2-halo-6,10-dimethyltridecane compounds, methods for their preparation, and methods for preparing 2,6,10-trimethyltridecane acid alkyl ester compounds therefrom

Abstract

The present invention relates to a 2-halo-6,10-dimethyltridecane compound (1), wherein X 1 represents a halogen atom. The present invention also relates to a process for preparing the above-mentioned 2-halo-6,10-dimethyltridecane compound (1), comprising the steps of: subjecting a nucleophile 3,7-dimethyldecyl compound (2), wherein M 1 represents Li, MgZ 1 , CuZ 1 or CuLiZ 1 , and Z 1 represents a halogen atom or a 3,7-dimethyldecyl group, to a nucleophilic addition reaction with propylene oxide (3) to form 6,10-dimethyl-2-tridecanol (4); and reacting the 6,10-dimethyl-2-tridecanol (4) thus obtained with a halogenating agent (5) to form the above-mentioned 2-halo-6,10-dimethyltridecane compounds (1).

Description

Technical Field

[0001] One embodiment of the present invention relates to a 2-halo-6,10-dimethyltridecane compound, a method for preparing the 2-halo-6,10-dimethyltridecane compound, and a method for preparing a 2,6,10-trimethyltridecanoic acid alkyl ester compound from the 2-halo-6,10-dimethyltridecane compound. Background Technology

[0002] The Neotropical brown bug (scientific name: *Euschistus heros*) is a South American soybean pest that feeds on the stems, leaves, pods, and seeds of soybeans. *Euschistus heros* larvae, aged two years or older, are known to damage seeds, and the degree of damage increases with developmental stage (Non-Patent Literature 1 listed below). Therefore, control is particularly important in the early stages of development, and pesticides (insecticides) are currently widely used for control. However, control using typical insecticides is difficult because they are often ineffective. Meanwhile, concerns about pesticide residues and the development of resistance have led to a focus on biological control methods, with high hopes placed on the use of pheromones (Non-Patent Literature 2 listed below).

[0003] According to reports, the pheromone components of Euschistus heroes are a mixture of alkyl 2,6,10-trimethyltridecanoate, methyl 2,6,10-trimethyltridecanoate, methyl 2,6,10-trimethyltridecanoate, methyl 2,6,10-trimethyldodecanoate, and methyl (2E,4E)-2,4-decadienoate (Non-Patent Literature 3 and 4 listed below).

[0004] The main component of this mixture, methyl 2,6,10-trimethyltridecanoate, is reportedly prepared via the following steps: For example, propyl magnesium bromide is reacted with cyclopropyl methyl ketone in an ether solvent via an addition reaction to form 2-cyclopropyl-2-pentanol. The resulting 2-cyclopropyl-2-pentanol is then reacted with 48% hydrobromic acid to form 1-bromo-4-methyl-3-heptene. The resulting 1-bromo-4-methyl-3-heptene is then converted to a Grignard reagent, which is then reacted with cyclopropyl methyl ketone via an addition reaction to form 2-cyclopropyl-6-methyl-5-nonen-2-ol. The resulting 2-cyclopropyl-6-methyl-5-nonen-2-ol is then reacted with 48% hydrobromic acid to form 1-bromo-4,8-dimethyl-3,7-undecadiene. Next, 2-methylmalonate was deprotonated with sodium hydride, and then reacted with the obtained 1-bromo-4,8-dimethyl-3,7-undecadiene to form 2-methyl-2-(4,8-dimethyl-3,7-undecadienyl)malonate. The obtained 2-methyl-2-(4,8-dimethyl-3,7-undecadienyl)malonate was then subjected to Krapcho decarboxylation in dimethyl sulfoxide (DMSO) solvent with sodium chloride and water to form methyl 2,6,10-trimethyl-5,9-tridecadienoate. Then, in the presence of a palladium-carbon (Pd / C) catalyst, the obtained methyl 2,6,10-trimethyl-5,9-tridecadienoate was hydrogenated to obtain methyl 2,6,10-trimethyltridecanoate (Non-Patent Literature 5 listed below).

[0005] Methyl 2,6,10-trimethyltridecanoate was also reported to be prepared by another method having the following steps. For example, 2-methylpentanol was brominated with bromine and triphenylphosphine to form 1-bromo-2-methylpentane. Furthermore, (±)-citronellol was p-sulfonated with p-toluenesulfonyl chloride in a pyridine solution to form citronellol p-toluenesulfonate. The resulting 1-bromo-2-methylpentane was reacted with magnesium to form a Grignard reagent, which was then coupled with the above-mentioned citronellol p-toluenesulfonate in the presence of a copper catalyst to form 2,6,10-trimethyl-2-tridecene. The resulting 2,6,10-trimethyl-2-tridecene was oxidized with selenium oxide in tert-butyl hydroperoxide, and then reduced with sodium borohydride to form 2,6,10-trimethyl-2-tridecene-1-ol. The resulting 2,6,10-trimethyl-2-tetren-1-ol was then hydrogenated in the presence of platinum oxide (Adams catalyst) to form 2,6,10-trimethyl-1-tetranol. The resulting 2,6,10-trimethyl-1-tetranol was then subjected to Jones oxidation with chromic acid, followed by carboxylic acid methylation with diazomethane to form methyl 2,6,10-trimethyltetranoate (Non-Patent Literature 6 listed below). Existing technology

[0006] [Non-patent literature]

[0007] [Non-patent literature 1] Magda Andreia Tessmerl et al., Neotropical Entomology., 2022, 51, 112-121.

[0008] [Non-Patent Literature 2] Elisabeth A. Hodgdon et al., The Canadian Entomologist, 2022, 154, e37, 1-17.

[0009] [Non-Patent Literature 3] M. Borges et al., J, Appl. Ent., 1998, 122, 335-338.

[0010] [Non-patent literature 4] Aijun Zhang et al., Neotropical Entomology, 2003, 32(4), 713-717.

[0011] [Non-Patent Literature 5] Kenji Mori et al., Liebigs Ann. Chem., 1994, 637-639.

[0012] [Non-Patent Literature 6] Paulo HG Zarbin et al., J. Chem. Ecol., 2000, 26(12), 2737-2746.

[0013] Purpose of the invention

[0014] However, the method for preparing methyl 2,6,10-trimethyltetrate in Non-Patent Literature 5 is unsuitable for industrial application due to the use of highly flammable sodium hydride and palladium on carbon. The preparation process is also unsuitable for industrial use because the large amount of dimethyl sulfoxide used as a solvent requires specialized equipment, has a strong odor, and raises concerns as a potential reproductive toxin. Furthermore, the method for preparing methyl 2,6,10-trimethyltetrate in Non-Patent Literature 5 is uneconomical due to the use of expensive starting material cyclopropyl methyl ketone and expensive reagent palladium on carbon. The recent sharp rise in palladium prices has made inexpensive preparation particularly difficult. In addition, the method for preparing methyl 2,6,10-trimethyltetrate in Non-Patent Literature 5 is a lengthy process involving seven steps, with a moderate yield of 30.34% across all seven steps.

[0015] Meanwhile, the method for preparing methyl 2,6,10-trimethyltridecanoate in Non-Patent Literature 6 uses selenium oxide and chromic acid, both of which are highly environmentally toxic and undesirable from a green chemistry perspective. Furthermore, industrialization is difficult due to the use of high-purity explosive tert-butylhydrogen peroxide. Using expensive platinum oxide is also uneconomical. Moreover, the method for preparing methyl 2,6,10-trimethyltridecanoate in Non-Patent Literature 6 is a lengthy process involving six steps, with a low yield of only 14.47%.

[0016] The preparation methods in Non-Patent Literature 5 and 6 both involve purifying methyl 2,6,10-trimethyltetrazocyanate by silica gel column chromatography, which makes these methods unsuitable for industrial applications because silica gel column chromatography purification is difficult to perform on an industrial scale of 100 kg or more.

[0017] This invention is made in view of the above circumstances and aims to provide a novel compound as a synthetic intermediate for the efficient preparation of alkyl 2,6,10-trimethyltridecanoate compounds. This invention also aims to provide a method for preparing this novel compound, and a method for preparing alkyl 2,6,10-trimethyltridecanoate compounds from this novel compound. Summary of the Invention

[0018] As a result of in-depth research to overcome the aforementioned problems of the prior art, the inventors have discovered a novel compound, 2-halo-6,10-dimethyltridecane. The 2-halo-6,10-dimethyltridecane compound according to embodiments of the present invention can be prepared inexpensively and in large quantities, and can be purified by distillation alone. Furthermore, in the final step, by preparing various alkyl 2,6,10-trimethyltridecanoate compounds separately, alkyl 2,6,10-trimethyltridecanoate compounds, including Euschistusheros's pheromone methyl 2,6,10-trimethyltridecanoate, can be synthesized comprehensively and efficiently.

[0019] According to a first aspect of the invention, a 2-halo-6,10-dimethyltridecane compound of the following general formula (1) is provided:

[0020]

[0021] Where X1 represents a halogen atom.

[0022] According to a second aspect of the present invention, a method for preparing a 2-halo-6,10-dimethyltridecane compound of the following general formula (1) is provided:

[0023]

[0024] Where X1 represents a halogen atom.

[0025] The method includes the following steps:

[0026] Nucleophilic 3,7-dimethyldecyl compounds of the following general formula (2):

[0027]

[0028] Where M 1 Indicates Li, Mg, Z 1 CuZ 1 or CuLiZ 1 And Z 1 This indicates a halogen atom or a 3,7-dimethyldecyl group.

[0029] It undergoes a nucleophilic addition reaction with propylene oxide of the following formula (3):

[0030]

[0031] To form 6,10-dimethyl-2-tridecaneol of formula (4):

[0032]

[0033] as well as

[0034] The 6,10-dimethyl-2-tetaneol (4) obtained therefrom is reacted with a halogenating agent (5) to form the above-mentioned 2-halo-6,10-dimethyltetane compound (1).

[0035] According to a third aspect of the present invention, a method for preparing the above-described 2-halo-6,10-dimethyltridecane compound (1) is provided.

[0036] The method also includes the following steps:

[0037] Make the following nucleophile 2-methylpentyl compound of general formula (6):

[0038]

[0039] Where M 2 Indicates Li, Mg, Z 2 CuZ 2 or CuLiZ 2 And Z 2 Indicates a halogen atom or a 2-methylpentyl group.

[0040] It undergoes a coupling reaction with sulfonate compounds (7) of the following general formula (7):

[0041]

[0042] Where X 2 Represents a halogen atom, and R 1 This indicates a hydrocarbon group having 1 to 7 carbon atoms.

[0043] To form 1-halo-3,7-dimethyldecane compounds of the following general formula (8):

[0044]

[0045] Where X 2 Represents halogen atoms,

[0046] as well as

[0047] The resulting 1-halo-3,7-dimethyldecane compound (8) was converted into the above-mentioned nucleophile 3,7-dimethyldecyl compound (2).

[0048] According to a fourth aspect of the present invention, a method for preparing alkyl ester compounds of the following general formula (11) is provided:

[0049]

[0050] Where R 2 Indicates an alkyl group having 1 to 12 carbon atoms.

[0051] The method includes the following steps:

[0052] The following 2-halo-6,10-dimethyltridecane compounds of general formula (1):

[0053]

[0054] Where X 1 Represents halogen atoms,

[0055] The nucleophile 1,5,9-trimethyldodecyl compound of the following general formula (9) is converted:

[0056]

[0057] as well as

[0058] The nucleophile 1,5,9-trimethyldodecyl compound (9) obtained therefrom is then subjected to a nucleophilic substitution reaction with an alkyl haloformate of the following general formula (10):

[0059]

[0060] Where X 4 Represents a halogen atom, and R 2 Indicates an alkyl group having 1 to 12 carbon atoms.

[0061] To form the above-mentioned alkyl ester compound 2,6,10-trimethyltridecanoate (11).

[0062] According to one embodiment of the present invention, the target compound 2,6,10-trimethyltetranoic acid alkyl ester can be prepared efficiently with low environmental impact, high yield, and fewer steps. According to one embodiment of the present invention, the target compound 2,6,10-trimethyltetranoic acid alkyl ester can be prepared economically. According to one embodiment of the present invention, these steps substantially do not produce compounds similar to the target compound. Therefore, purification by column chromatography is not required; purification can be performed by distillation, which allows for scalability. According to one embodiment of the present invention, a novel synthetic intermediate is provided for the preparation of the above-described 2,6,10-trimethyltetranoic acid alkyl ester compound. Detailed Implementation

[0063] (I) Preparation method of 2-halo-6,10-dimethyltridecane compounds of the following general formula (1)

[0064] (i) 2-Halo-6,10-dimethyltridecane compound (1) is represented by the following general formula (1):

[0065]

[0066] (ii) The method for preparing 2-halo-6,10-dimethyltridecane compound (1) will be explained in detail below.

[0067] For example, as shown in the following chemical reaction formula, a 1-halo-2-methylpentane compound of general formula (12) can be converted into a nucleophile 2-methylpentyl compound of general formula (6), and then the nucleophile 2-methylpentyl compound (6) can be coupled with a sulfonate compound of general formula (7) to form a 1-halo-3,7-dimethyldecane compound of general formula (8). The above 1-halo-3,7-dimethyldecane compound... (8) The nucleophile 3,7-dimethyldecyl compound of the following general formula (2) is converted, and then the nucleophile 3,7-dimethyldecyl compound (2) is subjected to a nucleophilic addition reaction with propylene oxide of the following general formula (3) to form 6,10-dimethyl-2-tetaneol of the following general formula (4). Then the above 6,10-dimethyl-2-tetaneol (4) is reacted with a halogenating agent (5) to prepare 2-halo-6,10-dimethyltetane compound (1).

[0068]

[0069] (a) First, the 2-halo-6,10-dimethyltridecane compound (1) and the method for preparing the 2-halo-6,10-dimethyltridecane compound (1) are explained.

[0070] 2-Halo-6,10-dimethyltridecane compound (1) is represented by the following general formula (1):

[0071]

[0072] In the above general formula (1), X 1 Represents a halogen atom. Halogen atom X 1 Specific examples include chlorine, bromine, and iodine atoms. Halogen atom X 1 Preferably, chlorine and bromine atoms are used. Preferred reactivity can be ensured by using the chlorine and bromine atoms. Halogen atom X 1 More preferably, it is a chlorine atom. By using the chlorine atom, even better reactivity can be ensured.

[0073] Specific examples of the 2-halo-6,10-dimethyltridecane compound (1) include 2-chloro-6,10-dimethyltridecane, 2-bromo-6,10-trimethyltridecane, and 2-iodo-6,10-dimethyltridecane. The 2-halo-6,10-dimethyltridecane compound (1) is preferably 2-chloro-6,10-dimethyltridecane and 2-bromo-6,10-dimethyltridecane. Preferred storage stability can be ensured by using the aforementioned 2-chloro-6,10-dimethyltridecane and 2-bromo-6,10-dimethyltridecane. The 2-halo-6,10-dimethyltridecane compound (1) is more preferably 2-chloro-6,10-dimethyltridecane. Further preferred storage stability can be ensured by using the aforementioned 2-chloro-6,10-dimethyltridecane.

[0074] (b) The halogenation reaction of 6,10-dimethyl-2-tetaneol (4) and halogenating agent (5) is explained in detail below.

[0075]

[0076] For example, the halogenation reaction can be carried out by toluenesulfonating the hydroxyl group of 6,10-dimethyl-2-tridecaneol (4) with a p-toluenesulfonyl halide compound, followed by halogenation of the hydroxyl group of 6,10-dimethyl-2-tridecaneol (4) with a metal salt or lithium halide compound, or by directly halogenating the hydroxyl group of 6,10-dimethyl-2-tridecaneol (4) with a halogenating agent.

[0077] Examples of halogenating agents (5) include halogen molecules such as chlorine, bromine, and iodine; hydrogen halide compounds such as hydrogen chloride, hydrogen bromide, and hydrogen iodide; methanesulfonyl halide compounds such as methanesulfonyl chloride, methanesulfonyl bromide, and methanesulfonyl iodide; benzenesulfonyl halide compounds such as benzenesulfonyl chloride, benzenesulfonyl bromide, and benzenesulfonyl iodide; p-toluenesulfonyl halide compounds such as p-toluenesulfonyl chloride, p-toluenesulfonyl bromide, and p-toluenesulfonyl iodide; thionyl halide compounds such as thionyl chloride, thionyl bromide, and thionyl iodide; phosphorus halide compounds such as phosphorus trichloride, phosphorus pentachloride, and phosphorus tribromide; and tetrahalogenated carbon compounds such as tetrahalogenated carbon. Carbon chloride, carbon tetrabromide, and carbon tetraiodide; alkylsilyl halide compounds, such as trimethylchlorosilane, trimethylbromosilane, trimethyliodosilane, triethylchlorosilane, triethylbromosilane, triethyliodosilane, triisopropylchlorosilane, triisopropylbromosilane, triisopropyliodosilane, tert-butyldimethylchlorosilane, tert-butyldimethylbromosilane, and tert-butyldimethyliodosilane; oxalyl halide compounds, such as oxalyl chloride, oxalyl bromide, and oxalyl iodide; and N-halosuccinimide compounds, such as N-chlorosuccinimide, N-bromosuccinimide, and N-iodosuccinimide. The halogenating agent (5) is preferably a methanesulfonyl halide compound, a benzenesulfonyl halide compound, a p-toluenesulfonyl halide compound, and a thionyl halide compound. By using the methanesulfonyl halide compound, benzenesulfonyl halide compound, p-toluenesulfonyl halide compound, and thionyl chloride compound, it is possible to ensure the suppression of side reactions. The halogenating agent (5) is more preferably a benzenesulfonyl halide compound and a p-toluenesulfonyl halide compound. By using the benzenesulfonyl halide compound and the p-toluenesulfonyl halide compound, it is possible to ensure even better suppression of side reactions and unpleasant odors. The halogenating agent (5) is even more preferably a benzenesulfonyl halide compound. By using the benzenesulfonyl halide compound, it is possible to ensure even better suppression of side reactions and unpleasant odors.

[0078] Halogenating agents can be used alone or in combination if needed. Halogenating agents are commercially available.

[0079] For each mol of 6,10-dimethyl-2-tetranol (4), the amount of halogenating agent is preferably 0.8 to 5.0 mol, more preferably 1.0 to 2.5 mol. By using the preferred and more preferred amounts, preferred reactivity and more preferred reactivity can be ensured.

[0080] If necessary, an alkali can be added to the halogenation reaction.

[0081] Examples of bases include hydroxides such as sodium hydroxide, potassium hydroxide, calcium hydroxide, and magnesium hydroxide; carbonates such as sodium carbonate, potassium carbonate, calcium carbonate, and magnesium carbonate; and amines such as triethylamine, N,N-diisopropylethylamine, piperidine, pyrrolidine, pyridine, dimethylpyridine, 4-dimethylaminopyridine, N,N-dimethylaniline, N,N-diethylaniline, and 1,8-diazabicyclo[5.4.0]-7-undecene (DBU).

[0082] When methanesulfonyl halide, benzenesulfonyl halide, or p-toluenesulfonyl halide is used as the above-mentioned halogenating agent, the base is preferably an amine, more preferably a pyridine, such as pyridine, dimethylpyridine, and 4-dimethylaminopyridine.

[0083] When thionyl halide compounds are used as halogenating agents, the base is preferably an amine, more preferably a trialkylamine, such as triethylamine.

[0084] Alkali can be used alone or in combination if needed. Alkali can be commercially available.

[0085] When using a base, the amount of base used per mol of 6,10-dimethyl-2-tetaneol (4) is preferably greater than 0 to 8.0 mol, more preferably greater than 0 to 3.0 mol. By using the preferred amount and the more preferred amount, preferred yield and / or economy, as well as more preferred yield and / or economy, can be ensured.

[0086] If necessary, metal salts can be incorporated into the halogenation reaction.

[0087] Examples of metal salts include lithium salts, such as lithium chloride, lithium bromide, and lithium iodide; sodium salts, such as sodium chloride, sodium bromide, and sodium iodide; potassium salts, such as potassium chloride, potassium bromide, and potassium iodide; calcium salts, such as calcium chloride, calcium bromide, and calcium iodide; and magnesium salts, such as magnesium chloride, magnesium bromide, and magnesium iodide.

[0088] For example, when toluenesulfonation is performed, followed by halogenation with a metal salt or lithium halide compound, the reaction is carried out with lithium salts such as lithium chloride, lithium bromide, and lithium iodide.

[0089] Metal salts can be used alone or in combination if needed. Metal salts are commercially available.

[0090] When using a metal salt, the amount of metal salt used per mol of 6,10-dimethyl-2-tetaneol (4) is preferably greater than 0 to 30.0 mol, more preferably greater than 0 to 5.0 mol. By using the preferred amount and the more preferred amount, preferred reactivity and more preferred reactivity can be ensured.

[0091] Although the in-situ addition of metal salts increases the concentration of halide ions, thereby improving reactivity, it is preferable not to incorporate the metal salts into the reaction. By not incorporating the metal salts, preferred economic efficiency and / or environmental protection can be ensured.

[0092] If necessary, a solvent can be incorporated into the halogenation reaction. Examples of solvents include general solvents such as ether solvents, such as tetrahydrofuran (THF), 2-methyltetrahydrofuran (2-MeTHF), diethyl ether, butyl ether, 4-methyltetrahydropyran (MTHP), cyclopentyl methyl ether, and 1,4-dioxane; hydrocarbon solvents, such as hexane, heptane, benzene, toluene, xylene, and cumene; and polar solvents, such as N,N-dimethylformamide (DMF), N,N-dimethylacetamide (DMAC), N-methylpyrrolidone (NMP), and dimethyl sulfoxide (DMSO). Butyrolactone (GBL), acetonitrile, acetone, N,N'-dimethylacrylurea (DMPU), hexamethylphosphoric triamine (HMPA), dichloromethane, and chloroform; and ester solvents such as methyl acetate, ethyl acetate, n-propyl acetate, and n-butyl acetate. The preferred solvents are 2-methyltetrahydrofuran, 4-methyltetrahydropyran, dichloromethane, and chloroform. 2-Butyrolactone, N-methylpyrrolidone, N,N-dimethylformamide, N,N-dimethylacetamide, and acetonitrile. By using the aforementioned 2-methyltetrahydrofuran, 4-methyltetrahydropyran, dichloromethane, chloroform, Butyrolactone, N-methylpyrrolidone, N,N-dimethylformamide, N,N-dimethylacetamide, and acetonitrile can ensure preferred reactivity. A more preferred solvent is 2-methyltetrahydrofuran. 2-Butyrolactone and acetonitrile. By using the 2-methyltetrahydrofuran, Butyrolactone and acetonitrile can ensure even better safety. The solvent is even more preferably... -Butyrolactone. By using the aforementioned... β-Butyrolactone can ensure, or even better, safety.

[0093] Solvents can be used alone or in combination if needed. Solvents can be commercially available.

[0094] When a solvent is incorporated into the halogenation reaction, the amount of solvent used per mol of 6,10-dimethyl-2-tetaneol (4) is preferably greater than 0 to 3000 g, more preferably greater than 0 to 1500 g, even more preferably greater than 0 to 800 g, and particularly preferably 200 to 600 g.

[0095] When a solvent is incorporated, the amount of starting material and the ease of preparation are reduced, so the reaction can be carried out without the aforementioned solvent by using a base as a solvent.

[0096] The reaction temperature of the halogenation reaction varies depending on the halogenating agent used, and is preferably -20 to 180°C, more preferably -10 to 120°C, and even more preferably 0 to 70°C. By using the preferred reaction temperature, the more preferred reaction temperature, and the even more preferred reaction temperature, preferred reactivity, and even more preferred reactivity can be ensured.

[0097] The reaction time for halogenation varies depending on the halogenating agent used and / or the production scale, and is preferably from 0.5 to 100 hours. By using the preferred reaction time, preferred reactivity can be ensured.

[0098] Examples of purification methods for halogenation reactions include purification by silica gel column chromatography and purification by distillation. Distillation is the preferred purification method. Using distillation ensures optimal industrial production.

[0099] (II) 6,10-dimethyl-2-tridecaneol of formula (4) and method for preparing 6,10-dimethyl-2-tridecaneol (4)

[0100] (i) 6,10-dimethyl-2-tetaneol (4) is represented by the following formula (4):

[0101]

[0102] (ii) The method for preparing 6,10-dimethyl-2-tetaneol (4) is explained in detail below.

[0103] For example, as shown in the following chemical reaction formula, 6,10-dimethyl-2-tetaneol (4) can be prepared by converting 1-halo-3,7-dimethyldecane compound (8) into nucleophile 3,7-dimethyldecyl compound (2), and then subjecting nucleophile 3,7-dimethyldecyl compound (2) to a nucleophilic addition reaction with propylene oxide (3).

[0104]

[0105] (a) First, the nucleophile 3,7-dimethyldecyl compound (2) is explained in detail below. The nucleophile 3,7-dimethyldecyl compound (2) is represented by the following general formula (2):

[0106]

[0107] In the above general formula (2), M 1 Indicates Li, Mg, Z 1 CuZ 1 or CuLiZ 1 And Z 1This represents a halogen atom or a 3,7-dimethyldecyl group. Halogen atom Z 1 Specific examples include chlorine, bromine, and iodine atoms. Halogen atoms (Z) 1 Preferably, chlorine and bromine atoms are used. Preferred reactivity can be ensured by using the chlorine and bromine atoms. Halogen atom Z 1 More preferably, it is a chlorine atom. By using the chlorine atom, even better reactivity can be ensured.

[0108] Specific examples of nucleophilic 3,7-dimethyldecyl compounds (2) include the following compounds:

[0109] 3,7-Dimethyldecyllithium (where M) 1 =Li);

[0110] 3,7-Dimethyldecyl magnesium halide compounds (where M) 1 =MgZ 1 Examples include 3,7-dimethyldecyl magnesium chloride, 3,7-dimethyldecyl magnesium bromide, and 3,7-dimethyldecyl magnesium iodide (i.e., Grignard reagents);

[0111] Bis(3,7-dimethyldecyl)cuprate compounds (where M) 1 =CuZ 1 ), such as bis(3,7-dimethyldecyl)cuprate; and

[0112] Gilman's reagent (where M) 1 =CuLiZ 1 ), such as lithium bis(3,7-dimethyldecyl)copper oxide compounds, such as lithium bis(3,7-dimethyldecyl)copper oxide (i.e., Gilman's reagent).

[0113] A Grignard reagent, such as a 3,7-dimethyldecyl magnesium halide compound, is preferred. Preferred reactivity can be ensured by using such a Grignard reagent, such as a 3,7-dimethyldecyl magnesium halide compound.

[0114] (b) The method for preparing the above nucleophile 3,7-dimethyldecyl compound (2) is explained in detail below.

[0115] The nucleophile 3,7-dimethyldecyl compound (2) can be prepared from the following 1-halo-3,7-dimethyldecane compound (8).

[0116]

[0117] In the above general formula (8), X 2 Represents a halogen atom. Halogen atom X 2 Specific examples include chlorine, bromine, and iodine atoms. Halogen atom X 2Preferably, chlorine and bromine atoms are used. Preferred reactivity can be ensured by using the chlorine and bromine atoms. Halogen atom X 2 More preferably, it is a chlorine atom. By using the chlorine atom, even better reactivity can be ensured.

[0118] Specific examples of the 1-halo-3,7-dimethyldecane compound (8) include 1-chloro-3,7-dimethyldecane, 1-bromo-3,7-dimethyldecane, and 1-iodo-3,7-dimethyldecane. The 1-halo-3,7-dimethyldecane compound (8) is preferably 1-chloro-3,7-dimethyldecane and 1-bromo-3,7-dimethyldecane. Preferred reactivity can be ensured by using the aforementioned 1-chloro-3,7-dimethyldecane and 1-bromo-3,7-dimethyldecane. The 1-halo-3,7-dimethyldecane compound (8) is more preferably 1-chloro-3,7-dimethyldecane. Further preferred reactivity can be ensured by using the aforementioned 1-chloro-3,7-dimethyldecane.

[0119] Next, as an example, the preparation of the nucleophile 3,7-dimethyldecyl compound (2) is described in detail, wherein M 1 MgZ 1 That is, 3,7-dimethyldecyl magnesium halide reagent (2:M) 1 =MgZ 1 (i.e., Grignard reagent) method.

[0120] Grignard reagent 3,7-dimethyldecyl magnesium halide reagent (2:M 1 =MgZ 1 (8) can be prepared, for example, by reacting the above-mentioned 1-halo-3,7-dimethyldecane compound (8) with magnesium in a solvent, as shown in the following chemical reaction formula:

[0121]

[0122] When preparing the 3,7-dimethyldecyl magnesium halide reagent (2), the amount of magnesium used is preferably 1.0 to 2.0 g atoms per mol of 1-halo-3,7-dimethyldecane compound (8). By using the preferred amount, optimal completion of the reaction can be ensured.

[0123] Examples of solvents include general solvents, such as ether solvents like tetrahydrofuran (THF), 2-methyltetrahydrofuran (2-MeTHF), diethyl ether, butyl ether, 4-methyltetrahydropyran (MTHP), cyclopentyl methyl ether, and 1,4-dioxane; and hydrocarbon solvents like hexane, heptane, benzene, toluene, xylene, and cumene. The solvents are preferably hydrocarbon solvents like toluene and xylene; and ether solvents like tetrahydrofuran, 2-methyltetrahydrofuran, and 4-methyltetrahydropyran. By using said hydrocarbon solvents, such as toluene and xylene; and ether solvents, such as tetrahydrofuran, 2-methyltetrahydrofuran, and 4-methyltetrahydropyran, a preferred reaction rate for the formation of the above-described Grignard reagent can be ensured. The solvents are more preferably tetrahydrofuran, 2-methyltetrahydrofuran, and 4-methyltetrahydropyran. By using said tetrahydrofuran, 2-methyltetrahydrofuran, and 4-methyltetrahydropyran, a more preferred reaction rate for the formation of the above-described Grignard reagent can be ensured.

[0124] Solvents can be used alone or in combination if needed. Solvents can be commercially available.

[0125] For each mol of 1-halo-3,7-dimethyldecane compound (8), 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. By using the preferred amount, the more preferred amount, and the even more preferred amount, preferred reactivity, and even more preferred reactivity can be ensured.

[0126] The reaction temperature varies depending on the solvent used, and is preferably 30 to 120°C, more preferably 50 to 100°C, and even more preferably 60 to 80°C. By using the preferred reaction temperature, the more preferred reaction temperature, and the even more preferred reaction rate, preferred reactivity, and even more preferred reactivity can be ensured.

[0127] The reaction time varies depending on the solvent used and / or the production scale, and is preferably from 0.5 to 100 hours. By using the preferred reaction time, optimal reactivity can be ensured.

[0128] (c) The nucleophilic addition reaction of the nucleophile 3,7-dimethyldecyl compound (2) and propylene oxide (3) is explained in detail below.

[0129] In the nucleophilic addition reaction, the amount of propylene oxide (3) per mol of the nucleophile 3,7-dimethyldecyl compound (2) 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. By using the preferred amount, the more preferred amount, and the even more preferred amount, preferred economy, and even more preferred economy can be ensured.

[0130] If desired, a solvent can be incorporated into the nucleophilic addition reaction. Examples of solvents include general solvents such as ether solvents, such as tetrahydrofuran (THF), 2-methyltetrahydrofuran (2-MeTHF), diethyl ether, butyl ether, 4-methyltetrahydropyran (MTHP), cyclopentyl methyl ether, and 1,4-dioxane; hydrocarbon solvents such as hexane, heptane, benzene, toluene, xylene, and cumene; and polar solvents such as N,N-dimethylformamide (DMF), N,N-dimethylacetamide (DMAC), N-methylpyrrolidone (NMP), and dimethyl sulfoxide (DMSO). The solvents used are 1,3-butyrolactone (GBL), acetonitrile, N,N'-dimethylacrylurea (DMPU), hexamethylphosphoric triamine (HMPA), dichloromethane, and chloroform. Preferably, the solvents are hydrocarbon solvents, such as toluene and xylene; and ether solvents, such as tetrahydrofuran, 2-methyltetrahydrofuran, and 4-methyltetrahydropyran. Preferred reactivity can be ensured by using the hydrocarbon solvents, such as toluene and xylene; and the ether solvents, such as tetrahydrofuran, 2-methyltetrahydrofuran, and 4-methyltetrahydropyran. More preferably, the solvents are tetrahydrofuran, 2-methyltetrahydrofuran, and 4-methyltetrahydropyran. Even better reactivity can be ensured by using the tetrahydrofuran, 2-methyltetrahydrofuran, and 4-methyltetrahydropyran.

[0131] Solvents can be used alone or in combination if needed. Solvents can be commercially available.

[0132] When a solvent is incorporated into the nucleophilic addition reaction, the amount of solvent used per mol of the nucleophile 3,7-dimethyldecyl compound (2) is preferably 30 to 5000 g, more preferably 50 to 3000 g, and even more preferably 100 to 1000 g. By using the preferred amount, the more preferred amount, and the even more preferred amount, preferred reactivity, and even more preferred reactivity can be ensured.

[0133] If desired, the nucleophilic addition reaction can be carried out in the presence of a catalyst.

[0134] Examples of catalysts include copper compounds, such as cuprous halides, such as cuprous chloride, cuprous bromide, and cuprous iodide, and copper halides, such as copper chloride, copper bromide, and copper iodide. The catalyst is preferably a cuprous halide. Preferred reactivity can be ensured by using said cuprous halide. Cuprous chloride is more preferably a catalyst. Even better reactivity can be ensured by using said cuprous chloride.

[0135] The catalyst can be used alone or in combination if needed. The catalyst can be commercially available.

[0136] For each mol of the nucleophile 3,7-dimethyldecyl compound (2), the amount of catalyst is preferably 0.0001 to 1.0 mol, more preferably 0.0005 to 0.3 mol, and even more preferably 0.001 to 0.1 mol. By using the preferred amounts, the more preferred amounts, and the even more preferred amounts, preferred reaction rates and / or post-treatments, more preferred reaction rates and / or post-treatments, and even more preferred response rates and / or post-treatments can be ensured.

[0137] The reaction temperature of the nucleophilic addition reaction varies depending on the nucleophile 3,7-dimethyldecyl compound (2) used, and is preferably -78 to 70°C, more preferably -20 to 50°C, and even more preferably 0 to 30°C. By using the preferred reaction temperature, the more preferred reaction temperature, and the even more preferred reaction temperature, preferred reactivity, and even more preferred reactivity can be ensured.

[0138] The reaction time for the nucleophilic addition reaction varies depending on the solvent used and / or the production scale, and is preferably from 0.5 to 100 hours. By using the preferred reaction time, preferred reactivity can be ensured.

[0139] Examples of purification methods for nucleophilic addition reactions include purification by silica gel column chromatography and purification by distillation. Distillation is preferred among the above purification methods. Using distillation purification ensures optimal industrial production.

[0140] (III) 1-Halo-3,7-dimethyldecane compound (8) and method for preparing 1-halo-3,7-dimethyldecane compound (8)

[0141] 1-Halo-3,7-dimethyldecane compound (8) can be prepared, for example, by converting 1-halo-2-methylpentane compound (12) into nucleophile 2-methylpentyl compound (6), and then coupling nucleophile 2-methylpentyl compound (6) with sulfonate compound (7), as shown in the following chemical reaction formula:

[0142]

[0143] (a) First, the nucleophile 2-methylpentyl compound (6) is explained in detail below. The nucleophile 2-methylpentyl compound (6) is represented by the following general formula (6):

[0144]

[0145] In the above general formula (6), M 2 Indicates Li, Mg, Z 2 CuZ 2 or CuLiZ 2And Z 2 This indicates a halogen atom or a 2-methylpentyl group. Halogen atom Z 2 Specific examples include chlorine, bromine, and iodine atoms. Halogen atoms (Z) 2 Preferably, chlorine and bromine atoms are used. Preferred reactivity can be ensured by using the chlorine and bromine atoms. Halogen atom Z 2 More preferably, it is a chlorine atom. By using the chlorine atom, even better reactivity can be ensured.

[0146] Specific examples of nucleophilic 2-methylpentyl compounds (6) include the following compounds:

[0147] 2-Methylpentyllithium (where M) 2 =Li);

[0148] 2-Methylpentyl magnesium halide compounds (where M) 2 =MgZ 2 Examples include 2-methylpentyl magnesium chloride, 2-methylpentyl magnesium bromide, and 2-methylpentyl magnesium iodide (i.e., Grignard reagents);

[0149] bis(2-methylpentyl)cuprate compounds (where M) 2 =CuZ 2 ), such as bis(2-methylpentyl)copperate; and

[0150] Gilman's reagent (where M) 2 =CuLiZ 2 ), such as bis(2-methylpentyl)copper lithium compounds, such as bis[2-methylpentyl]copper lithium (i.e., Gilman reagent).

[0151] A Grignard reagent, such as a 2-methylpentyl magnesium halide compound, is preferred. Preferred reactivity can be ensured by using such a Grignard reagent, such as a 2-methylpentyl magnesium halide compound.

[0152] (b) The method for preparing the above nucleophile 2-methylpentyl compound (6) is explained in detail below.

[0153] The nucleophile 2-methylpentyl compound (6) can be prepared from the following 1-halo-2-methylpentane compound (12).

[0154]

[0155] In the above general formula (12), X 4 Represents a halogen atom. Halogen atom X 4 Specific examples include chlorine, bromine, and iodine atoms. Halogen atom X 4 Preferably, chlorine and bromine atoms are used. Preferred reactivity can be ensured by using the chlorine and bromine atoms. Halogen atom X4 More preferably, it is a chlorine atom. By using the chlorine atom, even better reactivity can be ensured.

[0156] Specific examples of 1-halo-2-methylpentane compounds (12) include 1-chloro-2-methylpentane, 1-bromo-2-methylpentane, and 1-iodo-2-methylpentane. 1-chloro-2-methylpentane and 1-bromo-2-methylpentane are preferred. Preferred reactivity can be ensured by using said 1-chloro-2-methylpentane and 1-bromo-2-methylpentane. More preferably, 1-chloro-2-methylpentane is preferred. Further preferred reactivity can be ensured by using said 1-chloro-2-methylpentane.

[0157] Next, the preparation of the nucleophile 2-methylpentyl compound (6) will be described in detail, wherein M 2 MgZ 2 That is, 2-methylpentyl magnesium halide reagent (6:M) 2 =MgZ 2 (i.e., Grignard reagent) method.

[0158] For example, the Grignard reagent 2-methylpentyl magnesium halide reagent (6:M) can be prepared by reacting the above-mentioned 1-halo-2-methylpentane compound (12) with magnesium in a solvent. 2 =MgZ 2 As shown in the following chemical reaction formula:

[0159]

[0160] In the preparation of the 2-methylpentyl magnesium halide reagent (6), the amount of magnesium used is preferably 1.0 to 2.0 g atoms per mol of 1-halo-2-methylpentane compound (12). By using the preferred amount, optimal completion of the reaction can be ensured.

[0161] Examples of solvents include general solvents, such as ether solvents like tetrahydrofuran (THF), 2-methyltetrahydrofuran (2-MeTHF), diethyl ether, butyl ether, 4-methyltetrahydropyran (MTHP), cyclopentyl methyl ether, and 1,4-dioxane; and hydrocarbon solvents like hexane, heptane, benzene, toluene, xylene, and cumene. The solvents are preferably hydrocarbon solvents like toluene and xylene; and ether solvents like tetrahydrofuran, 2-methyltetrahydrofuran, and 4-methyltetrahydropyran. By using the hydrocarbon solvents, such as toluene and xylene; and the ether solvents, such as tetrahydrofuran, 2-methyltetrahydrofuran, and 4-methyltetrahydropyran, a preferred reaction rate for the formation of the Grignard reagent described above can be ensured. The solvents are more preferably tetrahydrofuran, 2-methyltetrahydrofuran, and 4-methyltetrahydropyran. By using the tetrahydrofuran, 2-methyltetrahydrofuran, and 4-methyltetrahydropyran, a more preferred reaction rate for the formation of the Grignard reagent described above can be ensured.

[0162] Solvents can be used alone or in combination if needed. Solvents can be commercially available.

[0163] For each mol of 1-halo-2-methylpentane compound (12), 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. By using the preferred amount, the more preferred amount, and the even more preferred amount, preferred reactivity, and even more preferred reactivity can be ensured.

[0164] The reaction temperature varies depending on the solvent used, and is preferably 30 to 120°C, more preferably 50 to 100°C, and even more preferably 60 to 80°C. By using the preferred reaction temperature, the more preferred reaction temperature, and the even more preferred reaction rate, preferred reactivity, and even more preferred reactivity can be ensured.

[0165] The reaction time varies depending on the solvent used and / or the production scale, and is preferably from 0.5 to 100 hours. By using the preferred reaction time, optimal reactivity can be ensured.

[0166] (c) The coupling reaction between the nucleophile 2-methylpentyl compound (6) and the sulfonate compound (7) is explained in detail below.

[0167] Sulfonate compounds (7) are represented by the following general formula (7):

[0168]

[0169] In the above general formula (7), X 2 Represents a halogen atom. Halogen atom X 2 Specific examples include chlorine, bromine, and iodine atoms. Halogen atom X 2 Preferably, chlorine and bromine atoms are used. Preferred reactivity can be ensured by using the chlorine and bromine atoms. Halogen atom X 2 More preferably, it is a chlorine atom. By using the chlorine atom, even better reactivity can be ensured.

[0170] R 1 This refers to a hydrocarbon group having 1 to 7 carbon atoms. Examples of hydrocarbon groups having 1 to 7 carbon atoms include straight-chain or branched alkyl groups having 1 to 5 carbon atoms, preferably 1 to 4 carbon atoms; and aryl groups having 6 to 7 carbon atoms.

[0171] Examples of straight-chain or branched alkyl groups having 1 to 5 carbon atoms include methyl, ethyl, n-propyl, isopropyl, n-butyl, 2-butyl, and n-pentyl. Examples of aryl groups having 6 to 7 carbon atoms include phenyl and tolyl. Straight-chain or branched alkyl groups having 1 to 7 carbon atoms are preferably phenyl and tolyl. Preferred reactivity can be ensured by using said phenyl and tolyl. Straight-chain or branched alkyl groups having 1 to 7 carbon atoms are more preferably phenyl. Further preferred reactivity can be ensured by using said phenyl.

[0172] Specific examples of sulfonate compounds (7) include the following compounds:

[0173] 5-Halo-3-methylmethanesulfonate compounds, such as 5-chloro-3-methylmethanesulfonate, 5-bromo-3-methylmethanesulfonate, and 5-iodo-3-methylmethanesulfonate;

[0174] 5-Halo-3-methylbenzenesulfonate compounds, such as 5-chloro-3-methylbenzenesulfonate, 5-bromo-3-methylbenzenesulfonate, and 5-iodo-3-methylbenzenesulfonate; and

[0175] 5-Halo-3-methyl-p-toluenesulfonate compounds, such as 5-chloro-3-methyl-p-toluenesulfonate, 5-bromo-3-methyl-p-toluenesulfonate, and 5-iodo-3-methyl-p-toluenesulfonate.

[0176] The sulfonate compound (7) is preferably 5-chloro-3-methylmethanesulfonate, 5-bromo-3-methylmethanesulfonate, 5-iodo-3-methylmethanesulfonate, 5-chloro-3-methylbenzenesulfonate, 5-bromo-3-methylbenzenesulfonate, 5-iodo-3-methylbenzenesulfonate, 5-chloro-3-methyl-p-toluenesulfonate, 5-bromo-3-methyl-p-toluenesulfonate, and 5-iodo-3-methyl-p-toluenesulfonate. Preferred reactivity can be ensured by using the aforementioned 5-chloro-3-methylmethanesulfonate, 5-bromo-3-methylmethanesulfonate, 5-iodo-3-methylmethanesulfonate, 5-chloro-3-methylbenzenesulfonate, 5-bromo-3-methylbenzenesulfonate, 5-iodo-3-methyl-p-toluenesulfonate, 5-bromo-3-methyl-p-toluenesulfonate, and 5-iodo-3-methyl-p-toluenesulfonate. The sulfonate compound (7) is more preferably 5-chloro-3-methylmethanesulfonate, 5-bromo-3-methylmethanesulfonate, 5-chloro-3-methylbenzenesulfonate, 5-bromo-3-methylbenzenesulfonate, 5-chloro-3-methyl-p-toluenesulfonate, and 5-bromo-3-methyl-p-toluenesulfonate. By using the aforementioned 5-chloro-3-methylmethanesulfonate, 5-bromo-3-methylmethanesulfonate, 5-chloro-3-toluenesulfonate, 5-bromo-3-methylbenzenesulfonate, 5-chloro-3-methyl-p-toluenesulfonate, and 5-bromo-3-methyl-p-toluenesulfonate, even better reactivity can be ensured. The sulfonate compound (7) is even more preferably 5-chloro-3-methylmethanesulfonate, 5-chloro-3-toluenesulfonate, and 5-chloro-3-methyl-p-toluenesulfonate. By using the aforementioned 5-chloro-3-methylmethanesulfonate, 5-chloro-3-methylbenzenesulfonate, and 5-chloro-3-methyl-p-toluenesulfonate, even better reactivity can be ensured. The sulfonate compound (7) is particularly preferred to be 5-chloro-3-methylbenzenesulfonate. By using the 5-chloro-3-methylbenzenesulfonate, particularly preferred reactivity can be ensured.

[0177] In the coupling reaction, the amount of sulfonate compound (7) per mol of nucleophile 2-methylpentyl compound (6) is preferably 0.7 to 2.0 mol, more preferably 0.8 to 1.7 mol, and even more preferably 0.9 to 1.4 mol. By using the preferred amount, the more preferred amount, and the even more preferred amount, preferred economy, and even more preferred economy can be ensured.

[0178] If necessary, a solvent can be incorporated into the coupling reaction. Examples of solvents include general solvents such as ether solvents, such as tetrahydrofuran (THF), 2-methyltetrahydrofuran (2-MeTHF), diethyl ether, butyl ether, 4-methyltetrahydropyran (MTHP), cyclopentyl methyl ether, and 1,4-dioxane; hydrocarbon solvents such as hexane, heptane, benzene, toluene, xylene, and cumene; and polar solvents such as N,N-dimethylformamide (DMF), N,N-dimethylacetamide (DMAC), N-methylpyrrolidone (NMP), and dimethyl sulfoxide (DMSO). The solvents used are 1,3-butyrolactone (GBL), acetonitrile, N,N'-dimethylacrylurea (DMPU), hexamethylphosphoric triamine (HMPA), dichloromethane, and chloroform. Preferably, the solvents are hydrocarbon solvents, such as toluene and xylene; and ether solvents, such as tetrahydrofuran, 2-methyltetrahydrofuran, and 4-methyltetrahydropyran. Preferred reactivity can be ensured by using the hydrocarbon solvents, such as toluene and xylene; and the ether solvents, such as tetrahydrofuran, 2-methyltetrahydrofuran, and 4-methyltetrahydropyran. More preferably, the solvents are tetrahydrofuran, 2-methyltetrahydrofuran, and 4-methyltetrahydropyran. Even better reactivity can be ensured by using the tetrahydrofuran, 2-methyltetrahydrofuran, and 4-methyltetrahydropyran.

[0179] Solvents can be used alone or in combination if needed. Solvents can be commercially available.

[0180] For each mol of the nucleophile 2-methylpentyl compound (6), 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. By using the preferred amount, the more preferred amount, and the even more preferred amount, preferred reactivity, and even more preferred reactivity can be ensured.

[0181] If desired, the coupling reaction of the nucleophile 2-methylpentyl compound (6) with the sulfonate compound (7) can be carried out in the presence of a catalyst.

[0182] Examples of catalysts include copper compounds, such as cuprous halides, such as cuprous chloride, cuprous bromide, and cuprous iodide, and copper halides, such as copper chloride, copper bromide, and copper iodide; iron compounds, such as ferrous(II) chloride, ferric(III) chloride, ferrous(II) bromide, ferric(III) bromide, ferrous(II) iodide, ferric(III) iodide, and ferric acetylacetone(III); silver compounds, such as silver chloride, silver nitrate, and silver acetate; titanium compounds, such as titanium tetrachloride, titanium tetrabromide, titanium methoxide(IV), titanium ethoxide(IV), titanium isopropoxide(IV), and titanium oxide(IV); palladium(II) compounds, such as dichlorobis(triphenylphosphine)palladium and dichloro[1,1'-bis(diphenylphosphine)ferrocene]palladium; and nickel compounds, such as nickel chloride, dichloro[1,2-bis(diphenylphosphine)ethane]nickel(II), and dichlorobis(triphenylphosphine)nickel(II). Copper compounds are preferred as catalysts. By using the copper compound, preferred reactivity and / or economy can be ensured. Copper halides, such as copper chloride, copper bromide, and copper iodide, are more preferred catalysts. By using the copper halides, such as copper chloride, copper bromide, and copper iodide, even better reactivity and / or economy can be ensured.

[0183] The catalyst can be used alone or in combination if needed. The catalyst can be commercially available.

[0184] For each mol of 1-halo-2-methylpentane compound (12), the amount of catalyst used is preferably 0.0001 to 1.0 mol, more preferably 0.0005 to 0.5 mol, and even more preferably 0.001 to 0.3 mol. By using the preferred amount, the more preferred amount, and the even more preferred amount, a preferred reaction rate and / or post-treatment, a more preferred reaction rate and / or post-treatment, and even a more preferred reaction rate and / or post-treatment can be ensured.

[0185] When the coupling reaction is carried out in the presence of a catalyst, a co-catalyst may be used if desired. Examples of co-catalysts include trialkyl phosphites having 3 to 9 carbon atoms, such as triethyl phosphite; and arylphosphine compounds having 18 to 44 carbon atoms, such as triphenylphosphine, tri-p-tolylphosphine, and 2,2'-bis(diphenylphosphine)-1,1'-binaphthyl (BINAP). Trialkyl phosphites are preferred as co-catalysts. Preferred reactivity is ensured by using said trialkyl phosphite. Triethyl phosphite is particularly preferred as a co-catalyst. Particularly preferred reactivity is ensured by using said triethyl phosphite.

[0186] If needed, the co-catalyst can be used alone or in combination. The co-catalyst can be commercially available.

[0187] For each mol of 1-halo-2-methylpentane compound (12), the amount of co-catalyst is preferably 0.0001 to 1.0 mol, more preferably 0.0005 to 0.5 mol, and even more preferably 0.001 to 0.3 mol.

[0188] When the coupling reaction is carried out in the presence of a catalyst, a lithium salt may be added if necessary. The lithium salt may be incorporated into the coupling reaction along with the aforementioned cocatalyst, or it may be incorporated alone without the cocatalyst. Examples of lithium salts include lithium halides, such as lithium chloride, lithium bromide, and lithium iodide; lithium nitrate; and lithium carbonate. Lithium halides, such as lithium chloride, and lithium nitrate are preferred. Preferred reactivity can be ensured by using said lithium halides, such as lithium chloride, and lithium nitrate.

[0189] Lithium salts can be used alone or in combination if needed. Lithium salts are commercially available.

[0190] In the coupling reaction, the amount of lithium salt used per mol of 1-halo-2-methylpentane compound (12) is preferably 0.0001 to 1.0 mol, more preferably 0.0005 to 0.5 mol, and even more preferably 0.001 to 0.3 mol. By using the preferred amount, the more preferred amount, and the even more preferred amount, preferred reactivity, and even more preferred reactivity can be ensured.

[0191] The reaction temperature of the coupling reaction varies depending on the nucleophile 2-methylpentyl compound (6) used, and is preferably -78 to 100°C, more preferably -25 to 70°C, even more preferably -10 to 50°C, and particularly preferably 10 to 35°C. By using the preferred reaction temperature, the more preferred reaction temperature, the even more preferred reaction temperature, and the particularly preferred reaction temperature, preferred reactivity, more preferred reactivity, even more preferred reactivity, and particularly preferred reactivity can be ensured.

[0192] The reaction time for the coupling reaction varies depending on the solvent used and / or the production scale, and is preferably from 0.5 to 100 hours. By using the preferred reaction time, preferred reactivity can be ensured.

[0193] Examples of purification methods for coupling reactions include purification by silica gel column chromatography and purification by distillation. Preferred industrial production can be ensured by using said distillation purification.

[0194] (IV) The following explains in detail how to synthesize alkyl 2,6,10-trimethyltetrazine ester compound (11) by converting 2-halo-6,10-dimethyltetrazine compound (1) into nucleophilic reagent 1,5,9-trimethyldodecyl compound (9), and then subjecting nucleophilic reagent 1,5,9-trimethyldodecyl compound (9) to nucleophilic substitution reaction with alkyl haloformate ester (10).

[0195]

[0196] (a) First, the nucleophile 1,5,9-trimethyldodecyl compound (9) is explained in detail below. The nucleophile 1,5,9-trimethyldodecyl compound (9) is represented by the following general formula (9):

[0197]

[0198] In the above general formula (9), M 3 Indicates Li, Mg, Z 3 CuZ 3 or CuLiZ 3 And Z 3 This indicates a halogen atom or 1,5,9-trimethyldodecyl. Halogen atom Z 3 Specific examples include chlorine, bromine, and iodine atoms. Halogen atoms (Z) 3 Preferably, chlorine and bromine atoms are used. Preferred reactivity can be ensured by using the chlorine and bromine atoms. Halogen atom Z 3 More preferably, it is a chlorine atom. By using the chlorine atom, even better reactivity can be ensured.

[0199] Specific examples of nucleophiles 1,5,9-trimethyldodecyl compounds (9) include the following compounds:

[0200] 1,5,9-Trimethyldodecyl lithium compounds (where M 3 =Li), such as 1,5,9-trimethyldodecyllithium;

[0201] 1,5,9-Trimethyldodecyl magnesium halide compounds (where M 3 =MgZ 3 Examples include 1,5,9-trimethyldodecyl magnesium chloride, 1,5,9-trimethyldodecyl magnesium bromide, and 1,5,9-trimethyldodecyl magnesium iodide (i.e., Grignard reagents);

[0202] Bis(1,5,9-trimethyldodecyl)cuprate compounds (where M 3 =CuZ 3 ), such as bis(1,5,9-trimethyldodecyl)cuprate; and

[0203] Gilman's reagent (where M) 3 =CuLiZ 3 ), such as bis(1,5,9-trimethyldodecyl)copper lithium compounds, such as bis(1,5,9-trimethyldodecyl)copper lithium (i.e., Gilman reagent).

[0204] A Grignard reagent, such as 1,5,9-trimethyldodecyl magnesium halide, is preferred. Preferred reactivity can be ensured by using the Grignard reagent, such as 1,5,9-trimethyldodecyl magnesium halide.

[0205] (b) The method for preparing the above nucleophile 1,5,9-trimethyldodecyl compound (9) is explained in detail below.

[0206] The nucleophile 1,5,9-trimethyldodecyl compound (9) can be prepared from the above-mentioned 2-halo-6,10-dimethyltridecane compound (1).

[0207] Next, the preparation of the nucleophile 1,5,9-trimethyldodecyl compound (9) is described in detail as an example, wherein M 3 MgZ 3 That is, 1,5,9-trimethyldodecyl magnesium halide reagent (9:M) 3 =MgZ 3 (i.e., Grignard reagent), the method.

[0208] For example, Grignard reagent 1,5,9-trimethyldodecyl magnesium halide (9:M) can be prepared by reacting the above-mentioned 2-halo-6,10-dimethyltridecane compound (1) with magnesium in a solvent. 3 =MgZ 3 As shown in the following chemical reaction formula:

[0209]

[0210] When preparing the nucleophile 1,5,9-trimethyldodecyl compound (9), the amount of magnesium used is preferably 1.0 to 2.0 g atoms per mol of 2-halo-6,10-dimethyltridecyl compound (1). By using this preferred amount, optimal completion of the reaction can be ensured.

[0211] Examples of solvents include general solvents, such as ether solvents like tetrahydrofuran (THF), 2-methyltetrahydrofuran (2-MeTHF), diethyl ether, butyl ether, 4-methyltetrahydropyran (MTHP), cyclopentyl methyl ether, and 1,4-dioxane; and hydrocarbon solvents like hexane, heptane, benzene, toluene, xylene, and cumene. The solvents are preferably hydrocarbon solvents like toluene and xylene; and ether solvents like tetrahydrofuran, 2-methyltetrahydrofuran, and 4-methyltetrahydropyran. By using the hydrocarbon solvents, such as toluene and xylene; and the ether solvents, such as tetrahydrofuran, 2-methyltetrahydrofuran, and 4-methyltetrahydropyran, a preferred reaction rate for the formation of the aforementioned Grignard reagent can be ensured. The solvents are more preferably tetrahydrofuran, 2-methyltetrahydrofuran, and 4-methyltetrahydropyran. By using the tetrahydrofuran, 2-methyltetrahydrofuran, and 4-methyltetrahydropyran, a more preferred reaction rate for the formation of the aforementioned Grignard reagent can be ensured.

[0212] Solvents can be used alone or in combination if needed. Solvents can be commercially available.

[0213] For each mol of 2-halo-6,10-dimethyltridecane compound (1), 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. By using the preferred amount, the more preferred amount, and the even more preferred amount, preferred reactivity, and even more preferred reactivity can be ensured.

[0214] The reaction temperature varies depending on the solvent used, and is preferably 30 to 120°C, more preferably 50 to 100°C, and even more preferably 60 to 80°C. By using the preferred reaction temperature, the more preferred reaction temperature, and the even more preferred reaction temperature, preferred reactivity, and even more preferred reactivity can be ensured.

[0215] The reaction time varies depending on the solvent used and / or the production scale, and is preferably from 0.5 to 100 hours. By using the preferred reaction time, preferred reactivity can be ensured.

[0216] (c) The method for preparing 2,6,10-trimethyltridecanoic acid alkyl ester compound (11) by subjecting the nucleophile 1,5,9-trimethyldodecyl compound (9) to a nucleophilic substitution reaction with a haloformic acid alkyl ester (10) is explained in detail below.

[0217] The above-mentioned alkyl halogenated carboxylic acid esters (10) are represented by the following general formula (10):

[0218]

[0219] In the above general formula (10), X 3Represents a halogen atom. Halogen atom X 3 Specific examples include chlorine, bromine, and iodine atoms. Halogen atom X 3 Preferably, chlorine and bromine atoms are used. Preferred reactivity can be ensured by using the chlorine and bromine atoms. Halogen atom X 3 More preferably, it is a chlorine atom. By using the chlorine atom, even better reactivity can be ensured.

[0220] R 2 The alkyl group has 1 to 12 carbon atoms, preferably 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms, even more preferably 1 to 4 carbon atoms, even more preferably 1 to 2 carbon atoms, and particularly preferably 1 carbon atom.

[0221] Specific examples of alkyl groups having 1 to 12 carbon atoms include methyl, ethyl, n-propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, and dodecyl.

[0222] The alkyl group is preferably methyl, ethyl, hexyl, and decyl, more preferably methyl and ethyl, and even more preferably methyl.

[0223] Specific examples of alkyl haloformates (10) include the following:

[0224] Alkyl chloroformate compounds, such as methyl chloroformate, ethyl chloroformate, propyl chloroformate, isopropyl chloroformate, butyl chloroformate, pentyl chloroformate, hexyl chloroformate, heptyl chloroformate, octyl chloroformate, nonyl chloroformate, decyl chloroformate, undecyl chloroformate, and dodecyl chloroformate.

[0225] Alkyl bromoformate compounds, such as methyl bromoformate, ethyl bromoformate, propyl bromoformate, isopropyl bromoformate, butyl bromoformate, pentyl bromoformate, hexyl bromoformate, heptyl bromoformate, octyl bromoformate, nonyl bromoformate, decyl bromoformate, undecyl bromoformate, and dodecyl bromoformate; and

[0226] Alkyl iodoformate compounds, such as methyl iodoformate, ethyl iodoformate, propyl iodoformate, isopropyl iodoformate, butyl iodoformate, pentyl iodoformate, hexyl iodoformate, heptyl iodoformate, octyl iodoformate, nonyl iodoformate, decyl iodoformate, undecyl iodopropionate, and dodecyl iodoformate.

[0227] The aforementioned compounds are preferably alkyl chloroformate compounds, such as methyl chloroformate, ethyl chloroformate, propyl chloroformate, isopropyl chloroformate, butyl chloroformate, pentyl chloroformate, hexyl chloroformate, heptyl chloroformate, octyl chloroformate, nonyl chloroformate, decyl chloroformate, undecyl chloroformate, and dodecyl chloroformate; and alkyl bromoformate compounds, such as methyl bromoformate, ethyl bromoformate, propyl bromoformate, isopropyl bromoformate, butyl bromoformate, pentyl bromoformate, hexyl bromoformate, heptyl bromoformate, octyl bromoformate, nonyl bromoformate, decyl bromoformate, and undecyl bromoformate. Alkyl esters and dodecyl bromoformate; more preferably alkyl chloroformate compounds, such as methyl chloroformate, ethyl chloroformate, propyl chloroformate, isopropyl chloroformate, butyl chloroformate, pentyl chloroformate, hexyl chloroformate, heptyl chloroformate, octyl chloroformate, nonyl chloroformate, decyl chloroformate, undecyl chloroformate, and dodecyl chloroformate; even more preferably methyl chloroformate, ethyl chloroformate, propyl chloroformate, isopropyl chloroformate, butyl chloroformate, pentyl chloroformate, and hexyl chloroformate; even more preferably methyl chloroformate and ethyl chloroformate; particularly preferably methyl chloroformate.

[0228] The above-mentioned alkyl ester compound (11) of 2,6,10-trimethyltridecanoate is represented by the following general formula (11):

[0229]

[0230] R 2 The alkyl group has 1 to 12 carbon atoms, preferably 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms, even more preferably 1 to 4 carbon atoms, further more preferably 1 to 2 carbon atoms, and particularly preferably 1 carbon atom.

[0231] Specific examples of alkyl groups having 1 to 12 carbon atoms include methyl, ethyl, n-propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, and dodecyl.

[0232] The alkyl group is preferably methyl, ethyl, hexyl, and decyl, more preferably methyl and ethyl, and even more preferably methyl.

[0233] Specific examples of alkyl ester compounds of 2,6,10-trimethyltriadecanoate (11) include alkyl ester compounds of 2,6,10-trimethyltriadecanoate, such as methyl 2,6,10-trimethyltriadecanoate, ethyl 2,6,10-trimethyltriadecanoate, propyl 2,6,10-trimethyltriadecanoate, butyl 2,6,10-trimethyltriadecanoate, pentyl 2,6,10-trimethyltriadecanoate, hexyl 2,6,10-trimethyltriadecanoate, heptyl 2,6,10-trimethyltriadecanoate, octyl 2,6,10-trimethyltriadecanoate, nonyl 2,6,10-trimethyltriadecanoate, decyl 2,6,10-trimethyltriadecanoate, undecyl 2,6,10-trimethyltriadecanoate, and dodecyl 2,6,10-trimethyltriadecanoate.

[0234] The above-mentioned compounds are preferably methyl 2,6,10-trimethyltetrate, ethyl 2,6,10-trimethyltetrate, ethyl 2,6,10-trimethyltetrate and decyl 2,6,10-trimethyltetrate; more preferably methyl 2,6,10-trimethyltetrate and ethyl 2,6,10-trimethyltetrate; and even more preferably methyl 2,6,10-trimethyltetrate.

[0235] In the above nucleophilic substitution reaction, the amount of alkyl haloformate (10) used per mol of nucleophile 1,5,9-trimethyldodecyl compound (9) is preferably 0.7 to 2.0 mol, more preferably 0.8 to 1.7 mol, and even more preferably 0.9 to 1.4 mol. By using the preferred amount, the more preferred amount, and the even more preferred amount, preferred economy, and even more preferred economy can be ensured.

[0236] If desired, a solvent can be incorporated into the nucleophilic substitution reaction. Examples of solvents include general solvents such as ether solvents, such as tetrahydrofuran (THF), 2-methyltetrahydrofuran (2-MeTHF), diethyl ether, butyl ether, 4-methyltetrahydropyran (MTHP), cyclopentyl methyl ether, and 1,4-dioxane; hydrocarbon solvents such as hexane, heptane, benzene, toluene, xylene, and cumene; and polar solvents such as N,N-dimethylformamide (DMF), N,N-dimethylacetamide (DMAC), N-methylpyrrolidone (NMP), and dimethyl sulfoxide (DMSO). The solvents used are 1,3-butyrolactone (GBL), acetonitrile, N,N'-dimethylacrylurea (DMPU), hexamethylphosphoric triamine (HMPA), dichloromethane, and chloroform. Preferably, the solvents are hydrocarbon solvents, such as toluene and xylene; and ether solvents, such as tetrahydrofuran, 2-methyltetrahydrofuran, and 4-methyltetrahydropyran. Preferred reactivity can be ensured by using the hydrocarbon solvents, such as toluene and xylene; and the ether solvents, such as tetrahydrofuran, 2-methyltetrahydrofuran, and 4-methyltetrahydropyran. More preferably, the solvents are tetrahydrofuran, 2-methyltetrahydrofuran, and 4-methyltetrahydropyran. Even better reactivity can be ensured by using the tetrahydrofuran, 2-methyltetrahydrofuran, and 4-methyltetrahydropyran.

[0237] Solvents can be used alone or in combination if needed. Solvents can be commercially available.

[0238] For each mol of the nucleophile 1,5,9-trimethyldodecyl compound (9), 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. By using the preferred amount, the more preferred amount, and the even more preferred amount, preferred reactivity, and even more preferred reactivity can be ensured.

[0239] If desired, a base can be incorporated into the nucleophilic substitution reaction. Examples of bases include pyridine and 4-dimethylaminopyridine (DMAP). 4-Dimethylaminopyridine is preferred. By using said 4-dimethylaminopyridine, preferred reactivity can be ensured.

[0240] Alkali can be used alone or in combination if needed. Alkali can be commercially available.

[0241] In the nucleophilic substitution reaction, the amount of base used is preferably 0.0001 to 1.0 mol per mol of 2-halo-6,10-dimethyltridecane compound (1), more preferably 0.001 to 0.3 mol. By using the preferred and more preferred amounts, preferred reactivity and more preferred reactivity can be ensured.

[0242] The reaction temperature of the nucleophilic substitution reaction varies depending on the nucleophile used, 1,5,9-trimethyldodecyl compound (9), and is preferably -78 to 100°C, more preferably -25 to 60°C, even more preferably -15 to 30°C, and particularly preferably -10 to 15°C. By using the preferred reaction temperature, the more preferred reaction temperature, the even more preferred reaction temperature, and the particularly preferred reaction temperature, preferred reactivity, more preferred reactivity, even more preferred reactivity, and particularly preferred reactivity can be ensured.

[0243] The reaction time for the nucleophilic substitution reaction varies depending on the solvent used and / or the production scale, and is preferably from 0.5 to 100 hours. By using this preferred reaction time, preferred reactivity can be ensured.

[0244] Examples of purification methods for nucleophilic substitution reactions include purification by silica gel column chromatography and purification by distillation. Distillation is preferred among the above purification methods. Preferred industrial production can be ensured by using said distillation purification. The olefins in the reaction mixture resulting from the removal of hydrogen halides in the halogenation step prior to purification can be completely separated by distillation in this step.

[0245] Therefore, according to one embodiment of the present invention, the synthetic intermediate 2-halo-6,10-dimethyltridecane compound (1) can be prepared readily and efficiently. According to one embodiment of the present invention, the alkyl 2,6,10-trimethyltridecanoate compound comprising the pheromone methyl 2,6,10-trimethyltridecanoate of the neotropical brown bug (Euschistus heros) can be comprehensively prepared from the 2-halo-6,10-dimethyltridecane compound (1) with high ease of preparation and fewer steps. Specifically, since the target compound can be selectively synthesized, the alkyl 2,6,10-trimethyltridecanoate ester (11) can be prepared efficiently without separation by column chromatography or the like, and the alkyl 2,6,10-trimethyltridecanoate compound can be prepared alone in the final step.

[0246] Example

[0247] The present invention is described with reference to the following embodiments. It should be noted that the present invention is not limited to or not restricted by these embodiments.

[0248] Unless otherwise stated, the term "purity" as used herein refers to the percentage of area in gas chromatography (GC). The term "product ratio" refers to the ratio of the percentage of area in GC. The term "yield" is calculated from the percentage of area determined by GC.

[0249] In the embodiments, reaction monitoring and yield calculation were performed under the following GC conditions.

[0250] GC conditions: GC: GC-2014 capillary gas chromatograph (Shimadzu Corporation); 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: 100℃, rising at a rate of 5℃ / min, up to 230℃.

[0251] Taking into account the purity (%GC) of the starting materials and products, the yield is calculated according to the following equation.

[0252] Yield (%) = {[(weight of product obtained through reaction × %GC) / molecular weight of product]} [(Weight of starting material in reaction × %GC) / Molecular weight of starting material] × 100

[0253] THF represents tetrahydrofuran, Ph represents phenyl, and GBL represents... -Butyrolactone.

[0254] Example 1: 1-Halo-3,7-dimethyldecane (8:X) 2 Preparation of Cl)

[0255]

[0256] Magnesium (275.55 g, 11.34 g atom) and tetrahydrofuran (3240.00 g) were placed in a reactor at room temperature and stirred at 60 to 65 °C for 36 minutes. Then, 1-chloro-2-methylpentane compound (12:X) was added at 60 to 75 °C. 4 =Cl)(1302.69 g, 10.80 mol, 100% purity) was added dropwise to the reactor. After the addition was complete, the reaction mixture was stirred at 75 to 80 °C for 3 hours to form 2-methylpentylmagnesium chloride (6:M 2 =MgCl).

[0257] Then, copper chloride (7.26 g, 0.054 mol), lithium chloride (4.59 g, 0.11 mol), tetrahydrofuran (3600.00 g), and 5-chloro-3-methylpentylbenzenesulfonate (7:X) were added. 2 =Cl,R 1 =Ph)(3377.04 g, 10.26 mol, purity 84.09%) was placed in another reactor, and then the above-mentioned 2-methylpentylmagnesium chloride (6:M) was added at 15 to 25 °C. 2 =MgCl) was added dropwise to the other reactor. After the addition was complete, the reaction mixture was stirred at 20 to 30°C for 4.5 hours. Methanol (1687.50 g) and water (780.00 g) were added to the reaction mixture, followed by phase separation. The resulting organic layer was then concentrated under reduced pressure, and the concentrate was distilled under reduced pressure to form 1-halo-3,7-dimethyldecane (8:X) 2 =Cl)(1657.24 g, 8.04 mol, purity 99.36%, bp = 90.1 to 96.1 °C / 0.044 kPa (0.33 mmHg)), yield 78.37%. Although 1-halo-3,7-dimethyldecane (8:X) was obtained from this, 2 =Cl) concentrated solution contains 1-halo-3,7-dimethyldecane (8:X) 2=Cl) and 1-chloro-2-methylpentane compound (12:X) 4 =Cl) reaction forms 4,8,12-trimethylpentadecane, but 4,8,12-trimethylpentadecane can be separated by the above distillation, and the content of the remaining 4,8,12-trimethylpentadecane after distillation is 0.5% or less.

[0258] The following is the 1-halo-3,7-dimethyldecane (8:X) obtained from this process. 2 =Cl) spectral data.

[0259] Nuclear magnetic resonance spectroscopy: 1 H-NMR (500 MHz, CDCl3): δ = 0.83-0.86 (3H, m), 0.86-0.92(6H, m), 1.12-1.43 (11H, m), 1.53-1.84 (3H, m), 3.50-3.62 (2H, m); 13 C-NMR (125 MHz, CDCl3): δ = 14.39, 19.05, 19.11, 19.60, 19.67, 20.12, 24.22, 30.37,30.41, 32.44, 32.47, 36.89, 36.94, 37.20, 37.25, 39.34, 39.44, 39.76, 39.84,43.37.

[0260] Mass spectrometry: EI mass spectrometry (70 eV): m / z 170 (M + -34), 155, 141, 127, 113, 98, 85, 71,57, 43, 29.

[0261] Infrared absorption spectrum (D-ATR): = 2957, 2928, 2871, 1463, 1379, 729, 659.

[0262] Example 2: Preparation of 6,10-dimethyl-2-tetranol (4)

[0263]

[0264] Magnesium (89.30 g, 3.68 g atoms) and tetrahydrofuran (1050.00 g) were placed in a reactor at room temperature and then stirred at 60 to 65 °C for 18 minutes. Then, 1-halo-3,7-dimethyldecane (8:X) prepared as in Example 1 was added at 60 to 75 °C. 2=Cl)(721.35 g, 3.50 mol, purity 99.36%) was added dropwise to the reactor. After the addition was complete, the reaction mixture was stirred at 70 to 75 °C for 3.5 hours to form 3,7-dimethyldecyl magnesium chloride (2:M 1 =MgCl).

[0265] The internal temperature of the reactor was then cooled to 0-10°C. Cuprous chloride (0.73 g, 0.0070 mol, 95% purity) was added to the reactor, followed by the dropwise addition of propylene oxide (233.77 g, 4.03 mol) at 5-30°C. After the addition was complete, the reaction mixture was stirred at 15-25°C for 2 hours. An aqueous solution of acetic acid (prepared from acetic acid (477.67 g) and water (1433.09 g)) and hexane (339.67 g) were then added to the reaction mixture, followed by phase separation. The resulting organic layer was then concentrated under reduced pressure, and the concentrate was distilled under reduced pressure to form 6,10-dimethyl-2-tridecaneol (4) (743.97 g, 3.19 mol, 97.85% purity, bp = 123.0-138.9°C / 0.093 kPa (0.70 mmHg)) in 91.05% yield.

[0266] The following are the spectral data of 6,10-dimethyl-2-tetaneol (4) obtained therefrom.

[0267] Nuclear magnetic resonance spectroscopy: 1 H-NMR (500 MHz, CDCl3): δ = 0.86 (9H, quin-like), 1.49(1H, br.s), 1.00-1.48 (21H, m), 3.79 (1H, tq, J = 6.1 Hz, 6.1 Hz); 13 C-NMR (125 MHz, CDCl3): δ = 14.40, 19.62, 19.68, 20.13, 23.23, 23.46, 23.49, 24.43,32.46, 32.48, 32.72, 32.74, 32.76, 36.99, 37.02, 37.08, 37.11, 37.31, 37.35,37.40, 39.37, 39.47, 39.68, 39.71, 68.18, 68.21.

[0268] Mass spectrometry: EI mass spectrometry (70 eV): m / z 227 (M + -1), 210, 182, 168, 154, 125, 111, 97,84, 69, 57, 45, 29.

[0269] Infrared absorption spectrum: (D-ATR): = 3334, 2958, 2927, 1463, 1377, 1120, 739.

[0270] Example 3: 2-Chloro-6,10-dimethyltridecane (1:X) 1 Preparation of Cl)

[0271]

[0272] The 6,10-dimethyl-2-tetaneol (4) (466.88 g, 2.00 mol, purity 97.85%), pyridine (237.30 g, 2.40 mol), and GBL (800.00 g) prepared as in Example 2 were placed in a reactor and then stirred at 0 to 10 °C for 42 minutes.

[0273] Then, benzenesulfonyl chloride (PhSO2Cl) (423.86 g, 3.00 mol) was added dropwise at 0 to 10 °C. After the addition was complete, the reaction mixture was heated to 60 to 65 °C and stirred for 20 hours. After stirring was complete, water (600.00 g) and hexane (500.00 g) were added to the reaction mixture, followed by phase separation. The aqueous layer was removed to obtain the organic layer. The organic layer obtained therefrom was washed with an aqueous solution of sodium hydroxide (25% by mass of sodium hydroxide and water (526.36 g) (210.51 g)) and then phase separated. The reaction mixture was then washed with an aqueous solution of acetic acid (prepared from acetic acid (41.93 g) and water (526.36 g)) and then phase separated. The reaction mixture was then washed with an aqueous solution of sodium bicarbonate (prepared from sodium bicarbonate (20.92 g) and water (526.36 g)) and then phase separated. The resulting organic layer was then concentrated under reduced pressure, and the concentrate was distilled under reduced pressure to form a 2-halo-6,10-dimethyltridecane compound (1:X). 1 =Cl)(444.75 g, 1.64 mol, purity 91.25%, bp = 107.1 to 119.0 °C / 0.044 kPa (0.33 mmHg)), yield 82.18%. An elimination reaction was carried out in the reaction to form an olefin compound, such as 6,10-dimethyl-1-tetrazene, with an overall yield of 8.0%. The distilled 2-halo-6,10-dimethyltetrazane compound (1:X) 1 =Cl) contains 6.5% of the above-mentioned olefins.

[0274] The following is the 2-chloro-6,10-dimethyltridecane (1:X) obtained therefrom. 1 =Cl) spectral data.

[0275] Nuclear magnetic resonance spectroscopy: 1 H-NMR (500 MHz, CDCl3): δ = 0.82-0.91 (9H, m), 1.02-1.56(19H, m), 1.60-1.76 (2H, m), 4.03 (1H, tq, J = 6.5 Hz, 6.5 Hz); 13 C-NMR (125MHz, CDCl3): δ = 14.40, 19.55, 19.63, 19.67, 19.69, 20.14, 24.14, 24.17,24.40, 24.42, 25.33, 25.39, 32.47, 32.49, 32.63, 32.66, 32.68, 36.40, 36.46,36.48, 36.55, 37.23, 37.27, 37.31, 37.34, 37.37, 37.39, 39.37, 39.47, 40.66,40.71, 58.93.

[0276] Mass spectrometry: EI mass spectrometry (70 eV): m / z 210 (M + -36), 195, 182, 167, 154, 133, 111, 97, 85, 71, 55, 43, 29.

[0277] Infrared absorption spectrum: (D-ATR): = 2956, 2927, 1462, 1378, 740, 616.

[0278] Example 4: Methyl 2,6,10-trimethyltridecanoate (11:R) 2 Preparation of CH3)

[0279]

[0280] Magnesium (40.08 g, 1.65 g atom) and tetrahydrofuran (471.30 g) were placed in a reactor at room temperature and then stirred at 60 to 65 °C for 32 minutes. Then, 2-chloro-6,10-dimethyltridecane (1:X) prepared as in Example 3 was added at 60 to 75 °C. 1 =Cl)(425.00 g, 1.57 mol, purity 91.25%) was added dropwise to the reactor. After the addition was complete, the reaction mixture was stirred at 75 to 80 °C for 2 hours to form 1,5,9-trimethyldodecyl magnesium chloride (9:M 3 =MgCl).

[0281] Then, methyl chloroformate (178.13 g, 1.89 mol, 100% purity) and tetrahydrofuran (314.20 g) were placed in another reactor, different from the reactor described above. The internal temperature of this other reactor was cooled to 0 to 10 °C, and then the above-mentioned 1,5,9-trimethyldodecyl magnesium chloride (9:M) was added at an internal temperature of 0 to 10 °C. 3 =MgCl) was added dropwise to the other reactor. After the addition was complete, the reaction mixture was stirred at 0 to 10°C for 3 hours. Then, an aqueous acetic acid solution (prepared from acetic acid (9.57 g) and water (538.63 g)) was added to the reaction mixture, followed by phase separation. The resulting organic layer was then concentrated under reduced pressure, and the concentrate was distilled under reduced pressure to form methyl 2,6,10-trimethyltridecanoate (11:R) 2 =CH3)(335.18 g, 1.21 mol, purity 97.96%, bp = 140.1 to 149.0 °C / 0.045 kPa (0.34 mmHg)), yield 77.26%. Alkenes that could not be separated in the previous steps, such as 6,10-dimethyl-1-tetrate, were completely separated by distillation and were not present in methyl 2,6,10-trimethyltetrate after distillation.

[0282] The following is the methyl 2,6,10-trimethyltridecanoate (11:R) obtained from this process. 2 Spectral data of CH3.

[0283] Nuclear magnetic resonance spectroscopy: 1 H-NMR (500 MHz, CDCl3): δ =; 0.83 (6H, d-like, J = 6.5Hz), 0.87 (3H, t, J = 6.9 Hz), 1.00-1.67 (21H, m), 2.43 (1H, tq, J = 6.9 Hz,6.9 Hz), 3.66 (3H, s) 13 C-NMR (125 MHz, CDCl3): δ = 14.38, 16.99, 17.10, 19.56,19.61, 19.67, 20.11, 24.41, 24.64, 24.66, 24.69, 32.46, 32.48, 32.58, 32.62,34.09, 34.13, 36.81, 36.90, 37.28, 37.31, 37.33, 37.36, 37.39, 39.37, 39.44,39.46, 51.40, 177.39.

[0284] Mass spectrometry: EI mass spectrometry (70 eV): m / z 270 (M + ), 255, 241, 227, 213, 199, 180, 157,143, 129, 111, 88, 43, 29.

[0285] Infrared absorption spectrum: (D-ATR): = 2955, 2928, 1741, 1463, 1378, 1195, 1167,740.

[0286] Example 5: Hexyl 2,6,10-trimethyltridecanoate (11:R) 2 Preparation of (CH2)5CH3)

[0287]

[0288] Magnesium (3.25 g, 0.13 g atom) and tetrahydrofuran (38.26 g) were placed in a reactor at room temperature and then stirred at 60 to 65 °C for 18 minutes. Then, 2-chloro-6,10-dimethyltridecane (1:X) prepared as in Example 3 was added at 60 to 75 °C. 1 =Cl)(34.24 g, 0.13 mol, purity 91.92%) was added dropwise to the reactor. After the addition was complete, the reaction mixture was stirred at 75 to 80 °C for 2 hours to form 1,5,9-trimethyldodecyl magnesium chloride (9:M 3 =MgCl).

[0289] Then, hexyl chloroformate (25.19 g, 0.15 mol, 100% purity) and tetrahydrofuran (25.50 g) were placed in another reactor, different from the one described above, and the internal temperature of this other reactor was cooled to 0 to 10 °C. Then, the above-mentioned 1,5,9-trimethyldodecyl magnesium chloride (9:M) was added at an internal temperature of 0 to 10 °C. 3 =MgCl) was added dropwise to the other reactor. After the addition was complete, the reaction mixture was stirred at 0 to 10 °C for 2.5 hours. Then, an aqueous acetic acid solution (prepared from acetic acid (0.78 g) and water (43.71 g)) was added to the reaction mixture, followed by phase separation. The resulting organic layer was then concentrated under reduced pressure, and the concentrate was purified by silica gel column chromatography (hexane:ethyl acetate = 50:1 to 20:1) to form 2,6,10-trimethyltridecanoic acid hexyl ester (11:R 2 =(CH2)5CH3)(39.41g, 0.11mol, purity 97.48%), yield 88.44%.

[0290] The following is the 2,6,10-trimethyltridecanoic acid hexyl ester (11:R) obtained from this process. 2 Spectral data of (CH2)5CH3.

[0291] Nuclear magnetic resonance spectroscopy: 1 H-NMR (500 MHz, CDCl3): δ = 0.83 (6H, d-like, J = 6.5 Hz), 0.88 (6H, q-like, J = 6.9 Hz), 1.01-1.11 (4H, m), 1.13 (3H, d, J = 6.9 Hz), 1.18-1.42 (19H, m), 1.58-1.68 (3H, quin-like, J = 6.9 Hz), 2.42 (1H, tq, J =6.9 Hz), 4.01-4.10 (2H, m); 13 C-NMR (125 MHz, CDCl3): δ = 13.98, 14.39, 17.08,17.18, 19.57, 19.61, 19.63, 19.67, 20.12, 22.53, 24.42, 24.67, 24.70, 25.60,28.64, 31.43, 32.47, 32.49, 32.63, 32.65, 32.67, 34.15, 34.18, 36.86, 36.96,37.32, 37.35, 37.40, 39.37, 39.47, 39.63, 39.66, 64.27, 177.02.

[0292] Mass spectrometry: EI mass spectrometry (70 eV): m / z 340 (M + ), 257, 227, 199, 180, 158, 129, 113, 97, 74, 43.

[0293] Infrared absorption spectrum: (D-ATR): = 2956, 2929, 1737, 1463, 1378, 1259, 1169.

[0294] Example 6: Decyl 2,6,10-trimethyltridecanoate (11:R) 2 Preparation of (CH2)9CH3)

[0295]

[0296] Magnesium (2.31 g, 0.095 g atom) and tetrahydrofuran (27.18 g) were placed in a reactor at room temperature and then stirred at 60 to 65 °C for 18 minutes. Then, 2-chloro-6,10-dimethyltridecane (1:X) prepared as in Example 3 was added at 60 to 75 °C. 1 =Cl)(24.33 g, 0.091 mol, purity 91.92%) was added dropwise to the reactor. After the addition was complete, the reaction mixture was stirred at 75 to 80 °C for 2 hours to form 1,5,9-trimethyldodecyl magnesium chloride (9:M 3 =MgCl).

[0297] Then, decyl chloroformate (24.00 g, 0.11 mol, 100% purity) and tetrahydrofuran (18.12 g) were placed in another reactor, different from the one described above, and the internal temperature of this other reactor was cooled to 0 to 10 °C. Then, the above-mentioned 1,5,9-trimethyldodecyl magnesium chloride (9:M) was added at an internal temperature of 0 to 10 °C. 3 =MgCl) was added dropwise to the other reactor. After the addition was complete, the reaction mixture was stirred at 0 to 10 °C for 2.5 hours. Then, an aqueous acetic acid solution (prepared from acetic acid (0.55 g) and water (31.06 g)) was added to the reaction mixture, followed by phase separation. The resulting organic layer was then concentrated under reduced pressure, and the concentrate was purified by silica gel column chromatography (hexane:ethyl acetate = 50:1 to 20:1) to form decyl 2,6,10-trimethyltridecanoate (11:R 2 =(CH2)9CH3)(31.28g, 0.078mol, purity 98.41%), yield 85.66%.

[0298] The following is the decyl 2,6,10-trimethyltridecanoate (11:R) obtained from this process. 2 Spectral data of (CH2)9CH3).

[0299] Nuclear magnetic resonance spectroscopy: 1 H-NMR (500 MHz, CDCl3): δ = 0.83 (6H, d-like, J = 6.9 Hz), 0.87 (6H, td, J = 7.1 Hz, 2.7 Hz), 1.01-1.11 (4H, m), 1.13 (3H, d, J = 6.9Hz), 1.19-1.41 (26H, m), 1.57-1.68 (3H, m), 2.42 (2H, tq, J = 6.9 Hz, 6.9Hz), 4.01-4.11 (2H, m); 13C-NMR (125 MHz, CDCl3): δ = 14.09, 14.40, 17.08,17.18, 19.58, 19.61, 19.64, 19.67, 20.12, 20.14, 22.67, 24.43, 24.69, 25.94,28.68, 29.25, 29.30, 29.53, 31.88, 32.48, 32.49, 32.63, 32.65, 32.67, 34.16,34.18, 36.87, 36.96, 37.31, 37.33, 37.36, 37.38, 37.41, 39.38, 39.48, 39.64, 39.66, 64.28, 177.03.

[0300] Mass spectrometry: EI mass spectrometry (70 eV): m / z 396 (M + ), 325, 283, 257, 214, 180, 140, 115, 97, 74, 43.

[0301] Infrared absorption spectrum: (D-ATR): = 2956, 2926, 1737, 1463, 1378, 1168.

Claims

1. The following 2-halo-6,10-dimethyltridecane compounds of general formula (1): Where X 1 This represents a halogen atom.

2. A method for preparing 2-halo-6,10-dimethyltridecane compounds of the following general formula (1): Where X 1 Represents halogen atoms, The method includes the following steps: Nucleophilic 3,7-dimethyldecyl compounds of the following general formula (2): Where M 1 Indicates Li, Mg, Z 1 CuZ 1 or CuLiZ 1 And Z 1 This indicates a halogen atom or a 3,7-dimethyldecyl group. It undergoes a nucleophilic addition reaction with propylene oxide of the following formula (3): To form 6,10-dimethyl-2-tridecaneol of formula (4): and The 6,10-dimethyl-2-tetaneol (4) obtained therefrom is reacted with a halogenating agent (5) to form the above-mentioned 2-halo-6,10-dimethyltetane compound (1).

3. The method for preparing 2-halo-6,10-dimethyltridecane compound (1) according to claim 2, further comprising the following steps: Make the following nucleophile 2-methylpentyl compound of general formula (6): Where M 2 Indicates Li, Mg, Z 2 CuZ 2 or CuLiZ 2 And Z 2 Indicates a halogen atom or a 2-methylpentyl group. It undergoes a coupling reaction with sulfonate compounds (7) of the following general formula (7): Where X 2 Represents a halogen atom, and R 1 This indicates a hydrocarbon group having 1 to 7 carbon atoms. To form 1-halo-3,7-dimethyldecane compounds of the following general formula (8): Where X 2 Represents halogen atoms, and The resulting 1-halo-3,7-dimethyldecane compound (8) was converted into the above-mentioned nucleophile 3,7-dimethyldecyl compound (2).

4. A method for preparing alkyl ester compounds of 2,6,10-trimethyltridecanoic acid of the following general formula (11): Where R 2 Indicates an alkyl group having 1 to 12 carbon atoms. The method includes the following steps: The following 2-halo-6,10-dimethyltridecane compounds of general formula (1): Where X 1 Represents halogen atoms, The nucleophile 1,5,9-trimethyldodecyl compound of the following general formula (9) is converted: and The nucleophile 1,5,9-trimethyldodecyl compound (9) obtained therefrom is then subjected to a nucleophilic substitution reaction with an alkyl haloformate of the following general formula (10): Where X 4 Represents a halogen atom, and R 2 Indicates an alkyl group having 1 to 12 carbon atoms. To form the above-mentioned alkyl ester compound 2,6,10-trimethyltridecanoate (11).

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