JP2012020954A - Method for producing vinyl ether compound - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for producing a vinyl ether compound, by which the high purity vinyl ether compound can be produced at a low cost with a general reaction apparatus without a special or expensive precious metal catalyst and a reactive gas.SOLUTION: The method for producing the vinyl ether compound comprises a process (A) of reacting a compound represented by formula (1) with a compound represented by formula (2) to obtain a compound represented by formula (3), and a process (B) of reacting the compound represented by formula (3) with a compound represented by formula (4) or formula (5) to obtain the vinyl ether compound represented by formula (6).

Description

  The present invention relates to a method for producing a vinyl ether compound useful as a raw material for pharmaceuticals, agricultural chemicals, polymers and the like.

  Vinyl ether compounds are useful raw materials for asymmetric acetal compounds, and are used as reactive diluents for inks and paints, as well as raw materials for chemicals such as pharmaceuticals, agricultural chemicals, and resist resins. Vinyl ethers are generally cationically polymerizable and are useful because they are used in polymer raw materials such as optical resins and transparent resins, UV curing agents and adhesives as crosslinking agents. Furthermore, since vinyl ether compounds have higher storage stability and less odor and skin irritation compared to acrylic compounds and styrene compounds, they also have the advantage of excellent workability and handling. However, since vinyl ether compounds are less in kind and more expensive than acrylic compounds, the demand for vinyl ether compounds is not sufficiently satisfied.

  Various methods for producing vinyl ether compounds are known (see, for example, Patent Documents 1 and 2 and Non-Patent Document 1). In Patent Document 1, a vinyl ether compound is obtained by reacting a carboxylic acid vinyl ester compound with a hydroxy compound in the presence of a transition metal catalyst such as an iridium compound. However, a transition metal catalyst used as a catalyst is generally expensive, and its catalytic activity changes under the influence of atmospheric oxygen and moisture, so that a stable yield cannot be obtained. Moreover, the boiling point of the produced | generated vinyl ether compound and an unreacted hydroxy compound is near, and even if it refine | purifies by distillation, a highly purified vinyl ether compound may not be obtained. In Patent Document 2, a vinyl ether compound is obtained by reacting an acetylene gas and a hydroxy compound. However, in order to use a reactive gas, special equipment such as a pressure-resistant reaction vessel is required. In Non-Patent Document 1, a vinyl ether compound is obtained by reacting an alcohol with an aldehyde compound in the presence of hydrochloric acid gas and then reacting with a base. However, since an acid gas is used, the reaction vessel is resistant to acid and corrosion. It is necessary to have. Further, after the reaction between the alcohol and the aldehyde compound, a dehydration / purification step is required, and the reaction with the next base cannot be carried out in the same reaction vessel.

JP 2005-126395 A Japanese Patent No. 3817316

Eur. J. et al. Org. Chem. 2005, 2548-57

  An object of the present invention is to provide a method for producing a high-purity vinyl ether compound at low cost using a general reaction apparatus without using a special or expensive noble metal catalyst or reactive gas.

  The present invention has the following configuration, which solves the above-described problems of the present invention.

[1] Step (A) of obtaining a compound represented by the following general formula (3) by reacting a compound represented by the following general formula (1) with a compound represented by the following general formula (2) The compound represented by the following general formula (3) reacts with the compound represented by the following general formula (4) or the following general formula (5) to give a vinyl ether compound represented by the following general formula (6). A process for producing a vinyl ether compound, comprising the step (B) of obtaining.

In the formula, R ¹ and R ² each independently represent a hydrogen atom, an alkyl group, an aryl group, or an aralkyl group. R ¹ and R ² may be linked to each other to form a ring.
R ³ represents an alkyl group, an aryl group or an aralkyl group.
R ⁴ represents an alkyl group, an alkenyl group, an aryl group or an aralkyl group.
R ⁵ , R ⁶ and R ⁷ each independently represents an alkyl group, an aryl group or an aralkyl group.
X represents a halogen atom.
R ⁸ represents a monovalent substituent.
n ₁ represents an integer of 0-4.

[2] A compound represented by the following general formula (1) reacts with a compound represented by the following general formula (8) or the following general formula (9), and the compound represented by the above general formula (1) The manufacturing method of the vinyl ether compound as described in said [1] including the process (C) which obtains.

^Wherein, R 1, ^{R 2} and ^{R 3} each have the same meanings as ^R 1, ^{R 2} and ^{R 3} in the general formula (1).

[3] The process for producing a vinyl ether compound according to the above [1] or [2], wherein the step (A) and the step (B) are collectively performed in the same reaction vessel.

[4] The method for producing a vinyl ether compound according to [2], wherein the step (C), the step (A), and the step (B) are collectively performed in the same reaction vessel.

[5] The method for producing a vinyl ether compound according to any one of [1] to [4] above, wherein the total number of carbon atoms of R ¹ , R ² and R ³ is 7 or more.

[6] In the general formulas (1) to (3) and (6), the total number of carbon atoms of R ¹ and R ² is 2 or less, the carbon number of R ³ is 7 or more, and R ⁴ The method for producing a vinyl ether compound according to any one of the above [1] to [4], wherein the number of carbon atoms is 7 or more.

[7] In the above general formulas (1) to (3), the total number of carbon atoms of R ¹ and R ² is 6 or more, and the carbon number of R ⁴ is 3 or less. [4] The method for producing a vinyl ether compound according to any one of [4].

[8] In any one of the above-mentioned [1] to [7], in the general formulas (1), (3) and (6), R ³ is a group represented by the following general formula (10) The manufacturing method of the vinyl ether compound as described in 1 ..

In the formula, n ₂ represents an integer of 1 to 6, and Y represents a cyclic alkyl group or an aryl group. * Indicates a bond connected to an oxygen atom.

[9] The method for producing a vinyl ether compound according to any one of [1] to [8] above, wherein a hydrocarbon solvent is used as a reaction solvent in each of the step (A) and the step (B). .

[10] The method for producing a vinyl ether compound according to any one of [1] to [9], wherein the same reaction solvent is used in the step (A) and the step (B).

[11] The method for producing a vinyl ether compound according to any one of [2] to [10], wherein a hydrocarbon solvent is used as a reaction solvent in the step (C).

[12] The method for producing a vinyl ether compound according to any one of the above [2] to [11], wherein the same reaction solvent is used in the step (C), the step (A) and the step (B). .

  The present invention preferably further has the following configuration.

[13] The method for producing a vinyl ether compound according to [6], wherein R ⁴ has 11 or more carbon atoms.

[14] The method for producing a vinyl ether compound according to [7], wherein R ⁴ has 2 or less carbon atoms.

[15] The method for producing a vinyl ether compound according to any one of [1] to [14], wherein a reaction activator is added in the step (C).

[16] The method for producing a vinyl ether compound according to any one of [2] to [15] above, wherein an acid catalyst is added in the step (C).

  According to the present invention, it is possible to produce a high purity vinyl ether compound at low cost using a general reaction apparatus without using a special or expensive noble metal catalyst or reactive gas.

Hereinafter, embodiments of the present invention will be described in detail.
In addition, in the description of the group (atomic group) in this specification, the description which does not describe substitution and unsubstituted includes both the thing which does not have a substituent, and the thing which has a substituent. Suppose that For example, an “alkyl group” that does not clearly indicate substitution or unsubstituted is not only an alkyl group that does not have a substituent (unsubstituted alkyl group) but also an alkyl group that has a substituent (substituted alkyl group) Is also included.

  The method for producing a vinyl ether compound according to the present invention is represented by the following general formula (3) by reacting a compound represented by the following general formula (1) with a compound represented by the following general formula (2). The step (A) for obtaining a compound, the compound represented by the following general formula (3), and the compound represented by the following general formula (4) or the following general formula (5) are reacted, and the following general formula (6) And (B) to obtain a vinyl ether compound represented by

In the formula, R ¹ and R ² each independently represent a hydrogen atom, an alkyl group, an aryl group, or an aralkyl group. R ¹ and R ² may be linked to each other to form a ring.
R ³ represents an alkyl group, an aryl group or an aralkyl group.
R ⁴ represents an alkyl group, an alkenyl group, an aryl group or an aralkyl group.
R ⁵ , R ⁶ and R ⁷ each independently represents an alkyl group, an aryl group or an aralkyl group. Two of R ⁵ , R ⁶ and R ⁷ may be linked to each other to form a ring.
X represents a halogen atom.
R ⁸ represents a monovalent substituent.
n ₁ represents an integer of 0-4.

  Hereinafter, each step will be described in detail.

[Process (A)]
Step (A) is a step of reacting a compound represented by the following general formula (1) with a compound represented by the following general formula (2) to obtain a compound represented by the following general formula (3). is there.

In the general formula (1), R ¹ and R ² each independently represent a hydrogen atom, an alkyl group, an aryl group, or an aralkyl group. R ¹ and R ² may be linked to each other to form a ring.

The alkyl group as R ¹ and R ² may be a linear alkyl group, a branched alkyl group, or a cyclic alkyl group, and a combination thereof is also preferable. The number of carbon atoms of the alkyl group is preferably 1-20, more preferably 1-10, and particularly preferably 1-6.

  The linear alkyl group is preferably a linear alkyl group having 1 to 20 carbon atoms, and is a linear alkyl group having 1 to 20 carbon atoms or a linear alkyl group having 1 to 10 carbon atoms. It is more preferable, and it is especially preferable that it is a C1-C6 linear alkyl group. Specific examples of the linear alkyl group include a methyl group, an ethyl group, an n-propyl group, an n-butyl group, an n-pentyl group, an n-hexyl group, an n-octyl group, and an n-dodecyl group. Can be mentioned. Of these, a methyl group, an ethyl group, and an n-propyl group are particularly preferable.

  As the branched alkyl group, a branched alkyl group having 1 to 10 carbon atoms is more preferable, and a branched alkyl group having 1 to 6 carbon atoms is particularly preferable. Specific examples of the branched alkyl group include, for example, isopropyl group, sec-butyl group, tert-butyl group, 2-ethylhexyl group, neopentyl group, etc. Among them, isopropyl group and tert-butyl group are preferable.

The cyclic alkyl group may be monocyclic or polycyclic, preferably a cyclic alkyl group having 3 to 20 carbon atoms, and preferably a cyclic alkyl group having 3 to 10 carbon atoms. More preferred. Specific examples of the cyclic alkyl group is, for example, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, adamantyl group, an isobornyl group, a norbornyl group, a tricyclo [5,2,1,0 ^2,6] decanyl group, etc. diamantyl group Among them, a cyclopentyl group, a cyclohexyl group, and an adamantyl group are preferable.

  As a combination of linear, branched, and cyclic alkyl groups, those having 4 to 10 carbon atoms are preferable, those having 7 to 10 carbon atoms are more preferable, and specific examples thereof include, for example, a cyclohexylmethyl group and cyclohexylethyl. Group and the like.

The R ¹ and R ² are may be formed by connecting each other to form a ring, preferably a 4-10 membered ring, 5 or 6-membered ring is more preferable.

The aryl group as R ¹ and R ² is preferably an aryl group having 4 to 20 carbon atoms, and more preferably an aryl group having 6 to 14 carbon atoms. This aryl group may have a hetero atom as a ring member, and may further have a substituent on the ring.
Specific examples of the aryl group include a phenyl group, a naphthyl group, an anthranyl group, a pyrenyl group, a pyridyl group, a pyrrolyl group, an indolyl group, a carbazolyl group, and a thiophenyl group. Among them, a phenyl group and a naphthyl group are preferable. .

  Examples of the substituent that the aryl group may have include a nitro group, a halogen atom such as a fluorine atom, a carboxy group, a hydroxyl group, an amino group, a cyano group, an alkyl group (preferably having a carbon number of 1 to 15), and an alkoxy group (preferably Has 1 to 15 carbon atoms, a cycloalkyl group (preferably 3 to 15 carbon atoms), an aryl group (preferably 6 to 14 carbon atoms), an alkoxycarbonyl group (preferably 2 to 7 carbon atoms), an acyl group (preferably Includes an acyloxy group (preferably having a carbon number of 2 to 12) and an alkoxycarbonyloxy group (preferably having a carbon number of 2 to 7).

The aralkyl group as R ¹ and R ² is preferably an aralkyl group having 6 to 21 carbon atoms, and more preferably an aralkyl group having 7 to 15 carbon atoms. This aralkyl group may have a hetero atom as a ring member, and may further have a substituent on the ring.
Specific examples of the aralkyl group include a benzyl group, a phenethyl group, a propylphenyl group, a naphthylmethyl group, a naphthylethyl group, and an anthranylmethyl group. Among them, a benzyl group, a phenethyl group, and a naphthylmethyl group are preferable.
Examples of the substituent that the aralkyl group may have include those listed as the substituents that the aryl group may have.

In the general formula (1), R ³ represents an alkyl group, an aryl group or an aralkyl group, and the range and specific examples of these carbon atoms are the same as those listed above as R ¹ and R ² , for example. Is mentioned.

R ³ is more preferably a group represented by the following general formula (10).

Wherein, _{n 2} represents an integer of 1-6, preferably an integer of 1 to 4, 1 or 2 are particularly preferred. Y represents a cyclic alkyl group or an aryl group. Examples of these carbon number ranges and specific examples include the same as those enumerated above as R ¹ and R ² .

  Specific examples of the group represented by the general formula (10) are shown below, but the present invention is not limited thereto.

  Specific examples of the compound represented by the general formula (1) are shown below, but the present invention is not limited thereto.

In the general formula (2), R ⁴ represents an alkyl group, an alkenyl group, an aryl group, or an aralkyl group.
R ⁴ preferably has 1 to 20 carbon atoms.

Examples of the carbon number range and specific examples of the alkyl group, aryl group, and aralkyl group of R ⁴ include the same as those enumerated above as R ¹ and R ² .
The alkenyl group for R ⁴ is preferably an alkenyl group having 2 to 20 carbon atoms, and includes a vinyl group, a propenyl group, a butenyl group, a hexenyl group, a heptanyl group, an octanyl group, a decanyl group, an undecanyl group, and a dodecanyl group. Can be mentioned.

  In general formula (2), X represents a halogen atom, preferably a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom, and more preferably a chlorine atom.

  Examples of the compound represented by the general formula (2) include acetyl chloride, propionyl chloride, butyric chloride, isobutyric chloride, pivaloyl chloride, isovaleryl chloride, valeryl chloride, tert-butylacetyl chloride, hexanoyl. Chloride, heptanoyl chloride, octanoyl chloride, nonanoyl chloride, 5-chlorovaleric acid chloride, 6-bromohexanoyl chloride, cyclohexanecarbonyl chloride, 2-ethylhexanoyl chloride, 2-propylvaleryl chloride, 3,5,5 5-trimethylhexanoyl chloride, decanoic acid chloride, undecanoyl chloride, lauroyl chloride, myristic acid chloride, palmitoyl chloride, heptadecanoyl chloride, stearoyl chloride, oleoyl chloride Linoleoyl chloride, 10-undecenoyl chloride, acetyl bromide, propionyl bromide, isobutyric acid bromide, valeryl bromide, 2-bromobutyryl bromide, 2-bromopropionyl bromide, and acetyl iodide. However, it is not limited to these.

R < ¹ > -R < ³ > and X in General formula (3) are synonymous with R < ¹ > -R < ³ > and X as described in General formula (1) or (2), respectively, A preferable example is also the same.

The number of carbon atoms in each of R ¹ , R ² and R ³ is not particularly limited, but the form in which the total number of carbon atoms in R ¹ , R ² and R ³ is 7 or more is one of preferred forms of the present invention. It is.
In this embodiment, the upper limit of the total number of carbon atoms of R ^{1 to} R ³ is preferably 60 or less, and more preferably 45 or less.

In the general formulas (1) to (3), (i) when the total number of carbon atoms of R ¹ and R ² is 2 or less and the carbon number of R ³ is 7 or more, the carbon number of R ⁴ is It is preferably 7 or more (more preferably, the carbon number of R ⁴ is 11 or more), and (ii) when the total number of carbon atoms of R ¹ and R ² is 6 or more, the carbon number of R ⁴ is 3 or less. (more preferably the carbon number of R ⁴ is 2 or less, more preferably carbon number of R ⁴ is 1) is preferably.
In other words, in the above form (i), the total number of carbon atoms of R ¹ and R ² is 2 or less, the carbon number of R ³ is 7 or more, and the carbon number of R ⁴ is 7 or more. The form (ii) is a form in which the total number of carbon atoms of R ¹ and R ² is 6 or more and the number of carbon atoms of R ⁴ is 3 or less.

In the above embodiment (i), the total number of carbon atoms of ^{R 1} and ^{R 2} are an integer of 0 to 2, more preferably 0 or 1. The number of carbon atoms in R ³ is preferably an integer of 7 to 20, more preferably an integer of 7 to 15, and still more preferably an integer of 7 to 10. The number of carbon atoms in R ⁴ is preferably an integer of 7 to 20, and more preferably an integer of 11 to 20.
In the above embodiment (ii), the total number of carbon atoms of ^{R 1} and ^{R 2} is preferably 6-20 integer, and more preferably an integer of 6 to 15. R ⁴ has 1 to 3 carbon atoms, and preferably 1 or 2.

In the above form (i), as the alkyl group, aryl group or aralkyl group of R ³ , heptyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group, tridecyl group, tetradecyl group, pentadecyl group, hexadecyl group Alkyl groups having 7 to 20 carbon atoms such as heptadecyl group, aryl groups having 7 to 20 carbon atoms such as toluyl group, naphthyl group and dimethylphenyl group, benzyl group, 1-phenylpropyl group and 2-phenylethyl group Examples thereof include aralkyl groups having 7 to 21 carbon atoms.
Examples of the alkyl group, alkenyl group, aryl group or aralkyl group of R ⁴ include heptanyl group, octanyl group, decanyl group, undecanyl group, dodecanyl group and the like in addition to the examples of the alkyl group, aryl group and aralkyl group of R ³ described above. The alkenyl group having 7 to 20 carbon atoms can be exemplified, and among them, an alkyl group is preferable.
The alkyl group as R ⁴ is more preferably an n-heptyl group, n-undecyl group, n-tridecyl group, n-pentadecyl group or n-heptadecyl group.

In the above embodiment (ii), as long as the total number of carbon atoms of ^{R 1} and ^{R 2} are 6 to 20 integer, ^{R 1} and ^{R 2} are not particularly limited.
Also, in (ii), since R ⁴ is 3 or less carbon atoms, the R ^4, an alkyl group having 1 to 3 carbon atoms, or there may be mentioned an alkenyl group having 2 or 3 carbon atoms Among these, an alkyl group having 1 to 3 carbon atoms is preferable. Specific examples of the alkyl group having 1 to 3 carbon atoms include a methyl group, an ethyl group, and a propyl group. Among them, a methyl group is preferable.

[Reaction solvent]
Solvents for the reaction in the step (A) include hydrocarbon solvents such as hexane, heptane, decane, benzene, toluene and xylene, halogen solvents such as dichloromethane, dichloroethane and chloroform, and ester solvents such as ethyl acetate and butyl acetate. Solvents, ether solvents such as tetrahydrofuran and diethyl ether, acetonitrile, and the like are preferably used. Of these, hydrocarbon solvents are more preferable, and hexane and heptane are particularly preferable. The solvent used in the step (C) described later can be used as it is as the solvent in the step (A). Further, when at least one of the compound represented by the general formula (1) and the compound represented by the general formula (2) is a liquid, the reaction of the step (A) can be performed without a solvent. More preferable in terms of cost and environment than when a solvent is used.

[Amount of Compound Represented by General Formula (2) with respect to Compound Represented by General Formula (1)]
In the step (A), the compound represented by the general formula (2) is preferably used at 1 to 10 mol, and used at 1 to 2 mol with respect to 1 mol of the compound represented by the general formula (1). More preferably.

[Other additives]
As an additive at the time of performing the reaction in the step (A), as a reaction activator, zinc chloride, zinc bromide, zinc iodide, zinc acetate, zinc trifluoromethanesulfonate, scandium trifluoromethanesulfonate (III), etc. May be added. As addition amount, 0.001-10 mol% is preferable with respect to the compound represented by General formula (1), and 0.01-0.1 mol% is still more preferable.

[Reaction temperature / time]
As temperature which performs reaction of a process (A), 0-100 degreeC is preferable, 25-80 degreeC is further more preferable, and 40-60 degreeC is especially preferable.
The time for performing the reaction in the step (A) is preferably 0.5 to 24 hours, more preferably 1 to 6 hours, and particularly preferably 1 to 2 hours.

[Processing after reaction]
In the reaction of step (A), an ester compound represented by the following general formula (11) is by-produced in an equimolar amount with respect to the compound represented by the above general formula (3).

In the general formula (11), ^{R 3} and ^{R 4} are each the same meaning as ^R 3, ^{R 4} in the general formula (1) and the general formula (2), and preferred examples are also the same.

  When the boiling point of the compound represented by the general formula (11) is relatively low (for example, the boiling point at normal pressure is 150 ° C. or lower), the compound is removed by distillation under reduced pressure after the reaction of (AI) step (A). Alternatively, it may not be removed at the end of the reaction in (AII) step (A), and may be used as a solvent in step (B) described later. When the boiling point of the compound represented by the general formula (11) is high (for example, the boiling point at normal pressure is higher than 150 ° C.), it is preferably used as a solvent in the step (B) described later (that is, the above form (AII ) Is preferred).

[Process (B)]
In the step (B), the compound represented by the general formula (3) is reacted with the compound represented by the general formula (4) or the general formula (5) to obtain a vinyl ether represented by the general formula (6). This is a step of obtaining a compound.

In general formula (4), R ⁵ , R ⁶ and R ⁷ each independently represents an alkyl group, an aryl group or an aralkyl group.

The number of carbon atoms of R ^{5 to} R ⁷ is preferably independently 1 to 20, more preferably 1 to 8, and still more preferably 1 to 3.

The alkyl group of R ⁵ , R ⁶ and R ⁷ may have a hetero atom such as an enzyme atom or a nitrogen atom, and may be any of a linear alkyl group, a branched alkyl group and a cyclic alkyl group, and has a carbon number An alkyl group having 1 to 20 carbon atoms is preferable, and an alkyl group having 1 to 6 carbon atoms is more preferable. Specific examples of the alkyl group for R ⁵ , R ⁶ and R ⁷ include, for example, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, n- A pentyl group, a neopentyl group, an n-hexyl group, a cyclohexyl group, an n-heptyl group, an n-octyl group, an n-dodecyl group, and the like can be given. Among them, a methyl group, an ethyl group, an n-propyl group, and an isopropyl group are preferable.

The aryl group of R ⁵ , R ⁶ and R ⁷ may have a hetero atom such as an oxygen atom or a nitrogen atom, and may further have a substituent on the ring.
The aryl group of R ⁵ , R ⁶ and R ⁷ is preferably an aryl group having 4 to 20 carbon atoms, and more preferably an aryl group having 6 to 10 carbon atoms. Specific examples of the aryl group include a phenyl group, a naphthyl group, an anthranyl group, a pyrenyl group, a pyridyl group, a pyrrolyl group, and an indolyl group, and among them, a phenyl group is preferable.
The aralkyl group of R ⁵ , R ⁶ and R ⁷ may have a hetero atom, and may further have a substituent on the ring.
The aralkyl group of R ⁵ , R ⁶ and R ⁷ is preferably an aralkyl group having 6 to 21 carbon atoms, and more preferably an aralkyl group having 7 to 15 carbon atoms. Examples of the aralkyl group include a benzyl group, a phenethyl group, a propylphenyl group, a naphthylmethyl group, a naphthylethyl group, and an anthranylmethyl group, and among them, a benzyl group is preferable.
The substituent that the aryl group and the aralkyl group may have on the ring is the same as the substituent that the aryl group represented by R ¹ and R ^{2 in} the general formula (1) may have.

Two of R ⁵ , R ⁶ and R ⁷ may be connected to each other to form a ring. Examples of the ring formed include a 5-membered ring, a 6-membered ring, and a 7-membered ring, and a 5-membered ring or a 6-membered ring is preferable.

  Examples of the compound represented by the general formula (4) include N, N-diethylmethylamine, triethylamine, N, N-dimethylisopropylamine, N, N-dimethylethylamine, N, N-diisopropylethylamine, and 1-methyl. Pyrrolidine, 1-ethylpyrrolidine, tripropylamine, triisobutylamine, triamylamine, trihexylamine, N, N-dicyclohexylmethylamine, trioctylamine, didecylmethylamine, tris (2-ethylhexyl) amine, N, N-dimethylhexadecylamine, tri-n-decylamine, N, N-diethylcyclohexylamine, N, N-dimethyl-n-octadecylamine, 1-methylpiperidine, 1-ethylpiperidine, N-methylmorpholine, N-ethyl Morpholine, N Phenylmorpholine, N- (4-pyridyl) morpholine, N, N-dimethylaniline, N, N-dimethyl-p-toluidine, N, N-dimethyl-o-toluidine, N, N-dimethyl-m-toluidine, N , N-dimethyl-1-naphthylamine, N, N-dimethyl-2-naphthylamine, N, N-diethylaniline, N, N-dipropylaniline, 4-dimethylaminopyridine, triphenylamine, tri-p-tolylamine, Examples include N-methyldiphenylamine, 1,8-diazabicyclo [5.4.0] -7-undecene, and 1,5-diazabicyclo [4.3.0] -5-nonene, but the present invention is limited to these. It is not something.

In the general formula (5), n ₁ is an integer from 0 to 4, preferably an integer of 0 to 3, more preferably an integer of 0 to 2, and more preferably 0 or 1 .
R ⁸ is a monovalent substituent. Examples of the monovalent substituent include an alkyl group, a halogen atom, an alkoxy group, and a dialkylamino group.
The carbon number of the alkyl group of R ⁸ is preferably 1-5, more preferably 1-3. Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, a tert-butyl group, and an n-pentyl group. preferable.
Examples of the halogen atom for R ⁸ include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, and among them, a chlorine atom and a bromine atom are preferable.
The number of carbon atoms of the alkoxy group for R ⁸ is preferably 1 to 5, and more preferably 1 to 3. Examples of the alkoxy group include a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, an n-butoxy group, a sec-butoxy group, a tert-butoxy group, and an n-pentyloxy group, and among them, a methoxy group and an ethoxy group. Is preferred.
The carbon number of the dialkylamino group of R ⁸ is preferably 1 to 3. Examples of the dialkylamino group include a dimethylamino group, a diethylamino group, and a dipropylamino group.

  Examples of the compound represented by the general formula (5) include pyridine, 2-picoline, 3-picoline, 4-picoline, 2,3-lutidine, 2,4-lutidine, 2,5-lutidine, and 2,6. -Lutidine, 3,4-lutidine, 3,5-lutidine, 2-ethylpyridine, 2,4,6-trimethylpyridine, 2-methoxypyridine, 3-methoxypyridine, 4-methoxypyridine, 2,6-dimethoxypyridine 2-chloro-6-methoxypyridine, 2-butoxypyridine, 2-chloropyridine, 3-chloropyridine, 4-chloropyridine, 2,6-dichloropyridine, 2-chloro-4-methylpyridine, 2-bromopyridine , 2-dimethylaminopyridine and 4-dimethylaminopyridine, but the present invention is not limited thereto.

[Reaction solvent]
As the solvent for performing the reaction in the step (B), a hydrocarbon solvent, a halogen solvent, an ether solvent, acetonitrile, or the like is preferably used. Specific examples of the hydrocarbon solvent, the halogen solvent, and the ether solvent include This is the same as that described in the step (A). Of these, hydrocarbon solvents are more preferable, and hexane and heptane are particularly preferable. When at least one of the compound represented by the general formula (3) and the compound represented by the general formula (4) or the general formula (5) is a liquid, the reaction of the step (B) is performed without a solvent. More preferably. Further, the solvent used in the step (A) may be used as it is as the solvent in the step (B), or the compound represented by the general formula (11) produced in the step (A) may be used as the solvent. .

[Use amount of compound represented by general formula (4) or general formula (5) with respect to the compound represented by general formula (3)]
In the step (B), the compound represented by the general formula (4) or the general formula (5) is used in an amount of 0.1 to 10 mol with respect to 1 mol of the compound represented by the general formula (3). Preferably, it is used at 1 to 5 moles.

[Reaction temperature / time]
As temperature which performs reaction of a process (B), 0-150 degreeC is preferable, 25-100 degreeC is further more preferable, and 50-100 degreeC is especially preferable.
The time for performing the reaction in the step (B) is preferably 0.5 to 24 hours, more preferably 1 to 10 hours, and particularly preferably 1 to 5 hours.

[Processing after reaction]
The organic layer obtained after the completion of the reaction in the step (B) is preferably washed with water to remove organic salts. Next, the organic layer is preferably dried and concentrated, and (BI) low-boiling byproducts are distilled off under reduced pressure or purified by distillation. When purification with high purity is difficult by the method (BI), it is preferable to purify by (BII) column chromatography.

  When purifying the form (AI) in the step (A) or the form (BI) in the step (B), the α-halogenated ether compound represented by the general formula (3) or the general formula ( 6) The more the difference in boiling point between the vinyl ether compound represented by 6) and the ester compound represented by the general formula (11) which is a by-product, the more the α-halogenated ether compound or vinyl ether compound obtained. The rate and purity are improved, which is preferable. By the way, even when producing the same α-halogenated ether compound or vinyl ether compound, by changing the type of the compound represented by the general formula (2) to be used, the structure of the by-product ester is changed, and the boiling point of the by-product ester is changed. Can be adjusted as appropriate. That is, particularly under a predetermined condition, by selecting the compound represented by the general formula (2) as a specific one, the difference in boiling point between the target product and the by-product is widened, and the purity and yield of the target product are increased. Can be improved. That is, as described in the above forms (i) and (ii), the compound represented by the general formula (2) is preferably selected as follows.

[Form (i)] When the total number of carbon atoms of R ¹ and R ² is 2 or less and the carbon number of R ³ is 7 or more If the carbon number of R ⁴ is small, the target product (ie, general formula (3) The boiling point of the α-halogenated ether compound represented by the formula (6) or the vinyl ether compound represented by the general formula (6)) and the by-product ester (that is, the ester compound represented by the general formula (11)) is close, yield, Since there is concern about a decrease in purity, it is preferable that R ⁴ has a larger number of carbon atoms. Specifically, the carbon number of R ⁴ is preferably 7 or more, and more preferably 11 or more. The detailed description of each group of the general formulas (1) to (3) in the form (i) is as described above.

[Form (ii)] When the total number of carbon atoms of R ¹ and R ² is 6 or more The above target product tends to have a higher boiling point than the by-product ester regardless of the carbon number of R ^4. . Therefore, the smaller the number of carbon atoms in R ^4, the wider the difference in boiling point, which is preferable. Specifically, the carbon number of R ⁴ is preferably 3 or less, more preferably 2 or less, and particularly preferably 1. Detailed description of each group of the general formulas (1) to (3) in the form (ii) is as described above.

It is preferable to perform a process (A) and a process (B) collectively in the same reaction container. Here, “batch in the same reaction vessel” means that the product of the step (A) (that is, the compound represented by the general formula (3)) is not isolated and the reaction is performed. It means that the steps (A) to (B) are performed collectively without transferring the liquid to another container. Thereby, since a manufacturing process can be simplified more, a vinyl ether compound can be manufactured more cheaply.
In this embodiment, it is preferable to use the solvent used in step (A) as it is as the solvent in step (B). That is, it is preferable that the solvent in the step (A) and the solvent in the step (B) are the same. Thereby, the manufacturing process can be further simplified.

[Process (C)]
In the method for producing the vinyl ether compound of the present invention, the compound represented by the following general formula (7) and the following general formula (8) or general formula (8) The process (C) which reacts the compound represented by 9) may be included.

In the general formula (7) ~ ^(9), R 1, ^{R 2} and ^{R 3} each have the same meaning as ^R 1, ^{R 2} and ^{R 3} in the general formula (1) and preferred examples are also the same.

  Hereinafter, although the specific example of a compound represented by General formula (7) is illustrated, this invention is not limited to these.

  Hereinafter, although the specific example of a compound represented by General formula (8) is illustrated, this invention is not limited to these.

  Hereinafter, although the specific example of a compound represented by General formula (9) is illustrated, this invention is not limited to these.

[Reaction solvent]
As the solvent for performing the reaction in the step (C), a hydrocarbon solvent, a halogen solvent, an ether solvent, acetonitrile, or the like is preferably used. Specific examples of the hydrocarbon solvent, the halogen solvent, and the ether solvent include This is the same as that described in the step (A). Among these, the hydrocarbon-based solvent is preferable because it forms an azeotrope with water and the Dean-Stark apparatus can remove water generated by the reaction. Of the hydrocarbon solvents, hexane and heptane are more preferable.

[Amount of Compound Represented by General Formula (8) or General Formula (9) with respect to Compound Represented by General Formula (7)]
In the step (C), the compound represented by the general formula (8) or the general formula (9) is used in an amount of 0.05 to 10 mol with respect to 1 mol of the compound represented by the general formula (7). Preferably, it is used at 0.5 to 5 mol.

[Other additives]
As an additive for the reaction in the step (C), it is preferable to add an acid catalyst. As the acid catalyst, inorganic acids such as sulfuric acid, nitric acid and phosphoric acid, and organic acids such as p-toluenesulfonic acid, camphorsulfonic acid, benzenesulfonic acid, naphthalenesulfonic acid and p-toluenesulfonic acid pyridinium salt are preferably used. Of these, p-toluenesulfonic acid and camphorsulfonic acid are preferred. The addition amount of the acid catalyst is preferably 0.001 mol% to 10 mol%, more preferably 0.01 mol% to 5 mol%, more preferably 0.1 mol, relative to the compound represented by the general formula (7). % To 1 mol% is particularly preferred.
As other additives, desiccants such as molecular sieves, anhydrous magnesium sulfate, and anhydrous sodium sulfate can be added.

[Reaction temperature / time]
The temperature at which the reaction in step (C) is performed is preferably selected from the range of 0 to 150 ° C. When using a solvent that forms an azeotrope with water and removing the water with a Dean-Stark apparatus, it is preferable to react at the boiling point of the solvent used. In cases other than the above, 20 to 80 ° C is preferable, and 25 to 60 ° C is more preferable.
The time for performing the reaction in the step (C) is preferably 0.5 to 24 hours, more preferably 1 to 10 hours, and particularly preferably 1 to 5 hours.

[Processing after reaction]
The solvent used in the reaction may be removed by distillation under reduced pressure, or may be used as it is as the solvent in the step (A) without being removed at the end of the reaction in the step (C). It is preferable to proceed to the step (A) as it is without performing any treatment other than removing the solvent.

It is preferable to perform a process (C), a process (A), and a process (B) collectively in the same reaction container. “Lumping in the same reaction vessel” means the product of step (C) (that is, the compound represented by the general formula (1)) and the product of step (A) (that is, general) This means that the step (C) to the step (B) are performed at once without performing an isolation operation of the compound represented by the formula (3) and without transferring the reaction solution to another container. To do. Thereby, since a manufacturing process can be simplified more, a vinyl ether compound can be manufactured more cheaply.
In this embodiment, it is preferable to use the solvent used in step (C) as it is as the solvent in step (A), and further use the solvent used in step (A) as it is as the solvent in step (B). That is, the solvent in the step (C), the solvent in the step (A), and the solvent in the step (B) are preferably the same. Thereby, the manufacturing process can be further simplified.

  EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, the content of this invention is not limited by this.

<Example 1: Synthesis 1 of vinyl ether (V-1)>
In a flask equipped with a Dean-Stark tube, 75 g (585 mmol) of 2-cyclohexylethanol, 51.5 g (390 mmol) of paraaldehyde, 0.68 g (2.9 mmol) of camphorsulfonic acid and 105 g of heptane were added and refluxed for 4 hours. (Step (C)). ^{From 1} H-NMR, it was confirmed that 92% of 2-cyclohexylethanol was converted to an acetal compound (a-1) and 8% existed unreacted. The reaction solution was allowed to cool to 50 ° C., 27.6 g (351 mmol) of acetyl chloride was added, and the mixture was stirred at 45 ° C. for 1 hour (step (A)). The disappearance of the acetal compound (a-1) was confirmed by ¹ H-NMR. After returning the reaction solution to 25 ° C., 71.0 g (702 mmol) of triethylamine was dropped, and after completion of the dropping, the mixture was stirred at 95 ° C. for 2 hours (step (B)). After allowing to cool to 25 ° C., 100 ml of a saturated aqueous ammonium chloride solution was added and stirred, and the aqueous layer was removed. Subsequently, the organic layer was washed with 200 mL of distilled water, dried over anhydrous sodium sulfate, and then the solvent was removed with an evaporator. When analysis by gas chromatography was performed at this time, a peak derived from 2-cyclohexylethanol was not confirmed. The crude product was then purified by distillation to obtain 25.2 g of a fraction. When the obtained fraction was analyzed by gas chromatography, 21.2 g (137.4 mmol) was vinyl ether (V-1), and 4.0 g was a by-product ester (a-3). The yield of vinyl ether (V-1) was 47%, and the purity determined by gas chromatography was 84%.

¹ H-NMR (400 MHz, CDCl ₃ ) δ = 6.43 (dd, 1H), 4.19 (d, 1H), 3.97 (d, 1H), 3.71 (t, 2H), 1. 90-0.84 (m, 13H).

<Example 2: Synthesis 2 of vinyl ether (V-1)>
In a flask equipped with a Dean-Stark tube, 75 g (585 mmol) of 2-cyclohexylethanol, 51.5 g (390 mmol) of paraaldehyde, 0.68 g (2.9 mmol) of camphorsulfonic acid and 105 g of heptane were added and refluxed for 4 hours. (Step (C)). ^{From 1} H-NMR, it was confirmed that 93% of 2-cyclohexylethanol was converted to an acetal compound (a-1) and 7% existed unreacted. After allowing the reaction solution to cool to 50 ° C., 76.8 g (351 mmol) of lauroyl chloride was added, and the mixture was stirred at 50 ° C. for 1 hour (step (A)). The disappearance of the acetal compound (a-1) was confirmed by ¹ H-NMR. After returning the reaction solution to 25 ° C., 71.0 g (702 mmol) of triethylamine was dropped, and after completion of the dropping, the mixture was stirred at 95 ° C. for 2 hours (step (B)). After allowing to cool to 25 ° C., 100 ml of a saturated aqueous ammonium chloride solution was added and stirred, and the aqueous layer was removed. Subsequently, the organic layer was washed with 200 mL of distilled water, dried over anhydrous sodium sulfate, and then the solvent was removed with an evaporator. When analysis by gas chromatography was performed at this time, a peak derived from 2-cyclohexylethanol was not confirmed. The crude product was then purified by distillation to obtain 30.6 g (198.4 mmol) of vinyl ether (V-1). The yield of vinyl ether (V-1) was 68%, and the purity determined by gas chromatography was 99.2%.

<Comparative Example 1: Synthesis of vinyl ether (V-1)>
In a flask equipped with a Dean-Stark tube, 38.5 g (300 mmol) of 2-cyclohexylethanol, 38.74 g (450 mmol) of vinyl acetate, 19.1 g (180 mmol) of sodium carbonate, and 150 g of toluene are gradually added. The temperature was raised to reflux. Di-μ-chlorobis (1,5-cyclooctadiene) diiridium (I) [Ir (cod) Cl] ₂ 0.5 g (0.75 mmol) was added thereto and refluxed for 3 hours. When the reaction solution was analyzed by gas chromatography, the conversion of 2-cyclohexylethanol was 89%, and 11% of unreacted 2-cyclohexylethanol remained. The reaction solution was allowed to cool to 25 ° C. and then washed 3 times with 200 mL of distilled water. The organic layer was dried over anhydrous magnesium sulfate, and then the solvent was distilled off with an evaporator. When the obtained crude product was purified by distillation, 32.0 g of a fraction was obtained. When the obtained fraction was analyzed by gas chromatography, 29.15 g (189 mmol) was vinyl ether (V-1), and 2.88 g was 2-cyclohexylethanol as a raw material. The yield of vinyl ether (V-1) was 63%, and the purity determined by gas chromatography was 91%.

<Example 3: Synthesis 3 of vinyl ether (V-1)>
In a flask equipped with a Dean-Stark tube, 50 g (390 mmol) of 2-cyclohexylethanol, 34.4 g (260 mmol) of paraaldehyde, 0.45 g (1.95 mmol) of camphorsulfonic acid, and 70 g of heptane were added and refluxed for 4 hours. (Step (C)). ^{From 1} H-NMR, it was confirmed that 92% of 2-cyclohexylethanol was converted to an acetal compound (a-1) and 8% existed unreacted. After cooling to 25 ° C., heptane was distilled off under reduced pressure. Next, 51.2 g (234 mmol) of lauroyl chloride was added to the reaction solution, and the mixture was stirred at 50 ° C. for 1 hour (step (A)). The disappearance of the acetal compound (a-1) was confirmed by ¹ H-NMR. After returning the reaction solution to 25 ° C., 60.5 g (468 mmol) of N, N-diisopropylethylamine was added dropwise, and after completion of the dropwise addition, the mixture was stirred at 95 ° C. for 2 hours (step (B)). After allowing to cool to 25 ° C., 100 ml of a saturated aqueous ammonium chloride solution was added and stirred, and the aqueous layer was removed. Subsequently, the organic layer was washed with 200 mL of a 5 wt% acetic acid aqueous solution and then with 200 mL of distilled water, dried over anhydrous sodium sulfate, and then the solvent was removed with an evaporator. When analysis by gas chromatography was performed at this time, a peak derived from 2-cyclohexylethanol was not confirmed. The crude product was then purified by distillation to obtain 20.6 g (133.5 mmol) of vinyl ether (V-1). The yield of vinyl ether (V-1) was 68%, and the purity determined by gas chromatography was 99.1%.

<Example 4: Synthesis of vinyl ether (V-2)>
To 10.0 g (60.16 mmol) of phenylacetaldehyde dimethyl acetal, 5.43 g (69.19 mmol) of acetyl chloride was added and stirred at 45 ° C. for 2 hours (step (A)). After confirming disappearance of the raw material by ¹ H-NMR, 10.5 g (103.8 mmol) of triethylamine was added and stirred at 90 ° C. for 2 hours (step (B)). After allowing to cool to 25 ° C., 30 mL of ethyl acetate and 50 mL of a saturated aqueous ammonium chloride solution were added, and after stirring for 10 minutes, the aqueous layer was removed. Subsequently, the organic layer was washed with 50 mL of distilled water, dried over anhydrous magnesium sulfate, and then the solvent was removed with an evaporator. By the above operation, 7.9 g (58.88 mmol) of vinyl ether (V-2) was obtained (yield 98%). ^{From 1} H-NMR, the ratio of E-form to Z-form of the obtained vinyl ether (V-2) was E: Z = 56: 44.

¹ H-NMR (400 MHz, CDCl ₃ ) δ = Z- (V-2) 7.62-7.10 (m, 5H), 6.15 (d, 1H), 5.21 (d, 1H), 3.79 (s, 3H), E- (V-2) 7.62-7.10 (m, 5H), 7.05 (d, 1H), 5.80 (d, 1H), 3.65 (S, 3H).

<Example 5: Synthesis 1 of vinyl ether (V-3)>
In a flask equipped with a Dean-Stark tube, 100 g (818.6 mmol) of 2-phenylethanol, 72.1 g (546 mmol) of paraaldehyde, 0.95 g (4.1 mmol) of camphorsulfonic acid and 100 g of hexane were added and refluxed for 3 hours. (Step (C)). ^{From 1} H-NMR, it was confirmed that 94% of 2-phenylethanol was converted to an acetal compound (b-1) and 6% existed unreacted. After allowing the reaction solution to cool to 50 ° C., 107.4 g (491.1 mmol) of lauroyl chloride was added, and the mixture was stirred at 50 ° C. for 1 hour (step (A)). The disappearance of the acetal compound (b-1) was confirmed by ¹ H-NMR. After returning the reaction solution to 25 ° C., 74.55 g (736.7 mmol) of triethylamine was added dropwise, and after completion of the dropwise addition, the mixture was stirred at 95 ° C. for 2 hours (step (B)). After allowing to cool to 25 ° C., 200 ml of a saturated aqueous ammonium chloride solution was added and stirred, and the aqueous layer was removed. Subsequently, the organic layer was washed with 200 mL of distilled water, dried over anhydrous sodium sulfate, and then the solvent was removed with an evaporator. When analysis by gas chromatography was performed at this time, a peak derived from 2-phenylethanol was not confirmed. The crude product was then purified by distillation to obtain 41.2 g (278 mol) of vinyl ether (V-3). The yield of vinyl ether (V-3) was 68%, and the purity determined by gas chromatography was 99.4%.

¹ H-NMR (400 MHz, CDCl ₃ ) δ = 7.38-7.20 (m, 5H), 6.46 (dd, 1H), 4.20 (d, 1H), 4.00 (d, 1H ), 3.88 (t, 2H), 2.98 (t, 2H).

<Example 6: Synthesis 2 of vinyl ether (V-3)>
The same procedure as in Example 5 was repeated except that 74.55 g (736.7 mmol) of triethylamine was changed to 58.27 g (736.7 mmol) of pyridine. The yield of vinyl ether (V-3) was 75%, and the purity determined by gas chromatography was 99.1%.

<Example 7: Synthesis 3 of vinyl ether (V-3)>
Distillation of 107.4 g (491.1 mmol) of lauroyl chloride to 134.99 g (491.1 mmol) of palmitoyl chloride and 74.55 g (736.7 mmol) of triethylamine to 109.94 g (736.7 mmol) of N, N-diethylaniline The organic layer was washed with 200 mL of water in the same manner as in Example 5 except that the washing with 200 mL of 0.1N hydrochloric acid was performed twice. The yield of vinyl ether (V-3) was 72%, and the purity determined by gas chromatography was 99.0%.

<Example 8: Synthesis 4 of vinyl ether (V-3)>
Other than changing 107.4 g (491.1 mmol) of lauroyl chloride to 147.78 g (491.1 mmol) of oleoyl chloride and 74.55 g (736.7 mmol) of triethylamine to 74.52 g (736.7 mmol) of 4-methylmorpholine. Was carried out in the same manner as in Example 5. The yield of vinyl ether (V-3) was 73%, and the purity determined by gas chromatography was 99.4%.

<Example 9: Synthesis 5 of vinyl ether (V-3)>
107.4 g (491.1 mmol) of lauroyl chloride was added to 148.76 g (491.1 mmol) of stearoyl chloride, and 74.55 g (736.7 mmol) of triethylamine was added to 1,8-diazabicyclo [5.4.0] undec-7-ene. 112.16 g (736.7 mmol) was subjected to the same procedure as in Example 5 except that the organic layer was washed with 200 mL of distilled water and washed twice with 200 mL of 0.1N hydrochloric acid aqueous solution. It was. The yield of vinyl ether (V-3) was 81%, and the purity determined by gas chromatography was 99.1%.

<Example 10: Synthesis of vinyl ether (V-4)>
To 45.0 g (270.73 mmol) of phenylacetaldehyde dimethyl acetal and 61.48 g (568.52 mmol) of benzyl alcohol, 5.16 g (27.08 mmol) of p-toluenesulfonic acid monohydrate was added and stirred at 100 ° C. for 12 hours. did. ^{From 1} H-NMR, it was confirmed that 93% of phenylacetaldehyde dimethyl acetal had been converted to an acetal compound (c-1). After removing unreacted raw materials by distillation under reduced pressure, 27.63 g (351.95 mmol) of acetyl chloride was added, and the mixture was stirred at 50 ° C. for 1.5 hours (step (A)). The disappearance of the acetal compound (c-1) was confirmed by ¹ H-NMR. After returning the reaction solution to 25 ° C., 41.09 g (406.10 mmol) of triethylamine was added dropwise, and after completion of the dropwise addition, the mixture was stirred at 95 ° C. for 2 hours (step (B)). After allowing to cool to 25 ° C., 200 ml of a saturated aqueous ammonium chloride solution was added and stirred, and the aqueous layer was removed. Subsequently, the organic layer was washed with 200 mL of distilled water, dried over anhydrous sodium sulfate, and then the solvent was removed with an evaporator. Subsequently, 42.13 g (200.34 mol) of vinyl ether (V-4) was obtained by removing the ester compound (c-3) from the crude product by distillation under reduced pressure. The yield of vinyl ether (V-4) was 74%, and the purity determined by gas chromatography was 97.2%. ^{From 1} H-NMR, the ratio of E-form to Z-form of the obtained vinyl ether (V-4) was E: Z = 53: 47.

¹ H-NMR (400 MHz, CDCl ₃ ) δ = Z- (V-4) 7.42-7.23 (m, 10H), 6.30 (d, 1H), 5.29 (d, 1H), 4.92 (s, 2H), E- (V-4) 7.42-72.3 (m, 10H), 7.10 (d, 1H), 5.98 (d, 1H), 5.01 (S, 2H).

<Example 11: Synthesis of vinyl ether (V-5)>
In a flask equipped with a Dean-Stark tube, 60.0 g (503.69 mmol) of 4-cyanophenol, 44.41 g (336.0 mmol) of paraaldehyde, 0.59 g (2.52 mmol) of camphorsulfonic acid, and 100 g of toluene were added. Reflux was performed for 2 hours. Thereafter, the step of adding 5 g of paraaldehyde every 1 hour was performed three times to reflux for a total of 5 hours (step (C)). ^{From 1} H-NMR, it was confirmed that 92% of 4-cyanophenol was converted to an acetal compound (d-1) and 8% existed unreacted. The reaction solution was allowed to cool to 50 ° C., 66.11 g (302.21 mmol) of lauroyl chloride was added, and the mixture was stirred at 50 ° C. for 1 hour (step (A)). The disappearance of the acetal compound (d-1) was confirmed by ¹ H-NMR. After returning the reaction solution to 25 ° C., 45.87 g (453.32 mmol) of triethylamine was added dropwise, and after completion of the dropwise addition, the mixture was stirred at 95 ° C. for 2 hours (step (B)). After allowing to cool to 25 ° C., 200 ml of a saturated aqueous ammonium chloride solution was added and stirred, and the aqueous layer was removed. Subsequently, the organic layer was washed with 200 mL of distilled water, dried over anhydrous sodium sulfate, and then the solvent was removed with an evaporator. When analysis by gas chromatography was performed at this time, a peak derived from 4-cyanophenol was not confirmed. The crude product was then purified by distillation to obtain 23.40 g (161.18 mmol) of vinyl ether (V-5). The yield of vinyl ether (V-5) was 64%, and the purity determined by gas chromatography was 99.4%.

¹ H-NMR (400 MHz, CDCl ₃ ) δ = 7.65 (m, 2H), 7.09 (m, 2H), 6.66 (dd, 1H), 4.97 (dd, 1H), 4. 67 (dd, 1H).

<Example 12: Synthesis of vinyl ether (V-6)>
In a flask equipped with a Dean-Stark tube, 82.61 g (763.90 mmol) of benzyl alcohol, 50.0 g (372.63 mmol) of 3-phenylpropanal, 0.87 g (3.73 mmol) of camphorsulfonic acid, and 120 g of hexane were added. Reflux was performed for 4 hours (step (C)). ^{From 1} H-NMR, it was confirmed that 94% of 3-phenylpropanal was converted to an acetal compound (e-1). The reaction solution was allowed to cool to 50 ° C., 40.95 g (521.68 mmol) of acetyl chloride was added, and the mixture was stirred at 50 ° C. for 1 hour (step (A)). The disappearance of the acetal compound (e-1) was confirmed by ¹ H-NMR. After returning the reaction solution to 25 ° C., 79.18 g (782.52 mmol) of triethylamine was added dropwise, and after completion of the dropwise addition, the mixture was stirred at 95 ° C. for 2 hours (step (B)). After allowing to cool to 25 ° C., 300 ml of a saturated aqueous ammonium chloride solution was added and stirred, and the aqueous layer was removed. Subsequently, the organic layer was washed with 300 mL of distilled water, dried over anhydrous sodium sulfate, and then the solvent was removed with an evaporator. When analysis by gas chromatography was performed at this time, no peak derived from benzyl alcohol was confirmed. Subsequently, 63.52 g (283.20 mol) of vinyl ether (V-6) was obtained by removing the ester compound (e-3) from the crude product by distillation under reduced pressure. The yield of vinyl ether (V-6) was 76%, and the purity determined by gas chromatography was 97.6%. ^{From 1} H-NMR, the ratio of E-form to Z-form of the obtained vinyl ether (V-6) was E: Z = 57: 43.

¹ H-NMR (400 MHz, CDCl ₃ ) δ = Z- (V-6) 7.43-7.16 (m, 10H), 6.15 (dt, 1H), 4.86 (s, 2H), 4.63 (dt, 1H), 3.49 (d, 2H), E- (V-6) 7.43-7.16 (m, 10H), 6.45 (dt, 1H), 5.06 (Dt, 1H), 4.76 (s, 2H), 3.28 (d, 2H).

<Example 13: Synthesis of vinyl ether (V-7)>
To 80 g (429.44 mmol) of cyclohexanecarboxaldehyde diethyl acetal, 63.36 g (515.33 mmol) of acetyl bromide was added and stirred at 50 ° C. for 1 hour (step (A)). The disappearance of cyclohexanecarboxaldehyde diethyl acetal was confirmed by ¹ H-NMR. After removing the produced ethyl acetate by distillation under reduced pressure, 78.22 g (773.00 mmol) of triethylamine was added dropwise, and after completion of the dropwise addition, the mixture was stirred at 95 ° C. for 2 hours (step (B)). After allowing to cool to 25 ° C., 300 ml of a saturated aqueous ammonium chloride solution was added and stirred, and the aqueous layer was removed. Subsequently, the organic layer was washed with 300 mL of distilled water, dried over anhydrous sodium sulfate, and then the solvent was removed with an evaporator. The crude product was then purified by distillation to obtain 43.36 g (309.20 mol) of vinyl ether (V-7). The yield of vinyl ether (V-7) was 72%, and the purity determined by gas chromatography was 99.1%.

¹ H-NMR (400 MHz, CDCl ₃ ) δ = 5.7 (m, 1H), 3.65 (q, 2H), 2.40-1.70 (m, 4H), 1.65 to 1.35 (M, 6H), 1.20 (t, 3H).

<Example 14: Synthesis of vinyl ether (V-8)>
35.60 g (162.75 mmol) of lauroyl chloride was added to 40 g (147.95 mmol) of isobutyraldehyde dibenzyl acetal, and the mixture was stirred at 50 ° C. for 2 hours (step (A)). The disappearance of isobutyraldehyde dibenzyl acetal was confirmed by ¹ H-NMR. After returning the reaction solution to 25 ° C., 24.70 g (244.13 mmol) of triethylamine was added dropwise, and after completion of the dropwise addition, the mixture was stirred at 95 ° C. for 2 hours (step (B)). After allowing to cool to 25 ° C., 200 ml of a saturated aqueous ammonium chloride solution was added and stirred, and the aqueous layer was removed. Subsequently, the organic layer was washed with 200 mL of distilled water, dried over anhydrous sodium sulfate, and then the solvent was removed with an evaporator. The crude product was then purified by distillation to obtain 16.56 g (102.09 mol) of vinyl ether (V-8). The yield of vinyl ether (V-8) was 69%, and the purity determined by gas chromatography was 99.3%.

¹ H-NMR (400 MHz, CDCl ₃ ) δ = 7.39-7.26 (m, 5H), 5.88 (s, 1H), 4.74 (s, 2H), 1.65 (s, 3H ), 1.54 (s, 3H).

  As described above, according to the examples, it was confirmed that the vinyl ether compound could be produced simply (without using a transition metal) and with sufficient yield and purity.

Claims (12)

A step (A) of reacting a compound represented by the following general formula (1) with a compound represented by the following general formula (2) to obtain a compound represented by the following general formula (3); A step of reacting a compound represented by the formula (3) with a compound represented by the following general formula (4) or the following general formula (5) to obtain a vinyl ether compound represented by the following general formula (6) ( And B). A method for producing a vinyl ether compound.

In the formula, R ¹ and R ² each independently represent a hydrogen atom, an alkyl group, an aryl group, or an aralkyl group. R ¹ and R ² may be linked to each other to form a ring.
R ³ represents an alkyl group, an aryl group or an aralkyl group.
R ⁴ represents an alkyl group, an alkenyl group, an aryl group or an aralkyl group.
R ⁵ , R ⁶ and R ⁷ each independently represents an alkyl group, an aryl group or an aralkyl group. Two of R ⁵ , R ⁶ and R ⁷ may be linked to each other to form a ring.
X represents a halogen atom.
R ⁸ represents a monovalent substituent.
n ₁ represents an integer of 0-4. A step of reacting a compound represented by the following general formula (7) with a compound represented by the following general formula (8) or the following general formula (9) to obtain a compound represented by the above general formula (1) The manufacturing method of the vinyl ether compound of Claim 1 containing (C).

^Wherein, R 1, ^{R 2} and ^{R 3} each have the same meanings as ^R 1, ^{R 2} and ^{R 3} in the general formula (1).   The manufacturing method of the vinyl ether compound of Claim 1 or 2 which performs the said process (A) and process (B) collectively in the same reaction container.   The manufacturing method of the vinyl ether compound of Claim 2 which performs the said process (C), the said process (A), and the said process (B) collectively in the same reaction container. The total number of carbon atoms of R ^1, R ² and R ³ is 7 or more, the production method of the vinyl ether compound according to any one of claims 1 to 4. In the general formulas (1) to (3) and (6), the total number of carbon atoms of R ¹ and R ² is 2 or less, the carbon number of R ³ is 7 or more, and the carbon number of R ⁴ The manufacturing method of the vinyl ether compound of any one of Claims 1-4 whose is 7 or more. In the general formula (1) to (3), the total number of carbon atoms of ^{R 1} and ^{R 2} are at least 6, and the carbon number of ^{R 4} is 3 or less, either of the preceding claims 1 The manufacturing method of the vinyl ether compound as described in a term. In the general formulas (1), (3), and (6), R ³ is a group represented by the following general formula (10), wherein the vinyl ether compound according to any one of claims 1 to 7 is used. Production method.

In the formula, n ₂ represents an integer of 1 to 6, and Y represents a cyclic alkyl group or an aryl group. * Indicates a bond connected to an oxygen atom.   The method for producing a vinyl ether compound according to any one of claims 1 to 8, wherein a hydrocarbon solvent is used as a reaction solvent in each of the step (A) and the step (B).   The manufacturing method of the vinyl ether compound of any one of Claims 1-9 which uses the same reaction solvent in the said process (A) and the said process (B).   The method for producing a vinyl ether compound according to any one of claims 2 to 10, wherein a hydrocarbon solvent is used as a reaction solvent in the step (C).   The manufacturing method of the vinyl ether compound of any one of Claims 2-11 which uses the same reaction solvent in the said process (C), the said process (A), and the said process (B).