Method for producing formylalkenyl alkoxymethyl ether compound and method for producing conjugated diene compound using the same

Abstract

To produce a formylalkenyl=alkoxymethyl=ether compound in high purity and high yield by suppressing deprotection of an alkoxymethyl group of a dialkoxyalkenyl=alkoxymethyl=ether compound, and selectively hydrolyzing only acetal.SOLUTION: The present invention provides a method of producing a formylalkenyl=alkoxymethyl=ether compound (2) represented by the general formula (2): R3CH2OCH2O(CH2)aCH=CHCHO (2) where, in the formula, R3 and a are the same as defined hereunder, by hydrolyzing a dialkoxyalkenyl=alkoxymethyl=ether compound represented by the general formula (1): R3CH2OCH2O(CH2)aCH=CHCH(OR1)(OR2) (1) where, in the formula, R1 and R2 are each independently a univalent 1-15C hydrocarbon group, or a bivalent 2-10C hydrocarbon group as R1-R2 generated by mutually bonding R1 and R2, R3 is a hydrogen atom, a 1-9C n-alkyl group or a phenyl group, a is an integer of 1-10, in the presence of acid while removing a generated alcohol compound.SELECTED DRAWING: None

Description

[Technical field]

[0001] The present invention relates to a method for producing a formyl alkenyl alkoxymethyl ether compound and a method for producing a conjugated diene compound using the same. [Background technology]

[0002] Formyl alkenyl alkoxymethyl ether compounds are very useful as synthetic precursors for insect pheromones having a conjugated diene skeleton, since they can be used to construct a conjugated diene skeleton through the Wittig reaction. Thysanoplusia Intermixta The sex pheromones of the moth, (5E,7Z)-5,7-dodecadien-1-ol and (5E,7Z)-5,7-dodecadienyl acetate, are known (Non-Patent Document 1 below). As a method for synthesizing a formylalkenyl alkoxymethyl ether compound, a method in which (Z)-5,5-diethoxy-3-pentenyl methoxymethyl ether is hydrolyzed using hydrochloric acid, followed by extraction with toluene (Patent Document 1 below), and a method in which 5-(methoxymethoxy)-2-pentyn-1-ol is hydroaluminized using lithium aluminum hydride, followed by Parikh-Doering oxidation (Non-Patent Document 2 below) have been reported. [Prior art documents] [Patent documents]

[0003] [Patent Document 1] JP 2009-132647 A [Non-patent literature]

[0004] [Non-Patent Document 1] T. Ando, ​​J. Chem. Ecol., 1998, 24(6), 1105-1116. [Non-Patent Document 2] Xiaoyu Wu et al.,Synthesis,2011,22,3675-3679. Summary of the Invention [Problem to be solved by the invention]

[0005] However, in Non-Patent Document 2, flammable lithium aluminum hydride is used, and therefore it is not suitable for industrial production. In addition, since dimethyl sulfoxide is used in the above-mentioned Parrick-Deering oxidation, dimethyl sulfide, which has a foul odor, is produced as a by-product during the reaction. If the concentration of dimethyl sulfide is high, it can cause oxygen deficiency and, in the worst case, can be fatal, and it can also react with an oxidizing agent to cause an accident such as a fire or explosion. Furthermore, a mixture of dimethyl sulfide, which is a special flammable material, and air is prone to explosion, so special manufacturing or processing equipment is required, and therefore it is not suitable for industrial production. In addition, since dichloromethane, which has a very high environmental load, is used as a solvent, it is not preferable from the environmental point of view.

[0006] On the other hand, in Patent Document 1, since the hydrolysis reaction is an equilibrium reaction, a certain amount of the raw material (Z)-5,5-diethoxy-3-pentenyl methoxymethyl ether remains, the reaction is not completed, and the progress of the reaction needs to be tracked by sampling the reaction solution. In addition, in the production method of Patent Document 1, it is necessary to selectively hydrolyze only diethyl acetal among diethyl acetal, which is a protecting group of a carbonyl group, and methoxymethyl group (MOM group), which is a protecting group of a hydroxyl group, present in the same molecule. However, since the ethanol generated during the hydrolysis reaction and the hydrochloric acid used in the hydrolysis reaction are the deprotection conditions for the methoxymethyl group, the deprotection of the methoxymethyl group also proceeds along with the hydrolysis of diethyl acetal, resulting in an unstable yield. Furthermore, the generated ethanol is 1,4-added to the target (E)-4-formyl-3-butenyl methoxymethyl ether, and (E)-4-formyl-3-ethoxybutyl methoxymethyl ether and the like are by-produced, resulting in a low purity. As described above, it is not easy to selectively hydrolyze only the dialkyl acetal among the dialkyl acetal and alkoxymethyl groups present in the same molecule. Therefore, a method for selectively hydrolyzing only the dialkyl acetal in the hydrolysis of a dialkoxyalkenyl alkoxymethyl ether compound and producing a formylalkenyl alkoxymethyl ether compound in high yield has been desired.

[0007] The present invention aims to solve the above problems, suppress deprotection of the alkoxymethyl group of a dialkoxyalkenyl alkoxymethyl ether compound, and selectively hydrolyze only the acetal to produce a formylalkenyl alkoxymethyl ether compound with high purity and high yield. Another object of the present invention is to provide a method for producing a formylalkenyl alkoxymethyl ether compound that is favorable from the viewpoints of environment and productivity. [Means for solving the problem]

[0008] As a result of intensive research, the present inventors have found that by carrying out a hydrolysis reaction in the presence of an acid and continuing the hydrolysis reaction while removing the alcohol compound produced in the hydrolysis reaction, a formyl alkenyl alkoxymethyl ether compound can be stably produced in high yield and high purity without using an extraction solvent and / or sampling the reaction solution during the reaction, thus completing the present invention.Furthermore, the present inventors have further found that (5E,7Z)-5,7-dodecadien-1-ol and (5E,7Z)-5,7-dodecadienyl acetate can be produced simply and in high yield using the produced formyl alkenyl alkoxymethyl ether compound as an intermediate, thus completing the present invention.

[0009] In one aspect of the invention, The following general formula (1) R 3 CH2OCH2O(CH2) a CH=CHCH(OR 1 )(OR 2 ) (1) (In the formula, R 1 and R 2 are each independently a monovalent hydrocarbon group having 1 to 15 carbon atoms, or R 1 and R 2 are bonded together R 1 -R 2 represents a divalent hydrocarbon group having 2 to 10 carbon atoms; R 3 represents a hydrogen atom, an n-alkyl group having 1 to 9 carbon atoms, or a phenyl group, and a represents an integer of 1 to 10. In the presence of an acid, a dialkoxyalkenyl alkoxymethyl ether compound represented by the following general formula (2) is hydrolyzed while removing the generated alcohol compound. R 3 CH2OCH2O(CH2) a CH=CHCHO (2) (In the formula, R 3 and a is as defined above. The present invention provides a method for producing a formyl alkenyl alkoxymethyl ether compound (2) represented by the formula:

[0010] In another embodiment of the present invention, after the hydrolysis reaction, the formyl alkenyl alkoxymethyl ether compound (2) (wherein a is 4) obtained above is reacted with a compound represented by the following general formula (3): [ka] (In the formula, each Ar independently represents an aryl group.) The triarylphosphonium pentylide compound represented by the following general formula (4) is subjected to a Wittig reaction with the CH3(CH2)3CH=CHCH=CH(CH2)4OCH2OCH2R 3 (4) (In the formula, R 3 is as defined above.) The (5E,7Z)-5,7-dodecadienyl alkoxymethyl ether compound (4) is then dealkoxymethylated to obtain a compound represented by the following formula (5): CH3(CH2)3CH=CHCH=CH(CH2)4OH (5) The present invention provides a method for producing (5E,7Z)-5,7-dodecadien-1-ol represented by the formula:

[0011] In still another embodiment of the present invention, the (5E,7Z)-5,7-dodecadien-1-ol (5) obtained above is acetylated to obtain a compound represented by the following formula (6): CH3(CH2)3CH=CHCH=CH(CH2)4OCOCH3(6) The present invention provides a method for producing (5E,7Z)-5,7-dodecadienyl acetate represented by the formula: Effect of the Invention

[0012] According to the present invention, the progress of the reaction can be confirmed by measuring the weight of the alcohol compound removed in the hydrolysis reaction, so that tracking of the reaction by sampling the reaction solution is not necessary, and workability and safety can be improved. Furthermore, according to the present invention, since the amount of alcohol compound present in the reaction system is small, by-products such as (E)-4-formyl-3-alkoxybutyl alkoxymethyl ether can be suppressed, and the reaction can be completed without leaving any dialkoxyalkenyl alkoxymethyl ether compound. Therefore, the formyl alkenyl alkoxymethyl ether compound (2) can be produced inexpensively with high productivity and high yield and high purity. Furthermore, according to the present invention, the produced formyl alkenyl alkoxymethyl ether compound (2) can be used to easily produce (5E,7Z)-5,7-dodecadien-1-ol (5) and (5E,7Z)-5,7-dodecadienyl acetate (6), which are sex pheromones of the chrysanthemum looper moth, with high yield. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0013] A formyl alkenyl alkoxymethyl ether compound represented by the following general formula (2) (hereinafter also referred to as "formyl alkenyl alkoxymethyl ether compound (2)") can be obtained by hydrolyzing a dialkoxy alkenyl alkoxymethyl ether compound represented by the following general formula (1) (hereinafter also referred to as "dialkoxy alkenyl alkoxymethyl ether compound (1)") in the presence of an acid. R 3 CH2OCH2O(CH2) a CH=CHCH(OR 1 )(OR 2 ) (1) R 3 CH2OCH2O(CH2) a CH=CHCHO (2)

[0014] First, the dialkoxyalkenyl alkoxymethyl ether compound (1) will be described below.

[0015] In the above general formula (1), R 1 and R 2 are each independently a monovalent hydrocarbon group having 1 to 15, preferably 1 to 4, carbon atoms, or R 1 and R 2 are bonded together R 1 -R 2 represents a divalent hydrocarbon group having 2 to 10 carbon atoms, preferably 2 to 5 carbon atoms, and more preferably 2 to 4 carbon atoms. R 1 and R 2 Examples of the monovalent hydrocarbon group include linear saturated hydrocarbon groups such as methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, n-tridecyl, n-tetradecyl, and n-pentadecyl; branched saturated hydrocarbon groups such as isopropyl, 2-methylbutyl, and t-butyl; branched unsaturated hydrocarbon groups such as 2-methyl-2-propenyl; cyclic saturated hydrocarbon groups such as cyclopropyl; and aryl groups such as phenyl, and may be hydrocarbon groups that are isomers of these. In addition, some of the hydrogen atoms of these hydrocarbon groups may be substituted with methyl, ethyl, etc. R 1 -R 2Examples of the divalent hydrocarbon group include linear 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; linear unsaturated hydrocarbon groups such as a 1-vinylethylene group; Examples of the saturated hydrocarbon group include branched saturated hydrocarbon groups such as 1,2-propylene, 2,2-dimethyl-1,3-propylene, 1,2-butylene, 1,3-butylene, 2,3-butylene, and 2,3-dimethyl-2,3-butylene groups, branched unsaturated hydrocarbon groups such as 2-methylene-1,3-propylene, and cyclic hydrocarbon groups such as 1,2-cyclopropylene and 1,2-cyclobutylene groups, and may be hydrocarbon groups which are isomers of these groups. In addition, some of the hydrogen atoms of these hydrocarbon groups may be substituted with methyl groups, ethyl groups, or the like. In consideration of the reactivity in deprotection, ease of purification, and ease of availability, the divalent hydrocarbon group is preferably a lower hydrocarbon group (preferably having 2 to 4 carbon atoms) which is highly reactive and from which by-products generated by deprotection can be easily removed by washing with water or concentration. Considering these, preferred examples of the divalent hydrocarbon group include an ethylene group, a 1,2-propylene group, a 1,3-propylene group, a 1,2-butylene group, a 1,3-butylene group, and a 2,3-dimethyl-2,3-butylene group.

[0016] In the above general formula (1), a represents an integer of 1 to 10, preferably 1 to 4.

[0017] In the above general formula (1), R 3 represents a hydrogen atom, an n-alkyl group having 1 to 9 carbon atoms, preferably 1 to 4 carbon atoms, or a phenyl group.

[0018] Specific examples of the dialkoxyalkenyl alkoxymethyl ether compound (1) include dialkoxybutenyl alkoxymethyl ether compounds such as dimethoxybutenyl methoxymethyl ether, diethoxybutenyl methoxymethyl ether, dipropoxybutenyl methoxymethyl ether, dibutoxybutenyl methoxymethyl ether, dipentyloxybutenyl methoxymethyl ether, dihexyloxybutenyl methoxymethyl ether, diheptyloxybutenyl methoxymethyl ether, dioctyloxybutenyl methoxymethyl ether, dinonyloxybutenyl methoxymethyl ether, and didecyloxybutenyl methoxymethyl ether; dimethoxypentenyl methoxymethyl ether, diethoxypentenyl methoxymethyl ether, dipropoxypentenyl methoxymethyl ether, dibutoxypentenyl methoxymethyl ether, dipentyloxypentenyl methoxymethyl ether, and diheptyloxybutenyl methoxymethyl ether. Dialkoxypentenyl methoxymethyl ether compounds such as xyloxypentenyl methoxymethyl ether, diheptyloxypentenyl methoxymethyl ether, dioctyloxypentenyl methoxymethyl ether, dinonyloxypentenyl methoxymethyl ether and didecyloxypentenyl methoxymethyl ether; dimethoxypentenyl ethoxymethyl ether, diethoxypentenyl ethoxymethyl ether, dipropoxypentenyl ethoxymethyl ether, dialkoxypentenyl ethoxymethyl ether compounds such as dibutoxypentenyl ethoxymethyl ether, dipentyloxypentenyl ethoxymethyl ether, dihexyloxypentenyl ethoxymethyl ether, diheptyloxypentenyl ethoxymethyl ether, dioctyloxypentenyl ethoxymethyl ether, dinonyloxypentenyl ethoxymethyl ether and didecyloxypentenyl ethoxymethyl ether;Dimethoxypentenyl propoxymethyl ether, diethoxypentenyl propoxymethyl ether, dipropoxypentenyl propoxymethyl ether, dibutoxypentenyl propoxymethyl ether, dipentyloxypentenyl propoxymethyl ether, dihexyloxypentenyl propoxymethyl ether, diheptyloxypentenyl propoxymethyl ether, dioctyloxypentenyl propoxymethyl ether, dinonyloxypentenyl Dialkoxypentenyl propoxymethyl ether compounds such as dimethoxypentenyl butoxymethyl ether, diethoxypentenyl butoxymethyl ether, dipropoxypentenyl butoxymethyl ether, dibutoxypentenyl butoxymethyl ether, dipentyloxypentenyl butoxymethyl ether, dihexyloxypentenyl butoxymethyl ether Dialkoxypentenyl butoxymethyl ether compounds such as diheptyloxypentenyl butoxymethyl ether, dioctyloxypentenyl butoxymethyl ether, dinonyloxypentenyl butoxymethyl ether and didecyloxypentenyl butoxymethyl ether; dimethoxypentenyl pentyloxymethyl ether, diethoxypentenyl pentyloxymethyl ether, dipropoxypentenyl pentyloxymethyl ether, dibutoxy dialkoxypentenyl pentyloxymethyl ether compounds such as pentenyl pentyloxymethyl ether, dipentyloxypentenyl pentyloxymethyl ether, dihexyloxypentenyl pentyloxymethyl ether, diheptyloxypentenyl pentyloxymethyl ether, dioctyloxypentenyl pentyloxymethyl ether, dinonyloxypentenyl pentyloxymethyl ether and didecyloxypentenyl pentyloxymethyl ether;Dimethoxypentenyl hexyloxymethyl ether, diethoxypentenyl hexyloxymethyl ether, dipropoxypentenyl hexyloxymethyl ether, dibutoxypentenyl hexyloxymethyl ether, dipentyloxypentenyl hexyloxymethyl ether, dihexyloxypentenyl hexyloxymethyl ether, diheptyloxypentenyl hexyloxymethyl ether, dioctyloxypentenyl hexyloxymethyl ether, dinonyloxypentenyl Dialkoxypentenyl hexyloxymethyl ether compounds such as dimethoxypentenyl heptyloxymethyl ether, diethoxypentenyl heptyloxymethyl ether, dipropoxypentenyl heptyloxymethyl ether, dibutoxypentenyl heptyloxymethyl ether, dipentyloxypentenyl heptyloxymethyl ether, dihexyloxypentenyl heptyloxymethyl ether, Dialkoxypentenyl heptyloxymethyl ether compounds such as diethyl ether, diheptyloxypentenyl heptyloxymethyl ether, dioctyloxypentenyl heptyloxymethyl ether, dinonyloxypentenyl heptyloxymethyl ether and didecyloxypentenyl heptyloxymethyl ether; dimethoxypentenyl octyloxymethyl ether, diethoxypentenyl octyloxymethyl ether, dipropoxypentenyl octyloxymethyl ether, dialkoxypentenyl octyloxymethyl ether compounds such as dibutoxypentenyl octyloxymethyl ether, dipentyloxypentenyl octyloxymethyl ether, dihexyloxypentenyl octyloxymethyl ether, diheptyloxypentenyl octyloxymethyl ether, dioctyloxypentenyl octyloxymethyl ether, dinonyloxypentenyl octyloxymethyl ether and didecyloxypentenyl octyloxymethyl ether;Dimethoxypentenyl nonyloxymethyl ether, diethoxypentenyl nonyloxymethyl ether, dipropoxypentenyl nonyloxymethyl ether, dibutoxypentenyl nonyloxymethyl ether, dipentyloxypentenyl nonyloxymethyl ether, dihexyloxypentenyl nonyloxymethyl ether, diheptyloxypentenyl nonyloxymethyl ether, dioctyloxypentenyl nonyloxymethyl ether, dinonyloxypentenyl Dialkoxypentenyl nonyloxymethyl ether compounds such as nonyloxymethyl ether and didecyloxypentenyl nonyloxymethyl ether; dimethoxypentenyl decyloxymethyl ether, diethoxypentenyl decyloxymethyl ether, dipropoxypentenyl decyloxymethyl ether, dibutoxypentenyl decyloxymethyl ether, dipentyloxypentenyl decyloxymethyl ether, dihexyloxypentenyl decyloxymethyl ether ether, dialkoxypentenyl decyloxymethyl ether compounds such as diheptyloxypentenyl decyloxymethyl ether, dioctyloxypentenyl decyloxymethyl ether, dinonyloxypentenyl decyloxymethyl ether and didecyloxypentenyl decyloxymethyl ether; dimethoxypentenyl benzyloxymethyl ether, diethoxypentenyl benzyloxymethyl ether, dipropoxypentenyl benzyloxymethyl ether, dibutyloxypentenyl benzyloxymethyl ether, dialkoxypentenyl benzyloxymethyl ether compounds such as thoxypentenyl benzyloxymethyl ether, dipentyloxypentenyl benzyloxymethyl ether, dihexyloxypentenyl benzyloxymethyl ether, diheptyloxypentenyl benzyloxymethyl ether, dioctyloxypentenyl benzyloxymethyl ether, dinonyloxypentenyl benzyloxymethyl ether and didecyloxypentenyl benzyloxymethyl ether;Dialkoxyhexenyl alkoxymethyl ether compounds such as dimethoxyhexenyl methoxymethyl ether, diethoxyhexenyl methoxymethyl ether, dipropoxyhexenyl methoxymethyl ether, dibutoxyhexenyl methoxymethyl ether, dipentyloxyhexenyl methoxymethyl ether, dihexyloxyhexenyl methoxymethyl ether, diheptyloxyhexenyl methoxymethyl ether, dioctyloxyhexenyl methoxymethyl ether, dinonyloxyhexenyl methoxymethyl ether and didecyloxyhexenyl methoxymethyl ether; dimethoxyheptenyl methoxymethyl ether, diethoxyheptenyl methoxymethyl ether, dipropoxyheptenyl methoxymethyl ether, dibutoxyheptenyl methoxymethyl ether, dipentyloxyheptenyl methoxymethyl ether, dihexyloxyheptenyl methoxymethyl ether Dialkoxyheptenyl methoxymethyl ether compounds such as diheptyloxyheptenyl methoxymethyl ether, dioctyloxyheptenyl methoxymethyl ether, dinonyloxyheptenyl methoxymethyl ether and didecyloxyheptenyl methoxymethyl ether; dimethoxyheptenyl ethoxymethyl ether, diethoxyheptenyl ethoxymethyl ether, dipropoxyheptenyl ethoxymethyl ether dialkoxyheptenyl ethoxymethyl ether compounds such as dibutoxyheptenyl ethoxymethyl ether, dipentyloxyheptenyl ethoxymethyl ether, dihexyloxyheptenyl ethoxymethyl ether, diheptyloxyheptenyl ethoxymethyl ether, dioctyloxyheptenyl ethoxymethyl ether, dinonyloxyheptenyl ethoxymethyl ether and didecyloxyheptenyl ethoxymethyl ether;Dialkoxyheptenyl propoxymethyl ether compounds such as dimethoxyheptenyl propoxymethyl ether, diethoxyheptenyl propoxymethyl ether, dipropoxyheptenyl propoxymethyl ether, dibutoxyheptenyl propoxymethyl ether, dipentyloxyheptenyl propoxymethyl ether, dihexyloxyheptenyl propoxymethyl ether, diheptyloxyheptenyl propoxymethyl ether, dioctyloxyheptenyl propoxymethyl ether, dinonyloxyheptenyl propoxymethyl ether and didecyloxyheptenyl propoxymethyl ether; dialkoxyheptenyl propoxymethyl ether compounds such as dimethoxyheptenyl butoxymethyl ether, diethoxyheptenyl butoxymethyl ether, dipropoxyheptenyl butoxymethyl ether, di Dialkoxyheptenyl butoxymethyl ether compounds such as butoxyheptenyl butoxymethyl ether, dipentyloxyheptenyl butoxymethyl ether, dihexyloxyheptenyl butoxymethyl ether, diheptyloxyheptenyl butoxymethyl ether, dioctyloxyheptenyl butoxymethyl ether, dinonyloxyheptenyl butoxymethyl ether and didecyloxyheptenyl butoxymethyl ether; dimethoxyheptenyl pentyloxymethyl ether, diethoxyheptenyl pentyloxymethyl ether, dipropoxyheptenyl pentyloxymethyl ether, dibutoxyheptenyl pentyloxymethyl ether, dipentyloxyheptenyl pentyloxymethyl ether, dihexyloxyheptenyl pentyloxymethyl ether; hexyloxymethyl ether, dimethoxyheptenyl hexyloxymethyl ether, diethoxyheptenyl hexyloxymethyl ether, dipropoxyheptenyl hexyloxymethyl ether, dibutoxyheptenyl hexyloxymethyl ether, dipentyloxyheptenyl hexyloxymethyl ether, dihexyloxyheptenyl hexyloxymethyl ether, diheptyloxyheptenyl hexyloxymethyl ether, dioctyloxyheptenyl hexyloxymethyl ether, dinonyloxyheptenyl hexyloxymethyl ether, dihexyloxyheptenyl hexyloxymethyl ether, dioctyloxyheptenyl hexyloxymethyl ether, dinonyloxyheptenyl hexyloxymethyl ether, dialkoxyheptenyl hexyloxymethyl ether compounds such as dimethoxyheptenyl heptyloxymethyl ether, diethoxyheptenyl heptyloxymethyl ether, dipropoxyheptenyl heptyloxymethyl ether, dibutoxyheptenyl heptyloxymethyl ether, dipentyloxyheptenyl heptyloxymethyl ether, dihexyloxyheptenyl heptyloxymethyl ether, diheptyloxyheptenyl heptyloxymethyl ether, dioctyloxyheptenyl heptyloxymethyl ether, dinonyloxyheptenyl heptyloxymethyl ether and didecyloxyheptenyl heptyloxymethyl ether; dialkoxyheptenyl heptyloxymethyl ether compounds such as dimethoxyheptenyl heptyloxymethyl ether, diethoxyheptenyl heptyloxymethyl ether, dipropoxyheptenyl heptyloxymethyl ether, dibutoxyheptenyl heptyloxymethyl ether, dipentyloxyheptenyl heptyloxymethyl ether, dihexyloxyheptenyl heptyloxymethyl ether, diheptyloxyheptenyl heptyloxymethyl ether, dioctyloxyheptenyl heptyloxymethyl ether, dinonyloxyheptenyl heptyloxymethyl ether and didecyloxyheptenyl heptyloxymethyl ether;Dimethoxyheptenyl octyloxymethyl ether, diethoxyheptenyl octyloxymethyl ether, dipropoxyheptenyl octyloxymethyl ether, dibutoxyheptenyl octyloxymethyl ether, dipentyloxyheptenyl octyloxymethyl ether, dihexyloxyheptenyl octyloxymethyl ether, diheptyloxyheptenyl octyloxymethyl ether, dioctyloxyheptenyl octyloxymethyl ether, dinonyloxyheptenyl octyloxymethyl ether Dialkoxyheptenyl octyloxymethyl ether compounds such as dimethoxyheptenyl nonyloxymethyl ether, diethoxyheptenyl nonyloxymethyl ether, dipropoxyheptenyl nonyloxymethyl ether, dibutoxyheptenyl nonyloxymethyl ether, dipentyloxyheptenyl nonyloxymethyl ether, dihexyloxyheptenyl Dialkoxyheptenyl nonyloxymethyl ether compounds such as nonyloxymethyl ether, diheptyloxyheptenyl nonyloxymethyl ether, dioctyloxyheptenyl nonyloxymethyl ether, dinonyloxyheptenyl nonyloxymethyl ether and didecyloxyheptenyl nonyloxymethyl ether; dimethoxyheptenyl decyloxymethyl ether, diethoxyheptenyl decyloxymethyl ether, dipropoxyheptenyl decyloxymethyl ether dialkoxyheptenyl decyloxymethyl ether compounds such as hexyloxyheptenyl decyloxymethyl ether, dibutoxyheptenyl decyloxymethyl ether, dipentyloxyheptenyl decyloxymethyl ether, dihexyloxyheptenyl decyloxymethyl ether, diheptyloxyheptenyl decyloxymethyl ether, dioctyloxyheptenyl decyloxymethyl ether, dinonyloxyheptenyl decyloxymethyl ether and didecyloxyheptenyl decyloxymethyl ether;Dimethoxyheptenyl benzyloxymethyl ether, diethoxyheptenyl benzyloxymethyl ether, dipropoxyheptenyl benzyloxymethyl ether, dibutoxyheptenyl benzyloxymethyl ether, dipentyloxyheptenyl benzyloxymethyl ether, dihexyloxyheptenyl benzyloxymethyl ether, diheptyloxyheptenyl benzyloxymethyl ether, dioctyloxyheptenyl benzyloxymethyl ether octenyl methoxymethyl ether, dimethoxyoctenyl benzyloxymethyl ether and didecyloxyheptenyl benzyloxymethyl ether; dimethoxyoctenyl methoxymethyl ether, diethoxyoctenyl methoxymethyl ether, dipropoxyoctenyl methoxymethyl ether, dibutoxyoctenyl methoxymethyl ether, dipentyloxyoctenyl methoxymethyl ether, diheptyl methoxymethyl ether, dialkoxyoctenyl alkoxymethyl ether compounds such as xyloxyoctenyl methoxymethyl ether, diheptyloxyoctenyl methoxymethyl ether, dioctyloxyoctenyl methoxymethyl ether, dinonyloxyoctenyl methoxymethyl ether and didecyloxyoctenyl methoxymethyl ether; dialkoxynonenyl alkoxymethyl ether compounds such as dimethoxynonenyl methoxymethyl ether, diethoxynonenyl methoxymethyl ether, dipropoxynonenyl methoxymethyl ether, dibutoxynonenyl methoxymethyl ether, dipentyloxynonenyl methoxymethyl ether, dihexyloxynonenyl methoxymethyl ether, diheptyloxynonenyl methoxymethyl ether, dioctyloxynonenyl methoxymethyl ether, dinonyloxynonenyl methoxymethyl ether and didecyloxynonenyl methoxymethyl ether;Dialkoxydecenyl alkoxymethyl ether compounds such as dimethoxydecenyl methoxymethyl ether, diethoxydecenyl methoxymethyl ether, dipropoxydecenyl methoxymethyl ether, dibutoxydecenyl methoxymethyl ether, dipentyloxydecenyl methoxymethyl ether, dihexyloxydecenyl methoxymethyl ether, diheptyloxydecenyl methoxymethyl ether, dioctyloxydecenyl methoxymethyl ether, dinonyloxydecenyl methoxymethyl ether and didecyloxydecenyl methoxymethyl ether; dimethoxyundecenyl methoxymethyl ether, diethoxyundecenyl methoxymethyl ether, dipropoxyundecenyl methoxymethyl ether, dibutoxyundecenyl methoxymethyl ether, dipentyloxyundecenyl methoxymethyl ether, dihexyloxyundecenyl methoxymethyl ether dialkoxyundecenyl alkoxymethyl ether compounds such as diheptyloxyundecenyl methoxymethyl ether, dioctyloxyundecenyl methoxymethyl ether, dinonyloxyundecenyl methoxymethyl ether and didecyloxyundecenyl methoxymethyl ether; dialkoxydodecenyl alkoxymethyl ether compounds such as dimethoxydodecenyl methoxymethyl ether, diethoxydodecenyl methoxymethyl ether, dipropoxydodecenyl methoxymethyl ether, dibutoxydodecenyl methoxymethyl ether, dipentyloxydodecenyl methoxymethyl ether, dihexyloxydodecenyl methoxymethyl ether, diheptyloxydodecenyl methoxymethyl ether, dioctyloxydodecenyl methoxymethyl ether, dinonyloxydodecenyl methoxymethyl ether and didecyloxydodecenyl methoxymethyl ether;and dialkoxytridecenyl alkoxymethyl ether compounds such as dimethoxytridecenyl methoxymethyl ether, diethoxytridecenyl methoxymethyl ether, dipropoxytridecenyl methoxymethyl ether, dibutoxytridecenyl methoxymethyl ether, dipentyloxytridecenyl methoxymethyl ether, dihexyloxytridecenyl methoxymethyl ether, diheptyloxytridecenyl methoxymethyl ether, dioctyloxytridecenyl methoxymethyl ether, dinonyloxytridecenyl methoxymethyl ether and didecyloxytridecenyl methoxymethyl ether.

[0019] The dialkoxyalkenyl alkoxymethyl ether compound (1) can be synthesized, for example, by acetalizing the alkyne terminal of an alkoxymethyl alkynyl ether compound and catalytically reducing the carbon-carbon triple bond.

[0020] Next, the above-mentioned formylalkenyl alkoxymethyl ether compound (2) will be explained below.

[0021] In the above general formula (2), R 3 and a is as defined in general formula (1) above.

[0022] Specific examples of the formyl alkenyl alkoxymethyl ether compound (2) include formyl butenyl methoxymethyl ether, formyl butenyl ethoxymethyl ether, formyl butenyl propoxymethyl ether, formyl butenyl butoxymethyl ether, formyl butenyl pentyloxymethyl ether, formyl butenyl hexyloxymethyl ether, formyl butenyl heptyloxymethyl ether, formyl butenyl octyloxymethyl ether, and formyl Formylbutenyl alkoxymethyl ether compounds such as butenyl nonyloxymethyl ether, formylbutenyl decyloxymethyl ether and formylbutenyl benzyloxymethyl ether; formylpentenyl methoxymethyl ether, formylpentenyl ethoxymethyl ether, formylpentenyl propoxymethyl ether, formylpentenyl butoxymethyl ether, formylpentenyl pentyloxymethyl ether, formylpentenyl hexyloxymethyl ether, Formylpentenyl alkoxymethyl ether compounds such as formylpentenyl methyl ether, formylpentenyl heptyloxymethyl ether, formylpentenyl octyloxymethyl ether, formylpentenyl nonyloxymethyl ether, formylpentenyl decyloxymethyl ether and formylpentenyl benzyloxymethyl ether; formylhexenyl methoxymethyl ether, formylhexenyl ethoxymethyl ether, formylhexenyl propoxymethyl ether formylhexenyl alkoxymethyl ether compounds such as formylhexenyl butoxymethyl ether, formylhexenyl pentyloxymethyl ether, formylhexenyl hexyloxymethyl ether, formylhexenyl heptyloxymethyl ether, formylhexenyl octyloxymethyl ether, formylhexenyl nonyloxymethyl ether, formylhexenyl decyloxymethyl ether and formylhexenyl benzyloxymethyl ether;Formylheptenyl methoxymethyl ether, formylheptenyl ethoxymethyl ether, formylheptenyl propoxymethyl ether, formylheptenyl butoxymethyl ether, formylheptenyl pentyloxymethyl ether, formylheptenyl hexyloxymethyl ether, formylheptenyl heptyloxymethyl ether, formylheptenyl octyloxymethyl ether, formylheptenyl nonyloxymethyl ether, Formylheptenyl alkoxymethyl ether compounds such as formylheptenyl decyloxymethyl ether and formylheptenyl benzyloxymethyl ether; formyloctenyl methoxymethyl ether, formyloctenyl ethoxymethyl ether, formyloctenyl propoxymethyl ether, formyloctenyl butoxymethyl ether, formyloctenyl pentyloxymethyl ether, formyloctenyl hexyloxymethyl ether formyloctenyl alkoxymethyl ether compounds such as formyloctenyl heptyloxymethyl ether, formyloctenyl octyloxymethyl ether, formyloctenyl nonyloxymethyl ether, formyloctenyl decyloxymethyl ether and formyloctenyl benzyloxymethyl ether; formylnonenyl methoxymethyl ether, formylnonenyl ethoxymethyl ether, formylnonenyl propoxymethyl ether, and the like. formylnonenyl alkoxymethyl ether compounds such as formylnonenyl butoxymethyl ether, formylnonenyl pentyloxymethyl ether, formylnonenyl hexyloxymethyl ether, formylnonenyl heptyloxymethyl ether, formylnonenyl octyloxymethyl ether, formylnonenyl nonyloxymethyl ether, formylnonenyl decyloxymethyl ether and formylnonenyl benzyloxymethyl ether;Formyldecenyl methoxymethyl ether, formyldecenyl ethoxymethyl ether, formyldecenyl propoxymethyl ether, formyldecenyl butoxymethyl ether, formyldecenyl pentyloxymethyl ether, formyldecenyl hexyloxymethyl ether, formyldecenyl heptyloxymethyl ether, formyldecenyl octyloxymethyl ether, formyldecenyl nonyloxymethyl ether, formyldecenyl decyloxymethyl ether Formyldecenyl alkoxymethyl ether compounds such as formylundecenyl benzyloxymethyl ether; formylundecenyl methoxymethyl ether, formylundecenyl ethoxymethyl ether, formylundecenyl propoxymethyl ether, formylundecenyl butoxymethyl ether, formylundecenyl pentyloxymethyl ether, formylundecenyl hexyloxymethyl ether, formylundecenyl formylundecenyl alkoxymethyl ether compounds such as formylundecenyl heptyloxymethyl ether, formylundecenyl octyloxymethyl ether, formylundecenyl nonyloxymethyl ether, formylundecenyl decyloxymethyl ether and formylundecenyl benzyloxymethyl ether; formyldodecenyl methoxymethyl ether, formyldodecenyl ethoxymethyl ether, formyldodecenyl propoxymethyl ether, formyldodecenyl alkoxymethyl ether compounds such as formyldodecenyl methoxymethyl ether, formyldodecenyl ethoxymethyl ether, formyldodecenyl propoxymethyl ether, formyldodecenyl alkoxymethyl ether compounds such as formyldodecenyl butoxymethyl ether, formyldodecenyl pentyloxymethyl ether, formyldodecenyl hexyloxymethyl ether, formyldodecenyl heptyloxymethyl ether, formyldodecenyl octyloxymethyl ether, formyldodecenyl nonyloxymethyl ether, formyldodecenyl decyloxymethyl ether and formyldodecenyl benzyloxymethyl ether;and formyltridecenyl alkoxymethyl ether compounds such as formyltridecenyl methoxymethyl ether, formyltridecenyl ethoxymethyl ether, formyltridecenyl propoxymethyl ether, formyltridecenyl butoxymethyl ether, formyltridecenyl pentyloxymethyl ether, formyltridecenyl hexyloxymethyl ether, formyltridecenyl heptyloxymethyl ether, formyltridecenyl octyloxymethyl ether, formyltridecenyl nonyloxymethyl ether, formyltridecenyl decyloxymethyl ether and formyltridecenyl benzyloxymethyl ether.

[0023] Next, the hydrolysis reaction of the dialkoxyalkenyl alkoxymethyl ether compound (1) will be described below.

[0024] The hydrolysis reaction can be carried out using, for example, an acid or water. The acid may be an inorganic acid such as hydrochloric acid or hydrobromic acid; p -Toluenesulfonic acid ( p -TsOH), benzenesulfonic acid, trifluoroacetic acid, acetic acid, formic acid, oxalic acid, iodotrimethylsilane, and titanium tetrachloride. p -Toluenesulfonic acid, acetic acid, formic acid and hydrochloric acid are preferred, with formic acid and hydrochloric acid being more preferred.

[0025] The amount of the acid used is preferably 0.0001 to 2.0 mol, more preferably 0.003 to 1.0 mol, per 1 mol of the dialkoxyalkenyl alkoxymethyl ether compound (1), from the viewpoint of productivity.

[0026] The acid may be used alone or, if necessary, in combination of two or more kinds, and may be either a commercially available acid or an independently synthesized acid.

[0027] From the viewpoint of reactivity, the amount of water used is preferably 0 to 3000 g, more preferably 0 to 300 g, per mol of the dialkoxyalkenyl alkoxymethyl ether compound (1). When the acid used is a water-containing compound, it is not necessary to add water.

[0028] The hydrolysis reaction may be carried out without a solvent, or may be carried out in the presence of a solvent, if necessary. By carrying out the hydrolysis without using a solvent, it is possible to prevent a decrease in the amount of the raw material charged or a decrease in productivity. When a solvent is used, examples of the solvent include common solvents, for example, ethers such as dibutyl ether, 4-methyltetrahydropyran, cyclopentyl methyl ether, and 1,4-dioxane; hydrocarbons such as heptane, benzene, toluene, xylene, and cumene; chlorine-based 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 solvent may be used alone or in combination with two or more solvents as required. In addition, commercially available solvents may be used. The solvent has a boiling point different from that of the alcohol compound (hereinafter also referred to as "alcohol compound (7)") produced by the hydrolysis reaction, and preferably has a boiling point higher than that of the alcohol compound (7). The amount of the solvent used in the hydrolysis reaction is preferably 0 to 2000 g, more preferably 0 to 500 g, per mol of the dialkoxyalkenyl alkoxymethyl ether compound (1).

[0029] The reaction temperature in the hydrolysis reaction is preferably 10 to 150°C, more preferably 30 to 80°C, from the viewpoint of reactivity. The reaction time in the hydrolysis reaction varies depending on the scale of the reaction, but is preferably 1 to 100 hours from the viewpoint of productivity.

[0030] The progress of the hydrolysis reaction can be confirmed, for example, by measuring the weight of the liquid obtained by distilling and removing the alcohol compound (7) produced in the hydrolysis reaction, or by tracking the hydrolysis reaction by GC, and preferably, from the viewpoint of safety and workability, it is preferable to measure the weight of the liquid obtained by distilling and removing the alcohol compound produced in the hydrolysis reaction. As a means for confirming that the hydrolysis reaction is progressing by measuring the weight of the obtained liquid, for example, a method of confirming that the hydrolysis reaction is progressing by distilling and removing the alcohol compound produced in the hydrolysis reaction does not reach the theoretical amount of the alcohol compound (7) calculated from the amount of the raw material charged, i.e., the dialkoxyalkenyl alkoxymethyl ether compound (1), and the weight of the obtained liquid still increases can be mentioned.

[0031] Among the dialkoxyalkenyl alkoxymethyl ether compounds (1), the present invention is particularly advantageous in the case of producing formylalkenyl alkoxymethyl ether compounds (2: a = 1-4) having 4 to 7 carbon atoms, which are highly soluble in water, that is, in the case of producing the above-mentioned formylalkenyl alkoxymethyl ether compounds (2: a = 1-4) which are aldehydes, by hydrolyzing dialkoxybutenyl alkoxymethyl ether compounds, dialkoxypentenyl alkoxymethyl ether compounds, dialkoxyhexenyl alkoxymethyl ether compounds, and dialkoxyheptenyl alkoxymethyl ether compounds. The following will be described as an example of the case of producing formylalkenyl alkoxymethyl ether compounds (2: a = 1-4) having 4 to 7 carbon atoms. Note that the case of producing formylalkenyl alkoxymethyl ether compounds (2: a = 5-10) having 8 to 13 carbon atoms is not excluded from the scope of the present invention. Usually, when these dialkoxyalkenyl alkoxymethyl ether compounds (1:a=1-4) are hydrolyzed to produce formyl alkenyl alkoxymethyl ether compounds (2:a=1-4), it is necessary to use water-insoluble dichloromethane, chloroform, diethyl ether, toluene, or xylene, which has excellent extracting power, as a solvent during the reaction or an extraction solvent. However, when these solvents are used, separation of the solvent by distillation is required, which reduces the amount of charge, resulting in a decrease in productivity, and the solvent becomes waste, which is bad for the environment. On the other hand, when these solvents are not used, the formyl alkenyl alkoxymethyl ether compounds (2:a=1-4) escape into the water layer, resulting in an extremely low yield of the formyl alkenyl alkoxymethyl ether compounds (2:a=1-4). In addition, when an alcohol is present in the reaction solution of the formyl alkenyl alkoxymethyl ether compound (2: a = 1 to 4), the solubility of the formyl alkenyl alkoxymethyl ether compound (2: a = 1 to 4) in the aqueous layer increases, resulting in a significant decrease in yield, or the yield is not stable even when the preparation is repeated under the same conditions (see Comparative Examples 1 to 6 below). However, in the present invention, by removing the alcohol compound produced by the hydrolysis while proceeding with the hydrolysis reaction, the formyl alkenyl alkoxymethyl ether compound (2: a = 1-4) having 4 to 7 carbon atoms can be separated from the aqueous layer to the organic layer while preventing or eliminating the loss of the formyl alkenyl alkoxymethyl ether compound (2: a = 1-4) due to migration to the aqueous layer, and therefore the yield and productivity of the formyl alkenyl alkoxymethyl ether compound (2: a = 1-4) can be improved (see Examples 1-4 and Comparative Examples 1-6 below). In addition, by removing the alcohol compound produced by the hydrolysis during the hydrolysis reaction, it is possible to purify the target formyl alkenyl alkoxymethyl ether compound (2: a = 1-4) by distillation without post-treatment or by reducing the post-treatment step.

[0032] In the above hydrolysis reaction, the dialkoxyalkenyl alkoxymethyl ether compound (1), an acid, and water as necessary are charged, and then heated to distill off the alcohol compound (7) produced by the hydrolysis reaction while the hydrolysis reaction is proceeding. For example, when the alcohol compound (7) is ethanol, the distillation is carried out by increasing the internal temperature to 40 to 50°C while the hydrolysis reaction is proceeding, and then reducing the pressure to 235 mmHg (31.3 kPa). The hydrolysis reaction can be carried out by distilling off the alcohol compound (7) under normal pressure, but considering the thermal stability of the formyl alkenyl alkoxymethyl ether compound (2), it is preferable to carry out the reaction under reduced pressure. The distillate is removed by gradually reducing the pressure to 50 mmHg (6.67 kPa) while distilling off the ethanol. The hydrolysis is completed when the distillation of ethanol is no longer observed. The absence of ethanol distillation can be confirmed, for example, by the fact that the weight of the liquid obtained by distilling and removing the alcohol compound produced in the hydrolysis reaction becomes equal to the amount of the alcohol compound (7) calculated from the amount of the charged raw material, i.e., the dialkoxyalkenyl alkoxymethyl ether compound (1), and the weight of the obtained liquid no longer changes. The term "internal temperature" refers to the temperature of the reaction liquid, and is synonymous with the reaction temperature.

[0033] Specific examples of the alcohol compound (7) include linear 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 ethylene glycol, 1,3-propanediol, 1,4-butanediol, and the like. diols such as 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, 2,2-dimethyl-1,3-propanediol, and 2,2-dimethyl-1,4-butanediol.

[0034] The alcohol compound (7) recovered by the distillation has a high purity and can be reused as a raw material for reactions other than the hydrolysis reaction, such as acetalization or dealkoxymethylation of aldehydes, etc. Therefore, the process according to the present invention is environmentally friendly and extremely advantageous economically.

[0035] As described above, the dialkoxyalkenyl alkoxymethyl ether compound (1) can be further hydrolyzed in the presence of an acid while removing the alcohol compound produced by the hydrolysis, thereby producing the formylalkenyl alkoxymethyl ether compound (2).

[0036] Next, a method for producing (5E,7Z)-5,7-dodecadien-1-ol (hereinafter also referred to as "(5E,7Z)-5,7-dodecadien-1-ol (5)"), which is the sex pheromone of the chrysanthemum looper moth and is represented by the following formula (5), using the formyl alkenyl alkoxymethyl ether compound (2: a = 4) obtained by the above-mentioned production method will be described below.

[0037] (5E,7Z)-5,7-dodecadien-1-ol (5) can be produced by subjecting a formylheptenyl alkoxymethyl ether compound (2: a = 4) and a triarylphosphonium pentylide compound represented by the following general formula (3) (hereinafter also referred to as "triarylphosphonium pentylide compound (3)") to a Wittig reaction to obtain a (5E,7Z)-5,7-dodecadienyl alkoxymethyl ether compound represented by the following general formula (4: a = 4) (hereinafter also referred to as "(5E,7Z)-5,7-dodecadienyl alkoxymethyl ether (4: a = 4)"), and then subjecting the (5E,7Z)-5,7-dodecadienyl alkoxymethyl ether (4: a = 4) to a dealkoxymethylation reaction.

[0038] [ka]

[0039] First, the Wittig reaction process will be described. In formula (3), each Ar independently represents an aryl group. The aryl group preferably has 6 to 7 carbon atoms. Examples of the aryl group include a phenyl group (Ph group (=C6H5)) and a tolyl group. From the viewpoint of ease of synthesis, the phenyl group is preferred, and it is more preferred that all three aryl groups are phenyl groups.

[0040] Specific examples of the triarylphosphonium pentylide compound (3) include triphenylphosphonium pentylide and tritolylphosphonium pentylide. The triarylphosphonium pentylide compound (3) may be used alone or in combination of two or more, if necessary.

[0041] In addition, the triarylphosphonium pentylide compound (3) can be prepared, for example, by reacting a 1-halopentane compound (hereinafter also referred to as "1-halopentane compound (8)") represented by the following general formula (8) with a phosphorus compound (hereinafter also referred to as "phosphorus compound (9)") represented by the following general formula (9) to obtain a pentynyltriarylphosphonium halide compound (hereinafter also referred to as "pentynyltriarylphosphonium halide compound (10)") represented by the following general formula (10), and by subjecting the above-mentioned pentynyltriarylphosphonium halide compound (10) to a deprotonation reaction with a base to obtain the triarylphosphonium pentylide compound (3).

[0042] [ka]

[0043] X in the 1-halopentane compound (8) represents a halogen atom, examples of which include a chlorine atom, a bromine atom, and an iodine atom. From the viewpoint of versatility, a chlorine atom and a bromine atom are preferred.

[0044] Specific examples of the 1-halopentane compound (8) include 1-chloropentane, 1-bromopentane, and 1-iodopentane.

[0045] In the general formula (9), Ar is as defined in the above general formula (3).

[0046] Specific examples of the phosphorus compound (9) include triarylphosphine compounds such as triphenylphosphine and tritolylphosphine, with triphenylphosphine being preferred from the viewpoint of reactivity.

[0047] The amount of the phosphorus compound (9) used is preferably 0.8 to 5.0 mol per mol of the 1-halopentane compound (8) from the viewpoint of reactivity.

[0048] In the preparation of the pentyltriarylphosphonium halide compound (10), a halide may be used, if necessary. Examples of the halide include sodium iodide, potassium iodide, sodium bromide, potassium bromide, and the like. From the viewpoint of reactivity, iodides such as sodium iodide and potassium iodide are preferred. The halide may be used alone or in combination of two or more kinds, if necessary. The halide may be a commercially available product. The amount of the halide used is preferably 0 to 5.0 mol per 1 mol of the 1-halopentane compound (8) from the viewpoint of reactivity.

[0049] In the preparation of the pentyltriarylphosphonium halide compound (10), a base may be added, if necessary. 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,N-diethylaniline, and pyridine. From the viewpoint of handling, alkali metal carbonates are preferred. The base may be used alone or in combination with two or more kinds, if necessary. In addition, commercially available bases may be used. The amount of the base used is preferably 0 to 2.0 mol per 1 mol of the 1-halopentane compound (8) from the viewpoint of reactivity.

[0050] The reaction temperature (optimum temperature) in the preparation of the pentyltriarylphosphonium halide compound (10) varies depending on the solvent used, but is preferably 60 to 180°C. The reaction time in the preparation of the pentyltriarylphosphonium halide compound (10) varies depending on the solvent used or the reaction scale, but is preferably 0.5 to 55 hours.

[0051] In the general formula (10), Y represents a halogen atom, examples of which include a chlorine atom, a bromine atom, and an iodine atom. In the preparation of the pentyltriarylphosphonium halide compound (10), when no halide is used, the Y is the same halogen atom as X in the general formula (8), whereas when an iodide is used as the halide, the Y is the same halogen atom as X or an iodine atom.

[0052] In the general formula (10), Ar is as defined in the above general formula (3).

[0053] Specific examples of the pentyltriarylphosphonium halide compound (10) include pentyltriphenylphosphonium halide compounds such as pentyltriphenylphosphonium chloride, pentyltriphenylphosphonium bromide, and pentyltriphenylphosphonium iodide; and pentyltritolylphosphonium halide compounds such as pentyltritolylphosphonium chloride, pentyltritolylphosphonium bromide, and pentyltritolylphosphonium iodide.

[0054] The triarylphosphonium pentylide compound (3) may be directly converted to the triarylphosphonium pentylide compound (3) by adding a base to the same reaction system as that used for preparing the pentyltriarylphosphonium halide (10) and subjecting it to a deprotonation reaction, or the pentyltriarylphosphonium halide (10) may be isolated and purified, and then subjected to a deprotonation reaction with a base to convert it to the triarylphosphonium pentylide compound (3).

[0055] Examples of the base used in the deprotonation reaction of pentyltriarylphosphonium halide (10) include alkyl lithiums such as n-butyllithium and tert-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. From the viewpoint of reactivity, metal alkoxides are preferred, and potassium tert-butoxide, sodium methoxide and sodium ethoxide are more preferred. The amount of the base used is preferably 0.7 to 5.0 mol per mol of the 1-halopentane compound (8) from the viewpoint of reactivity.

[0056] The reaction temperature (optimum temperature) in the deprotonation reaction of the pentyltriarylphosphonium halide (10) varies depending on the solvent or base used, but is preferably -78 to 40°C. The reaction time in the deprotonation reaction of the pentyltriarylphosphonium halide (10) varies depending on the solvent used or the reaction scale, but is preferably 0.5 to 50 hours.

[0057] In the preparation of the pentyltriarylphosphonium halide compound (10) and the deprotonation reaction of the pentyltriarylphosphonium halide (10), a solvent may be used, if necessary. 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,N-dimethylacetamide, N-methylpyrrolidone, dimethyl sulfoxide, γ-butyrolactone, acetonitrile, dichloromethane, and chloroform. From the viewpoint of reactivity, ether solvents such as tetrahydrofuran and 4-methyltetrahydropyran, and polar solvents such as acetonitrile, N,N-dimethylformamide, and N,N-dimethylacetamide are preferred. The solvent may be used alone or in combination with two or more solvents as required. In addition, commercially available solvents may be used. From the viewpoint of reactivity, the amount of the solvent used is preferably 10 to 6000 g, more preferably 50 to 4000 g, per mol of the 1-halopentane compound (8) or the pentyltriarylphosphonium halide compound (10).

[0058] The amount of the triarylphosphonium pentylide compound (3) used is preferably 1.0 to 4.0 mol, more preferably 1.0 to 2.0 mol, per 1 mol of the formylalkenyl alkoxymethyl ether compound (2), from the viewpoint of reactivity.

[0059] In the above Wittig reaction, a solvent may be used, if necessary. 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,N-dimethylacetamide, N-methylpyrrolidone, dimethyl sulfoxide, γ-butyrolactone, acetonitrile, dichloromethane, and chloroform. From the viewpoint of reactivity, ether solvents such as tetrahydrofuran and 4-methyltetrahydropyran, and polar solvents such as acetonitrile, N,N-dimethylformamide, and N,N-dimethylacetamide are preferred. The solvent may be used alone or in combination of two or more kinds, if necessary. In addition, commercially available solvents may be used. The amount of the solvent used is preferably 10 to 6000 g, more preferably 50 to 4000 g, per mol of the formyl alkenyl alkoxymethyl ether compound (2) from the viewpoint of reactivity.

[0060] The optimum reaction temperature for the Wittig reaction varies depending on the solvent used, but is preferably -78 to 40°C. The reaction time in the Wittig reaction varies depending on the reaction scale, but is preferably 0.5 to 50 hours.

[0061] Specific examples of the (5E,7Z)-5,7-dodecadienyl alkoxymethyl ether compound (4) include (5E,7Z)-5,7-dodecadienyl methoxymethyl ether, (5E,7Z)-5,7-dodecadienyl ethoxymethyl ether, (5E,7Z)-5,7-dodecadienyl propoxymethyl ether, (5E,7Z)-5,7-dodecadienyl butoxymethyl ether, and (5E,7Z)-5,7-dodecadienyl pentyloxymethyl ether. Examples of dodecadienyl hexyloxymethyl ether include (5E,7Z)-5,7-dodecadienyl heptyloxymethyl ether, (5E,7Z)-5,7-dodecadienyl octyloxymethyl ether, (5E,7Z)-5,7-dodecadienyl nonyloxymethyl ether, (5E,7Z)-5,7-dodecadienyl decyloxymethyl ether and (5E,7Z)-5,7-dodecadienyl benzyloxymethyl ether.

[0062] Next, the dealkoxymethylation step will be described. The dealkoxymethylation reaction of the (5E,7Z)-5,7-dodecadienyl alkoxymethyl ether compound (4: a=4) can be carried out, for example, using an acid and an alcohol compound represented by the following general formula (11) (hereinafter also referred to as "alcohol compound (11)"). R 4 OH (11) Examples of the acid used in the alkoxymethylation reaction 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. p Toluenesulfonic acid and hydrochloric acid are preferred. The acid may be used alone or in combination with two or more kinds, if necessary. In addition, commercially available acids may be used. The amount of the acid used is preferably 0.001 to 10.0 mol, more preferably 0.01 to 3.0 mol, per mol of the (5E,7Z)-5,7-dodecadienyl alkoxymethyl ether compound (4) from the viewpoint of completing the reaction.

[0063] In the general formula (11), R 4 represents a monovalent hydrocarbon having 1 to 15 carbon atoms, preferably 1 to 6 carbon atoms in terms of cost or versatility. The monovalent hydrocarbon group is R 1 and R 2 is the same as the monovalent hydrocarbon group. Examples of the alcohol compound (11) include linear 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. From the viewpoint of reactivity, however, methanol and ethanol are preferred. Two or more kinds of alcohol compounds (11) may be used as necessary. As the alcohol compound (11), a commercially available product or the alcohol compound (7) recovered from the above hydrolysis reaction can be used. The amount of the alcohol compound (11) used is preferably 1.0 to 100 mol, more preferably 1.0 to 40 mol, per mol of the (5E,7Z)-5,7-dodecadienyl alkoxymethyl ether compound (4) from the viewpoint of reactivity. In the dealkoxymethylation reaction, a solvent other than the alcohol compound (11) may be used, if necessary. Examples of the solvent include common solvents, such as ethers such as dibutyl ether, 4-methyltetrahydropyran, cyclopentyl methyl ether, and 1,4-dioxane; hydrocarbons such as heptane, benzene, toluene, xylene, and cumene; chlorine-based 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 solvent may be used alone or in combination with two or more solvents as required. In addition, commercially available solvents may be used. The amount of the solvent used in the dealkoxymethylation reaction is preferably 0 to 2000 g, more preferably 0 to 500 g, per mol of the (5E,7Z)-5,7-dodecadienyl alkoxymethyl ether compound (4). The use of such a solvent reduces the amount of the reaction mixture charged, resulting in a decrease in productivity. Therefore, the reaction may be carried out without using any of the above solvents.

[0064] (5E,7Z)-5,7-dodecadienyl acetate represented by the following formula (6) (hereinafter also referred to as "(5E,7Z)-5,7-dodecadienyl acetate (6)") can be produced by an acetylation reaction of (5E,7Z)-5,7-dodecadien-1-ol (5) obtained by the above-mentioned production method.

[0065] [ka]

[0066] The acetylation reaction of (5E,7Z)-5,7-dodecadien-1-ol (5) can be carried out, for example, using an acetylating agent.

[0067] Examples of the acetylating agent include acid anhydrides such as acetic anhydride, acetyl halide compounds such as acetyl chloride, acetyl bromide, and acetyl iodide, and acetate compounds such as methyl acetate and ethyl acetate. From the viewpoint of versatility, acetic anhydride and acetyl halide compounds are preferred. The amount of the acetylating agent used is preferably 1.0 to 10.0 mol, and more preferably 1.0 to 5.0 mol, per mol of (5E,7Z)-5,7-dodecadien-1-ol (5) from the viewpoints of reactivity and economic efficiency.

[0068] In the acetylation reaction, an acid or a base may be used, if necessary. The acid may be a mineral acid such as hydrochloric acid, sulfuric acid, or nitric acid; benzenesulfonic acid; p -aromatic sulfonic acids such as toluenesulfonic acid; and Lewis acids such as boron trifluoride etherate and tetraisopropyl orthotitanate. The acid may be used alone or in combination of two or more kinds, if necessary. The amount of the acid used is preferably 0.01 to 1.00 mol, and more preferably 0.01 to 0.50 mol, per mol of (5E,7Z)-5,7-dodecadien-1-ol (5), from the viewpoints of reactivity and economic efficiency.

[0069] Examples of the base include trialkylamines such as trimethylamine, triethylamine, and N,N-diisopropylethylamine; aromatic amine compounds such as pyridine, N,N-dimethylaniline, N,N-diethylaniline, and 4-dimethylaminopyridine; and metal alkoxides such as potassium t-butoxide, sodium methoxide, and sodium ethoxide. The base may be used alone or in combination of two or more types, if necessary. The amount of the base used is preferably 1.0 to 10.0 mol, and more preferably 1.0 to 3.0 mol, per mol of (5E,7Z)-5,7-dodecadien-1-ol (5), from the viewpoints of reactivity and economic efficiency.

[0070] The acetylation reaction may be carried out in the presence of a solvent, if necessary. Examples of the solvent include general solvents, for example, ethers such as tetrahydrofuran, diethyl ether, dibutyl ether, 4-methyltetrahydropyran, cyclopentyl methyl ether, and 1,4-dioxane; hydrocarbons such as heptane, benzene, toluene, xylene, and cumene; chlorine-based 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, with hydrocarbons such as toluene and xylene being preferred. The solvent may be used alone or in combination with two or more solvents as required. In addition, commercially available solvents may be used. The amount of the solvent used in the acetylation reaction is preferably 0 to 2000 g, more preferably 0 to 500 g, relative to 1 mol of the (5E,7Z)-5,7-dodecadien-1-ol (5).

[0071] In the manner described above, a method for producing (5E,7Z)-5,7-dodecadien-1-ol (5) and (5E,7Z)-5,7-dodecadienyl acetate (6), which are sex pheromones of the chrysanthemum looper moth, is provided using the formyl alkenyl alkoxymethyl ether compound (2: a = 4). EXAMPLES

[0072] The present invention will be described in detail below with reference to examples, but the present invention is not limited to the following examples. In the following, unless otherwise specified, "purity" refers to the area percentage obtained by gas chromatography (GC) analysis, "production ratio" refers to the relative ratio of the area percentage obtained by GC analysis, and "yield" refers to the yield calculated based on the area percentage obtained by GC analysis. In each example, reaction monitoring and yield calculation were performed under the following GC conditions. GC conditions: GC: Shimadzu Corporation capillary gas chromatograph GC-2014, column: DB-WAX, 0.25 mm x 0.25 mm φ x 30 m, carrier gas: He (1.55 mL / min), detector: FID, column temperature: 150°C, 5°C / min heating to 230°C. The yield was calculated according to the following formula, taking into account the purity (%GC) of the raw materials and the product. Yield (%) = {[(weight of product obtained by reaction × %GC) / molecular weight of product] ÷[(weight of starting material in reaction × %GC) / molecular weight of starting material]} × 100

[0073] Example 1 Formyl B Thenyl methoxymethyl ether (2:R 3 =H;a=2)<CH3OCH2O(CH2)2CH=CHCHO> Manufacturing

[0074] [ka]

[0075] At room temperature, a reactor was charged with diethoxypentenyl methoxymethyl ether (1:R 3 =H; a=2) (795.07 g, 3.54 mol, purity 97.05%) and water (106.32 g, 5.90 mol) were added and stirred for 1 hour at 30 to 40° C. After stirring, formic acid (8.14 g, 0.16 mol, purity 88%) was added dropwise at 30 to 45° C. to carry out hydrolysis, and then 20 mass % hydrochloric acid (0.64 g, 0.0035 mol as hydrogen chloride) was added dropwise at 30 to 45° C., and the mixture was stirred at 40 to 45° C. for 30 minutes. Subsequently, while the hydrolysis proceeded, the pressure was reduced to 235 mmHg (31.3 kPa) at an internal temperature of 40 to 55°C, and then gradually reduced to 50 mmHg (6.67 kPa), and ethanol (325.85 g, 7.01 mol, purity 99.11%) produced by the hydrolysis was distilled and removed. Distillation ceased 4 hours after the start of pressure reduction. When the distillate disappeared, toluene (557.04 g), water (218.20 g), salt (65.00 g), and 20% by mass hydrochloric acid (12.89 g, 0.071 mol as hydrogen chloride) were added and separated, and the aqueous layer was removed to obtain an organic layer. Subsequently, the obtained organic layer was washed with saline, separated, and the aqueous layer was removed to obtain an organic layer. Furthermore, the obtained organic layer was washed with an aqueous sodium hydrogen carbonate solution, separated, and the aqueous layer was removed to obtain an organic layer. The obtained organic layer was distilled under reduced pressure to obtain formyl amine. B Thenyl methoxymethyl ether (2:R 3 =H; a=2) (496.73 g, 3.29 mol, purity 95.41%, bp = 87.2-87.6 °C / 3.0 mmHg (0.40 kPa)) was obtained in a yield of 93.00%. The progress of the hydrolysis was confirmed by the distillation of ethanol. Specifically, 3.54 mol (raw material diethoxypentenyl methoxymethyl ether (1:R 3 Since the theoretical amount of ethanol produced by the above hydrolysis is 326.18 g (number of moles of H; a=2) × 46.07 (molecular weight of ethanol) × 2 (number of alcohol moieties in one molecule of raw material), the hydrolysis was determined to be in progress when the amount was less than the theoretical amount, and was determined to be completed when the amount was substantially the same as the theoretical amount (325.85 g as above) and the weight of the distilled ethanol no longer changed.

[0076] Formyl B Thenyl methoxymethyl ether (2:R 3 =H;a=2) [Nuclear Magnetic Resonance Spectrum] 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); 13 C-NMR (500MHz, CDCl3): δ=32.94,55.27,65.40,96.40,134.19,154.87,193.75 [Mass spectrum] EI-mass spectrum (70 eV): m / z 114 (M + -30), 99, 83, 75, 55, 45 [Infrared absorption spectrum] (NaCl): ν=2934, 2886, 2824, 1691, 1151, 1110, 1043, 974, 918

[0077] Example 2 Formyl B Thenyl methoxymethyl ether (2:R 3 =H;a=2)<CH3OCH2O(CH2)2CH=CHCHO> Manufacturing

[0078] [ka]

[0079] At room temperature, a reactor was charged with diethoxypentenyl methoxymethyl ether (1:R 3 =H; a=2) (283.84 g, 1.26 mol, purity 97.05%) and water (37.96 g, 2.11 mol) were added and stirred for 22 minutes at 30 to 40° C. After stirring, formic acid (2.56 g, 0.049 mol, purity 88%) was added dropwise at 30 to 45° C. to carry out hydrolysis, and then 20 mass % hydrochloric acid (0.23 g, 0.0013 mol as hydrogen chloride) was added dropwise at 30 to 45° C., and the mixture was stirred at 40 to 45° C. for 100 minutes. Subsequently, while the hydrolysis was proceeding, the pressure was reduced to 235 mmHg (31.3 kPa) at an internal temperature of 40 to 55°C, and then gradually reduced to 50 mmHg (6.67 kPa) to distill and remove ethanol (123.12 g, 2.61 mol, purity 97.51%) produced by the hydrolysis. Distillation ceased 4 hours after the start of pressure reduction. When the distillate disappeared, the pressure was further reduced to 3.0 mmHg (0.40 kPa) and distilled under reduced pressure to remove formyl ethanol. B Thenyl methoxymethyl ether (2:R 3 =H; a=2) (182.44 g, 1.20 mol, purity 94.59%, bp = 87.6-88.6 °C / 3.0 mmHg (0.40 kPa)) was obtained in a yield of 94.88%. The progress of the hydrolysis was confirmed by the same method as in Example 1 above.

[0080] The above obtained formyl B The various spectral data of thenyl methoxymethyl ether were the same as those obtained in Example 1.

[0081] Comparative Example 1 Formyl B Thenyl methoxymethyl ether (2:R 3 =H;a=2)<CH3OCH2O(CH2)2CH=CHCHO> Manufacturing

[0082] [ka]

[0083] At room temperature, a reactor was charged with diethoxypentenyl methoxymethyl ether (1:R 3=H; a=2) (283.84 g, 1.26 mol, purity 97.05%) and toluene (80.00 g) were added and stirred at 10 to 15°C for 6 minutes. After stirring, 8% by mass hydrochloric acid (145.13 g, 0.32 mol as hydrogen chloride) was added dropwise at 15 to 20°C to carry out hydrolysis, and the reaction was tracked using GC at 15 to 20°C. The reaction was stopped after confirming that the reaction rate was 99.5% or more. At this time, the maturation (reaction) time from the dropwise addition of 8% by mass hydrochloric acid to the end of the reaction was 1 hour. Toluene (200.00 g) was further added to the reaction mixture, followed by separation, and the aqueous layer was removed to obtain an organic layer. The obtained organic layer was then washed with saline, separated, and the aqueous layer was removed to obtain an organic layer. The obtained organic layer was further washed with an aqueous sodium hydrogen carbonate solution, separated, and the aqueous layer was removed to obtain an organic layer. The obtained organic layer was distilled under reduced pressure to obtain formyl amine. B Thenyl methoxymethyl ether (2:R 3 =H; a=2) (131.78 g, 0.84 mol, purity 91.47%, bp = 87.2-87.6 °C / 3.0 mmHg (0.40 kPa)) was obtained in a yield of 66.25%. Note that each of the aqueous layers removed above contained ethanol produced by hydrolysis.

[0084] The above obtained formyl B The various spectral data of thenyl methoxymethyl ether were the same as those obtained in Example 1.

[0085] Comparative Example 2 Formyl B Thenyl methoxymethyl ether (2:R 3 =H;a=2)<CH3OCH2O(CH2)2CH=CHCHO> Manufacturing

[0086] [ka]

[0087] When the experiment was repeated under the same conditions as in Comparative Example 1, BThenyl methoxymethyl ether (2:R 3 =H; a=2) (171.49 g, 1.06 mol, purity 89.12%, bp=87.2-87.6°C / 3.0 mmHg (0.40 kPa)) was obtained in a yield of 84.00%. Although Comparative Example 1 and Comparative Example 2 were carried out under the same conditions, the yields were 66.25% (Comparative Example 1) and 84.00% (Comparative Example 2), and the yields were not stable.

[0088] The above obtained formyl B The various spectral data of thenyl methoxymethyl ether were the same as those obtained in Example 1.

[0089] Comparative Example 3 Formyl B Thenyl methoxymethyl ether (2:R 3 =H;a=2)<CH3OCH2O(CH2)2CH=CHCHO> Manufacturing

[0090] [ka]

[0091] At room temperature, a reactor was charged with diethoxypentenyl methoxymethyl ether (1:R 3 =H; a=2) (283.84 g, 1.26 mol, purity 97.05%) and water (37.96 g, 2.11 mol) were added and stirred for 1 hour at 30 to 40° C. After stirring, formic acid (2.56 g, 0.049 mol, purity 88%) was added dropwise at 30 to 45° C. to carry out hydrolysis, and then 20 mass % hydrochloric acid (0.23 g, 0.0013 mol as hydrogen chloride) was added dropwise at 30 to 45° C., and stirred for 30 minutes at 40 to 45° C. Next, while the hydrolysis was proceeding, the reaction was monitored using GC at an internal temperature of 40 to 55°C, and the reaction was stopped after it was confirmed that the reaction rate had reached 99.5% or more. At this time, the maturation (reaction) time from the dropwise addition of 20% by mass hydrochloric acid to the termination of the reaction was 4.5 hours. Toluene (200.00 g) was further added to the reaction mixture, followed by separation, and the aqueous layer was removed to obtain an organic layer. The organic layer obtained was then washed with saline, separated, and the aqueous layer was removed to obtain an organic layer. The organic layer obtained was further washed with an aqueous sodium hydrogen carbonate solution, separated, and the aqueous layer was removed to obtain an organic layer. The organic layer obtained was distilled under reduced pressure to obtain formyl B Thenyl methoxymethyl ether (2:R 3 =H; a=2) (149.40 g, 0.93 mol, purity 90.10%, bp=82.6-85.4°C / 3.0 mmHg (0.40 kPa)) was obtained in a yield of 73.98%. Comparative Example 3 was carried out under the same conditions as Example 1 except that ethanol was distilled and removed, but the yield was 73.98% and the purity was 90.10%, which were lower than those of Example 1, which had a yield of 93.00% and a purity of 95.41%.

[0092] The above obtained formyl B The various spectral data of thenyl methoxymethyl ether were the same as those obtained in Example 1.

[0093] Example 3 Formyl B Thenyl ethoxymethyl ether (2:R 3 =CH3;a=2)<CH3CH2OCH2O(CH2)2CH=CHCHO> Manufacturing

[0094] [ka]

[0095] At room temperature, a reactor was charged with diethoxypentenyl methoxymethyl ether (1:R 3=CH3; a=2) (308.10 g, 1.26 mol, purity 95.16%) and water (37.96 g, 2.11 mol) were added and stirred for 22 minutes at 30 to 40° C. After stirring, formic acid (2.56 g, 0.049 mol, purity 88%) was added dropwise at 30 to 45° C. to carry out hydrolysis, and then 20 mass % hydrochloric acid (0.23 g, 0.0013 mol as hydrogen chloride) was added dropwise at 30 to 45° C., and the mixture was stirred at 40 to 45° C. for 60 minutes. Subsequently, while the hydrolysis proceeded, the pressure was reduced to 235 mmHg (31.3 kPa) at an internal temperature of 40 to 55°C, and then gradually reduced to 50 mmHg (6.67 kPa), and ethanol (119.02 g, 2.53 mol, purity 97.75%) produced by the hydrolysis was distilled and removed. Distillation ceased 4 hours after the start of pressure reduction. When the distillate disappeared, toluene (234.56 g), water (77.90 g), salt (23.21 g), and 20 mass% hydrochloric acid (4.60 g, 0.025 mol as hydrogen chloride) were added, and the mixture was separated, and the aqueous layer was removed. The organic layer obtained was then washed with saline, separated, and the aqueous layer was removed to obtain an organic layer. The organic layer obtained was further washed with an aqueous sodium hydrogen carbonate solution, separated, and the aqueous layer was removed to obtain an organic layer. The organic layer obtained was distilled under reduced pressure to obtain formyl amine. B Thenyl ethoxymethyl ether (2:R 3 =CH3; a=2) (197.56 g, 1.139 mol, purity 91.20%, bp = 85.0-86.1 °C / 3.0 mmHg (0.40 kPa)) was obtained in a yield of 90.26%. The progress of the hydrolysis was confirmed by the same method as in Example 1 above.

[0096] Formyl B Thenyl ethoxymethyl ether (2:R 3 =CH3;a=2) [Nuclear Magnetic Resonance 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); 13 C-NMR(500MHz,CDCl3):δ=15.05,32.96,63.34,65.40,95.07,134.17,154.96,193.76 [Mass spectrum] EI-mass spectrum (70 eV): m / z 128 (M + -30), 113, 98, 83, 70, 59, 41 [Infrared absorption spectrum] (NaCl): ν=2976, 2931, 2878, 1692, 1114, 1099, 1042, 975, 847

[0097] Comparative Example 4 Formyl B Thenyl ethoxymethyl ether (2:R 3 =CH3;a=2)<CH3CH2OCH2O(CH2)2CH=CHCHO> Manufacturing

[0098] [ka]

[0099] At room temperature, a reactor was charged with diethoxypentenyl ethoxymethyl ether (1:R 3=CH3; a=2) (308.10 g, 1.26 mol, purity 95.16%) and toluene (80.00 g) were added and stirred at 10 to 15°C for 31 minutes. After stirring, 8% by mass hydrochloric acid (145.13 g, 0.32 mol as hydrogen chloride) was added dropwise at 15 to 20°C to carry out hydrolysis, and the reaction was tracked using GC at 15 to 20°C. The reaction was stopped after confirming that the reaction rate was 99.5% or more. At this time, the maturation (reaction) time from the dropwise addition of 8% by mass hydrochloric acid to the end of the reaction was 1 hour. Toluene (200.00 g) was further added to the reaction mixture, followed by separation, and the aqueous layer was removed to obtain an organic layer. The obtained organic layer was then washed with saline, separated, and the aqueous layer was removed to obtain an organic layer. The obtained organic layer was further washed with an aqueous sodium hydrogen carbonate solution, separated, and the aqueous layer was removed to obtain an organic layer. The obtained organic layer was distilled under reduced pressure to obtain formyl amine. B Thenyl ethoxymethyl ether (2:R 3 =CH3; a=2) (141.18 g, 0.74 mol, purity 82.61%, bp = 85.0-86.1 °C / 3.0 mmHg (0.40 kPa)) was obtained in a yield of 58.42%. Note that each of the aqueous layers removed above contained ethanol produced by hydrolysis.

[0100] The above obtained formyl B Thenyl ethoxymethyl ether (2:R 3 The various spectral data of the compound (=CH3; a=2) were identical to those obtained in Example 3.

[0101] Comparative Example 5 Formyl B Thenyl ethoxymethyl ether (2:R 3 =CH3;a=2)<CH3CH2OCH2O(CH2)2CH=CHCHO> Manufacturing

[0102] [ka]

[0103] When the experiment was repeated under the same conditions as in Comparative Example 4, formyl B Thenyl ethoxymethyl ether (2:R 3 =CH3; a=2) (171.46 g, 0.90 mol, purity 82.91%, bp=85.0-86.1°C / 3.0 mmHg (0.40 kPa)) was obtained in a yield of 71.21%. Although Comparative Example 4 and Comparative Example 5 were carried out under the same conditions, the yields were 58.42% (Comparative Example 4) and 71.21% (Comparative Example 5), and the yields were not stable.

[0104] The above obtained formyl B Thenyl ethoxymethyl ether (2:R 3 The various spectral data of the compound (=CH3; a=2) were identical to those obtained in Example 3.

[0105] Example 4 Formira Kise Nyl=Methoxymethyl=Ether (2:R 3 =H;a=4)<CH3OCH2O(CH2)4CH=CHCHO> Manufacturing

[0106] [ka]

[0107] At room temperature, a reactor was charged with diethoxyheptenyl methoxymethyl ether (1:R 3 =H; a=4) (500.00 g, 1.95 mol, purity 95.97%) and water (58.60 g, 3.25 mol) were added and stirred for 12 minutes at 30 to 40° C. After stirring, formic acid (3.95 g, 0.076 mol, purity 88%) was added dropwise at 30 to 45° C. to carry out hydrolysis, and then 20 mass % hydrochloric acid (0.35 g, 0.0019 mol as hydrogen chloride) was added dropwise at 30 to 45° C., and the mixture was stirred at 40 to 45° C. for 104 minutes. Subsequently, while the hydrolysis proceeded, the pressure was reduced to 235 mmHg (31.3 kPa) at an internal temperature of 40 to 55°C, and then gradually reduced to 50 mmHg (6.67 kPa), and ethanol (192.43 g, 4.12 mol, purity 98.74%) produced by the hydrolysis was distilled and removed. Distillation ceased 4.5 hours after the start of pressure reduction. When the distillate disappeared, toluene (362.06 g), water (120.25 g), salt (35.83 g), and 20 mass% hydrochloric acid (7.10 g, 0.039 mol as hydrogen chloride) were added and separated, and the aqueous layer was removed to obtain an organic layer. Subsequently, the obtained organic layer was washed with saline, separated, and the aqueous layer was removed to obtain an organic layer. Furthermore, the obtained organic layer was washed with an aqueous sodium hydrogen carbonate solution, separated, and the aqueous layer was removed to obtain an organic layer. The obtained organic layer was distilled under reduced pressure to obtain formyl ether. Kise Nyl=Methoxymethyl=Ether (2:R 3 =H; a=4) (340.59 g, 1.83 mol, purity 92.73%, bp = 108.2-109.8 °C / 3.0 mmHg (0.40 kPa)) was obtained in a yield of 94.14%. The progress of the hydrolysis was confirmed by the same method as in Example 1 above.

[0108] Formira Kise Nyl=Methoxymethyl=Ether (2:R 3 =H;a=4) [Nuclear Magnetic Resonance Spectrum] 1 H-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); 13 C-NMR (500MHz, CDCl3): δ=24.52,29.10,32.33,55.07,67.09,96.33,133.06,158.26,193.95 [Mass spectrum] EI-mass spectrum (70 eV): m / z 127 (M + -45), 114, 81, 68, 55, 45 [Infrared absorption spectrum] (NaCl): ν=2938, 2882, 2822, 1692, 1149, 1111, 1043, 977, 918

[0109] Comparative Example 6 Formira Kise Nyl=Methoxymethyl=Ether (2:R 3 =H;a=4)<CH3OCH2O(CH2)4CH=CHCHO> Manufacturing

[0110] [ka]

[0111] At room temperature, a reactor was charged with diethoxyheptenyl methoxymethyl ether (1:R 3 =H; a=4) (100.00 g, 0.39 mol, purity 95.97%) and toluene (24.70 g) were added and stirred at 10 to 15°C for 3 minutes. After stirring, 8% by mass hydrochloric acid (44.80 g, 0.098 mol as hydrogen chloride) was added dropwise at 15 to 20°C to carry out hydrolysis, and the reaction was tracked using GC at 15 to 20°C. The reaction was stopped after it was confirmed that the reaction rate was 99.5% or more. At this time, the maturation (reaction) time from the dropwise addition of 8% by mass hydrochloric acid to the end of the reaction was 1 hour. Toluene (61.74 g) was further added to the reaction mixture, followed by separation, and the aqueous layer was removed to obtain an organic layer. The obtained organic layer was then washed with saline, separated, and the aqueous layer was removed to obtain an organic layer. The obtained organic layer was further washed with an aqueous sodium hydrogen carbonate solution, separated, and the aqueous layer was removed to obtain an organic layer. The obtained organic layer was distilled under reduced pressure to obtain formyl hexane. Kise Nyl=Methoxymethyl=Ether (2:R 3 =CH3; a = 4) (61.03 g, 0.32 mol, purity 90.97%, bp = 108.2-109.8 °C / 3.0 mmHg (0.40 kPa)) was obtained in a yield of 82.75%.

[0112] The above obtained formyl Kise Nyl=Methoxymethyl=Ether (2:R 3 =H; a=4) were identical to the various spectral data obtained in Example 4.

[0113] Example 5 (5E,7Z)-5,7-dodecadienyl alkoxymethyl ether compounds (4:R 3 =H;a=4)<CH3(CH2)3CH=CHCH=CH(CH2)4OCH2OCH3> Manufacturing

[0114] [ka]

[0115] At room temperature, 1-bromopentane (8: X = Br) (182.77g, 1.21mol), triphenylphosphine (9: all Ar = Ph) (315.50g, 1.20mol) and N,N-dimethylformamide (DMF) (200.00g) were added to the reactor, and the mixture was stirred at 110-120 ° C for 9 hours to prepare pentyltriphenylphosphonium = bromide (10: Y = Br; all Ar = Ph). Next, tetrahydrofuran (872.84g) was added dropwise to the reactor at 30-40 ° C., and after the dropwise addition, the reaction solution was cooled to -5-10 ° C., potassium = t-butoxide (131.29g, 1.17mol) was added, and the mixture was stirred for 1 hour to prepare triphenylphosphonium = pentylide (3: Ar = Ph).

[0116] Thereafter, the formyl ester prepared in Example 4 above was added to the Kise Nyl=Methoxymethyl=Ether (2:R 3A mixture of 5E,7Z)-5,7-dodecadienyl alkoxymethyl ether compound (4:R =H; a=4) (185.72 g, 1.00 mol, purity 92.73%) was added dropwise at -72 to -61°C, and after completion of the dropwise addition, the mixture was warmed to room temperature and stirred at 25 to 30°C for 1 hour. Water (592.67 g) was then added to the reaction mixture, which was then separated. The aqueous layer was removed to obtain an organic layer. The obtained organic layer was distilled under reduced pressure to obtain (5E,7Z)-5,7-dodecadienyl alkoxymethyl ether compound (4:R =H; a=4) (185.72 g, 1.00 mol, purity 92.73%). 3 =H; a=4) (230.28 g, 0.97 mol, purity 95.82%; 5E7Z:5E7E:5Z7Z=91.8:6.6:1.6, bp=104.0-123.5 °C / 3.0 mmHg (0.40 kPa)) was obtained in a yield of 97.48%.

[0117] (5E,7Z)-5,7-dodecadienyl alkoxymethyl ether compounds (4:R 3 =H;a=4) [Nuclear Magnetic Resonance Spectrum] 1 H-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),3.5 2(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); 13 C-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 spectrum] EI-mass spectrum (70 eV): m / z 226 (M + ), 194, 181, 163, 150, 137, 121, 107, 95, 79, 67, 45 [Infrared absorption spectrum] (NaCl): ν=2929, 2872, 1458, 1440, 1150, 1112, 1044, 983, 949, 921, 732

[0118] Example 6 (5E,7Z)-5,7-dodecadien-1-ol (5)<CH3(CH2)3CH=CHCH=CH(CH2)4OH> Manufacturing

[0119] [ka]

[0120] The (5E,7Z)-5,7-dodecadienyl alkoxymethyl ether compound (4:R 3 =H; a=4) (210.84 g, 0.89 mol, purity 95.82%; 5E7Z:5E7E:5Z7Z=91.8:6.6:1.6) and methanol (446.25 g, 13.93 mol) were charged into a reactor equipped with a distillation column and stirred at 45 to 50°C, and 20% by mass hydrochloric acid (44.63 g, 0.24 mol as hydrogen chloride) was added dropwise thereto at 45 to 50°C. The reaction solution was then heated to 60°C and stirred for 3 hours. After the stirring, the internal temperature was raised to 65-70°C, and a mixture of dimethoxymethane and methanol by-products was distilled and removed from the distillation column. The reaction solution was sampled during the reaction, and when the reaction rate reached 100%, distillation was stopped, the reaction solution was cooled to 35°C, water (286g) was added and separated, and the aqueous layer was removed to obtain an organic layer. The obtained organic layer was distilled under reduced pressure to obtain (5E,7Z)-5,7-dodecadien-1-ol (5) (162.54g, 0.81mol, purity 91.35%; 5E7Z:5E7E:5Z7Z=91.1:7.1:1.8, bp=106.2-115.6°C / 3.0mmHg (0.40kPa)) in a yield of 91.26%.

[0121] (5E,7Z)-5,7-dodecadien-1-ol (5) [Nuclear Magnetic Resonance Spectrum] 1H-NMR (500MHz, CDCl3): δ=0.89(3H,t,J=7.3Hz),1.24-1.40(4H,m),1.46(2H,quin-lik e,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,7.3 Hz),5.93(1H,dd,J=11.1Hz,11.1Hz),6.31(1H,dddt,J=15.1Hz,11.0Hz,1.5Hz,1.5Hz); 13 C-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 spectrum] EI-mass spectrum (70 eV): m / z 182 (M + ), 164, 149, 135, 121, 107, 93, 79, 67, 55, 41 [Infrared absorption spectrum] (NaCl): ν=3338, 2956, 2930, 1457, 1059, 982, 949, 730

[0122] Example 7 (5E,7Z)-5,7-dodecadienyl acetate (6)<CH3(CH2)3CH=CHCH=CH(CH2)4OCOCH3> Manufacturing

[0123] [ka]

[0124] At room temperature, (5E,7Z)-5,7-dodecadien-1-ol (5) (154.50 g, 0.77 mol, purity 91.35%; 5E7Z:5E7E:5Z7Z=91.1:7.1:1.8) and pyridine (97.98 g, 1.24 mol) prepared in Example 6 were added to a reactor, and the mixture was stirred at 15 to 25 ° C for 13 minutes. After stirring, acetic anhydride (94.85 g, 0.93 mol) was added dropwise at 20 to 40 ° C, and the mixture was stirred at 30 to 35 ° C for 6 hours. Next, water (203.36 g) was added to the reaction liquid, and the mixture was separated, and the aqueous layer was removed to obtain an organic layer. The obtained organic layer was distilled under reduced pressure to obtain (5E,7Z)-5,7-dodecadienyl acetate (6) (181.52 g, 0.76 mol, purity 93.93%; 5E7Z:5E7E:5Z7Z=91.5:6.8:1.7, bp=120.0-123.0°C / 4.0 mmHg (0.40 kPa)) in a yield of 98.17%.

[0125] (5E,7Z)-5,7-dodecadienyl acetate (6) [Nuclear Magnetic Resonance Spectrum] 1 H-NMR (500MHz, CDCl3): δ=0.89(3H,t,J=7.3Hz),1.27-1.40(4H,m),1.45(2H,quin-l ike,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=14.5H z,6.9Hz),5.93(1H,dd,J=11.1Hz,11.1Hz),6.30(1H,ddd,J=15.3Hz,11.1Hz,1.2Hz); 13 C-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 spectrum] EI-mass spectrum (70 eV): m / z 224 (M +), 181, 164, 149, 136, 121, 107, 93, 79, 67, 55 [Infrared absorption spectrum] (NaCl): ν=2956, 2930, 2859, 1742, 1457, 1365, 1238, 1039, 984, 950, 733

[0126] One embodiment of the present invention is summarized below. [Section A1] The following general formula (1) R 3 CH2OCH2O(CH2) a CH=CHCH(OR 1 )(OR 2 ) (1) (In the formula, R 1 and R 2 are each independently a monovalent hydrocarbon group having 1 to 15 carbon atoms, or R 1 and R 2 are bonded together R 1 -R 2 represents a divalent hydrocarbon group having 2 to 10 carbon atoms; R 3 represents a hydrogen atom, an n-alkyl group having 1 to 9 carbon atoms, or a phenyl group, and a represents an integer of 1 to 10. In the presence of an acid, a dialkoxyalkenyl alkoxymethyl ether compound represented by the following general formula (2) is hydrolyzed while removing the generated alcohol compound. R 3 CH2OCH2O(CH2) a CH=CHCHO (2) (In the formula, R 3 and a is as defined above. A step of obtaining a formyl alkenyl alkoxymethyl ether compound (2) represented by the formula: A method for producing a formyl alkenyl alkoxymethyl ether compound (2), comprising at least the steps of: [Section A2] The method for producing a formyl alkenyl alkoxymethyl ether compound according to item A1, wherein the acid is formic acid, hydrochloric acid or a mixture thereof. [Section A3] A method for producing the formyl alkenyl alkoxymethyl ether compound (2) according to the above item A1 or A2, wherein a=4; The formyl alkenyl alkoxymethyl ether compound (2) and a compound represented by the following general formula (3) [ka] (In the formula, each Ar independently represents an aryl group.) The triarylphosphonium pentylide compound represented by the following general formula (4) is subjected to a Wittig reaction with the CH3(CH2)3CH=CHCH=CH(CH2)4OCH2OCH2R 3 (4) (In the formula, R 3 is as defined above.) obtaining a (5E,7Z)-5,7-dodecadienyl alkoxymethyl ether compound represented by the formula: The (5E,7Z)-5,7-dodecadienyl alkoxymethyl ether compound (4) is dealkoxymethylated to obtain a compound represented by the following formula (5): CH3(CH2)3CH=CHCH=CH(CH2)4OH (5) and obtaining (5E,7Z)-5,7-dodecadien-1-ol (5) represented by the formula: A method for producing (5E,7Z)-5,7-dodecadien-1-ol (5), comprising at least [Section A4] A method for producing (5E,7Z)-5,7-dodecadien-1-ol (5) according to the above item A3; The (5E,7Z)-5,7-dodecadien-1-ol (5) is subjected to an acetylation reaction to obtain a compound represented by the following formula (6): CH3(CH2)3CH=CHCH=CH(CH2)4OCOCH3(6) and obtaining (5E,7Z)-5,7-dodecadienyl acetate (6) represented by the formula: A method for producing (5E,7Z)-5,7-dodecadienyl acetate (6), comprising at least

[0127] Another embodiment of the present invention is summarized below. [Section B1] The following general formula (1) R 3 CH2OCH2O(CH2) a CH=CHCH(OR 1 )(OR 2 ) (1) (In the formula, R 1 and R 2 are each independently a monovalent hydrocarbon group having 1 to 15 carbon atoms, or R 1 and R 2 are bonded together R 1 -R 2 represents a divalent hydrocarbon group having 2 to 10 carbon atoms; R 3 represents a hydrogen atom, an n-alkyl group having 1 to 9 carbon atoms, or a phenyl group, and a represents an integer of 1 to 10. In the presence of an acid, a dialkoxyalkenyl alkoxymethyl ether compound represented by the following general formula (2) is hydrolyzed while removing the generated alcohol compound. R 3 CH2OCH2O(CH2) a CH=CHCHO (2) (In the formula, R 3 and a is as defined above. A step of obtaining a formyl alkenyl alkoxymethyl ether compound (2) represented by the formula: At least The acid is hydrochloric acid, hydrobromic acid, p toluenesulfonic acid, benzenesulfonic acid, trifluoroacetic acid, acetic acid, formic acid, oxalic acid, iodotrimethylsilane or titanium tetrachloride, or combinations thereof; A method for producing formyl alkenyl alkoxymethyl ether compound (2). [Section B2] The acid is hydrochloric acid, p The method according to item B1, wherein the acid is toluenesulfonic acid, acetic acid, formic acid, or a combination thereof. [Section B3] The method for producing a formyl alkenyl alkoxymethyl ether compound according to item B1, wherein the acid is formic acid, hydrochloric acid, or a combination thereof. [Section B4] A method for producing the formyl alkenyl alkoxymethyl ether compound (2) according to any one of the above items B1 to B3, wherein a=4; The formyl alkenyl alkoxymethyl ether compound (2) and a compound represented by the following general formula (3) [ka] (In the formula, each Ar independently represents an aryl group.) The triarylphosphonium pentylide compound represented by the following general formula (4) is subjected to a Wittig reaction with the CH3(CH2)3CH=CHCH=CH(CH2)4OCH2OCH2R 3 (4) (In the formula, R 3 is as defined above.) obtaining a (5E,7Z)-5,7-dodecadienyl alkoxymethyl ether compound represented by the formula: The (5E,7Z)-5,7-dodecadienyl alkoxymethyl ether compound (4) is dealkoxymethylated to obtain a compound represented by the following formula (5): CH3(CH2)3CH=CHCH=CH(CH2)4OH (5) and obtaining (5E,7Z)-5,7-dodecadien-1-ol (5) represented by the formula: A method for producing (5E,7Z)-5,7-dodecadien-1-ol (5), comprising at least [Section B5] A method for producing (5E,7Z)-5,7-dodecadien-1-ol (5) according to item B4 above; The (5E,7Z)-5,7-dodecadien-1-ol (5) is subjected to an acetylation reaction to obtain a compound represented by the following formula (6): CH3(CH2)3CH=CHCH=CH(CH2)4OCOCH3(6) and obtaining (5E,7Z)-5,7-dodecadienyl acetate (6) represented by the formula: A method for producing (5E,7Z)-5,7-dodecadienyl acetate (6), comprising at least

Claims

1. The following general formula (1) R ３ CH ２ OCH ２ O(CH ２ ) ａ CH=CHCH(OR １ )(OR ２ ) (1) (In the formula, R １ and R ２ each independently represents a monovalent hydrocarbon group having 1 to 15 carbon atoms, or R １ and R ２ are bonded to each other １ -R ２ represents a divalent hydrocarbon group having 2 to 10 carbon atoms; R ３ represents a hydrogen atom, an n-alkyl group having 1 to 9 carbon atoms, or a phenyl group, and a represents an integer of 1 to 10. In the presence of an acid, a dialkoxyalkenyl alkoxymethyl ether compound represented by the following general formula (2) is hydrolyzed while removing the generated alcohol compound. R ３ CH ２ SO ２ O(CH ２ ) ａ CH=CHCHO (22) (In the formula, R ３ and a is as defined above. A step of obtaining a formyl alkenyl alkoxymethyl ether compound (2) represented by the formula: At least the acid is hydrochloric acid, hydrobromic acid, p-toluenesulfonic acid, benzenesulfonic acid, trifluoroacetic acid, formic acid, oxalic acid, or iodotrimethylsilane, or a combination thereof; A method for producing a formyl alkenyl alkoxymethyl ether compound (2).

2. The manufacturing method described in claim 1, wherein the acid is hydrochloric acid, p-toluenesulfonic acid, or formic acid, or a combination thereof.

3. The method for producing a formyl alkenyl alkoxymethyl ether compound according to claim 1, wherein the acid is formic acid, hydrochloric acid, or a combination thereof.

4. A method for producing a compound according to any one of claims 1 to 3, wherein the hydrolysis reaction is carried out in the presence of water in addition to the acid.

5. The method of claim 4, wherein the amount of water used in the hydrolysis reaction is 300 g or less per 1 mol of the dialkoxyalkenyl alkoxymethyl ether compound (1).

6. A manufacturing method described in any one of claims 1 to 5, wherein the reaction temperature in the hydrolysis reaction is 10 to 150°C.

7. A method for producing a product described in any one of claims 1 to 6, wherein the removal of the produced alcohol compound is carried out under normal pressure or reduced pressure.

8. A method for producing a product described in any one of claims 1 to 7, wherein the removal of the produced alcohol compound is carried out under reduced pressure.

9. A method for producing a formyl alkenyl alkoxymethyl ether compound (2) according to any one of claims 1 to 8, wherein a=4; The formyl alkenyl alkoxymethyl ether compound (2) and a compound represented by the following general formula (3) 【Chemistry 1】 (In the formula, each Ar independently represents an aryl group.) and a triarylphosphonium pentylide compound represented by the following general formula (4) is subjected to a Wittig reaction. CH ３ (CH) ２ ) ３ CH=CHCH=CH(CH ２ ) ４ OCH ２ OCH ２ R ３ (4) (In the formula, R ３ is as defined above.) obtaining a (5E,7Z)-5,7-dodecadienyl alkoxymethyl ether compound represented by the formula: The (5E,7Z)-5,7-dodecadienyl alkoxymethyl ether compound (4) is dealkoxymethylated to obtain a compound represented by the following formula (5): CH ３ (CH ２ ) ３ CH=CHCH=CH(CH ２ ) ４ OH (5) obtaining (5E,7Z)-5,7-dodecadien-1-ol (5) represented by A method for producing (5E,7Z)-5,7-dodecadien-1-ol (5), comprising at least

10. The method for producing (5E,7Z)-5,7-dodecadien-1-ol (5) according to claim 9, The (5E,7Z)-5,7-dodecadien-1-ol (5) is subjected to an acetylation reaction to obtain a compound represented by the following formula (6): CH ３ (CH ２ ) ３ CH=CHCH=CH(CH ２ ) ４ P.S. ３ (6) obtaining (5E,7Z)-5,7-dodecadienyl acetate (6) represented by the formula: A method for producing (5E,7Z)-5,7-dodecadienyl acetate (6), comprising at least

11. The following general formula (1) R ３ CH ２ OCH ２ O(CH ２ ) ａ CH=CHCH(OR １ )(OR ２ ) (1) (In the formula, R １ and R ２ each independently represents a monovalent hydrocarbon group having 1 to 15 carbon atoms, or R １ and R ２ are bonded to each other １ -R ２ represents a divalent hydrocarbon group having 2 to 10 carbon atoms; R ３ represents a hydrogen atom, an n-alkyl group having 1 to 9 carbon atoms, or a phenyl group, and a represents an integer of 1 to 10. In the presence of an acid, a dialkoxyalkenyl alkoxymethyl ether compound represented by the following general formula (2) is hydrolyzed while removing the generated alcohol compound. R ３ CH ２ SO ２ O(CH ２ ) ａ CH=CHCHO (22) (In the formula, R ３ and a is as defined above. A step of obtaining a formyl alkenyl alkoxymethyl ether compound (2) represented by the formula: At least The acid is hydrochloric acid, hydrobromic acid, p-toluenesulfonic acid, benzenesulfonic acid, trifluoroacetic acid, acetic acid, formic acid, oxalic acid, iodotrimethylsilane, or a combination thereof, and the amount of the acid used is 0.0001 to 2.0 mol per 1 mol of the dialkoxyalkenyl alkoxymethyl ether compound (1). A method for producing a formyl alkenyl alkoxymethyl ether compound (2).

12. The method of claim 11, wherein the acid is hydrochloric acid, p-toluenesulfonic acid, acetic acid, or formic acid, or a combination thereof.

13. The method for producing a formyl alkenyl alkoxymethyl ether compound according to claim 11, wherein the acid is formic acid, hydrochloric acid, or a combination thereof.

14. A method for producing a compound according to any one of claims 11 to 13, wherein the hydrolysis reaction is carried out in the presence of water in addition to the acid.

15. The method according to claim 14, wherein the amount of water used in the hydrolysis reaction is 300 g or less per 1 mol of the dialkoxyalkenyl alkoxymethyl ether compound (1).

16. A manufacturing method described in any one of claims 11 to 15, wherein the reaction temperature in the hydrolysis reaction is 10 to 150°C.

17. A method for producing a product described in any one of claims 11 to 16, wherein the removal of the produced alcohol compound is carried out under normal pressure or reduced pressure.

18. A method for producing a compound according to any one of claims 11 to 17, wherein the acid is acetic acid.

19. A method for producing a formyl alkenyl alkoxymethyl ether compound (2) according to any one of claims 11 to 18, wherein a=4; The formyl alkenyl alkoxymethyl ether compound (2) and a compound represented by the following general formula (3) 【Chemistry 2】 (In the formula, each Ar independently represents an aryl group.) The triarylphosphonium pentylide compound represented by the following general formula (4) is subjected to a Wittig reaction with CH ３ (CH) ２ ) ３ CH=CHCH=CH(CH ２ ) ４ OCH ２ OCH ２ R ３ (4) (In the formula, R ３ is as defined above.) obtaining a (5E,7Z)-5,7-dodecadienyl alkoxymethyl ether compound represented by the formula: The (5E,7Z)-5,7-dodecadienyl alkoxymethyl ether compound (4) is dealkoxymethylated to obtain a compound represented by the following formula (5): CH ３ (CH ２ ) ３ CH=CHCH=CH(CH ２ ) ４ OH (5) obtaining (5E,7Z)-5,7-dodecadien-1-ol (5) represented by A method for producing (5E,7Z)-5,7-dodecadien-1-ol (5), comprising at least

20. The method for producing (5E,7Z)-5,7-dodecadien-1-ol (5) according to claim 19, The (5E,7Z)-5,7-dodecadien-1-ol (5) is subjected to an acetylation reaction to obtain a compound represented by the following formula (6): CH ３ (CH ２ ) ３ CH=CHCH=CH(CH ２ ) ４ P.S. ３ (6) obtaining (5E,7Z)-5,7-dodecadienyl acetate (6) represented by the formula: A method for producing (5E,7Z)-5,7-dodecadienyl acetate (6), comprising at least

Images