JP4448677B2 - Production method of vinyl ether compounds - Google Patents

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 as raw materials for fine chemicals such as pharmaceuticals and agricultural chemicals, as well as polymer raw materials such as resist resins, optical resins, transparent resins, and crosslinkable resins. In particular, a vinyl ether compound having a non-aromatic cyclic skeleton such as an alicyclic skeleton or a lactone skeleton can improve transparency and dry etching property when used as a comonomer of a polymer. As expected. In addition, a vinyl ether compound having a plurality of vinyl groups is suitable as a raw material monomer for a crosslinkable resin because it can impart high solvent resistance. Furthermore, since the vinyl ether compound has low odor and less skin irritation compared with the acrylic compound, there is an advantage that it is excellent in handleability and workability. However, in the market, since vinyl ether compounds are less in kind than acrylic compounds (monomers) and are expensive in price, the present situation is that they cannot sufficiently meet the needs.

  As a method for producing a vinyl ether compound, a method in which acetylene and an alcohol are reacted in the presence of an alkali metal hydroxide or an alkali metal alcoholate catalyst is known. However, this method is disadvantageous in that it uses acetylene which is difficult to handle as a raw material. As another method for producing a vinyl ether compound, a method is known in which an alcohol and a vinyl ester are reacted at a temperature of −75 ° C. to −15 ° C. in the presence of a mercury salt of a strong acid (see Patent Document 1). However, this method is not preferred as an industrial production method because it requires the use of highly toxic mercury and requires reaction at an extremely low temperature.

  As another method for producing a vinyl ether compound, a method of reacting a carboxylic acid vinyl ester compound with a hydroxy compound in the presence of a transition element compound such as an iridium compound is known (see Patent Document 2). According to this method, the target vinyl ether compound can be easily obtained under mild conditions. However, this method is not necessarily sufficient in terms of yield.

US Pat. No. 2,579,411 JP 2003-73321 A

Accordingly, an object of the present invention is to provide a method capable of obtaining a vinyl ether compound in a high yield under mild conditions.
Another object of the present invention is to provide a method for producing a vinyl ether compound capable of suppressing deactivation of a catalyst.

  As a result of intensive studies to achieve the above object, the present inventors have made a reaction when a vinyl ester compound and a hydroxy compound are reacted while removing by-product water in the presence of a transition element compound catalyst and a base. It proceeded quickly and found that the corresponding vinyl ether compound was obtained in a high yield, thereby completing the present invention.

（式中、Ｒ¹、Ｒ²、Ｒ³及びＲ⁴は、同一又は異なって、水素原子又は有機基を示す）
で表されるビニルエステル化合物と、下記式（２）

（式中、Ｒ⁵は有機基を示し、ｋは自然数を示す）
で表されるヒドロキシ化合物とを、副生する水を除去しながら反応させて、対応する下記式（３）

［式中、Ｒ⁵、ｋは前記に同じ。Ｒ⁶は、水素原子又は下記式（４）

（式中、Ｒ²、Ｒ³、Ｒ⁴は前記に同じ）
で表される基を示す。但し、ｋ個のＲ⁶のうち少なくとも１つは式（４）で表される基である］
で表されるビニルエーテル化合物を生成させることを特徴とするビニルエーテル化合物の製造法を提供する。 That is, in the present invention, an iridium compound catalyst is added to the system under heating at 50 ° C. or higher in the presence of an alkali metal carbonate , and the following formula (1)

(Wherein R ¹ , R ² , R ³ and R ⁴ are the same or different and represent a hydrogen atom or an organic group)
And a vinyl ester compound represented by the following formula (2)

(Wherein R ⁵ represents an organic group and k represents a natural number)
And a hydroxy compound represented by the formula (3) corresponding to the following formula (3):

[Wherein R ⁵ and k are the same as defined above. R ⁶ is a hydrogen atom or the following formula (4)

(Wherein R ² , R ³ and R ⁴ are the same as above)
The group represented by these is shown. However, at least one of k R ⁶ is a group represented by the formula (4)]
The vinyl ether compound represented by these is produced | generated, The manufacturing method of the vinyl ether compound characterized by the above-mentioned is provided.

In this specification, in addition to the above invention, in the presence of a transition element compound catalyst and a base, a vinyl ester compound represented by the above formula (1) and a hydroxy compound represented by the above formula (2) The method of producing a vinyl ether compound characterized by reacting while removing by-product water to produce the corresponding vinyl ether compound represented by the above formula (3), the transition element compound catalyst under heating, The method for producing the vinyl ether compound added to the system is also described.

  In addition, the vinyl ether compound and the vinyl ester compound in this specification include compounds in which a hydrogen atom of a vinyl group is substituted with a substituent. The transition element means a group IIIA element, a group IVA element, a group VA element, a group VIA element, a group VIIA element, a group VIII element, and a group IB element in the periodic table. The “organic group” in the present specification is used in a broad sense including not only a carbon atom-containing group but also a nonmetal atom-containing group such as, for example, a halogen atom, a nitro group, or a sulfonic acid group.

  According to the production method of the present invention, a vinyl ether compound can be produced in a high yield under mild conditions. Further, the deactivation of the catalyst is suppressed, and the catalytic activity can be maintained for a long time.

[Transition element compounds]
In the present invention, a transition element compound (including a single transition element) is used as a catalyst. The transition element compounds can be used alone or in combination of two or more. Transition elements include Group IIIA elements such as lanthanum and cerium (especially lanthanoid elements); Group IVA elements such as titanium and zirconium; Group VA elements such as vanadium; Group VIA elements such as chromium, molybdenum and tungsten; Group elements; Group VIII elements such as iron, cobalt, nickel, ruthenium, rhodium, palladium, osmium, iridium and platinum; Group IB elements such as copper and silver. Among these, group VIII elements are preferable, and platinum group elements (ruthenium, rhodium, palladium, osmium, iridium and platinum), and particularly iridium are particularly preferable.

  Examples of transition element compounds include transition element simple substances (metals), oxides, sulfides, hydroxides, halides (fluorides, chlorides, bromides, iodides), sulfates, and oxo acids containing transition elements. Or an inorganic compound such as a salt or an inorganic complex thereof; an organic compound such as a cyanide, an organic acid salt (such as an acetate salt), or an organic complex. Among these, an organic complex is particularly preferable. The ligand of the complex includes a known ligand. The valence of the transition element in the transition element compound is about 0 to 6, preferably 0 to 3. In particular, in the case of an iridium compound, monovalent or trivalent is preferable.

  Typical examples of transition element compounds are iridium, for example, metal iridium, iridium oxide, iridium sulfide, iridium hydroxide, iridium fluoride, iridium chloride, iridium bromide, iridium iodide, iridium sulfate, iridium. Inorganic compounds such as acids or salts thereof (for example, potassium iridate), inorganic iridium complexes [for example, hexaammineiridium (III) salts, chloropentammineiridium (III) salts, etc.]; iridium cyanide, organic iridium complexes [ For example, tris (acetylacetonato) iridium, dodecacarbonyltetrairidium (0), chlorotricarbonyliridium (I), di-μ-chlorotetrakis (cyclooctene) diiridium (I), di-μ-chlorotetrakis (ethylene) ) Irijiu (I), di-μ-chlorobis (1,5-cyclooctadiene) diiridium (I), di-μ-chlorodichlorobis (pentamethylcyclopentadienyl) diiridium (III), trichlorotris (triethyl Phosphine) iridium (III), pentahydridobis (trimethylphosphine) iridium (V), chlorocarbonylbis (triphenylphosphine) iridium (I), chloroethylenebis (triphenylphosphine) iridium (I), (pentamethylcyclopenta Dienyl) dicarbonyliridium (I), bis {1,2-bis (diphenylphosphino) ethane} iridium (I) chloride, pentamethylcyclopentadienylbis (ethylene) iridium (I), carbonylmethylbis ( Triphenylphosphine) iridium ( I), (1,5-cyclooctadiene) (diphosphine) iridium (I) halide, 1,5-cyclooctadiene (1,2-bis (diphenylphosphino) ethane) iridium (I) hexafluorophosphoric acid Salt, (1,5-cyclooctadiene) bis (trialkylphosphine) iridium (I) halide, bis (1,5-cyclooctadiene) iridium tetrafluoroborate, (1,5-cyclooctadiene) (acetonitrile And organic compounds such as iridium tetrafluoroborate].

  Preferred iridium compounds include iridium complexes. Among these, organic iridium complexes, especially unsaturated hydrocarbons such as cyclopentene, dicyclopentadiene, cyclooctene, 1,5-cyclooctadiene, ethylene, pentamethylcyclopentadiene, benzene, toluene; nitriles such as acetonitrile; Organic iridium complexes having ethers such as tetrahydrofuran as ligands [e.g., di-μ-chlorotetrakis (cyclooctene) diiridium (I), di-μ-chlorotetrakis (ethylene) diiridium (I), di- μ-chlorobis (1,5-cyclooctadiene) diiridium (I), bis (1,5-cyclooctadiene) iridium tetrafluoroborate, (1,5-cyclooctadiene) (acetonitrile) iridium tetrafluoroborate, etc. ] Is preferredThe iridium compounds can be used alone or in admixture of two or more. Moreover, an iridium compound and another transition element compound can also be used together.

  Examples of transition element compounds other than iridium compounds include compounds corresponding to the above iridium compounds [for example, dichloro (1,5-cyclooctadiene) ruthenium, dichloro (1,5-cyclooctadiene) platinum, dichlorobis (1,5- Cyclooctadiene) dirhodium etc.]. In transition element compounds other than iridium compounds, for example, cyclopentene, dicyclopentadiene, cyclooctene, 1,5-cyclooctadiene, ethylene, pentamethylcyclopentadiene, benzene, toluene and other unsaturated hydrocarbons; acetonitrile and other nitriles Organic complexes having ethers such as tetrahydrofuran as ligands are particularly preferred.

  The transition element compound can be used as it is or in a form supported on a carrier. Examples of the carrier include a conventional carrier for supporting a catalyst, for example, inorganic metal oxides such as silica, alumina, silica-alumina, zeolite, titania, and magnesia, and activated carbon. In the carrier-supported catalyst, the amount of the transition element compound supported is, for example, about 0.1 to 50% by weight, preferably about 1 to 20% by weight, based on the carrier. The catalyst can be supported by a conventional method such as an impregnation method, a precipitation method, or an ion exchange method.

  The amount of the transition element compound used is, for example, 0.0001 to 1 mol, preferably 0.0002 to 0.1 mol, more preferably 0.0005 to 0.01 mol, relative to 1 mol of the hydroxy compound used as the reaction component. Degree.

[Vinyl ester compounds]
In the vinyl ester compound represented by the formula (1), R ¹ , R ² , R ³ and R ⁴ each represent a hydrogen atom or an organic group. The organic group may be an organic group that does not inhibit this reaction (for example, an organic group that is non-reactive under the reaction conditions in the present method), such as a halogen atom, a hydrocarbon group, a heterocyclic group, Substituted oxycarbonyl group (alkoxycarbonyl group, aryloxycarbonyl group, aralkyloxycarbonyl group, cycloalkyloxycarbonyl group, etc.), carboxyl group, substituted or unsubstituted carbamoyl group, cyano group, nitro group, sulfur acid group, sulfur acid ester Group, acyl group (aliphatic acyl group such as acetyl group; aromatic acyl group such as benzoyl group), alkoxy group (such as C _1-6 alkoxy group such as methoxy group and ethoxy group), N, N-disubstituted Examples thereof include amino groups (N, N-dimethylamino group, piperidino group, etc.), and groups in which two or more of these are bonded. The carboxyl group and the like may be protected with a protecting group known or commonly used in the field of organic synthesis. Examples of the halogen atom include fluorine, chlorine, bromine and iodine atoms. Of these organic groups, a hydrocarbon group, a heterocyclic group, and the like are preferable.

  The hydrocarbon group and the heterocyclic group also include a hydrocarbon group and a heterocyclic group having a substituent. The hydrocarbon group includes an aliphatic hydrocarbon group, an alicyclic hydrocarbon group, an aromatic hydrocarbon group, and a group in which these are bonded. Examples of the aliphatic hydrocarbon group include 1 to 20 carbon atoms (preferably 1 to 1) such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, s-butyl, t-butyl, pentyl, hexyl, decyl, and dodecyl groups. 10, more preferably an alkyl group of about 1 to 3); an alkenyl group of about 2 to 20 carbon atoms (preferably 2 to 10, more preferably 2 to 3) such as vinyl, allyl, 1-butenyl group; Examples thereof include alkynyl groups having about 2 to 20 carbon atoms (preferably 2 to 10, more preferably 2 to 3) such as propynyl groups.

As the alicyclic hydrocarbon group, a cycloalkyl group having about 3 to 20 members (preferably 3 to 15 members, more preferably 5 to 8 members) such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl and cyclooctyl groups; Cycloalkenyl groups of about 3 to 20 members (preferably 3 to 15 members, more preferably 5 to 8 members) such as pentenyl and cyclohexenyl groups; perhydronaphthalen-1-yl group, norbornyl, adamantyl, tetracyclo [4 4.0.1, ^2,5 . 1 ^7,10 ] bridged cyclic hydrocarbon groups such as dodecan-3-yl groups. Examples of the aromatic hydrocarbon group include aromatic hydrocarbon groups having about 6 to 14 (preferably 6 to 10) carbon atoms such as phenyl and naphthyl groups.

The hydrocarbon group in which an aliphatic hydrocarbon group and an alicyclic hydrocarbon group are bonded includes a cycloalkyl-alkyl group such as cyclopentylmethyl, cyclohexylmethyl, 2-cyclohexylethyl group (for example, C _3-20 cycloalkyl- C _1-4 alkyl group and the like). The hydrocarbon group in which an aliphatic hydrocarbon group and an aromatic hydrocarbon group are bonded to each other includes an aralkyl group (for example, a C _7-18 aralkyl group) and an alkyl-substituted aryl group (for example, about 1 to about 4). A phenyl group substituted with a C _1-4 alkyl group or a naphthyl group).

Preferred hydrocarbon groups include C _1-10 alkyl groups, C _2-10 alkenyl groups, C _2-10 alkynyl groups, C _3-15 cycloalkyl groups, C _6-10 aromatic hydrocarbon groups, C _3-15 A cycloalkyl-C _1-4 alkyl group, a C _7-14 aralkyl group and the like are included.

  The hydrocarbon group includes various substituents such as halogen atoms, oxo groups, hydroxyl groups, substituted oxy groups (for example, alkoxy groups, aryloxy groups, aralkyloxy groups, acyloxy groups, etc.), carboxyl groups, substituted oxycarbonyls. Group (alkoxycarbonyl group, aryloxycarbonyl group, aralkyloxycarbonyl group, etc.), substituted or unsubstituted carbamoyl group, cyano group, nitro group, substituted or unsubstituted amino group, sulfo group, heterocyclic group, etc. May be. The hydroxyl group and carboxyl group may be protected with a protective group commonly used in the field of organic synthesis. In addition, an aromatic or non-aromatic heterocycle may be condensed with the ring of the alicyclic hydrocarbon group or aromatic hydrocarbon group.

The heterocyclic ring constituting the heterocyclic group in R ^{1 and the} like includes an aromatic heterocyclic ring and a non-aromatic heterocyclic ring. Examples of such a heterocycle include heterocycles containing an oxygen atom as a hetero atom (for example, 5-membered rings such as furan, tetrahydrofuran, oxazole, and γ-butyrolactone ring, 4-oxo-4H-pyran, tetrahydropyran, and morpholine. 6-membered ring such as ring, condensed ring such as benzofuran, 4-oxo-4H-chromene, chroman ring, 3-oxatricyclo [4.3.1.1 ^4,8 ] undecan-2-one ring, 3- A bridged ring such as an oxatricyclo [4.2.1.0 ^4,8 ] nonan-2-one ring), a heterocycle containing a sulfur atom as a hetero atom (eg, thiophene, thiazole, thiadiazole ring, etc.) A ring, a 6-membered ring such as a 4-oxo-4H-thiopyran ring, a condensed ring such as a benzothiophene ring), a heterocycle containing a nitrogen atom as a hetero atom (for example, 5-membered rings such as roll, pyrrolidine, pyrazole, imidazole, triazole ring, 6-membered rings such as pyridine, pyridazine, pyrimidine, pyrazine, piperidine, piperazine ring, indole, indoline, quinoline, acridine, naphthyridine, quinazoline, purine ring, etc. Condensed ring and the like). In addition to the substituents that the hydrocarbon group may have, the heterocyclic group includes an alkyl group (eg, a C _1-4 alkyl group such as a methyl or ethyl group), a cycloalkyl group, an aryl group It may have a substituent such as (for example, phenyl, naphthyl group).

Preferred R ¹ , R ² , R ³ and R ⁴ include a hydrogen atom and a hydrocarbon group (for example, a C _1-10 alkyl group, a C _2-10 alkenyl group, a C _2-10 alkynyl group, a C _3-15 cyclohexane). Alkyl group, C _6-10 aromatic hydrocarbon group, C _3-12 cycloalkyl-C _1-4 alkyl group, C _7-14 aralkyl group, etc.). In particular, R ¹ is preferably a C _1-3 alkyl group such as a methyl group, an ethyl group, or a propyl group, and a phenyl group. R ² , R ³ and R ⁴ are particularly preferably a C _1-3 alkyl group such as a hydrogen atom or a methyl group.

  Representative examples of the vinyl ester compound represented by the formula (1) include vinyl acetate, isopropenyl acetate, 1-propenyl acetate, 2-methyl-1-propenyl acetate, 1,2-dimethyl-1-propenyl acetate, Examples include vinyl propionate, isopropenyl propionate, 1-propenyl propionate, 2-methyl-1-propenyl propionate, 1,2-dimethyl-1-propenyl propionate, vinyl formate, vinyl benzoate and the like.

[Hydroxy compounds]
In the production method of the present invention, a wide range of hydroxy compounds (such as alcohols and phenols) can be used as reaction components. In the formula (2), the organic group in R ^5, may be any organic group which does not inhibit the reaction (e.g., non-reactive organic groups under the reaction conditions in the process), for example, the R ¹ , R ² , R ³ and R ⁴ are the same as the organic group. Typical organic groups include hydrocarbon groups and heterocyclic groups. Examples of the hydrocarbon group and the heterocyclic group include the same hydrocarbon groups and heterocyclic groups as those described above for R ¹ , R ² , R ³ and R ⁴ . The hydrocarbon group and heterocyclic group also include a hydrocarbon group having a substituent and a heterocyclic group (including a case where a ring is condensed to these). The substituent is not particularly limited as long as it does not inhibit the reaction, and examples thereof include the same substituents that the hydrocarbon group and heterocyclic group in R ¹ and the like may have. k means the number of hydroxyl groups bonded to R ⁵ and represents a natural number. k is usually 1 to 20, preferably 1 to 15 and more preferably about 1 to 10.

  Hydroxy compounds include primary alcohols, secondary alcohols, tertiary alcohols, phenols and the like. The hydroxy compound may have a plurality of hydroxyl groups, and may be any of monohydric alcohol, dihydric alcohol, polyhydric alcohol, monohydric phenol, dihydric phenol, polyhydric phenol, and the like.

  Typical primary alcohols include, for example, methanol, ethanol, 1-propanol, 1-butanol, 2-methyl-1-propanol, 1-hexanol, 1-octanol, 1-decanol, 1-hexadecanol, 2-buten-1-ol, ethylene glycol, trimethylene glycol, glycerin, hexamethylene glycol, pentaerythritol and the like saturated or unsaturated having about 1 to 30 carbon atoms (preferably 1 to 20, more preferably 1 to 15) Aliphatic primary alcohols; saturated or unsaturated alicyclic primary alcohols such as cyclohexylmethyl alcohol and 2-cyclohexylethyl alcohol; aromatic primary alcohols such as benzyl alcohol, 2-phenylethyl alcohol and cinnamon alcohol; 2-hydroxymethyl And heterocyclic primary alcohols, such as lysine. Examples of the primary alcohol having a substituent at the hydrocarbon moiety include glycolic acid esters such as methyl glycolate and ethyl glycolate; alkylene glycol monoalkyl ethers such as ethylene glycol monomethyl ether; alkylenes such as ethylene glycol monoacetate And glycol monoesters.

Typical secondary alcohols include, for example, 2-propanol, sec-butyl alcohol, 2-pentanol, 3-pentanol, 3,3-dimethyl-2-butanol, 2-octanol, 4-decanol, 2 -C3-C30 (preferably vicinal diols such as hexadecanol, 2-penten-4-ol, glycerin, 1,2-propanediol, 2,3-butanediol and 2,3-pentanediol (preferably 3-20, more preferably 3-15) saturated or unsaturated aliphatic secondary alcohols; 1-cyclopentylethanol, 1-cyclohexylethanol, and the like, an aliphatic hydrocarbon group to a carbon atom to which a hydroxyl group is bonded. A secondary alcohol in which an alicyclic hydrocarbon group (such as a cycloalkyl group) is bonded; cyclobutanol, Clopentanol, cyclohexanol, cyclooctanol, cyclododecanol, 2-cyclohepten-1-ol, 2-cyclohexen-1-ol, 2-adamantanol, 2-adamantanol having an oxo group in the adamantane ring, 2-hydroxy Norbornane, 3-hydroxytetracyclo [4.4.0.1 ^2,5 . 1 ^{7, 10} ] dodecane and other saturated or unsaturated alicyclic secondary alcohols (bridged) of about 3 to 20 members (preferably 3 to 15 members, more preferably 5 to 15 members, especially 5 to 8 members) Cyclic secondary alcohols); aromatic secondary alcohols such as 1-phenylethanol, 1-phenylpropanol, 1-phenylmethylethanol, diphenylmethanol; heterocyclics such as 1- (2-pyridyl) ethanol Secondary alcohol is exemplified.

  As a typical tertiary alcohol, for example, a saturated or unsaturated aliphatic group having about 4 to 30 carbon atoms (preferably 4 to 20, more preferably 4 to 15) such as t-butyl alcohol and t-amyl alcohol. Tertiary alcohol; aliphatic hydrocarbon group and alicyclic hydrocarbon group (cycloalkyl group, bridged cyclic hydrocarbon group, etc.) such as 1-cyclohexyl-1-methylethanol and the like bonded to hydroxyl group carbon atom Secondary alcohol to which 1 is bonded; a hydroxyl group and an aliphatic group on one carbon atom constituting an alicyclic ring (cycloalkane ring, bridged carbocycle, etc.) such as 1-methyl-1-cyclohexanol Tertiary alcohol to which a hydrocarbon group is bonded; a bridged carbocyclic ring-containing tertiary alcohol having a hydroxyl group at the bridge head position of the bridged carbocycle such as 1-adamantanol Call; 1-phenyl-1-aromatic tertiary alcohols such as methyl ethanol; 1-methyl-1- (2-pyridyl), such as heterocyclic tertiary alcohols such as ethanol.

  Representative phenols include, for example, compounds in which a hydroxyl group is bonded to an aromatic carbocycle such as phenol, cresol, 1-hydroxynaphthalene; 2-hydroxypyridine, 3-hydroxypyridine, 4-hydroxypyridine, 3 Examples include compounds in which a hydroxyl group is bonded to an aromatic heterocyclic ring such as -hydroxyfuran and 3-hydroxythiophene. Each representative compound of the above hydroxy compounds may have various substituents as long as the reaction is not inhibited.

（式中、環Ｚは下記式（６）〜（13）

（式中、Ｘ¹、Ｘ²、Ｘ³、Ｘ⁴、Ｘ⁵、Ｘ⁶、Ｘ⁷、Ｘ⁸は、各環を構成する原子に結合している置換基であり、ハロゲン原子、アルキル基、ハロアルキル基、アリール基、保護基で保護されていてもよいヒドロキシル基、保護基で保護されていてもよいヒドロキシメチル基、保護基で保護されていてもよいアミノ基、保護基で保護されていてもよいカルボキシル基、保護基で保護されていてもよいスルホ基、オキソ基、ニトロ基、シアノ基、又は保護基で保護されていてもよいアシル基を示す。Ｘ¹が２以上の場合、それらは互いに結合して、式中のシクロヘキサン環を構成する炭素原子と共に４員以上の環を形成していてもよい。ａ、ｂ、ｃ、ｄ、ｅ、ｆ、ｇ、ｈは０以上の整数を示す。ａ、ｂ、ｃ、ｄ、ｅ、ｆ、ｇ又はｈが２以上の場合、括弧内の置換基は同一であってもよく異なっていてもよい。ｐ、ｑ、ｒは０〜３の整数を示す）
で表される何れかの環式基を示し、Ｗ¹は２価の炭化水素基を示す。ｎは０又は１を示し、ｍは１〜８の整数を示す。ｍが２以上の場合、括弧内の基は同一であってもよく異なっていてもよい］
で表される脂環式炭素骨格又はラクトン骨格を有するヒドロキシ化合物が含まれる。 Further, preferred hydroxy compounds include the following formula (5):

(In the formula, ring Z represents the following formulas (6) to (13)

(In the formula, X ¹ , X ² , X ³ , X ⁴ , X ⁵ , X ⁶ , X ⁷ , X ⁸ are substituents bonded to the atoms constituting each ring, halogen atoms, alkyl groups , A haloalkyl group, an aryl group, a hydroxyl group that may be protected with a protecting group, a hydroxymethyl group that may be protected with a protecting group, an amino group that may be protected with a protecting group, or a group that is protected with a protecting group A carboxyl group that may be protected, a sulfo group that may be protected with a protecting group, an oxo group, a nitro group, a cyano group, or an acyl group that may be protected with a protecting group, when X ¹ is 2 or more, They may be bonded to each other to form a 4-membered or higher ring together with the carbon atoms constituting the cyclohexane ring in the formula, wherein a, b, c, d, e, f, g, and h are 0 or more. An integer, where a, b, c, d, e, f, g or h is 2 or more And the substituents in parentheses may be the same or different. P, q, and r represent an integer of 0 to 3)
And W ¹ represents a divalent hydrocarbon group. n represents 0 or 1, and m represents an integer of 1 to 8. when m is 2 or more, the groups in parentheses may be the same or different.]
Hydroxy compounds having an alicyclic carbon skeleton or a lactone skeleton represented by the formula:

X ¹ , X ² , X ³ , X ⁴ , X ⁵ , X ⁶ , X ⁷ , X ⁸ are each ring (ring shown in the formula, for example, cyclohexane ring, adamantane ring, norbornane ring, tetracyclo [4.4 .0.1 ^{2,5 .1,7,10} ] dodecane ring, 4-oxatricyclo [5.2.1.0 ^2,6 ] decane-3,5-dione ring, γ-butyrolactone ring, 4-oxa Tricyclo [5.2.1.0 ^2,6 ] decan-3-one ring, 3-oxatricyclo [4.2.1.0 ^4,8 ] nonan-2-one ring, 3-oxatricyclo [4.3.1.1 ^4,8 ] represents a substituent bonded to the atoms constituting the undecan-2-one ring and the like. Examples of the halogen atom in X ^{1 and the} like include a fluorine atom, a chlorine atom, and a bromine atom. Examples of the alkyl group in X ¹ include a C _1-10 alkyl group (preferably a C _1-5 alkyl group) such as methyl, ethyl, propyl, isopropyl, butyl, hexyl, and decyl group. Examples of the haloalkyl group in X ^{1 and the} like include C _1-10 haloalkyl groups such as chloromethyl, trifluoromethyl, and pentafluoroethyl groups (preferably C _1-5 haloalkyl groups). Examples of the aryl group in X ^{1 and the} like include phenyl and naphthyl groups. The aromatic ring of the aryl group includes, for example, a halogen atom such as a fluorine atom, a C _1-4 alkyl group such as a methyl group, a C _1-5 haloalkyl group such as a trifluoromethyl group, a C _1-4 such as a hydroxyl group and a methoxy group. It may have a substituent such as an alkoxy group such as an alkoxy group, amino group, dialkylamino group, carboxyl group or methoxycarbonyl group, an acyl group such as nitro group, cyano group or acetyl group.

As a protecting group such as a hydroxyl group, a hydroxymethyl group, a carboxyl group, a sulfo group, and an amino group in X ^{1 and the} like, a protecting group commonly used in the field of organic synthesis can be used. Examples of the acyl group in X ¹ include C _1-6 aliphatic acyl groups such as formyl, acetyl, propionyl, butyryl, isobutyryl, and pivaloyl groups; aromatic acyl groups such as acetoacetyl groups; benzoyl groups, and the like. . As the protecting group for the acyl group, a protecting group conventionally used in the field of organic synthesis can be used. Examples of the protected form of the acyl group include acetal (including hemiacetal).

When X ¹ is 2 or more, they are bonded to each other to form a 4-membered or more ring formed together with the carbon atom constituting the cyclohexane ring in the formula (6), for example, cyclopentane ring, cyclohexane ring, perhydro Examples thereof include alicyclic carbon rings such as naphthalene ring (decalin ring); lactone rings such as γ-butyrolactone ring and δ-valerolactone ring.

  a, b, c, d, e, f, g and h are, for example, an integer of 0 to 5, preferably an integer of 0 to 3.

W ¹ represents a divalent hydrocarbon group. The divalent hydrocarbon group includes a divalent aliphatic hydrocarbon group, a divalent alicyclic hydrocarbon group, a divalent aromatic hydrocarbon group, and a hydrocarbon group in which two or more of these are bonded. One or more monovalent hydrocarbon groups (aliphatic hydrocarbon group, alicyclic hydrocarbon group, aromatic hydrocarbon group or hydrocarbon group in which two or more of these are bonded) are bonded to these hydrocarbon groups. It may be. The divalent hydrocarbon group includes a hydrocarbon group having a substituent. Examples of the substituent include the same groups as the substituent X ^{1 of the} ring Z.

  Representative examples of divalent hydrocarbon groups include, for example, alkylene groups such as methylene, methylmethylene, ethylmethylene, dimethylmethylene, ethylmethylmethylene, ethylene, trimethylene, and tetramethylene groups; alkenylene groups such as propenylene groups; 1 , 3-cyclopentylene, 1,2-cyclohexylene, 1,3-cyclohexylene, cycloalkylene groups such as 1,4-cyclohexylene group; cycloalkylidene groups such as cyclopentylidene, cyclohexylidene group An arylene group such as a phenylene group; a benzylidene group;

（式中、Ｒ⁷及びＲ⁸は、同一又は異なって、水素原子又は炭化水素基を示す。Ｒ⁷及びＲ⁸は、互いに結合して、隣接する炭素原子と共に脂環式環を形成していてもよい）
で表される基が含まれる。 Preferred examples of W ¹ include, for example, the following formula (14)

(In the formula, R ⁷ and R ⁸ are the same or different and each represents a hydrogen atom or a hydrocarbon group. R ⁷ and R ⁸ are bonded to each other to form an alicyclic ring together with adjacent carbon atoms. May be)
The group represented by these is included.

Examples of the hydrocarbon group for R ⁷ and R ⁸ include the same groups as the hydrocarbon groups for R ¹ and the like. The hydrocarbon group includes a hydrocarbon group having a substituent. Examples of the substituent include the same group as the substituent that the hydrocarbon group in R ¹ and the like may have, or the same group as the substituent X ¹ and the like of the ring Z and the like.

R ⁷ and R ⁸ are preferably hydrogen atoms; C _1-10 alkyl groups such as methyl, ethyl, propyl, isopropyl and butyl groups (particularly C _1-5 alkyl groups); substituents such as cyclopentyl groups and cyclohexyl groups. A cycloalkyl group optionally having a substituent; a bridged cyclic group optionally having a substituent such as a norbornan-2-yl group and an adamantan-1-yl group. Examples of the substituent that the cycloalkyl group or the bridged cyclic group may have are, for example, the same as the above-described substituent X ¹ and the like, protected with a halogen atom, an alkyl group, a haloalkyl group, an aryl group, or a protective group. May be a hydroxyl group that may be protected with a protecting group, an amino group that may be protected with a protecting group, a carboxyl group that may be protected with a protecting group, or a group that is protected with a protecting group Examples thereof include a good sulfo group, an oxo group, a nitro group, a cyano group, and an acyl group which may be protected with a protecting group.

  m is preferably an integer of 1 to 4, more preferably an integer of 1 to 3.

  Typical examples of the hydroxy compound represented by the formula (5) include the following compounds. Examples of the hydroxy compound in which the ring Z is a group represented by the formula (6) include 1,2-cyclohexanediol, 1,3-cyclohexanediol, 1,4-cyclohexanediol, cis-3,3,5-trimethyl. -1-cyclohexanol, trans-3,3,5-trimethyl-1-cyclohexanol, 2-isopropyl-5-methyl-1-cyclohexanol (menthol), 2-hydroxy-7-oxabicyclo [3.2. 1] and octane-6-one.

  Examples of the hydroxy compound in which the ring Z is a group represented by the formula (7) include 2-methyl-2-adamantanol, 1,3-adamantanediol, 1,3,5-adamantanetriol, 1,3,5 , 7-adamantanetetraol, 3,5-dimethyl-1-adamantanol, 5,7-dimethyl-1,3-adamantanediol, 4-oxo-1-adamantanol, 3-hydroxy-α, α-dimethyl- Examples include 1-adamantane methanol, 1-adamantane methanol, α, α-dimethyl-1-adamantane methanol, α, α, α ′, α′-tetramethyl-1,3-adamantane dimethanol and the like.

Examples of the hydroxy compound in which the ring Z is a group represented by the formula (8) include 2,5-norbornanediol, 2,3-norbornanediol, 5-methoxycarbonyl-2-hydroxynorbornane, α-methyl-α- (Norbornan-2-yl) -2-norbornanemethanol, 2-norbornanemethanol, α, α-dimethyl-2-norbornanemethanol, 3,4-dihydroxytetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodecane, 3,8-dihydroxytetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodecane, 3-tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodecane methanol, 8-hydroxy-3-tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodecane methanol, 9-hydroxy-3-tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodecane methanol and the like.

Examples of the hydroxy compound in which the ring Z is a group represented by the formula (9) include, for example, 8-hydroxy-4-oxatricyclo [5.2.1.0 ^2,6 ] decane-3,5-dione, 4 -Hydroxy-11-oxapentacyclo [6.5.1.1 ^3,6 . 0 ^2,7 . 0 ^{9, 13]} such as pentadecane-10,12-dione, and the like.

Examples of the hydroxy compound in which the ring Z is a group represented by the formula (10) include α-hydroxy-γ, γ-dimethyl-γ-butyrolactone, α-hydroxy-α, γ, γ-trimethyl-γ-butyrolactone, α-hydroxy-γ, γ-dimethyl-β-methoxycarbonyl-γ-butyrolactone, 8-hydroxy-4-oxatricyclo [5.2.1.0 ^2,6 ] decan-3-one, 9-hydroxy- 4-oxatricyclo [5.2.1.0 ^2,6 ] decan-3-one, 8,9-dihydroxy-4-oxatricyclo [5.2.1.0 ^2,6 ] decane-3- ON etc. are mentioned.

  Examples of the hydroxy compound in which the ring Z is a group represented by the formula (11) include 4-hydroxy-2,7-dioxabicyclo [3.3.0] octane-3,6-dione.

Examples of the hydroxy compound in which the ring Z is a group represented by the formula (12) include 5-hydroxy-3-oxatricyclo [4.2.1.0 ^4,8 ] nonan-2-one, 5-hydroxy -5-methyl-3-oxatricyclo [4.2.1.0 ^4,8 ] nonan-2-one, 5-hydroxy-9-methyl-3-oxatricyclo [4.2.1.0 ^{4 , 8} ] nonan-2-one and the like.

Examples of the hydroxy compound in which ring Z is a group represented by formula (13) include, for example, 6-hydroxy-3-oxatricyclo [4.3.1.1 ^4,8 ] undecan-2-one, 6,8. -Dihydroxy-3-oxatricyclo [4.3.1.1 ^4,8 ] undecan-2-one and the like.

  Since the vinyl ether compound obtained from the hydroxy compound represented by formula (5) has an alicyclic skeleton or a lactone skeleton, functions such as transparency, dry etching resistance, and substrate adhesion when used as a constituent monomer of the polymer Is particularly useful as a raw material monomer for resist resins.

（式中、Ｒ⁹、Ｒ¹⁰、Ｒ¹¹、Ｒ¹²は、同一又は異なって、水素原子、又は置換若しくは非置換の炭化水素基を示す。Ｗ²は単結合又は連結基を示す。Ａｒは２価の芳香族炭化水素基を示す。ｓは０〜４の整数、ｔは０〜４の整数、ｕは１〜６の整数、ｖは０〜５の整数、ｗは０又は１を示す。式中に示されるｓ個の基、ｔ個の基、ｕ個の基、ｖ個の基は、複数個の場合、それぞれ、同一であっても異なっていてもよい）
で表される芳香族系ビニルエーテル化合物が含まれる。 Furthermore, preferred hydroxy compounds include the following formula (15):

(Wherein R ⁹ , R ¹⁰ , R ¹¹ and R ¹² are the same or different and each represents a hydrogen atom or a substituted or unsubstituted hydrocarbon group. W ² represents a single bond or a linking group. Ar represents A divalent aromatic hydrocarbon group, s is an integer of 0 to 4, t is an integer of 0 to 4, u is an integer of 1 to 6, v is an integer of 0 to 5, and w is 0 or 1. In the case where there are a plurality of s groups, t groups, u groups and v groups shown in the formula, they may be the same or different.
The aromatic vinyl ether compound represented by these is included.

In the formula (15), the hydrocarbon group in R ⁹ , R ¹⁰ , R ¹¹ , R ¹² is an aliphatic hydrocarbon group, an alicyclic hydrocarbon group, an aromatic hydrocarbon group, or a group in which a plurality of these are bonded. Is included. Examples of the aliphatic hydrocarbon group include linear or branched alkyl groups such as methyl, ethyl, propyl, isopropyl, butyl, and hexyl groups (for example, alkyl groups having about 1 to 6 carbon atoms); vinyl Alkenyl groups such as allyl groups (for example, alkenyl groups having about 2 to 6 carbon atoms); alkynyl groups such as propynyl groups (for example, alkynyl groups having about 2 to 6 carbon atoms). Examples of the alicyclic hydrocarbon group include monocyclic or polycyclic alicyclic hydrocarbon groups having about 3 to 15 members, such as cyclopropyl, cyclopentyl, and cyclohexyl groups. Examples of the aromatic hydrocarbon group include monocyclic or polycyclic aromatic hydrocarbon groups having about 6 to 20 carbon atoms such as phenyl and naphthyl groups. Examples of the group in which a plurality of aliphatic hydrocarbon groups and the like are bonded include aralkyl groups such as benzyl and 2-phenylethyl groups.

  These hydrocarbon groups include various substituents such as halogen atoms, oxo groups, hydroxyl groups, substituted oxy groups (eg, alkoxy groups, aryloxy groups, aralkyloxy groups, acyloxy groups), carboxyl groups, substituted oxy groups. Has a carbonyl group (alkoxycarbonyl group, aryloxycarbonyl group, aralkyloxycarbonyl group, etc.), substituted or unsubstituted carbamoyl group, cyano group, nitro group, substituted or unsubstituted amino group, sulfo group, heterocyclic group, etc. It may be. The hydroxyl group, carboxyl group, amino group and the like may be protected with a protective group commonly used in the field of organic synthesis.

R ⁹ and R ¹⁰ , R ¹¹ and R ¹² may be bonded to each other to form a ring together with adjacent carbon atoms. Examples of such a ring include a 3- to 8-membered cycloalkane ring such as a cyclopropane ring, a cyclobutane ring, a cyclopentane ring, and a cyclohexane ring.

R ⁹ , R ¹⁰ , R ¹¹ , and R ¹² include a hydrogen atom; an alkyl group having 1 to 4 carbon atoms such as a methyl and ethyl group; a 3 to 6 membered cycloalkyl group; a substituted or unsubstituted phenyl group, and the like. A hydrogen atom or a methyl group is particularly preferable.

In the formula (15), the linking group in W ² may be a divalent group such as an alkylene group, alkenylene group, arylene group, oxygen atom (ether bond), sulfur atom (thioether bond), substituent. A —NH— group, a carbonyl group, a thiocarbonyl group, a sulfonyl group (—SO ₂ —), an ester bond (—COO—), an amide bond (—CONH—), and a plurality of these bonded A bivalent group etc. are mentioned. Examples of the alkylene group include linear or branched alkylene groups having about 1 to 6 carbon atoms such as methylene, ethylene, propylene, dimethylmethylene, trimethylene, tetramethylene, pentamethylene, and hexamethylene groups. . W ² is particularly preferably a single bond, a linear or branched alkylene group having 1 to 4 carbon atoms, an arylene group, an oxygen atom, a sulfur atom, a carbonyl group, a thiocarbonyl group, or a sulfonyl group.

  Examples of the divalent aromatic hydrocarbon group (arylene group) shown as Ar include a phenylene group and a naphthylene group. The aromatic ring constituting the divalent aromatic hydrocarbon group may have a substituent. Examples of such substituents include halogen atoms, alkyl groups (for example, alkyl groups having 1 to 4 carbon atoms such as methyl, ethyl, propyl, and butyl groups), and alkenyl groups (for example, vinyl and allyl groups). Alkenyl group having 2 to 4 carbon atoms, etc.), haloalkyl group (for example, haloalkyl group having 1 to 3 carbon atoms such as chloromethyl, trifluoromethyl group, etc.), aryl group (for example, phenyl group, naphthyl group, etc.), acyl Group (acyl group having about 1 to 6 carbon atoms such as acetyl group), acyloxy group (acyloxy group having about 1 to 6 carbon atoms such as acetoxy group), alkoxy group (methoxy, ethoxy group, etc. About 6 alkoxy groups), hydroxyl group, hydroxymethyl group, substituted or unsubstituted amino group, carboxyl group, sulfo group, nitro group, shear Such as a group, and the like. The hydroxyl group, hydroxymethyl group, amino group, carboxyl group and the like may be protected with a protective group commonly used in the field of organic synthesis. In addition, when there are a plurality of substituents, these substituents may be bonded to form an alicyclic ring together with carbon atoms constituting the aromatic ring.

  In formula (15), s and t are preferably integers of 0 to 2 (particularly 0 or 1), and u and v are preferably integers of 1 to 3.

The following compounds are illustrated as a typical compound represented by Formula (15).
(A) Compounds where w = 0 and s = 0: hydroquinone, resorcinol, catechol, 1,3,5-trihydroxybenzene, 1,5-dihydroxynaphthalene, etc. (b) w = 0, s = 1, u = 1 compounds: (1-hydroxy-1-methylethyl) benzene, 1- (1-hydroxy-1-methylethyl) -4-methylbenzene, 1- (1-hydroxy-1-methylethyl) naphthalene and the like ( c) Compounds where w = 0, s = 1, u = 2-6: 1,2- (or 1,3-, 1,4-) bis (hydroxymethyl) benzene, 1,2- (or 1, 3-, 1,4-) bis (1-hydroxy-1-methylethyl) benzene, 1,2- (or 1,3-, 1,4-) bis (1-hydroxy-1-phenylethyl) benzene, 1,2,3- (or 1,2,4- 1,3,5) Tris (hydroxymethyl) benzene, 1,5-bis (hydroxymethyl) naphthalene, 1,5-bis (1-hydroxy-1-methylethyl) naphthalene, etc. (d) w = 0, s = Compounds having an integer of 2-4: 2-hydroxyethylbenzene, 3-hydroxypropylbenzene, etc. (e) Compounds having w = 1 and s = t = 0: 3,3 ′, 5,5′-tetrakis (hydroxy) Biphenyl, bis (3,5-dihydroxyphenyl) methane, 2,2-bis (3,5-dihydroxyphenyl) propane, (2,4-dihydroxyphenyl) -phenyl-ketone, bis (2-hydroxyphenyl) ketone, 4,4 '-(dihydroxy) diphenylsulfone, 4,4'-(dihydroxy) diphenylsulfone, (2,4-dihydroxypheny )-(4-hydroxyphenyl) -ketone, bis (2,4-dihydroxyphenyl) ketone, 2,2′-dihydroxy-1,1′-binaphthalene, etc. (f) w = 1 and s and t are 1 to 1 Compounds that are integers of 4: 4,4'-bis (1-hydroxy-1-methylethyl) biphenyl, bis [4- (1-hydroxy-1-methylethyl) phenyl] methane, 2,2-bis [4 -(1-hydroxy-1-methylethyl) phenyl] propane, bis [4- (1-hydroxy-1-methylethyl) phenyl] ether, bis [4- (1-hydroxy-1-methylethyl) phenyl] ketone Such

  The vinyl ether compound obtained from the hydroxy compound represented by the formula (15) is useful as a curing agent for cationic polymerization, and particularly a vinyl ether compound having a plurality of vinyl groups can impart high solvent resistance. Useful as a raw material monomer.

[reaction]
The reaction of the vinyl ester compound represented by the formula (1) and the hydroxy compound represented by the formula (2) is performed in the presence or absence of a solvent. Examples of the solvent include aliphatic hydrocarbons such as hexane, heptane, and octane; alicyclic hydrocarbons such as cyclohexane; aromatic hydrocarbons such as benzene, toluene, xylene, and ethylbenzene; chloroform, dichloromethane, 1,2- Halogenated hydrocarbons such as dichloroethane; ethers such as diethyl ether, dimethoxyethane, tetrahydrofuran and dioxane; ketones such as acetone and methyl ethyl ketone; esters such as methyl acetate, ethyl acetate, isopropyl acetate and butyl acetate; N, N-dimethylformamide; Amides such as N, N-dimethylacetamide; nitriles such as acetonitrile, propionitrile, and benzonitrile. These solvents are used alone or in admixture of two or more.

  The use amount of the vinyl ester compound represented by the formula (1) is, for example, 0.8 to 10 equivalents, preferably 1 to 10 equivalents relative to 1 equivalent of the hydroxy compound represented by the formula (2) (1 mol of the hydroxy group to be etherified). Is 1 to 5 equivalents, more preferably 1 to 2.5 equivalents, and particularly preferably about 1 to 1.25 equivalents. A large excess of the vinyl ester compound represented by the formula (1) may be used.

  In the present invention, the reaction is carried out in the presence of a base. Examples of the base include alkali metal hydroxides such as lithium hydroxide, sodium hydroxide, potassium hydroxide, and cesium hydroxide; alkaline earth metal hydroxides such as magnesium hydroxide, calcium hydroxide, and barium hydroxide; Alkali metal carbonates such as lithium carbonate, sodium carbonate, potassium carbonate, cesium carbonate; alkaline earth metal carbonates such as magnesium carbonate; alkali metal hydrogen carbonates such as lithium hydrogen carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, cesium hydrogen carbonate Examples include salt.

  The amount of the base used is, for example, 0.01 to 3 equivalents, preferably 0.1 to 2 equivalents, more preferably 1 equivalent to 1 equivalent of the hydroxy compound represented by the formula (2) (1 mol of the hydroxy group to be etherified). Is about 0.15 to 1.3 equivalents.

  The reaction may be performed in the presence of a polymerization inhibitor. The reaction temperature can be appropriately selected depending on the reaction components and the type of catalyst, and is, for example, about 50 to 170 ° C, preferably 70 to 150 ° C, and more preferably about 90 to 130 ° C. The reaction may be carried out at normal pressure or under reduced pressure or increased pressure. The atmosphere of the reaction is not particularly limited as long as the reaction is not inhibited, and may be any of an air atmosphere, a nitrogen atmosphere, an argon atmosphere, and the like.

  Further, the reaction can be carried out by any method such as batch, semi-batch and continuous methods. For example, while continuously or intermittently supplying one or more of the vinyl ester compound represented by the formula (1), the hydroxy compound represented by the formula (2), the transition element compound catalyst, and the base into the system. The reaction can be performed. In particular, when the vinyl ester compound represented by the formula (1) is continuously or intermittently supplied into the system, the yield of the target compound is often improved.

  The transition element compound catalyst is preferably added to the system under heating. When the reaction is carried out in this manner, the catalytic activity is maintained, the reaction proceeds smoothly, and the yield of the target compound can be further improved. The temperature of the reaction system when the catalyst is added to the system is more preferably 50 ° C. or higher (for example, 50 ° C. to reaction temperature). For example, when the reaction is performed by gradually raising the temperature of the solution containing the catalyst from room temperature to the desired reaction temperature, the reaction rate tends to decrease because the catalyst is deactivated.

  An important feature of the present invention is that the reaction is carried out while removing by-product water. When the vinyl ester compound represented by the formula (1) is reacted with the hydroxy compound represented by the formula (2), the vinyl ether compound as the target product and the carboxylic acid corresponding to the vinyl ester compound of the formula (1) ( RCOOH) is generated, but this carboxylic acid is trapped by the base in the system, and as a result, a salt of carboxylic acid and water are by-produced. In the present invention, the reaction is carried out while removing the by-produced water. By this operation, the yield of the vinyl ether compound is dramatically improved. If water produced as a by-product is present in the system as it is, the target product cannot be obtained in high yield because of catalyst deactivation or decomposition of raw material components.

  The method for removing water is not particularly limited. For example, the reaction is performed under reflux, and (i) a method of distilling water out of the system, preferably together with a reaction solvent, (ii) molecular sieve, anhydrous sodium sulfate, A method of capturing water by allowing a dehydrating agent such as anhydrous magnesium sulfate to exist in the system, and (iii) a method of separately providing a dehydrating zone such as a packed column packed with the dehydrating agent and circulating a part of the reaction solution therethrough Etc. In the method (i), as the reaction solvent in the case of distilling water out of the system together with the reaction solvent, a solvent that is azeotropic with water and can be separated from water, such as benzene, toluene, xylene, hexane, Cyclohexane and the like are preferable. The vinyl ester compound represented by the formula (1) can also be used as a reaction solvent that is distilled off together with water. The solvent distilled off together with water can be returned to the reaction system after being separated from water.

In the method of the present invention, the corresponding vinyl ether compound represented by the formula (3) is produced by the reaction under mild conditions. In formula (3), R ⁵ is the same as described above. k means the number of groups: —OR ⁶ bonded to R ⁵ , and represents a natural number. R ⁶ represents a hydrogen atom or a group represented by the formula (4). At least one (1 or more) of k R ⁶ is a group represented by the formula (4). The number of the group (substituted or unsubstituted vinyl group) represented by the formula (4) in the compound of the formula (3) which is the target compound is the ratio of the compound of the formula (1) and the compound of the formula (2). The amount of the base, the amount of the catalyst, the reaction temperature, the reaction time, and the like can be appropriately controlled.

  After completion of the reaction, the reaction product can be separated and purified by separation means such as filtration, concentration, distillation, extraction, crystallization, recrystallization, column chromatography, etc., or a separation means combining these. The vinyl ether compound represented by the formula (3) thus obtained is a raw material for fine chemicals such as pharmaceuticals and agricultural chemicals; a raw material for polymers such as resist resins, optical resins, transparent resins, crosslinkable resins, and curing for cationic polymerization. It can be used as an agent.

  Hereinafter, the present invention will be described in more detail based on examples, but the present invention is not limited to these examples.

Example 1 (referred to as a reference example)
The cooling pipe and the condensate were separated, the organic layer was returned to the reaction vessel, and a 200 ml reaction vessel equipped with a decanter for discharging the aqueous layer out of the system was charged with di-μ-chlorobis (1,5-cycloocta Diene) diiridium (I) [Ir (cod) Cl] ₂ (134.2 mg, 0.2 mmol), sodium carbonate (12.7 g, 0.12 mol), 1,4-cyclohexanediol (11.6 g, 0. 1). 1 mol), vinyl propionate (25 g, 0.25 mol), and toluene (60 ml) were charged, and the temperature was gradually raised to reflux. The reaction was carried out for 5 hours under reflux while removing by-product water with a decanter. When the reaction solution was analyzed by gas chromatography, the conversion of 1,4-cyclohexanediol was 94%, 74% for 1,4-cyclohexanediol divinyl ether and 10% for 1,4-cyclohexanediol monovinyl ether. It was produced in a yield.

Example 2
Sodium carbonate (12.7 g, 0.12 mol) was added to a 200 ml reaction vessel equipped with a decanter for separating the condenser and the condensate, returning the organic layer to the reaction vessel, and discharging the aqueous layer out of the system. 1,4-cyclohexanediol (11.6 g, 0.1 mol), vinyl propionate (25 g, 0.25 mol), and toluene (60 ml) were charged, and the temperature was gradually raised to reflux. Di-μ-chlorobis (1,5-cyclooctadiene) diiridium (I) [Ir (cod) Cl] ₂ (134.2 mg, 0.2 mmol) was added thereto, and water by-produced under reflux. Was removed with a decanter and allowed to react for 5 hours. When the reaction solution was analyzed by gas chromatography, the conversion of 1,4-cyclohexanediol was 96%, 86% of 1,4-cyclohexanediol divinyl ether and 2% of 1,4-cyclohexanediol monovinyl ether. It was produced in a yield.

Example 3
Sodium carbonate (6.36 g, 0.06 mol) was added to a 200 ml reaction vessel equipped with a decanter for separating the condenser and the condensate, returning the organic layer to the reaction vessel, and discharging the aqueous layer out of the system. After charging 1-octanol (13 g, 0.1 mol), vinyl propionate (15 g, 0.15 mol), and toluene (60 ml), the temperature was gradually raised to reflux. Di-μ-chlorobis (1,5-cyclooctadiene) diiridium (I) [Ir (cod) Cl] ₂ (67.1 mg, 0.1 mmol) was added thereto, and water by-produced under reflux. Was allowed to react for 3 hours. When the reaction solution was analyzed by gas chromatography, the conversion of 1-octanol was 95%, and (1-octyl) -vinyl ether was produced in a yield of 90%.

Comparative Example 1
In a 200 ml reaction vessel equipped with a condenser, sodium carbonate (6.36 g, 0.06 mol), 1-octanol (13 g, 0.1 mol), vinyl propionate (15 g, 0.15 mol), and toluene (60 ml) were added. After charging, the temperature was gradually raised to reflux. Di-μ-chlorobis (1,5-cyclooctadiene) diiridium (I) [Ir (cod) Cl] ₂ (67.1 mg, 0.1 mmol) was added thereto, and the mixture was reacted for 5 hours under reflux. It was. When the reaction solution was analyzed by gas chromatography, the conversion of 1-octanol was 15%, and (1-octyl) -vinyl ether was produced in a yield of 14%.

Example 4
Sodium carbonate (6.36 g, 0.06 mol) was added to a 200 ml reaction vessel equipped with a decanter for separating the condenser and the condensate, returning the organic layer to the reaction vessel, and discharging the aqueous layer out of the system. After charging 1-octanol (13 g, 0.1 mol), vinyl acetate (12.9 g, 0.15 mol), and toluene (60 ml), the temperature was gradually raised to reflux. Di-μ-chlorobis (1,5-cyclooctadiene) diiridium (I) [Ir (cod) Cl] ₂ (67.1 mg, 0.1 mmol) was added thereto, and water by-produced under reflux. Was allowed to react for 7 hours while removing with a decanter. When the reaction solution was analyzed by gas chromatography, the conversion of 1-octanol was 86%, and (1-octyl) -vinyl ether was produced in a yield of 80%.

Example 5
A condenser and a condensate were separated, the organic layer was returned to the reaction vessel, and a 300 ml autoclave equipped with a decanter for discharging the aqueous layer out of the system was charged with sodium carbonate (9.54 g, 0.09 mol), 1-Octanol (19.5 g, 0.15 mol), vinyl acetate (19.4 g, 0.23 mol), and toluene (90 ml) were charged, and the temperature was gradually raised to a liquid temperature of 100 ° C. To this was added di-μ-chlorobis (1,5-cyclooctadiene) diiridium (I) [Ir (cod) Cl] ₂ (100.7 mg, 0.15 mmol). The reaction was carried out for 3 hours in a closed system under reflux at a liquid temperature of 100 ° C. while removing by-product water with a decanter. When the reaction solution was analyzed by gas chromatography, the conversion of 1-octanol was 95%, and (1-octyl) -vinyl ether was produced in a yield of 90%.

Example 6
Sodium carbonate (12.7 g, 0.12 mol) was added to a 200 ml reaction vessel equipped with a decanter for separating the condenser and the condensate, returning the organic layer to the reaction vessel, and discharging the aqueous layer out of the system. 1,4-cyclohexanediol (11.6 g, 0.1 mol), vinyl acetate (21 g, 0.25 mol), and toluene (60 ml) were charged, and the temperature was gradually raised to reflux. Di-μ-chlorobis (1,5-cyclooctadiene) diiridium (I) [Ir (cod) Cl] ₂ (134.2 mg, 0.2 mmol) was added thereto, and water by-produced under reflux. Was allowed to react for 10 hours. When the reaction solution was analyzed by gas chromatography, the conversion of 1,4-cyclohexanediol was 92%, 1,4-cyclohexanediol divinyl ether was 81%, 1,4-cyclohexanediol monovinyl ether was 6%. It was produced in a yield.

Example 7
A condenser and a condensate were separated, the organic layer was returned to the reaction vessel, and a 300 ml autoclave equipped with a decanter for discharging the aqueous layer out of the system was charged with sodium carbonate (12.7 g, 0.12 mol), 1,4-Cyclohexanediol (11.6 g, 0.1 mol), vinyl acetate (21 g, 0.25 mol), and toluene (90 ml) were charged, and then the temperature was gradually raised to a liquid temperature of 100 ° C. To this was added di-μ-chlorobis (1,5-cyclooctadiene) diiridium (I) [Ir (cod) Cl] ₂ (134.2 mg, 0.2 mmol). The reaction was allowed to proceed for 5 hours in a closed system under reflux at a liquid temperature of 100 ° C. while removing by-product water with a decanter. When the reaction solution was analyzed by gas chromatography, the conversion of 1,4-cyclohexanediol was 99%, 1,4-cyclohexanediol divinyl ether was 87%, and 1,4-cyclohexanediol monovinyl ether was 1%. It was produced in a yield.

Example 8
In a 200 ml reaction vessel fitted with a condenser, sodium carbonate (6.36 g, 0.06 mol), 1-octanol (13 g, 0.1 mol), vinyl propionate (15 g, 0.15 mol), toluene (60 ml), and After charging molecular sieves 4A (10 g), the temperature was gradually raised to reflux. Di-μ-chlorobis (1,5-cyclooctadiene) diiridium (I) [Ir (cod) Cl] ₂ (67.1 mg, 0.1 mmol) was added thereto and reacted for 3 hours under reflux. It was. When the reaction solution was analyzed by gas chromatography, the conversion of 1-octanol was 92%, and (1-octyl) -vinyl ether was produced in a yield of 91%.

Example 9
In a 200 ml reaction vessel fitted with a condenser, sodium carbonate (6.36 g, 0.06 mol), 1-octanol (13 g, 0.1 mol), vinyl propionate (15 g, 0.15 mol), toluene (60 ml), and After charging anhydrous sodium sulfate (15 g), the temperature was gradually raised to reflux. Di-μ-chlorobis (1,5-cyclooctadiene) diiridium (I) [Ir (cod) Cl] ₂ (67.1 mg, 0.1 mmol) was added thereto and reacted for 3 hours under reflux. It was. When the reaction solution was analyzed by gas chromatography, the conversion of 1-octanol was 97%, and (1-octyl) -vinyl ether was produced in a yield of 88%.

Example 10
Sodium carbonate (6.36 g, 0.06 mol) was added to a 200 ml reaction vessel equipped with a decanter for separating the condenser and the condensate, returning the organic layer to the reaction vessel, and discharging the aqueous layer out of the system. After charging 1-octanol (13 g, 0.1 mol), vinyl propionate (15 g, 0.15 mol), and toluene (60 ml), the temperature was gradually raised to reflux. Di-μ-chlorobis (1,5-cyclooctadiene) diiridium (I) [Ir (cod) Cl] ₂ (67.1 mg, 0.1 mmol) was added thereto, and water by-produced under reflux. Was allowed to react for 3 hours. When the reaction solution was analyzed by gas chromatography, the conversion of 1-octanol was 97%, and (1-octyl) -vinyl ether was produced in a yield of 86%.

Claims (1)

In the presence of an alkali metal carbonate , an iridium compound catalyst is added to the system under heating at 50 ° C. or higher, and the following formula (1)

(Wherein R ¹ , R ² , R ³ and R ⁴ are the same or different and represent a hydrogen atom or an organic group)
And a vinyl ester compound represented by the following formula (2)

(Wherein R ⁵ represents an organic group and k represents a natural number)
And a hydroxy compound represented by the formula (3) corresponding to the following formula (3):

[Wherein R ⁵ and k are the same as defined above. R ⁶ is a hydrogen atom or the following formula (4)

(Wherein R ² , R ³ and R ⁴ are the same as above)
The group represented by these is shown. However, at least one of k R ⁶ is a group represented by the formula (4)]
A method for producing a vinyl ether compound, comprising producing a vinyl ether compound represented by the formula: