Substituted undecylenic compounds and substituted undecenyl triaryl phosphonium halides and methods of making compounds and mixtures therefrom

Abstract

The present invention relates to a process for the preparation of (4Z)-11,11-dialkoxy-4-undecenyl triaryl phosphonium halides of general formula (3-Z), wherein Y represents a halogen atom, Ar represents independently of each other an aryl group, R 1 and R 2 represent independently of each other a monovalent hydrocarbon group having 1 to 15 carbon atoms, or R 1 and R 2 may together form a divalent hydrocarbon group R 1 -R 2 having 2 to 10 carbon atoms, which process comprises: subjecting a (7Z)-11-halo-1,1-dialkoxy-7-undecene compound of general formula (1-Z), wherein X 1 represents a halogen atom, R 1 and R 2 are as defined above, to a phosphonium salt forming reaction with a phosphine compound of general formula (2), wherein Ar is as defined above, to form said compound (3-Z); and also relates to a compound of general formula (A) L(CH2)3CH=CH(CH2)5CH(OR 1 )(OR 2 )(A), wherein R 1 and R 2 are as defined above.

Description

Technical Field

[0001] This invention relates to 11-halo-1,1-dialkoxy-7-undecene compounds and methods for preparing 11,11-dialkoxy-4-undecene triarylphosphonium halides, trienaldehyde compounds, and diene compounds from the same.

[0002] The present invention also relates to 11,11-dialkoxy-4-undecenyltriarylphosphonium halides and methods for preparing trienaldehyde compounds and dienaldehyde compounds therefrom. Background Technology

[0003] The citrus leafminer (Phyllocnistis citrella) is one of the most serious pests of citrus, widely distributed in North, Central, and South America (such as the United States, Brazil, and Argentina); Mediterranean countries (such as Spain and Italy); Asia (such as Japan, Taiwan, Indonesia, the Philippines, and India); Oceania (such as Australia); Middle Eastern countries (such as Saudi Arabia); and Africa (such as Tunisia and South Africa). The citrus leafminer infests and damages leaves, severely impacting the growth of small and young trees. The holes dug by the pest can lead to the development of citrus canker. Therefore, controlling the citrus leafminer is crucial. Furthermore, because the citrus leafminer invades the leaf mesophyll, pesticides applied through typical spraying methods cannot reach the pest, making pesticide control difficult. Due to concerns about pesticide residues, biological control methods are gaining attention, and the use of sex pheromones shows promise as one such method.

[0004] According to reports, the sex pheromone component of the citrus leafminer is an aldehyde with 16 carbon atoms. Specifically, outside of Japan, it is a 3:1 mixture of (7Z,11Z,13E)-7,11,13-hexadecanetrienal and (7Z,11Z)-7,11-hexadecanedienal (Non-Patent Documents 1 and 2 listed below), while in Japan it is only (7Z,11Z)-7,11-hexadecanedienal (Non-Patent Document 3 listed below).

[0005] A method for preparing (7Z,11Z,13E)-7,11,13-hexadecanetrienal is described in Non-Patent Literature 1 listed below. In this method, the starting material 2-(5-bromopentyl)-1,3-dioxane is iodinated in acetone with sodium iodide to form 2-(5-iodopentyl)-1,3-dioxane. Next, the thus obtained 2-(5-iodopentyl)-1,3-dioxane undergoes a coupling reaction with (5-chloro-1-pentyn-1-yl)lithium in hexamethylphosphoric triamine (HMPA) and tetrahydrofuran (THF) to form 2-(10-chloro-6-decyl-1-yl)-1,3-dioxane. Next, the 2-(10-chloro-6-decyl-1-yl)-1,3-dioxane obtained therefrom is reacted with potassium acetate in HMPA to form 10-(1,3-dioxan-2-yl)-4-decynyl acetate. Subsequently, the 10-(1,3-dioxan-2-yl)-4-decynyl acetate obtained therefrom is hydrogenated using 5% palladium-barium sulfate as a catalyst and quinoline as a catalyst poison to reduce the carbon-carbon triple bond to a carbon-carbon double bond, thereby forming (4Z)-10-(1,3-dioxan-2-yl)-4-decenyl acetate. Next, the (4Z)-10-(1,3-dioxan-2-yl)-4-decenyl acetate obtained therefrom is hydrolyzed in methanol with an aqueous potassium hydroxide solution to form (4Z)-10-(1,3-dioxan-2-yl)-4-decen-1-ol. The hydroxyl group of the (4Z)-10-(1,3-dioxan-2-yl)-4-decen-1-ol obtained therefrom is oxidized in dichloromethane with pyridinium dichromate (PDC) to form (4Z)-10-(1,3-dioxan-2-yl)-4-decenal. The (4Z)-10-(1,3-dioxan-2-yl)-4-decenal obtained therefrom undergoes a Wittig reaction with separately prepared triphenylphosphonium(2E)-2-pentene ylide in THF and HMPA to form 2-(6Z,10Z,12E)-6,10,12-pentadecatrien-1-yl-1,3-dioxane. Subsequently, the obtained 2-(6Z,10Z,12E)-6,10,12-pentadecatrien-1-yl-1,3-dioxane was reacted with methanol in the presence of p-toluenesulfonic acid to form (3E,5Z,9Z)-16,16-dimethoxy-3,5,9-hexadecanetriene. Finally, the obtained (3E,5Z,9Z)-16,16-dimethoxy-3,5,9-hexadecanetriene was hydrolyzed in THF with hydrochloric acid.

[0006] Another method for preparing (7Z,11Z,13E)-7,11,13-hexadecanetrienal is described in Non-Patent Literature 2 listed below. In this method, the hydroxyl group of the starting material 3-bromo-1-propanol is protected to form 1-bromo-3-(tert-butyldimethylsiloxy)propane. Next, tetrahydro-2-(7-octyyn-1-yloxy)-2H-pyran, prepared separately, is reacted with n-butyllithium in THF, and then reacted with the 1-bromo-3-(tert-butyldimethylsiloxy)propane obtained above in a mixture of THF and N,N'-dimethylacrylurea (DMPU) to form 1-(tert-butyldimethylsiloxy)-11-(tetrahydropyranoxy)-4-undecaneyne. The tert-butyldimethylsilyl group of the resulting 1-(tert-butyldimethylsiloxy)-11-(tetrahydropyranoxy)-4-undecynylene was removed in THF using tetra-n-butylammonium fluoride (TBAF). The resulting compound was then hydrogenated using nickel boride (P-2Ni) as a catalyst to reduce the carbon-carbon triple bond to a carbon-carbon double bond, thereby forming (4Z)-11-(tetrahydropyranoxy)-4-undecen-1-ol. The hydroxyl group of the resulting (4Z)-11-(tetrahydropyranoxy)-4-undecen-1-ol was iodinated in THF in the presence of imidazole and triphenylphosphine (TPP) with iodine, and then reacted with TPP in toluene to form (4Z)-11-(tetrahydropyranoxy)-4-undecenyltriphenylphosphonium iodide. The resulting (4Z)-11-(tetrahydropyranoxy)-4-undecenyltriphenylphosphonium iodide reacts with n-butyllithium in a DMPU, followed by a Wittig reaction with (2E)-2-pentenal to form (7Z,11Z,13E)-1-(tetrahydropyranoxy)-hexadecanetriene. The resulting (7Z,11Z,13E)-1-(tetrahydropyranoxy)-hexadecanetriene then reacts with methanol in the presence of p-toluenesulfonic acid to form (7Z,11Z,13E)-7,11,13-hexadecanetrienol. Finally, the hydroxyl group of the resulting (7Z,11Z,13E)-7,11,13-hexadecanetrienol is oxidized with pyridinium chlorochromate (PCC).

[0007] A method for preparing (7Z,11Z)-7,11-hexadecadienal is described in Non-Patent Literature 1 listed below. In this method, the starting material 1,3-dibromopropane is coupled with [2-(1,3-dioxane-2-yl)ethyl]magnesium bromide in THF to form 2-(5-bromopentyl)-1,3-dioxane. Next, the resulting 2-(5-bromopentyl)-1,3-dioxane is reacted with lithium acetylate in HMPA and THF to form 2-(6-heptyne-1-yl)-1,3-dioxane. Next, the resulting 2-(6-heptyne-1-yl)-1,3-dioxane is reacted with n-butyllithium in THF, and then coupled with (3Z)-1-bromo-3-octene in HMPA to form 2-[(11Z)-11-hexadecene-7-alkynoxy]tetrahydro-2H-pyran. Subsequently, the obtained 2-[(11Z)-11-hexadecene-7-alkynoxy]tetrahydro-2H-pyran was hydrogenated using 5% palladium-barium sulfate as a catalyst and quinoline as a catalyst poison to reduce the carbon-carbon triple bond to a carbon-carbon double bond, thereby forming 2-[(7Z,11Z)-7,11-hexadecadien-1-yloxy]tetrahydro-2H-pyran. The obtained 2-[(7Z,11Z)-7,11-hexadecadien-1-yloxy]tetrahydro-2H-pyran was then reacted with methanol in the presence of p-toluenesulfonic acid to form (5Z,9Z)-16,16-dimethoxy-5,9-hexadecadiene. Finally, the obtained (5Z,9Z)-16,16-dimethoxy-5,9-hexadecadiene was hydrolyzed in THF with hydrochloric acid.

[0008] Another method for preparing (7Z,11Z)-7,11-hexadecadienal is described in Non-Patent Literature 2 listed below. In this method, the starting material tetrahydro-2-(7-octyyn-1-yloxy)-2H-pyran is reacted with n-butyllithium in THF, and then reacted with 1-chloro-3-iodopropane to form 2-[(11-chloro-7-undecyn-1-yl)oxy]tetrahydro-2H-pyran. The resulting 2-[(11-chloro-7-undecyn-1-yl)oxy]tetrahydro-2H-pyran is iodinated in acetone with sodium iodide to form 2-[(11-iodo-7-undecyn-1-yl)oxy]tetrahydro-2H-pyran. Subsequently, the obtained 2-[(11-iodo-7-undecyn-1-yl)oxy]tetrahydro-2H-pyran reacted with TPP in toluene to form 11-(tetrahydropyranoxy)-4-undecynyltriphenylphosphonium iodide. Next, the obtained 11-(tetrahydropyranoxy)-4-undecynyltriphenylphosphonium iodide reacted with n-butyllithium in DMPU, followed by a Wittig reaction with pentanal to form (11Z)-1-(tetrahydropyranoxy)-hexadecene-7-yne. The obtained (11Z)-1-(tetrahydropyranoxy)-hexadecene-7-yne then reacted with methanol in the presence of p-toluenesulfonic acid to form (11Z)-11-hexadecene-7-yne-1-ol. The resulting (11Z)-11-hexadecene-7-yn-1-ol was hydrogenated using nickel boride (P-2Ni) as a catalyst to reduce the carbon-carbon triple bond to a carbon-carbon double bond, thereby forming (7Z,11Z)-7,11-hexadecadienol. Finally, the hydroxyl group of the resulting (7Z,11Z)-7,11-hexadecadienol was oxidized in dichloromethane using pyridinium chlorochromate (PCC).

[0009] List of Literature

[0010] [Non-patent literature]

[0011] [Non-patent literature 1] Walter S. Leal et al., 2006, J. Chem. Ecol., 32(1): 155-168.

[0012] [Non-patent literature 2] Jocelyn G. Millar et al., 2006, J. Chem. Ecol., 32(1): 169-194.

[0013] [Non-Patent Literature 3] T. Ando, ​​J. Pestic. Sci., 30(4), 2005, 361-367.

[0014] The problem to be solved by this invention

[0015] However, in the two methods described in Non-Patent Literature 1 for the preparation of (7Z,11Z,13E)-7,11,13-hexadecanetrienal and (7Z,11Z)-7,11-hexadecadienal, the carcinogenic hexamethylphosphoric triamine is used extensively as a solvent, which hinders the practical application of these methods. The n-butyllithium used in the method described in Non-Patent Literature 1 is difficult to handle because it is sensitive to air and water and is easily flammable when exposed to air. Furthermore, the hydrogenation reaction in the method described in Non-Patent Literature 1 uses an expensive palladium catalyst, reducing the economic advantages of these methods. Quinoline, used as a catalyst poison, has recently been identified as having adverse effects on humans, making its use in industrial processes difficult. Additionally, the PDC (chromium compound) used in the oxidation reaction in the method for preparing (7Z,11Z,13E)-7,11,13-hexadecanetrienal poses extremely high environmental hazards; moreover, the oxidation reaction often involves an explosion hazard. Therefore, this method is difficult to implement on an industrial scale. Furthermore, the overall yield of this method is extremely low, at 14%, and involves up to nine steps. The method for preparing (7Z,11Z)-7,11-hexadecadienal also has an extremely low overall yield of 15% and involves up to six steps.

[0016] The two methods described in Non-Patent Literature 2 for preparing (7Z,11Z,13E)-7,11,13-hexadecanetrienal and (7Z,11Z)-7,11-hexadecadienal use n-butyllithium, which is sensitive to air and water, readily combustible when exposed to air, and difficult to handle. The use of the chromium compound PCC in the oxidation reaction causes extremely serious environmental hazards. Oxidation reactions are often explosive. Therefore, these methods are difficult to implement on an industrial scale. Furthermore, the dichloromethane used as a solvent in these methods causes serious environmental hazards and is therefore detrimental to environmental protection. The overall yield of the method for preparing (7Z,11Z,13E)-7,11,13-hexadecanetrienal is extremely low, at 7%, and includes up to nine steps. The overall yield of the method for preparing (7Z,11Z)-7,11-hexadecadienal is extremely low, at 22%, and includes up to seven steps.

[0017] Furthermore, the methods described in Non-Patent Literature 1 and 2 for preparing (7Z,11Z,13E)-7,11,13-hexadecanetrienal and (7Z,11Z)-7,11-hexadecadienal do not share a common synthetic intermediate, and these compounds must be prepared separately. Therefore, from an economic perspective, these methods are unsuitable for preparing the two components of the citrus leafminer sex pheromone. Summary of the Invention

[0018] This invention was made under these circumstances, with the aim of providing a method for efficiently preparing two components of the citrus leafminer sex pheromone from a common synthetic intermediate using fewer steps.

[0019] The inventors conducted in-depth research to overcome the aforementioned problems in the prior art, and discovered that (4Z)-11,11-dialkoxy-4-undecenyltriarylphosphonium halide is a common synthetic intermediate for the preparation of two components used in the sex pheromone preparation of citrus leafminer moth: (7Z,11Z,13E)-7,11,13-hexadectrienal and (7Z,11Z)-7,11-hexadecadienal. The inventors also discovered that (7Z,11Z,13E)-7,11,13-hexadectrienal and (7Z,11Z)-7,11-hexadecadienal can be prepared from (4Z)-11,11-dialkoxy-4-undecenyltriarylphosphonium halide in high yield and with fewer steps, thus completing this invention.

[0020] The inventors also discovered that (7Z)-11-halo-1,1-dialkoxy-7-undecene is a synthetic intermediate for preparing (4Z)-11,11-dialkoxy-4-undecene-triarylphosphonium halide, and (4Z)-11,11-dialkoxy-4-undecene-triarylphosphonium halide is a common synthetic intermediate for the two components of the sex pheromone, and thus completed the present invention.

[0021] According to a first aspect of the present invention, the present invention provides a method for preparing (4Z)-11,11-dialkoxy-4-undecenyltriarylphosphonium halides of the following general formula (3-Z):

[0022]

[0023] Where Y represents a halogen atom, Ar represents an aryl group independently, and R 1 and R 2 Each can be independently represented by a monovalent hydrocarbon group having 1 to 15 carbon atoms, or R 1 and R 2 They can together form divalent hydrocarbon groups R with 2 to 10 carbon atoms. 1 -R 2 ,

[0024] The method includes:

[0025] Make (7Z)-11-halo-1,1-dialkoxy-7-undecene compounds of the following general formula (1-Z):

[0026]

[0027] Where X 1 Represents a halogen atom, and R 1 and R 2 As defined above,

[0028] It undergoes a phosphonium salt formation reaction with phosphine compounds of the following general formula (2):

[0029] PAr3(2)

[0030] Ar is defined as above.

[0031] To form (4Z)-11,11-dialkoxy-4-undecenyltriarylphosphonium halide (3-Z).

[0032] According to a second aspect of the present invention, the present invention provides a method for preparing (3E,5Z,9Z)-16,16-dialkoxy-3,5,9-hexadecanetriene compounds of the following general formula (6):

[0033]

[0034] Where R 1 and R 2 As defined above,

[0035] The method includes:

[0036] (4Z)-11,11-dialkoxy-4-undecenyltriarylphosphonium halide (3-Z) is deprotonated in the presence of a base to form a mixture of reaction products, wherein the (4Z)-11,11-dialkoxy-4-undecenyltriarylphosphonium halide (3-Z) can be prepared by the method for preparing (4Z)-11,11-dialkoxy-4-undecenyltriarylphosphonium halide (3-Z) according to the first aspect of the invention or according to any other preparation method, and

[0037] The reaction product mixture is subjected to a Wittig reaction with (2E)-2-pentenal of formula (5):

[0038]

[0039] To form (3E,5Z,9Z)-16,16-dialkoxy-3,5,9-hexadecanetriene compound (6).

[0040] According to a third aspect of the present invention, the present invention provides a method for preparing (7Z,11Z,13E)-7,11,13-hexadecanetrienal of formula (7):

[0041]

[0042] The method includes:

[0043] The aforementioned method for preparing (3E,5Z,9Z)-16,16-dialkoxy-3,5,9-hexadecanetriene compound (6), and

[0044] The (3E,5Z,9Z)-16,16-dialkoxy-3,5,9-hexadecanetriene compound (6) is hydrolyzed to form (7Z,11Z,13E)-7,11,13-hexadecanetriene aldehyde (7).

[0045] According to a fourth aspect of the present invention, the present invention provides a method for preparing (5Z,9Z)-16,16-dialkoxy-5,9-hexadecadiene compounds of the following general formula (9):

[0046]

[0047] Where R 1 and R 2 As defined above,

[0048] The method includes:

[0049] (4Z)-11,11-dialkoxy-4-undecenyltriarylphosphonium halide (3-Z) is deprotonated in the presence of a base to form a mixture of reaction products, wherein the (4Z)-11,11-dialkoxy-4-undecenyltriarylphosphonium halide (3-Z) can be prepared by the method for preparing (4Z)-11,11-dialkoxy-4-undecenyltriarylphosphonium halide (3-Z) according to the first aspect of the invention or according to any other preparation method, and

[0050] The reaction product mixture is reacted with pentanal of formula (8) to undergo a Wittig reaction:

[0051] CH3(CH2)3CHO(8)

[0052] To form (5Z,9Z)-16,16-dialkoxy-5,9-hexadecadiene compound (9).

[0053] According to a fifth aspect of the present invention, the present invention provides a method for preparing (7Z,11Z)-7,11-hexadecadienal of formula (10):

[0054]

[0055] The method includes:

[0056] The aforementioned method for preparing (5Z,9Z)-16,16-dialkoxy-5,9-hexadecadiene compound (9), and

[0057] The (5Z,9Z)-16,16-dialkoxy-5,9-hexadecadiene compound (9) is hydrolyzed to form (7Z,11Z)-7,11-hexadecadienal (10).

[0058] According to a sixth aspect of the present invention, the present invention provides a method for preparing a mixture comprising a (3E,5Z,9Z)-16,16-dialkoxy-3,5,9-hexadecanetriene compound of the following general formula (6):

[0059]

[0060] Where R 1 and R 2 As defined above

[0061] And the following (5Z,9Z)-16,16-dialkoxy-5,9-hexadecadiene compounds of general formula (9):

[0062]

[0063] Where R 1 and R 2 As defined above,

[0064] The method includes:

[0065] (4Z)-11,11-dialkoxy-4-undecenyltriarylphosphonium halide (3-Z) is deprotonated in the presence of a base to form a mixture of reaction products, wherein the (4Z)-11,11-dialkoxy-4-undecenyltriarylphosphonium halide (3-Z) can be prepared by the method for preparing (4Z)-11,11-dialkoxy-4-undecenyltriarylphosphonium halide (3-Z) according to the first aspect of the invention or according to any other preparation method, and

[0066] The reaction product mixture is reacted with (2E)-2-pentenal of formula (5):

[0067]

[0068] And the pentaldehyde in equation (8) undergoes the Wittig reaction:

[0069] CH3(CH2)3CHO(8)

[0070] To form a mixture comprising (3E,5Z,9Z)-16,16-dialkoxy-3,5,9-hexadecanetriene compound (6) and (5Z,9Z)-16,16-dialkoxy-5,9-hexadecanetriene compound (9).

[0071] According to a seventh aspect of the invention, the invention provides a method for preparing a mixture comprising (7Z,11Z,13E)-7,11,13-hexadecanetrienal of formula (7):

[0072]

[0073] And (7Z,11Z)-7,11-hexadecadienal of formula (10):

[0074]

[0075] The method includes:

[0076] The aforementioned method for preparing a mixture comprising (3E,5Z,9Z)-16,16-dialkoxy-3,5,9-hexadecadiene compound (6) and (5Z,9Z)-16,16-dialkoxy-5,9-hexadecadiene compound (9), and

[0077] The mixture comprising (3E,5Z,9Z)-16,16-dialkoxy-3,5,9-hexadecanetriene compound (6) and (5Z,9Z)-16,16-dialkoxy-5,9-hexadecanediene compound (9) is subjected to hydrolysis reaction conditions to form a mixture comprising (7Z,11Z,13E)-7,11,13-hexadecanetrienal (7) and (7Z,11Z)-7,11-hexadecanedienal (10).

[0078] According to an eighth aspect of the present invention, the present invention provides compounds of the following general formula (A):

[0079] L(CH2)3CH=CH(CH2)5CH(OR 1 (OR) 2 (A)

[0080] Where R 1 and R 2 Each can be independently represented by a monovalent hydrocarbon group having 1 to 15 carbon atoms, or R 1 and R 2 They can together form divalent hydrocarbon groups R with 2 to 10 carbon atoms. 1 -R 2 L represents X 1 Or Y - Ar3P + , where X 1 Y represents a halogen atom, and Ar represents an aryl group independently.

[0081] When L is X 1 At that time, the compound is a 11-halo-1,1-dialkoxy-7-undecene compound of the following general formula (1):

[0082] X 1 (CH2)3CH=CH(CH2)5CH(OR 1 (OR) 2 (1).

[0083] When L is Y - Ar3P + At that time, the compound is a 11,11-dialkoxy-4-undecenyltriarylphosphonium halide of the following general formula (3):

[0084] Y - Ar3P + (CH2)3CH=CH(CH2)5CH(OR 1 (OR) 2 (3).

[0085] According to the present invention, (7Z,11Z,13E)-7,11,13-hexadecanetrienal (7), (7Z,11Z)-7,11-hexadecadienal (10), or mixtures thereof, are prepared in fewer steps and in high yield. According to the present invention, 11-halo-1,1-dialkoxy-7-undecene compound (1) and 11,11-dialkoxy-4-undecenetriarylphosphonium halide (3) are prepared as synthetic intermediates for the preparation of (7Z,11Z,13E)-7,11,13-hexadecanetrienal (7) and (7Z,11Z)-7,11-hexadecadienal (10). Detailed Implementation

[0086] A. Compounds of general formula (A)

[0087] Compounds of the following general formula (A):

[0088] L(CH2)3CH=CH(CH2)5CH(OR 1 (OR) 2 (A)

[0089] This will be described later. In general formula (A), R 1 and R 2 Each can be independently represented by a monovalent hydrocarbon group having 1 to 15 carbon atoms, or R 1 and R 2 They can together form divalent hydrocarbon groups R with 2 to 10 carbon atoms. 1 -R 2 L represents X 1 Or Y - Ar3P + , where X 1 Y and Ar represent halogen atoms, and Ar independently represent aryl groups.

[0090] When L in general formula (A) is X 1 When compound (A) is a 11-halo-1,1-dialkoxy-7-undecene compound of the following general formula (1):

[0091] X 1 (CH2)3CH=CH(CH2)5CH(OR 1 (OR) 2 (1).

[0092] When L in general formula (A) is Y - Ar3P + When compound (A) is a 11,11-dialkoxy-4-undecenyltriarylphosphonium halide of the following general formula (3):

[0093] Y - Ar3P + (CH2)3CH=CH(CH2)5CH(OR 1 (OR) 2 (3).

[0094] (A-1). 11-Halo-1,1-Dialkoxy-7-Undecene Compound (1) and its Preparation Method

[0095] First, the 11-halo-1,1-dialkoxy-7-undecene compound (1) will be described.

[0096] X 1 (CH2)3CH=CH(CH2)5CH(OR 1 (OR) 2 (1)

[0097] X 1 This represents the halogen atom as defined in general formula (A). Specifically, halogen atom X... 1 It can be a chlorine atom, a bromine atom, or an iodine atom. Considering the handling process, chlorine and bromine atoms are preferred.

[0098] In general formula (1), R 1 and R 2 Each of the above can independently represent a monovalent hydrocarbon group having 1 to 15 carbon atoms, preferably 1 to 10 carbon atoms, more preferably 1 to 4 carbon atoms, or R 1 and R 2 They can together form a divalent hydrocarbon group R having 2 to 10 carbon atoms, preferably 2 to 4 carbon atoms. 1 -R 2 .

[0099] Examples of monovalent hydrocarbon groups include straight-chain saturated hydrocarbon groups, such as methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl, and n-dodecyl groups; branched-chain saturated hydrocarbon groups, such as isopropyl, 2-isobutyl, and 2-methylbutyl groups; straight-chain unsaturated hydrocarbon groups, such as 2-propenyl groups; branched-chain unsaturated hydrocarbon groups, such as 2-methyl-2-propenyl groups; cyclic saturated hydrocarbon groups, such as cyclopropyl groups; and their isomers. Some of the hydrogen atoms in the hydrocarbon group may be replaced by a methyl or ethyl group.

[0100] For processing purposes, the monovalent hydrocarbon group is preferably a methyl group, an ethyl group, a n-propyl group, or a n-butyl group.

[0101] Examples of divalent hydrocarbon groups include straight-chain saturated hydrocarbon groups, such as ethylene, 1,3-propylene, and 1,4-butylene; branched-chain saturated hydrocarbon groups, such as 1,2-propylene, 2,2-dimethyl-1,3-propylene, 1,2-butylene, 1,3-butylene, 2,3-butylene, and 2,3-dimethyl-2,3-butylene; straight-chain unsaturated hydrocarbon groups, such as 1-vinylethylene; branched-chain unsaturated hydrocarbon groups, such as 2-methylene-1,3-propylene; cyclic hydrocarbon groups, such as 1,2-cyclopropenyl and 1,2-cyclobutenyl; and their isomers. Some of the hydrogen atoms in the hydrocarbon group may be replaced by a methyl or ethyl group.

[0102] Divalent hydrocarbon groups are preferably lower hydrocarbon groups having 2 to 4 carbon atoms, because they are readily available and highly reactive in deprotection, and the byproducts formed in deprotection are easily removed by washing or concentration.

[0103] In view of these, particularly preferred examples of divalent hydrocarbon groups include ethylene, 1,3-propylene, 1,2-propylene, 1,2-butylene, 1,3-butylene, and 2,3-dimethyl-2,3-butylene.

[0104] 11-Halo-1,1-dialkoxy-7-undecene compounds (1) include (7Z)-11-halo-1,1-dialkoxy-7-undecene compounds of general formula (1-Z) and (7E)-11-halo-1,1-dialkoxy-7-undecene compounds (1-E).

[0105] Specific examples of (7Z)-11-halo-1,1-dialkoxy-7-undecene compounds (1-Z) include the following compounds:

[0106] (7Z)-11-chloro-1,1-dialkoxy-7-undecene compound (1-Z:X) 1=Cl), such as (7Z)-11-chloro-1,1-dimethoxy-7-undecene, (7Z)-11-chloro-1,1-diethoxy-7-undecene, (7Z)-11-chloro-1,1-dipropoxy-7-undecene, (7Z)-11-chloro-1,1-dibutoxy-7-undecene, (7Z)-11-chloro-1,1-dipentoxy-7-undecene, (7Z)-11-chloro-1,1-dihexyloxy-7-undecene, (7Z)-11-chloro-1,1-diheptoxy-7-undecene, (7Z)-11-chloro-1,1-dioctyloxy-7-undecene, (7Z)-11-chloro-1,1-dinonoxy-7-undecene and (7Z)-11-chloro-1,1-didecoxy-7-undecene;

[0107] (7Z)-11-bromo-1,1-dialkoxy-7-undecene compound (1-Z:X) 1 =Br), such as (7Z)-11-bromo-1,1-dimethoxy-7-undecene, (7Z)-11-bromo-1,1-diethoxy-7-undecene, (7Z)-11-bromo-1,1-dipropoxy-7-undecene, (7Z)-11-bromo-1,1-dibutoxy-7-undecene, (7Z)-11-bromo-1,1-dipentoxy-7-undecene Carbene, (7Z)-11-bromo-1,1-dihexyloxy-7-undecene, (7Z)-11-bromo-1,1-diheptyloxy-7-undecene, (7Z)-11-bromo-1,1-dioctyloxy-7-undecene, (7Z)-11-bromo-1,1-dinonoxy-7-undecene and (7Z)-11-bromo-1,1-didecyloxy-7-undecene; and

[0108] (7Z)-11-iodo-1,1-dialkoxy-7-undecene compound (1-Z:X) 1 =I), such as (7Z)-11-iodo-1,1-dimethoxy-7-undecene, (7Z)-11-iodo-1,1-diethoxy-7-undecene, (7Z)-11-iodo-1,1-dipropoxy-7-undecene, (7Z)-11-iodo-1,1-dibutoxy-7-undecene, (7Z)-11-iodo-1,1-dipentoxy-7-undecene, (7Z)-11-iodo-1,1-dihexyloxy-7-undecene, (7Z)-11-iodo-1,1-diheptoxy-7-undecene, (7Z)-11-iodo-1,1-dioctyloxy-7-undecene, (7Z)-11-iodo-1,1-dinonoxy-7-undecene and (7Z)-11-iodo-1,1-didecoxy-7-undecene.

[0109] Specific examples of (7E)-11-halo-1,1-dialkoxy-7-undecene compounds (1-E) include the following compounds:

[0110] (7E)-11-chloro-1,1-dialkoxy-7-undecene compound (1-E:X) 1 =Cl), such as (7E)-11-chloro-1,1-dimethoxy-7-undecene, (7E)-11-chloro-1,1-diethoxy-7-undecene, (7E)-11-chloro-1,1-dipropoxy-7-undecene, (7E)-11-chloro-1,1-dibutoxy-7-undecene, (7E)-11-chloro-1,1-dipentoxy-7-undecene, (7E)-11-chloro-1,1-dihexyloxy-7-undecene, (7E)-11-chloro-1,1-diheptoxy-7-undecene, (7E)-11-chloro-1,1-diheptoxy-7-undecene, (7E)-11-chloro-1,1-dioctyloxy-7-undecene, (7E)-11-chloro-1,1-dinonoxy-7-undecene and (7E)-11-chloro-1,1-didecoxy-7-undecene;

[0111] (7E)-11-bromo-1,1-dialkoxy-7-undecene compound (1-E:X) 1 =Br), such as (7E)-11-bromo-1,1-dimethoxy-7-undecene, (7E)-11-bromo-1,1-diethoxy-7-undecene, (7E)-11-bromo-1,1-dipropoxy-7-undecene, (7E)-11-bromo-1,1-dibutoxy-7-undecene, (7E)-11-bromo-1,1-dipentoxy-7-undecene Carbene, (7E)-11-bromo-1,1-dihexyloxy-7-undecene, (7E)-11-bromo-1,1-diheptyloxy-7-undecene, (7E)-11-bromo-1,1-dioctyloxy-7-undecene, (7E)-11-bromo-1,1-dinonyloxy-7-undecene and (7E)-11-bromo-1,1-didecyloxy-7-undecene; and

[0112] (7E)-11-iodo-1,1-dialkoxy-7-undecene compound (1-E:X) 1=I), such as (7E)-11-iodo-1,1-dimethoxy-7-undecene, (7E)-11-iodo-1,1-diethoxy-7-undecene, (7E)-11-iodo-1,1-dipropoxy-7-undecene, (7E)-11-iodo-1,1-dibutoxy-7-undecene, (7E)-11-iodo-1,1-dipentoxy-7-undecene, (7E)-11-iodo-1,1-dihexyloxy-7-undecene, (7E)-11-iodo-1,1-diheptoxy-7-undecene, (7E)-11-iodo-1,1-dioctyloxy-7-undecene, (7E)-11-iodo-1,1-dinonoxy-7-undecene and (7E)-11-iodo-1,1-didecoxy-7-undecene.

[0113] Considering the preparation of citrus leafminer sex pheromones, 11-halo-1,1-dialkoxy-7-undecene compound (1) is preferably (7Z)-11-halo-1,1-dialkoxy-7-undecene compound (1-Z), especially (7Z)-11-chloro-1,1-dialkoxy-7-undecene compound (1-Z:X). 1 =Cl), (7Z)-11-bromo-1,1-dialkoxy-7-undecene compound (1-Z:X 1 =Br) and (7Z)-11-iodo-1,1-dialkoxy-7-undecene compounds (1-Z:X 1 =I).

[0114] In the following description, the preparation method of 11-halo-1,1-dialkoxy-7-undecene compound (1) is described using (7Z)-11-halo-1,1-dialkoxy-7-undecene compound (1-Z). When (7E)-11-halo-1,1-dialkoxy-7-undecene compound (1-E) is used instead of (7Z)-11-halo-1,1-dialkoxy-7-undecene compound (1-Z), the corresponding reaction is carried out in a similar manner to form the corresponding compound.

[0115] (7Z)-11-halo-1,1-dialkoxy-7-undecene compounds (1-Z) can be prepared, for example, according to the following reaction formula comprising three steps:

[0116]

[0117] In the reaction equation, R 1 R 2 and X 1 As defined by general formula (1), X 2 and X 3The symbol represents a halogen atom, M represents Li or MgZ, where Z represents a halogen atom or a 6,6-dialkoxyhexyl group.

[0118] First, a 6-halo-1,1-dialkoxyhexane compound of general formula (14) is reacted with magnesium or lithium in a solvent to prepare a 6,6-dialkoxyhexyl nucleophile of general formula (15) (Step 1). The 6,6-dialkoxyhexyl nucleophile (15) thus prepared is coupled with a 1-halo-5-halo-1-pentyne compound of general formula (16) in the presence of a catalyst to prepare an 11-halo-1,1-dialkoxy-7-undecyne compound of general formula (17) if necessary (Step 2). The carbon-carbon triple bond of the 11-halo-1,1-dialkoxy-7-undecyne compound (17) thus prepared is then reduced to form the target compound (7Z)-11-halo-1,1-dialkoxy-7-undecene compound (1-Z) (Step 3).

[0119] The preparation method of (7Z)-11-halo-1,1-dialkoxy-7-undecene compound (1-Z) will be described in further detail below.

[0120] The following describes 6-halo-1,1-dialkoxyhexane compound (14).

[0121] R in general formula (14) 1 and R 2 As defined by general formula (1).

[0122] X in general formula (14) 3 This represents a halogen atom. Specifically, halogen atom X... 3 It can be a chlorine atom, a bromine atom, or an iodine atom; considering reactivity, a chlorine atom or a bromine atom is preferred.

[0123] Specific examples of 6-halo-1,1-dialkoxyhexane compounds (14) include the following compounds:

[0124] 6-Chloro-1,1-dialkoxyhexane compound (14:X) 3 =Cl), such as 6-chloro-1,1-dimethoxyhexane, 6-chloro-1,1-diethoxyhexane, 6-chloro-1,1-dipropoxy-hexane, 6-chloro-1,1-dibutoxy-hexane, 6-chloro-1,1-dipentoxy-hexane, 6-chloro-1,1-dihexyloxy-hexane, 6-chloro-1,1-diheptoxy-hexane, 6-chloro-1,1-dioctyloxy-hexane, 6-chloro-1,1-dinonoxy-hexane and 6-chloro-1,1-didecoxy-hexane;

[0125] 6-Bromo-1,1-dialkoxyhexane compound (14:X) 3=Br), such as 6-bromo-1,1-dimethoxyhexane, 6-bromo-1,1-diethoxyhexane, 6-bromo-1,1-dipropoxy-hexane, 6-bromo-1,1-dibutoxy-hexane, 6-bromo-1,1-dipentoxy-hexane, 6-bromo-1,1-dihexyloxy-hexane, 6-bromo-1,1-diheptoxy-hexane, 6-bromo-1,1-dioctyloxy-hexane, 6-bromo-1,1-dinonoxy-hexane and 6-bromo-1,1-didecoxy-hexane; and

[0126] 6-Iodo-1,1-dialkoxyhexane compound (14:X) 3 =I), such as 6-iodo-1,1-dimethoxyhexane, 6-iodo-1,1-diethoxyhexane, 6-iodo-1,1-dipropoxy-hexane, 6-iodo-1,1-dibutoxy-hexane, 6-iodo-1,1-dipentoxy-hexane, 6-iodo-1,1-dihexyloxy-hexane, 6-iodo-1,1-diheptoxy-hexane, 6-iodo-1,1-dioctyloxy-hexane, 6-iodo-1,1-dinonoxy-hexane and 6-iodo-1,1-didecoxy-hexane.

[0127] Considering reactivity, 6-halo-1,1-dialkoxyhexane compound (14) is preferably 6-chloro-1,1-dialkoxyhexane compound (14:X) 3 =Cl) and 6-bromo-1,1-dialkoxyhexane compound (14:X 3 =Br).

[0128] first step

[0129] The preparation of the 6,6-dialkoxyhexyl nucleophile (15) includes, for example, reacting a 6-halo-1,1-dialkoxyhexane compound (14) with magnesium in a solvent to form a 6,6-dialkoxyhexyl nucleophile (15: M = MgZ) as a Grignard reagent (hereinafter also referred to as the "Grignard reagent preparation reaction", as shown in the following chemical reaction formula:

[0130]

[0131] Considering the completion of the reaction, the amount of magnesium to be used in the Grignard reagent preparation reaction is preferably 1.0 to 2.0 g atoms relative to each mol of 6-halo-1,1-dialkoxyhexane compound (14).

[0132] Examples of solvents used in Grignard reagent preparation reactions include ethers such as tetrahydrofuran, 2-methyltetrahydrofuran (2-MeTHF), diethyl ether, and 4-methyltetrahydropyran; and hydrocarbons such as toluene, xylene, and hexane. Considering the reaction rate of Grignard reagent preparation, the solvent is preferably an ether, such as tetrahydrofuran, 2-methyltetrahydrofuran, diethyl ether, and 4-methyltetrahydropyran, more preferably tetrahydrofuran and 2-methyltetrahydrofuran.

[0133] Solvents may be used alone or in combination if necessary. Solvents may be commercially available products.

[0134] Considering reactivity, the amount of solvent used is preferably 30 to 5000 g, more preferably 50 to 3000 g, relative to each mol of 6-halo-1,1-dialkoxyhexane compound (14).

[0135] The reaction temperature in the preparation of Grignard reagents varies depending on the solvent to be used, and is preferably between 0°C and 120°C, taking into account reactivity.

[0136] The reaction time for the preparation of Grignard reagents varies depending on the solvent to be used and / or the production scale, but is preferably 0.5 to 100 hours, taking into account reactivity.

[0137] Another method for preparing the 6,6-dialkoxyhexyl nucleophile (15) includes, for example, reacting a 6-halo-1,1-dialkoxyhexane compound (14) with lithium in a solvent to form the 6,6-dialkoxyhexyl nucleophile (15) as an organolithium reagent (hereinafter also referred to as the "lithium reagent preparation reaction"), as shown in the following chemical reaction formula:

[0138]

[0139] Considering the completion of the reaction, the amount of lithium used in the lithium reagent preparation reaction is preferably 1.0 to 2.0 g atoms relative to each mol of 6-halo-1,1-dialkoxyhexane compound (14).

[0140] Examples of solvents used in the preparation of lithium reagents include ethers such as tetrahydrofuran, 2-methyltetrahydrofuran, diethyl ether, and 4-methyltetrahydropyran; and hydrocarbons such as toluene, xylene, and hexane. Considering the reaction rate of lithium reagent preparation, the solvent is preferably an ether, such as tetrahydrofuran, 2-methyltetrahydrofuran, diethyl ether, or 4-methyltetrahydropyran; or a hydrocarbon, such as toluene, xylene, or hexane, more preferably tetrahydrofuran, 2-methyltetrahydrofuran, toluene, or hexane.

[0141] Solvents may be used alone or in combination if necessary. Solvents may be commercially available products.

[0142] Considering reactivity, the amount of solvent used is preferably 30 to 5000 g, more preferably 50 g to 3000 g, relative to each mol of 6-halo-1,1-dialkoxyhexane compound (14).

[0143] The reaction temperature in the lithium reagent preparation reaction varies depending on the solvent to be used, and is preferably between -40°C and 120°C, taking into account reactivity.

[0144] The reaction time for the lithium reagent preparation reaction varies depending on the solvent to be used and / or the production scale, and is preferably 0.5 to 100 hours, taking into account reactivity.

[0145] The 6,6-dialkoxyhexyl nucleophile (15) will be described below.

[0146] R in general formula (15) 1 and R 2 As defined by general formula (1).

[0147] In general formula (15), M represents Li or MgZ, where Z represents a halogen atom or a 6,6-dialkoxyhexyl group. Specifically, the halogen atom Z is a chlorine atom, a bromine atom, or an iodine atom. Considering reactivity, a chlorine atom or a bromine atom is preferred, and a chlorine atom is more preferred.

[0148] 6,6-Dialkoxyhexyl nucleophiles (15) include 6,6-dialkoxyhexyl magnesium halides (15: M = MgZ, Z = halogen atom) and bis(6,6-dialkoxyhexyl)magnesium compounds (15: M = MgZ, Z = 6,6-dialkoxyhexyl group).

[0149] Specific examples of 6,6-dialkoxyhexyl magnesium halides (15: M = MgZ, Z = halogen atom) include the following compounds:

[0150] 6,6-Dialkoxyhexyllithium compounds (15:M=Li), such as 6,6-dimethoxyhexyllithium, 6,6-diethoxyhexyllithium, 6,6-dipropoxy-hexyllithium, 6,6-dibutoxy-hexyllithium, 6,6-dipentoxy-hexyllithium, 6,6-dihexyloxy-hexyllithium, 6,6-diheptoxy-hexyllithium, 6,6-dioctyloxy-hexyllithium, 6,6-dinonoxy-hexyllithium and 6,6-didecoxy-hexyllithium;

[0151] 6,6-Dialkoxyhexyl magnesium chloride compounds (15: M = MgZ, Z = chlorine atom), such as 6,6-dimethoxyhexyl magnesium chloride, 6,6-diethoxyhexyl magnesium chloride, 6,6-dipropoxyhexyl magnesium chloride, 6,6-dibutoxyhexyl magnesium chloride, 6,6-dipentoxyhexyl magnesium chloride, 6,6-dihexyloxyhexyl magnesium chloride, 6,6-diheptoxyhexyl magnesium chloride, 6,6-dioctyloxyhexyl magnesium chloride, 6,6-dinonoxyhexyl magnesium chloride and 6,6-didecoxyhexyl magnesium chloride;

[0152] 6,6-Dialkoxyhexyl magnesium bromide compounds (15: M = MgZ, Z = bromine atom), such as 6,6-dimethoxyhexyl magnesium bromide, 6,6-diethoxyhexyl magnesium bromide, 6,6-dipropoxyhexyl magnesium bromide, 6,6-dibutoxyhexyl magnesium bromide, 6,6-dipentoxyhexyl magnesium bromide, 6,6-dihexyloxyhexyl magnesium bromide, 6,6-diheptoxyhexyl magnesium bromide, 6,6-dioctyloxyhexyl magnesium bromide, 6,6-dinonoxyhexyl magnesium bromide, and 6,6-didecoxyhexyl magnesium bromide; and

[0153] 6,6-Dialkoxyhexyl magnesium iodide compounds (15: M = MgZ, Z = iodine atom), such as 6,6-dimethoxyhexyl magnesium iodide, 6,6-diethoxyhexyl magnesium iodide, 6,6-dipropoxyhexyl magnesium iodide, 6,6-dibutoxyhexyl magnesium iodide, 6,6-dipentoxyhexyl magnesium iodide, 6,6-dihexyloxyhexyl magnesium iodide, 6,6-diheptoxyhexyl magnesium iodide, 6,6-dioctyloxyhexyl magnesium iodide, 6,6-dinonoxyhexyl magnesium iodide, and 6,6-didecoxyhexyl magnesium iodide.

[0154] Specific examples of bis(6,6-dialkoxyhexyl)magnesium compounds (15: M = MgZ, Z = 6,6-dialkoxyhexyl group) include bis(6,6-dimethoxyhexyl)magnesium, bis(6,6-diethoxyhexyl)magnesium, bis(6,6-dipropoxyhexyl)magnesium, bis(6,6-dibutoxyhexyl)magnesium, bis(6,6-dipentoxyhexyl)magnesium, bis(6,6-dihexyloxyhexyl)magnesium, bis(6,6-diheptoxyhexyl)magnesium, bis(6,6-dioctyloxyhexyl)magnesium, bis(6,6-dinonoxyhexyl)magnesium, and bis(6,6-didecoxyhexyl)magnesium.

[0155] Considering ease of preparation, the 6,6-dialkoxyhexyl nucleophile (15) is preferably a 6,6-dialkoxyhexyl magnesium halide compound (15: M = MgZ, Z = halogen atom), such as 6,6-dialkoxyhexyl magnesium chloride compound (15: M = MgZ, Z = chlorine atom).

[0156] If necessary, the 6,6-dialkoxyhexyl nucleophile (15) can be used alone or in combination.

[0157] The 6,6-dialkoxyhexyl nucleophile (15) can be commercially available or prepared internally.

[0158] The following describes 1-halo-5-halo-1-pentyne compounds (16).

[0159] In general formula (16), X 1 As defined by general formula (1), and X 2 It is a halogen atom. Specifically, halogen atom X 2It can be a chlorine atom, a bromine atom, or an iodine atom; considering reactivity, a bromine atom or an iodine atom is preferred.

[0160] Specific examples of 1-halo-5-halo-1-pentyne compounds (16) include the following compounds:

[0161] 1-Chloro-5-halo-1-pentyne compound (16:X) 2 = chlorine atom), such as 1-chloro-5-chloro-1-pentyne, 1-chloro-5-bromo-1-pentyne and 1-chloro-5-iodo-1-pentyne;

[0162] 1-Bromo-5-halo-1-pentyne compound (16:X) 2 =bromine atom), such as 1-bromo-5-chloro-1-pentyne, 1-bromo-5-bromo-1-pentyne and 1-bromo-5-iodo-1-pentyne; and

[0163] 1-Iodo-5-halo-1-pentyne compound (16:X) 2 =Iodine atom), such as 1-iodo-5-chloro-1-pentyne, 1-iodo-5-bromo-1-pentyne and 1-iodo-5-iodo-1-pentyne.

[0164] Considering ease of preparation, 1-halo-5-halo-1-pentyne compound (16) is preferably 1-bromo-5-halo-1-pentyne compound (16:X) 2 = bromine atom), such as 1-bromo-5-chloro-1-pentyne.

[0165] If necessary, 1-halo-5-halo-1-pentyne compound (16) may be used alone or in combination.

[0166] 1-Halo-5-Halo-1-pentyne compound (16) may be commercially available or internally prepared.

[0167] If necessary, the coupling reaction can be carried out in a solvent. Examples of solvents include common solvents such as ethers, such as diethyl ether, butyl ether, 4-methyltetrahydropyran, tetrahydrofuran (THF), 2-methyltetrahydrofuran, cyclopentyl methyl ether, and 1,4-dioxane; hydrocarbons, such as hexane, heptane, benzene, toluene, xylene, and cumene; chlorinated solvents, such as trichloroethylene, dichloromethane, and chloroform; aprotic polar solvents, such as dimethyl sulfoxide, γ-butyrolactone (GBL), N-methylpyrrolidone (NMP), N,N-dimethylformamide (DMF), N,N-dimethylacetamide (DMAC), and hexamethylphosphoric triamine (HMPA); and nitriles, such as acetonitrile and propionitrile. Considering reactivity, the solvent is preferably toluene, xylene, tetrahydrofuran, 2-methyltetrahydrofuran, 4-methyltetrahydropyran, or acetonitrile, more preferably tetrahydrofuran or 2-methyltetrahydrofuran.

[0168] Solvents may be used alone or in combination if necessary. Solvents may be commercially available products.

[0169] Considering reactivity, the amount of solvent used is preferably 30 to 8000 g, more preferably 50 to 5000 g, relative to each mol of 1-halo-5-halo-1-pentyne compound (16).

[0170] Step 2

[0171] If necessary, the coupling reaction between the 6,6-dialkoxyhexyl nucleophile (15) and the 1-halo-5-halo-1-pentyne compound (16) can be carried out in the presence of a catalyst.

[0172] Examples of catalysts include copper compounds, including cuprous halides such as cuprous chloride, cuprous bromide, and cuprous iodide; and copper halides such as copper chloride, copper bromide, and copper iodide; iron compounds such as ferric chloride (II), ferric chloride (III), ferric bromide (II), ferric bromide (III), ferric iodide (II), ferric iodide (III), and ferric acetylacetone (III); silver compounds such as silver chloride, silver nitrate, and silver acetate; titanium compounds such as titanium tetrachloride, titanium tetrabromide, titanium methoxide (IV), titanium ethoxide (IV), titanium isopropoxide (IV), and titanium oxide (IV); palladium (II) compounds such as dichlorobis(triphenylphosphine)palladium and dichloro[1,1'-bis(diphenylphosphine)ferrocene]palladium; and nickel compounds such as nickel chloride, dichloro[1,2]-bis(diphenylphosphine)ethane]nickel (II), and dichlorobis(triphenylphosphine)nickel (II). When the 6,6-dialkoxyhexyl nucleophile (15) is a Grignard reagent, i.e., a 6,6-dialkoxyhexyl magnesium halide compound (15: M = MgZ), the catalyst is preferably a copper compound, more preferably a copper halide, such as copper chloride, copper bromide or copper iodide, taking into account reactivity and / or economy.

[0173] If necessary, catalysts can be used alone or in combination. Catalysts can be commercially available products.

[0174] Considering the reaction rate and post-treatment, the amount of catalyst used is preferably 0.0003 to 0.500 mol, more preferably 0.003 to 0.200 mol, relative to each mol of 1-halo-5-halo-1-pentyne compound (16).

[0175] When the coupling reaction is carried out in the presence of a catalyst, a co-catalyst may be used if necessary. Examples of co-catalysts include trialkyl phosphites having 3 to 9 carbon atoms, such as triethyl phosphite; and arylphosphine compounds having 18 to 44 carbon atoms, such as triphenylphosphine, thimerylphosphine, and 2,2'-bis(diphenylphosphino)-1,1'-binaphthyl (BINAP). Trialkyl phosphites are preferred for their reactivity, and triethyl phosphite is particularly preferred.

[0176] If necessary, the co-catalyst can be used alone or in combination. The co-catalyst can be a commercially available product.

[0177] The amount of co-catalyst used is preferably 0.0001 to 1.00 mol, more preferably 0.001 to 0.300 mol, relative to each mol of 1-halo-5-halo-1-pentyne compound (16).

[0178] When organolithium reagents are used in coupling reactions, N,N,N',N'-tetramethylethylenediamine (TMEDA), hexamethylphosphoric triamine (HMPA), or N,N'-dimethylacrylurea (DMPU) may be added if necessary to increase the reaction rate.

[0179] When the coupling reaction is carried out in the presence of a catalyst, a lithium salt may be added if necessary. Examples of lithium salts include lithium halides, such as lithium chloride, lithium bromide, and lithium iodide; lithium nitrate; and lithium carbonate. Considering reactivity, lithium halides (such as lithium chloride) and lithium nitrate are preferred.

[0180] Lithium salts can be used alone or in combination if necessary. Lithium salts are commercially available products.

[0181] Considering reactivity, the amount of lithium salt used in the coupling reaction is preferably 0.0001 to 1.00 mol, more preferably 0.001 to 0.300 mol, relative to each mol of 1-halo-5-halo-1-pentyne compound (16).

[0182] The reaction temperature in the coupling reaction varies depending on the 6,6-dialkoxyhexyl nucleophile (15) to be used, and is preferably -78°C to 100°C, more preferably -25°C to 60°C, taking into account reactivity.

[0183] The reaction time for the coupling reaction varies depending on the solvent to be used and / or the production scale, but is preferably 0.5 to 100 hours, taking into account reactivity.

[0184] The following describes 11-halo-1,1-dialkoxy-7-undecyne compound (17).

[0185] X in general formula (17) 1 R 1 and R2 As defined by general formula (1).

[0186] Specific examples of 11-halo-1,1-dialkoxy-7-undecyne compounds (17) include the following compounds:

[0187] 11-Chloro-1,1-dialkoxy-7-undecyne compound (17:X) 1 = chlorine atom), such as 11-chloro-1,1-dimethoxy-7-undecyne, 11-chloro-1,1-diethoxy-7-undecyne, 11-chloro-1,1-dipropoxy-7-undecyne, 11-chloro-1,1-dibutoxy-7-undecyne, 11-chloro-1,1-dipentoxy-7-undecyne, 11-chloro-1,1-dihexyloxy-7-undecyne, 11-chloro-1,1-diheptoxy-7-undecyne, 11-chloro-1,1-dioctyloxy-7-undecyne, 11-chloro-1,1-dinonoxy-7-undecyne and 11-chloro-1,1-didecoxy-7-undecyne;

[0188] 11-Bromo-1,1-dialkoxy-7-undecyne compound (17:X) 1 =bromine atom), such as 11-bromo-1,1-dimethoxy-7-undecyne, 11-bromo-1,1-diethoxy-7-undecyne, 11-bromo-1,1-dipropoxy-7-undecyne, 11-bromo-1,1-dibutoxy-7-undecyne, 11-bromo-1,1-dipentoxy-7-undecyne, 11-bromo-1,1-dihexyloxy-7-undecyne, 11-bromo-1,1-diheptoxy-7-undecyne, 11-bromo-1,1-dioctyloxy-7-undecyne, 11-bromo-1,1-dinonoxy-7-undecyne and 11-bromo-1,1-didecoxy-7-undecyne; and

[0189] 11-Iodo-1,1-dialkoxy-7-undecyne compound (17:X) 1 =Iodine atom), such as 1-iodo-1,1-dimethoxy-7-undecyne, 11-iodo-1,1-diethoxy-7-undecyne, 11-iodo-1,1-dipropoxy-7-undecyne, 11-iodo-1,1-dibutoxy-7-undecyne, 11-iodo-1,1-dipentoxy-7-undecyne, 11-iodo-1,1-dihexyloxy-7-undecyne, 11-iodo-1,1-diheptoxy-7-undecyne, 11-iodo-1,1-dioctyloxy-7-undecyne, 11-iodo-1,1-dinonoxy-7-undecyne and 11-iodo-1,1-didecoxy-7-undecyne.

[0190] Step 3

[0191] Examples of reduction reactions in which the carbon-carbon triple bond of 11-halo-1,1-dialkoxy-7-undecyne compound (17) is reduced to form (7Z)-11-halo-1,1-dialkoxy-7-undecene compound (1-Z) are preferably (i) catalytic hydrogenation, (ii) reduction in an alcohol solvent with zinc, (iii) reduction by hydroboration followed by protonation of dialkylborane, (iv) reduction in the presence of a palladium catalyst (e.g., palladium acetate) using potassium hydroxide and N,N-dimethylformamide (DMF), (v) reduction by hydrosilylation to obtain vinylsilane followed by desilylation, (vi) Birch reduction, (vii) ammonia-free Birch reduction, or (viii) Benkeser reduction. Considering selectivity and productivity, (i) catalytic hydrogenation, (ii) reduction with zinc, or (iii) reduction with hydroboration followed by protonation of dialkylborane are preferred, with (i) catalytic hydrogenation being more preferred.

[0192] Considering ease of preparation, in the reductions carried out by (i) to (viii), in which the carbon-carbon triple bond of 11-halo-1,1-dialkoxy-7-undecyn compound (17) is reduced to form (7E)-11-halo-1,1-dialkoxy-7-undecyn compound (1-E), the reduction reaction is preferably carried out by (vi) Birch reduction, (vii) ammonia-free Birch reduction, or (viii) Benkeser reduction, with (viii) Benkeser reduction being the most preferred.

[0193] (i) Catalytic hydrogenation reaction

[0194] Catalytic hydrogenation is carried out using hydrogen gas in the presence of a metal catalyst.

[0195] Examples of metal catalysts used in catalytic hydrogenation reactions include, but are not limited to, nickel catalysts such as nickel boride catalysts; nickel (0) nanoparticles (Francisco Alonso et al., Tetrahedron, 2007, 63, 93-102) and lacquer nickel (e.g., U-Ni-A and U-Ni-B); and palladium catalysts such as lindra catalysts and palladium on carbon Pd / CaCO3, Pd / BaSO4, Pd / Al2O3, Hg-doped Pd / SiO2, Pd / MCM-41, palladium nanoparticles in hydrotalcite, Pd / Zn alloys, and Pd-PEI (palladium on carbon poisoned by polyethyleneimine polymer (PEI)). Examples of nickel boride catalysts include, but are not limited to, P-1 and P-2 nickel boride catalysts (Thomas J. Caggiano et al., Encyclopedia of Reagents for Organic Synthesis: 3694-3699) (hereinafter also referred to as "P-2Ni" catalysts); and nickel dispersed on graphite (such as Ni-Gr1 and Ni-Gr2), Caubere catalysts (Nic), and nickel on borohydride exchange resins (Ni2B-BER) (Laurence Balas, HAL, 2021; https: / / hal.archives-ouvertes.fr / hal-00801666). For economic reasons, Lindela catalysts and nickel catalysts are preferred.

[0196] The amount of metal catalyst used varies depending on the catalyst to be used. When using a solid catalyst such as a Lindela catalyst, considering reactivity, it is preferably 0.01 to 50 g relative to each mol of 11-halo-1,1-dialkoxy-7-undecyne compound (17). For each mol of 11-halo-1,1-dialkoxy-7-undecyne compound (17), the P-2Ni catalyst is preferably used in an amount equivalent to 0.0001 to 2.0 mol of nickel compound.

[0197] Solid catalysts can be dispersed in solvents.

[0198] When a metal catalyst has high activity, a catalyst poison may be used if necessary.

[0199] Examples of catalyst poisons include amine compounds such as pyridine, quinoline, and ethylenediamine; phosphorus compounds such as triphenylphosphine, thylphosphine, and triethyl phosphite; and sulfur compounds such as benzene mercaptan, diphenyl sulfide, dimethyl sulfide, and dimethyl sulfoxide.

[0200] The amount of catalyst poison used varies depending on the catalyst poison to be used, taking into account the reaction rate and geometric selectivity, preferably 0.0001 to 20.0 mol, more preferably 0.001 to 2.0 mol, relative to each mol of 11-halo-1,1-dialkoxy-7-undecyne compound (17).

[0201] Examples of solvents used in catalytic hydrogenation reactions include hydrocarbons such as hexane, heptane, benzene, toluene, xylene, and cumene; nitriles such as acetonitrile and propionitrile; esters such as methyl acetate, ethyl acetate, n-propyl acetate, and n-butyl acetate; and alcohols such as methanol, ethanol, propanol, butanol, pentanol, hexanol, 2-propanol, 2-butanol, and cyclohexanol.

[0202] Solvents may be used alone or in combination if necessary. Solvents may be commercially available products.

[0203] When using a Lindela catalyst, hydrocarbons such as hexane, heptane, toluene, or xylene are preferred solvents due to reactivity. When using a nickel catalyst, alcohols such as methanol, ethanol, propanol, butanol, or 2-propanol are preferred solvents due to reactivity. When using a palladium catalyst such as palladium on carbon, esters such as methyl acetate or ethyl acetate are preferred solvents due to reactivity.

[0204] The amount of catalyst used varies depending on the catalyst and / or solvent to be used, and is preferably 0 to 1000 g relative to each mol of 11-halo-1,1-dialkoxy-7-undecyne compound (17), taking into account reactivity.

[0205] The reaction temperature in the catalytic hydrogenation reaction varies depending on the catalyst and / or solvent to be used, and is preferably from 0°C to 160°C, more preferably from 20°C to 100°C, taking into account geometric selectivity.

[0206] Considering the yield, the reaction time for the catalytic hydrogenation reaction is preferably 0.5 to 100 hours.

[0207] (ii) Reduction reaction with zinc in an alcohol solvent

[0208] The reduction reaction can be carried out using zinc in an alcohol solvent.

[0209] The alcohol to be used as a solvent preferably has 1 to 10 carbon atoms, more preferably 1 to 5 carbon atoms. Examples of alcohols to be used as solvents include straight-chain alcohols such as methanol, ethanol, propanol, butanol, pentanol, hexanol, heptanol, octanol, nonanol, and decanol; branched-chain alcohols such as 2-propanol and 2-butanol; and cyclic alcohols such as cyclohexanol. Considering reactivity, alcohols having 1 to 5 carbon atoms, such as methanol, ethanol, propanol, butanol, pentanol, and 2-propanol, are preferred.

[0210] Considering reactivity, the amount of alcohol used is preferably 46 to 1000 g relative to each mol of 11-halo-1,1-dialkoxy-7-undecyne compound (17).

[0211] Considering reactivity, the amount of zinc used is preferably 1.0 to 1000 mol, more preferably 1.0 to 200 mol, relative to each mol of 11-halo-1,1-dialkoxy-7-undecyne compound (17).

[0212] Because zinc has low reactivity, the reduction reaction may require a long reaction time. Therefore, if necessary, a pre-prepared zinc activator or activated zinc can be used.

[0213] Examples of activators include 1,2-dibromoethane, cuprous chloride, cuprous bromide, cuprous iodide, lithium bromide, iodine, and trimethylchlorosilane.

[0214] If necessary, activators may be used alone or in combination.

[0215] Considering reactivity, the amount of activator used is preferably 0.01 to 10.0 mol relative to each mol of 11-halo-1,1-dialkoxy-7-undecyne compound (17).

[0216] Activated zinc can be prepared, for example, by treating metallic zinc with an acid such as hydrochloric acid, reducing zinc chloride with metallic lithium in tetrahydrofuran or 2-methyltetrahydrofuran, or by reacting metallic zinc with 1,2-dibromoethane and lithium dibromocopper oxide in tetrahydrofuran or 2-methyltetrahydrofuran.

[0217] The reaction temperature in the reduction reaction varies depending on the solvent used, but considering reactivity, it is preferably between 20°C and 180°C.

[0218] To ensure the reaction is complete, the preferred reaction time for the reduction reaction is 0.5 to 150 hours.

[0219] (iii) Reduction by hydroboration followed by protonation with dialkylborane

[0220] In this reduction, dialkylborane is first used in the solvent for hydroboration.

[0221] The dialkylborane to be used in the hydroboration preferably has 4 to 18 carbon atoms, more preferably 6 to 12 carbon atoms.

[0222] Examples of dialkylboranes include dicyclohexylborane, diisopentylborane, diisopentylborane, 9-boronbicyclo[3.3.1]nonane (9-BBN), diisopinocampheylborane, catecholborane, and pinacolborane. Considering reactivity, dicyclohexylborane and diisopentylborane are preferred.

[0223] Considering reactivity, the amount of dialkylborane used is preferably 1.0 to 4.0 mol relative to each mol of 11-halo-1,1-dialkoxy-7-undecyne compound (17).

[0224] Examples of solvents used in hydroboration include ethers such as tetrahydrofuran, 2-methyltetrahydrofuran, diethyl ether, butyl ether, 4-methyltetrahydropyran, cyclopentyl methyl ether, 1,4-dioxane, and diethylene glycol dimethyl ether; and hydrocarbons such as hexane, heptane, benzene, toluene, xylene, and cumene. Ethers, such as tetrahydrofuran, 2-methyltetrahydrofuran, 4-methyltetrahydropyran, and diethylene glycol dimethyl ether, are preferred due to their reactivity.

[0225] Solvents may be used alone or in combination if necessary. Solvents may be commercially available products.

[0226] Considering reactivity, the amount of solvent used is preferably 100 to 3000 g relative to each mol of 11-halo-1,1-dialkoxy-7-undecyne compound (17).

[0227] Considering geometric selectivity, the reaction temperature for hydroboration is preferably between -20°C and 50°C.

[0228] The reaction time for hydroboration varies depending on the reaction temperature and / or reaction scale, but is preferably 0.5 to 100 hours, taking into account reactivity.

[0229] For reduction, after hydroboration, protonation is performed in a solvent using an acid.

[0230] Examples of acids used in protonation following hydroboration include carboxylic acids such as acetic acid, propionic acid, butyric acid, valeric acid, neopentanoic acid, heptanoic acid, trifluoroacetic acid, chloroacetic acid, formic acid, and oxalic acid; sulfonic acids such as p-toluenesulfonic acid; and mineral acids such as sulfuric acid, hydrochloric acid, nitric acid, and phosphoric acid. Considering reactivity, carboxylic acids, such as acetic acid and propionic acid, are preferred.

[0231] Considering reactivity, the amount of acid used is preferably 2.0 to 20.0 mol relative to each mol of 11-halo-1,1-dialkoxy-7-undecyne compound (17).

[0232] The solvent and its amount used in protonation can be the same as those used in hydroboration, since protonation can be carried out in the reaction system after hydroboration.

[0233] The reaction temperature for protonation varies depending on the reagents used, but is preferably between 0°C and 150°C, taking into account the reaction rate.

[0234] The protonation reaction time varies depending on the reaction temperature and / or production scale, and is preferably 1 to 70 hours, taking reactivity into account.

[0235] (iv) Reduction reaction using potassium hydroxide and N,N-dimethylformamide (DMF) in the presence of a palladium catalyst (such as palladium acetate).

[0236] The reduction reaction is carried out in the presence of a palladium catalyst (such as palladium acetate) using potassium hydroxide and N,N-dimethylformamide (DMF), preferably at 100°C to 180°C for 0.5 to 100 hours.

[0237] (v) Reduction via hydrosilylation to obtain vinylsilane followed by desilylation

[0238] Hydrosilylation is performed using trialkylsilanes and metal catalysts (such as Wilkinson or Trost catalysts).

[0239] Considering reactivity, the amount of metal catalyst used is preferably 0.0001 to 4.0 mol, more preferably 0.001 to 1.0 mol, relative to each mol of 11-halo-1,1-dialkoxy-7-undecyne compound (17).

[0240] Hydrosilylation is preferably carried out at 5°C to 100°C for 0.5 to 100 hours.

[0241] The desilylation process following hydrosilylation is preferably carried out at 5°C to 80°C for 0.5 to 100 hours using an acid such as sulfuric acid or hydrochloric acid and at least one selected from hydrogen iodide, acetyl chloride, titanium tetrachloride and iodine.

[0242] (vi) Burch Restoration

[0243] Burch reduction of ammonia using metals.

[0244] Considering reactivity, the amount of ammonia used is preferably 1.0 to 10,000 mol, more preferably 10 to 3,000 mol, relative to each mol of 11-halo-1,1-dialkoxy-7-undecyne compound (17).

[0245] Examples of metals include alkali metals such as potassium, sodium, and lithium; and alkaline earth metals such as calcium and magnesium.

[0246] Considering reactivity, the amount of metal used is preferably 1.0 to 1000 mol, more preferably 1.0 to 100 mol, relative to each mol of 11-halo-1,1-dialkoxy-7-undecyne compound (17).

[0247] In Birch reduction, in addition to ammonia, a proton source is preferably added.

[0248] Examples of proton sources include alcohols such as methanol, ethanol, n-propanol, 2-propanol, and 2-methyl-2-propanol; as well as tetrahydrofuran (THF) and 2-methyltetrahydrofuran.

[0249] If necessary, proton sources can be used alone or in combination. Proton sources can be commercially available products.

[0250] Considering reactivity, the amount of proton source used is preferably 1.0 to 10,000 mol, more preferably 1.0 to 3,000 mol, relative to each mol of 11-halo-1,1-dialkoxy-7-undecyne compound (17).

[0251] Considering reactivity, the reaction temperature in the Birch reduction is preferably -78°C to 0°C, more preferably -78°C to -33°C.

[0252] The reaction time for Birch reduction varies depending on the production scale, but is preferably 0.5 to 100 hours, taking into account reactivity.

[0253] (vii) Ammonia-free Birch reduction

[0254] Ammonia-free Birch reduction is performed using metals in crown ethers.

[0255] Examples of crown ethers include 12-crown-4, 15-crown-5, 18-crown-6, dibenzo-18-crown-6, and diazo-18-crown-6.

[0256] Crown ethers may be used alone or in combination if necessary. Crown ethers are commercially available products.

[0257] Considering reactivity, the amount of crown ether used is preferably 1.0 to 100.0 mol, more preferably 1.0 to 20.0 mol, relative to each mol of 11-halo-1,1-dialkoxy-7-undecyne compound (17).

[0258] Examples of metals include alkali metals such as potassium, sodium, and lithium; and alkaline earth metals such as calcium and magnesium.

[0259] Considering reactivity, the amount of metal used is preferably 1.0 to 100.0 mol, more preferably 1.0 to 20.0 mol, relative to each mol of 11-halo-1,1-dialkoxy-7-undecyne compound (17).

[0260] In ammonia-free Birch reduction, in addition to crown ethers, a proton source is preferably added. Examples of proton sources include alcohols such as methanol, ethanol, n-propanol, 2-propanol, and 2-methyl-2-propanol; as well as tetrahydrofuran (THF) and 2-methyltetrahydrofuran.

[0261] If necessary, proton sources can be used alone or in combination. Proton sources can be commercially available products.

[0262] Considering reactivity, the amount of proton source used is preferably 1.0 to 100.0 mol, more preferably 1.0 to 20.0 mol, relative to each mol of 11-halo-1,1-dialkoxy-7-undecyne compound (17).

[0263] The reaction temperature in ammonia-free Birch reduction varies depending on the metal and / or crown ether to be used, and is preferably -78°C to 100°C, more preferably -40°C to 40°C, taking into account reactivity.

[0264] The reaction time for ammonia-free Birch reduction varies depending on the metal, the crown ether to be used, and / or the production scale, and is preferably 0.1 to 100 hours, more preferably 0.1 to 5 hours, taking into account reactivity.

[0265] (viii) Benkeser restoration

[0266] Benkeser reduction of alkylamines using metals.

[0267] Examples of alkylamines include lower amines such as methylamine, ethylamine, propylamine, and 1,3-propanediamine.

[0268] Considering reactivity, the amount of alkylamine used is preferably 1.0 to 5000 mol, more preferably 1.0 to 1000 mol, relative to each mol of 11-halo-1,1-dialkoxy-7-undecyne compound (17).

[0269] Examples of metals include alkali metals such as potassium, sodium, and lithium; and alkaline earth metals such as calcium and magnesium.

[0270] Considering reactivity, the amount of metal used is preferably 1.0 to 1000 mol, more preferably 1.0 to 100 mol, relative to each mol of 11-halo-1,1-dialkoxy-7-undecyne compound (17).

[0271] Considering reactivity, the reaction temperature in the Benkeser reduction is preferably -78°C to 100°C, more preferably -78°C to 60°C.

[0272] The reaction time for Benkeser reduction varies depending on the production scale, but is preferably 0.5 to 100 hours, taking into account reactivity.

[0273] 11-Halo-1,1-dialkoxy-7-undecene compound (1) can be used to prepare synthetic intermediates for the preparation of (7E)-7-dodecenal (the sex pheromone of Coniesa iqnefusalis), (7Z)-7-tetradecenal (the sex pheromone of Spaelotis clandestine), and (7Z)-7-hexadecenal (the sex pheromone of Bollworm).

[0274] (A-2). 11,11-Dialkoxy-4-undecenyltriarylphosphonium halide (3)

[0275] Next, we will explain 11,11-dialkoxy-4-undecenyltriarylphosphonium halide (3).

[0276] Y - Ar3P + (CH2)3CH=CH(CH2)5CH(OR 1 (OR) 2 (3)

[0277] Y represents a halogen atom, as defined by general formula (A). Specifically, the halogen atom Y can be a chlorine atom, a bromine atom, or an iodine atom. Considering reactivity, bromine and iodine atoms are preferred.

[0278] R in general formula (3) 1 and R 2 As defined by general formula (1).

[0279] In general formula (3), Ar represents an aryl group independently. The aryl group preferably has 6 to 24 carbon atoms, more preferably 6 to 12 carbon atoms, and even more preferably 6 to 7 carbon atoms. Examples of aryl groups include phenyl groups (Ph groups), tolyl groups, naphthyl groups, and anthracene groups. For ease of synthesis, phenyl groups are preferred. More preferably, all three aryl groups are phenyl groups.

[0280] 11,11-dialkoxy-4-undecenyltriarylphosphonium halides (3) include (4Z)-11,11-dialkoxy-4-undecenyltriarylphosphonium halides of general formula (3-Z) and (4E)-11,11-dialkoxy-4-undecenyltriarylphosphonium halides of general formula (3-E).

[0281] Specific examples of (4Z)-11,11-dialkoxy-4-undecenyltriarylphosphonium halides (3-Z) include the following compounds:

[0282] (4Z)-11,11-dialkoxy-4-undecenyltriphenylphosphonium chloride compounds (3-Z: Y = chlorine atom, Ar = phenyl group), such as (4Z)-11,11-dimethoxy-4-undecenyltriphenylphosphonium chloride, (4Z)-11,11-diethoxy-4-undecenyltriphenylphosphonium chloride, (4Z)-11,11-dipropoxy-4-undecenyltriphenylphosphonium chloride, (4Z)-11,11-dibutoxy-4-undecenyltriphenylphosphonium chloride, (4Z)-11,11-dibutoxy-4-undecenyltriphenylphosphonium chloride, (4Z)-11,11-dibutoxy-4-undecenyltriphenylphosphonium chloride, (4Z)-11,11-dibutoxy-4-undecenyltriphenylphosphonium chloride, (4Z)-11,11-diprop ... (4Z)-11,11-dipentoxy-4-undecenyltriphenylphosphonium chloride, (4Z)-11,11-dihexyloxy-4-undecenyltriphenylphosphonium chloride, (4Z)-11,11-diheptoxy-4-undecenyltriphenylphosphonium chloride, (4Z)-11,11-dioctyloxy-4-undecenyltriphenylphosphonium chloride, (4Z)-11,11-dinonoxy-4-undecenyltriphenylphosphonium chloride and (4Z)-11,11-didecoxy-4-undecenyltriphenylphosphonium chloride;

[0283] (4Z)-11,11-dialkoxy-4-undecenyltrimethylphosphonium chloride compounds (3-Z: Y = chlorine atom, Ar = tolyl group), such as (4Z)-11,11-dimethoxy-4-undecenyltrimethylphosphonium chloride, (4Z)-11,11-diethoxy-4-undecenyltrimethylphosphonium chloride, (4Z)-11,11-dipropoxy-4-undecenyltrimethylphosphonium chloride, (4Z)-11,11-dibutoxy-4-undecenyltrimethylphosphonium chloride, (4Z)-11,11-dibutoxy-4-undecenyltrimethylphosphonium chloride, (4Z)-11,11-dibutoxy-4-undecenyltrimethylphosphonium chloride, (4Z)-11,11-diprop ... Phosphorus chloride (4Z)-11,11-dipentoxy-4-undecenyltrimethylphosphorus chloride, (4Z)-11,11-dihexyloxy-4-undecenyltrimethylphosphorus chloride, (4Z)-11,11-diheptoxy-4-undecenyltrimethylphosphorus chloride, (4Z)-11,11-dioctyloxy-4-undecenyltrimethylphosphorus chloride, (4Z)-11,11-dinonoxy-4-undecenyltrimethylphosphorus chloride and (4Z)-11,11-didecoxy-4-undecenyltrimethylphosphorus chloride;

[0284] (4Z)-11,11-dialkoxy-4-undecenyltriphenylphosphonium bromide compounds (3-Z: Y = bromine atom, Ar = phenyl group), such as (4Z)-11,11-dimethoxy-4-undecenyltriphenylphosphonium bromide, (4Z)-11,11-diethoxy-4-undecenyltriphenylphosphonium bromide, (4Z)-11,11-dipropoxy-4-undecenyltriphenylphosphonium bromide, (4Z)-11,11-dibutoxy-4-undecenyltriphenylphosphonium bromide, (4Z)-11,11-dibutoxy-4-undecenyltriphenylphosphonium bromide, (4Z)-11,11-dibutoxy-4-undecenyltriphenylphosphonium bromide, (4Z)-11,11-diprop ... (4Z)-11,11-dipentoxy-4-undecenyltriphenylphosphonium bromide, (4Z)-11,11-dihexyloxy-4-undecenyltriphenylphosphonium bromide, (4Z)-11,11-diheptoxy-4-undecenyltriphenylphosphonium bromide, (4Z)-11,11-dioctyloxy-4-undecenyltriphenylphosphonium bromide, (4Z)-11,11-dinonoxy-4-undecenyltriphenylphosphonium bromide and (4Z)-11,11-didecoxy-4-undecenyltriphenylphosphonium bromide;

[0285] (4Z)-11,11-dialkoxy-4-undecenyltrimethylphosphonium bromide compounds (3-Z: Y = bromine atom, Ar = tolyl group), such as (4Z)-11,11-dimethoxy-4-undecenyltrimethylphosphonium bromide, (4Z)-11,11-diethoxy-4-undecenyltrimethylphosphonium bromide, (4Z)-11,11-dipropoxy-4-undecenyltrimethylphosphonium bromide, (4Z)-11,11-dibutoxy-4-undecenyltrimethylphosphonium bromide, (4Z)-11,11-dibutoxy-4-undecenyltrimethylphosphonium bromide, (4Z (4Z)-11,11-dipentoxy-4-undecenyltrimethylphosphonium bromide, (4Z)-11,11-dihexyloxy-4-undecenyltrimethylphosphonium bromide, (4Z)-11,11-diheptoxy-4-undecenyltrimethylphosphonium bromide, (4Z)-11,11-dioctyloxy-4-undecenyltrimethylphosphonium bromide, (4Z)-11,11-dinonoxy-4-undecenyltrimethylphosphonium bromide and (4Z)-11,11-didecoxy-4-undecenyltrimethylphosphonium bromide;

[0286] (4Z)-11,11-dialkoxy-4-undecenyltriphenylphosphonium iodide compounds (3-Z: Y = iodine atom, Ar = phenyl group), such as (4Z)-11,11-dimethoxy-4-undecenyltriphenylphosphonium iodide, (4Z)-11,11-diethoxy-4-undecenyltriphenylphosphonium iodide, (4Z)-11,11-dipropoxy-4-undecenyltriphenylphosphonium iodide, (4Z)-11,11-dibutoxy-4-undecenyltriphenylphosphonium iodide, (4Z... -11,11-dipentoxy-4-undecenyltriphenylphosphonium iodide, (4Z)-11,11-dihexyloxy-4-undecenyltriphenylphosphonium iodide, (4Z)-11,11-diheptoxy-4-undecenyltriphenylphosphonium iodide, (4Z)-11,11-dioctyloxy-4-undecenyltriphenylphosphonium iodide, (4Z)-11,11-dinonoxy-4-undecenyltriphenylphosphonium iodide and (4Z)-11,11-didecoxy-4-undecenyltriphenylphosphonium iodide; and

[0287] (4Z)-11,11-dialkoxy-4-undecenyltrimethylphosphonium iodide compounds (3-Z: Y = iodine atom, Ar = tolyl group), such as (4Z)-11,11-dimethoxy-4-undecenyltrimethylphosphonium iodide, (4Z)-11,11-diethoxy-4-undecenyltrimethylphosphonium iodide, (4Z)-11,11-dipropoxy-4-undecenyltrimethylphosphonium iodide, (4Z)-11,11-dibutoxy-4-undecenyltrimethylphosphonium iodide, (4Z)-11,11-dibutoxy-4-undecenyltrimethylphosphonium iodide, (4Z)-11,11-dibutoxy-4-undecenyltrimethylphosphonium iodide, (4Z)-11,11-diprop ... Phosphorus iodide (4Z)-11,11-dipentoxy-4-undecenyltrimethylphosphonium iodide, Phosphorus iodide (4Z)-11,11-dihexyloxy-4-undecenyltrimethylphosphonium iodide, Phosphorus iodide (4Z)-11,11-diheptoxy-4-undecenyltrimethylphosphonium iodide, Phosphorus iodide (4Z)-11,11-dioctyloxy-4-undecenyltrimethylphosphonium iodide, Phosphorus iodide (4Z)-11,11-dinonoxy-4-undecenyltrimethylphosphonium iodide and Phosphorus iodide (4Z)-11,11-didecoxy-4-undecenyltrimethylphosphonium iodide.

[0288] Considering ease of preparation, (4Z)-11,11-dialkoxy-4-undecenyltriarylphosphonium halide (3-Z) is preferably (4Z)-11,11-dialkoxy-4-undecenyltriphenylphosphonium chloride (3-Z: Y = chlorine atom, Ar = phenyl group), (4Z)-11,11-dialkoxy-4-undecenyltriphenylphosphonium bromide (3-Z: Y = bromine atom, Ar = phenyl group) or (4Z)-11,11-dialkoxy-4-undecenyltriphenylphosphonium iodide (3-Z: Y = iodine atom, Ar = phenyl group).

[0289] Specific examples of (4E)-11,11-dialkoxy-4-undecenyltriarylphosphonium halides (3-E) include the following compounds:

[0290] (4E)-11,11-dialkoxy-4-undecenyltriphenylphosphonium chloride compounds (3-E: Y = chlorine atom, Ar = phenyl group), such as (4E)-11,11-dimethoxy-4-undecenyltriphenylphosphonium chloride, (4E)-11,11-diethoxy-4-undecenyltriphenylphosphonium chloride, (4E)-11,11-dipropoxy-4-undecenyltriphenylphosphonium chloride, (4E)-11,11-dibutoxy-4-undecenyltriphenylphosphonium chloride, (4E... (4E)-11,11-dipentoxy-4-undecenyltriphenylphosphonium chloride, (4E)-11,11-dihexyloxy-4-undecenyltriphenylphosphonium chloride, (4E)-11,11-diheptoxy-4-undecenyltriphenylphosphonium chloride, (4E)-11,11-dioctyloxy-4-undecenyltriphenylphosphonium chloride, (4E)-11,11-dinonoxy-4-undecenyltriphenylphosphonium chloride and (4E)-11,11-didecoxy-4-undecenyltriphenylphosphonium chloride;

[0291] (4E)-11,11-dialkoxy-4-undecenyltrimethylphosphonium chloride compounds (3-E: Y = chlorine atom, Ar = tolyl group), such as (4E)-11,11-dimethoxy-4-undecenyltrimethylphosphonium chloride, (4E)-11,11-diethoxy-4-undecenyltrimethylphosphonium chloride, (4E)-11,11-dipropoxy-4-undecenyltrimethylphosphonium chloride, (4E)-11,11-dibutoxy-4-undecenyltrimethylphosphonium chloride, (4E Phosphorus chloride (4E)-11,11-dipentoxy-4-undecenyltrimethylphosphorus chloride, (4E)-11,11-dihexyloxy-4-undecenyltrimethylphosphorus chloride, (4E)-11,11-diheptoxy-4-undecenyltrimethylphosphorus chloride, (4E)-11,11-dioctyloxy-4-undecenyltrimethylphosphorus chloride, (4E)-11,11-dinonoxy-4-undecenyltrimethylphosphorus chloride and (4E)-11,11-didecoxy-4-undecenyltrimethylphosphorus chloride;

[0292] (4E)-11,11-dialkoxy-4-undecenyltriphenylphosphonium bromide compounds (3-E: Y = bromine atom, Ar = phenyl group), such as (4E)-11,11-dimethoxy-4-undecenyltriphenylphosphonium bromide, (4E)-11,11-diethoxy-4-undecenyltriphenylphosphonium bromide, (4E)-11,11-dipropoxy-4-undecenyltriphenylphosphonium bromide, (4E)-11,11-dibutoxy-4-undecenyltriphenylphosphonium bromide, (4E (4E)-11,11-dipentoxy-4-undecenyltriphenylphosphonium bromide, (4E)-11,11-dihexyloxy-4-undecenyltriphenylphosphonium bromide, (4E)-11,11-diheptoxy-4-undecenyltriphenylphosphonium bromide, (4E)-11,11-dioctyloxy-4-undecenyltriphenylphosphonium bromide, (4E)-11,11-dinonoxy-4-undecenyltriphenylphosphonium bromide and (4E)-11,11-didecoxy-4-undecenyltriphenylphosphonium bromide;

[0293] (4E)-11,11-dialkoxy-4-undecenyltrimethylphosphonium bromide compounds (3-E: Y = bromine atom, Ar = tolyl group), such as (4E)-11,11-dimethoxy-4-undecenyltrimethylphosphonium bromide, (4E)-11,11-diethoxy-4-undecenyltrimethylphosphonium bromide, (4E)-11,11-dipropoxy-4-undecenyltrimethylphosphonium bromide, (4E)-11,11-dibutoxy-4-undecenyltrimethylphosphonium bromide, (4E Phosphorus bromide (4E)-11,11-dipentoxy-4-undecenyltrimethylphosphorus bromide, Phosphorus bromide (4E)-11,11-dihexyloxy-4-undecenyltrimethylphosphorus bromide, Phosphorus bromide (4E)-11,11-diheptoxy-4-undecenyltrimethylphosphorus bromide, Phosphorus bromide (4E)-11,11-dioctyloxy-4-undecenyltrimethylphosphorus bromide, Phosphorus bromide (4E)-11,11-dinonoxy-4-undecenyltrimethylphosphorus bromide and Phosphorus bromide (4E)-11,11-didecoxy-4-undecenyltrimethylphosphorus bromide;

[0294] (4E)-11,11-dialkoxy-4-undecenyltriphenylphosphonium iodide compounds (3-E: Y = iodine atom, Ar = phenyl group), such as (4E)-11,11-dimethoxy-4-undecenyltriphenylphosphonium iodide, (4E)-11,11-diethoxy-4-undecenyltriphenylphosphonium iodide, (4E)-11,11-dipropoxy-4-undecenyltriphenylphosphonium iodide, (4E)-11,11-dibutoxy-4-undecenyltriphenylphosphonium iodide, (4E... -11,11-dipentoxy-4-undecenyltriphenylphosphonium iodide, (4E)-11,11-dihexyloxy-4-undecenyltriphenylphosphonium iodide, (4E)-11,11-diheptoxy-4-undecenyltriphenylphosphonium iodide, (4E)-11,11-dioctyloxy-4-undecenyltriphenylphosphonium iodide, (4E)-11,11-dinonoxy-4-undecenyltriphenylphosphonium iodide, and (4E)-11,11-didecoxy-4-undecenyltriphenylphosphonium iodide; and

[0295] (4E)-11,11-dialkoxy-4-undecenyltrimethylylphosphonium iodide compounds (3-E: Y = iodine atom, Ar = tolyl group), such as (4E)-11,11-dimethoxy-4-undecenyltrimethylylphosphonium iodide, (4E)-11,11-diethoxy-4-undecenyltrimethylylphosphonium iodide, (4E)-11,11-dipropoxy-4-undecenyltrimethylylphosphonium iodide, (4E)-11,11-dibutoxy-4-undecenyltrimethylylphosphonium iodide, (4E Phosphorus iodide (4E)-11,11-dipentoxy-4-undecenyltrimethylphosphonium iodide, Phosphorus iodide (4E)-11,11-dihexyloxy-4-undecenyltrimethylphosphonium iodide, Phosphorus iodide (4E)-11,11-diheptoxy-4-undecenyltrimethylphosphonium iodide, Phosphorus iodide (4E)-11,11-dioctyloxy-4-undecenyltrimethylphosphonium iodide, Phosphorus iodide (4E)-11,11-dinonoxy-4-undecenyltrimethylphosphonium iodide and Phosphorus iodide (4E)-11,11-didecoxy-4-undecenyltrimethylphosphonium iodide.

[0296] Considering ease of preparation, (4E)-11,11-dialkoxy-4-undecenyltriarylphosphonium halide (3-E) is preferably (4E)-11,11-dialkoxy-4-undecenyltriphenylphosphonium chloride (3-E: Y = chlorine atom, Ar = phenyl group), (4E)-11,11-dialkoxy-4-undecenyltriphenylphosphonium bromide (3-E: Y = bromine atom, Ar = phenyl group) or (4E)-11,11-dialkoxy-4-undecenyltriphenylphosphonium iodide (3-E: Y = iodine atom, Ar = phenyl group).

[0297] As described below, (4Z)-11,11-dialkoxy-4-undecenyltriarylphosphonium halide (3-Z) can be used as a common synthetic intermediate in the preparation of (7Z,11Z,13E)-7,11,13-hexadecanetrienal (7) and (7Z,11Z)-7,11-hexadecanedienal (10).

[0298] The preparation methods of (4Z)-11,11-dialkoxy-4-undecenyltriarylphosphonium halide (3-Z) and (4E)-11,11-dialkoxy-4-undecenyltriarylphosphonium halide (3-E) will be described in Part B below.

[0299] Preparation method of B.11,11-dialkoxy-4-undecenyltriarylphosphonium halide (3)

[0300] In the following description, the preparation method of 11,11-dialkoxy-4-undecenyltriarylphosphonium halide (3) is described using (4Z)-11,11-dialkoxy-4-undecenyltriarylphosphonium halide (3-Z). When (4E)-11,11-dialkoxy-4-undecenyltriarylphosphonium halide (3-E) is used instead of (4Z)-11,11-dialkoxy-4-undecenyltriarylphosphonium halide (3-Z), the corresponding reaction proceeds in a similar manner to form the corresponding compound.

[0301] (4Z)-11,11-dialkoxy-4-undecenyltriarylphosphonium halide (3-Z) can be prepared, for example, by a phosphonium salt formation reaction of (7Z)-11-halo-1,1-dialkoxy-7-undecenyl compound (1-Z) with a phosphonium salt of the following general formula (2), as shown in the following chemical reaction formula:

[0302]

[0303] Examples of phosphine compounds (2) include triarylphosphine compounds such as triphenylphosphine, trimethylphosphine, trinaphthylphosphine, and trianthraphosphine. Triphenylphosphine is preferred due to its reactivity.

[0304] Considering reactivity, the amount of phosphine compound (2) used is preferably 0.8 to 5.0 mol relative to each mol of (7Z)-11-halo-1,1-dialkoxy-7-undecene compound (1-Z).

[0305] Phosphorus salt formation reaction

[0306] If necessary, halides may be added during the preparation of (4Z)-11,11-dialkoxy-4-undecenyltriarylphosphonium halide (3-Z).

[0307] Examples of halides include iodides, such as sodium iodide and potassium iodide; and bromides, such as sodium bromide and potassium bromide. Iodides, such as sodium iodide and potassium iodide, are preferred due to their reactivity.

[0308] When no halide is added in the preparation of (4Z)-11,11-dialkoxy-4-undecenyltriarylphosphonium halide (3-Z), Y in general formula (3-Z) and X in general formula (1-Z) are different. 1 They are the same halogen atom. When an iodide is added as a halide in the preparation, Y in the general formula (3-Z) is an iodine atom or X in the general formula (1-Z) of (7Z)-11-halo-1,1-dialkoxy-7-undecene compound (1-Z). 1 They are the same halogen atoms.

[0309] Halides may be used alone or in combination if necessary. Halides may be commercially available products.

[0310] Considering reactivity, the amount of halide used is preferably 0.1 to 10.0 mol, more preferably 0.8 to 4.0 mol, relative to each mol of (7Z)-11-halo-1,1-dialkoxy-7-undecene compound (1-Z).

[0311] If necessary, a base may be added in the preparation of (4Z)-11,11-dialkoxy-4-undecenyltriarylphosphonium halide (3-Z).

[0312] Examples of bases include alkali metal carbonates, such as potassium carbonate and sodium carbonate; alkaline earth metal carbonates, such as calcium carbonate and magnesium carbonate; and amines, such as triethylamine, tripropylamine, triisopropylamine, tributylamine, N,N-diethylaniline, and pyridine. Alkali metal carbonates are preferred for handling purposes.

[0313] If necessary, alkalis can be used alone or in combination. Alkaliss can be commercially available products.

[0314] Considering reactivity, the amount of base used is preferably 0.001 to 1.0 mol relative to each mol of (7Z)-11-halo-1,1-dialkoxy-7-undecene compound (1-Z).

[0315] If necessary, a solvent may be added in the preparation of (4Z)-11,11-dialkoxy-4-undecenyltriarylphosphonium halide (3-Z).

[0316] Examples of solvents include ether solvents such as tetrahydrofuran, 2-methyltetrahydrofuran, diethyl ether, butyl ether, 4-methyltetrahydropyran, cyclopentyl methyl ether, and 1,4-dioxane; hydrocarbon solvents such as hexane, heptane, benzene, toluene, xylene, and cumene; and polar solvents such as N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone, dimethyl sulfoxide, γ-butyrolactone, acetonitrile, dichloromethane, and chloroform. Considering reactivity, ether solvents such as tetrahydrofuran, 2-methyltetrahydrofuran, and 4-methyltetrahydropyran are preferred; as are polar solvents such as acetonitrile, N,N-dimethylformamide, and N,N-dimethylacetamide.

[0317] Solvents may be used alone or in combination if necessary. Solvents may be commercially available products.

[0318] Considering reactivity, the amount of solvent used is preferably 50 to 7000 g relative to each mol of (7Z)-11-halo-1,1-dialkoxy-7-undecene compound (1-Z).

[0319] The reaction temperature in the preparation of (4Z)-11,11-dialkoxy-4-undecenyltriarylphosphonium halide (3-Z) varies depending on the solvent to be used, and is preferably from 30°C to 180°C, more preferably from 50°C to 150°C.

[0320] The reaction time for preparing (4Z)-11,11-dialkoxy-4-undecenyltriarylphosphonium halide (3-Z) varies depending on the solvent to be used and / or the production scale, and is preferably from 0.5 to 100 hours.

[0321] C. (3E,5Z,9Z)-16,16-dialkoxy-3,5,9-hexadecadiene compounds (6) and (5Z,9Z)-16,16-dialkoxy-5,9-hexadecadiene compounds (9) and their preparation methods

[0322] (C-1). The following describes (3E,5Z,9Z)-16,16-dialkoxy-3,5,9-hexadecanetriene compound (6) and its preparation method.

[0323] (3E,5Z,9Z)-16,16-dialkoxy-3,5,9-hexadecanetriene compound (6) can be prepared according to the following chemical reaction formula. First, (4Z)-11,11-dialkoxy-4-undecenyltriarylphosphonium halide (3-Z) is deprotonated in the presence of a base to obtain a mixture of reaction products. The mixture of reaction products obtained by the deprotonation reaction is estimated to contain triarylphosphonium (4Z)-11,11-dialkoxy-4-undecenyl ylide compound (4) as a reaction product (in the following description, the reaction product is regarded as triarylphosphonium (4Z)-11,11-dialkoxy-4-undecenyl ylide compound (4)). Next, the mixture of reaction products undergoes a Wittig reaction with (2E)-2-pentenal of formula (5), for example, in situ, to form (3E,5Z,9Z)-16,16-dialkoxy-3,5,9-hexadecanetriene compound (6).

[0324]

[0325] First, the triarylphosphonium (4Z)-11,11-dialkoxy-4-undecene ylide compound (4) contained in the mixture of reaction products will be described.

[0326] R in general formula (4) 1 and R 2 As defined by general formula (1), and Ar as defined by general formula (3).

[0327] Specific examples of triarylphosphonium(4Z)-11,11-dialkoxy-4-undecene ylide compounds (4) include the following compounds:

[0328] Triphenylphosphonium (4Z)-11,11-dialkoxy-4-undecene ylide compounds (4:Ar = phenyl group), such as triphenylphosphonium (4Z)-11,11-dimethoxy-4-undecene ylide, triphenylphosphonium (4Z)-11,11-diethoxy-4-undecene ylide, triphenylphosphonium (4Z)-11,11-dipropoxy-4-undecene ylide, triphenylphosphonium (4Z)-11,11-dibutoxy-4-undecene ylide, and triphenylphosphonium (4Z). -11,11-dipentoxy-4-undecene ylide, triphenylphosphonium(4Z)-11,11-dihexyloxy-4-undecene ylide, triphenylphosphonium(4Z)-11,11-diheptoxy-4-undecene ylide, triphenylphosphonium(4Z)-11,11-dioctyloxy-4-undecene ylide, triphenylphosphonium(4Z)-11,11-dinonoxy-4-undecene ylide and triphenylphosphonium(4Z)-11,11-didecoxy-4-undecene ylide; and

[0329] Trimethylphosphonium (4Z)-11,11-dialkoxy-4-undecene ylide compounds (4:Ar = tolyl group), such as trimethylphosphonium (4Z)-11,11-dimethoxy-4-undecene ylide, trimethylphosphonium (4Z)-11,11-diethoxy-4-undecene ylide, trimethylphosphonium (4Z)-11,11-dipropoxy-4-undecene ylide, trimethylphosphonium (4Z)-11,11-dibut ...methoxy-4-undecene ylide, trimethylphosphonium (4Z)-11,11-dimethoxy-4-undecene ylide, trimethylphosphonium (4Z)-11,11-dimethoxy-4-undecene ylide, trimethylphosphonium (4Z)-11,11-dimethoxy-4-undecene ylide, trimethylphosphonium (4Z)-11,11-dimethoxy-4-undecene ylide, trimethylphosphonium (4Z)-11,11-dimethoxy-4-undecene ylide, trimethylphosphonium ( Trimethylphosphonium (4Z)-11,11-dipentoxy-4-undecene ylide, trimethylphosphonium (4Z)-11,11-dihexyloxy-4-undecene ylide, trimethylphosphonium (4Z)-11,11-diheptoxy-4-undecene ylide, trimethylphosphonium (4Z)-11,11-dioctyloxy-4-undecene ylide, trimethylphosphonium (4Z)-11,11-dinonoxy-4-undecene ylide and trimethylphosphonium (4Z)-11,11-didecoxy-4-undecene ylide.

[0330] Considering ease of preparation, the triarylphosphonium (4Z)-11,11-dialkoxy-4-undecene ylide compound (4) is preferably triphenylphosphonium (4Z)-11,11-dialkoxy-4-undecene ylide compound (4: Ar = phenyl group).

[0331] Deprotonation reaction

[0332] The reaction product mixture can be prepared as follows: after preparing (4Z)-11,11-dialkoxy-4-undecenyltriarylphosphonium halide (3-Z), a base is added to the reaction system to directly form triarylphosphonium (4Z)-11,11-dialkoxy-4-undecenyl ylide compound (4), or by purifying (4Z)-11,11-dialkoxy-4-undecenyltriarylphosphonium halide (3-Z) and then reacting the purified product with a base to form triarylphosphonium (4Z)-11,11-dialkoxy-4-undecenyl ylide compound (4).

[0333] Examples of bases used in the preparation of reaction product mixtures include alkyllithiums, such as n-butyllithium and tert-butyllithium; organometallic reagents, such as methylmagnesium chloride, methylmagnesium bromide, sodium acetylation, and potassium acetylation; metal alkoxides, such as potassium tert-butoxide, sodium tert-butoxide, potassium methoxide, sodium methoxide, potassium ethoxide, and sodium ethoxide; and metal amines, such as lithium diisopropylamino and sodium di(trimethylsilyl)amino. Considering reactivity, the base is preferably a metal alkoxide, more preferably potassium tert-butoxide, sodium methoxide, or sodium ethoxide.

[0334] Considering reactivity, the amount of base used is preferably 0.7 to 5.0 mol relative to each mol of (7Z)-11-halo-1,1-dialkoxy-7-undecene compound (1-Z) or (4Z)-11,11-dialkoxy-4-undecene triarylphosphonium halide (3-Z).

[0335] If necessary, a solvent may be added in the preparation of (4Z)-11,11-dialkoxy-4-undecenyltriarylphosphonium halide (3-Z) and triarylphosphonium (4Z)-11,11-dialkoxy-4-undecenyl ylide compound (4).

[0336] Examples of solvents include ether solvents such as tetrahydrofuran, 2-methyltetrahydrofuran, diethyl ether, butyl ether, 4-methyltetrahydropyran, cyclopentyl methyl ether, and 1,4-dioxane; hydrocarbon solvents such as hexane, heptane, benzene, toluene, xylene, and cumene; and polar solvents such as N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone, dimethyl sulfoxide, γ-butyrolactone, acetonitrile, dichloromethane, and chloroform. Considering reactivity, ether solvents such as tetrahydrofuran, 2-methyltetrahydrofuran, and 4-methyltetrahydropyran are preferred; as are polar solvents such as acetonitrile, N,N-dimethylformamide, and N,N-dimethylacetamide.

[0337] Solvents may be used alone or in combination if necessary. Solvents may be commercially available products.

[0338] Considering reactivity, the amount of solvent used is preferably 50 to 7000 g relative to each mol of (7Z)-11-halo-1,1-dialkoxy-7-undecene compound (1-Z) or (4Z)-11,11-dialkoxy-4-undecene triarylphosphonium halide (3-Z).

[0339] The reaction temperature in preparing the reaction mixture varies depending on the solvent and / or base to be used, and is preferably from -78°C to 70°C. For example, when a metal alkoxide is used as the base, the optimal temperature is from -78°C to 25°C.

[0340] The reaction time for preparing the reaction mixture varies depending on the solvent to be used and / or the production scale, and is preferably from 0.5 to 100 hours.

[0341] Next, the (3E,5Z,9Z)-16,16-dialkoxy-3,5,9-hexadecanetriene compound (6) will be described below.

[0342]

[0343] R in general formula (6) 1 and R 2 As defined by general formula (1).

[0344] Specific examples of (3E,5Z,9Z)-16,16-dialkoxy-3,5,9-hexadecanetriene compounds (6) include the following compounds:

[0345] (3E,5Z,9Z)-16,16-dimethoxy-3,5,9-hexadecanetriene, (3E,5Z,9Z)-16,16-diethoxy-3,5,9-hexadecanetriene, (3E,5Z,9Z)-16,16-dipropoxy-3,5,9-hexadecanetriene, (3E,5Z,9Z)-16,16-dibutoxy-3,5,9-hexadecanetriene, (3E,5Z,9Z)-16,16-dipentoxy-3,5,9-hexadecanetriene, (3E,5Z,9Z)-16,16-dihexyloxy-3,5,9-hexadecanetriene, (3E,5Z,9Z)-16,16-diheptoxy-3,5,9-hexadecanetriene, (3E,5Z,9Z)-16,16-dioctyloxy-3,5,9-hexadecanetriene, (3E,5Z,9Z)-16,16-dinonoxy-3,5,9-hexadecanetriene, and (3E,5Z,9Z)-16,16-didecoxy-3,5,9-hexadecanetriene.

[0346] Considering economic factors, the (3E,5Z,9Z)-16,16-dialkoxy-3,5,9-hexadecanetriene compound (6) is preferably (3E,5Z,9Z)-16,16-dimethoxy-3,5,9-hexadecanetriene or (3E,5Z,9Z)-16,16-diethoxy-3,5,9-hexadecanetriene.

[0347] Wittig reaction

[0348] Considering reactivity, the amount of triphenylphosphonium (4Z)-11,11-dialkoxy-4-undecene ylide compound (4) used is preferably 1.0 to 4.0 mol, more preferably 1.0 to 2.0 mol, relative to each mol of (2E)-2-pentenal (5).

[0349] If necessary, the triarylphosphonium (4Z)-11,11-dialkoxy-4-undecene ylide compound (4) may be used alone or in combination with it.

[0350] (2E)-2-pentenal (5) can be commercially available or prepared internally, for example by oxidation of (2E)-2-penten-1-ol or hydrolysis of (2E)-1,1-dialkoxy-2-pentene.

[0351] Solvents may be used in the Wittig reaction if necessary.

[0352] Examples of solvents include ether solvents such as tetrahydrofuran, 2-methyltetrahydrofuran, diethyl ether, butyl ether, 4-methyltetrahydropyran, cyclopentyl methyl ether, and 1,4-dioxane; hydrocarbon solvents such as hexane, heptane, benzene, toluene, xylene, and cumene; and polar solvents such as N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone, dimethyl sulfoxide, γ-butyrolactone, acetonitrile, dichloromethane, and chloroform. Considering reactivity, ether solvents such as tetrahydrofuran, 2-methyltetrahydrofuran, and 4-methyltetrahydropyran are preferred; as are polar solvents such as acetonitrile, N,N-dimethylformamide, and N,N-dimethylacetamide.

[0353] Solvents may be used alone or in combination if necessary. Solvents may be commercially available products.

[0354] Considering reactivity, the amount of solvent used is preferably 50 to 7000 g relative to each mol of (2E)-2-pentenal (5).

[0355] The reaction temperature in the Wittig reaction varies depending on the solvent used, and is preferably between -78°C and 80°C. The Wittig reaction is more preferably carried out between -78°C and 30°C to achieve Z-selectivity. The Wittig reaction can be carried out between -78°C and -40°C, followed by treatment of the resulting synthetic intermediate with a strong base (such as lithium phenyl) to induce a modified Schlosser process, thereby achieving E-selectivity. The Wittig reaction can be carried out in an E-selective manner by adding lithium halides under typical Wittig reaction conditions.

[0356] The reaction time of the Wittig reaction varies depending on the production scale, and is preferably 0.5 to 100 hours.

[0357] (C-2). The following describes (5Z,9Z)-16,16-dialkoxy-5,9-hexadecadiene compound (9) and its preparation method.

[0358] (5Z,9Z)-16,16-dialkoxy-5,9-hexadecadiene compound (9) can be prepared according to the following chemical reaction. First, (4Z)-11,11-dialkoxy-4-undecenyltriarylphosphonium halide (3-Z) is deprotonated in the presence of a base to obtain a mixture of reaction products. The mixture of reaction products obtained by the deprotonation reaction is estimated to contain triarylphosphonium (4Z)-11,11-dialkoxy-4-undecenyl ylide compound (4) as a reaction product (in the following description, the reaction product is regarded as triarylphosphonium (4Z)-11,11-dialkoxy-4-undecenyl ylide compound (4)). Next, the mixture of reaction products undergoes a Wittig reaction with pentaldehyde of formula (8), for example, in situ, to form (5Z,9Z)-16,16-dialkoxy-5,9-hexadecadiene compound (9).

[0359]

[0360] Examples of (4Z)-11,11-dialkoxy-4-undecenyltriarylphosphonium halide (3-Z) and their preparation methods are described in Parts (A-2) and (B).

[0361] The triarylphosphonium (4Z)-11,11-dialkoxy-4-undecene ylide compound (4) contained in the reaction product mixture and its preparation method are described in part (C-1).

[0362] Next, the (5Z,9Z)-16,16-dialkoxy-5,9-hexadecadiene compound (9) will be described below.

[0363]

[0364] R in general formula (9) 1 and R 2 As defined by general formula (1).

[0365] Specific examples of (5Z,9Z)-16,16-dialkoxy-5,9-hexadecadiene compounds (9) include the following compounds:

[0366] (5Z,9Z)-16,16-dimethoxy-5,9-hexadecadiene, (5Z,9Z)-16,16-diethoxy-5,9-hexadecadiene, (5Z,9Z)-16,16-dipropoxy-5,9-hexadecadiene, (5Z,9Z)-16,16-dibutoxy-5,9-hexadecadiene, (5Z,9Z)-16,16-dipentoxy-5,9-hexadecadiene, (5Z,9Z)-16,16-dihexyloxy-5,9-hexadecadiene, (5Z,9Z)-16,16-diheptoxy-5,9-hexadecadiene, (5Z,9Z)-16,16-dioctyloxy-5,9-hexadecadiene, (5Z,9Z)-16,16-dinonoxy-5,9-hexadecadiene and (5Z,9Z)-16,16-didecoxy-5,9-hexadecadiene.

[0367] Considering economic factors, the (5Z,9Z)-16,16-dialkoxy-5,9-hexadecadiene compound (9) is preferably (5Z,9Z)-16,16-dimethoxy-5,9-hexadecadiene or (5Z,9Z)-16,16-diethoxy-5,9-hexadecadiene.

[0368] Wittig reaction

[0369] Considering reactivity, the amount of triarylphosphonium (4Z)-11,11-dialkoxy-4-undecene ylide compound (4) used is preferably 1.0 to 4.0 mol, more preferably 1.0 to 2.0 mol, relative to each mol of pentanal (8).

[0370] If necessary, the triarylphosphonium (4Z)-11,11-dialkoxy-4-undecene ylide compound (4) may be used alone or in combination with it.

[0371] Pentanal (8) can be a commercially available product.

[0372] When the Wittig reaction is carried out in the presence of a solvent, the amount of solvent used is preferably 50 to 7000 g relative to each mol of pentanal (8), taking into account reactivity.

[0373] Other conditions for the Wittig reaction are as described in section (C-1).

[0374] (C-3). The preparation method of a mixture comprising (3E,5Z,9Z)-16,16-dialkoxy-3,5,9-hexadecadiene compound (6) and (5Z,9Z)-16,16-dialkoxy-5,9-hexadecadiene compound (9) will be described below.

[0375] (5Z,9Z)-16,16-dialkoxy-5,9-hexadecadiene compound (9) can be prepared according to the following chemical reaction. First, (4Z)-11,11-dialkoxy-4-undecenyltriarylphosphonium halide (3-Z) is deprotonated in the presence of a base to form a mixture of reaction products. The mixture of reaction products obtained by the deprotonation reaction is estimated to contain triarylphosphonium (4Z)-11,11-dialkoxy-4-undecenyl ylide compound (4) as a reaction product (the reaction product is regarded as triarylphosphonium (4Z)-11,11-dialkoxy-4-undecenyl ylide compound (4) in the following description). Next, the mixture of reaction products undergoes a Wittig reaction with (2E)-2-pentenal (5) and pentanal (8), for example, in situ, to form a mixture comprising (3E,5Z,9Z)-16,16-dialkoxy-3,5,9-hexadecadiene compound (6) and (5Z,9Z)-16,16-dialkoxy-5,9-hexadecadiene compound (9).

[0376]

[0377] The triarylphosphonium (4Z)-11,11-dialkoxy-4-undecene ylide compound (4) contained in the reaction product mixture and its preparation method are described in part (C-1).

[0378] The (3E,5Z,9Z)-16,16-dialkoxy-3,5,9-hexadecadiene compound (6) prepared from (2E)-2-pentenal (5) and a mixture of reaction products, and the (5Z,9Z)-16,16-dialkoxy-5,9-hexadecadiene compound (9) prepared from pentanal (8) and a mixture of reaction products, are as described in parts (C-1) and (C-2).

[0379] When preparing a mixture comprising (3E,5Z,9Z)-16,16-dialkoxy-3,5,9-hexadecanetriene compound (6) and (5Z,9Z)-16,16-dialkoxy-5,9-hexadecanediene compound (9), the ratio of (3E,5Z,9Z)-16,16-dialkoxy-3,5,9-hexadecanetriene compound (6) and (5Z,9Z)-16,16-dialkoxy-5,9-hexadecanediene compound (9) can be adjusted by adjusting the ratio of (2E)-2-pentenal (5) to pentanal (8).

[0380] (2E)-2-pentenal (5) and pentanal (8) can be used as a mixture of them or added separately.

[0381] D. (7Z,11Z,13E)-7,11,13-hexadecadienal compounds (7) and (7Z,11Z)-7,11-hexadecadienal (10) and their preparation methods

[0382] (D-1). The following describes (7Z,11Z,13E)-7,11,13-hexadecanetrienal compound (7) and its preparation method.

[0383] (7Z,11Z,13E)-7,11,13-hexadecanetrienal (the sex pheromone of the citrus leafminer) can be prepared by hydrolyzing (3E,5Z,9Z)-16,16-dialkoxy-3,5,9-hexadecanetriene (6) as shown in the following chemical reaction formula.

[0384]

[0385] (3E,5Z,9Z)-16,16-dialkoxy-3,5,9-hexadecanetriene compound (6) and its preparation method are described in part (C-1).

[0386] hydrolysis reaction

[0387] In the hydrolysis reaction, if necessary, (3E,5Z,9Z)-16,16-dialkoxy-3,5,9-hexadecanetriene compound (6) may be one or more.

[0388] For example, hydrolysis can be carried out using acid and water.

[0389] Examples of acids include inorganic acids such as hydrochloric acid and hydrobromic acid; p-toluenesulfonic acid, benzenesulfonic acid, trifluoroacetic acid, acetic acid, formic acid, oxalic acid, trimethylsilane iodochloride, and titanium tetrachloride. Acetic acid, formic acid, and oxalic acid are preferred considering reactivity.

[0390] Acids may be used alone or in combination if necessary. Acids may be commercially available products.

[0391] The amount of acid used is preferably 0.01 to 10.0 mol relative to each mol of (3E,5Z,9Z)-16,16-dialkoxy-3,5,9-hexadecanetriene compound (6).

[0392] Considering reactivity, the amount of water used is preferably 18 to 7000 g, more preferably 18 to 3000 g, relative to each mol of (3E,5Z,9Z)-16,16-dialkoxy-3,5,9-hexadecanetriene compound (6).

[0393] In addition to acid or water, a solvent may be added during the hydrolysis reaction if necessary.

[0394] Examples of solvents include hydrocarbon solvents such as toluene, xylene, hexane, heptane, benzene, and cumene; ether solvents such as tetrahydrofuran, 2-methyltetrahydrofuran, diethyl ether, butyl ether, 4-methyltetrahydropyran, cyclopentyl methyl ether, and 1,4-dioxane; polar solvents such as N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone, dimethyl sulfoxide, acetonitrile, acetone, γ-butyrolactone, dichloromethane, and chloroform; and alcohol solvents such as methanol and ethanol.

[0395] Solvents may be used alone or in combination if necessary. Solvents may be commercially available.

[0396] The optimal solvent depends on the acid to be used. For example, when oxalic acid is used as the acid, tetrahydrofuran, 2-methyltetrahydrofuran, acetone, and γ-butyrolactone are preferred in consideration of reactivity.

[0397] Considering reactivity, the amount of solvent used is preferably 0 to 7000 g, more preferably 18 to 3000 g, relative to each mol of (3E,5Z,9Z)-16,16-dialkoxy-3,5,9-hexadecanetriene compound (6) or (5Z,9Z)-16,16-dialkoxy-5,9-hexadecanetriene compound (9) or relative to a total of 1 mol of a mixture of (3E,5Z,9Z)-16,16-dialkoxy-3,5,9-hexadecanetriene compound (6) and (5Z,9Z)-16,16-dialkoxy-5,9-hexadecanetriene compound (9).

[0398] The reaction temperature in the hydrolysis reaction varies depending on the acid and / or solvent to be used, and is preferably between 5°C and 180°C, taking into account reactivity.

[0399] The reaction time for the hydrolysis reaction varies depending on the acid and / or solvent to be used and / or the production scale, but is preferably 0.5 to 100 hours, taking into account reactivity.

[0400] (D-2). The following describes (7Z,11Z)-7,11-hexadecadienal (10) and its preparation method.

[0401] (7Z,11Z)-7,11-hexadecadienal (10) (the sex pheromone of the citrus leafminer) can be prepared by hydrolyzing (5Z,9Z)-16,16-dialkoxy-5,9-hexadecadien compound (9) as shown in the following chemical reaction formula.

[0402]

[0403] (5Z,9Z)-16,16-dialkoxy-5,9-hexadecadiene compound (9) and its preparation method are described in part (C-2).

[0404] hydrolysis reaction

[0405] In the hydrolysis reaction, if necessary, (5Z,9Z)-16,16-dialkoxy-5,9-hexadecadiene compound (9) may be one or more.

[0406] For example, hydrolysis can be carried out using acid and water.

[0407] The acid is as described in part (D-1).

[0408] The amount of acid used is preferably 0.01 to 10.0 mol relative to each mol of (5Z,9Z)-16,16-dialkoxy-5,9-hexadecadiene compound (9).

[0409] Considering reactivity, the amount of water used is preferably 18 to 7000 g, more preferably 18 to 3000 g, relative to each mol of (5Z,9Z)-16,16-dialkoxy-5,9-hexadecadiene compound (9).

[0410] In addition to acid or water, a solvent may be added during the hydrolysis reaction if necessary.

[0411] The solvent is as described in section (D-1).

[0412] Considering reactivity, the amount of solvent used is preferably 0 to 7000 g, more preferably 18 to 3000 g, relative to each mol of (5Z,9Z)-16,16-dialkoxy-5,9-hexadecadiene compound (9).

[0413] Other conditions for the hydrolysis reaction are as described in section (D-1).

[0414] (D-3). The preparation method of a mixture containing (7Z,11Z,13E)-7,11,13-hexadecadienal (7) and (7Z,11Z)-7,11-hexadecadienal (10) will be described below.

[0415] A mixture containing (3E,5Z,9Z)-16,16-dialkoxy-3,5,9-hexadecanetriene (6) and (5Z,9Z)-16,16-dialkoxy-5,9-hexadecanediene (9) is subjected to hydrolysis to form (D-3) a mixture containing (7Z,11Z,13E)-7,11,13-hexadecanetrienal (7) and (7Z,11Z)-7,11-hexadecanedienal (10).

[0416]

[0417] The method for preparing a mixture comprising (3E,5Z,9Z)-16,16-dialkoxy-3,5,9-hexadecadiene compound (6) and (5Z,9Z)-16,16-dialkoxy-5,9-hexadecadiene compound (9) is as described in part (C-3).

[0418] In preparing a mixture comprising (3E,5Z,9Z)-16,16-dialkoxy-3,5,9-hexadecadiene compound (6) and (5Z,9Z)-16,16-dialkoxy-5,9-hexadecadiene compound (9), it is possible to use a mixture comprising (3E,5Z,9Z)-16,16-dialkoxy-3,5,9-hexadecadiene compound (6) and (5Z,9Z)-16,16-dialkoxy-5,9-hexadecadiene compound (9). The ratio of (3E,5Z,9Z)-16,16-dialkoxy-3,5,9-hexadecanetriene compound (6) to (5Z,9Z)-16,16-dialkoxy-5,9-hexadecanetriene compound (9) in the mixture is adjusted to regulate the ratio of (3E,5Z,9Z)-16,16-dialkoxy-3,5,9-hexadecanetriene compound (6) to (5Z,9Z)-16,16-dialkoxy-5,9-hexadecanetriene compound (9). Therefore, for example, a mixture comprising (7Z,11Z,13E)-7,11,13-hexadecanetrienal compound (7) and (7Z,11Z)-7,11-hexadecanedienal (10) in a ratio of 3:1 can be prepared immediately, which is a sex pheromone composition of the citrus leafminer moth.

[0419] hydrolysis reaction

[0420] For example, hydrolysis can be carried out using acid and water.

[0421] The acid is as described in part (D-1).

[0422] The amount of acid used is preferably 0.01 to 10.0 mol relative to a total of 1 mol of (3E,5Z,9Z)-16,16-dialkoxy-3,5,9-hexadecadiene compound (6) and (5Z,9Z)-16,16-dialkoxy-5,9-hexadecadiene compound (9).

[0423] Considering reactivity, the amount of water used is preferably 18 to 7000 g, more preferably 18 to 3000 g, relative to a total of 1 mol of (3E,5Z,9Z)-16,16-dialkoxy-3,5,9-hexadecadiene compound (6) and (5Z,9Z)-16,16-dialkoxy-5,9-hexadecadiene compound (9).

[0424] In addition to acid or water, a solvent may be added during the hydrolysis reaction if necessary.

[0425] The solvent is as described in section (D-1).

[0426] Considering reactivity, the amount of solvent used is preferably 0 to 7000 g, more preferably 18 to 3000 g, relative to a total of 1 mol of (3E,5Z,9Z)-16,16-dialkoxy-3,5,9-hexadecadiene compound (6) and (5Z,9Z)-16,16-dialkoxy-5,9-hexadecadiene compound (9).

[0427] Other conditions for the hydrolysis reaction are as described in section (D-1).

[0428] Example

[0429] The present invention will be described with reference to the following embodiments. It should be understood that the present invention is not limited to or not restricted by these embodiments.

[0430] Unless otherwise specified, the term "purity" as used herein refers to the percentage of area obtained by gas chromatography (GC). The term "production ratio" refers to the ratio of the percentage of area obtained by GC. The term "yield" is calculated from the percentage of area determined by GC.

[0431] In the examples, reaction monitoring and yield calculation were performed under the following GC conditions.

[0432] GC conditions: GC-2014 capillary gas chromatograph (Shimadzu Corporation); column: DB-WAX (DB-5), 0.25μm×0.25mmφ×30m; carrier gas: He (1.55mL / min); detector: FID; column temperature: 150℃, increased at a rate of 5℃ / min, up to 230℃.

[0433] Taking into account the purity (%GC) of the starting materials and products, the yield is calculated according to the following equation.

[0434] Yield (%) = {[(mass of product obtained from the reaction × %GC) / molecular weight of product] ÷ [(mass of starting material in the reaction × %GC) / molecular weight of starting material]} × 100.

[0435] THF represents tetrahydrofuran, P-2Ni represents p-2 nickel boride, EDA represents ethylenediamine, Me represents a methyl group, and Et represents an ethyl group. t Bu represents a tert-butyl group, and Ph represents a phenyl group.

[0436] Example 1: Preparation of (7Z)-11-chloro-1,1-dimethoxy-7-undecyne (17:X) 1 =Cl, R 1 =R 2 =Me)

[0437]

[0438] Magnesium (51.64 g, 2.13 g atom) and tetrahydrofuran (607.20 g) were placed in a reactor at room temperature and stirred at 60-65°C for 31 minutes. After stirring, 6-chloro-1,1-dimethoxyhexane (14:X) was added dropwise at 60-75°C. 1 =Cl, R 1 =R 2 =Me)(367.17g, 2.02mol, purity 99.59%). After the addition was complete, the mixture was stirred at 75°C to 80°C for 2 hours to prepare 6,6-dimethoxyhexyl magnesium chloride (15:M=MgCl, R...). 1 =R 2 =Me).

[0439] Subsequently, copper chloride (3.24 g, 0.024 mol), lithium chloride (2.04 g, 0.048 mol), triethyl phosphite (16.11 g, 0.097 mol), tetrahydrofuran (306.53 g), and 1-bromo-5-chloro-1-pentyne (16:X) were added. 1 =Cl,X 2 =Br)(340.14 g, 1.86 mol, purity 99.34%) was placed in another reactor, and 6,6-dimethoxyhexyl magnesium chloride (15:M=MgCl, R=Br) prepared above was added dropwise to it at 15°C to 30°C. 1 =R 2 =Me). After the addition was complete, the mixture was stirred at 25°C to 35°C for 1.5 hours. Next, an aqueous solution of acetic acid (prepared from acetic acid (253.00 g) and water (759.00 g)) was added to the reaction mixture, followed by phase separation and removal of the aqueous phase. The resulting organic phase was washed with an aqueous solution of sodium hydroxide (3.25 mol) (520.00 g) and then concentrated under reduced pressure. The concentrate was distilled under reduced pressure to obtain (7Z)-11-chloro-1,1-dimethoxy-7-undecyne (17:X 1 =Cl, R 1 =R 2 =Me)(425.97g, 1.64mol, purity 95.12%, bp = 123.0℃ to 131.1℃ / 0.40kPa (3.0mmHg)), yield 88.18%.

[0440] The following is the (7Z)-11-chloro-1,1-dimethoxy-7-undecyne (17:X) prepared from this process. 1 =Cl, R 1 =R 2 =Me) spectral data.

[0441] Nuclear magnetic resonance spectrum:1 H-NMR (500MHz, CDCl3): δ = 1.30-1.42 (4H, m), 1.47 (2H, quin-like, J = 7.3Hz), 1.59 (2H, dt, J = 9.2Hz, 5.7Hz), 1.91 (2H, tt, J = 6.5Hz) ,6.5Hz),2.13(2H,tt,J=7.3Hz,2.3Hz),2.32(2H,tt,J=6.9Hz,2.3Hz),3.30(6H,s),3.63(2H,t,J=6.5Hz),4.34(1H,t,J=6.1Hz); 13 C-NMR (500MHz, CDCl3): δ=16.16,18.58,24.10,28.62,28.88,31.74,32.37,43.75,52.60,78.10,81.19,104.45.

[0442] Mass spectrometry: EI-mass spectrometry (70 eV): m / z 245 (M + -1),215,185,137,119,105,91,75.

[0443] Infrared absorption spectrum (D-ATR): νmax=2938,2860,1457,1437,1386,1291,1192,1127,1076,1053,969,910,652.

[0444] Example 2: Preparation of (7Z)-11-chloro-1,1-diethoxy-7-undecyne (17:X) 1 =Cl, R 1 =R 2 =Et)

[0445]

[0446] Magnesium (89.30 g, 3.67 g atom) and tetrahydrofuran (1050.00 g) were placed in a reactor at room temperature and stirred at 60-65°C for 17 minutes. After stirring, 6-chloro-1,1-diethoxyhexane (14:X) was added dropwise at 60-75°C. 1 =Cl, R 1 =R 2 =Et)(744.93g, 3.50mol, purity 98.08%). After the addition was complete, the mixture was stirred at 75°C to 80°C for 2 hours to prepare 6,6-diethoxyhexyl magnesium chloride (15:M=MgCl, R=Et)(744.93g, 3.50mol, purity 98.08%). 1 =R 2 =Et).

[0447] Subsequently, copper chloride (5.60 g, 0.042 mol), lithium chloride (3.54 g, 0.084 mol), triethyl phosphite (27.86 g, 0.17 mol), tetrahydrofuran (530.08 g), and 1-bromo-5-chloro-1-pentyne (16:X) were added. 1 =Cl,X 2 =Br)(584.30 g, 3.22 mol, purity 100%) was placed in another reactor, and 6,6-diethoxyhexyl magnesium chloride (15: M = MgCl, R = Br) prepared above was added dropwise at 15 °C to 30 °C. 1 =R 2 =Me). After the addition was complete, the mixture was stirred at 25°C to 35°C for 1.5 hours. Next, an aqueous solution of acetic acid (prepared from acetic acid (437.50 g) and water (1312.50 g)) was added to the reaction mixture, followed by phase separation and removal of the aqueous phase. The resulting organic phase was washed with an aqueous solution of sodium hydroxide (5.63 mol) (900.00 g) and then concentrated under reduced pressure. The concentrate was distilled under reduced pressure to obtain (7Z)-11-chloro-1,1-diethoxy-7-undecyne (17:X 1 =Cl, R 1 =R 2 =Me)(798.79g, 2.71mol, purity 93.24%, bp = 148.1℃ to 154.2℃ / 0.40kPa (3.0mmHg)), yield 84.25%.

[0448] The following is the (7Z)-11-chloro-1,1-diethoxy-7-undecyne (17:X) prepared from this process. 1 =Cl, R 1 =R 2 Spectral data of Et.

[0449] Nuclear magnetic resonance spectroscopy: 1 H-NMR (500MHz, CDCl3): δ = 1.19 (6H, t, J = 7.3Hz), 1.29-1.42 (2H, m), 1.47 (2H, quin-like, J = 7.3Hz), 1.60 (2H, dt, J = 9.2Hz, 5.8Hz), 1.91 (2H, tt, J = 6.5Hz), 2 .13(2H,tt,J=6.5Hz),2.13(2H,tt,J=7.3Hz,2.3Hz),2.32(2H,tt,J=6.9Hz,2. 3Hz), 3.47 (2H, tt, J = 8.2Hz, 6.9Hz), 3.59-3.66 (4H, m), 4.46 (1H, t, J = 5.8Hz); 13C-NMR (500MHz, CDCl3): δ=15.32,16.16,18.58,24.25,28.64,28.90,31.72,33.47,43.76,60.84,78.05,81.23,102.82.

[0450] Mass spectrometry: EI-mass spectrometry (70 eV): m / z 273 (M + -1),229,183,165,151,137,123,103,57.

[0451] Infrared absorption spectrum (D-ATR): νmax=2974,2932,2862,1442,1374,1345,1291,1128,1061,1001,653.

[0452] Example 3: Preparation of 11-chloro-1,1-dimethoxy-7-undecene (1-Z:X) 1 =Cl, R 1 =R 2 =Me)

[0453]

[0454] The (7Z)-11-chloro-1,1-methoxy-7-undecyne (17:X) obtained in Example 1 was used 1 =Cl, R 1 =R 2 =Me)(788.66 g, 3.04 mol, purity 95.12%), P-2Ni catalyst (381.12 g, 0.096 mol Ni), and EDA (8.32 g) were placed in a reactor at room temperature, and hydrogen was injected into the reactor while stirring at 45°C to 55°C for 11.5 hours. GC confirmed a conversion of 100%, and then water (132.98 g) was added to the reaction mixture. Phase separation was then performed, and the aqueous phase was removed to obtain the organic phase. The resulting organic phase was concentrated under reduced pressure. The concentrate was distilled under reduced pressure to obtain 11-chloro-1,1-dimethoxy-7-undecene (1-Z:X 1 =Cl, R 1 =R 2 =Me)(785.92g, 2.88mol, purity 91.17%, bp = 123.1℃ to 142.1℃ / 0.40kPa (3.0mmHg)), yield 94.74%.

[0455] The following is the 11-chloro-1,1-dimethoxy-7-undecene (1-Z:X) prepared from this process. 1 =Cl, R 1 =R 2=Me) spectral data.

[0456] Nuclear magnetic resonance spectroscopy: 1 H-NMR (500MHz, CDCl3): δ = 1.24-1.39 (6H, m), 1.55-1.61 (2H, m), 1.81 (2H, dt, J = 6.9Hz, 6.9Hz), 2.04 (2H, q-like, J = 6.9Hz), 2.18 (2H, dt, J = 7.3Hz, 7.3Hz),3.30(6H,s),3.52(2H,t,J=6.5Hz),4.35(1H,t,J=5.7Hz),5.30(1 H,dtt,J=10.7Hz,7.3Hz,1.5Hz),5.42(1H,dtt,J=10.7Hz,7.3Hz,1.5HZ); 13 C-NMR (500MHz, CDCl3): δ=24.33, 24.44, 27.08, 29.06, 29.54, 32.41, 32.43, 44.46, 52.55, 104.47, 127.63, 131.45.

[0457] Mass spectrometry: EI-mass spectrometry (70 eV): m / z 247 (M + -1),217,184,158,134,121,97,75,55,41.

[0458] Infrared absorption spectrum (D-ATR): νmax=2932,2857,1457,1444,1127,1074,1055,965,912,726,653.

[0459] Example 4: Preparation of 11-chloro-1,1-diethoxy-7-undecene (1-Z:X) 1 =Cl, R 1 =R 2 =Et)

[0460]

[0461] The (7Z)-11-chloro-1,1-ethoxy-7-undecyne (17:X) obtained in Example 2 was used. 1 =Cl, R 1 =R 2=Et)(798.79 g, 2.71 mol, purity 93.24%), P-2Ni catalyst (339.53 g, 0.10 mol Ni), and EDA (7.43 g) were placed in a reactor at room temperature, and hydrogen was injected into the reactor while stirring at 45°C to 55°C for 10 hours. GC confirmed a conversion of 100%. Water (118.46 g) was then added to the reaction mixture, followed by phase separation and removal of the aqueous phase to obtain the organic phase. The resulting organic phase was concentrated under reduced pressure. The concentrate was distilled under reduced pressure to obtain 11-chloro-1,1-diethoxy-7-undecene (1-Z:X 1 =Cl, R 1 =R 2 =Et)(781.02g, 2.49mol, purity 88.26%, bp = 150.0℃ to 165.0℃ / 0.40kPa (3.0mmHg)), yield 91.79%. The product contains 1-ethoxy-11-chloro-1,7-undecadiene (0.061mol, content 1.8%) as an impurity, which is converted from (7Z)-11-chloro-1,1-ethoxy-7-undecyne (17:X) during distillation. 1 =Cl, R 1 =R 2 It is obtained by removing ethanol from the ethoxy group of Et.

[0462] The following is the 11-chloro-1,1-diethoxy-7-undecene (1-Z:X) prepared from this process. 1 =Cl, R 1 =R 2 Spectral data of Et.

[0463] Nuclear magnetic resonance spectroscopy: 1 H-NMR (500MHz, CDCl3): δ=1.19(6H,t,J=6.9Hz),1.26-1.39(6H,m),1.56-1.64(2H,m),1.8 1(2H,tt,J=6.9Hz,6.9Hz),2.03(2H,q-like,J=6.9Hz),2.18(2H,dt,J=7.1Hz,7.1Hz),3.48 (2H,dt,J=9.4Hz,7.3Hz),3.52(2H,t,J=6.9Hz),3.62(2H,dq,J=9.4Hz,7.3Hz),4.46(1H,t, J=5.7Hz),5.29(1H,dtt,J=10.7Hz,7.3Hz,1.5Hz),5.41(1H,dtt,J=10.7Hz,7.3Hz,1.5Hz); 13C-NMR (500MHz, CDCl3): δ=15.32, 24.31, 24.59, 27.10, 29.07, 29.55, 32.42, 33.51, 44.46, 60.78, 102.86, 127.58, 131.49.

[0464] Mass spectrometry: EI-mass spectrometry (70 eV): m / z 275 (M + -1),231,185,148,103,85,57,41.

[0465] Infrared absorption spectrum (D-ATR): νmax=2975,2930,2858,1444,1373,1344,1128,1062,1001,727,653.

[0466] Example 5: Preparation of (3E,5Z,9Z)-16,16-dimethoxy-3,5,9-hexadecanetriene (6:R) 1 =R 2 =Me)

[0467]

[0468] The 11-chloro-1,1-dimethoxy-7-undecene (1-Z:X) obtained in Example 3 1 =Cl, R 1 =R 2 =Me)(261.97g, 0.96mol, purity 91.17%), triphenylphosphine (2:Ar=Ph) (252.40g, 0.96mol), sodium iodide (155.89g, 1.04mol), potassium carbonate (7.74g, 0.056mol), and acetonitrile (360.00g) were placed in a reactor at room temperature and stirred at 75°C to 85°C for 16 hours to prepare (4Z)-11,11-dimethoxy-4-undecenyltriphenylphosphonium iodide (3:Y=I, Ar=Ph, R=Me)(261.97g, 0.96mol, purity 91.17%), triphenylphosphine (2:Ar=Ph) (252.40g, 0.96mol), sodium iodide (155.89g, 1.04mol), potassium carbonate (7.74g, 0.056mol), and acetonitrile (360.00g). 1 =R 2 =Me).

[0469] Next, tetrahydrofuran (640.00 g) was added dropwise to the reactor at 30°C to 40°C. After the addition was complete, the reaction mixture was cooled to 0°C to -15°C. Subsequently, potassium tert-butoxide (103.23 g, 0.92 mol) was added, and the mixture was stirred for 1 hour to obtain a reaction product mixture. The reaction product mixture is estimated to contain triphenylphosphonium (4Z)-11,11-dimethoxy-4-undecene ylide (4:Ar=Ph, R 1 =R 2 =Me) as a reaction product.

[0470] Then, (2E)-2-pentenal (5) (68.09 g, 0.80 mol, purity 98.84%, 2E:2Z = 98.7:1.3) was added dropwise to the reactor at -79°C to -60°C. After the addition was complete, the mixture was stirred at 20°C to 30°C for 12 hours. Subsequently, brine (prepared from sodium chloride (121.26 g) and water (1212.40 g)) was added to the reaction mixture, followed by phase separation and removal of the aqueous phase to obtain the organic phase. The organic phase was concentrated under reduced pressure to obtain the crude product (3E,5Z,9Z)-16,16-dimethoxy-3,5,9-hexadecanetriene (6:R) 1 =R 2 =Me)(228.31g, 0.77mol, purity 94.02%, 3E5Z9Z:3E5E9Z=92.2:7.8), crude yield 95.68%.

[0471] The following is the (4Z)-11,11-dimethoxy-4-undecenyltriphenylphosphonium iodide (3:Y=I,Ar=Ph,R) prepared from this process. 1 =R 2 =Me) spectral data.

[0472] Nuclear magnetic resonance spectroscopy: 1 H-NMR (500MHz, CDCl3): δ=1.22-1.34(6H,m),1.45-1.54(2H,m),1.64(2H,sext-lik e,J=7.6Hz),1.99(2H,dt,J=6.9Hz,6.9Hz),2.24(2H,dt,J=7.3Hz,7.3Hz),3.23(6H ,s),3.20-3.28(2H,m),4.29(1H,t,J=5.7Hz),5.31(1H,dtt,J=10.7Hz,7.3Hz,1.5H z),5.45(1H,dtt,J=10.7Hz,7.3Hz,1.2Hz),7.68-7.75(12H,m),7.83-7.89(3H,m); 13 C-NMR (500MHz, CDCl3): δ=0.80,0.76,1.13,1.30,1.47,1.63,1.80,105.42,118.87,119.56,131.12,131.22,134.54,134.62,136.00,136.03.

[0473] Infrared absorption spectrum (D-ATR): νmax=2930,2856,1438,1161,1113,1055,996,736,723,691,531,509.

[0474] The following is the (3E,5Z,9Z)-16,16-dimethoxy-3,5,9-hexadecanetriene (6:R) prepared from this process. 1 =R 2 =Me) spectral data.

[0475] Nuclear magnetic resonance spectroscopy: 1 H-NMR (500MHz, CDCl3): δ=1.01(3H,t,J=7.3Hz),1.24-1.39(6H,m),1.55-1.61(2H,m),2.03(2H ,q-like,J=6.9Hz),2.12(4H,quin-like,J=7.3Hz),2.21(2H,dt,J=7.7Hz,7.7Hz),3.30(6H,s) ,4.35(1H,t,J=5.7Hz),5.30(1H,dt,J=10.7Hz,7.3Hz),5.33-5.41(2H,m),5.70(1H,dt,J=14.9 Hz, 6.5Hz), 5.96 (1H, dd, J = 11.1Hz, 11.1Hz), 6.29 (1H, dddt, J = 14.9Hz, 11.1Hz, 1.5Hz, 1.5Hz); 13 C-NMR (500MHz, CDCl3): δ=13.59,24.47,25.85,27.14,27.32,27.80,29.10,2 9.59,32.42,52.53,104.47,124.59,128.93,129.02,129.22,130.33,136.38.

[0476] Mass spectrometry: EI-mass spectrometry (70 eV): m / z 280 (M + -1),248,217,166,121,94,75.

[0477] Infrared absorption spectrum (D-ATR): νmax=2932,2856,1460,1385,1127,1077,1056,982,947,737.

[0478] Example 6: Preparation of (3E,5Z,9Z)-16,16-diethoxy-3,5,9-hexadecanetriene (6:R) 1 =R 2 =Et)

[0479]

[0480] The 11-chloro-1,1-diethoxy-7-undecene (1-Z:X) containing 1-ethoxy-11-chloro-1,7-undecadiene (0.034 mol, content 1.8%) obtained in Example 4 was used. 1 =Cl, R 1 =R 2 =Et)(436.61g, 1.39mol, purity 88.26%), triphenylphosphine (2:Ar=Ph) (374.92g, 1.46mol), potassium carbonate (12.00g, 0.087mol), and acetonitrile (558.00g) were placed in a reactor at room temperature and stirred at 75°C to 85°C for 15.5 hours to prepare (4Z)-11,11-diethoxy-4-undecenyltriphenylphosphonium iodide (3:Y=I;;Ar=Ph, R) 1 =R 2 =Et).

[0481] Next, tetrahydrofuran (992.00 g) was added dropwise to the reactor at 30°C to 40°C. After the addition was complete, the reaction mixture was cooled to 5°C to -10°C. Subsequently, potassium tert-butoxide (153.05 g, 1.36 mol) was added, and the reaction mixture was stirred for 1 hour to obtain a mixture of reaction products. The mixture of reaction products is estimated to contain triphenylphosphonium (4Z)-11,11-diethoxy-4-undecene ylide (4:Ar=Ph, R 1 =R 2 =Et) as a reaction product.

[0482] Then, (2E)-2-pentenal (5) (106.27 g, 1.24 mol, purity 98.15%, 2E:2Z = 98.7:1.3) was added dropwise to the reactor at -10°C to 5°C. After the addition was complete, the mixture was stirred at 15°C to 25°C for 2 hours. Subsequently, brine (prepared from sodium chloride (187.95 g) and water (1879.22 g)) was added to the reaction mixture, followed by phase separation and removal of the aqueous phase to obtain the organic phase. The organic phase was concentrated under reduced pressure to obtain the crude product (3E,5Z,9Z)-16,16-dimethoxy-3,5,9-hexadecanetriene (6:R) 1 =R 2 =Et)(375.58g, 0.91mol, purity 74.36%, 3E5Z9Z:3E5E9Z = 87.4:12.6), crude yield 73.01%. The crude product contains impurities derived from 1-ethoxy-11-chloro-1,7-undecadiene (7Z,11Z,,13E)-1-ethoxy-1,7,11,13-hexadecathetene (0.037mol, content 2.6%).

[0483] The following is the (4Z)-11,11-diethoxy-4-undecenyltriphenylphosphonium iodide (3:Y=I,Ar=Ph,R) prepared from this process. 1 =R 2 Spectral data of Et.

[0484] Nuclear magnetic resonance spectroscopy: 1 H-NMR (500MHz, CDCl3): δ = 1.11 (6H, t, J = 7.3Hz), 1.21-1.36 (6H, m), 1.48 (2H, dt, J = 8.8Hz, 5.7Hz), 1.65 (2H,sext-like,J=7.7Hz),1.99(2H,dt,J=7.3Hz,7.3Hz),2.24(2H,dt,J=7.3Hz,7.3Hz),3.20-3.28(2H, m),3.42(2H,dq,J=7.3Hz,9.6Hz),3.57(2H,dq,J=6.9Hz,9.6Hz),4.41(1H,t,J=5.8Hz),5.31(1H,dtt,J =10.7Hz,7.3Hz,1.5Hz),5.45(1H,dtt,J=11.1Hz,7.3Hz,1.5Hz),7.68-7.75(12H,m),7.83-7.88(3H,m); 13 C-NMR (500MHz, CDCl3): δ=0.80,0.97,1.14,1.30,1.46,1.63,1.80,15.68,29.73,34.48,103.70,118.87,119.56,131.12,131.22,134.54,134.2.

[0485] Infrared absorption spectrum (D-ATR): νmax=2973,2927,2858,1587,1438,1373,1113,1060,996,737,723,691,530,509.

[0486] The following is the (3E,5Z,9Z)-16,16-diethoxy-3,5,9-hexadecanetriene (6:R) prepared from this process. 1 =R 2 Spectral data of Et.

[0487] Nuclear magnetic resonance spectroscopy: 1H-NMR (500MHz, CDCl3): δ=1.01(3H,t,J=7.3Hz), 1.20(6H,t,J=7.3Hz), 1.29-1.39(6H,m), 1.57-1.63(2H,m), 2.02( 2H,q-like,J=6.5Hz), 2.12(4H,tt,J=7.7Hz,7.7Hz), 2.21(2H,dt,J=7.3Hz,7.3Hz), 3.48(2H,dq,J=9.4Hz,7.3Hz), 3.63(2H,dq,J=9.4Hz,7.3HZ),4.47(1H,t,J=5.7Hz),5.30(1H,dt,J=10.7Hz,7.3Hz),5.37(2H,dt,J=5.8Hz,3.5Hz) ,5.70(1H,dt,J=14.9Hz,6.9Hz),5.96(1H,dd,J=11.1Hz,11.1Hz),6.29(1H,dddt,J=14.9Hz,11.1Hz,1.5Hz,1.5Hz); 13 C-NMR (500MHz, CDCl3): δ=13.59,15.33,24.63,25.85,27.15,27.31,27.79,29.1 0,29.59,33.51,60.76,102.87,124.58,128.91,128.97,129.23,130.37,136.38.

[0488] Mass spectrometry: EI-mass spectrometry (70 eV): m / z 307 (M + -1),262,217,121,95,67,41.

[0489] Infrared absorption spectrum (D-ATR): νmax=2973,2930,2857,1457,1443,1373,1344,1128,1062,983,946,737.

[0490] Example 7: Preparation of (5Z,9Z)-16,16-dimethoxy-5,9-hexadecadiene (9:R) 1 =R 2 =Me)

[0491]

[0492] The 11-chloro-1,1-dimethoxy-7-undecene (1-Z:X) obtained in Example 3 1 =Cl, R 1 =R 2=Me)(130.99g, 0.48mol, purity 91.17%), triphenylphosphine (2:Ar=Ph) (126.20g, 0.48mol), sodium iodide (77.94g, 0.52mol), potassium carbonate (3.87g, 0.028mol), and acetonitrile (180.00g) were placed in a reactor at room temperature and stirred at 75°C to 85°C for 17 hours to obtain (4Z)-11,11-dimethoxy-4-undecenyltriphenylphosphonium iodide (3:Y=I,Ar=Ph,R=Me)(130.99g, 0.48mol, purity 91.17%). 1 =R 2 =Me).

[0493] Next, tetrahydrofuran (320.00 g) was added dropwise to the reactor at 30°C to 40°C. After the addition was complete, the reaction mixture was cooled to 0°C to -15°C. Subsequently, potassium tert-butoxide (51.62 g, 0.46 mol) was added, and the mixture was stirred for 1 hour to obtain a reaction product mixture. The reaction product mixture is estimated to contain triphenylphosphonium (4Z)-11,11-dimethoxy-4-undecene ylide (4:Ar=Ph, R 1 =R 2 =Me) as a reaction product.

[0494] Subsequently, pentanal (8) (36.27 g, 0.40 mol, purity 95.00%) was added dropwise to the reactor at -70°C to -60°C. After the addition was complete, the mixture was stirred at 20°C to 30°C for 12 hours. Then, brine (prepared from sodium chloride (60.63 g) and water (606.20 g)) was added to the reaction mixture, followed by phase separation and removal of the aqueous phase to obtain the organic phase. The organic phase was concentrated under reduced pressure to obtain the crude product (5Z,9Z)-16,16-dimethoxy-5,9-hexadecadiene (9:R) 1 =R 2 =Me)(117.29g, 0.38mol, purity 90.59%, 5Z9Z and 5E9Z types were not separated by GC), crude yield 94.04%.

[0495] The following is the (5Z,9Z)-16,16-dimethoxy-5,9-hexadecadiene (9:R) prepared from this process. 1 =R 2 =Me) spectral data.

[0496] Nuclear magnetic resonance spectroscopy: 1H-NMR (500MHz, CDCl3): δ = 0.89 (3H, t, J = 7.3Hz), 1.24-1.39 (10H, m), 1.55-1.62 (2H, m), 1. 99-2.05(4H,m),2.05-2.09(4H,m),3.30(6H,s),4.35(1H,t,J=6.1Hz),5.32-5.42(4H,m); 13 C-NMR (500MHz, CDCl3): δ=13.97,22.32,24.48,26.93,27.13,27.36,27.40, 29.11,29.61,31.90,32.43,52.53,104.48,129.09,129.28,130.12,130.31.

[0497] Mass spectrometry: EI-mass spectrometry (70 eV): m / z 281 (M + -1),250,219,149,136,121,108,93,75,55,41.

[0498] Infrared absorption spectrum (D-ATR): νmax=2928,2857,1463,1385,1128,1078,1056,966,728.

[0499] Example 8: Preparation of (3E,5Z,9Z)-16,16-dimethoxy-3,5,9-hexadecanetriene (6:R) 1 =R 2 =Me) and (5Z,9Z)-16,16-dimethoxy-5,9-hexadecadiene (9:R 1 =R 2 =Me) mixture (12)

[0500]

[0501] The 11-chloro-1,1-dimethoxy-7-undecene (1-Z:X) obtained in Example 3 1 =Cl, R 1 =R 2 =Me)(44.75g, 0.16mol, purity 91.17%), triphenylphosphine (2:Ar=Ph) (43.13g, 0.16mol), sodium iodide (26.64g, 0.18mol), potassium carbonate (1.32g, 0.0096mol), and acetonitrile (61.52g) were placed in a reactor at room temperature and stirred at 75°C to 85°C for 15.5 hours to prepare (4Z)-11,11-dimethoxy-4-undecenyltriphenylphosphonium iodide (3:Y=I, Ar=Ph, R=Me)(44.75g, 0.16mol, purity 91.17%), triphenylphosphine (2:Ar=Ph) (43.13g, 0.16mol), sodium iodide (26.64g, 0.18mol), potassium carbonate (1.32g, 0.0096mol), and acetonitrile (61.52g). 1=R 2 =Me).

[0502] Next, tetrahydrofuran (109.36 g) was added dropwise to the reactor at 30°C to 40°C. After the addition was complete, the reaction mixture was cooled to 0°C to -15°C. Subsequently, potassium tert-butoxide (17.64 g, 0.16 mol) was added, and the mixture was stirred for 1 hour to obtain a reaction product mixture. The reaction product mixture is estimated to contain triphenylphosphonium (4Z)-11,11-dimethoxy-4-undecene ylide (4:Ar=Ph,R 1 =R 2 =Me) as a reaction product.

[0503] Subsequently, a mixture (11) of (2E)-2-pentenal (5) (8.72 g, 0.10 mol, 98.84% purity) and pentanal (8) (3.10 g, 0.034 mol, 95.00% purity) was added dropwise to the reactor at -70°C to -60°C. After the addition was complete, the mixture was stirred at 20°C to 30°C for 12 hours. Subsequently, brine (prepared from sodium chloride (20.72 g) and water (207.17 g)) was added to the reaction mixture, followed by phase separation and removal of the aqueous phase to obtain the organic phase. The organic phase was concentrated under reduced pressure to obtain (3E,5Z,9Z)-16,16-dimethoxy-3,5,9-hexadecanetriene (6:R 1 =R 2 =Me)(40.84g, 0.092mol, content 63.06%, 3E5Z9Z:3E5E9Z=90.9:9.1) and (5Z,9Z)-16,16-dimethoxy-5,9-hexadecadiene (9:R 1 =R 2 =Me)(40.84g, 0.30mol, content 20.59%, 5Z9Z type and 5E9Z type without GC separation) mixture (12), crude yield 88.97%.

[0504] (3E,5Z,9Z)-16,16-dimethoxy-3,5,9-hexadecanetriene (6:R) was thus prepared. 1 =R 1 =Me) and (5Z,9Z)-16,16-dimethoxy-5,9-hexadecadiene (9:R 1 =R 1 The spectral data of (Me) were the same as those measured in Examples 5 and 7, respectively.

[0505] Example 9: Preparation of (7Z,11Z,13E)-7,11,13-hexadecanetrienal (7)

[0506]

[0507] The crude product (3E,5Z,9Z)-16,16-dimethoxy-3,5,9-hexadecanetriene (6:R) obtained in Example 5 was used... 1 =R 2 =Me)(228.31g, 0.77mol, purity 94.02%, 3E5Z9Z:3E5E9Z = 92.2:7.8), oxalic acid dihydrate (289.48g, 2.30mol), tetrahydrofuran (765.40g), and pure water (765.40g) were placed in a reactor and stirred at 60°C to 65°C for 3.5 hours. The reaction mixture was cooled to 50°C, and hexane (225.10g) was added. The mixture was stirred for 30 minutes. After stirring was complete, the reaction mixture was allowed to stand for phase separation, and then the aqueous phase was removed to obtain the organic phase. The organic phase was concentrated under reduced pressure, and the concentrate was distilled under reduced pressure (125.0 °C to 134.5 °C / 0.40 kPa (3.0 mmHg) to obtain (7Z,11Z,13E)-7,11,13-hexadecanetrienal (7) (159.21 g, 0.64 mol, purity 94.47%, 7Z11Z13E:7Z11E13E = 91.6:8.4), with an overall yield of 80.21% for Examples 5 and 9. (7Z,11Z,13E)-7,11,13-hexadecanetrienal (7) was obtained from the starting material 1-bromo-5-chloro-1-pentyne (16:X 1 =Cl,X 2 =Br), the overall yield of Examples 1, 3, 5 and 9 was 67.01%.

[0508] The following are the spectral data of (7Z,11Z,13E)-7,11,13-hexadecanetrienal (7) prepared therefrom.

[0509] Nuclear magnetic resonance spectroscopy: 1H-NMR (500MHz, CDCl3): δ = 1.01 (3H, t, J = 7.3Hz), 1.29-1.41 (4H, m), 1.63 (2H, quin-like, J = 7.3Hz) ,2.04(2H,q-like,J=6.9Hz),2.08-2.15(4H,m),2.21(2H,dt,J=7.3Hz,7.3Hz),2.41(2H,dt,J=1.9H z,7.3Hz),5.29(1H,dt,J=11.1Hz,7.3Hz),5.33-5.41(2H,m),5.70(1H,dt,J=14.9Hz,6.5Hz),5.96( 1H,dd,J=11.1Hz,11.1Hz),6.29(1H,dddt,J=15.0Hz,11.1Hz,1.5Hz,1.5Hz),9.75(1H,t,J=1.9Hz); 13 C-NMR (500MHz, CDCl3): δ=13.58,21.94,25.84,26.98,27.31,27.75,28.7 4,29.36,43.83,124.55,128.96,129.14,129.25,129.99,136.41,202.72.

[0510] Mass spectrometry: EI-mass spectrometry (70 eV): m / z 234 (M + ),149,135,122,107,95,79,67,55,41.

[0511] Infrared absorption spectrum (D-ATR): νmax = 2962, 2931, 2856, 1727, 1460, 983, 947, 739.

[0512] Example 10: Preparation of (7Z,11Z,13E)-7,11,13-hexadecanetrienal (7)

[0513]

[0514] The (3E,5Z,9Z)-16,16-diethoxy-3,5,9-hexadecanetriene (6:R) obtained in Example 6 1 =R 1=Et)(375.58 g, 0.91 mol, purity 74.36%, 3E5Z9Z:3E5E9Z = 87.4:12.6)(containing (7Z,11Z,13E)-1-ethoxy-1,7,11,13-hexadecatetraene (0.037 mol, content 2.6%) as impurities), oxalic acid dihydrate (356.53 g, 2.83 mol), tetrahydrofuran (942.67 g), and pure water (942.67 g) were placed in a reactor and stirred at 60°C to 65°C for 2 hours. The reaction mixture was cooled to 50°C, and hexane (277.24 g) was added. The mixture was stirred for 30 minutes. After stirring was complete, the reaction mixture was allowed to stand for phase separation, and then the aqueous phase was removed to obtain the organic phase. The organic phase was concentrated under reduced pressure, and the concentrate was distilled under reduced pressure (125.0°C to 134.5°C / 0.40 kPa (3.0 mmHg)) to obtain (7Z,11Z,13E)-7,11,13-hexadecanetrienal (7) (221.37 g, 0.90 mol, purity 94.79%, 7Z11Z13E:7Z11E13E = 86.6:13.4), with an overall yield of 72.20% in Examples 6 and 10. It should be noted that (7Z,11Z,13E)-1-ethoxy-1,7,11,13-hexadecanetetraene was also hydrolyzed to form (7Z,11Z,13E)-7,11,13-hexadecanetrienal (7). (7Z,11Z,13E)-7,11,13-hexadecanetrienal (7) is derived from the starting material 1-bromo-5-chloro-1-pentyne (16:X) 1 =Cl,X 2 =Br) was prepared, and the overall yield of Examples 2, 4, 6 and 10 was 55.83%.

[0515] The spectral data of (7Z,11Z,13E)-7,11,13-hexadecanetrienal (7) prepared in this way are the same as those determined in Example 9.

[0516] Example 11: Preparation of (7Z,11Z)-7,11-hexadecadienal (10)

[0517]

[0518] The crude product (5Z,9Z)-16,16-dimethoxy-5,9-hexadecadiene (9:R) obtained in Example 7 was used. 1 =R 2=Me)(117.29 g, 0.38 mol, purity 90.59%, 5Z9Z and 5E9Z types without GC separation), oxalic acid dihydrate (150.19 g, 1.19 mol), tetrahydrofuran (397.10 g), and pure water (397.10 g) were placed in a reactor and stirred at 60-65°C for 3 hours. The reaction mixture was cooled to 50°C, and hexane (116.79 g) was added. The mixture was stirred for 30 minutes. After stirring was complete, the reaction mixture was allowed to stand for phase separation, and then the aqueous phase was removed to obtain the organic phase. The organic phase was concentrated under reduced pressure, and the concentrate was distilled under reduced pressure (110.4°C to 130.6°C / 0.40 kPa (3.0 mmHg)) to obtain (7Z,11Z)-7,11-hexadecadienal (10) (87.73 g, 0.35 mol, purity 93.90%, 7Z11Z:7Z11E = 94.7:5.3), with an overall yield of 87.13% for Examples 7 and 10. (7Z,11Z)-7,11-hexadecadienal (10) was derived from the starting material 1-bromo-5-chloro-1-pentyne (16:X 1 =Cl,X 2 =Br) was prepared, and the overall yield of Examples 1, 3, 7 and 11 was 72.79%.

[0519] The following are the spectral data of (7Z,11Z)-7,11-hexadecadienal (10) prepared therefrom.

[0520] Nuclear magnetic resonance spectroscopy: 1 H-NMR (500MHz, CDCl3): δ = 0.89 (3H, t, J = 7.3Hz), 1.25-1.39 (8H, m), 1.63 (2H, tt, J = 7.3Hz, 7.3Hz), 2.02 (4H, qui n-like,J=6.2Hz),2.07(4H,t,J=2.7Hz),2.41(2H,dt,J=1.9Hz,7.3Hz),5.31-5.41(4H,m),9.76(1H,tJ=1.9Hz); 13 C-NMR (500MHz, CDCl3): δ=13.96,21.95,22.31,26.92,26.96,27.31,27.39,28.75,29.38,31.88,43.84,129.02,129.51,129.79,130.35,202.74.

[0521] Mass spectrometry: EI-mass spectrometry (70 eV): m / z 236 (M + ),218,193,137,123,109,95,81,67,55,41.

[0522] Infrared absorption spectrum (D-ATR): νmax = 2928, 2857, 2715, 1728, 1458, 727.

[0523] Example 12: Preparation of a mixture (13) of (7Z,11Z,13E)-7,11,13-hexadecadienal (7) and (7Z,11Z)-7,11-hexadecadienal (10).

[0524]

[0525] The (3E,5Z,9Z)-16,16-dimethoxy-3,5,9-hexadecanetriene (6:R) obtained in Example 8 1 =R 2 =Me)(40.84g, 0.092mol, content 63.06%, 3E5Z9Z:3E5E9Z=90.9:9.1) and (5Z,9Z)-16,16-dimethoxy-5,9-hexadecadiene (9:R 1 =R 2 A mixture (12) of α-Me (40.84 g, 0.30 mol, 20.59% purity, 5Z9Z and 5E9Z types without GC separation), oxalic acid dihydrate (45.99 g, 0.36 mol), tetrahydrofuran (121.60 g), and pure water (121.60 g) was placed in a reactor and stirred at 60-65°C for 3 hours. The reaction mixture was cooled to 50°C, and hexane (35.76 g) was added. The mixture was stirred for 30 minutes. After stirring was complete, the reaction mixture was allowed to stand for phase separation, and then the aqueous phase was removed to obtain the organic phase. The organic phase was concentrated under reduced pressure, and the concentrate was distilled under reduced pressure (110.4°C to 123.0°C / 0.40 kPa (3.0 mmHg)) to obtain a mixture (13) of (7Z,11Z,13E)-7,11,13-hexadecadienal (7) (24.42 g, 0.078 mol, content 75.23%, 7Z11Z13E:7Z11E13E = 90.6:9.4) and (7Z,11Z)-7,11-hexadecadienal (10) (24.42 g, 0.023 mol, content 21.83%, 7Z11Z:7Z11E = 94.3:5.7), with an overall yield of 75.37% in Examples 8 and 12.

[0526] The spectral data of (7Z,11Z,13E)-7,11,13-hexadecadienal (7) and (7Z,11Z)-7,11-hexadecadienal (10) prepared in this way are the same as those determined in Examples 9 and 11, respectively.

Claims

1. A method for preparing (4Z)-11,11-dialkoxy-4-undecenyltriarylphosphonium halides of the following general formula (3-Z): Where Y represents a halogen atom, Ar represents an aryl group independently, and R 1 and R 2 Each can be independently represented by a monovalent hydrocarbon group having 1 to 15 carbon atoms, or R 1 and R 2 They can together form divalent hydrocarbon groups R with 2 to 10 carbon atoms. 1 -R 2 , The method includes: Make (7Z)-11-halo-1,1-dialkoxy-7-undecene compounds of the following general formula (1-Z): Where X 1 Represents a halogen atom, and R 1 and R 2 As defined above, It undergoes a phosphonium salt formation reaction with phosphine compounds of the following general formula (2): PAr3(2) Ar is defined as above. To form (4Z)-11,11-dialkoxy-4-undecenyltriarylphosphonium halide (3-Z).

2. A method for preparing (3E,5Z,9Z)-16,16-dialkoxy-3,5,9-hexadecanetriene compounds of the following general formula (6): Where R 1 and R 2 Each can be independently represented by a monovalent hydrocarbon group having 1 to 15 carbon atoms, or R 1 and R 2 They can together form divalent hydrocarbon groups R with 2 to 10 carbon atoms. 1 -R 2 , The method includes: The method for preparing (4Z)-11,11-dialkoxy-4-undecenyltriarylphosphonium halide (3-Z) according to claim 1, The (4Z)-11,11-dialkoxy-4-undecenyltriarylphosphonium halide (3-Z) was deprotonated in the presence of a base to form a mixture of reaction products, and The mixture of reaction products is subjected to a Wittig reaction with (2E)-2-pentenal of formula (5): To form (3E,5Z,9Z)-16,16-dialkoxy-3,5,9-hexadecanetriene compound (6).

3. A method for preparing (7Z,11Z,13E)-7,11,13-hexadecanetrienal of formula (7): The method includes: The method for preparing (3E,5Z,9Z)-16,16-dialkoxy-3,5,9-hexadecanetriene compound (6) according to claim 2, and The (3E,5Z,9Z)-16,16-dialkoxy-3,5,9-hexadecanetriene compound (6) is hydrolyzed to form (7Z,11Z,13E)-7,11,13-hexadecanetriene aldehyde (7).

4. A method for preparing (5Z,9Z)-16,16-dialkoxy-5,9-hexadecadiene compounds of the following general formula (9): Where R 1 and R 2 Each can be independently represented by a monovalent hydrocarbon group having 1 to 15 carbon atoms, or R 1 and R 2 They can together form divalent hydrocarbon groups R with 2 to 10 carbon atoms. 1 -R 2 , The method includes: The method for preparing (4Z)-11,11-dialkoxy-4-undecenyltriarylphosphonium halide (3-Z) according to claim 1, The (4Z)-11,11-dialkoxy-4-undecenyltriarylphosphonium halide (3-Z) was deprotonated in the presence of a base to form a mixture of reaction products, and The mixture of reaction products is reacted with pentanal of formula (8) to undergo a Wittig reaction: CH3(CH2)3CHO (8) To form (5Z,9Z)-16,16-dialkoxy-5,9-hexadecadiene compound (9).

5. A method for preparing (7Z,11Z)-7,11-hexadecadienal of formula (10): The method includes: The method for preparing (5Z,9Z)-16,16-dialkoxy-5,9-hexadecadiene compound (9) according to claim 4, and The (5Z,9Z)-16,16-dialkoxy-5,9-hexadecadiene compound (9) is hydrolyzed to form (7Z,11Z)-7,11-hexadecadienal (10).

6. A method for preparing a mixture comprising a (3E,5Z,9Z)-16,16-dialkoxy-3,5,9-hexadecanetriene compound of the following general formula (6): Where R 1 and R 2 Each can be independently represented by a monovalent hydrocarbon group having 1 to 15 carbon atoms, or R 1 and R 2 They can together form divalent hydrocarbon groups R with 2 to 10 carbon atoms. 1 -R 2 , And the following (5Z,9Z)-16,16-dialkoxy-5,9-hexadecadiene compounds of general formula (9): Where R 1 and R 2 As defined above, The method includes: The method for preparing (4Z)-11,11-dialkoxy-4-undecenyltriarylphosphonium halide (3-Z) according to claim 1, The (4Z)-11,11-dialkoxy-4-undecenyltriarylphosphonium halide (3-Z) was deprotonated in the presence of a base to form a mixture of reaction products, and The reaction product mixture is reacted with (2E)-2-pentenal of formula (5): And the pentaldehyde in equation (8) undergoes the Wittig reaction: CH3(CH2)3CHO (8) To form the mixture comprising (3E,5Z,9Z)-16,16-dialkoxy-3,5,9-hexadecanetriene compound (6) and (5Z,9Z)-16,16-dialkoxy-5,9-hexadecanetriene compound (9).

7. A method for preparing a mixture comprising (7Z,11Z,13E)-7,11,13-hexadecanetrienal of formula (7): And (7Z,11Z)-7,11-hexadecadienal of formula (10): The method includes: The method for preparing a mixture comprising (3E,5Z,9Z)-16,16-dialkoxy-3,5,9-hexadecadiene compound (6) and (5Z,9Z)-16,16-dialkoxy-5,9-hexadecadiene compound (9) according to claim 6, and The mixture comprising the (3E,5Z,9Z)-16,16-dialkoxy-3,5,9-hexadecanetriene compound (6) and the (5Z,9Z)-16,16-dialkoxy-5,9-hexadecanetriene compound (9) is subjected to hydrolysis reaction conditions to form a mixture comprising (7Z,11Z,13E)-7,11,13-hexadecanetrienal (7) and (7Z,11Z)-7,11-hexadecanetrienal (10).

8. A method for preparing (3E,5Z,9Z)-16,16-dialkoxy-3,5,9-hexadecanetriene compounds of the following general formula (6): Where R 1 and R 2 Each can be independently represented by a monovalent hydrocarbon group having 1 to 15 carbon atoms, or R 1 and R 2 They can together form divalent hydrocarbon groups R with 2 to 10 carbon atoms. 1 -R 2 , The method includes: Deprotonation of (4Z)-11,11-dialkoxy-4-undecenyltriarylphosphonium halides of the following general formula (3-Z) in the presence of a base: Where Y represents a halogen atom, Ar represents an aryl group independently, and R 1 and R 2 As defined above, To form a mixture of reaction products, and The mixture of reaction products is subjected to a Wittig reaction with (2E)-2-pentenal of formula (5): To form (3E,5Z,9Z)-16,16-dialkoxy-3,5,9-hexadecanetriene compound (6).

9. A method for preparing (7Z,11Z,13E)-7,11,13-hexadecanetrienal of the following general formula (7): The method includes: The method for preparing (3E,5Z,9Z)-16,16-dialkoxy-3,5,9-hexadecanetriene compound (6) according to claim 8, and The (3E,5Z,9Z)-16,16-dialkoxy-3,5,9-hexadecanetriene compound (6) is hydrolyzed to form (7Z,11Z,13E)-7,11,13-hexadecanetriene aldehyde (7).

10. A method for preparing (5Z,9Z)-16,16-dialkoxy-5,9-hexadecadiene compounds of the following general formula (9): Where R 1 and R 2 Each can be independently represented by a monovalent hydrocarbon group having 1 to 15 carbon atoms, or R 1 and R 2 They can together form divalent hydrocarbon groups R with 2 to 10 carbon atoms. 1 -R 2 , The method includes: Deprotonation of (4Z)-11,11-dialkoxy-4-undecenyltriarylphosphonium halides of the following general formula (3-Z) in the presence of a base: Where Y represents a halogen atom, Ar represents an aryl group independently, and R 1 and R 2 As defined above, To form a mixture of reaction products, and The mixture of reaction products is subjected to a Wittig reaction with pentanal of formula (8): CH3(CH2)3CHO (8) To form (5Z,9Z)-16,16-dialkoxy-5,9-hexadecadiene compound (9).

11. A method for preparing (7Z,11Z)-7,11-hexadecadienal of formula (10): The method includes: The method for preparing (5Z,9Z)-16,16-dialkoxy-5,9-hexadecadiene compound (9) according to claim 10, and The (5Z,9Z)-16,16-dialkoxy-5,9-hexadecadiene compound (9) is hydrolyzed to form (7Z,11Z)-7,11-hexadecadienal (10).

12. A method for preparing a mixture comprising a (3E,5Z,9Z)-16,16-dialkoxy-3,5,9-hexadecanetriene compound of the following general formula (6): Where R 1 and R 2 Each can be independently represented by a monovalent hydrocarbon group having 1 to 15 carbon atoms, or R 1 and R 2 They can together form divalent hydrocarbon groups R with 2 to 10 carbon atoms. 1 -R 2 , And the following (5Z,9Z)-16,16-dialkoxy-5,9-hexadecadiene compounds of general formula (9): Where R 1 and R 2 As defined above, The method includes: Deprotonation of (4Z)-11,11-dialkoxy-4-undecenyltriarylphosphonium halides of the following general formula (3-Z) in the presence of a base: Where Y represents a halogen atom, Ar represents an aryl group independently, and R 1 and R 2 As defined above, To form a mixture of reaction products, and The reaction product mixture is reacted with (2E)-2-pentenal of formula (5): And the pentaldehyde in equation (8) undergoes the Wittig reaction: CH3(CH2)3CHO (8) To form a mixture comprising (3E,5Z,9Z)-16,16-dialkoxy-3,5,9-hexadecanetriene compound (6) and (5Z,9Z)-16,16-dialkoxy-5,9-hexadecanetriene compound (9).

13. A method for preparing a mixture comprising (7Z,11Z,13E)-7,11,13-hexadecanetrienal of formula (7): And (7Z,11Z)-7,11-hexadecadienal of formula (10): The method includes: The method for preparing a mixture comprising (3E,5Z,9Z)-16,16-dialkoxy-3,5,9-hexadecadiene compound (6) and (5Z,9Z)-16,16-dialkoxy-5,9-hexadecadiene compound (9) according to claim 12, and The mixture comprising the (3E,5Z,9Z)-16,16-dialkoxy-3,5,9-hexadecanetriene compound (6) and the (5Z,9Z)-16,16-dialkoxy-5,9-hexadecanetriene compound (9) is subjected to hydrolysis reaction conditions to form a mixture comprising (7Z,11Z,13E)-7,11,13-hexadecanetrienal (7) and (7Z,11Z)-7,11-hexadecanetrienal (10).

14. A compound of the following general formula (A): L(CH2)3CH=CH(CH2)5CH(OR 1 )(OR 2 ) (A) Where R 1 and R 2 Each can be independently represented by a monovalent hydrocarbon group having 1 to 15 carbon atoms, or R 1 and R 2 They can together form divalent hydrocarbon groups R with 2 to 10 carbon atoms. 1 -R 2 L represents X 1 Or Y - Ar3P + , where X 1 Y represents a halogen atom, and Ar represents an aryl group independently of each other.

15. The compound according to claim 14, wherein the compound is a 11-halo-1,1-dialkoxy-7-undecene compound of the following general formula (1): X 1 (CH2)3CH=CH(CH2)5CH(OR 1 )(OR 2 ) (1)。 16. The compound according to claim 14, wherein the compound is a 11,11-dialkoxy-4-undecenyltriarylphosphonium halide of the following general formula (3): Y - Ar3P + (CH2)3CH=CH(CH2)5CH(OR 1 )(OR 2 ) (3)。

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