JP2001220369A - alpha-VINYLOXYALKYLACRYLIC ACID ESTERS AND METHOD FOR PRODUCING THE SAME - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a new α-vinyloxyalkylacrylic acid ester of the following general formula (1) CH2=C(COOR1)-CHR2-O-CH=CH2 (R1 is a hydrogen atom, an organic residue or a counter ion; R2 is a hydrogen atom or an organic resi due). SOLUTION: This α-vinyloxyalkylacrylic acid ester can be produced, for example, by transetherifying an α-hydroxyalkylacrylic acid ester of the following general formula (2) CH2=C(COOR1)-CHR2-OH (R1 is a hydrogen atom, an organic residue or a counter ion; R2 is a hydrogen atom or an organic residue) with a vinyl ether of the following general formula (3) CH2=CH-O-R3 (R3 is an organic residue).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to α-vinyloxyalkyl acrylates, which are novel acrylate derivatives containing a vinyl group, and to a process for producing the same. More specifically, the present invention provides a useful vinyl group widely used as a raw material for medical and agricultural chemicals, an organic synthetic intermediate, a resin modifier, a resin modifier, an adhesive, a crosslinking agent, a powder coating, and a polymerizable material. The present invention relates to a novel acrylate derivative and a method for producing the same.

[0002]

Conventionally, 2-vinyloxyethyl (meth) acrylate and the like have been known as vinyl group-containing acrylate derivatives.

[0003]

However, the above-mentioned conventional vinyl group-containing acrylate derivatives are:
A vinyl group is introduced into an acryl group via an ester bond, and therefore, the vinyl group may be eliminated by hydrolysis.

The present invention has been made in view of the above circumstances, and has as its object to provide an acrylate derivative containing a vinyl group, from which the vinyl group is not eliminated.

[0005]

Means for Solving the Problems The inventors of the present invention have conducted intensive studies to provide a vinyl group-containing acrylate derivative from which a vinyl group is not eliminated, and as a result, have found that a vinyl group-containing acrylate ester is obtained. As a derivative, novel α-vinyloxyalkyl acrylates were successfully obtained, and the present invention was completed.

That is, the present invention provides a compound represented by the following general formula (1): CH ₂ ＣC (COOR ¹ ) —CHR ² —O—CH ＝ CH ₂ (where R ¹ is a hydrogen atom, an organic residue or a counter ion And R ² represents a hydrogen atom or an organic residue).

Further, another invention of the present invention provides a compound represented by the following general formula (2): CH ₂ ＣC (COOR ¹ ) —CHR ² —OH (wherein R ¹ represents a hydrogen atom, an organic residue or a counter ion) And R ² represents a hydrogen atom or an organic residue, and α-hydroxyalkyl acrylates represented by the following general formula (3): CH ₂ ＣＨCH—O—R ³ (wherein R ^{3 represents} Represents an organic residue) by a transesterification reaction with a vinyl ether represented by the general formula (1) (hereinafter referred to as Production Method I of the present invention). ). It is preferable that the reaction is performed in the presence of a polymerization inhibitor.

Further, another invention of the present invention provides a compound represented by the following general formula (2): CH ₂ ＣC (COOR ¹ ) —CHR ² —OH (wherein R ¹ represents a hydrogen atom, an organic residue or a counter ion) And R ² represents a hydrogen atom or an organic residue, and an α-hydroxyalkyl acrylate ester represented by the following general formula (4): R ⁴ COO—CH ＝ CH ₂ (wherein R ⁴ is A method for producing α-vinyloxyalkyl acrylates represented by the general formula (1) by subjecting a carboxylic acid vinyl ester represented by a hydrogen atom or an organic residue) to a vinyl exchange reaction (hereinafter, referred to as the following) , Which may be referred to as the production method (II) of the present invention). It is preferable that the reaction is performed in the presence of a polymerization inhibitor.

[0009]

DESCRIPTION OF THE PREFERRED EMBODIMENTS One embodiment of the present invention will be described below in detail. The α-vinyloxyalkyl acrylate of the present invention, which is a vinyl group-containing acrylate derivative represented by the general formula (1), is characterized in that the substituent represented by R ¹ in the formula is a hydrogen atom, It is not particularly limited as long as the compound is a residue or a counter ion, and the substituent represented by R ² in the formula is a hydrogen atom or an organic residue.

The organic residue represented by R ¹ includes, for example, a linear, branched or cyclic alkyl group having 1 to 18 carbon atoms, a hydroxyalkyl group having 1 to 8 carbon atoms,
20 alkoxyalkyl groups, halogenated (for example, chlorinated, brominated or fluorinated) alkyl groups having 1 to 8 carbon atoms, or aryl groups. Of these, carbon number 1
ア ル キ ル 4 alkyl groups are preferably used.

The counter ion represented by R ¹ is not particularly limited, but specifically includes, for example, alkali metals such as lithium, sodium, potassium and cesium; magnesium, calcium, strontium, Alkaline earth metals such as barium; zinc, nickel, tin, lead,
Transition metals such as silver; and ions of ammonium compounds such as ammonia, monomethylamine, dimethylamine, trimethylamine, and triethylamine.

The organic residue represented by R ² includes, for example, a linear, branched, or cyclic alkyl group having 1 to 18 carbon atoms, a hydroxyalkyl group having 1 to 8 carbon atoms,
20 alkoxyalkyl groups, halogenated (for example, chlorinated, brominated or fluorinated) alkyl groups having 1 to 8 carbon atoms, or aryl groups. Of these, carbon number 1
ア ル キ ル 4 alkyl groups are preferably used.

Representative examples of the α-vinyloxyalkyl acrylate represented by the general formula (1) are not particularly limited, but specific examples thereof include α-vinyloxymethyl acrylate. Ethyl α-vinyloxymethyl acrylate, propyl α-vinyloxymethyl acrylate, butyl α-vinyloxymethyl acrylate, ethylhexyl α-vinyloxymethyl acrylate, α- (1-
Methyl vinyloxyethyl) acrylate, ethyl α- (1-vinyloxyethyl) acrylate, propyl α- (1-vinyloxyethyl) acrylate, butyl α- (1-vinyloxyethyl) acrylate, ethylhexyl α- (1-vinyloxyethyl) acrylate, α-vinyloxymethyl acrylate, sodium α-vinyloxymethyl acrylate, and the like.

The method for producing the α-vinyloxyalkyl acrylate of the present invention is not particularly limited.
It can be efficiently produced with high yield by the following two production methods.

The production method (I) according to the present invention comprises the above-mentioned general formula (2)
Α-vinyloxy represented by the general formula (1), wherein the α-hydroxyalkyl acrylate represented by the general formula (3) and a vinyl ether represented by the general formula (3) are subjected to an ether exchange reaction. This is a method for producing alkyl acrylates. In addition, the production method of the present invention (I
I) is characterized in that the α-hydroxyalkyl acrylate represented by the general formula (2) is subjected to vinyl exchange reaction with the vinyl carboxylate represented by the general formula (4). Item 4. A method for producing an α-vinyloxyalkyl acrylate according to Item 1.

In the production method (I) of the present invention,
Α-hydroxyalkyl represented by the general formula (2)
The acrylates are represented by R in the formula¹Replacement indicated by
The group is a hydrogen atom, an organic residue or a counter ion;
R^TwoIs a hydrogen atom or an organic residue.
It is not particularly limited as long as the compound is formed.
No. R¹An organic residue and a counter ion represented by^TwoRepresented by
Is an α-bi represented by the above general formula (1).
R in Niloxyalkyl Acrylates ¹You
And R^TwoIs the same as the definition.

Representative examples of the α-hydroxyalkyl acrylate represented by the general formula (2) are not particularly limited, but specific examples thereof include α-hydroxymethyl acrylate and α-hydroxymethyl acrylate. -Ethyl hydroxymethyl acrylate, propyl α-hydroxymethyl acrylate, butyl α-hydroxymethyl acrylate, ethylhexyl α-hydroxymethyl acrylate, α- (1-
Methyl hydroxyethyl) acrylate, ethyl α- (1-hydroxyethyl) acrylate, propyl α- (1-hydroxyethyl) acrylate, butyl α- (1-hydroxyethyl) acrylate, α- (1-hydroxyethyl) ) Ethylhexyl acrylate, α-hydroxymethyl acrylic acid, sodium α-hydroxymethyl acrylate and the like.

The vinyl ether represented by the general formula (3) used as a raw material in the production method (I) of the present invention is:
There is no particular limitation as long as the group represented by R ³ in the formula is a compound composed of an organic residue. As the organic residue represented by R ³ , for example, a linear group having 1 to 18 carbon atoms,
A branched or cyclic alkyl group, a hydroxyalkyl group having 1 to 8 carbon atoms, an alkoxyalkyl group having 2 to 20 carbon atoms, an acetoxyalkyl group having 2 to 20 carbon atoms, 1 carbon atom
~ 8 halogenated (e.g. chlorinated, brominated or fluorinated) alkyl, alkenyl, or aryl groups. Among them, an alkyl group having 1 to 10 carbon atoms is preferably used.

Representative examples of the vinyl ethers represented by the general formula (2) are not particularly limited, but specific examples include methyl vinyl ether, ethyl vinyl ether, n-propyl vinyl ether, isopropyl vinyl ether, and n -Butyl vinyl ether, t-butyl vinyl ether, pentyl vinyl ether, hexyl vinyl ether, heptyl vinyl ether, octyl vinyl ether, nonyl vinyl ether, decanyl vinyl ether, allyl vinyl ether, phenyl vinyl ether, benzyl vinyl ether and the like.

The vinyl carboxylate represented by the general formula (4) used as a raw material in the production method (II) of the present invention is characterized in that the group represented by R ⁴ in the formula is a hydrogen atom or an organic residue. The compound is not particularly limited as long as the compound is used. As an organic residue represented by R ⁴ ,
For example, a linear, branched or cyclic alkyl group having 1 to 18 carbon atoms, a hydroxyalkyl group having 1 to 8 carbon atoms, an alkoxyalkyl group having 2 to 20 carbon atoms, an acetoxyalkyl group having 2 to 20 carbon atoms, It is a halogenated (for example, chlorinated, brominated or fluorinated) alkyl group, alkenyl group, or aryl group having 1 to 8 carbon atoms. Among them, an alkyl group having 1 to 10 carbon atoms is preferably used.

Representative examples of the vinyl carboxylate represented by the general formula (4) are not particularly limited, but specific examples thereof include vinyl formate, vinyl acetate, vinyl propionate, and butyric acid. Vinyl, vinyl isobutyrate, vinyl valerate, vinyl pivalate, vinyl hexanoate, vinyl heptanoate, vinyl octanoate, vinyl nonanoate, vinyl decanoate, vinyl laurate, vinyl 2-ethylhexanoate, vinyl neononanoate, neodecane Vinyl acrylate, vinyl palmitate, vinyl stearate, vinyl cyclohexanoate, vinyl acrylate, vinyl methacrylate,
And vinyl crotonate, vinyl benzoate, vinyl cinnamate and the like.

In the production method of the present invention, the α-hydroxyalkyl acrylate represented by the general formula (2) and the vinyl ether represented by the general formula (3) or the general formula (4) The molar ratio of the carboxylic acid vinyl esters in the initial stage of the reaction is not particularly limited, but may be α-hydroxyalkyl acrylates / vinyl ethers, or α-hydroxyalkyl acrylates / vinyl carboxylate. The molar ratio of the compounds may be in the range of 50/1 to 1/50. Also in the above range, it is preferably in the range of 30/1 to 1/30, more preferably in the range of 20/1 to 1/20, particularly preferably in the range of 10/1 to 1/10. The above range is preferable in terms of yield, productivity and economy.

The catalyst used in the production method of the present invention is, but not limited to, a palladium compound. The palladium-based compound is not particularly limited, but specifically, palladium chloride, palladium acetate, palladium nitrate, palladium oxide, diacetato (1,10-phenanthroline) palladium, diacetato (2,2′-bipyridine) ) Palladium, diacetato (ethylenediamine) palladium, diacetato (2,4
-Pentanediamine) palladium, diacetato (1,2
-Cyclohexanediamine) palladium, diacetato (N, N, N ', N'-tetramethylenediamine) palladium, dichloro (1,10-phenanthroline) palladium, dichloro (2,2'-bipyridine) palladium, dichloro (ethylenediamine) palladium , Dichloro (2,4-pentanediamine) palladium, dichloro (1,2-cyclohexanediamine) palladium, dichloro (N, N, N ', N'-tetramethylenediamine)
Palladium, (2,2′-bipyridine) dinitropalladium, (2,2′-bipyridine) dimethylpalladium,
Dineopentyl (2,2'-bipyridine) palladium,
Dichlorobis (pyridine) palladium, dichlorobis (hydrazine) palladium, diamminedibromopalladium, tetraamminedichloropalladium, diamminedinitropalladium, bis (acetonitrile) dichloropalladium, bis (benzonitrile) dichloropalladium, dichlorobis (isocyanide) palladium, dichlorobis (phenylisocyanide) palladium, tetrachlorobis (.eta. ethylene) dipalladium, di -η- chloro - bis [chloro (ethylene) palladium, dichloro (ethylene) palladium, (eta ³ - allyl) (eta ⁵ - cyclopentadienyl) palladium , (eta ³ - allyl) (eta ⁵ - pentamethylcyclopentadienyl) palladium, dichloro (eta ^{4-1,5-cyclooctadiene)} palladium,
(Chloro) (eta ^{4-1,5-cyclooctadiene)} (methyl) palladium, bis (.eta. allyl) dichloro dipalladium, di -η- chloro - bis [.eta. allylpalladium], dichlorobis (phosphine) palladium, Dichlorobis (tributylphosphine) palladium, bromo (methyl) bis (triethylphosphine) palladium,
trans-dimethylbis (triphenylphosphine) palladium, dinitrobis (phosphine) palladium, amminedichloro (phosphine) palladium, dichloro (η
⁴ -tetraphenylcyclobutadiene) palladium, tetrachlorobis (phosphine) dipalladium, bis (8
-Quinolinolato) palladium, bis (salicylaldehyde oximato) palladium, bis (dimethylglyoximato) palladium, bis (benzylmethylglyoximato) palladium, bis (N-ethylsalicylaldiminato) palladium, bis (acetylacetonato) Palladium, [bis (acetylacetone) ethylenediaminato]
Palladium, bis (glycinato) palladium, (η-1
-Acetyl-2-hydroxyallyl) chloro (triphenylphosphine) palladium, di-η-chlorobis [(η-1-acetyl-2-hydroxyallyl) palladium] and the like. Of these, palladium chloride,
Palladium acetate, palladium nitrate, bis (acetonitrile) dichloropalladium, bis (benzonitrile) dichloropalladium, diacetato (1,10-phenanthroline) palladium, diacetato (2,2′-bipyridine) palladium, diacetato (ethylenediamine) palladium, diacetato ( 2,4-pentanediamine) palladium, diacetato (1,2-cyclohexanediamine) palladium, dichloro (1,10-phenanthroline) palladium, dichloro (2,2′-bipyridine) palladium, dichloro (ethylenediamine) palladium,
Dichloro (2,4-pentanediamine) palladium and dichloro (1,2-cyclohexanediamine) palladium are preferred.

Among these, palladium complexes which have been synthesized and isolated in advance as palladium complexes are added not only to the reaction system, but also to palladium compounds such as palladium acetate and palladium chloride, and 1,10-phenanthroline, A method of generating a palladium complex in a reaction system by a ligand such as 2′-bipyridine may be used.

The amount of the palladium compound used is determined by the α-hydroxyalkyl acrylate represented by the general formula (2), the vinyl ether represented by the general formula (3) and the general formula (4). Depending on the type and combination of the represented carboxylic acid vinyl esters, the vinyl ethers or the carboxylic acid vinyl esters 1
It may be used in an amount of 0.001 to 0.1 mol, more preferably 0.005 to 0.05 mol, per mol. The range of the amount of the catalyst used is preferable from the viewpoints of catalytic activity, productivity, economy, and stability of the catalyst.

In the production method (I) of the present invention, an ether exchange reaction between an α-hydroxyalkyl acrylate represented by the general formula (2) and a vinyl ether represented by the general formula (3) results in Α expressed by (1)
-When a vinyloxyalkyl acrylate is produced, 1,10-
It is preferable to further add a nitrogen compound such as phenanthroline, 2,2′-bipyridine, ethylenediamine, 2,4-pentanediamine, or 1,2-cyclohexanediamine from the viewpoint of improving the yield. As nitrogen compounds,
Although not particularly limited, 1,10-phenanthroline, 2,2′-bipyridine, ethylenediamine,
Examples include 2,4-pentanediamine, 1,2-cyclohexanediamine, N, N, N ′, N′-tetramethylenediamine, pyridine, hydrazine and the like. Among them, 1,10-phenanthroline, 2,2′-bipyridine, ethylenediamine, 2,4-pentanediamine,
1,2-cyclohexanediamine is more preferred,
10-phenanthroline or 2,2'-bipyridine is particularly preferred. The amount of the nitrogen compound to be added is 0 to 1 mol per palladium atom constituting the palladium complex.
A range of 100 moles is preferred, more preferably 1-80.
It is in the range of mol, particularly preferably in the range of 5 to 50 mol. The range of the addition amount of the nitrogen compound is the catalyst activity,
It is preferable in terms of productivity, economy, and stability of the catalyst.

In the present invention, an α-hydroxyalkyl acrylate represented by the general formula (2) and a carboxylic acid vinyl ester represented by the general formula (4) are subjected to a vinyl exchange reaction to obtain a compound represented by the general formula (1). In the case of producing the α-vinyloxyalkyl acrylate represented by the formula (1), the presence of a basic compound in the reaction system is preferred from the viewpoint of improving the yield. The basic compound is not particularly limited, but specifically, lithium formate,
Sodium formate, potassium formate, magnesium formate, calcium formate, barium formate, lithium acetate, sodium acetate, potassium acetate, magnesium acetate, calcium acetate, barium, lithium propionate, sodium propionate, potassium propionate, magnesium propionate, propion Alkali metals such as calcium oxide, barium propionate, lithium carbonate, sodium carbonate, potassium carbonate, magnesium carbonate, calcium carbonate, barium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, sodium paratoluenesulfonate, potassium chloride, calcium chloride and / or Or alkaline earth metal salts; phosphates of transition metal atoms such as titanium phosphate, chromium phosphate, manganese phosphate, iron phosphate, cobalt phosphate and nickel phosphate; Oxygenates such as sodium gustinate, sodium tellurite, sodium molybdate, sodium selenate, sodium chromate, sodium thiosulfate; disodium ethylenediaminetetraacetate, trisodium ethylenediaminetetraacetate, tetrasodium ethylenediaminetetraacetate, ethylenediaminetetrasodium Barium disodium acetate, disodium ethylenediaminetetraacetate
Cadmium, disodium calcium ethylenediaminetetraacetate, disodium cobalt cobalt ethylenediaminetetraacetate, disodium copper copper ethylenediaminetetraacetate, disodium mercury ethylenediaminetetraacetate, disodium magnesium ethylenediaminetetraacetate, disodium manganese ethylenediaminetetraacetate Disodium / nickel ethylenediaminetetraacetate / nickel, disodium / lead ethylenediaminetetraacetate / zinc, ethylenediaminetetraacetate / zinc, sodium ethylenediaminetetraacetate / iron,
Examples include ethylenediaminetetraacetic acid complex salts such as dipotassium ethylenediaminetetraacetate, tripotassium ethylenediaminetetraacetate, and dipotassium ethylenediaminetetraacetate / magnesium. These can be used alone or in an appropriate combination of two or more. Among these,
Sodium hydrogencarbonate, calcium chloride, sodium molybdate, sodium tungstate, sodium thiosulfate, disodium / zinc ethylenediaminetetraacetate / zinc are preferably used. In particular, sodium hydrogen carbonate, sodium molybdate, and disodium / zinc ethylenediaminetetraacetate are more preferably used.

The amount of the basic compound to be added is 0.0 to 1 mol of palladium atoms constituting the palladium catalyst.
01 to 3 mol, preferably 0.01 to 2 mol, more preferably 0.05 to 1.8 mol, particularly preferably 0.1 to 1 mol.
What is necessary is just to add so that it may be in the range of 1.5 mol. The range of the addition amount of the basic compound is preferable from the viewpoint of catalytic activity, productivity, economy, and catalyst stability.

In the production method (I) of the present invention, α-hydroxyalkyl acrylates represented by the general formula (2) as raw materials and α-hydroxyalkyl acrylates represented by the general formula (1) as a product are used. -Vinyloxyalkyl acrylates are polymerizable compounds, and are preferably reacted in the presence of a polymerization inhibitor in terms of yield because they suppress polymerization of these compounds. Examples of the polymerization inhibitor include, but are not particularly limited to, quinone-based polymerization inhibitors such as hydroquinone, methoxyhydroquinone, benzoquinone, and p-tert-butylcatechol; 2,6-di-tert-butylphenol, and 2,4. Alkyl phenols such as -di-tert-butylphenol, 2-tert-butyl-4,6-dimethylphenol, 2,6-di-tert-butyl-4-methylphenol, and 2,4,6-tri-tert-butylphenol Polymerization inhibitors; amine-based polymerization inhibitors such as alkylated diphenylamine, N, N'-diphenyl-p-phenylenediamine, phenothiazine;
And copper dithiocarbamate-based polymerization inhibitors such as copper dimethyldithiocarbamate, copper diethyldithiocarbamate, and copper dibutyldithiocarbamate. These can be used alone or in an appropriate combination of two or more. Among these, quinone-based polymerization inhibitors, particularly hydroquinone, methoxyhydroquinone, benzoquinone, p-tert-butylcatechol and phenothiazine are preferably used.

The amount of the polymerization inhibitor depends on the kind of the α-hydroxyalkyl acrylate represented by the general formula (1) to be used. 001 to 5% by weight, preferably 0.005 to 1% by weight, particularly preferably 0.0
What is necessary is just to add so that it may be in the range of 1-0.1 weight%. The range of the addition amount of the polymerization inhibitor is a polymerization suppression effect,
It is preferable in terms of yield, productivity, and economy.

[0031] The reaction temperature is preferably in the range of -40 ° C to 150 ° C, more preferably in the range of -10 ° C to 100 ° C, and particularly preferably in the range of 10 ° C to 80 ° C. The above reaction temperature range is preferable in terms of yield, productivity and economy. The reaction time may be appropriately set according to the type and combination of the α-hydroxyalkyl acrylates, vinyl ethers or vinyl carboxylate, the catalyst and the organic solvent, the amount used, and the like, so that the reaction is completed. . The reaction pressure depends on the combination of the type of α-hydroxyalkyl acrylate represented by the general formula (1) and the reaction temperature, but is not particularly limited as long as the reaction system is kept in a liquid state. Instead, the pressure may be normal pressure (atmospheric pressure), reduced pressure, or increased pressure.

In the present invention, it is not necessary to use a solvent, but an organic solvent can be used. Examples of the organic solvent include, but not limited to, aromatic hydrocarbons such as benzene, toluene, and xylene; aliphatic hydrocarbons such as pentane, hexane, cyclohexane, and heptane; and diethyl ether, diisopropyl ether, and the like. Ethers; ketones such as acetone and methyl ethyl ketone; polar solvents such as dimethylformamide and dimethyl sulfoxide; and halogenated hydrocarbons such as chloroform, methylene chloride, dichloroethane and chlorobenzene.

The amount of the organic solvent used depends on the combination of the α-hydroxyalkyl acrylate represented by the general formula (1) and the vinyl ether or vinyl carboxylate used. 0 to 2 of the total amount of the alkyl acrylates and the vinyl ethers or carboxylic acid vinyl esters.
00% by weight, preferably 0 to 100% by weight, more preferably 0 to 80% by weight, particularly preferably 0 to 70% by weight
It may be used so as to be within the range. The range of the amount of the organic solvent used is preferable in terms of productivity and economy.

The α-vinyloxyalkyl acrylates produced according to the present invention are represented by the above-mentioned general formula (1), wherein R ¹ and R ² are each as defined in the above-mentioned general formula (1). The same is true. Α- produced according to the present invention
Vinyloxyalkyl acrylates can be obtained by purifying the reaction solution. The purification means is not particularly limited, but can be separated and purified by a distillation method, an extraction method, a column chromatography method, or the like. These methods may be implemented in combination.
Of these, the distillation method is particularly preferred.

[0035]

EXAMPLES The present invention will be described in more detail with reference to the following Examples, but it should not be construed that the invention is limited thereto. Example 1 Ethyl vinyl ether 1 was placed in a flask having a capacity of 200 ml.
14.03 g (1.58 mol), 17.52 g (0.15 mol) of methyl α-hydroxymethyl acrylate, 0.97 g (2.4 mmol) of diacetato (1,10-phenanthroline) palladium (II), phenothiazine The reaction was completed by charging 9.4 mg and stirring at 30 ° C. for 24 hours. After the completion of the reaction, ethyl vinyl ether was distilled off under reduced pressure, and the residue was separated and purified using column chromatography. In the column chromatography, a solution of benzene: acetone = 6: 1 (volume ratio) was used as a developing solvent. Silica gel was used as the adsorbent.

With respect to the substance obtained as described above, ¹ H
-The substance was identified by NMR, IR, and elemental analysis. As a result, it was confirmed that the above-mentioned substance as a reaction product was a novel α-vinyloxyalkyl acrylate according to the present invention, that is, α-vinyloxymethyl acrylate. FIG. 1 shows a ¹ H-NMR chart of the reaction product, and FIG. 2 shows an IR spectrum thereof. The results of the elemental analysis were as follows. C: 59.10% (theoretical value: 59.14%), H: 7.1
2% (theoretical value: 7.07%), N: not detected (theoretical value: 0.00%) In addition, GC-14B type gas chromatography (manufactured by Shimadzu Corporation; hereinafter, referred to as "GC") As a result, the yield of the target methyl α-vinyloxymethyl acrylate was 55 mol%.

EXAMPLE 2 20.08 g (0.1%) of α-hydroxyalkyl acrylate was added to ethyl α-hydroxymethyl acrylate.
5 mol), 0.91 g (2.4 mmol) of diacetato (2,2′-bipyridine) palladium,
9.2 mg of p-tert-butylcatechol was used as a polymerization inhibitor.
The same operation as in Example 1 was performed, except that 5.62 g (36.0 mmol) of 2,2′-bipyridine was added. After the completion of the reaction, ethyl vinyl ether was distilled off under reduced pressure, and the residue was separated and purified using column chromatography.
In the column chromatography, a solution of benzene: acetone = 6: 1 (volume ratio) was used as a developing solvent.
Silica gel was used as the adsorbent.

With respect to the substance obtained as described above, ¹ H
-The substance was identified by NMR, IR, and elemental analysis. As a result, it was confirmed that the above-mentioned substance as a reaction product was a novel α-vinyloxyalkyl acrylate according to the present invention, that is, ethyl α-vinyloxymethyl acrylate. FIG. 3 shows a ¹ H-NMR chart of the reaction product, and FIG. 4 shows an IR spectrum thereof. The results of the elemental analysis were as follows. C: 61.55% (theoretical value: 61.52%), H: 7.7
5% (theoretical value: 7.74%), N: not detected (theoretical value: 0.00%) As a result of measuring the reaction solution by GC, the yield of the target ethyl α-vinyloxymethyl acrylate was 68 mol. %Met.

Example 3 25.43 g of vinyl acetate was placed in a flask having a capacity of 100 ml.
(0.30 mol), 11.63 g (0.10 mol) of methyl α-hydroxymethylacrylate, 88.7 mg (0.50 mmol) of palladium chloride, and 5.8 mg of methoxyhydroquinone, and stirred at 40 ° C. Hold for 30 minutes. As a result of measuring the reaction solution by GC, the yield of the target methyl α-vinyloxymethyl acrylate was 4
3 mol%.

Example 4 α-Hydroxyalkyl acrylates were converted to 14.32 g (0.1%) of ethyl α-hydroxymethyl acrylate.
1 mol), and 41.7 mg (0. 1 mol) of sodium hydrogen carbonate.
The same operation as in Example 3 was performed except that 50 mmol) was added. As a result of measuring the reaction solution by GC, the yield of the target ethyl α-vinyloxymethyl acrylate was 56
Mole%.

[0041]

The α-vinyloxyalkyl acrylate of the present invention is a characteristic acrylate derivative containing a vinyl group, and is therefore used as a raw material for medicinal and agricultural chemicals, an organic synthetic intermediate, a crosslinking agent, and a powder coating. , Resin modifiers, and polymerizable materials. According to the production method of the present invention, the α-vinyloxyalkyl acrylates can be efficiently produced with high yield.

[0042]

[Brief description of the drawings]

FIG. 1 is a ¹ H-NMR chart of α-vinyloxymethyl acrylate obtained in Example 1.

FIG. 2 is an IR chart of α-vinyloxymethyl acrylate obtained in Example 1.

FIG. 3 is a ¹ H-NMR chart of ethyl α-vinyloxymethyl acrylate obtained in Example 2.

FIG. 4 is an IR chart of ethyl α-vinyloxymethyl acrylate obtained in Example 2.

Claims (3)

[Claims] 1. The following general formula (1): CH ₂ ＣC (COOR ¹ ) —CHR ² —O—CH ＝ CH
₂ (wherein, R ¹ represents a hydrogen atom, an organic residue, or a counter ion, and R ² represents a hydrogen atom or an organic residue), α-vinyloxyalkyl acrylates. 2. The following general formula (2): CH ₂ ＣC (COOR ¹ ) —CHR ² —OH (wherein R ¹ represents a hydrogen atom, an organic residue or a counter ion, and R ² represents a hydrogen atom or An α-hydroxyalkyl acrylate represented by an organic residue) and a compound represented by the following general formula (3): CH ₂ ＣＨCH—O—R ³ (wherein, R ³ represents an organic residue). The method for producing α-vinyloxyalkyl acrylates according to claim 1, wherein an ether exchange reaction is carried out with the vinyl ethers represented. 3. The following general formula (2): CH ₂ ＣC (COOR ¹ ) —CHR ² —OH (wherein R ¹ represents a hydrogen atom, an organic residue or a counter ion, and R ² represents a hydrogen atom or An α-hydroxyalkyl acrylate represented by an organic residue) and the following general formula (4): R ⁴ COO—CH ＝ CH ₂ (wherein, R ⁴ represents a hydrogen atom or an organic residue) 3. The method for producing α-vinyloxyalkyl acrylates according to claim 1, wherein the vinyl carboxylate represented by the formula (1) is subjected to a vinyl exchange reaction.