5-(2-butyl-1,3-dioxolan-2-yl)-1-methylpentyl acetate and process for preparing 2,7-diacetoxyundecane therefrom

Abstract

To provide a novel compound as a synthetic intermediate for efficiently preparing 2,7-diacetoxyundecane, and to provide a process for preparing the novel compound, and a process for preparing 2,7-diacetoxyundecane from the novel compound.SOLUTION: There is provided 5-(2-butyl-1,3-dioxolan-2-yl)-1-methylpentyl acetate represented by the following formula (1). There is also provided a process for preparing 2,7-diacetoxyundecane, the process comprising the steps of: eliminating a ketal from the compound in the presence of an acid or a peroxide to prepare 10-acetoxy-5-undecanone; optionally subjecting the 10-acetoxy-5-undecanone to a reduction reaction to form 10-acetoxy-5-undecanol; and subjecting the 10-acetoxy-5-undecanol to an acetylation reaction to form 2,7-diacetoxyundecane.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to 5-(2-butyl-1,3-dioxolan-2-yl)-1-methylpentyl acetate and a method for producing 2,7-diacetoxyundecane using the same. [Background technology]

[0002] Pear gall midge (scientific name: Contarinia pyrivora Pear gall midge is a European fruit tree pest that feeds on pears. The larvae of the pear gall midge invade the fruit and feed on it. Fruit damaged by the pear gall midge turn black and fall from the tree. Because the larvae penetrate the fruit, conventional pesticides are often ineffective due to poor contact, making control difficult. Furthermore, due to concerns about residual pesticides, biological control methods are gaining attention, and the use of sex pheromone substances is one promising method (Non-Patent Document 1 listed below).

[0003] It has been reported that the sex pheromone composition of pear gall midge is a mixture of 2,7-diacetoxyundecane and 7-(acetoxy)-2-undecanone (Non-Patent Document 2 listed below).

[0004] Among these, a method for producing the main component, 2,7-diacetoxyundecane, has been reported, for example, by reacting 1,4-dibromobutane, 1-pentanal, and acetaldehyde with magnesium in tetrahydrofuran (THF) to synthesize a mixture of three types: 5,10-tetradecanediol, 2,7-octanediol, and 2,7-undecanediol. Next, the resulting mixture of 5,10-tetradecanediol, 2,7-octanediol, and 2,7-undecanediol is separated and purified by silica gel column chromatography to isolate and purify 2,7-undecanediol. Subsequently, the resulting 2,7-undecanediol is acetylated with acetic anhydride in the presence of pyridine (see Non-Patent Document 2 below). [Prior art documents] [Non-patent literature]

[0005] [Non-Patent Document 1] Elisabeth A. Hodgdon et al.,The Canadian Entomologist,2022,154,e37,1-17. [Non-patent document 2] Lakmali Amarawardana et al.,Thesis Uni. Greenwich,2009,1-184. Summary of the Invention [Problem to be solved by the invention]

[0006] However, in the method for producing 2,7-diacetoxyundecane described in Non-Patent Document 2, three types of diols are produced in the first step, and the target intermediate, 2,7-undecanediol, is highly water-soluble, which is presumably resulting in a low yield. Furthermore, acetaldehyde, which is used in the first step, is carcinogenic and a causative agent of sick house syndrome. Therefore, its handling requires specialized equipment and strict wastewater treatment, making it unsuitable for industrial production. Additionally, while silica gel column chromatography is used to separate and purify the three types of diols, silica gel column chromatography purification is difficult to implement on an industrial scale (over 100 kg), making it unsuitable for industrial production.

[0007] The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a novel compound that is a synthetic intermediate for efficiently producing 2,7-diacetoxyundecane. Another object of the present invention is to provide a method for producing the novel compound, and a method for producing 2,7-diacetoxyundecane from the novel compound. [Means for solving the problem]

[0008] The present inventors conducted extensive research to solve the above-mentioned problems and discovered a novel compound, 5-(2-butyl-1,3-dioxolan-2-yl)-1-methylpentyl acetate. The 5-(2-butyl-1,3-dioxolan-2-yl)-1-methylpentyl acetate of the present invention can be produced inexpensively and in large quantities, and can be purified solely by distillation. Furthermore, the present inventors discovered that 2,7-diacetoxyundecane can be efficiently produced using the 5-(2-butyl-1,3-dioxolan-2-yl)-1-methylpentyl acetate.

[0009] According to a first aspect of the present invention, a compound represented by the following formula (1): [ka] It is possible to provide 5-(2-butyl-1,3-dioxolan-2-yl)-1-methylpentyl acetate represented by the following formula:

[0010] According to a second aspect of the present invention, a compound represented by the following general formula (2): [ka] (In the formula, X 1 represents a halogen atom or a 3-(2-butyl-1,3-dioxolan-2-yl)propyl group. The organomagnesium compound (2) represented by the following formula (3): [ka] and then reacting the compound represented by the following general formula (4): [ka] (In the formula, X 2 represents a halogen atom, an acetoxy group, a methoxy group, or an ethoxy group. and reacting the compound with an acetylating agent represented by the formula: The present invention provides a method for producing 5-(2-butyl-1,3-dioxolan-2-yl)-1-methylpentyl acetate (1), which comprises:

[0011] According to a third aspect of the present invention, a compound represented by the following formula (1): [ka] 5-(2-butyl-1,3-dioxolan-2-yl)-1-methylpentyl acetate represented by the following formula (5): [ka] A step of obtaining 10-acetoxy-5-undecanone represented by the formula The present invention provides a method for producing 10-acetoxy-5-undecanone (5), which comprises:

[0012] According to a fourth aspect of the present invention, the 10-acetoxy-5-undecanone (5) is reduced to give a compound of the following formula (6): [ka] obtaining 10-acetoxy-5-undecanol represented by the formula: The 10-acetoxy-5-undecanol (6) is subjected to an acetylation reaction to obtain a compound of the following formula (7): [ka] and obtaining 2,7-diacetoxyundecane represented by the formula: The present invention provides a method for producing 2,7-diacetoxyundecane (7), which comprises: [Effects of the Invention]

[0013] According to the present invention, the target compound, 2,7-diacetoxyundecane, can be produced efficiently with a high yield and with a low environmental impact. Furthermore, according to the present invention, the target compound, 2,7-diacetoxyundecane, can be produced economically. According to the present invention, since compounds similar to the target compound are hardly produced in each step, purification by column chromatography is not necessary, and purification by distillation, which is suitable for scale-up, is possible. Furthermore, according to the present invention, a novel synthetic intermediate useful for producing the above-mentioned 2,7-diacetoxyundecane, can be provided. DETAILED DESCRIPTION OF THE INVENTION

[0014] Regarding the production method of 5-(2-butyl-1,3-dioxolan-2-yl)-1-methylpentyl acetate (1) represented by the following general formula (1): A method for producing the above 5-(2-butyl-1,3-dioxolan-2-yl)-1-methylpentyl acetate (1) will be described. [ka]

[0015] As shown in the following chemical reaction scheme, 5-(2-butyl-1,3-dioxolan-2-yl)-1-methylpentyl acetate (1) can be prepared, for example, by subjecting an organomagnesium compound represented by the following general formula (2) to a nucleophilic addition reaction with propylene oxide represented by the following formula (3), followed by an acetylation reaction with an acetylating agent represented by the following general formula (4).

[0016] [ka]

[0017] (i) The above organomagnesium compound (2) will be explained below. X in the above general formula (2) 1 represents a halogen atom or a 3-(2-butyl-1,3-dioxolan-2-yl)propyl group. 1 Specific examples of the alkyl group include a chlorine atom, a bromine atom, and an iodine atom. From the viewpoint of ease of handling, a chlorine atom and a bromine atom are preferred, and a chlorine atom is more preferred.

[0018] Specific examples of the organomagnesium compound (2) include organomagnesium compounds (Grignard reagents) such as [3-(2-butyl-1,3-dioxolan-2-yl)propyl]chloromagnesium, [3-(2-butyl-1,3-dioxolan-2-yl)propyl]bromomagnesium, and [3-(2-butyl-1,3-dioxolan-2-yl)propyl]iodomagnesium, and from the viewpoint of ease of preparation (versatility), [3-(2-butyl-1,3-dioxolan-2-yl)propyl]chloromagnesium is preferred. The organomagnesium compound (2) may be used alone or in combination with two or more compounds as required. The organomagnesium compound (2) can be prepared, for example, by the production method described below.

[0019] (ii) Next, the nucleophilic addition reaction of the organomagnesium compound (2) with propylene oxide (3) and the subsequent acetylation reaction with an acetylating agent (4) will be described below. In the nucleophilic addition reaction, the amount of propylene oxide (3) used is preferably 0.8 to 2.0 mol, more preferably 0.9 to 1.7 mol, and even more preferably 1.0 to 1.5 mol per 1 mol of the organomagnesium compound (2) from the viewpoint of economy.

[0020] The nucleophilic addition reaction may be carried out in the presence of a solvent, if necessary. Examples of the solvent include common solvents, such as ether solvents such as tetrahydrofuran (THF), 2-methyltetrahydrofuran (2-MeTHF), diethyl ether, dibutyl ether, 4-methyltetrahydropyran (MTHP), cyclopentyl methyl ether, and 1,4-dioxane; hydrocarbon solvents such as hexane, heptane, benzene, toluene, xylene, and cumene; N , N -dimethylformamide (DMF), N , N -dimethylacetamide (DMAC), N -methylpyrrolidone (NMP), dimethyl sulfoxide (DMSO), γ-butyrolactone (GBL), acetonitrile, N , N Examples of suitable solvents include polar solvents such as '-dimethylpropylene urea (DMPU), hexamethylphosphoric triamide (HMPA), dichloromethane, and chloroform. From the viewpoint of reactivity, however, hydrocarbon solvents such as toluene and xylene, and ether solvents such as tetrahydrofuran, 2-methyltetrahydrofuran, and 4-methyltetrahydropyran are preferred, with tetrahydrofuran, 2-methyltetrahydrofuran, and 4-methyltetrahydropyran being more preferred. The solvent may be used alone or in combination with two or more solvents as required. Commercially available solvents may also be used. The amount of the solvent used is preferably 30 to 5000 g, more preferably 50 to 3000 g, and even more preferably 100 to 1000 g, per mole of the organomagnesium compound (2), from the viewpoint of reactivity.

[0021] A catalyst may be used in the nucleophilic addition reaction, if necessary. Examples of the catalyst include copper compounds of monovalent copper halides such as cuprous chloride, cuprous bromide, and cuprous iodide, and divalent copper halides such as cupric chloride, cupric bromide, and cupric iodide. From the viewpoint of reactivity, monovalent copper halides are preferred, and cuprous chloride is more preferred. The catalyst may be used alone or in combination of two or more types as required. Commercially available catalysts may also be used. The amount of the catalyst used is preferably 0.0003 to 0.3 mol, more preferably 0.001 to 0.1 mol, per mol of the organomagnesium compound (2), from the viewpoint of reaction rate and / or post-treatment.

[0022] The reaction temperature in the nucleophilic addition reaction varies depending on the organomagnesium compound (2) used, but is preferably −78 to 70° C., more preferably −20 to 50° C., and even more preferably 0 to 30° C., from the viewpoint of reactivity. The reaction time for the nucleophilic addition reaction varies depending on the solvent used and / or the reaction scale, but is preferably 0.5 to 100 hours from the viewpoint of reactivity.

[0023] Examples of the acetylating agent used in the acetylation reaction include acetyl halides such as acetyl chloride, acetyl bromide, and acetyl iodide; acetic anhydride; and alkyl acetates such as methyl acetate and ethyl acetate. From the viewpoint of reactivity, ethyl acetate, acetyl chloride, and acetic anhydride are preferred, acetyl chloride and acetic anhydride are more preferred, and acetic anhydride is even more preferred.

[0024] In the acetylation reaction, the amount of the acetylating agent (4) used is preferably 0.8 to 2.0 mol, more preferably 0.9 to 1.7 mol, and even more preferably 1.0 to 1.5 mol, per 1 mol of the organomagnesium compound (2), from the viewpoint of economy.

[0025] The acetylation reaction may be carried out in the presence of a solvent, if necessary. Examples of the solvent include common solvents, such as ether solvents such as tetrahydrofuran (THF), 2-methyltetrahydrofuran (2-MeTHF), diethyl ether, dibutyl ether, 4-methyltetrahydropyran (MTHP), cyclopentyl methyl ether, and 1,4-dioxane; hydrocarbon solvents such as hexane, heptane, benzene, toluene, xylene, and cumene; N , N -dimethylformamide (DMF), N , N -dimethylacetamide (DMAC), N -methylpyrrolidone (NMP), dimethyl sulfoxide (DMSO), γ-butyrolactone (GBL), acetonitrile, N , N Examples of suitable solvents include polar solvents such as '-dimethylpropylene urea (DMPU), hexamethylphosphoric triamide (HMPA), dichloromethane, and chloroform. From the viewpoint of reactivity, however, hydrocarbon solvents such as toluene and xylene, and ether solvents such as tetrahydrofuran, 2-methyltetrahydrofuran, and 4-methyltetrahydropyran are preferred, with tetrahydrofuran, 2-methyltetrahydrofuran, and 4-methyltetrahydropyran being more preferred. The solvent may be used alone or in combination with two or more solvents as required. Commercially available solvents may also be used. The amount of the solvent used is preferably 30 to 5000 g, more preferably 50 to 3000 g, and even more preferably 100 to 1000 g, per mole of the organomagnesium compound (2), from the viewpoint of reactivity.

[0026] The reaction temperature in the acetylation reaction varies depending on the organomagnesium compound (2) used, but from the viewpoint of reactivity, it is preferably −30 to 100° C., more preferably 0 to 80° C., and even more preferably 20 to 60° C. In the acetylation step, salts may precipitate at low temperatures, making stirring difficult, so from the viewpoint of stirring efficiency, it is desirable to carry out the reaction at 20° C. or higher. The reaction time for the acetylation reaction varies depending on the solvent used and / or the reaction scale, but is preferably 0.5 to 100 hours from the viewpoint of reactivity.

[0027] Although 5-(2-butyl-1,3-dioxolan-2-yl)-1-methylpentyl acetate (1) was produced by reacting with propylene oxide and then with an acetylating agent, it is also possible to synthesize 10-hydroxy-5-undecanone without reacting with propylene oxide and then with an acetylating agent, and then synthesize 2,7-diacetoxyundecane via 2,7-undecanediol. However, in this case, the free hydroxyl group may react with the ketone intramolecularly or intermolecularly during the deprotection step of the acetal. Furthermore, 2,7-undecanediol is more water-soluble than 10-acetoxy-5-undecanol (6), the intermediate of this invention, and therefore is presumed to be difficult to extract after the reaction. In light of this, a desirable approach is to react 2,7-diacetoxyundecane with propylene oxide, then react with an acetylating agent to produce 5-(2-butyl-1,3-dioxolan-2-yl)-1-methylpentyl acetate (1), and then synthesize 2,7-diacetoxyundecane using 5-(2-butyl-1,3-dioxolan-2-yl)-1-methylpentyl acetate (1) as a key intermediate.

[0028] (iii) Next, a method for producing the organomagnesium compound (2) will be described below. The organomagnesium compound (2) can be prepared according to the method described below.

[0029] The organomagnesium compound (2) is a Grignard reagent.

[0030] The organomagnesium compound (2) can be prepared, for example, by reacting a 2-butyl-2-(3-halopropyl)-1,3-dioxolane compound represented by the following general formula (8) with magnesium in a solvent at a constant temperature, as shown in the following chemical reaction formula:

[0031] [ka]

[0032] (a) First, the above 2-butyl-2-(3-halopropyl)-1,3-dioxolane compound (8) will be explained below. X in the above general formula (8) 1 represents a halogen atom. Halogen atom X 1 Specific examples of the aryl group include a chlorine atom, a bromine atom, and an iodine atom. From the viewpoint of ease of handling, a bromine atom and a chlorine atom are preferred, and a chlorine atom is more preferred. Specific examples of the 2-butyl-2-(3-halopropyl)-1,3-dioxolane compound (8) include 2-butyl-2-(3-chloropropyl)-1,3-dioxolane, 2-butyl-2-(3-bromopropyl)-1,3-dioxolane, and 2-butyl-2-(3-iodopropyl)-1,3-dioxolane.

[0033] The 2-butyl-2-(3-halopropyl)-1,3-dioxolane compound (8) may be used singly or, if necessary, in combination of two or more kinds. The 2-butyl-2-(3-halopropyl)-1,3-dioxolane compound (8) may be a commercially available product or may be independently synthesized.

[0034] The amount of magnesium used is preferably 0.8 to 2.0 gram atoms, more preferably 0.9 to 1.6 gram atoms, and even more preferably 1.0 to 1.4 gram atoms per mole of the 2-butyl-2-(3-halopropyl)-1,3-dioxolane compound (8) from the viewpoint of completing the reaction. Examples of the solvent include common solvents, for example, ether solvents such as tetrahydrofuran (THF), 2-methyltetrahydrofuran (2-MeTHF), diethyl ether, dibutyl ether, 4-methyltetrahydropyran (MTHP), cyclopentyl methyl ether, and 1,4-dioxane; and hydrocarbon solvents such as hexane, heptane, benzene, toluene, xylene, and cumene. From the viewpoint of the reaction rate of production of the Grignard reagent, hydrocarbon solvents such as toluene and xylene are preferred; and ether solvents such as tetrahydrofuran, 2-methyltetrahydrofuran, and 4-methyltetrahydropyran are more preferred, with tetrahydrofuran, 2-methyltetrahydrofuran, and 4-methyltetrahydropyran being even more preferred. The solvent may be used alone or in combination with two or more solvents as required. Commercially available solvents may also be used. The amount of the solvent used is preferably 30 to 5000 g, more preferably 50 to 3000 g, and even more preferably 100 to 1000 g, per mole of the 2-(3-halopropyl)-2-butyl-1,3-dioxolane compound (8) from the viewpoint of reactivity.

[0035] The reaction temperature in the reaction with magnesium is preferably -10 to 80°C, more preferably 10 to 70°C, even more preferably 30 to 65°C, and particularly preferably 45 to 60°C, from the viewpoint of suppressing side reactions. The reaction time for the reaction with magnesium varies depending on the solvent used and / or the reaction scale, but from the viewpoint of reactivity, it is preferably 0.5 to 100 hours, more preferably 1 to 30 hours, even more preferably 1.5 to 15 hours, and particularly preferably 2 to 8 hours.

[0036] Grignard reagents are usually prepared by reacting the corresponding halide with magnesium, but this Grignard reagent (organomagnesium compound) (2) undergoes a cyclization reaction above a certain temperature. Specifically, the cyclization reaction proceeds slowly at an internal temperature above 60°C, but rapidly at temperatures above 95°C, forming a four-membered ring compound. Therefore, temperature is extremely important for obtaining the desired Grignard reagent, organomagnesium compound (2), in good yield, and it is desirable to prepare it at a temperature between 30 and 60°C.

[0037] [ka]

[0038] (b) Next, a method for producing the above 2-butyl-2-(3-halopropyl)-1,3-dioxolane compound (8) will be described below. The 2-butyl-2-(3-halopropyl)-1,3-dioxolane compound (8) can be prepared according to conventional methods or according to the method described below.

[0039] The 2-butyl-2-(3-halopropyl)-1,3-dioxolane compound (8) can be prepared, for example, by acetalization of a 1-halo-4-octanone compound represented by the following general formula (9) with ethylene glycol represented by the following formula (10) in the presence of an acid, as shown in the following chemical reaction formula:

[0040] [ka]

[0041] The above 1-halo-4-octanone compound (9) will be explained below. X in the above general formula (9) 1 represents a halogen atom, and specific examples thereof include a chlorine atom, a bromine atom, and an iodine atom, with a bromine atom and a chlorine atom being preferred.

[0042] Specific examples of the 1-halo-4-octanone compound (9) include 1-chloro-4-octanone, 1-bromo-4-octanone, and 1-iodo-4-octanone, and from the viewpoint of ease of preparation (versatility), 1-chloro-4-octanone and 1-bromo-4-octanone are preferred. The 1-halo-4-octanone compound (9) may be used alone or, if necessary, in combination with two or more other compounds. The 1-halo-4-octanone compound (9) may be commercially available or may be prepared, for example, by the nucleophilic substitution reaction of 4-chlorobutyryl chloride with butylmagnesium halide.

[0043] In the acetalization reaction, the amount of ethylene glycol (10) used is preferably 0.8 to 2.0 mol, more preferably 0.9 to 1.7 mol, and even more preferably 1.0 to 1.5 mol, per 1 mol of the 1-halo-4-octanone compound (9), from the viewpoint of economy.

[0044] In the acetalization reaction, an acid may be used, if necessary. Examples of such acids include mineral acids such as hydrochloric acid, sulfuric acid, and nitric acid; carboxylic acids such as formic acid and oxalic acid; benzenesulfonic acid and p -toluenesulfonic acid and other aromatic sulfonic acids; and Lewis acids such as aluminum trichloride, aluminum ethoxide, aluminum isopropoxide, aluminum oxide, boron trifluoride, boron trichloride, boron tribromide, magnesium chloride, magnesium bromide, magnesium iodide, zinc chloride, zinc bromide, zinc iodide, tin tetrachloride, tin tetrabromide, dibutyltin dichloride, dibutyltin dimethoxide, dibutyltin oxide, magnesium chloride, magnesium bromide, titanium tetrachloride, titanium tetrabromide, titanium(IV) methoxide, titanium(IV) ethoxide, titanium(IV) isopropoxide and titanium(IV) oxide. From the viewpoint of reactivity, benzenesulfonic acid and p -Toluenesulfonic acid is preferred. One or more kinds of the acid may be used, if necessary. When the acid is used, the amount of the acid used is preferably 0.0001 to 1.00 mol, more preferably 0.0005 to 0.5 mol, and even more preferably 0.001 to 0.1 mol, relative to 1 mol of the 1-halo-4-octanone compound (9), from the viewpoints of reactivity and economy.

[0045] In the acetalization reaction, trialkyl orthoformate may be used as needed. Trialkyl orthoformates include trimethyl orthoformate and triethyl orthoformate, with trimethyl orthoformate being preferred. When the trialkyl orthoformate is used, the amount of the trialkyl orthoformate used is preferably 0.8 to 2.00 mol, more preferably 0.9 to 1.7 mol, and even more preferably 1.0 to 1.5 mol, relative to 1 mol of the 1-halo-4-octanone compound (9), from the viewpoints of reactivity and economy.

[0046] The acetalization reaction may be carried out in the presence of a solvent, if necessary. Examples of the solvent include common solvents, such as ether solvents such as tetrahydrofuran (THF), 2-methyltetrahydrofuran (2-MeTHF), diethyl ether, dibutyl ether, 4-methyltetrahydropyran (MTHP), cyclopentyl methyl ether, and 1,4-dioxane; hydrocarbon solvents such as hexane, heptane, benzene, toluene, xylene, and cumene; N , N -dimethylformamide (DMF), N , N -dimethylacetamide (DMAC), N -methylpyrrolidone (NMP), dimethyl sulfoxide (DMSO), γ-butyrolactone (GBL), acetonitrile, N , N Examples of suitable solvents include polar solvents such as '-dimethylpropylene urea (DMPU), hexamethylphosphoric triamide (HMPA), dichloromethane, and chloroform. From the viewpoint of reactivity, however, hydrocarbon solvents such as toluene and xylene, and ether solvents such as tetrahydrofuran, 2-methyltetrahydrofuran, and 4-methyltetrahydropyran are preferred, with hexane, toluene, and xylene being more preferred, and toluene and xylene being even more preferred. The solvent may be used alone or in combination with two or more solvents as required. Commercially available solvents may also be used. The amount of the solvent used is preferably 30 to 5000 g, more preferably 50 to 3000 g, and even more preferably 100 to 1000 g, per mole of the 1-halo-4-octanone compound (9), from the viewpoint of reactivity.

[0047] The reaction temperature in the acetalization reaction is preferably 0 to 120°C, more preferably 10 to 100°C, and even more preferably 40 to 80°C, from the viewpoint of reactivity. The reaction time for the acetalization reaction varies depending on the solvent used and / or the reaction scale, but is preferably 0.5 to 100 hours from the viewpoint of reactivity.

[0048] <ii>Regarding the method for producing 2,7-diacetoxyundecane represented by the following general formula (7), 2,7-Diacetoxyundecane, one of the target compounds of the present invention, represented by the following general formula (7), is prepared according to the production method shown in the following chemical reaction scheme. Specifically, the acetal of 5-(2-butyl-1,3-dioxolan-2-yl)-1-methylpentyl acetate (1) is deprotected to synthesize 10-acetoxy-5-undecanone (5). Subsequently, the ketone moiety of 10-acetoxy-5-undecanone (5) is selectively reduced with a reducing agent to synthesize 10-acetoxy-5-undecanol (6). Next, the hydroxyl group of 10-acetoxy-5-undecanol (6) is acetylated with an acetylating agent to synthesize 2,7-diacetoxyundecane (7).

[0049] [ka]

[0050] (iv) First, the method for producing the above 10-acetoxy-5-undecanone (5) will be described. 10-Acetoxy-5-undecanone (5) can be prepared by deprotecting the acetal of 5-(2-butyl-1,3-dioxolan-2-yl)-1-methylpentyl acetate (1) with an acid or peroxide.

[0051] [ka]

[0052] The deprotection reaction can be carried out in the presence of, for example, an acid or a peroxide. Specifically, the deprotection reaction can be carried out by, for example, (1) an exchange reaction using an acid, (2) an acid hydrolysis reaction, or (3) an oxidation reaction using a peroxide or the like. Acids used in the exchange reaction and acid hydrolysis reaction include mineral acids such as hydrochloric acid, sulfuric acid, and nitric acid; carboxylic acids such as formic acid and acetic acid; benzenesulfonic acid and p -toluenesulfonic acid and other aromatic sulfonic acids; and Lewis acids such as aluminum trichloride, aluminum ethoxide, aluminum isopropoxide, aluminum oxide, boron trifluoride, boron trichloride, boron tribromide, magnesium chloride, magnesium bromide, magnesium iodide, zinc chloride, zinc bromide, zinc iodide, tin tetrachloride, tin tetrabromide, dibutyltin dichloride, dibutyltin dimethoxide, dibutyltin oxide, magnesium chloride, magnesium bromide, titanium tetrachloride, titanium tetrabromide, titanium(IV) methoxide, titanium(IV) ethoxide, titanium(IV) isopropoxide and titanium(IV) oxide. From the viewpoint of reactivity, benzenesulfonic acid and p -Toluenesulfonic acid is preferred. One or more kinds of the acid may be used, if necessary. When the acid is used, the amount of the acid used is preferably 0.0001 to 1.00 mol, more preferably 0.0005 to 0.5 mol, and even more preferably 0.001 to 0.1 mol, per 1 mol of 5-(2-butyl-1,3-dioxolan-2-yl)-1-methylpentyl acetate (1), from the viewpoints of reactivity and economy. Peroxides used in oxidation reactions include perchloric acid (HClO4), tert -butyl hydroperoxide ( t —BuOOH) and 2,3-dichloro-5,6-dicyano-1,4-benzoquinone (DDQ).

[0053] In the deprotection reaction, water may be further used together with the acid as needed. The amount of water used is preferably more than 0 to 7000 g, more preferably 10 to 3000 g, and even more preferably 18 to 1000 g, per mole of 5-(2-butyl-1,3-dioxolan-2-yl)-1-methylpentyl acetate (1) from the viewpoint of reactivity.

[0054] In the deprotection reaction, a solvent may be further used, if necessary, in addition to the above-mentioned acid or water. Examples of the solvent include ether solvents such as tetrahydrofuran (THF), 2-methyltetrahydrofuran (2-MeTHF), diethyl ether, dibutyl ether, 4-methyltetrahydropyran (MTHP), cyclopentyl methyl ether, and 1,4-dioxane; hydrocarbon solvents such as hexane, heptane, benzene, toluene, xylene, and cumene; N , N -dimethylformamide (DMF), N , N Examples of suitable solvents include polar solvents such as dimethylacetamide (DMAC), N-methylpyrrolidone (NMP), dimethyl sulfoxide (DMSO), γ-butyrolactone (GBL), acetonitrile, acetone, N,N'-dimethylpropyleneurea (DMPU), hexamethylphosphoric triamide (HMPA), dichloromethane, and chloroform; ester solvents such as methyl acetate, ethyl acetate, n-propyl acetate, and n-butyl acetate; and alcohol solvents such as methanol and ethanol. From the viewpoint of reactivity, N , N -dimethylformamide (DMF), N , N Polar solvents such as dimethylacetamide (DMAC), N-methylpyrrolidone (NMP), dimethyl sulfoxide (DMSO), γ-butyrolactone (GBL), acetonitrile, acetone, N,N'-dimethylpropyleneurea (DMPU), hexamethylphosphoric triamide (HMPA), dichloromethane, and chloroform are preferred, with γ-butyrolactone (GBL) and acetone being more preferred, and acetone being even more preferred. The solvent may be used alone or in combination with two or more solvents as required. Commercially available solvents may also be used. When the solvent is used, the amount of the solvent used is preferably more than 0 to 7000 g, more preferably 50 to 3000 g, and even more preferably 100 to 1500 g, per 1 mol of 5-(2-butyl-1,3-dioxolan-2-yl)-1-methylpentyl acetate (1) from the viewpoint of reactivity.

[0055] The reaction temperature in the deprotection reaction varies depending on the acid and / or solvent used, but is preferably −15 to 180° C., more preferably 5 to 120° C., and even more preferably 40 to 80° C. from the viewpoint of reactivity. The reaction time for the deprotection reaction varies depending on the acid used, the solvent used and / or the reaction scale, but is preferably 0.5 to 100 hours.

[0056] (v) Next, a method for producing the above 10-acetoxy-5-undecanol (6) will be described. 10-Acetoxy-5-undecanol (6) can be prepared by reducing 10-acetoxy-5-undecanone (5) with a reducing agent.

[0057] [ka]

[0058] Examples of reducing agents include alkali metal borohydrides such as lithium borohydride, sodium borohydride, potassium borohydride, and sodium triacetoxyborohydride; alkaline earth metal borohydrides such as magnesium borohydride and calcium borohydride; alkali metal cyanoborohydrides such as lithium cyanoborohydride, sodium cyanoborohydride, and potassium cyanoborohydride; alkaline earth metal cyanoborohydrides such as magnesium cyanoborohydride and calcium cyanoborohydride; sodium tri-sec-butylborohydride and lithium tri-sec-butylborohydride; and alkali metal tri-sec-butylborohydride; as well as diisobutylaluminum hydride, sodium bis(2-methoxyethoxy)aluminum hydride (Red-Al), and lithium aluminum hydride. From the viewpoint of selective reduction, sodium borohydride, lithium borohydride, sodium triacetoxyborohydride, lithium cyanoborohydride, sodium cyanoborohydride, and potassium cyanoborohydride are preferred, sodium borohydride, sodium triacetoxyborohydride, and sodium cyanoborohydride are more preferred, and sodium borohydride is even more preferred. The reducing agent may be used alone or in combination of two or more types, if necessary. Commercially available reducing agents can be used. The amount of the reducing agent used varies depending on the reducing agent used, but from the viewpoint of reactivity, it is preferably 0.25 to 5.0 mol per 1 mol of 10-acetoxy-5-undecanone (5). When sodium borohydride is used as the reducing agent, it is preferably 0.25 to 5.0 mol, more preferably 0.35 to 3.0 mol, and even more preferably 0.5 to 1.5 mol per 1 mol of 10-acetoxy-5-undecanone (5).

[0059] The reduction reaction may be carried out in the presence of a solvent, if necessary. Examples of the solvent include ether solvents such as tetrahydrofuran (THF), 2-methyltetrahydrofuran (2-MeTHF), diethyl ether, dibutyl ether, 4-methyltetrahydropyran (MTHP), cyclopentyl methyl ether, and 1,4-dioxane; hydrocarbon solvents such as hexane, heptane, benzene, toluene, xylene, and cumene; N , N -dimethylformamide (DMF), N , N Examples of suitable solvents include polar solvents such as dimethylacetamide (DMAC), N-methylpyrrolidone (NMP), dimethyl sulfoxide (DMSO), γ-butyrolactone (GBL), acetonitrile, acetone, N,N'-dimethylpropyleneurea (DMPU), hexamethylphosphoric triamide (HMPA), dichloromethane, and chloroform; ester-based solvents such as methyl acetate, ethyl acetate, n-propyl acetate, and n-butyl acetate; alcohol-based solvents such as methanol and ethanol; and water. An appropriate solvent may be selected depending on the reducing agent used. For example, when an alkali metal borohydride salt is used as the reducing agent, an alcoholic solvent such as ethanol, or a mixed solvent of an alcoholic solvent and another solvent is preferred. The solvent may be used alone or in combination with two or more solvents as required. Commercially available solvents may also be used. When the solvent is used, the amount of the solvent used is preferably more than 0 to 7000 g, more preferably 50 to 3000 g, and even more preferably 100 to 1500 g, per mole of 10-acetoxy-5-undecanone (5) from the viewpoint of reactivity. The solvent may be used alone or, if necessary, in combination with two or more solvents. Commercially available solvents can be used.

[0060] A base may be used in the reduction reaction, if necessary. Examples of the base include alkali metal hydroxides such as lithium hydroxide, sodium hydroxide, and potassium hydroxide; alkaline earth metal hydroxides such as calcium hydroxide, magnesium hydroxide, and barium hydroxide; alkali metal carbonates such as sodium carbonate and potassium carbonate; alkaline earth metal carbonates such as calcium carbonate, magnesium carbonate, and barium carbonate; alkali metal bicarbonates such as sodium bicarbonate and potassium bicarbonate; and alkaline earth metal bicarbonates such as calcium bicarbonate and magnesium bicarbonate. From the viewpoint of handling, for example, when an alkali metal borohydride salt is used as the reducing agent, an alkali metal hydroxide such as sodium hydroxide is preferred, sodium hydroxide and potassium hydroxide are more preferred, and sodium hydroxide is even more preferred. One type of base may be used, or two or more types may be used as necessary. Commercially available bases can be used. When the base is a solid, it may be added to the reaction mixture as a solid, or may be dissolved in advance in the solvent used in the reduction reaction. From the viewpoint of reactivity, the amount of the base used is preferably more than 0 to 10.00 mol, more preferably 0.0001 to 1.0 mol, and even more preferably 0.001 to 0.1 mol, per 1 mol of 10-acetoxy-5-undecanone (5).

[0061] The reaction temperature in the reduction reaction varies depending on the reducing agent used, but is preferably −15 to 180° C., more preferably 0 to 100° C., and even more preferably 10 to 60° C. from the viewpoint of reactivity. The reaction time for the reduction reaction varies depending on the reducing agent used, the solvent used and / or the reaction scale, but is preferably 0.5 to 100 hours.

[0062] 10-Acetoxy-5-undecanol (6) has its hydroxyl group at the 10-position protected with an acetyl group, making it more lipophilic than diols such as 2,7-undecanediol. This allows for high-yield recovery without the need for large amounts of extraction solvent, and without loss to the aqueous layer.

[0063] (vi) 2,7-diacetoxyundecane (7) and its production method A method for producing 2,7-diacetoxyundecane (7) is described below. 2,7-Diacetoxyundecane (7) can be prepared by acetylating the above 10-acetoxy-5-undecanol (6).

[0064] [ka]

[0065] The acetylation reaction can be carried out, for example, by a method in which a hydroxyl group is acetylated using an acetylating agent. Examples of the acetylating agent include acetic acid; acid anhydrides such as acetic anhydride; acetyl halide compounds such as acetyl chloride, acetyl bromide, and acetyl iodide; and acetate ester compounds such as methyl acetate, ethyl acetate, propyl acetate, butyl acetate, pentyl acetate, and hexyl acetate. As the acetylating agent, from the viewpoint of reactivity, an acid anhydride or an acetyl halide compound is preferred, an acid anhydride is more preferred, and acetic anhydride is even more preferred. The amount of the acetylating agent used is preferably 0.8 to 15.0 mol, more preferably 1.0 to 10.0 mol, and even more preferably 1.2 to 3.0 mol, per mol of 10-acetoxy-5-undecanol (6), from the viewpoints of reactivity and economy.

[0066] The acetylation may be carried out using an acid or a base, if necessary. Examples of the acid include mineral acids such as hydrochloric acid, sulfuric acid, and nitric acid; benzenesulfonic acid; p aromatic sulfonic acids such as toluenesulfonic acid; and Lewis acids such as aluminum trichloride, aluminum ethoxide, aluminum isopropoxide, aluminum oxide, boron trifluoride, boron trichloride, boron tribromide, magnesium chloride, magnesium bromide, magnesium iodide, zinc chloride, zinc bromide, zinc iodide, tin tetrachloride, tin tetrabromide, dibutyltin dichloride, dibutyltin dimethoxide, dibutyltin oxide, magnesium chloride, magnesium bromide, titanium tetrachloride, titanium tetrabromide, titanium(IV) methoxide, titanium(IV) ethoxide, titanium(IV) isopropoxide, and titanium(IV) oxide. One or more kinds of the acid may be used, if necessary. When the acid is used, the amount of the acid used is preferably more than 0 to 3.0 mol, more preferably 0.001 to 1.5 mol, and even more preferably 0.01 to 1.0 mol, per 1 mol of 10-acetoxy-5-undecanol (6), from the viewpoints of reactivity and economy.

[0067] The base includes the following compounds: Trimethylamine, triethylamine and N , N - Trialkylamine compounds such as diisopropylethylamine; cyclic amine compounds such as piperidine, pyrrolidine, and 1,8-diazabicyclo[5.4.0]-7-undecene (DBU); Pyridine, lutidine, N , N -dimethylaniline, N , N -diethylaniline, N , N - aromatic amine compounds such as dibutylaniline and 4-dimethylaminopyridine; metal alkoxides such as sodium methoxide, sodium ethoxide, sodium t-butoxide, sodium t-amyloxide, lithium methoxide, lithium ethoxide, lithium t-butoxide, lithium t-amyloxide, potassium methoxide, potassium ethoxide, potassium t-butoxide, and potassium t-amyloxide; Alkyllithium such as methyllithium, ethyllithium, propyllithium, n-butyllithium, sec-butyllithium, tert-butyllithium, pentyllithium, hexyllithium, heptyllithium, octyllithium, nonyllithium and decyllithium; Grignard reagents such as methylmagnesium chloride, methylmagnesium bromide and methylmagnesium iodide, ethylmagnesium chloride, ethylmagnesium bromide and ethylmagnesium iodide, propylmagnesium chloride, propylmagnesium bromide and propylmagnesium iodide, butylmagnesium chloride, butylmagnesium bromide and butylmagnesium iodide, pentylmagnesium chloride, pentylmagnesium bromide and pentylmagnesium iodide, hexylmagnesium chloride, hexylmagnesium bromide and hexylmagnesium iodide, heptylmagnesium chloride, heptylmagnesium bromide and heptylmagnesium iodide, octylmagnesium chloride, octylmagnesium bromide and octylmagnesium iodide, nonylmagnesium chloride, nonylmagnesium bromide and nonylmagnesium iodide, decylmagnesium chloride, decylmagnesium bromide and decylmagnesium iodide; Metal acetylides such as lithium acetylide, sodium acetylide, potassium acetylide, calcium acetylide, and silver acetylide; and Inorganic metal salts such as potassium carbonate, sodium carbonate and calcium carbonate. One type of base may be used, or two or more types may be used as needed. When the base is used, the amount of the base used is preferably more than 0 to 10.0 mol, more preferably 0.01 to 5.0 mol, and even more preferably 0.1 to 3.0 mol, relative to 1 mol of 10-acetoxy-5-undecanol (6), from the viewpoints of reactivity and economy.

[0068] The acetylation may be carried out in the presence of a solvent, if necessary. Examples of the solvent include ether solvents such as tetrahydrofuran, 2-methyltetrahydrofuran (2-MeTHF), diethyl ether, dibutyl ether, 4-methyltetrahydropyran, cyclopentyl methyl ether, and 1,4-dioxane; hydrocarbon solvents such as hexane, heptane, benzene, toluene, xylene, and cumene; and N , N -dimethylformamide, N , N Examples of the solvent include polar solvents such as dimethylacetamide, N-methylpyrrolidone, dimethyl sulfoxide, γ-butyrolactone, acetonitrile, dichloromethane, chloroform, and hexamethylphosphoric triamide (HMPA). From the viewpoint of reactivity, ether solvents such as tetrahydrofuran, 2-methyltetrahydrofuran, and 4-methyltetrahydropyran; and hydrocarbon solvents such as toluene and xylene are preferred. The solvent may be used alone or in combination with two or more solvents as required. Commercially available solvents may also be used. The acetylation may be carried out in the presence of a solvent, if necessary, but the reaction may also be carried out without a solvent. When the solvent is used, the amount of the solvent used in the acetylation is preferably more than 0 to 5000 g, more preferably 30 to 2000 g, and even more preferably 70 to 1000 g, per mole of the 10-acetoxy-5-undecanol (6).

[0069] The reaction temperature for the acetylation varies depending on the acetylating agent and / or solvent used, but is preferably −40 to 120° C., more preferably −20 to 100° C., and even more preferably 0 to 80° C. from the viewpoint of reactivity. The reaction time for the acetylation is preferably 0.5 to 100 hours from the viewpoint of reactivity.

[0070] As described above, according to the present invention, the synthetic intermediate 5-(2-butyl-1,3-dioxolan-2-yl)-1-methylpentyl acetate (1) can be produced simply and efficiently. Furthermore, according to the present invention, Pear gall midge (scientific name: Contarinia pyrivora 2,7-Diacetoxyundecane (7), the sex pheromone of the genus Pseudomonas spp., can be efficiently produced in a short process with high productivity. In other words, because the target compound can be selectively synthesized, 2,7-diacetoxyundecane (7) can be efficiently produced without the need for separation and purification by column chromatography or the like.

[0071] [Example] The present invention will be specifically explained below by showing examples, but the present invention is not limited to the following examples. In the following, unless otherwise specified, "purity" refers to the area percentage obtained by gas chromatography (GC) analysis, "production ratio" refers to the relative ratio of the area percentage obtained by GC analysis, and "yield" was calculated based on the area percentage obtained by GC analysis. In each example, reaction monitoring and yield calculation were performed under the following GC conditions. GC conditions: GC: Shimadzu Corporation Capillary Gas Chromatograph GC-2014, Column: DB-5, 0.25 μm x 0.25 mm φ x 30 m, Carrier gas: He (1.55 mL / min), Detector: FID, Column temperature: 150°C, 5°C / min temperature increase to 230°C.

[0072] The yield was calculated according to the following formula, taking into account the purity (%GC) of the raw materials and the product. Yield (%) = {(weight of product obtained by reaction × %GC) / molecular weight of product} ÷[(weight of starting material in reaction × %GC) / molecular weight of starting material]} × 100 THF is tetrahydrofuran, OFE is triethyl orthoformate, and 2-MeTHF is 2-methyltetrahydrofuran. p -TsOH p -toluenesulfonic acid, Ac2O represents acetic anhydride.

[0073] [Example 1] 2-Butyl-2-(3-chloropropyl)-1,3-dioxolane compound (8:X 1 =Cl)

[0074] [ka]

[0075] At room temperature, the reactor was charged with 2-butyl-2-(3-chloropropyl)-1,3-dioxolane compound (9:X 1 =Cl) (793.15 g, 4.78 mol, purity 98.07%), ethylene glycol (10) (326.50 g, 5.26 mol, purity 100%), p Toluenesulfonic acid monohydrate (1.65 g, 0.0087 mol, purity 100%) and toluene (1653.81 g) were added and stirred at 60 to 70°C for 32 minutes. Next, trimethyl orthoformate (558.21 g, 5.26 mol, purity 100%) was added dropwise to the reactor at 60 to 70°C. After completion of the dropwise addition, the mixture was stirred at 60 to 70°C for 3.5 hours. Next, the internal temperature was cooled to 10 to 20°C, and then 25% by mass aqueous sodium hydroxide solution (700.00 g) was added to the reaction solution and the mixture was separated. 25% by mass aqueous sodium hydroxide solution (10.00 g) and water (100.00 g) were added and mixed, followed by separation. The resulting organic layer was concentrated under reduced pressure, and the residue was distilled under reduced pressure to obtain 2-butyl-2-(3-chloropropyl)-1,3-dioxolane compound (8:X). 1 =Cl) (940.84 g, 4.38 mol, purity 96.32%, bp = 110.5-113.7 °C / 0.044 kPa (0.33 mmHg)) was obtained in a yield of 91.69%.

[0076] The 2-butyl-2-(3-chloropropyl)-1,3-dioxolane compound (8:X 1 The spectral data for (=Cl) is shown below. [Nuclear Magnetic Resonance Spectrum] 1 H-NMR (500MHz, CDCl3): δ=0.89(3H,t,J=7.3Hz),1.26-1.37(4H,m),1.52-1.61(2H, m),1.72-1.77(2H,m),1.81-1.88(2H,m),3.55(2H,t,J=6.9Hz),3.91-3.94(4H,m); 13 C-NMR (125MHz, CDCl3): δ=14.01,22.94,25.95,27.15,34.27,36.99,45.30,64.91,111.30 [Mass spectrum] EI-mass spectrum (70 eV): m / z 207 (M + +1), 149, 129, 105, 77, 57 [Infrared absorption spectrum] (D-ATR): ν=2957, 2874, 1461, 1445, 1314, 1083, 1045, 948, 887, 652

[0077] [Example 2] [3-(2-butyl-1,3-dioxolan-2-yl)propyl]chloromagnesium (2:X 1 =Cl)

[0078] [ka]

[0079] Magnesium (35.72 g, 1.47 gram atoms) and tetrahydrofuran (770.00 g) were added to a reactor at room temperature and stirred at 55-60°C for 38 minutes. Next, the 2-butyl-2-(3-chloropropyl)-1,3-dioxolane compound (8:X) prepared in Example 1 was added to the reactor. 1 =Cl) (300.45 g, 1.40 mol, purity 96.32%) was added dropwise at an internal temperature of 55 to 60°C. After the addition was completed, the mixture was stirred at 50 to 60°C for 2 hours to obtain [3-(2-butyl-1,3-dioxolan-2-yl)propyl]chloromagnesium (2:X 1 =Cl) was prepared.

[0080] The [3-(2-butyl-1,3-dioxolan-2-yl)propyl]chloromagnesium (2:X) obtained above 1 The spectral data for (=Cl) is shown below. [Nuclear Magnetic Resonance Spectrum] 1 H-NMR (500MHz, CDCl3): δ=-0.72(2H,t,J=7.2Hz),0.83(3H,t,J=7.2Hz),1.19-1.38(4H,m),1.40-1.63(6H,m),3.75-3.88(4H,m); 13 C-NMR (125MHz, CDCl3): δ=7.76,14.24,23.66,24.29,26.80,36.21,44.29,64.73,67.21,113.76 [Infrared absorption spectrum] (D-ATR): ν=1365, 1033, 950, 516

[0081] [Example 3] Preparation of 5-(2-butyl-1,3-dioxolan-2-yl)-1-methylpentyl acetate (1)

[0082] [ka]

[0083] Next, [3-(2-butyl-1,3-dioxolan-2-yl)propyl]chloromagnesium (2:X) prepared in Example 2 was added. 1 Cuprous chloride (CuCl) (0.29 g, 0.0027 mol, purity 95%) was added to a reactor containing propylene oxide (3) at an internal temperature of 0-10°C and stirred for 19 minutes. Subsequently, propylene oxide (3) (93.51 g, 1.61 mol, purity 100%) was added dropwise at 0-20°C. After the dropwise addition was completed, the mixture was stirred at 15-25°C for 2.5 hours. Next, acetic anhydride (4) (164.36 g, 1.61 mol, purity 100%) was added dropwise to the reaction mixture at 20-60°C, and after the dropwise addition was completed, the mixture was stirred at 30-35°C for 1.5 hours. Next, an aqueous acetic acid solution (acetic acid (164.36 g) and water (541.33 g)) was added and the layers were separated. The resulting organic layer was concentrated under reduced pressure, and the residue was distilled under reduced pressure to give 5-(2-butyl-1,3-dioxolan-2-yl)-1-methylpentyl acetate (1) (347.47 g, 1.17 mol, purity 91.90%, bp = 115.8-138.5 °C / 0.056 kPa (0.42 mmHg)) in a yield of 83.75%.

[0084] The spectral data of the 5-(2-butyl-1,3-dioxolan-2-yl)-1-methylpentyl acetate (1) obtained above is shown below. [Nuclear Magnetic Resonance Spectrum] 1 H-NMR (500MHz, CDCl3): δ=0.88(3H,t,J=6.9Hz),1.18(3H,d,J=6.5Hz),1.23-1.39( 8H,m),1.41-1.61(7H,m),2.00(3H,s),3.90(3H,s),4.86(1H,tq,J=6.2Hz,6.2Hz); 13 C-NMR (125MHz, CDCl3): δ=14.01,19.88,21.32,22.96,23.64,25.66,25.99,35.86,36.84,36.98,64.86,70.96,111.70,170.71 [Mass spectrum] EI-mass spectrum (70 eV): m / z 241 (M + -31), 215, 155, 129, 99, 57, 43 [Infrared absorption spectrum] (D-ATR): ν=2945, 2872, 1737, 1465, 1372, 1245, 1079, 1024, 949

[0085] [Example 4] Preparation of 10-acetoxy-5-undecanone (5)

[0086] [ka]

[0087] At room temperature, a reactor was charged with 5-(2-butyl-1,3-dioxolan-2-yl)-1-methylpentyl acetate (1) (334.20 g, 1.13 mol, purity 91.90%) prepared in Example 3, water (40.63 g, 2.26 mol), acetone (600.00 g), and p Toluenesulfonic acid monohydrate (2.15 g, 0.011 mol) was added and stirred at 60-65° C. for 2.5 hours. Next, after cooling the internal temperature to 10-20° C., 25% by mass aqueous sodium hydroxide solution (3.24 g) was added to the reaction solution, and the mixture was concentrated under reduced pressure to remove acetone. The resulting organic layer was washed with sodium bicarbonate (3.12 g) and water (156.00 g) and then separated. The resulting organic layer was concentrated again under reduced pressure, and the residue was distilled under reduced pressure to obtain 10-acetoxy-5-undecanone (5) (269.86 g, 1.10 mol, purity 92.65%, bp = 120.0-129.0° C. / 0.39 kPa (2.9 mmHg)) in a yield of 97.04%.

[0088] The spectral data of the 10-acetoxy-5-undecanone (5) obtained above is shown below. [Nuclear Magnetic Resonance Spectrum] 1 H-NMR(500MHz,CDCl3):δ=;0.88(3H,t,J=7.3Hz),1.17(3H,d,J=6.1Hz),1.28(4H,sext-like,J=7 .3Hz),1.40-1.61(6H,m),2.00(3H,s),2.37(4H,q-like,J=7.3Hz),4.86(1H,tq,J=6.1Hz,6.1Hz) 13 C-NMR (125MHz, CDCl3): δ=13.79,19.88,21.29,22.31,23.54,25.01,25.92,35.67,42.47,42.50,70.71,170.68,211.09 [Mass Spectrum] EI-Mass Spectrum (70 eV): m / z 228 (M + ), 186, 168, 153, 139, 126, 111, 97, 85, 69, 57, 43 [Infrared absorption spectrum] (D-ATR): ν=2936, 2872, 1735, 1715, 1463, 1372, 1245, 1131, 1023

[0089] [Example 5] Preparation of 10-acetoxy-5-undecanol (6)

[0090] [ka]

[0091] Sodium borohydride (NaBH4) (24.49 g, 0.65 mol, purity 100%), ethanol (EtOH) (118.26 g), 25% by mass aqueous sodium hydroxide solution (NaOH aq.) (4.08 g), and water (95.17 g) were added to a reactor at room temperature and stirred at 20 to 25°C for 4 minutes. Next, a mixture of 10-acetoxy-5-undecanone (5) (265.96 g, 1.08 mol, purity 92.65%) and toluene (118.26 g) prepared in Example 4 was added dropwise to the reactor at 25 to 40°C. After completion of the dropwise addition, the mixture was stirred at 30 to 40°C for 3 hours. Next, the aqueous layer was separated from the reaction mixture, and an aqueous acetic acid solution (acetic acid (12.08 g) and water (120.77 g)) was added to the resulting organic layer and mixed. The layers were then separated. The resulting organic layer was concentrated under reduced pressure, and the residue was distilled under reduced pressure to obtain the product 10-acetoxy-5-undecanol (6) (256.54 g, 1.01 mol, purity 90.87%, bp = 121.0-132.9 °C / 0.24 kPa (1.8 mmHg)) in a 93.80% yield. The resulting product contained 10-acetoxy-5-undecanol (6) as well as a few percent of 2,7-diacetoxyundecane (7).

[0092] The spectral data of the 10-acetoxy-5-undecanol (6) obtained above is shown below. [Nuclear Magnetic Resonance Spectrum] 1 H-NMR (500MHz, CDCl3): δ=0.89(3H,t,J=7.3Hz),1.19(3H,d,J=6.1Hz),1.23-1. 63(14H,m),1.61(1H,br.s),2.01(3H,s),3.52-3.62(1H,m),4.84-4.92(1H,m); 13 C-NMR(125MHz,CDCl3):δ=14.02,19.90,19.93,21.32,22.71,25.40,25.4 4,27.79,35.85,35.88,37.17,37.25,70.89,70.92,71.72,71.78,170.79 [Mass spectrum] EI-mass spectrum (70 eV): m / z 213 (M + -17), 129, 113, 95, 69, 56, 43 [Infrared absorption spectrum] (D-ATR): ν = 3420, 2933, 2860, 1738, 1717, 1464, 1373, 1245, 1127, 1023

[0093] [Example 6] Preparation of 2,7-diacetoxyundecane (7)

[0094] [ka]

[0095] 10-Acetoxy-5-undecanol (6) (253.64 g, 1.00 mol, purity 90.87%) prepared in Example 5, pyridine (166.28 g, 2.10 mol, purity 100%), and toluene (109.71 g) were added to a reactor at room temperature and stirred for 2 minutes at 20 to 30°C. Next, acetic anhydride (AcO) (183.95 g, 1.80 mol, purity 100%) was added dropwise to the reactor at 25 to 35°C. After completion of the dropwise addition, the mixture was stirred at 30 to 35°C for 19 hours. Next, water (268.89 g) was added to the reaction mixture and the mixture was separated. To the resulting organic layer, sodium chloride (8.07 g), sodium bicarbonate (10.13 g), and water (101.12 g) were added and mixed. The resulting organic layer was then separated and concentrated under reduced pressure. The residue was distilled under reduced pressure to give 2,7-diacetoxyundecane (7) (301.84 g, 1.07 mol, purity 96.65%, bp = 126.1-132.1°C / 0.043 kPa (0.32 mmHg)) in a yield of 107.00%. Since the raw material contained 2,7-diacetoxyundecane (7) along with 10-acetoxy-5-undecanol (6) (Example 5), the yield of the two steps in Examples 5 and 6 was calculated to be 99.26%.

[0096] The spectral data of the 2,7-diacetoxyundecane (7) obtained above is shown below. [Nuclear Magnetic Resonance Spectrum] 1 H-NMR (500MHz, CDCl3): δ=0.87(3H,t,J=7.3Hz),1.18(3H,d,J=6.1Hz),1.20-1.39 (8H,m),1.39-1.60(6H,m),2.00(3H,s),2.02(3H,d,J=0.8Hz),4.80-4.90(2H,m); 13 C-NMR (125MHz, CDCl3): δ=13.92,19.88,19.91,21.20,21.30,22.54,25.11,25.2 5,27.43,33.76,33.78,33.96,35.75,35.77,70.80,74.13,74.16,170.69,170.85 [Mass spectrum] EI-mass spectrum (70 eV): m / z 273 (M + +1), 129, 113, 95, 68, 43 [Infrared absorption spectrum] (D-ATR): ν = 2936, 2862, 1737, 1373, 1243, 1022

[0097] [Reference example 1] Preparation of 2-(1-butylcyclobutan-1-yloxy)ethanol (11)

[0098] [ka]

[0099] Magnesium (Mg) (1.07 g, 0.044 gram atom) and 2-methyltetrahydrofuran (12.00 g) were added to a reactor at room temperature and stirred at 60-65°C for 22 minutes. Next, the 2-butyl-2-(3-chloropropyl)-1,3-dioxolane compound (8:X) prepared in Example 1 was added to the reactor. 1 HCl) (8.58 g, 0.040 mol, purity 96.32%) was added dropwise at 60-65°C. After the addition was completed, the mixture was stirred at 75-80°C for 3 hours and then at 95-100°C for 3 hours. Next, an aqueous ammonium chloride solution (ammonium chloride (NH4Cl) (1.00 g) and water (40.00 g)) and 20% by mass hydrochloric acid (10.00 g) were added and the mixture was separated. The resulting organic layer was concentrated under reduced pressure, and the residue was distilled under reduced pressure to obtain 2-(1-butylcyclobutan-1-yloxy)ethanol (11) (5.26 g, 0.028 mol, purity 91.81%, bp = 85.0-96.0°C / 0.45 kPa (3.4 mmHg)) in a 70.09% yield.

[0100] The spectral data of the 2-(1-butylcyclobutan-1-yloxy)ethanol (11) obtained above is shown below. [Nuclear Magnetic Resonance Spectrum] 1 H-NMR (500MHz, CDCl3): δ=0.91(3H,t,J=7.3Hz),1.23-1.37(4H,m),1.51-1.63(3H,m),1.69-1.78(1H,m),1. 83-1.90(2H,m),2.05(2H,dq,J=2.7Hz,9.6Hz),2.22(1H,br.s),3.33(2H,t,J=4.6Hz),3.69(2H,t,J=4.6Hz); 13 C-NMR (125MHz, CDCl3): δ=12.58,14.09,23.01,25.05,32.01,34.93,62.10,62.47,79.29 [Mass spectrum] EI-mass spectrum (70 eV): m / z 172 (M + ), 157, 143, 129, 115, 102, 83, 71, 59, 41 [Infrared absorption spectrum] (D-ATR): ν=3423, 2957, 2932, 2862, 1459, 1256, 1054, 963, 891< / ii>

Claims

1. The following formula (1): 【Chemical 1】 5-(2-butyl-1,3-dioxolan-2-yl)-1-methylpentyl acetate represented by the formula:

2. The following general formula (2): 【Chemistry 2】 (In the formula, X １ represents a halogen atom or a 3-(2-butyl-1,3-dioxolan-2-yl)propyl group. The organomagnesium compound (2) represented by the following formula (3): 【Chemistry 3】 and then reacting the compound represented by the following general formula (4): 【Chemistry 4】 (In the formula, X ２ represents a halogen atom, an acetoxy group, a methoxy group, or an ethoxy group. By reacting with an acetylating agent represented by the following formula (1): 【Chemistry 5】 A step of obtaining 5-(2-butyl-1,3-dioxolan-2-yl)-1-methylpentyl acetate (1) represented by the formula: A method for producing 5-(2-butyl-1,3-dioxolan-2-yl)-1-methylpentyl acetate (1), comprising:

3. The following formula (1): 【Chemistry 6】 In the presence of an acid or a peroxide, 5-(2-butyl-1,3-dioxolan-2-yl)-1-methylpentyl acetate represented by the following formula (5): 【Chemistry 7】 A step of obtaining 10-acetoxy-5-undecanone represented by the formula: A method for producing 10-acetoxy-5-undecanone (5), comprising:

4. A method for producing 10-acetoxy-5-undecanone (5) according to claim 3; The 10-acetoxy-5-undecanone (5) is reduced to give the compound of the following formula (6): 【Chemistry 8】 obtaining 10-acetoxy-5-undecanol represented by the formula: The 10-acetoxy-5-undecanol (6) is subjected to an acetylation reaction to obtain a compound represented by the following formula (7): 【Chemistry 9】 and a step of obtaining 2,7-diacetoxyundecane represented by the formula: A method for producing 2,7-diacetoxyundecane (7), comprising:

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