107,95,81,67,55,43;(GC retention time=15.36 minutes)(7E,9E bodies): m / z 242(M + ),199,171,158,143,123,109,95,81,67,55,41. (Infrared absorption spectrum) (ATR method): ν (cm) -1 )740,949,987,1039,1239,1365,1456,1742,2858,2928,2956.

[0291] Examples 3-7 (7E,11E)-7,9,11-Tridecatrienylenyl acetate(6:n=4,R 2 Production of (1-propenyl group)

[0292] [ka]

[0293] (4E,10Z)-4,6,10-hexadecatrienyl chloride (5:X) used in Example 3-1 as the organic halogen compound (5) 2 =Cl,n=1,R 2 Instead of the (3Z)-3-nonenyl group, use (7E,11E)-7,9,11-tridecatrienyl chloride (5:X) obtained according to Example 2-16. 2 =Cl,n=4,R 2 The same procedure as in Example 3-1 was followed, except that (7E,11E)-7,9,11-tridecatrienyl acetate (6:n=4,R 2 =1-propenyl group) (198.53g: 0.84 mol, yield 83.9%, purity 98.3%) was obtained.

[0294] The (7E,11E)-7,9,11-tridecatrienylenyl acetate obtained above (6:n=4,R 2Analysis by gas chromatography revealed two cis-trans isomers of the (1-propenyl group) at retention times of 13.15 min and 13.57 min [isomer formation ratio = 49.3 (GC retention time 13.15 min): 50.7 (GC retention time 13.57 min)]. The above (7E,11E)-7,9,11-tridecatrienyl acetate (6:n=4,R 2 The above yields and quantities of the 1-propenyl group are described as a mixture of the two cis-trans isomers.

[0295] Also, the above (7E,11E)-7,9,11-tridecatrienylenyl=acetate(6:n=4,R 2 To determine the stereochemistry of the two cis-trans isomers of the 1-propenyl group, 1 H-NMR and 2D NMR 13 The spin coupling constant between double-bonded hydrogen nuclei was confirmed from 13C non-irradiated HSQC slice data. As a result, it was considered that the cis-trans isomer detected at GC retention time 13.15 minutes is (7E,9Z,11E)-7,9,11-tridecatrienyl acetate, and the cis-trans isomer detected at GC retention time 13.57 minutes is (7E,9E,11E)-7,9,11-tridecatrienyl acetate.

[0296] The (7E,11E)-7,9,11-tridecatrienylenyl acetate obtained above (6:n=4,R 2 The spectral data for the 1-propenyl group are shown below. (Nuclear magnetic resonance spectrum) 1 H-NMR(600MHz, CDCl3):δ 1.29-1.43(6H,m),1.58-1.64(2H,m),1.76(1.5H,d,J=6.7Hz),1.80(1.5H,d,J=6.8Hz),2.04(3H,s),2.08(1H,q,J=7.7Hz),2.11(1H,q, J=6.9Hz),4.04(1H,t,J=6.7Hz),4.05(1H,t,J=6.7Hz),5.61-5.75(2H,m),5.80-5.86(1H,m),6.00-6.10(2H,m),6.45-6.52(1H,m)ppm. 13 C-NMR(150MHz, CDCl3):δ 18.40,18.52,21.14,25.91,25.92,28.67,28.89,28.94,29.33,32.80,32.95,64.71,126.02,127. 28,127.48,127.72,128.98,130.01,130.65,130.71,130.95,131.89,134.24,135.25,171.36ppm. 1 H-NMR and 2D NMR 13 Spin coupling constants (7E, 9Z, 11E) between double-bonded hydrogen nuclei, obtained from non-irradiated HSQC slice data: J 7,8 =15.2Hz(7th-8th place),J 9,10 =11.3Hz(9-10th place),J 11,12 =14.8Hz(11-12th place);(7E,9E,11E) body:J 7,8 =14.6Hz(7th-8th place),J 9,10 =14.6Hz(9-10th place),J 11,12 =15.0Hz(11th-12th place). (Mass spectrum) EI (70 eV) (GC retention time = 13.15 mins) (7E, 9Z, 11E) Body: m / z 236 (M + ),147,133,119,105,91,79,67,55,43;(GC retention time = 13.57 minutes) (7E,9E,11E) body: m / z 236(M + ),147,133,119,105,91,79,67,55,43. (Infrared absorption spectrum) (ATR method): ν (cm) -1 )606,723,926,964,997,1038,1240,1365,1437,1740,2855,2929,3013.

[0297] Examples 3-8 (11E)-11,13-Hexadecadienyl=acetate(6:n=8,R 2 Production of ethyl group

[0298] [ka]

[0299] (4E,10Z)-4,6,10-hexadecatrienyl chloride (5:X) used in Example 3-1 as the organic halogen compound (5) 2 =Cl,n=1,R 2 Instead of the (3Z)-3-nonenyl group, use (11E)-11,13-hexadecadienyl chloride (5:X) obtained according to Example 2-17. 2 =Cl,n=8,R 2 The same procedure as in Example 3-1 was followed, except that (11E)-11,13-hexadecadienyl acetate (6:n=8,R 2 (=ethyl group) (204.73g: 0.73 mol, yield 73.4%, purity 91.0%) was obtained.

[0300] The (11E)-11,13-hexadecadienyl acetate obtained above (6:n=8,R 2 Analysis by gas chromatography revealed two cis-trans isomers of the (11E)-11,13-hexadecadienyl acetate (6:n=8,R) at retention times of 19.24 min and 19.72 min [isomer formation ratio = 43.8 (GC retention time 19.24 min): 56.2 (GC retention time 19.72 min)]. 2 The above yields and quantities of (ethyl group) are described as a mixture of the two cis-trans isomers.

[0301] Also, the above (11E)-11,13-hexadecadienyl=acetate(6:n=8,R 2 To determine the stereochemistry of the two cis-trans isomers of the ethyl group, 1 H-NMR and 2D NMR 13The spin coupling constant between double-bonded hydrogen nuclei was confirmed from 13C non-irradiated HSQC slice data. As a result, it was considered that the cis-trans isomer detected at GC retention time 19.24 minutes is (11E,13Z)-11,13-hexadecadienyl acetate, and the cis-trans isomer detected at GC retention time 19.72 minutes is (11E,13E)-11,13-hexadecadienyl acetate.

[0302] The (11E)-11,13-hexadecadienyl acetate obtained above (6:n=8,R 2 The spectral data for various groups (=ethyl group) are shown below. (Nuclear magnetic resonance spectrum) 1 H-NMR (600 MHz, CDCl3): δ 0.99(3H,t,J=7.5Hz),1.24-1.40(14H,m),1.61(2H.quin,J=7.1Hz),2.02-2. 10(6.1H,m),2.17(0.9H,quin,J=7.7Hz),4.05(2H,t,J=6.9Hz),5.29(0.4H,dt ,J=10.6,7.7Hz),5.53-5.62(1.2H,m),5.65(0.4H,dt,J=15.0,7.4Hz),5.91( 0.4H,t,J=10.8Hz),5.97-6.03(1.2H,m),6.29(0.4H,dd,J=14.7,11.7Hz)ppm. 13 C-NMR(150MHz, CDCl3):δ 13.78,14.46,21.14,21.16,25.72,26.04,28.74,29.33,29.36,29.38,29.54,29.57,29.61,29.63, 32.74,33.01,64.80,125.62,128.17,129.53,130.45,131.77,132.60,133.99,134.84,171.38ppm. 1 H-NMR and 2D NMR 13 Spin coupling constants (11E, 13Z) between double-bonded hydrogen nuclei, obtained from non-irradiated HSQC slice data: J 11,12 =14.9Hz(11th-12th place),J 13,14=10.7Hz(13-14th place);(11E,13E) body:J 11,12 =14.9Hz(11th-12th place),J 13,14 =14.9Hz(13th-14th place). (Mass Spectrum) EI (70 eV) (GC retention time = 19.24 mins) (11E, 13Z) Body: m / z 280 (M + ),251,220,177,149,135,121,95,82,79,67,55,43;(GC retention time=19.72 min)(11E,13E) body: m / z 280(M + ),251,220,177,149,135,121,95,82,79,67,55,43. (Infrared absorption spectrum) (ATR method): ν (cm) -1 )606,722,947,987,1038,1237,1364,1463,1742,2854,2928,2962,3018.

[0303] Example 4 The following Example 4-1 describes the production of an alcohol compound represented by the following general formula (7), as shown in the reaction equation below.

[0304] [ka]

[0305] Example 4-1 (4E,10Z)-4,6,10-Hexadecatrienyl=Alcohol(7:n=1,R 2 Production of (3Z)-3-nonenyl group

[0306] [ka]

[0307] The reactor, equipped with a stirrer, condenser, and thermometer, was purged with nitrogen, and the (4E,10Z)-4,6,10-hexadecatrienyl acetate (6:n=1,R) obtained according to Example 3-1 was added to the reactor. 2(3Z)-3-nonenyl group (278.43g: 1.00 mol, purity 97.3%) and methanol (CH3OH) (360.0g) were added and the mixture was heated to a temperature of 40°C to 45°C. 25 wt% sodium hydroxide aqueous solution (188.0g) was added dropwise to the mixture over 2 hours at a temperature of 45°C to 60°C. After the addition was complete, the reaction mixture was stirred at a temperature of 50°C to 60°C for 4 hours. After stirring, water (200.0g) was added to the reactor to dilute it, and the mixture was separated into an organic layer and an aqueous layer. The organic layer was washed with a 20 wt% sodium chloride aqueous solution (250.0g). After removing the solvent from the organic layer under reduced pressure, the resulting crude product was purified by vacuum distillation to obtain (4E,10Z)-4,6,10-hexadecatrienyl=alcohol (7:n=1,R 2 =(3Z)-3-nonenyl group) (231.7g: 0.98 mol, yield 98.6%, purity 97.7%) was obtained.

[0308] The (4E,10Z)-4,6,10-hexadecatrienyl alcohol obtained above (7:n=1,R 2 Analysis by gas chromatography revealed that the (3Z)-3-nonenyl group produced two cis-trans isomers at retention times of 17.37 min and 18.42 min [isomer production ratio = 41.2 (GC retention time 17.37 min: (4E,6Z,10Z)-4,6,10-hexadecatrienyl=alcohol): 58.8 (GC retention time 18.42 min: (4E,6E,10Z)-4,6,10-hexadecatrienyl=alcohol]. The above (4E,10Z)-4,6,10-hexadecatrienyl=alcohol (7:n=1,R 2 The above yields and quantities of (3Z)-3-nonenyl group are described as a mixture of the two cis-trans isomers.

[0309] The (4E,10Z)-4,6,10-hexadecatrienyl alcohol obtained above (7:n=1,R 2 The spectral data for the (3Z)-3-nonenyl group are shown below. (Nuclear magnetic resonance spectrum) 1H-NMR (500MHz, CDCl3): δ 0.82(3H,t,J=7.1Hz),1.23-1.37(6H,m),1.50(1H,s),1.63-1.70(2H,m), 2.02(2H.quin,J=6.5Hz),2.09-2.23(6H,m),3.65(1.2H,t,J=6.0Hz),3.66 (0.8H,t,J=6.5Hz),5.30-5.41(2.6H,m),5.54-5.61(1H,m),5.67(0.4H,dt ,J=14.8,7.3Hz)5.93-6.06(1.6H,m),6.34(0.4H,dd,J=15.1,10.9Hz)ppm. 13 C-NMR (126MHz, CDCl3): δ 14.05,22.54,27.06,27.20,27.28,28.86,29.12,29.34,29.36,31.48,32.25,32.68,62.42,1 26.19,128.66,128.77,129.77,130.34,130.51,130.61,130.91,131.39,132.21,133.65ppm. (Mascuit)EI (70eV) (GC retention time = 17.37 minutes) (4E, 6Z, 10Z) body: m / z 236 (M + ), 177, 147, 125, 107, 91, 79, 67, 55, 41, 29.; (GC retention time = 18.42 minutes) (4E, 6E, 10Z) volume: m / z 236 (M + ),177,147,125,107,91,79,67,55,41,29. (Infrared ray absorption radiation) (ATR method): ν (cm -1 )728,947,986,1058,1448,2856,2926,2954,3008,3324.

Claims

1. The following general formula (1): 【Chemistry 1】 (In the formula, n represents the number of methylene groups from 1 to 10, X １ and X ２ (The '' represents halogen atoms that may be the same or different from each other, and 'Ph' represents a phenyl group.) The (ω-halo-2-alkenyl)triphenylphosphonium halide compound represented by The following general formula (2): 【Chemistry 2】 (In the formula, X ３ (This represents a halogen atom.) In the presence of lithium halide represented by the following general formula (3): 【Transformation 3】 (In the formula, R １ (where represents a linear or branched alkyl group having 1 to 6 carbon atoms, and M represents an alkali metal atom.) An alkali metal alkosyl represented by the following formula (4) is reacted with a phosphorus ylide to obtain a reaction product mixture, and then the reaction product mixture is reacted with the following general formula (4): 【Chemistry 4】 (In the formula, R ２ (This represents a monovalent hydrocarbon group having 1 to 10 carbon atoms, which can be linear, branched, or aromatic.) When the aldehyde compound represented by is subjected to the Wittig reaction, the following general formula (5): 【Transformation 5】 (In the formula, R ２ In the above general formula (4), n and X ２ This is defined as in the general formula (1) above. A process to obtain an organic halogen compound represented by A method for producing an organic halogen compound (5) comprising at least [the specified element].

2. A method for producing an organic halogen compound (5) according to claim 1, The organic halogen compound (5) is subjected to an acetoxylation reaction to obtain the following general formula (6): 【Transformation 6】 (In the formula, R ２ In the above general formula (4), n is as defined in the above general formula (1), and Ac represents an acetyl group. Steps to obtain an acetate compound represented by A method for producing an acetate compound (6) comprising at least [the specified element].

3. A method for producing an acetate compound (6) according to claim 2, The acetate compound (6) is subjected to a hydrolysis reaction to obtain the following general formula (7): 【Transformation 7】 (where R ２ is as defined in the above general formula (4), and n is as defined in the above general formula (1).) Steps to obtain the alcohol compound represented by A method for producing an alcohol compound (7) comprising at least [the specified element].

4. The following general formula (8): 【Transformation 8】 (In the formula, n represents the number of methylene groups from 1 to 10, X １ and X ２ Each represents a halogen atom independently. The ω-halo-2-alkenyl halide compound represented by is subjected to a substitution reaction with triphenylphosphine, resulting in the following general formula (1): 【Chemistry 9】 (In the formula, n, １ and X ２ (This is defined as in the general formula (8) above, and Ph represents a phenyl group.) Steps to obtain the (ω-halo-2-alkenyl)triphenylphosphonium halide compound represented by A method for producing a (ω-halo-2-alkenyl)triphenylphosphonium halide compound (1) comprising at least [a specific compound].

5. The following general formula (1): 【Chemistry 10】 (In the formula, n represents the number of methylene groups from 1 to 10, X １ and X ２ (The '' represents halogen atoms that may be the same or different from each other, and 'Ph' represents a phenyl group.) (ω-halo-2-alkenyl)triphenylphosphonium = halide compound represented by .

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