阅读说明：本技术 制备甲炔基烷氧甲基醚化合物的方法和由其制备共轭二烯化合物的方法 (Method for producing alkynylalkoxymethyl ether compound and method for producing conjugated diene compound therefrom ) 是由 三宅裕树 金生刚 山下美与志 于 2021-03-26 设计创作，主要内容包括：本发明提供一种制备具有以下通式(2)R～(3)CH-2OCH-2O(CH-2)-aCH＝CHCHO(2)的甲酰基链烯基烷氧甲基醚化合物的方法,其中R～(3)表示氢原子、具有1至9个碳原子的正链烷基基团、或苯基基团；且“a”表示1至10的整数,所述方法包括：在酸存在下水解以下通式(1)的二烷氧基链烯基烷氧甲基醚化合物：R～(3)CH-2OCH-2O(CH-2)-aCH＝CHCH(OR～(1))(OR～(2))(1),其中R～(1)和R～(2)彼此独立地表示具有1至15个碳原子一价烃基,或R～(1)和R～(2)可一起形成具有2至10个碳原子的二价烃基R～(1)-R～(2)；而且R～(3)和“a”如上限定,同时除去所生成的醇化合物以形成甲酰基链烯基烷氧甲基醚化合物(2)。(The invention provides a method for preparing a compound with the following general formula (2) R 3 CH 2 OCH 2 O(CH 2 ) a Process for the preparation of formylalkenylalkoxymethyl ether compounds of CH ═ CHCHO (2) wherein R is 3 Represents a hydrogen atom, a n-alkanyl group having 1 to 9 carbon atoms, or a phenyl group; and "a" represents an integer from 1 to 10, the method comprising: hydrolyzing a dialkoxyalkenylalkoxymethyl ether compound of the following general formula (1) in the presence of an acid: r 3 CH 2 OCH 2 O(CH 2 ) a CH＝CHCH(OR 1 )(OR 2 ) (1) wherein R 1 And R 2 Independently of one another, represents a monovalent hydrocarbon radical having from 1 to 15 carbon atoms, or R 1 And R 2 May together form a divalent hydrocarbon radical R having from 2 to 10 carbon atoms 1 ‑R 2 (ii) a And R 3 And "a" is as defined above, while removing the produced alcohol compound to form the formylalkenylalkoxymethyl ether compound (2).)

1. A process for producing a formylalkenylalkoxymethyl ether compound having the following general formula (2):

R³CH₂OCH₂O(CH₂)_aCH＝CHCHO (2)

wherein R is³Represents a hydrogen atom, a n-alkanyl group having 1 to 9 carbon atoms, or a phenyl group; and "a" represents an integer of 1 to 10,

the method comprises the following steps:

hydrolyzing a dialkoxyalkenylalkoxymethyl ether compound of the following general formula (1) in the presence of an acid:

R³CH₂OCH₂O(CH₂)_aCH＝CHCH(OR¹)(OR²) (1)

wherein R is¹And R²Independently of one another, a monovalent hydrocarbon radical having from 1 to 15 carbon atoms, or R¹And R²May together form a divalent hydrocarbon radical R having from 2 to 10 carbon atoms¹-R²(ii) a And R³And "a" is as defined above,

while removing the produced alcohol compound to form the formylalkenylalkoxymethyl ether compound (2).

2. The process for producing a formylalkenylalkoxymethyl ether compound (2) according to claim 1, wherein the acid is formic acid, hydrochloric acid or a combination thereof.

3. A process for preparing (5E,7Z) -5, 7-dodecadien-1-ol of the following formula (5):

CH₃(CH₂)₃CH＝CHCH＝CH(CH₂)₄OH (5)

the method comprises the following steps:

the process for producing a formylalkenylalkoxymethyl ether compound (2) according to claim 1 or 2, provided that "a" is 4,

subjecting the obtained formylalkenylalkoxymethyl ether compound (2) and a triarylphosphonium amyl ylide compound of the following general formula (3) to wittig reaction:

wherein Ar independently of one another represents an aryl group,

to form a (5E,7Z) -5, 7-dodecadienylalkoxymethyl ether compound of the following general formula (4):

CH₃(CH₂)₃CH＝CHCH＝CH(CH₂)₄OCH₂OCH₂R³ (4)

wherein R is³As defined above; and is

Subjecting the (5E,7Z) -5, 7-dodecadienylalkoxymethyl ether compound (4) to dealkyloxymethylation to form (5E,7Z) -5, 7-dodecadien-1-ol (5).

4. A process for preparing (5E,7Z) -5, 7-dodecadienylacetate of the following formula (6):

CH₃(CH₂)₃CH＝CHCH＝CH(CH₂)₄OCOCH₃ (6)

the method comprises the following steps:

the process for producing (5E,7Z) -5, 7-dodecadien-1-ol (5) according to claim 3, and

the obtained (5E,7Z) -5, 7-dodecadien-1-ol (5) is acetylated to form (5E,7Z) -5, 7-dodecadienylacetate (6).

Technical Field

The present invention relates to a process for producing a methylalkoxymethyl ether compound and a process for producing a conjugated diene compound therefrom.

Background

The formylalkenylalkoxymethyl ether compound is useful for constructing a conjugated diene skeleton by a wittig reaction, and is therefore extremely useful as a precursor for synthesizing an insect pheromone having a conjugated diene skeleton. Examples of insect pheromones having a conjugated diene skeleton include (5E,7Z) -5, 7-dodecadien-1-ol and (5E,7Z) -5, 7-dodecadienylacetate, which are sex pheromones of spodoptera aurita (thysanophila intrnixta) (non-patent document 1 listed below).

Reported methods for synthesizing a formylalkenylalkoxymethyl ether compound include a method comprising hydrolyzing (Z) -5, 5-diethoxy-3-pentenylmethoxymethyl ether with hydrochloric acid and then extracting with toluene (patent document 1 listed below), and a method comprising subjecting 5- (methoxymethoxy) -2-pentyn-1-ol to aluminum hydrogenation with lithium aluminum hydride and then to Parikh-Doering oxidation (non-patent document 2 listed below).

List of existing documents

[ patent document 1] Japanese laid-open patent application No. 2009-132647

[ non-patent document 1] T.Ando, J.chem.Ecol.,1998,24(6),1105-1116.

[ non-patent document 2] Xiaoyu Wu et al, Synthesis,2011,22, 3675-.

Problems to be solved by the invention

However, the method described in non-patent document 2 uses lithium aluminum hydride that may ignite, and thus the method is not suitable for industrial application. The aforementioned Parikh-Doering oxidation reaction uses dimethyl sulfoxide to produce dimethyl sulfide as an offensive by-product in the reaction. High concentrations of dimethyl sulfide may lead to oxygen deficit in the air and, at worst, death. Dimethyl sulfide can react with an oxidizing agent to cause accidents such as fire or explosion. In addition, as a specific flammable material, a mixed gas of dimethyl sulfide and air is explosive, and thus special production equipment or treatment equipment is required. Therefore, the method described in non-patent document 2 is not suitable for industrial application. In addition, methylene chloride is used as a solvent in the process. Methylene chloride causes an extremely high environmental load, and is disadvantageous from the viewpoint of environmental protection.

Meanwhile, in the method described in patent document 1, hydrolysis is an equilibrium reaction. Therefore, a certain amount of the starting material (Z) -5, 5-diethoxy-3-pentenylmethoxymethyl ether remains unreacted and thus the reaction is not completed, and it is necessary to monitor the progress of the reaction while sampling the reaction mixture. In the method described in patent document 1, it is necessary to selectively hydrolyze a diethyl acetal moiety as a protecting group of a carbonyl group, not a methoxymethyl (MOM) group as a protecting group of a hydroxyl group. However, the ethanol formed in the hydrolysis of the methoxymethyl group and the hydrochloric acid used in the hydrolysis lead to the release of the protective methoxymethyl group. Therefore, the yield is unstable. In addition, the ethanol formed results in 1, 4-addition to the target compound (E) -4-formyl-3-butenyl methoxymethyl ether to form by-product (E) -4-formyl-3-ethoxybutyl methoxymethyl ether, resulting in low purity. Therefore, it is not easy to selectively hydrolyze only the dialkylacetal moiety among the dialkylacetal moiety and the alkoxymethyl group present in the same molecule. Therefore, a method for selectively hydrolyzing a dialkylacetal moiety in a dialkoxyalkenylalkoxymethyl ether compound to produce a formylalkenylalkoxymethyl ether compound in high yield is required.

Disclosure of Invention

It is an object of the present invention to overcome the above problems and to produce a formylalkenylalkoxymethyl ether compound with high purity and high yield by suppressing the removability of the alkoxymethyl group of a dialkoxyalkenylalkoxymethyl ether compound and selectively hydrolyzing only the acetal moiety. It is another object of the present invention to provide a process for producing a formylalkenylalkoxymethyl ether compound, which is preferable in view of environmental protection and productivity.

As a result of intensive studies, the present inventors have found that a formylalkenylalkoxymethyl ether compound can be stably produced in high yield and high purity without using an extraction solvent and/or sampling the reaction mixture during the reaction by carrying out hydrolysis in the presence of an acid and simultaneously removing an alcohol compound formed by the hydrolysis with the progress of the hydrolysis, thereby completing the present invention. The present inventors have also found a process for producing (5E,7Z) -5, 7-dodecadien-1-ol and (5E,7Z) -5, 7-dodecadienylacetate from a formylalkenylalkoxymethyl ether compound in high yield, thereby completing the present invention.

In one aspect of the present invention, there is provided a process for producing a formylalkenylalkoxymethyl ether compound having the following general formula (2):

R³CH₂OCH₂O(CH₂)_aCH＝CHCHO (2)

wherein R is³Represents a hydrogen atom, a n-alkanyl group having 1 to 9 carbon atoms, or a phenyl group; and "a" represents an integer from 1 to 10, the method comprising:

hydrolyzing a dialkoxyalkenylalkoxymethyl ether compound of the following general formula (1) in the presence of an acid:

R³CH₂OCH₂O(CH₂)_aCH＝CHCH(OR¹)(OR²) (1)

wherein R is¹And R²Independently of one another, represents a monovalent hydrocarbon radical having from 1 to 15 carbon atoms, or R¹And R²May together form a divalent hydrocarbon radical R having from 2 to 10 carbon atoms¹-R²(ii) a And R³And "a" is as defined above,

while removing the resultant alcohol compound to form a formylalkenylalkoxymethyl ether compound (2).

In another aspect of the present invention, there is provided a process for preparing (5E,7Z) -5, 7-dodecadien-1-ol of the following formula (5):

CH₃(CH₂)₃CH＝CHCH＝CH(CH₂)₄OH (5)

the method comprises the following steps:

the above-mentioned process for producing a formylalkenylalkoxymethyl ether compound (2), with the proviso that "a" is 4,

subjecting the obtained formylalkenylalkoxymethyl ether compound (2) and a triarylphosphonium pentylylide compound of the following general formula (3) to wittig reaction:

wherein Ar independently of one another represents an aryl group,

to form a (5E,7Z) -5, 7-dodecadienylalkoxymethyl ether compound of the following general formula (4):

CH₃(CH₂)₃CH＝CHCH＝CH(CH₂)₄OCH₂OCH₂R³ (4)

wherein R is³As defined above; and is

(5E,7Z) -5, 7-dodecadienylalkoxymethyl ether compound (4) is subjected to dealkyloxymethylation to form (5E,7Z) -5, 7-dodecadien-1-ol (5).

In another aspect of the present invention, there is provided a method for preparing (5E,7Z) -5, 7-dodecadienylacetate of the following formula (6):

CH₃(CH₂)₃CH＝CHCH＝CH(CH₂)₄OCOCH₃ (6)

the method comprises the following steps:

the above-mentioned process for producing (5E,7Z) -5, 7-dodecadien-1-ol (5), and

the obtained (5E,7Z) -5, 7-dodecadien-1-ol (5) is acetylated to form (5E,7Z) -5, 7-dodecadienylacetate (6).

According to the present invention, the progress of hydrolysis can be monitored by measuring the weight of the alcohol compound removed during the reaction. This eliminates the need to sample the reaction mixture for monitoring the progress of the reaction and also improves operability and safety. According to the present process, the amount of alcohol present in the reaction system in the reaction is small. Therefore, the formation of by-products of (E) -4-formyl-3-alkoxybutylalkoxymethyl ether is suppressed, and the reaction is further completed without leaving unreacted dialkoxyalkenylalkoxymethyl ether compound. Thus, the formylalkenylalkoxymethyl ether compound (2) can be produced in high yield, high yield and high purity with less cost. Further, according to the present invention, sex pheromones (5E,7Z) -5, 7-dodecadien-1-ol (5) and (5E,7Z) -5, 7-dodecadienyl acetate (6) of spodoptera littoralis can be produced in high yield starting from the formylalkenylalkoxymethyl ether compound (2) thus produced.

Detailed Description

The formylalkenylalkoxymethyl ether compound of the following general formula (2) (hereinafter also referred to as formylalkenylalkoxymethyl ether compound (2)) is obtained by hydrolyzing a dialkoxyalkenylalkoxymethyl ether compound of the following general formula (1) (hereinafter also referred to as dialkoxyalkenylalkoxymethyl ether compound (1)) in the presence of an acid.

R³CH₂OCH₂O(CH₂)_aCH＝CHCH(OR¹)(OR²) (1)

R³CH₂OCH₂O(CH₂)_aCH＝CHCHO (2)

The dialkoxyalkenylalkoxymethyl ether compound (1) is first described below.

In the general formula (1), R¹And R²Independently of one another, a monovalent hydrocarbon radical having 1 to 15, preferably 1 to 4, carbon atoms, or R¹And R²May together form a divalent hydrocarbon group having 2 to 10 carbon atoms, preferably 2 to 5 carbon atoms, more preferably 2 to 4 carbon atomsR¹-R²。

For R¹And R²Examples of the monovalent hydrocarbon group of (a) include straight-chain saturated hydrocarbon groups such as a methyl group, an ethyl group, a n-propyl group, a n-butyl group, a n-pentyl group, a n-hexyl group, a n-heptyl group, a n-octyl group, a n-nonyl group, a n-decyl group, a n-undecyl group, a n-dodecyl group, a n-tridecyl group, a n-tetradecyl group, and a n-pentadecyl group; branched saturated hydrocarbon groups such as an isopropyl group, a 2-methylbutyl group and a tert-butyl group; branched unsaturated hydrocarbon groups such as 2-methyl-2-propenyl group; cyclic saturated hydrocarbon groups such as cyclopropyl groups; aryl groups, such as phenyl groups; and isomers thereof. Part of the hydrogen atoms in the hydrocarbon group may be substituted with a methyl group or an ethyl group.

R¹And R²Examples of the divalent hydrocarbon group of (2) include straight-chain saturated hydrocarbon groups such as an ethylene group, a 1, 3-propylene group, a 1, 4-butylene group, a 1, 5-pentylene group, a 1, 6-hexylene group, a 1, 7-heptylene group, a 1, 8-octylene group, a 1, 9-nonylene group, a 1, 10-decylene group, a 1, 11-undecylene group, a 1, 12-dodecylene group, a 1, 13-tridecylene group, a 1, 14-tetradecylene group and a 1, 15-pentadecylene group; straight chain unsaturated hydrocarbon groups such as 1-vinyl ethylene groups; branched saturated hydrocarbon groups such as a 1, 2-propylene group, a 2, 2-dimethyl-1, 3-propylene group, a 1, 2-butylene group, a 1, 3-butylene group, a 2, 3-butylene group and a 2, 3-dimethyl-2, 3-butylene group; branched unsaturated hydrocarbon groups such as 2-methylene-1, 3-propylene groups; cyclic hydrocarbon groups such as a 1, 2-cyclopropylene group and a 1, 2-cyclobutylene group; and isomers thereof. Part of the hydrogen atoms in the hydrocarbon group may be substituted with a methyl group or an ethyl group.

The divalent hydrocarbon group is preferably a highly reactive lower hydrocarbon group (preferably having 2 to 4 carbon atoms) because it is easily available, shows good reactivity in deprotection, and forms a by-product which is easily removed by washing or evaporation, thereby making purification easier.

In this sense, preferred examples of the divalent hydrocarbon group include: ethylene, 1, 2-propylene, 1, 3-propylene, 1, 2-butylene, 1, 3-butylene and 2, 3-dimethyl-2, 3-butylene.

In the general formula (1), "a" represents an integer of 1 to 10, preferably 1 to 4.

In the general formula (1), R³Represents a hydrogen atom, an n-alkanyl group having 1 to 9 carbon atoms, preferably 1 to 4 carbon atoms, or a phenyl group.

Specific examples of the dialkoxybutylkyloxymethyl ether compound (1) include dialkoxybutylalkoxymethyl ether compounds such as dimethoxybutenyl methoxymethyl ether, diethoxybutylalkoxymethyl ether, dipropoxybutylalkoxymethyl ether, dibutoxybutylalkoxymethyl ether, dipentyloxybutylalkoxymethyl ether, dihexyloxybutenyl methoxymethyl ether, diheptyloxybutenyl methoxymethyl ether, dioctyloxybutenyl methoxymethyl ether, dinonyloxybutylalkoxymethyl ether and didecyloxybutylalkoxymethyl ether; dialkoxypentenylmethoxymethyl ether compounds such as dimethoxypentenylmethoxymethyl ether, diethoxypentenmethoxymethyl ether, dipropoxypentenmethoxymethyl ether, dibutoxypentenmethoxymethyl ether, dipentyoxypentoxymethyl ether, dihexopentenylmethoxymethyl ether, diheptyloxypentenylmethoxymethyl ether, dioctyloxypentenylmethoxymethyl ether, dinonyloxypentoxymethyl ether and didecyloxypentenmethoxymethyl ether; dialkoxypentenyethoxymethyl ether compounds such as dimethoxypentenylethoxymethyl ether, diethoxypenteneethoxymethyl ether, dipropoxypenteneethoxymethyl ether, dibutoxypenteneethoxymethyl ether, dipentyloxopeneneethoxymethyl ether, dihexaoxypenteneethoxymethyl ether, diheptyloxypentenylethoxymethyl ether, dioctyloxypentenylethoxymethyl ether, dinonyloxypenteneethoxymethyl ether and didecylpentenyloxyethoxymethyl ether; dialkoxypentoxypropoxymethyl ether compounds such as dimethoxypentenylpropoxymethyl ether, diethoxypentoxypropoxymethyl ether, dipropoxypentoxypropoxymethyl ether, dibutoxypentoxypropoxymethyl ether, dipentyoxypentoxypropoxymethyl ether, dihexopentenylpropoxymethyl ether, diheptyloxypentenylpropoxymethyl ether, dioctyloxypentenylpropoxymethyl ether, dinonyloxypropoxymethyl ether and didecyloxypentoxypropoxymethyl ether; dialkoxypentenbutoxymethyl ether compounds such as dimethoxypentenylbutoxymethyl ether, diethoxypentoxybutylmethyl ether, dipropoxypentoxybutylmethyl ether, dibutoxypentoxybutylmethyl ether, dipentyoxypentoxybutylmethyl ether, dihexopentenylbutoxymethyl ether, diheptyloxypentenylbutoxymethyl ether, dioctyloxypentenylbutoxymethyl ether, dinoxypentoxybutylmethyl ether and didecanyloxypentenylbutoxymethyl ether; dialkoxypentopentyloxymethyl ether compounds such as dimethoxypentenylpentoxymethyl ether, diethoxypentopentylpentoxymethyl ether, dipropoxypentoxypentoxymethyl ether, dibutoxypentopentyloxypentoxymethyl ether, dipentyoxypentoxypentoxypentoxymethyl ether, dihexopentenylpentoxymethyl ether, diheptyloxypentenylpentoxymethyl ether, dioctyloxypentenylpentoxymethyl ether, dinonyloxypentopentylpentoxymethyl ether and didecyloxypentoxypentoxymethyl ether; dialkoxypentenylhexyloxymethylether compounds such as dimethoxypentenylhexyloxymethylether, diethoxypentenylhexyloxymethylether, dipropoxypentenylhexyloxymethylether, dibutoxypentenylhexyloxymethylether, dipentyloxypenthexyloxymethylether, dihexopentenylhexyloxymethylether, diheptyloxypentenylhexyloxymethylether, dioctyloxypentenylhexyloxymethylether, dinoxypentenylhexyloxymethylether and didecyloxypenthexyloxymethylether; dialkoxypentenylheptoxymethyl ether compounds such as dimethoxypentenylheptoxymethyl ether, diethoxypentenylheptoxymethyl ether, dipropoxypentenylheptoxymethyl ether, dibutoxypentenylheptoxymethyl ether, dipentyoxypentenylheptoxymethyl ether, dihexopentenylheptoxymethyl ether, dihexyloxypentenylheptoxymethyl ether, dihexyloxypentenylheptyloxymethyl ether, dioctoxypentenylheptyloxymethyl ether, dinonyloxypentenylheptyloxymethyl ether and didecyloxypentenylheptyloxymethyl ether; dialkoxypentenyloctyloxymethylether compounds such as dimethoxypentenyloctyxymethyl ether, diethoxypentenyloctyloxymethylether, dipropoxypentenyloctyloxymethylether, dibutoxypentenyloctyloxymethylether, dipentyloxypentenyloctyloxymethylether, dihexylpentenyloctyxymethyl ether, diheptyloxypentenyloctyloxymethyl ether, dioctyloxypentenyloxymethyl ether, dinonyloxypentenyloctyloxymethylether and didecyloxypentenyloctyloxymethylether; dialkoxypentenylnonoxymethyl ether compounds such as dimethoxypentenylnonoxymethyl ether, diethoxypentylnonoxymethyl ether, dipropoxypentonyxymethyl ether, dibutoxypentylnonoxymethyl ether, dipentyloxynyloxymethyl ether, dihexopentenylnonoxymethyl ether, diheptyloxypentenylnonoxymethyl ether, dioctyloxypentenylnonoxymethyl ether, dinoxypentenylnonoxymethyl ether and didecyloxypentonyxymethyl ether; dialkoxypentecyloxymethyl ether compounds such as dimethoxypentenyldecyloxymethyl ether, diethoxypentecyloxymethyl ether, dipropoxypentecyloxymethyl ether, dibutoxypentecyloxymethyl ether, dipentyloxypentecyloxymethyl ether, dihexopentenyldecyloxymethyl ether, diheptyloxypentenyldecyloxymethyl ether, dioctyloxypentenyldecyloxymethyl ether, dinoxypentenyldecyloxymethyl ether and didecyloxypentecyloxymethyl ether; dialkoxypentyloxybenzyloxymethyl ether compounds such as dimethoxypentenylbenzyloxy methyl ether, diethoxypentyloxybenzyloxymethyl ether, dipropoxypentyloxybenzyloxymethyl ether, dibutoxypentyloxybenzyloxymethyl ether, dipentyoxypentyloxybenzyloxymethyl ether, dihexopentenyloxybenzyloxymethyl ether, diheptyloxypentenyloxybenzyloxymethyl ether, dioctyloxypentenyloxybenzyloxymethyl ether, dinonyloxypentyloxybenzyloxymethyl ether and didecyloxypentyloxybenzyloxymethyl ether; dialkoxyhexenylalkoxymethyl ether compounds such as dimethoxyhexenylmethoxymethyl ether, diethoxyhexenylmethoxymethyl ether, dipropoxyhexenylmethoxymethyl ether, dibutoxyhexenylmethoxymethyl ether, dipentyoxyhexenylmethoxymethyl ether, dihexohexenylmethoxymethyl ether, diheptyloxyhexenylmethoxymethyl ether, dioctyloxyhexenylmethoxymethyl ether, dinonyloxyhexenylmethoxymethyl ether and didecyloxyhexenylmethoxymethyl ether; dialkoxyheptenylmethoxymethyl ether compounds such as dimethoxyheptenylmethoxymethyl ether, diethoxyheptenylmethoxymethyl ether, dipropoxyheptenylmethoxymethyl ether, dibutoxyheptenylmethoxymethyl ether, dipentyloxyethenylmethoxymethyl ether, dihexyheptenylmethoxymethyl ether, diheptyloxyheptenylmethoxymethyl ether, dioctyloxyheptenylmethoxymethyl ether, dinonyloxyheptenylmethoxymethyl ether and didecyloxyheptenylmethoxymethyl ether; dialkoxyheptenyl ethoxymethyl ether compounds such as dimethoxyheptenyl ethoxymethyl ether, diethoxyheptenyl ethoxymethyl ether, dipropoxyheptenyl ethoxymethyl ether, dibutoxyheptenyl ethoxymethyl ether, dipentyloxyethenyl ethoxymethyl ether, dihexoxyheptenyl ethoxymethyl ether, diheptyloxyheptenyl ethoxymethyl ether, dioctyloxyheptenyl ethoxymethyl ether, dinonyloxyheptenyl ethoxymethyl ether and didecyloxyheptenyl ethoxymethyl ether; dialkoxyheptylpropyloxymethyl ether compounds such as dimethoxyheptylpropyloxymethyl ether, diethoxyheptylpropyloxymethyl ether, dipropoxyheptylpropyloxymethyl ether, dibutoxyheptylpropyloxymethyl ether, dipentyloxylpropyloxymethyl ether, dihexyheptylpropyloxymethyl ether, diheptyloxyheptylpropyloxymethyl ether, dioctyloxyheptylpropyloxymethyl ether, dinoyloxy heptylpropyloxymethyl ether and didecyloxyheptylpropyloxymethyl ether; dialkoxyheptenylbutoxymethyl ether compounds such as dimethoxyheptenylbutoxymethyl ether, diethoxyheptenylbutoxymethyl ether, dipropoxyheptenylbutoxymethyl ether, dibutoxyheptenylbutoxymethyl ether, dipentyloxyeptobutoxymethyl ether, dihexoheptyloxybutoxymethyl ether, diheptyloxyheptyloxybutoxymethyl ether, dioctyloxyheptyloxybutoxymethyl ether, dinonyloxyheptenylbutoxymethyl ether and didecyloxyheptenylbutoxymethyl ether; dialkoxyheptenylpentyloxymethyl ether compounds such as dimethoxyheptenylpentyloxymethyl ether, diethoxyheptenylpentyloxymethyl ether, dipropoxyheptenylpentyloxymethyl ether, dibutoxyheptenylpentyloxymethyl ether, dipentyloxyphenylpentyloxymethyl ether, dihexyheptenylpentyloxymethyl ether, dihexyloheptyloxyheptenylpentyloxymethyl ether, dioctyloxyheptyloxypentyloxymethyl ether, dinonyloxyheptenylpentyloxymethyl ether and didecyloxyheptenylpentyloxymethyl ether; dialkoxyheptenylhexyloxymethyl ether compounds such as dimethoxyheptenylhexyloxymethyl ether, diethoxyheptenylhexyloxymethyl ether, dipropoxyheptenylhexyloxymethyl ether, dibutoxyheptenylhexyloxymethyl ether, dipentyloxyeheptyloxyhexyloxymethyl ether, dihexyheptenylhexyloxymethyl ether, dihexyloxyheptyloxyhexyloxymethyl ether, dioctyloxyheptyloxyhexyloxymethyl ether, dinonyloxyheptyloxyhexyloxymethyl ether compounds and didecyloxyheptyloxyhexyloxymethyl ether; dialkoxyheptenylheptyloxymethyl ether compounds such as dimethoxyheptyloxymethyl ether, diethoxyheptyloxymethyl ether, dipropoxyheptyloxymethyl ether, dibutoxyheptyloxymethyl ether, dipentyloxynyloxyheptyloxymethyl ether, dihexoheptyloxymethyl ether, dihexyloxyheptyloxymethyl ether, dioctyloxyheptyloxymethyl ether, dinonyloxyheptyloxymethyl ether and didecyloxyheptyloxymethyl ether; dialkoxyheptenyloctyloxymethyl ether compounds such as dimethoxyheptenyloctyloxymethyl ether, diethoxyheptenyloctyloxymethyl ether, dipropoxyheptenyloctyloxymethyl ether, dibutoxyheptenyloctyloxymethyl ether, dipentyloxyeheptenyloctyloxymethyl ether, dihexyheptenyloctyloxymethyl ether, dihexyheptyloxyheptenyloctyloxymethyl ether, dioctyloxyheptenyloctyloxymethyl ether, dinonyloxyheptenyloctyloxymethyl ether and didecyloxyheptenyloctyloxymethyl ether; dialkoxyheptenylnonyloxymethyl ether compounds such as dimethoxyheptenylnonyloxymethyl ether, diethoxyheptenylnonyloxymethyl ether, dipropoxyheptenylnonyloxymethyl ether, dibutoxyheptenylnonyloxymethyl ether, dipentyloxyeheptenylnonyloxymethyl ether, dihexyheptenylnonyloxymethyl ether, dihexyloxyheptenylnonyloxymethyl ether, dioctyloxyheptenylnonyloxymethyl ether, dinonyloxyheptenylnonyloxymethyl ether and didecyloxyheptenylnonyloxymethyl ether; dialkoxyheptenyldecyloxymethyl ether compounds such as dimethoxyheptenyldecyloxymethyl ether, diethoxyheptenyldecyloxymethyl ether, dipropoxyheptenyldecyloxymethyl ether, dibutoxyheptenyldecyloxymethyl ether, dipentyloxyedecyloxymethyl ether, dihexoheptenyldecyloxymethyl ether, diheptyloxyheptyloxydecyloxymethyl ether, dioctyloxyheptyloxydecyloxymethyl ether, dinonyloxyheptenyldecyloxymethyl ether and didecylheptyloxydecyloxyexydecyloxymethyl ether; dialkoxyheptenylbenzyloxymethyl ether compounds such as dimethoxyheptenylbenzyloxymethyl ether, diethoxyheptenylbenzyloxymethyl ether, dipropoxyheptenylbenzyloxymethyl ether, dibutoxyheptenylbenzyloxymethyl ether, dipentyloxyenylbenzyloxymethyl ether, dihexyheptenylbenzyloxymethyl ether, dihexyloheptyloxybenzyloxymethyl ether, dioctyloxyheptenylbenzyloxymethyl ether, dinonyloxyheptenylbenzyloxymethyl ether and didecyloxyheptenylbenzyloxymethyl ether; dialkoxyoctenylalkoxymethyl ether compounds such as dimethoxyoctenylmethoxymethyl ether, diethoxyoctenylmethoxymethyl ether, dipropoxyoctenylmethoxymethyl ether, dibutoxyoctenylmethoxymethyl ether, dipentyloxyoxyoctenylmethoxymethyl ether, dihexyloxyoctenylmethoxymethyl ether, diheptyloxyoctenylmethoxymethyl ether, dioctyloxyoctenylmethoxymethyl ether, dinonyloxyoctenylmethoxymethyl ether and didecyloxyoctenylmethoxymethyl ether; dialkoxy nonenyl alkoxymethyl ether compounds such as dimethoxy nonenyl methoxymethyl ether, diethoxy nonenyl methoxymethyl ether, dipropoxy nonenyl methoxymethyl ether, dibutoxy nonenyl methoxymethyl ether, dipentyoxy nonenyl methoxymethyl ether, dihexoxynonenyl methoxymethyl ether, diheptoxy nonenyl methoxymethyl ether, dioctyloxy nonenyl methoxymethyl ether, dinonyloxy nonenyl methoxymethyl ether, and didecyloxy nonenyl methoxymethyl ether; dialkoxydecenylalkoxymethyl ether compounds such as dimethoxydecenylmethoxymethyl ether, diethoxydecenylmethoxymethyl ether, dipropoxydecenylmethoxymethyl ether, dibutoxydecenylmethoxymethyl ether, dipentyloxydenylmethoxymethyl ether, dihexodecylenylmethoxymethyl ether, diheptyloxydecenylmethoxymethyl ether, dioctyloxydecenylmethoxymethyl ether, dinonyloxydecenylmethoxymethyl ether and didecyloxybutenylmethoxymethyl ether; dialkoxyundecenyloxymethyl ether compounds such as dimethoxyundecenylmethoxymethyl ether, diethoxyundecenylmethoxymethyl ether, dipropoxyundecenylmethoxymethyl ether, dibutoxyundecenylmethoxymethyl ether, dipentyloxydendecenylmethoxymethyl ether, dihexoundecenylmethoxymethyl ether, diheptyloxyundecenylmethoxymethyl ether, dioctyloxyundecenylmethoxymethyl ether, dinonyloxyundecenylmethoxymethyl ether and didecyloxyundecenylmethoxymethyl ether; dialkoxydodecenylalkoxymethyl ether compounds such as dimethoxydodecenylmethoxymethyl ether, diethoxydodecenylmethoxymethyl ether, dipropoxydodecenylmethoxymethyl ether, dibutoxydodecenylmethoxymethyl ether, dipentyloxydidodecenylmethoxymethyl ether, dihexododecenylmethoxymethyl ether, diheptyloxydodecenylmethoxymethyl ether, dioctyloxydodecenylmethoxymethyl ether, dinoyloxydodecenylmethoxymethyl ether and didecyloxydodecenylmethoxymethyl ether; and dialkoxytridecylalkoxymethyl ether compounds such as dimethoxytridecenylmethoxymethyl ether, diethoxytridecylmethoxymethyl ether, dipropoxytridecylmethoxymethyl ether, dibutoxytridecylmethoxymethyl ether, dipentyoxytridecylmethoxymethyl ether, dihexyloxytridecenylmethoxymethyl ether, diheptyloxytridecenylmethoxymethyl ether, dioctyloxytridecenylmethoxymethyl ether, dinonyloxytridecylmethoxymethyl ether and didecyloxytridecylmethoxymethyl ether.

For example, dialkoxyalkenylalkoxymethyl ether compounds (1) can be synthesized by acetalizing (acetalize) the terminal alkynyl group of alkoxymethyl alkynyl ether compounds and catalytically reducing carbon-carbon triple bonds.

Next, the formylalkenylalkoxymethyl ether compound (2) will be explained below.

In the general formula (2), R³And "a" is the same as in the general formula (1).

Specific examples of the formylalkenylalkoxymethyl ether compound (2) include formylbutenalkoxymethyl ether compounds such as formylbutenylmethoxymethyl ether, formylbutenethoxymethyl ether, formylbutenpropoxymethyl ether, formylbutenbutoxymethyl ether, formylbutenpentoxymethyl ether, formylbutenhexoxymethyl ether, formylbutenheptyloxymethyl ether, formylbutenyloctyloxymethyl ether, formylbutenonyloxymethyl ether, formylbutendecyloxymethyl ether, and formylbutenbenzyloxymethyl ether; formylpentenyl alkoxymethyl ether compounds such as formylpentenyl methoxymethyl ether, formylpentenyl ethoxymethyl ether, formylpentenyl propoxymethyl ether, formylpentenyl butoxymethyl ether, formylpentenyl pentoxymethyl ether, formylpentenyl hexyloxymethyl ether, formylpentenyl heptyloxymethyl ether, formylpentenyl octyloxymethyl ether, formylpentenyl nonyloxymethyl ether, formylpentenyl decyloxymethyl ether, and formylpentenyl benzyloxymethyl ether; formyl hexenyl alkoxymethyl ether compounds such as formyl hexenyl methoxymethyl ether, formyl hexenyl ethoxymethyl ether, formyl hexenyl propoxymethyl ether, formyl hexenyl butoxymethyl ether, formyl hexenyl pentoxymethyl ether, formyl hexenyl hexyloxymethyl ether, formyl hexenyl heptyloxymethyl ether, formyl hexenyl octyloxymethyl ether, formyl hexenyl nonyloxymethyl ether, formyl hexenyl decyloxymethyl ether, and formyl hexenyl benzyloxymethyl ether; formyl heptenyl alkoxymethyl ether compounds such as formyl heptenyl methoxymethyl ether, formyl heptenyl ethoxymethyl ether, formyl heptenyl propoxymethyl ether, formyl heptenyl butoxymethyl ether, formyl heptenyl pentoxymethyl ether, formyl heptenyl hexoxymethyl ether, formyl heptenyl heptyloxymethyl ether, formyl heptenyl octoxymethyl ether, formyl heptenyl nonenoxymethyl ether, formyl heptenyl decexymethyl ether, and formyl heptenyl benzyloxymethyl ether; formyl octenyl alkoxymethyl ether compounds such as formyl octenyl methoxymethyl ether, formyl octenyl ethoxymethyl ether, formyl octenyl propoxymethyl ether, formyl octenyl butoxymethyl ether, formyl octenyl pentoxymethyl ether, formyl octenyl hexoxymethyl ether, formyl octenyl heptyloxymethyl ether, formyl octenyl octoxymethyl ether, formyl octenyl nonenyl nonoxymethyl ether, formyl octenyl decexymethyl ether, and formyl octenyl benzyloxymethyl ether; formylnonenylalkoxymethyl ether compounds such as formylnonenylmethoxymethyl ether, formylnonenylethoxymethyl ether, formylnonenylpropoxymethyl ether, formylnonenylbutoxymethyl ether, formylnonenylpentyloxymethyl ether, formylnonenylhexyloxymethyl ether, formylnonenylheptyloxymethyl ether, formylnonenyloctyloxymethyl ether, formylnonenylnonenylnonyloxymethyl ether, formylnonenyldecyloxymethyl ether, and formylnonenylbenzyloxymethyl ether; formyldecenylalkoxymethyl ether compounds such as formyldecenylmethoxymethyl ether, formyldecenylethoxymethyl ether, formyldecenylpropoxymethyl ether, formyldecenylbutoxymethyl ether, formyldecenylpentoxymethyl ether, formyldecenylhexyloxymethyl ether, formyldecenylheptyloxymethyl ether, formyldecenyloctyloxymethyl ether, formyldecenylnonyloxymethyl ether, formyldecenyldecyloxymethyl ether, and formyldecenylbenzyloxymethyl ether; formylundecylenic alkoxymethyl ether compounds such as formylundecylenic methoxymethyl ether, formylundecylenic ethoxymethyl ether, formylundecylenic propoxymethyl ether, formylundecylenic butoxymethyl ether, formylundecylenic pentoxymethyl ether, formylundecylenic hexoxymethyl ether, formylundecylenic heptyloxymethyl ether, formylundecylenic octyloxymethyl ether, formylundecylenic nonyloxymethyl ether, formylundecylenic decyloxymethyl ether, and formylundecylenic benzyloxymethyl ether; formyldodecenylalkoxymethyl ether compounds such as formyldodecenylmethoxymethyl ether, formyldodecenylethoxymethyl ether, formyldodecenylpropoxymethyl ether, formyldodecenylbutoxymethyl ether, formyldodecenylpentoxymethyl ether, formyldodecenylhexoxymethyl ether, formyldodecenylheptyloxymethyl ether, formyldodecenyloctyloxymethyl ether, formyldodecenylnonyloxymethyl ether, formyldodecenyldecyloxymethyl ether, and formyldodecenylbenzyloxymethyl ether; and formyltridecenyl alkoxymethyl ether compounds such as formyltridecenyl methoxymethyl ether, formyltridecenyl ethoxymethyl ether, formyltridecenyl propoxymethyl ether, formyltridecenyl butoxymethyl ether, formyltridecenyl pentoxymethyl ether, formyltridecenyl hexoxymethyl ether, formyltridecenyl heptyloxymethyl ether, formyltridecenyl octoxymethyl ether, formyltridecenyl nonenyloxymethyl ether, formyltridecenyl decyloxymethyl ether, and formyltridecenyl benzyloxymethyl ether.

Then, the hydrolysis to be performed for the dialkoxyalkenylalkoxymethyl ether compound (1) will be described below.

The hydrolysis may be carried out, for example, in the presence of an acid or water.

Examples of the acid include inorganic acids such as hydrochloric acid and hydrobromic acid; p-toluenesulfonic acid (p-TsOH), benzenesulfonic acid, trifluoroacetic acid, acetic acid, formic acid, oxalic acid, iodotrimethylsilane and titanium tetrachloride. In view of reactivity, p-toluenesulfonic acid, acetic acid, formic acid and hydrochloric acid are preferable, and formic acid and hydrochloric acid are more preferable.

In view of the yield, the amount of the acid used is preferably 0.0001 to 2.0 moles, more preferably 0.003 to 1.0 mole per mole of the dialkoxyalkenylalkoxymethyl ether compound (1).

The acids may be used alone or in combination, if necessary. The acid may be one commercially available or may be prepared indoors.

In view of the yield, the amount of water used is preferably 0 to 3000g, more preferably 0 to 300g, per mole of the dialkoxyalkenylalkoxymethyl ether compound (1). When the acid to be used comprises water, further water addition may not be necessary.

The hydrolysis may be carried out in the absence of a solvent or in the presence of a solvent, if necessary. Performing the hydrolysis in the absence of solvent allows for a reduction in the amount of feed and may also avoid a reduction in yield.

Examples of the solvent include common solvents, for example, ethers such as butyl ether, 4-methyltetrahydropyran, cyclopentyl methyl ether and 1, 4-dioxane; hydrocarbons such as heptane, benzene, toluene, xylene, and cumene; chlorinated solvents, such as trichloroethylene; aprotic polar solvents such as dimethyl sulfoxide, γ -butyrolactone and hexamethylphosphoric triamide; nitriles such as acetonitrile and propionitrile; and esters such as n-propyl acetate and n-butyl acetate.

The solvents may be used alone or in combination, if necessary. The solvent may be one commercially available.

It is preferable that the boiling point of the solvent is different from and higher than the boiling point of the alcohol formed in the hydrolysis (hereinafter also referred to as the alcohol compound (7)).

The amount of the solvent used for the hydrolysis is preferably 0 to 2000g, more preferably 0 to 500g, per mole of the dialkoxyalkenylalkoxymethyl ether compound (1).

The reaction temperature in the hydrolysis is preferably 10 to 150 deg.c, more preferably 30 to 80 deg.c, in view of reactivity.

The reaction time in the hydrolysis varies depending on the scale of the reaction and is preferably 1 to 100 hours in view of the yield.

It can be known whether the hydrolysis is still proceeding, for example, by distilling off and weighing the alcohol compound (7) formed in the hydrolysis or monitoring the hydrolysis by GC. The former is preferable in view of safety and workability. More specifically, in the former manner, if the weight of alcohol distilled off is less than the theoretical weight of alcohol calculated based on the amount of the dialkoxyalkenylalkoxymethyl ether compound (1) as the starting material fed, and the weight increases with time, the hydrolysis is still proceeding.

The present invention is particularly advantageous when the dialkoxyalkenylalkoxymethyl ether compound (1) is a formylalkenylalkoxymethyl ether compound (2: a ═ 1-4) having high water solubility and having 4 to 7 carbon atoms. This is the case when a dialkoxybutylalkoxymethyl ether compound, dialkoxypentoxyalkylmethyl ether compound, dialkoxyhexenylalkoxymethyl ether compound or dialkoxyheptenylalkoxymethyl ether compound is hydrolyzed to prepare a formylalkenylalkoxymethyl ether compound (2: a ═ 1-4) which is an aldehyde. The preparation of a formylalkenylalkoxymethyl ether compound having 4 to 7 carbon atoms (2: a ═ 1-4) will be explained below as an example. It should be noted that this does not mean that the preparation of formylalkenylalkoxymethyl ether compounds having 8 to 13 carbon atoms (2: a ═ 5-10) is excluded from the scope of the present invention.

In general, when a formylalkenylalkoxymethyl ether compound (2: a ═ 1-4) is produced by hydrolyzing a dialkoxyalkenylalkoxymethyl ether compound (1: a ═ 1-4), it is necessary to use dichloromethane, chloroform, diethyl ether, toluene, or xylene which is insoluble in water and has a high extraction ability, as a solvent or extraction solvent in the reaction. However, when such a solvent is used, the solvent should be separated by distillation, and further, the solvent occupies the reactor volume to reduce the amount of raw material to be fed. The separated solvent is a waste material and may cause environmental problems. Meanwhile, when such a solvent is not used, the formyl alkenylalkoxymethyl ether compound (2: a ═ 1-4) is partially transferred to the aqueous phase, so that the yield of the formyl alkenylalkoxymethyl ether compound (2: a ═ 1-4) is extremely low. If an alcohol is present in the reaction mixture containing the formylalkenylalkoxymethyl ether compound (2: a ═ 1-4), the solubility of the formylalkenylalkoxymethyl ether compound (2: a ═ 1-4) in the aqueous phase increases, which leads to a great decrease in yield or fluctuation in yield even under the same conditions in repeated preparations (see comparative examples 1 to 6 below).

In contrast, in the present invention, the alcohol formed in the hydrolysis is removed in the hydrolysis process, so that the partitioning of the formylalkenylalkoxymethyl ether compound having 4 to 7 carbon atoms (2: a ═ 1-4) from the aqueous phase to the aqueous phase is reduced or eliminated, so that the formylalkenylalkoxymethyl ether compound (2: a ═ 1-4) is separated in high yield and yield from the aqueous phase to the organic phase (see examples 1 to 4 and comparative examples 1 to 6 below). The alcohol formed in the hydrolysis is removed in the hydrolysis, and such a reaction mixture may be subjected to distillation to obtain a purified target compound formylalkenylalkoxymethyl ether compound (2: a ═ 1-4), without post-treatment or with a reduced post-treatment step.

In the above hydrolysis, the dialkoxyalkenylalkoxymethyl ether compound (1), an acid and optionally water are fed into a reaction vessel and heated during the hydrolysis to distill off the alcohol compound (7) formed in the hydrolysis. When the alcohol compound (7) is ethanol, the distillation is performed, for example, by raising the internal temperature to 40 to 50 ℃ during the hydrolysis and then lowering the pressure to 235mmHg (31.3 kPa). The hydrolysis may be carried out by distilling off the alcohol compound (7) under normal pressure, but is preferably carried out under reduced pressure in view of the thermal stability of the formylalkenylalkoxymethyl ether compound (2). The alcohol distillation was continued by gradually decreasing the pressure to 50mmHg (6.67 kPa). Hydrolysis was judged to be complete when no more ethanol was distilled off. The fact that no more ethanol is distilled off can be determined by the following facts: the weight of the distillate did not change and was equal to the weight of the theoretical amount of the alcohol compound (7) calculated from the amount of the starting dialkoxyalkenylalkoxymethyl ether compound (1).

It should be noted that the term "internal temperature" refers to the temperature of the reaction mixture and is also referred to as the reaction temperature.

Specific examples of the alcohol compound (7) include straight-chain alcohols such as methanol, ethanol, n-propanol, n-butanol, n-pentanol, n-hexanol, n-heptanol, n-octanol, n-nonanol, n-decanol, n-undecanol, n-dodecanol, n-tridecanol, n-tetradecanol, and n-pentadecanol; branched alcohols such as isopropanol and 2-butanol; and diols such as ethylene glycol, 1, 3-propanediol, 1, 4-butanediol, 1, 5-pentanediol, 1, 6-hexanediol, 1, 7-heptanediol, 1, 8-octanediol, 1, 9-nonanediol, 1, 10-decanediol, 1, 11-undecanediol, 1, 12-dodecanediol, 1, 13-tridecanediol, 1, 14-tetradecanediol, 1, 15-pentadecanediol, 1, 2-propanediol, 2-dimethyl-1, 3-propanediol and 2, 2-dimethyl-1, 4-butanediol.

The alcohol compound (7) recovered from the distillation has high purity and thus can be used as a raw material for other reactions than the current hydrolysis, such as acetalization or dealkyloxymethylation of aldehyde. The process according to the invention is therefore environmentally friendly and economically very advantageous.

Thus, the formylalkenylalkoxymethyl ether compound (2) can be produced by hydrolyzing the dialkoxyalkenylalkoxymethyl ether compound (1) in the presence of an acid while removing an alcohol compound formed further along with the progress of the hydrolysis in the hydrolysis.

Next, a method for producing sex pheromone (5E,7Z) -5, 7-dodecadien-1-ol (hereinafter also referred to as (5E,7Z) -5, 7-dodecadien-1-ol (5)) of heliothis virescens from the methoxyalkenylalkoxymethyl ether compound (2: a ═ 4) obtained in the above-described production process will be described.

(5E,7Z) -5, 7-dodecadien-1-ol (5) was prepared by: a formylheptenylalkoxymethyl ether compound (2: a ═ 4) and a triarylphosphonium pentylylide compound of the following general formula (3) (hereinafter also referred to as triarylphosphonium pentylylide compound (3)) were subjected to wittig reaction to prepare a (5E,7Z) -5, 7-dodecadienylalkoxymethyl ether compound of the following formula (4: a ═ 4) (hereinafter also referred to as (5E,7Z) -5, 7-dodecadienylalkoxymethyl ether (4: a ═ 4)), followed by dealkyloxymethylation of the (5E,7Z) -5, 7-dodecadienylalkoxymethyl ether (4: a ═ 4).

The wittig reaction step will now be explained below.

In the general formula (3), Ar represents an aryl group independently of each other.

The aryl group preferably has 6 to 7 carbon atoms.

Examples of aryl groups include phenyl groups (Ph group (-C)₆H₅) And tolyl groups. In view of ease of synthesis, a phenyl group is preferred, and more preferably, all three aryl groups are phenyl groups.

Specific examples of triarylphosphonium amyl ylide compounds (3) include triphenylphosphonium amyl ylide and tritylphosphonium amyl ylide compounds.

If desired, the triarylphosphonium amyl ylide compounds (3) can be used alone or in combination.

The triarylphosphonium amyl ylide compound (3) can be prepared by the following method: for example, a 1-halopentane compound represented by the following general formula (8) (hereinafter also referred to as 1-halopentane compound (8)) is reacted with a phosphorus compound described by the following general formula (9) (hereinafter also referred to as phosphorus compound (9)) to form a pentyltriarylphosphonium halide represented by the following general formula (10) (hereinafter also referred to as pentyltriarylphosphonium halide (10)), and then the pentyltriarylphosphonium halide (10) is deprotonated with a base to form a triarylphosphonium pentylylide compound (3).

X in the 1-halogenopentane compound (8) represents a halogen atom. Examples of the halogen atom include a chlorine atom, a bromine atom and an iodine atom. In view of versatility, a chlorine atom and a bromine atom are preferable.

Specific examples of the 1-halogenopentane compound (8) include 1-chloropentane, 1-bromopentane and 1-iodopentane.

In formula (9), Ar is as defined for formula (3).

Specific examples of the phosphorus compound (9) include triarylphosphine compounds such as triphenylphosphine and tritylphosphine. In view of reactivity, triphenylphosphine is preferable.

In view of reactivity, the phosphorus compound (9) is preferably used in an amount of 0.8 to 5.0 moles per mole of the 1-halopentane compound (8).

If necessary, the halide may be incorporated into the reaction mixture used to prepare the pentyltriarylphosphonium halide (10).

Examples of the halide include sodium iodide, potassium iodide, sodium bromide and potassium bromide, and in view of reactivity, iodide such as sodium iodide and potassium iodide is preferable.

The halides may be used alone or in combination, if necessary. The halide may be one commercially available.

In view of reactivity, the halide is preferably used in an amount of 0 to 5.0 moles per mole of the 1-halopentane compound (8).

If necessary, a base may be incorporated into the reaction mixture used to prepare the pentyltriarylphosphonium halide (10).

Examples of the base include alkali metal carbonates such as potassium carbonate and sodium carbonate; alkaline earth metal carbonates such as calcium carbonate and magnesium carbonate; and amines such as triethylamine, tripropylamine, triisopropylamine, tributylamine, N-diethylaniline and pyridine. From the viewpoint of handling, alkali metal carbonates are preferred.

The bases may be used alone or in combination. The base may be one that is commercially available.

In view of reactivity, the amount of the base to be used is preferably 0 to 2.0 moles per mole of the 1-halopentane compound (8).

The reaction temperature (optimum temperature) in the preparation of the pentyltriarylphosphonium halide (10) varies depending on the solvent used, and is preferably 60 to 180 ℃.

The reaction time for preparing the pentyltriarylphosphonium halide (10) varies depending on the solvent used and the scale of production, and is preferably 0.5 to 55 hours.

Y in the general formula (10) represents a halogen atom. Examples of the halogen atom include a chlorine atom, a bromine atom and an iodine atom.

In the case where no halide is used in the preparation of pentyltriarylphosphonium halide (10), Y is the same halogen atom as X in the general formula (8). When an iodide is used as the halide in the preparation, Y is the same halogen atom or iodine atom as X described above.

In the general formula (10), Ar is as defined in the general formula (3).

Specific examples of the pentyltriarylphosphonium halide (10) include pentyltriphenylphosphonium halides such as pentyltriphenylphosphonium chloride, pentyltriphenylphosphonium bromide, and pentyltriphenylphosphonium iodide; and pentyltrimethylphenylphosphonium halides, such as pentyltrimethylphenylphosphonium chloride, pentyltrimethylphenylphosphonium bromide and pentyltrimethylphenylphosphonium iodide.

The triarylphosphonium amyl ylide compound (3) can be prepared by the following method: the triarylphosphonium pentyl ylide compound (3) can be obtained directly by adding a base directly to the reaction system in which the pentyltriarylphosphonium halide (10) has been prepared to perform deprotonation reaction, or by isolating and purifying the pentyltriarylphosphonium halide (10) and then deprotonating it with a base to obtain the triarylphosphonium pentyl ylide compound (3).

Examples of the base used in deprotonating pentyltriarylphosphonium halide (10) include alkyllithium such as n-butyllithium and t-butyllithium; organometallic reagents such as methylmagnesium chloride, methylmagnesium bromide, sodium acetylide and potassium acetylide; metal alkoxides such as potassium tert-butoxide, sodium tert-butoxide, potassium methoxide, sodium methoxide, potassium ethoxide, and sodium ethoxide; and metal amides such as lithium diisopropylamide and sodium bis (trimethylsilyl) amide. In view of reactivity, metal alkoxides are preferable, and potassium tert-butoxide, sodium methoxide, and sodium ethoxide are more preferable.

In view of reactivity, the amount of the base to be used is preferably 0.7 to 5.0 moles per mole of the 1-halopentane compound (8).

The reaction temperature (optimum temperature) in the deprotonated pentyltriarylphosphonium halide (10) varies depending on the solvent and base used, and is preferably from-78 to 40 ℃.

The reaction time for deprotonating the pentyltriarylphosphonium halide (10) varies depending on the solvent used and the scale of production, and is preferably from 0.5 to 50 hours.

If necessary, a solvent may be used in the preparation of the pentyltriarylphosphonium halide (10) and in the deprotonation of the pentyltriarylphosphonium halide (10).

Examples of the solvent include ethereal solvents such as tetrahydrofuran, diethyl ether, dibutyl ether, 4-methyltetrahydropyran, cyclopentyl methyl ether and 1, 4-dioxane; hydrocarbon solvents such as hexane, heptane, benzene, toluene, xylene, and cumene; and polar solvents such as N, N-dimethylformamide, N-dimethylacetamide, N-methylpyrrolidone, dimethylsulfoxide, γ -butyrolactone, acetonitrile, dichloromethane, and chloroform. In view of reactivity, ether solvents such as tetrahydrofuran and 4-methyltetrahydropyran, and polar solvents such as acetonitrile, N-dimethylformamide and N, N-dimethylacetamide are preferable.

The solvents may be used alone or in combination. The solvent may be one commercially available.

In view of reactivity, the amount of the solvent to be used is preferably 10 to 6000g, more preferably 50 to 4000g, per mole of the 1-halogenopentane compound (8) or the pentyltriarylphosphonium halide (10).

In view of reactivity, the triarylphosphonium amyl ylide compound (3) is used in an amount of preferably 1.0 to 4.0 moles, more preferably 1.0 to 2.0 moles, per mole of the formylalkenylalkoxymethyl ether compound (2).

If necessary, a solvent may be used in the wittig reaction.

Examples of the solvent include ether solvents such as tetrahydrofuran, diethyl ether, dibutyl ether, 4-methyltetrahydropyran, cyclopentyl methyl ether and 1, 4-dioxane; hydrocarbon solvents such as hexane, heptane, benzene, toluene, xylene, and cumene; and polar solvents such as N, N-dimethylformamide, N-dimethylacetamide, N-methylpyrrolidone, dimethylsulfoxide, γ -butyrolactone, acetonitrile, dichloromethane, and chloroform. In view of reactivity, ether solvents such as tetrahydrofuran and 4-methyltetrahydropyran and polar solvents such as acetonitrile, N-dimethylformamide and N, N-dimethylacetamide are preferable.

The solvents may be used alone or in combination, if necessary. The solvent may be one commercially available.

In view of reactivity, the amount of the solvent to be used is preferably 10 to 6000g, more preferably 50 to 4000g, per mole of the formylalkenylalkoxymethyl ether compound (2).

The optimum temperature for the wittig reaction varies with the solvent used, preferably from-78 to 40 ℃.

The reaction time in the wittig reaction varies depending on the scale of production and is preferably 0.5 to 50 hours.

Specific examples of the (5E,7Z) -5, 7-dodecadienylalkoxymethyl ether compound (4) include (5E,7Z) -5, 7-dodecadienylmethoxymethyl ether, (5E,7Z) -5, 7-dodecadienylethoxymethyl ether, (5E,7Z) -5, 7-dodecadienylpropoxymethyl ether, (5E,7Z) -5, 7-dodecadienylbutoxymethyl ether, (5E,7Z) -5, 7-dodecadienylpentyloxymethyl ether, (5E,7Z) -5, 7-dodecadienylhexyloxymethyl ether, (5E,7Z) -5, 7-dodecadienylheptyloxymethyl ether, (5E,7Z) -5, 7-dodecadienyloctyloxymethyl ether, (5E,7Z) -5, 7-dodecadienylnonyloxymethyl ether, (5E,7Z) -5, 7-dodecadienyldecyloxymethyl ether, and (5E,7Z) -5, 7-dodecadienylbenzyloxymethyl ether.

Next, the dealkyloxymethylation step will be explained.

Dealkyloxymethylation of the (5E,7Z) -5, 7-dodecadienylalkoxymethyl ether compound (4: a ═ 4) can be carried out using, for example, an acid and an alcohol compound of the following general formula (11) (hereinafter also referred to as alcohol compound (11)).

R⁴OH(11)

Examples of the acid used in dealkoxymethylation include inorganic acids such as hydrochloric acid and hydrobromic acid; and p-toluenesulfonic acid (p-TsOH), benzenesulfonic acid, trifluoroacetic acid, acetic acid, formic acid, oxalic acid, iodotrimethylsilane and titanium tetrachloride. In view of reactivity, p-toluenesulfonic acid and hydrochloric acid are preferred.

The acids may be used alone or in combination, if necessary. The acid may be one that is commercially available.

In view of completion of the reaction, the amount of the acid to be used is preferably 0.001 to 10.0 moles, more preferably 0.01 to 3.0 moles per mole of the (5E,7Z) -5, 7-dodecadienylalkoxymethyl ether compound (4).

In the general formula (11), R is in view of price or versatility⁴Represents a monovalent hydrocarbon having 1 to 15 carbon atoms, preferably having 1 to 6 carbon atoms. A monovalent hydrocarbon group and R in the general formula (1)¹And R²The monovalent hydrocarbon groups are the same.

Examples of the alcohol compound (11) include straight-chain alcohols such as methanol, ethanol, n-propanol, n-butanol, n-pentanol, n-hexanol, n-heptanol, n-octanol, n-nonanol, n-decanol, n-undecanol, n-dodecanol, n-tridecanol, n-tetradecanol, and n-pentadecanol; and branched alcohols such as isopropanol and 2-butanol. Methanol and ethanol are preferable in view of reactivity.

The alcohol compounds (11) may be used in combination, if necessary.

The alcohol compound (11) may be a commercially available one, or the alcohol compound (7) recovered in hydrolysis.

In view of reactivity, the alcohol compound (11) is used in an amount of preferably 1.0 to 100 moles, more preferably 1.0 to 40 moles per mole of the (5E,7Z) -5, 7-dodecadienylalkoxymethyl ether compound (4).

In the dealkyloxymethylation, if necessary, a solvent may be used in addition to the alcohol compound (11).

Examples of the solvent include common solvents, for example, ethers such as butyl ether, 4-methyltetrahydropyran, cyclopentyl methyl ether and 1, 4-dioxane; hydrocarbons such as heptane, benzene, toluene, xylene, and cumene; chlorinated solvents, such as trichloroethylene; aprotic polar solvents such as dimethyl sulfoxide, γ -butyrolactone and hexamethylphosphoric triamide; nitriles such as acetonitrile and propionitrile; and esters such as n-propyl acetate and n-butyl acetate.

The solvents may be used alone or in combination, if necessary. The solvent may be one commercially available.

The amount of the solvent used in the dealkyloxymethylation is preferably from 0 to 2000g, more preferably from 0 to 500g, per mole of the (5E,7Z) -5, 7-dodecadienylalkoxymethyl ether compound (4).

The solvent occupies the inner space of the reactor to reduce the space for the raw material, thereby lowering the yield. Therefore, the reaction can be carried out without using a solvent.

(5E,7Z) -5, 7-dodecadienylacetate of the following formula (6) (hereinafter also referred to as (5E,7Z) -5, 7-dodecadienylacetate (6)) can be obtained by acetylating (5E,7Z) -5, 7-dodecadien-1-ol (5) by the above-described method.

Acetylation of (5E,7Z) -5, 7-dodecadien-1-ol (5) can be carried out using, for example, an acetylating agent.

Examples of acetylating agents include anhydrides such as acetic anhydride; acetyl halides such as acetyl chloride, acetyl bromide and acetyl iodide; and acetate compounds such as methyl acetate and ethyl acetate. Acetic anhydride and acetyl halide are preferable in view of versatility.

The amount of the acetylating agent used is preferably 1.0 to 10.0 moles, more preferably 1.0 to 5.0 moles per mole of (5E,7Z) -5, 7-dodecadien-1-ol (5) in view of reactivity and cost efficiency.

If necessary, an acid or a base may be used in the acetylation reaction.

Examples of the acid include mineral acids such as hydrochloric acid, sulfuric acid and nitric acid; aromatic sulfonic acids such as benzenesulfonic acid and p-toluenesulfonic acid; and lewis acids such as boron trifluoride etherate and tetraisopropyl orthotitanate.

The acids may be used alone or in combination. The acid may be one that is commercially available.

In view of reactivity and cost efficiency, the amount of the acid to be used is preferably 0.01 to 1.00mol, more preferably 0.01 to 0.50 mol, per mol of (5E,7Z) -5, 7-dodecadien-1-ol (5).

Examples of the base include trialkylamines such as trimethylamine, triethylamine and N, N-diisopropylethylamine; aromatic amine compounds such as pyridine, N-dimethylaniline, N-diethylaniline and 4-dimethylaminopyridine; and metal alkoxides such as potassium tert-butoxide, sodium methoxide and sodium ethoxide.

The bases may be used alone or in combination, if necessary.

The amount of the base to be used is preferably 1.0 to 10.0 moles, more preferably 1.0 to 3.0 moles per mole of (5E,7Z) -5, 7-dodecadien-1-ol (5) in view of reactivity and cost effectiveness.

If necessary, a solvent may be used in the acetylation reaction.

Examples of the solvent include common solvents such as ethers, e.g., tetrahydrofuran, diethyl ether, dibutyl ether, 4-methyltetrahydropyran, cyclopentylmethyl ether and 1, 4-dioxane; hydrocarbons such as heptane, benzene, toluene, xylene, and cumene; chlorinated solvents such as dichloromethane, chloroform and trichloroethylene; aprotic polar solvents such as dimethyl sulfoxide, γ -butyrolactone, N-methylpyrrolidone and hexamethylphosphoric triamide; nitriles such as acetonitrile and propionitrile; and esters such as methyl acetate, ethyl acetate, n-propyl acetate, and n-butyl acetate. Hydrocarbons such as toluene and xylene are preferred.

The solvents may be used alone or in combination, if necessary. The solvent may be one commercially available.

The amount of the solvent used in the acetylation is preferably 0 to 2000g, preferably 0 to 500g, per mole of (5E,7Z) -5, 7-dodecadien-1-ol (5).

Accordingly, there is provided a process for producing sex pheromones (5E,7Z) -5, 7-dodecadien-1-ol (5) and (5E,7Z) -5, 7-dodecadienyl acetate (6) of spodoptera littoralis from a formylalkenylalkoxymethyl ether compound (2: a ═ 4).

Examples

The invention will be further described with reference to the following examples. It is to be understood that the invention is not limited to or by the examples.

The term "purity" as used herein, unless otherwise indicated, refers to area percentages as determined by Gas Chromatography (GC). The term "yield" refers to the ratio of area percentages determined by GC. The term "yield" is calculated from the area percentage determined by GC.

In the examples, the monitoring of the reaction was carried out under the following GC conditions.

GC conditions were as follows: capillary gas chromatograph GC-2014(Shimadzu Corporation); column: DB-WAX, 0.25mm by 30 m; carrier gas: he (1.55 mL/min); a detector: FID; temperature of the column: at 150 ℃ the temperature was increased at a rate of 5 ℃/min up to 230 ℃.

The yield was calculated according to the following equation, taking into account the purity (% GC) of the starting material and the product.

Yield (%) { [ (mass of product obtained by reaction ×% GC)/molecular weight of product ]/[ (mass of raw material in reaction ×% GC)/molecular weight of raw material ] } × 100

Example 1: preparation of formylpentenyl methoxymethyl ether (2: R)³＝H；a＝2)，CH₃OCH₂O(CH₂)₂CH＝CHCHO

Diethoxypentenyl methoxymethyl ether (1: R)³H; a 2) (795.07g, 3.54mol, 97.05% pure) and water (106.32g, 5.90mol) were placed in the reactor at room temperature and stirred at 30 to 40 ℃ for 1 hour. After completion of the stirring, formic acid (8.14g, 0.16mol, purity 88%) was added dropwise at 30 to 45 ℃ to cause hydrolysis. Subsequently, 20 mass% hydrochloric acid (0.64g, 0.0035mol of hydrogen chloride) was added dropwise at 30 to 45 ℃ and stirred at 40 to 45 ℃ for 30 minutes.

Subsequently, in the hydrolysis process, the internal temperature is 40 to 55 ℃The pressure was reduced to 235mmHg (31.3kPa) and then gradually to 50mmHg (6.67kPa), wherein the ethanol formed in the hydrolysis (325.85g, 7.01mol, purity 99.11%) was distilled off and removed. 4 hours after the start of the depressurization, no more distillate appeared. Then, toluene (557.04g), water (218.20g), sodium chloride (65.00g), and 20 mass% hydrochloric acid (12.89g, 0.071mol of hydrogen chloride) were added to cause phase separation. The aqueous phase was removed to obtain an organic phase. The organic phase was then washed with brine and then phase separated. The aqueous phase was removed to obtain an organic phase. The organic phase obtained is further washed with aqueous sodium bicarbonate solution and then phase separated. The aqueous phase was removed to obtain an organic phase. The resulting organic phase was distilled under reduced pressure to obtain formylpentenylmethoxymethyl ether (2: R)³H; a 2) (496.73g, 3.29mol, purity 95.41%, b.p. 87.2 to 87.6 ℃/3.0mmHg (0.40kPa)), yield 93.00%.

The progress of hydrolysis was confirmed by measuring the amount of ethanol distilled off. Specifically, the theoretical amount of ethanol formed in the hydrolysis was 326.18g ═ 3.54mol of the starting diethoxypentenylmethoxymethyl ether (1: R)³H; a ═ 2)) × 46.07 (molecular mass of ethanol) × 2 (number of ethanol fractions per feed molecule); when the amount of ethanol formed in the hydrolysis is less than the theoretical amount, it is judged that the hydrolysis is still proceeding. As described above, when the amount of ethanol formed became 325.85g, was substantially the same as the theoretical amount, and did not increase any more, it was judged that hydrolysis was complete.

Formylpentenylmethoxymethyl ether (2: R)³＝H；a＝2)

Nuclear magnetic resonance spectroscopy:¹H-NMR(500MHz,CDCl₃):δ＝2.61(2H,ddt,J＝1.6Hz,6.5Hz,6.5Hz),3.23(3H,s),3.68(2H,t,J＝6.2Hz),4.60(2H,s),6.16(1H,ddt,J＝15.6Hz,10.7Hz,1.6Hz),6.86(1H,dt,J＝15.6Hz,6.5Hz),9.49(1H,d,J＝11.0Hz)；¹³C-NMR(500MHz,CDCl₃):δ＝32.94,55.27,65.40,96.40,134.19,154.87,193.75.

mass Spectrometry EI-Mass Spectrometry (70eV): M/z 114 (M)⁺-30),99,83,75,55,45.

And (3) infrared absorption spectrum (NaCl): nu 2934,2886,2824,1691,1151,1110,1043,974,918.

EXAMPLE 2 preparation of formylpentenylmethoxymethyl ether (2: R)³＝H；a＝2)，CH₃OCH₂O(CH₂)₂CH＝CHCHO

Diethoxypentenyl methoxymethyl ether (1: R)³H; a ═ 2) (283.84g, 1.26mol, purity 97.05%) and water (37.96g, 2.11mol) were placed in the reactor at room temperature and stirred for 22 minutes at 30 to 40 ℃. After completion of the stirring, formic acid (2.56g, 0.049mol, purity 88%) was added dropwise at 30 to 45 ℃ to cause hydrolysis. Subsequently, 20 mass% hydrochloric acid (0.23g, 0.0013mol of hydrogen chloride) was added dropwise at 30 to 45 ℃ and stirred at 40 to 45 ℃ for 100 minutes.

Subsequently, in the hydrolysis, the pressure was reduced to 235mmHg (31.3kPa) and then gradually reduced to 50mmHg (6.67kPa) under conditions of an internal temperature of 40 to 55 ℃, wherein ethanol (123.12g, 2.61mol, purity 97.51%) formed in the hydrolysis was distilled off and removed. 4 hours after the start of the depressurization, no more distillate appeared. Then, the pressure was further reduced to 3.0mmHg (0.40kPa), and the reaction mixture was distilled under reduced pressure to obtain formylpentenylmethoxymethyl ether (2: R)³H; a 2) (182.44g, 1.20mol, purity 94.59%, b.p. 87.6 to 88.6 ℃/3.0mmHg (0.40kPa)), yield 94.88%.

The progress of hydrolysis was confirmed in the same manner as in example 1.

The various spectral data of the formylpentenylmethoxymethyl ether thus prepared are identical to those obtained in example 1.

Comparative example 1 preparation of formylpentenylmethoxymethyl ether (2: R)³＝H；a＝2)，CH₃OCH₂O(CH₂)₂CH＝CHCHO

Diethoxypentenyl methoxymethyl ether (1: R)³H; a ═ 2) (283.84g, 1.26mol, purity 97.05%) and toluene (80.00g) were placed in the reactor at room temperature and stirred for 6 minutes at 10 to 15 ℃. After completion of the stirring, 8 mass% hydrochloric acid (145.13g, 0.32mol of hydrogen chloride) was added dropwise at 15 to 20 ℃ to carry out hydrolysis. The progress of hydrolysis was monitored by GC at 15 to 20 ℃. After the conversion was confirmed to be 99.5% or more, the reaction was stopped. The reaction time from the dropwise addition of 8 mass% hydrochloric acid to the termination of the reaction was 1 hour. Toluene (200.00g) was further added to the reaction mixture, followed by phase separation. The aqueous phase was then removed to obtain an organic phase. The organic phase was then washed with brine and then phase separated. The aqueous phase was then removed to obtain an organic phase. The organic phase obtained is further washed with aqueous sodium bicarbonate solution and then phase separated. The aqueous phase was then removed to obtain an organic phase. The organic phase obtained is subjected to distillation under reduced pressure to obtain formylpentenylmethoxymethyl ether (2: R)³H; a 2) (131.78g, 0.84mol, purity 91.47%, b.p. 87.2 to 87.6 ℃/3.0mmHg (0.40kPa)), yield 66.25%. Each removed aqueous phase contains ethanol formed in the hydrolysis.

The various spectral data of the formylpentenylmethoxymethyl ether thus prepared are identical to those obtained in example 1.

Comparative example 2 preparation of formylpentenylmethoxymethyl ether (2: R)³＝H；a＝2)，CH₃OCH₂O(CH₂)₂CH＝CHCHO

The procedure of comparative example 1 was repeated to obtain formylpentenylmethoxymethyl ether (2: R)³H; a 2) (171.49g, 1.06mol, purity 89.12%, b.p. 87.2 to 87.6 ℃/3.0mmHg (0.40kPa)), yield 84.00%. Although comparative examples 1 and 2 were performed under the same conditions, the yield in comparative example 1 was 66.25%, and that in comparative example 2 was 84.00%. Thus, the yield was changed.

The various spectral data of the formylpentenylmethoxymethyl ether thus prepared are identical to those obtained in example 1.

Comparative example 3 preparation of formylpentenylmethoxymethyl ether (2: R)³＝H；a＝2)，CH₃OCH₂O(CH₂)₂CH＝CHCHO

Diethoxypentenyl methoxymethyl ether (1: R)³H; a ═ 2) (283.84g, 1.26mol, purity 97.05%) and water (37.96g, 2.11mol) were placed in the reactor at room temperature and stirred at 30 to 40 ℃ for 1 hour. After completion of the stirring, formic acid (2.56g, 0.049mol, purity 88%) was added dropwise at 30 to 45 ℃ to allow hydrolysis to proceed. Subsequently, 20 mass% hydrochloric acid (0.23g, 0.0013mol of hydrogen chloride) was added dropwise at 30 to 45 ℃ and stirred at 40 to 45 ℃ for 30 minutes.

Subsequently, the progress of hydrolysis was monitored by GC at an internal temperature of 40 to 55 ℃. After the conversion was confirmed to be 99.5% or more, the reaction was stopped. The reaction time from the dropwise addition of 20 mass% hydrochloric acid to the termination of the reaction was 4.5 hours. Toluene (200.00g) was further added to the reaction mixture, followed by phase separation. The aqueous phase was then removed to obtain an organic phase. The organic phase was then washed with brine and then phase separated. The aqueous phase was then removed to obtain an organic phase. The organic phase obtained is further washed with aqueous sodium bicarbonate solution and then phase separated. The aqueous phase was then removed to obtain an organic phase. The resulting organic phase was subjected to distillation under reduced pressure to obtain formylpentenylmethoxymethyl ether (2: R)³H; a 2) (149.40g, 0.93mol, purity 90.10%, b.p. 82.6 to 85.4 ℃/3.0mmHg (0.40kPa)), yield 73.98%. Although comparative example 3 was performed under the same conditions as example 1 except that ethanol was distilled and removed, comparative example 3 yielded 73.98% and 90.10% purity, which were lower than 93.00% yield and 95.41% purity of example 1.

The various spectral data of the formylpentenylmethoxymethyl ether thus prepared are identical to those obtained in example 1.

EXAMPLE 3 preparation of formylpentenyl ethoxymethyl ether (2: R)³＝CH₃；a＝2)，CH₃CH₂OCH₂O(CH₂)₂CH＝CHCHO

Diethoxypentenylmethoxymethyl ether (1: R) was reacted at room temperature³＝CH₃(ii) a a 2) (308.10g, 1.26mol, purity 95.16%) and water (37.96g, 2.11mol) were placed in the reactor and stirred at 30 to 40 ℃ for 22 minutes. After completion of the stirring, formic acid (2.56g, 0.049mol, purity 88%) was added dropwise at 30 to 45 ℃ to allow hydrolysis to proceed. Subsequently, 20 mass% hydrochloric acid (0.23g, 0.0013mol of hydrogen chloride) was added dropwise at 30 to 45 ℃ and stirred at 40 to 45 ℃ for 60 minutes.

Subsequently, in the progress of hydrolysis, the pressure was reduced to 235mmHg (31.3kPa) with an internal temperature of 40 to 55 ℃ and then gradually reduced to 50mmHg (6.67 kPa). The ethanol formed in the hydrolysis (119.02g, 2.53mol, purity 97.75%) was distilled off. 4 hours after the start of the depressurization, no more distillate appeared. Then, toluene (234.56g), water (77.90g), sodium chloride (23.21g), and 20 mass% hydrochloric acid (4.60g, 0.025mol of hydrogen chloride) were added to cause phase separation. The aqueous phase was removed to obtain an organic phase. The organic phase was then washed with brine and then phase separated. The aqueous phase was then removed to obtain an organic phase. The organic phase obtained is further washed with aqueous sodium bicarbonate solution and then phase separated. The aqueous phase was then removed to obtain an organic phase. The organic phase obtained is subjected to distillation under reduced pressure to obtain formylpentenyl ethoxymethyl ether (2: R)³＝CH₃(ii) a a 2) (197.56g, 1.139mol, purity 91.20%, b.p. 85.0 to 86.1 ℃/3.0mmHg (0.40kPa)), yield 90.26%.

The progress of hydrolysis was confirmed in the same manner as in example 1.

Formylpentenyl ethoxymethyl ether (2: R)³＝CH₃；a＝2)

Nuclear magnetic resonanceVibration spectrum:¹H-NMR(500MHz,CDCl₃):δ＝1.19(3H,t,J＝6.9Hz),2.60(2H,ddt,J＝15.6Hz,6.5Hz,6.5Hz),3.56(2H,q,J＝6.9Hz),3.69(2H,t,J＝6.5Hz),4.65(2H,s),6.16(1H,ddt,J＝15.6Hz,8.1Hz,1.5Hz),6.85(1H,dt,J＝15.6Hz,6.5Hz),9.49(1H,d,J＝8.0Hz)；¹³C-NMR(500MHz,CDCl₃):δ＝15.05,32.96,63.34,65.40,95.07,134.17,154.96,193.76

mass Spectrometry EI-Mass Spectrometry (70eV): M/z 128 (M)⁺-30),113,98,83,70,59,41.

And (3) infrared absorption spectrum (NaCl): nu 2976,2931,2878,1692,1114,1099,1042,975,847.

Comparative example 4 preparation of formylpentenyl ethoxymethyl ether (2: R)³＝CH₃；a＝2)，CH₃CH₂OCH₂O(CH₂)₂CH＝CHCHO

Diethoxypentenyl ethoxymethyl ether (1: R)³＝CH₃(ii) a a ═ 2) (308.10g, 1.26mol, purity 95.16%) and toluene (80.00g) were placed in the reactor at room temperature and stirred at 10 to 15 ℃ for 31 minutes. After completion of the stirring, 8 mass% hydrochloric acid (145.13g, 0.32mol of hydrogen chloride) was added dropwise at 15 to 20 ℃ to allow hydrolysis to proceed. The progress of hydrolysis was monitored by GC at 15 to 20 ℃. After the conversion was confirmed to be 99.5% or more, the reaction was stopped. The reaction time from the dropwise addition of 8 mass% hydrochloric acid to the termination of the reaction was 1 hour. Toluene (200.00g) was further added to the reaction mixture, followed by phase separation. The aqueous phase was then removed to obtain an organic phase. The organic phase was then washed with brine and then phase separated. The aqueous phase was then removed to obtain an organic phase. The organic phase obtained is further washed with aqueous sodium bicarbonate solution and then phase separated. The aqueous phase was then removed to obtain an organic phase. The organic phase obtained is subjected to distillation under reduced pressure to obtain formylpentenyl ethoxymethyl ether (2: R)³＝CH₃(ii) a a 2) (141.18g, 0.74mol, purity 82.61%, b.p. 85.0 to 86.1 ℃/3.0mmHg (0.40kPa)), yield 58.42% of the total weight of the composition. Each removed aqueous phase contains ethanol formed in the hydrolysis.

The formylpentenyl ethoxymethyl ether (2: R) thus prepared³＝CH₃(ii) a a ═ 2) were identical to those obtained in example 3.

Comparative example 5: preparation of formylpentenyl ethoxymethyl ether (2: R)³＝CH₃；a＝2)，CH₃CH₂OCH₂O(CH₂)₂CH＝CHCHO

The procedure of comparative example 4 was repeated to obtain formylpentenylethoxymethyl ether (2: R)³＝CH₃(ii) a a 2) (171.46g, 0.90mol, purity 82.91%, b.p. 85.0 to 86.1 ℃/3.0mmHg (0.40kPa)), yield 71.21%. Although comparative examples 4 and 5 were performed under the same conditions, the yield was 58.42% in comparative example 4 and 71.21% in comparative example 5. Thus, the yield was changed.

The formylpentenyl ethoxymethyl ether (2: R) thus prepared³＝CH₃(ii) a a ═ 2) were identical to those obtained in example 3.

Example 4: preparation of formyl heptenyl methoxymethyl ether (2: R)³＝H；a＝4)，CH₃OCH₂O(CH₂)₄CH＝CHCHO

Diethoxy heptenyl methoxy methyl ether (1: R)³H; a-4) (500.00g, 1.95mol, purity 95.97%) and water (58.60g, 3.25mol) were placed in the reactor at room temperature and stirred at 30 to 40 ℃ for 12 minutes. After completion of the stirring, formic acid (3.95g, 0.076mol, purity 88%) was added dropwise at 30 to 45 ℃ to cause hydrolysis. Subsequently, 20 mass% hydrochloric acid (0.35g, 0.0019mol of hydrogen chloride) was added dropwise at 30 to 45 ℃And stirred at 40 to 45 ℃ for 104 minutes.

Subsequently, in the progress of hydrolysis, the pressure was reduced to 235mmHg (31.3kPa) with an internal temperature of 40 to 55 ℃ and then gradually reduced to 50mmHg (6.67 kPa). The ethanol formed in the hydrolysis (192.43g, 4.12mol, purity 98.74%) was distilled off. 4.5 hours after the start of the depressurization, no more distillate appeared. Then, toluene (362.06g), water (120.25g), sodium chloride (35.83g), and 20 mass% hydrochloric acid (7.10g, 0.039mol of hydrogen chloride) were added to cause phase separation. The aqueous phase was then removed to obtain an organic phase. The organic phase was then washed with brine and then phase separated. The aqueous phase was then removed to obtain an organic phase. The organic phase obtained is further washed with aqueous sodium bicarbonate solution and then phase separated. The aqueous phase was then removed to obtain an organic phase. The resulting organic phase was subjected to distillation under reduced pressure to obtain formylheptenylmethoxymethyl ether (2: R)³H; a 4) (340.59g, 1.83mol, purity 92.73%, b.p. 108.2 to 109.8 ℃/3.0mmHg (0.40kPa)), yield 94.14%.

The progress of hydrolysis was confirmed in the same manner as in example 1.

Formyl heptenyl methoxymethyl ether (2: R)³＝H；a＝4)

Nuclear magnetic resonance spectroscopy:¹H-NMR(500MHz,CDCl₃):δ＝1.55-1.66(4H,m),2.35(2H,ddt,J＝1.6Hz,7.1Hz,7.1Hz),3.33(3H,s),3.52(2H,t,J＝6.1Hz),4.59(2H,s),6.10(1H,ddt,J＝15.7Hz,8.0Hz,1.6Hz),6.83(1H,dt,J＝15.7Hz,6.9Hz),9.48(1H,d,J＝8.0Hz)；¹³C-NMR(500MHz,CDCl₃):δ＝24.52,29.10,32.33,55.07,67.09,96.33,133.06,158.26,193.95.

mass Spectrometry EI-Mass Spectrometry (70eV): M/z 127 (M)⁺-45),114,81,68,55,45.

And (3) infrared absorption spectrum (NaCl): nu 2938,2882,2822,1692,1149,1111,1043,977,918.

Comparative example 6 preparation of formyl heptenyl methoxymethyl ether (2: R)³＝H；a＝4)，CH₃OCH₂O(CH₂)₄CH＝CHCHO

Diethoxy heptenyl methoxy methyl ether (1: R)³H; a-4) (100.00g, 0.39mol, purity 95.97%) and toluene (24.70g) were placed in the reactor at room temperature and stirred at 10 to 15 ℃ for 3 minutes. After completion of the stirring, 8 mass% hydrochloric acid (44.80g, 0.098mol of hydrogen chloride) was added dropwise at 15 to 20 ℃ to carry out hydrolysis. The progress of hydrolysis was monitored by GC at 15 to 20 ℃. After the conversion was confirmed to be 99.5% or more, the reaction was stopped. The reaction time from the dropwise addition of 8 mass% hydrochloric acid to the termination of the reaction was 1 hour. Toluene (61.74g) was further added to the reaction mixture, followed by phase separation. The aqueous phase was then removed to obtain an organic phase. The organic phase was then washed with brine and then phase separated. The aqueous phase was then removed to obtain an organic phase. The organic phase obtained is further washed with aqueous sodium bicarbonate solution and then phase separated. The aqueous phase was then removed to obtain an organic phase. The resulting organic phase was subjected to distillation under reduced pressure to obtain formylheptenylmethoxymethyl ether (2: R)³CH 3; a ═ 4) (61.03g, 0.32mol, purity 90.97%, b.p. ═ 108.2 to 109.8 ℃/3.0mmHg (0.40kPa)), yield 82.75%.

Formyl heptenyl methoxymethyl ether (2: R) thus prepared³H; a-4) are identical to those obtained in example 4.

Example 5: preparation of (5E,7Z) -5, 7-dodecadienylalkoxymethyl ether Compound (4: R)³＝H；a＝4)，CH₃(CH₂)₃CH＝CHCH＝CH(CH₂)₄OCH₂OCH₃

1-bromopentane (8: X ═ Br) (182.77g, 1.21mol), triphenylphosphine (9: each Ar ═ Ph) (315.50g, 1.20mol) and N, N-Dimethylformamide (DMF) (200.00g) were placed in a reactor at room temperature and stirred at 110-. Subsequently, tetrahydrofuran (872.84g) was added dropwise to the reaction mixture at 30-40 ℃. After the addition was complete, the reaction mixture was cooled to-5 to 10 ℃, and potassium tert-butoxide (131.29g, 1.17mol) was added and stirred for 1 hour to prepare triphenylphosphonium amyl ylide (3: Ar ═ Ph).

The formyl heptenylmethoxymethyl ether (2: R) obtained in example 4 was then added dropwise at-72 to-61 deg.C³H; a is 4) (185.72g, 1.00mol, purity 92.73%). After completion of the dropwise addition, the mixture was warmed to room temperature and stirred at 25 to 30 ℃ for 1 hour. Water (592.67g) was then added to the reaction mixture, followed by phase separation. The aqueous phase was then removed to obtain an organic phase. The resulting organic phase was distilled under reduced pressure to obtain (5E,7Z) -5, 7-dodecadienylalkoxymethyl ether compound (4: R)³H; a-4) (230.28g, 0.97mol, purity 95.82%; 5E 7Z: 5E 7E: 5Z7Z ═ 91.8: 6.6: 1.6, b.p. -, 104.0 to 123.5 ℃/3.0mmHg (0.40kPa)), the yield was 97.48%.

(5E,7Z) -5, 7-dodecadienylalkoxymethyl ether compound (4: R)³＝H；a＝4)

Nuclear magnetic resonance spectroscopy:¹H-NMR(500MHz,CDCl₃):δ＝0.90(3H,t,J＝7.3Hz),1.28-1.39(4H,m),1.42-1.51(2H,quin-like,J＝7.3Hz),1.57-1.64(2H,quin-like,J＝7.3Hz),2.10-2.18(4H,m),3.35(3H,s),3.52(2H,t,J＝6.5Hz),4.61(2H,s),5.30(1H,dt,J＝10.9Hz,7.6Hz),5.64(1H,dt,J＝14.5Hz,7.6Hz),5.93(1H,dd,J＝11.1Hz,11.1Hz),6.29(1H,dddt,J＝14.9Hz,11.1Hz,2.7Hz,1.2Hz)；¹³C-NMR(500MHz,CDCl₃):δ＝13.92,22.28,25.96,27.35,29.22,31.85,32.55,55.04,67.54,96.32,125.95,128.43,130.27,133.94.

mass Spectrometry EI-Mass Spectrometry (70eV): M/z 226 (M)⁺),194,181,163,150,137,121,107,95,79,67,45.

And (3) infrared absorption spectrum (NaCl): nu 2929,2872,1458,1440,1150,1112,1044,983,949,921,732.

Example 6: preparation of (5E,7Z) -5, 7-dodecadien-1-ol (5), CH₃(CH₂)₃CH＝CHCH＝CH(CH₂)₄OH

(5E,7Z) -5, 7-dodecadienylalkoxymethyl ether compound (4: R) obtained in example 5³H; a is 4) (210.84g, 0.89mol, purity 95.82%; 5E 7Z: 5E 7E: 5Z7Z ═ 91.8: 6.6: 1.6) and methanol (446.25g, 13.93mol) were placed in a reactor equipped with a distillation column and stirred at 45 to 50 ℃ and then 20 mass% hydrochloric acid (44.63g, 0.24mol of hydrogen chloride) was added dropwise to the mixture at 45 to 50 ℃.

Subsequently, the reaction mixture was heated to 60 ℃ and stirred for 3 hours. After completion of the stirring, the internal temperature was raised to 65 to 70 ℃, and a mixture of by-product dimethoxymethane and by-product methanol was distilled off and removed by a distillation column. The reaction mixture was sampled during the reaction. After confirming that the conversion was 100%, the distillation was stopped. The reaction mixture was cooled to 35 ℃ and water (286g) was added to the reaction mixture, followed by phase separation. The aqueous phase was then removed to obtain an organic phase. The obtained organic phase was distilled under reduced pressure to obtain (5E,7Z) -5, 7-dodecadien-1-ol (5) (162.54g, 0.81mol, purity 91.35%; 5E 7Z: 5E 7E: 5Z7Z ═ 91.1: 7.1: 1.8, b.p.: 106.2-115.6 ℃/3.0mmHg (0.40kPa)) in a yield of 91.26%.

(5E,7Z) -5, 7-dodecadien-1-ol (5)

Nuclear magnetic resonance spectroscopy:¹H-NMR(500MHz,CDCl₃):δ＝0.89(3H,t,J＝7.3Hz),1.24-1.40(4H,m),1.46(2H,quin-like,J＝7.3Hz),1.58(2H,quin-like,J＝7.3Hz),1.72(1H,br.s),2.14(4H,sext-like,J＝6.5Hz),3.64(2H,t,J＝6.5Hz),5.30(1H,dt,J＝10.9Hz,7.6Hz),5.64(1H,dt,J＝14.6Hz,7.3Hz),5.93(1H,dd,J＝11.1Hz,11.1Hz),6.31(1H,dddt,J＝15.1Hz,11.0Hz,1.5Hz,1.5Hz)；¹³C-NMR(500MHz,CDCl₃):δ＝13.92,22.28,25.45,27.35,31.84,32.20,32.50,62.73,125.97,128.39,130.33,133.90.

mass Spectrometry EI-Mass Spectrometry (70eV): M/z 182 (M)⁺),164,149,135,121,107,93,79,67,55,41.

And (3) infrared absorption spectrum (NaCl): nu 3338,2956,2930,1457,1059,982,949,730.

Example 7: preparation of (5E,7Z) -5, 7-dodecadienylacetate (6), CH₃(CH₂)₃CH＝CHCH＝CH(CH₂)₄OCOCH₃

(5E,7Z) -5, 7-dodecadien-1-ol (5) (154.50g, 0.77mol, purity 91.35%; 5E 7Z: 5E 7E: 5Z7Z ═ 91.1: 7.1: 1.8) obtained in example 6 and pyridine (97.98g, 1.24mol) were placed in a reactor at room temperature and stirred at 15 to 25 ℃ for 13 minutes. After completion of stirring, acetic anhydride (94.85g, 0.93mol) was added dropwise at 20 to 40 ℃ and stirred at 30 to 35 ℃ for 6 hours. Next, water (203.36g) was added to the reaction mixture, followed by phase separation. The aqueous phase was then removed to obtain an organic phase. The obtained organic phase was distilled under reduced pressure to obtain (5E,7Z) -5, 7-dodecadienylacetic acid ester (6) (181.52g, 0.76mol, purity 93.93%; 5E 7Z: 5E 7E: 5Z7Z ═ 91.5: 6.8: 1.7, b.p.: 120.0-123.0 ℃/4.0mmHg (0.53kPa)) in 98.17% yield.

(5E,7Z) -5, 7-dodecadienylacetate (6)

Nuclear magnetic resonance spectroscopy:¹H-NMR(500MHz,CDCl₃):δ＝0.89(3H,t,J＝7.3Hz),1.27-1.40(4H,m),1.45(2H,quin-like,J＝7.6Hz),1.63(2H,quin-like,J＝6.9Hz),2.03(3H,s),2.14(4H,sext-like,J＝6.9Hz),4.05(2H,t,J＝6.5Hz),5.31(1H,dt,J＝10.7Hz,7.6Hz),5.62(1H,dt,J＝14.5Hz,6.9Hz),5.93(1H,dd,J＝11.1Hz,11.1Hz),6.30(1H,ddd,J＝15.3Hz,11.1Hz,1.2Hz)；¹³C-NMR(500MHz,CDCl₃):δ＝13.91,20.94,22.27,25.65,27.35,28.07,31.83,32.33,64.34,126.15,128.34,130.45,133.53,171.13.

mass Spectrometry EI-Mass Spectrometry (70eV): M/z 224 (M)⁺),181,164,149,136,121,107,93,79,67,55.

And (3) infrared absorption spectrum (NaCl): nu 2956,2930,2859,1742,1457,1365,1238,1039,984,950,733.