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 The pear gall midge is a European fruit tree pest that feeds on pears. The larvae of the pear gall midge burrow into the fruit and feed on it. Fruit damaged by the pear gall midge turns black and falls off the tree. Because the larvae burrow into the fruit, conventional pesticides are often ineffective due to poor contact, making control difficult. Furthermore, due to concerns about pesticide residues, biological control methods are attracting attention, and the use of sex pheromone substances is one of the promising approaches (see Non-Patent Literature 1 below).

[0003] The sex pheromone composition of pear gall midge has been reported to be a mixture of 2,7-diacetoxyundecane and 7-(acetoxy)-2-undecanone (see Non-Patent Document 2 below).

[0004] One method for producing the main component, 2,7-diacetoxyundecane, involves reacting 1,4-dibromobutan, 1-pentanal, and acetaldehyde with magnesium in tetrahydrofuran (THF) to synthesize a mixture of three substances: 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, a method has been reported for producing the obtained 2,7-undecanediol by acetylating it with acetic anhydride in the presence of pyridine (see Non-Patent Literature 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. [Overview of the project] [Problems that the invention aims to solve]

[0006] However, in the method for producing 2,7-diacetoxyundecane described in Non-Patent Literature 2, three types of diols are produced in the first step, and it is presumed that the yield will be poor because 2,7-undecanediol, an intermediate of the target product, is highly water-soluble. Furthermore, acetaldehyde used in the first step is carcinogenic and a cause of sick building syndrome, so its handling requires specialized equipment and strict wastewater treatment, making it unsuitable for industrial production. In addition, the three types of diols are separated and purified by silica gel column chromatography, but this method 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 aims to provide a novel compound that is a synthetic intermediate for the efficient production of 2,7-diacetoxyundecane. The present invention also aims 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] As a result of intensive studies to solve the above problems, the present inventors have found 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 according to the present invention can be produced at low cost in large quantities and can be purified only by distillation. Further, the present inventors have found 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, the following formula (1):

Chemical formula

[0010] According to a second aspect of the present invention, the following general formula (2):

Chemical formula

Chemical formula

Chemical formula

[0011] According to a third aspect of the present invention, the following formula (1): [ka] 5-(2-butyl-1,3-dioxolan-2-yl)-1-methylpentyl acetate, represented by the following formula (5), is obtained by deprotecting the ketal in the presence of an acid or peroxide: [ka] Steps to obtain 10-acetoxy-5-undecanone represented by A method for producing 10-acetoxy-5-undecanone (5), including the above, can be provided.

[0012] According to a fourth aspect of the present invention, the 10-acetoxy-5-undecanone (5) is reduced by the following formula (6): [ka] A step to obtain 10-acetoxy-5-undecanol represented by, By acetylating the aforementioned 10-acetoxy-5-undecanol (6), the following formula (7) is obtained: [ka] The process of obtaining 2,7-diacetoxyundecane represented by A method for producing 2,7-diacetoxyundecane (7) can be provided. [Effects of the Invention]

[0013] According to the present invention, the target compound, 2,7-diacetoxyundecane, can be produced efficiently and in high yield with minimal 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 product are hardly produced in each step, purification by column chromatography is unnecessary, and purification can be performed by distillation, which is suitable for scale-up. Moreover, according to the present invention, a novel synthetic intermediate useful for producing the above-mentioned 2,7-diacetoxyundecane can be provided. [Modes for carrying out the invention]

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

[0015] 5-(2-butyl-1,3-dioxolan-2-yl)-1-methylpentyl acetate (1) can be prepared, for example, by nucleophilically adding an organomagnesium compound represented by the following general formula (2) to a propylene oxide represented by the following formula (3), as shown in the following chemical reaction equation, and then acetylating it with an acetylating agent represented by the following general formula (4).

[0016] [ka]

[0017] (i) The organomagnesium compound (2) described above will be explained below. X in the above general formula (2) 1 X represents a halogen atom or a 3-(2-butyl-1,3-dioxolan-2-yl)propyl group. 1 Specifically, examples include chlorine atoms, bromine atoms, and iodine atoms, with chlorine atoms and bromine atoms being preferred from the viewpoint of ease of handling, and chlorine atoms being more preferred.

[0018] Specific examples of organomagnesium compounds (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]iodommagnesium. 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 one type or, if necessary, two or more types. Furthermore, the organomagnesium compound (2) can be prepared, for example, by the manufacturing method described later.

[0019] (ii) Next, the nucleophilic addition reaction between the organomagnesium compound (2) and propylene oxide (3), followed by the acetylation reaction with the acetylating agent (4), will be explained below. In this nucleophilic addition reaction, the amount of propylene oxide (3) used is preferably 0.8 to 2.0 moles, more preferably 0.9 to 1.7 moles, and even more preferably 1.0 to 1.5 moles per mole (mol) of organomagnesium compound (2), from an economic standpoint.

[0020] A solvent may be used in the nucleophilic addition reaction as needed. Examples of solvents include common solvents such as ether-based solvents like tetrahydrofuran (THF), 2-methyltetrahydrofuran (2-MeTHF), diethyl ether, dibutyl ether, 4-methyltetrahydropyran (MTHP), cyclopentyl methyl ether, and 1,4-dioxane; and hydrocarbon-based 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 polar solvents include dimethylpropylene urea (DMPU), hexamethylphosphoric triamide (HMPA), dichloromethane, and chloroform. However, from the viewpoint of reactivity, 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 one type or, if necessary, two or more types. Furthermore, commercially available solvents can be used. The amount of 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 organomagnesium compound (2), from the viewpoint of reactivity.

[0021] A catalyst may be used in the nucleophilic addition reaction as needed. Examples of catalysts 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 of one type or, if necessary, two or more types. Furthermore, commercially available catalysts can be used. The amount of catalyst used is preferably 0.0003 to 0.3 moles, more preferably 0.001 to 0.1 moles, per mole of 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 from the viewpoint of reactivity, it is preferably -78 to 70°C, more preferably -20 to 50°C, and even more preferably 0 to 30°C. The reaction time in this nucleophilic addition reaction varies depending on the solvent and / or reaction scale used, but from the viewpoint of reactivity, it is preferably 0.5 to 100 hours.

[0023] Examples of acetylating agents used in the acetylation reaction include halogenated acetyls 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 acetylating agent (4) used is preferably 0.8 to 2.0 moles, more preferably 0.9 to 1.7 moles, and even more preferably 1.0 to 1.5 moles per mole of organomagnesium compound (2), from an economic standpoint.

[0025] A solvent may be used in the acetylation reaction as needed. Examples of solvents include common solvents such as ether-based solvents like tetrahydrofuran (THF), 2-methyltetrahydrofuran (2-MeTHF), diethyl ether, dibutyl ether, 4-methyltetrahydropyran (MTHP), cyclopentyl methyl ether, and 1,4-dioxane; and hydrocarbon-based 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 polar solvents include dimethylpropylene urea (DMPU), hexamethylphosphoric triamide (HMPA), dichloromethane, and chloroform. However, from the viewpoint of reactivity, 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 one type or, if necessary, two or more types. Furthermore, commercially available solvents can be used. The amount of 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 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, salt 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 in the acetylation reaction varies depending on the solvent and / or reaction scale used, but from the viewpoint of reactivity, it is preferably 0.5 to 100 hours.

[0027] 5-(2-butyl-1,3-dioxolan-2-yl)-1-methylpentyl acetate (1) is produced by reacting with propylene oxide and then with an acetylating agent. However, it is also possible to synthesize 10-hydroxy-5-undecanone by reacting with propylene oxide and then without reacting 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 / intermolecularly during the acetal deprotection step. Furthermore, since 2,7-undecanediol is more water-soluble than 10-acetoxy-5-undecanol (6), an intermediate of the present invention, it is presumed that extraction after the reaction will be difficult. Given this background, a method is preferred in which 2,7-diacetoxyundecane is synthesized by reacting with propylene oxide, then with an acetylating agent to produce 5-(2-butyl-1,3-dioxolan-2-yl)-1-methylpentyl acetate (1), and then using 5-(2-butyl-1,3-dioxolan-2-yl)-1-methylpentyl acetate (1) as a key intermediate.

[0028] (iii) Next, the method for producing the above 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 equation.

[0031] [ka]

[0032] (a) First, the above 2-butyl-2-(3-halopropyl)-1,3-dioxolane compound (8) will be described below. X in the above general formula (8) 1 X represents a halogen atom. Halogen atom X 1 Specifically, examples include chlorine atoms, bromine atoms, and iodine atoms, with bromine atoms and chlorine atoms being preferred from the viewpoint of ease of handling, and chlorine atoms being more preferred. Specific examples of 2-butyl-2-(3-halopropyl)-1,3-dioxolane compounds (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] One or more types of 2-butyl-2-(3-halopropyl)-1,3-dioxolane compound (8) may be used as needed. Furthermore, 2-butyl-2-(3-halopropyl)-1,3-dioxolane compound (8) may be commercially available or independently synthesized.

[0034] The amount of magnesium used is preferably 0.8 to 2.0 grams, more preferably 0.9 to 1.6 grams, and even more preferably 1.0 to 1.4 grams per mole of 2-butyl-2-(3-halopropyl)-1,3-dioxolane compound (8), from the viewpoint of completing the reaction. Examples of the above solvents include common solvents such as ether-based solvents like tetrahydrofuran (THF), 2-methyltetrahydrofuran (2-MeTHF), diethyl ether, dibutyl ether, 4-methyltetrahydropyran (MTHP), cyclopentyl methyl ether, and 1,4-dioxane; and hydrocarbon-based solvents such as hexane, heptane, benzene, toluene, xylene, and cumene. However, from the viewpoint of the reaction rate for the production of the above Grignard reagent, hydrocarbon-based solvents such as toluene and xylene, and ether-based solvents such as tetrahydrofuran, 2-methyltetrahydrofuran, and 4-methyltetrahydropyran are preferred, tetrahydrofuran, 2-methyltetrahydrofuran, and 4-methyltetrahydropyran are more preferred, and tetrahydrofuran is even more preferred. The solvent may be one type or, if necessary, two or more types. Furthermore, commercially available solvents can be used. The amount of 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 2-(3-halopropyl)-2-butyl-1,3-dioxolane compound (8), from the viewpoint of reactivity.

[0035] The reaction temperature in the above 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 in the above reaction with magnesium varies depending on the solvent and / or reaction scale used, 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] Normally, Grignard reagents are prepared by the reaction of 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 gradually above an internal temperature of 60°C, and rapidly above 95°C to form a four-membered ring compound. Therefore, temperature is extremely important in order to obtain the desired Grignard reagent, organomagnesium compound (2), in good yield, and it is desirable to prepare it at 30-60°C.

[0037] [ka]

[0038] (b) Next, the method for producing the above-mentioned 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 by conventional methods or by the methods described below.

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

[0040] [ka]

[0041] The above 1-halo-4-octanone compound (9) will be explained below. X in the general formula (9) above 1 represents halogen atoms, specifically chlorine atoms, bromine atoms, and iodine. atom Examples include bromine atoms and chlorine atoms, which are preferred.

[0042] Specific examples of 1-halo-4-octanone compounds (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. One or more types of 1-halo-4-octanone compounds (9) may be used as needed. The 1-halo-4-octanone compounds (9) may be commercially available or can be prepared, for example, by a nucleophilic substitution reaction between 4-chlorobutyryl chloride and butylmagnesium halide.

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

[0044] An acid may be used in the acetalization reaction as needed. The 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 - 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 are examples, and from the viewpoint of reactivity, benzenesulfonic acid and p -Toluene sulfonic acid is preferred. The acid may be of one type or, if necessary, two or more types. When using the acid, the amount of the acid used is preferably 0.0001 to 1.00 moles, more preferably 0.0005 to 0.5 moles, and even more preferably 0.001 to 0.1 moles per mole of 1-halo-4-octanone compound (9), from the viewpoint of reactivity and economy.

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

[0046] A solvent may be used in the acetalization reaction as needed. Examples of solvents include common solvents such as ether-based solvents like tetrahydrofuran (THF), 2-methyltetrahydrofuran (2-MeTHF), diethyl ether, dibutyl ether, 4-methyltetrahydropyran (MTHP), cyclopentyl methyl ether, and 1,4-dioxane; and hydrocarbon-based 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 Polar solvents such as dimethylpropylene urea (DMPU), hexamethylphosphoric triamide (HMPA), dichloromethane, and chloroform are examples, but from the viewpoint of reactivity, hydrocarbon solvents such as toluene and xylene, and ether solvents such as tetrahydrofuran, 2-methyltetrahydrofuran, and 4-methyltetrahydropyran are preferred, hexane, toluene, and xylene are more preferred, and toluene and xylene are even more preferred. The solvent may be one type or, if necessary, two or more types. Furthermore, commercially available solvents can be used. The amount of 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 1-halo-4-octanone compound (9), from the viewpoint of reactivity.

[0047] From the viewpoint of reactivity, 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. The reaction time in the acetalization reaction varies depending on the solvent and / or reaction scale used, but from the viewpoint of reactivity, it is preferably 0.5 to 100 hours.

[0048] <ii>Regarding the method for producing 2,7-diacetoxyundecane represented by the following general formula (7): One of the target compounds of the present invention, 2,7-diacetoxyundecane, represented by the following general formula (7), is prepared according to the production method shown in the following chemical reaction equation. 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, 10-acetoxy-5-undecanol (6) is synthesized by selectively reducing only the ketone moiety of 10-acetoxy-5-undecanone (5) with a reducing agent. Next, 2,7-diacetoxyundecane (7) is synthesized by acetylating the hydroxyl group of 10-acetoxy-5-undecanol (6) with an acetylating agent.

[0049] [ka]

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

[0051] [ka]

[0052] Deprotection reactions can be carried out, for example, in the presence of an acid or a peroxide. Specifically, the deprotection reaction can be carried out, for example, by (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 exchange reactions and acid hydrolysis reactions 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 - 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 are examples, and from the viewpoint of reactivity, benzenesulfonic acid and p -Toluene sulfonic acid is preferred. The acid may be of one type or, if necessary, two or more types. When using the acid, the amount of the acid used is preferably 0.0001 to 1.00 moles, more preferably 0.0005 to 0.5 moles, and even more preferably 0.001 to 0.1 moles per mole of 5-(2-butyl-1,3-dioxolan-2-yl)-1-methylpentyl acetate (1), from the viewpoint of reactivity and economy. Examples of peroxides used in oxidation reactions include perchloric acid (HClO4), tert -Butyl hydroperoxide ( t Examples include -BuOOH) and 2,3-dichloro-5,6-dicyano-1,4-benzoquinone (DDQ).

[0053] In the deprotection reaction, water may be used in addition to the acid described above, 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 addition to the acid or water mentioned above, a solvent may be used in the deprotection reaction as needed. The solvents include ether-based 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-based solvents such as hexane, heptane, benzene, toluene, xylene, and cumene. N , N -Dimethylformamide (DMF), N , N Examples of polar solvents include dimethylacetamide (DMAC), N-methylpyrrolidone (NMP), dimethyl sulfoxide (DMSO), γ-butyrolactone (GBL), acetonitrile, acetone, N,N'-dimethylpropylene urea (DMPU), hexamethylphosphoric triamide (HMPA), dichloromethane, and chloroform; ester solvents such as methyl acetate, ethyl acetate, n-propyl acetate, and n-butyl acetate; and alcoholic solvents such as methanol and ethanol. From the perspective of reactivity, these include polar solvents such as dimethylacetamide (DMAC), N-methylpyrrolidone (NMP), dimethyl sulfoxide (DMSO), γ-butyrolactone (GBL), acetonitrile, acetone, N,N'-dimethylpropylene urea (DMPU), hexamethylphosphoric triamide (HMPA), dichloromethane, and chloroform; ester solvents such as methyl acetate, ethyl acetate, n-propyl acetate, and n-butyl acetate; and alcoholic solvents such as methanol and ethanol. 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'-dimethylpropylene urea (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 one type or, if necessary, two or more types. Furthermore, commercially available solvents can be used. When using the solvent, the amount of 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 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 from the viewpoint of reactivity, it is preferably -15 to 180°C, more preferably 5 to 120°C, and even more preferably 40 to 80°C. The reaction time in 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] (ii) Next, a method for producing the above-mentioned 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] Reducing agents include alkali metal salts of borohydride such as lithium borohydride, sodium borohydride, potassium borohydride, and sodium triacetoxyborohydride; alkaline earth metal salts of borohydride such as magnesium borohydride and calcium borohydride; alkali metal salts of cyanoborohydride such as lithium cyanoborohydride, sodium cyanoborohydride, and potassium cyanoborohydride; alkaline earth metal salts of cyanoborohydride such as magnesium cyanoborohydride and calcium cyanoborohydride; sodium tri-sec-butylborohydride and lithium tri-sec-butylborohydride, etc. Examples include tri-sec-butylboro alkali metal salts of hydride; 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. One type of reducing agent, or two or more types as needed, may be used. Commercially available reducing agents can be used. The amount of reducing agent used varies depending on the reducing agent used, but from the viewpoint of reactivity, it is preferably 0.25 to 5.0 moles per mole of 10-acetoxy-5-undecanone(5). When sodium borohydride is used as the reducing agent, it is preferably 0.25 to 5.0 moles per mole of 10-acetoxy-5-undecanone(5), more preferably 0.35 to 3.0 moles, and even more preferably 0.5 to 1.5 moles.

[0059] A solvent may be used in the reduction reaction as needed. Examples of such solvents include ether-based 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-based solvents such as hexane, heptane, benzene, toluene, xylene, and cumene. N , N -Dimethylformamide (DMF), N , N Examples of solvents include polar solvents such as dimethylacetamide (DMAC), N-methylpyrrolidone (NMP), dimethyl sulfoxide (DMSO), γ-butyrolactone (GBL), acetonitrile, acetone, N,N'-dimethylpropylene urea (DMPU), hexamethylphosphoric triamide (HMPA), dichloromethane, and chloroform; ester solvents such as methyl acetate, ethyl acetate, n-propyl acetate, and n-butyl acetate; alcohol solvents such as methanol and ethanol; and water. A suitable solvent can be selected depending on the reducing agent used. For example, when using an alkali metal borohydride as the reducing agent, an alcohol-based solvent such as ethanol, or a mixed solvent of an alcohol-based solvent and another solvent, is preferred. The solvent may be one type or, if necessary, two or more types. Furthermore, commercially available solvents can be used. When using the solvent, 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 one type or, if necessary, two or more types. Commercially available solvents can be used.

[0060] A base may be used in the reduction reaction as needed. Examples of such bases 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 using an alkali metal boron hydride salt as a 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 as needed. Commercially available bases can be used. If the base is a solid, it may be added to the reaction mixture in its solid form, or it may be dissolved beforehand in the solvent used in the reduction reaction. From the viewpoint of reactivity, the amount of base used is preferably more than 0 to 10.00 moles, more preferably 0.0001 to 1.0 moles, and even more preferably 0.001 to 0.1 moles per mole of 10-acetoxy-5-undecanone(5).

[0061] The reaction temperature in the reduction reaction varies depending on the reducing agent used, but from the viewpoint of reactivity, it is preferably -15 to 180°C, more preferably 0 to 100°C, and even more preferably 10 to 60°C. The reaction time in 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 position 10 protected by an acetyl group, resulting in increased lipophilicity compared to diols such as 2,7-undecanediol. Therefore, it is possible to recover the product in good yield without loss to the aqueous layer, even without using a large amount of extraction solvent.

[0063] (iii) 2,7-Diacetoxyundecane (7) and method for producing the same The method for producing 2,7-diacetoxyundecane (7) is described below. 2,7-Diacetoxyundecane (7) can be prepared by acetylating the above-mentioned 10-acetoxy-5-undecanol (6).

[0064] [ka]

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

[0066] An acid or base may be used in the acetylation process, if necessary. The acids include mineral acids such as hydrochloric acid, sulfuric acid, and nitric acid; benzenesulfonic acid and p Examples include 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. The acid may be of one type or, if necessary, two or more types. When using the acid, the amount of the acid used is preferably more than 0 to 3.0 moles, more preferably 0.001 to 1.5 moles, and even more preferably 0.01 to 1.0 moles, per mole of 10-acetoxy-5-undecanol(6), from the viewpoint of reactivity and economy.

[0067] Examples of such bases include 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; Metallic 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. The base may be one type or, if necessary, two or more types. When using the base, the amount of the base used is preferably more than 0 to 10.0 moles, more preferably 0.01 to 5.0 moles, and even more preferably 0.1 to 3.0 moles, per mole of 10-acetoxy-5-undecanol(6), from the viewpoint of reactivity and economy.

[0068] A solvent may be used in the acetylation process, if necessary. The solvents include ether-based solvents such as tetrahydrofuran, 2-methyltetrahydrofuran (2-MeTHF), diethyl ether, dibutyl ether, 4-methyltetrahydropyran, cyclopentyl methyl ether, and 1,4-dioxane; hydrocarbon-based solvents such as hexane, heptane, benzene, toluene, xylene, and cumene; and, N , N -Dimethylformamide, N , N -Dimethylacetamide, N Examples of polar solvents include methylpyrrolidone, dimethyl sulfoxide, γ-butyrolactone, acetonitrile, dichloromethane, chloroform, and hexamethylphosphoric triamide (HMPA). From the viewpoint of reactivity, ether-based solvents such as tetrahydrofuran, 2-methyltetrahydrofuran, and 4-methyltetrahydropyran, as well as hydrocarbon-based solvents such as toluene and xylene, are preferred. The solvent may be one type or, if necessary, two or more types. Furthermore, commercially available solvents can be used. The acetylation may be carried out using a solvent if necessary, but it may also be carried out without a solvent. When using the solvent, the amount of solvent used for 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 10-acetoxy-5-undecanol(6).

[0069] The reaction temperature in the acetylation varies depending on the acetylating agent and / or solvent used, but from the viewpoint of reactivity, it 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 in the acetylation is preferably 0.5 to 100 hours.

[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, from 5-(2-butyl-1,3-dioxolan-2-yl)-1-methylpentyl acetate (1), Pear gall midge (scientific name: Contarinia pyrivora The sex pheromone 2,7-diacetoxyundecane (7) can be produced in a short process, with high productivity and efficiency. In other words, because the target compound can be selectively synthesized, 2,7-diacetoxyundecane (7) can be produced efficiently without the need for separation and purification by column chromatography or the like.

[0071] [Examples] The present invention will be specifically described below with reference to examples, but the present invention is not limited to the following examples. In the following, "purity" refers to the area percentage obtained by gas chromatography (GC) analysis unless otherwise specified, and "production ratio" refers to the relative ratio of the area percentages obtained by GC analysis. Furthermore, "yield" was calculated based on the area percentages obtained by GC analysis. In each example, reaction monitoring and yield calculation were performed according to the following GC conditions. GC conditions: GC: Shimadzu Corporation capillary gas chromatograph GC-2014, column: DB-5, 0.25 μm x 0.25 mm φ x 30 m, carrier gas: He (1.55 mL / min), detector: FID, column temperature: 150°C, increasing temperature by 5°C / min to 230°C.

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

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

[0074] [Chemical formula]

[0075] At room temperature, 1-chloro-4-octanone (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 -p-toluenesulfonic acid monohydrate (1.65 g, 0.0087 mol, purity 100%) and toluene (1653.81 g) were added to the reactor, and the mixture was stirred at 60 - 70 °C for 32 minutes. Next, trimethyl orthoformate (558.21 g, 5.26 mol, purity 100%) was added dropwise to the reactor at 60 - 70 °C. After the dropwise addition was completed, the mixture was stirred at 60 - 70 °C for 3.5 hours. Then, after cooling the internal temperature to 10 - 20 °C, a 25% by mass aqueous sodium hydroxide solution (700.00 g) was added to the reaction solution and separated. The organic layer was mixed with a 25% by mass aqueous sodium hydroxide solution (10.00 g) and water (100.00 g), then separated again. The obtained organic layer was concentrated under reduced pressure, and the residue was subjected to vacuum distillation to obtain 2-butyl-2-(3-chloropropyl)-1,3-dioxolane compound (8:X 1 =Cl) (940.84 g, 4.38 mol, purity 96.32%, b.p. = 110.5 - 113.7 °C / 0.044 kPa (0.33 mmHg)) in a yield of 91.69%.

[0076] The 2-butyl-2-(3-chloropropyl)-1,3-dioxolane compound obtained above (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 (70eV): 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 Manufacturing of =Cl)

[0078] [ka]

[0079] At room temperature, magnesium (35.72 g, 1.47 gram atoms) and tetrahydrofuran (770.00 g) were added to the reactor 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 [3-(2-butyl-1,3-dioxolan-2-yl)propyl]chloromagnesium (2:X) was added dropwise at an internal temperature of 55-60°C. After the addition was complete, the mixture was stirred at 50-60°C for 2 hours. 1 A solution (=Cl) was prepared.

[0080] [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, we prepared [3-(2-butyl-1,3-dioxolan-2-yl)propyl]chloromagnesium (2:X) in Example 2. 1 Cuprous chloride (CuCl) (0.29 g, 0.0027 mol, 95% purity) was added to a reactor containing (Cl) at an internal temperature of 0-10°C and stirred for 19 minutes. Subsequently, propylene oxide (3) (93.51 g, 1.61 mol, 100% purity) was added dropwise at 0-20°C. After the addition was complete, the mixture was stirred at 15-25°C for 2.5 hours. Next, acetic anhydride (4) (164.36 g, 1.61 mol, 100% purity) was added dropwise to the reaction mixture at 20-60°C, and the mixture was stirred at 30-35°C for 1.5 hours after the addition was complete. Next, an aqueous acetic acid solution (acetic acid (164.36 g) and water (541.33 g)) was 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 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℃ / 0.056 kPa (0.42 mmHg)) in yield 83.75%.

[0084] The spectral data for 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 (70eV): 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, the reactor was filled 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 -Toluene sulfonic acid monohydrate (2.15 g, 0.011 mol) was added and the mixture was 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 mixture and 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 separated. The resulting organic layer was then 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 for 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 (70eV): 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] At room temperature, sodium borohydride (NaBH4) (24.49 g, 0.65 mol, 100% purity), ethanol (EtOH) (118.26 g), 25% by mass aqueous sodium hydroxide solution (NaOHaq.) (4.08 g), and water (95.17 g) were added to the reactor and stirred at 20-25°C for 4 minutes. Next, a mixture of 10-acetoxy-5-undecanone (5) (265.96 g, 1.08 mol, 92.65% purity) prepared in Example 4 and toluene (118.26 g) was added dropwise to the reactor at 25-40°C. After the addition was complete, the mixture was stirred at 30-40°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. Then, the mixture was separated, and the resulting organic layer was concentrated under reduced pressure. The residue was then distilled under reduced pressure to obtain 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 yield 93.80%. The obtained product contained 10-acetoxy-5-undecanol (6) along with several percent of 2,7-diacetoxyundecane (7).

[0092] The spectral data of 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 (70eV): 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] Production of 2,7-diacetoxyundecane (7)

[0094] [ka]

[0095] At room temperature, 10-acetoxy-5-undecanol (6) (253.64 g, 1.00 mol, 90.87% purity), pyridine (166.28 g, 2.10 mol, 100% purity), and toluene (109.71 g) prepared in Example 5 were added to a reactor and stirred at 20-30°C for 2 minutes. Next, acetic anhydride (Ac2O) (183.95 g, 1.80 mol, 100% purity) was added dropwise to the reactor at 25-35°C. After the addition was complete, the mixture was stirred at 30-35°C for 19 hours. Next, water (268.89 g) was added to the reaction mixture and separated. Then, sodium chloride (8.07 g), sodium bicarbonate (10.13 g), and water (101.12 g) were added to the resulting organic layer and mixed. The mixture was then separated again, and the resulting organic layer was concentrated under reduced pressure. The residue was then distilled under reduced pressure to obtain 2,7-diacetoxyundecane (7) (301.84 g, 1.07 mol, purity 96.65%, bp=126.1~132.1℃ / 0.043 kPa (0.32 mmHg)) in a yield of 107.00%. Since the raw materials contained 2,7-diacetoxyundecane (7) along with 10-acetoxy-5-undecanol (6) (Example 5), the two-step yield for Examples 5 and 6 was calculated to be 99.26%.

[0096] The spectral data of 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 (70eV): 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] Production of 2-(1-butylcyclobutan-1-yloxy)ethanol (11)

[0098] [ka]

[0099] At room temperature, magnesium (Mg) (1.07 g, 0.044 gram atoms) and 2-methyltetrahydrofuran (12.00 g) were added to the reactor 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 8.58 g, 0.040 mol, purity 96.32% of ammonium chloride (NH4Cl) was added dropwise at 60-65°C. After the addition was complete, the mixture was stirred at 75-80°C for 3 hours and then at 95-100°C for 3 hours. Next, 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 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 yield of 70.09%.

[0100] The spectral data of 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 (70eV): 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): 【Chemistry 1】 5-(2-butyl-1,3-dioxolan-2-yl)-1-methylpentyl acetate is represented as 5-(2-butyl-1,3-dioxolan-2-yl).

2. The following general formula (2): 【Chemistry 2】 (In the formula, X １ (This 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): 【Transformation 3】 The propylene oxide represented by the following nucleophilic addition reaction is subjected to the following general formula (4): 【Chemistry 4】 (In the formula, X ２ (This represents a halogen atom, acetoxy group, methoxy group, or ethoxy group.) By reacting with an acetylating agent represented by the following formula (1): 【Transformation 5】 Steps to obtain 5-(2-butyl-1,3-dioxolan-2-yl)-1-methylpentyl acetate (1) represented by A method for producing 5-(2-butyl-1,3-dioxolan-2-yl)-1-methylpentyl acetate (1), which contains [the specified compound].

3. The following formula (1): 【Transformation 6】 5-(2-butyl-1,3-dioxolan-2-yl)-1-methylpentyl acetate, represented by the following formula (5), is obtained by deprotecting the ketal in the presence of an acid or peroxide: 【Transformation 7】 Steps to obtain 10-acetoxy-5-undecanone represented by A method for producing 10-acetoxy-5-undecanone (5), which includes the above.

4. A method for producing 10-acetoxy-5-undecanone (5) according to claim 3, The above 10-acetoxy-5-undecanone (5) is reduced by the following formula (6): 【Transformation 8】 A step to obtain 10-acetoxy-5-undecanol represented by, By acetylating the aforementioned 10-acetoxy-5-undecanol (6), the following formula (7) is obtained: 【Chemistry 9】 A step to obtain 2,7-diacetoxyundecane represented by the following: A method for producing 2,7-diacetoxyundecane (7), which includes the above.

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