JP4895267B2 - Method for producing 3,6-epoxy-1,2,3,6-tetrahydrophthalic anhydride derivative - Google Patents

Description

  The present invention relates to a method for producing a 3,6-epoxy-1,2,3,6-tetrahydrophthalic anhydride derivative.

In recent years, (meth) acrylic acid esters having both an alicyclic skeleton and a lactone skeleton have been used as monomers for resist resins (see, for example, Patent Document 1). A 3,6-epoxy-1,2,3,6-tetrahydrophthalic anhydride derivative is useful as a synthetic intermediate of (meth) acrylic acid ester having both alicyclic skeleton and lactone skeleton.
As a method for producing this 3,6-epoxy-1,2,3,6-tetrahydrophthalic anhydride derivative, for example, Patent Document 2 discloses a Diels-Alder reaction of furan and maleic anhydride in an appropriate solvent. Is described.
WO02 / 046179 International Publication Pamphlet Special table 2002-520415 gazette

However, in the method described in Patent Document 2, when the reaction is performed at a high temperature, a Retro Diels-Alder reaction is caused, so that the reaction must be performed at room temperature. Moreover, when it was made to react at room temperature, there existed a problem that reaction time required 2 days.
An object of the present invention is to provide a process capable of producing the 3,6-epoxy-1,2,3,6-tetrahydrophthalic anhydride derivative in a short time and with good yield under mild conditions. .

The present invention provides a furan derivative represented by the following formula (1) in an organic solvent,
(In formula (1), R ₁ , R ₂ , R ₃ and R ₄ are each independently a hydrogen atom, a halogen atom, a formyl group, a cyano group, a carboxyl group, or an alkyl optionally having a substituent. A group, an alkoxy group, an alkylthio group, an alkoxycarbonyl group, an acyl group, an acyloxy group, an organic sulfinyl group, or an organic sulfonyl group.)
Maleic anhydride represented by the following formula (2):
Reacting in the presence of a Lewis acid having a boron atom ,
The present invention relates to a method for producing a 3,6-epoxy-1,2,3,6-tetrahydrophthalic anhydride derivative represented by the following formula (3).
(In formula (3), R ₁ , R ₂ , R ₃ and R ₄ have the same meanings as in formula (1).)

  According to the production method of the present invention, a 3,6-epoxy-1,2,3,6-tetrahydrophthalic anhydride derivative that is useful as a monomer raw material for a resist material in a short time and in a high yield under mild conditions. Can be manufactured.

First, the organic solvent used in the present invention will be described.
The organic solvent is not particularly limited as long as it does not adversely influence the reaction. For example, aliphatic hydrocarbons such as pentane, hexane, heptane, octane, petroleum ether; benzene, toluene, xylene, ethylbenzene, cumene, etc. Aromatic hydrocarbons; ethers such as diethyl ether, tetrahydrofuran, diisopropyl ether, dimethoxyethane, dibutyl ether, 1,4-dioxane; halogenated hydrocarbons such as dichloromethane, chloroform, carbon tetrachloride, dichloroethane, trichloroethane, chlorobenzene, dichlorobenzene Or a mixed solvent thereof.

Among these, tetrahydrofuran, toluene, diisopropyl ether or hexane is preferable from the viewpoint of yield. When tetrahydrofuran, toluene, diisopropyl ether, or hexane is used, the Retro Diels-Alder reaction tends to be suppressed.
Although the usage-amount of an organic solvent is not restrict | limited in particular, It is preferable that it is the range of 10-10000 mass parts with respect to 100 mass parts of furan derivatives mentioned later. When the amount of the organic solvent used is 10 parts by mass or more, the yield tends to be improved, and when it is 10000 parts by mass or less, the reaction time tends to be shortened. The lower limit of the amount of the organic solvent used is more preferably 100 parts by mass or more, and the upper limit is preferably 1000 parts by mass or less.

Next, the following general formula (1) will be described.

In the furan derivative represented by the general formula (1), R ₁ , R ₂ , R ₃ and R ₄ each independently have a hydrogen atom, a halogen atom, a formyl group, a cyano group, a carboxyl group or a substituent. And an alkyl group, an alkoxy group, an alkylthio group, an alkoxycarbonyl group, an acyl group, an acyloxy group, an organic sulfinyl group, and an organic sulfonyl group, which may be present.
Hereinafter, R _{1 to} R ₄ will be described.
The halogen atom is not particularly limited, and examples thereof include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

Although it does not restrict | limit especially as an alkyl group of the alkyl group which may have a substituent, A branched or linear C1-C10 alkyl group is preferable. The alkyl group of the alkyl group which may have a substituent particularly preferably has 1 to 6 carbon atoms, for example, methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, tert-butyl group, A hexyl group etc. are mentioned.
The substituent of the alkyl group which may have a substituent is not particularly limited, and examples thereof include halogen atoms such as fluorine atom, chlorine atom, bromine atom and iodine atom; methoxy group, ethoxy group, propoxy group, butoxy group And alkoxy groups such as tert-butyldimethylsilyloxy group and tert-butyldiphenylsilyloxy group. Here, the carbon number of the alkoxy group as a substituent of the alkyl group is not particularly limited, but 1 to 6 is preferable. Moreover, the carbon number of the alkyl group in the silyloxy group is not particularly limited, but 1 to 6 is preferable. The trisubstituted silyloxy group refers to a silyloxy group substituted with three substituents selected from an alkyl group and a phenyl group.

The alkoxy group is not particularly limited, and examples thereof include linear or branched alkoxy groups such as methoxy group, ethoxy group, propoxy group, and butoxy group. The number of carbon atoms of the alkoxy group is not particularly limited, but 1 to 10 is preferable and 1 to 6 is particularly preferable.
The alkylthio group is not particularly limited, and examples thereof include linear or branched alkylthio groups such as a methylthio group, an ethylthio group, a propylthio group, and a butylthio group. The number of carbon atoms of the alkylthio group is not particularly limited, but 1 to 10 is preferable, and 1 to 6 is particularly preferable.

The alkoxycarbonyl group is not particularly limited, and examples thereof include alkoxycarbonyl groups such as a methoxycarbonyl group, an ethoxycarbonyl group, and a tert-butoxycarbonyl group. The number of carbon atoms of the alkoxycarbonyl group is not particularly limited, but 1 to 10 is preferable, and 1 to 6 is particularly preferable.
The acyl group is not particularly limited, and examples thereof include alkanoyl groups such as acetyl group, propanoyl group, butanoyl group and pivaloyl group; and aroyl groups such as benzoyl group. The number of carbon atoms of the alkanoyl group is not particularly limited, but is preferably 2 to 10, and particularly preferably 2 to 6.
The acyloxy group is not particularly limited, and examples thereof include alkanoyloxy groups such as acetoxy group, propanoyloxy group, butanoyloxy group and pivaloyloxy group; and aroyloxy groups such as benzoyloxy group. The number of carbon atoms of the alkanoyloxy group is not particularly limited, but is preferably 2 to 10, and particularly preferably 2 to 6.

The organic sulfinyl group is a sulfinyl group to which an organic group is bonded, and includes an alkylsulfinyl group which may have a substituent, an arylsulfinyl group which may have a substituent, and the like. The alkyl part of the alkylsulfinyl group is not particularly limited, but an alkyl group having 1 to 6 carbon atoms is preferable. Examples of the aryl moiety of the arylsulfinyl group include a phenyl group.
The substituent that the alkylsulfinyl group may have is not particularly limited, and examples thereof include an alkoxy group (preferably an alkoxy group having 1 to 6 carbon atoms), a halogen atom, a cyano group, and a nitro group. Examples of the substituent that the arylsulfinyl group may have on the aromatic ring include an alkyl group (preferably an alkyl group having 1 to 6 carbon atoms) and an alkoxy group (preferably an alkoxy group having 1 to 6 carbon atoms). , Halogen atom, cyano group, nitro group and the like.
Specific examples of the organic sulfinyl group include a methanesulfinyl group, an ethanesulfinyl group, a benzenesulfinyl group, and a p-toluenesulfinyl group.

The organic sulfonyl group is a sulfonyl group to which an organic group is bonded, and has an alkylsulfonyl group which may have a substituent, an arylsulfonyl group which may have a substituent, a halosulfonyl group, and a substituent. And an alkoxysulfonyl group which may be present. The alkyl part of the alkylsulfonyl group is preferably an alkyl group having 1 to 6 carbon atoms, and the alkoxy part of the alkoxysulfonyl group is preferably an alkoxy group having 1 to 6 carbon atoms. Examples of the aryl moiety of the arylsulfonyl group include a phenyl group.
Examples of the substituent that the alkylsulfonyl group and alkoxysulfonyl group may have include an alkoxy group (preferably an alkoxy group having 1 to 6 carbon atoms), a halogen atom, a cyano group, and a nitro group. Examples of the substituent that the arylsulfonyl group may have on the aromatic ring include an alkyl group (preferably an alkyl group having 1 to 6 carbon atoms) and an alkoxy group (preferably an alkoxy group having 1 to 6 carbon atoms). , Halogen atom, cyano group, nitro group and the like. As a halogen atom which a halosulfonyl group has, a chlorine atom, a bromine atom, etc. are mentioned, for example.

Specific examples of the organic sulfonyl group include, for example, a methanesulfonyl group, an ethanesulfonyl group, a benzenesulfonyl group, a p-toluenesulfonyl group, a chlorosulfonyl group, a bromosulfonyl group, a methoxysulfonyl group, an ethoxysulfonyl group, and a trifluoromethoxysulfonyl group. Etc.
Having described R ₁ to R _4, in the groups described above, in terms of ease of availability, hydrogen atom is preferable.

Next, the non-maleic acid represented by the following formula (2) will be described.

A commercially available maleic anhydride represented by the formula (2) can be used.
Although the usage-amount of maleic anhydride is not specifically limited, The range of 5-2000 mol part is preferable with respect to 100 mol part of furan derivatives represented by Formula (1). When the amount of maleic anhydride used is 5 mol parts or more, the yield and reaction time tend to be shortened, and when it is 2000 mol parts or less, the reaction time tends to be shortened. The lower limit of the amount of maleic anhydride used is more preferably 15 parts by mole or more, and the upper limit is more preferably 500 parts by mole or less.

Next, the Lewis acid will be described.
The Lewis acid that can be used in the present invention is not particularly limited, but examples thereof include aluminum compounds such as anhydrous aluminum chloride, aluminum bromide, diethylaluminum chloride; gallium bromide, gallium iodide, anhydrous ferric chloride, anhydrous bromide Metals belonging to Group 4 and Group 5 such as ferric, zinc chloride, zinc bromide, zinc iodide, titanium chloride, titanium iodide, anhydrous stannous chloride, stannous bromide, anhydrous stannic chloride Compounds contained: Hydrofuran complex salt (BH ₃ .THF), borane-dimethyl sulfide complex salt (BH _3. (CH ₃ ) ₂ S), boron trichloride, boron tribromide, boron trifluoride-diethyl ether complex salt (BF _{3 · (C 2 H 5) 2} O), chloroborane - diethyl ether complex _{(BH 2 Cl · (C 2} H 5) 2 O), chloroborane - dimethyl sulfide complex (BH ₂ Cl (CH _{3) 2} S), dichloroborane - dimethyl sulfide complex _{(BHCl 2 · (CH 3)} 2 S), Buromoboran - dimethyl sulfide complex _{(BH 2 Br · (CH 3} ) 2 S), dibromo borane - dimethyl sulfide complex Borane compounds such as (BHBr _2. (CH ₃ ) ₂ S); 4,6-trimethylbenzoyloxy) borane, bis (chloroacetoxy) borane, triacetoxyborane, tri (fluoroacetoxy) borane, tripropionyloxyborane, tri Acyloxyborane compounds such as acryloyloxyborane and trimethacryloyloxyborane; Dioxoborane compounds such as α- [2,6-bis (isopropoxy) benzoyl] oxy-5-oxo-1,3,2-dioxaborane; 4-isopropyl- 3-paratoluenesulfonyl-1 3,2 Okisazaborijin 5-one, and the like Okisazaborijin compounds such as 4-t-butyl-3-p-toluenesulfonyl-1,3,2 Okisazaborijin 5-one.

  Among these, anhydrous aluminum chloride, anhydrous ferric chloride, zinc chloride, borane-tetrahydrofuran complex, borane-dimethyl sulfide complex, boron trichloride, boron tribromide, boron trifluoride-diethyl ether complex, chloroborane-diethyl ether Using boron compounds such as complex salts, chloroborane-dimethylsulfide complex salts, dichloroborane-dimethylsulfide complex salts, bromoborane-dimethylsulfide complex salts, dibromoborane-dimethylsulfide complex salts, the above acyloxyborane compounds, the above dioxoborane compounds or the above oxazaboridine compounds. It is particularly preferable to use a boron compound from the viewpoint of ease of post-treatment operation and obtaining a target compound with high selectivity.

  Although the usage-amount of a Lewis' acid is not restrict | limited in particular, It is preferable that it is the range of 0.1-100 mol part with respect to 100 mol part of furan derivatives represented by Formula (1). When the amount of Lewis acid used is 0.1 mol part or more, the reaction time tends to be shortened and the yield tends to improve, and when it is 100 mol part or less, the production of by-products tends to decrease. . The lower limit of the amount of Lewis acid used is more preferably 0.5 mol parts or more, and the lower limit is more preferably 20 mol parts or less.

  In the present invention, the reaction temperature is not particularly limited, but is preferably in the range of -80 ° C to 80 ° C. When the reaction temperature is -80 ° C or higher, the reaction time is shortened and the yield tends to be improved. When the reaction temperature is 80 ° C or lower, the Retro Diels-Alder reaction tends to be suppressed and the yield is improved. There is a tendency. The lower limit of the reaction time is more preferably −20 ° C. or higher, and the upper limit is more preferably 30 ° C. or lower.

In the present invention, the furan derivative represented by the above formula (1) and the maleic anhydride represented by the above formula (2) are reacted in the presence of a Lewis acid, and represented by the following formula (3). 3,6-epoxy-1,2,3,6-tetrahydrophthalic anhydride derivative is obtained.
In the formula (3), R ₁ , R ₂ , R ₃ and R ₄ have the same meaning as in the formula (1).

The 3,6-epoxy-1,2,3,6-tetrahydrophthalic anhydride derivative thus obtained can be isolated and purified by a method used for usual isolation and purification of organic compounds. it can.
For example, water is added to the reaction mixture, extraction is performed by adding an organic solvent such as pentane, hexane, petroleum ether, benzene, toluene, diethyl ether, diisopropyl ether, ethyl acetate, dichloromethane, chloroform, etc. Concentrate and purify the resulting crude product by recrystallization, distillation, chromatography or the like, if necessary. Depending on the reaction conditions, the product precipitates in the reaction system as the reaction proceeds, so the reaction solution after the reaction can be filtered off as it is, or the product is precipitated by cooling the reaction solution. And the obtained crystals can be isolated by filtration.

EXAMPLES Hereinafter, although an Example demonstrates this invention further more concretely, this invention is not restrict | limited at all by these Examples.
Example 1
The inside of a 3000 ml three-necked flask equipped with a thermometer and a mechanical stirrer was purged with nitrogen, and 500 ml of toluene, 132 g (2 mol) of distilled furan and 981 g (10.0 mol) of maleic anhydride were placed therein. Cooled to 0 ° C. To this mixed solution, 0.108 ml (0.10 mol) of a 0.93M tetrahydrofuran solution of borane-tetrahydrofuran complex salt (BH ₃ .THF) was added dropwise over 20 minutes while maintaining the internal temperature at 2 ° C. or lower. The reaction was carried out by stirring at the same temperature of 0 ° C. for 10 hours. Thereafter, toluene and tetrahydrofuran were removed under reduced pressure, and the produced crystals were filtered off with a glass filter, washed with 300 ml of hexane cooled to 5 ° C. or lower, dried for 2 hours under reduced pressure, and 3,6- 282.4 g (yield 85%) of epoxy-1,2,3,6-tetrahydrophthalic anhydride was obtained.

Example 2
The reaction was conducted in the same manner as in Example 1 except that tetrahydrofuran was used instead of toluene as the organic solvent.
Thereafter, tetrahydrofuran was removed under reduced pressure, and the resulting crystals were filtered off with a glass filter, washed with 300 ml of hexane cooled to 5 ° C. or lower, dried under reduced pressure for 2 hours, and 3,6-epoxy- 286.1 g (yield 86%) of 1,2,3,6-tetrahydrophthalic anhydride was obtained.

Example 3
The reaction was performed in the same manner as in Example 1 except that diisopropyl ether was used instead of toluene as the organic solvent.
Thereafter, diisopropyl ether and tetrahydrofuran were removed under reduced pressure, and the resulting crystals were filtered off with a glass filter, washed with 300 ml of hexane cooled to 5 ° C. or lower, and then dried under reduced pressure for 2 hours to obtain 3, 6 as colorless crystals. -289.1 g (yield 87%) of epoxy-1,2,3,6-tetrahydrophthalic anhydride was obtained.

Example 4
The reaction was performed in the same manner as in Example 1 except that hexane was used instead of toluene as the organic solvent.
Thereafter, hexane and tetrahydrofuran were removed under reduced pressure, and the produced crystals were separated by filtration with a glass filter, washed with 300 ml of hexane cooled to 5 ° C. or lower, and then dried under reduced pressure for 2 hours to give 3,6- 265.8 g (yield 80%) of epoxy-1,2,3,6-tetrahydrophthalic anhydride was obtained.

Example 5
The reaction was carried out in the same manner as in Example 1 except that diethyl ether was used instead of toluene as the organic solvent.
Thereafter, diethyl ether and tetrahydrofuran were removed under reduced pressure, and the resulting crystals were separated by filtration with a glass filter, washed with 300 ml of hexane cooled to 5 ° C. or lower, and then dried under reduced pressure for 2 hours. -232.4 g (yield 70%) of epoxy-1,2,3,6-tetrahydrophthalic anhydride was obtained.

Comparative Example 1
The inside of a 3000 ml three-necked flask equipped with a thermometer and a mechanical stirrer was purged with nitrogen, and 500 ml of toluene, 132 g (2 mol) of distilled furan and 981 g (10.0 mol) of maleic anhydride were placed therein. The temperature was raised to ° C. The reaction was carried out with stirring at the same temperature for 48 hours.
Thereafter, toluene was removed under reduced pressure, and the produced crystals were filtered off with a glass filter, washed with 300 ml of hexane cooled to 5 ° C. or lower, and then dried under reduced pressure for 2 hours to obtain 3,6 epoxy-1 as colorless crystals. , 2,3,6 Tetrahydrophthalic anhydride was obtained 99.7 g (yield 30%).
Thus, in the reaction without using Lewis acid, the yield was low.

The 3,6-epoxy-1,2,3,6-tetrahydrophthalic anhydride derivative obtained by the production method of the present invention is a resist material used in the field of microfabrication in the production of semiconductor devices and liquid crystal devices. Useful as a monomer raw material. For example, 9-methacryloyloxy-4,10-dioxatricyclo [5.2.1.0 ^2,6 ] decan-3-one or 10-methacryloyloxy-4,10-dioxa which is a resin monomer for resist It is particularly useful as a raw material for the synthesis of tricyclo [5.2.1.0 ^2,6 ] decan-3-one.

Claims (3)

In an organic solvent, a furan derivative represented by the following formula (1);
(In formula (1), R ₁ , R ₂ , R ₃ and R ₄ are each independently a hydrogen atom, a halogen atom, a formyl group, a cyano group, a carboxyl group, or an alkyl optionally having a substituent. A group, an alkoxy group, an alkylthio group, an alkoxycarbonyl group, an acyl group, an acyloxy group, an organic sulfinyl group, or an organic sulfonyl group.)
Maleic anhydride represented by the following formula (2):
A method for producing a 3,6-epoxy-1,2,3,6-tetrahydrophthalic anhydride derivative represented by the following formula (3) by reacting in the presence of a Lewis acid having a boron atom .
(In formula (3), R ₁ , R ₂ , R ₃ and R ₄ have the same meanings as in formula (1).)   The method for producing a 3,6-epoxy-1,2,3,6-tetrahydrophthalic anhydride derivative according to claim 1, wherein the organic solvent is tetrahydrofuran, toluene, diisopropyl ether or hexane. The 3,6-epoxy-1,2,3,6-tetrahydrophthalic acid according to claim 1 or 2, wherein the Lewis acid is used in an amount of 0.5 to 20 mol parts per 100 mol parts of the furan derivative. A method for producing an anhydride derivative.