JP2002212174A - 2-oxatricyclo[4.2.1.04,8]nonan-3-one derivative and method for producing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a new 2-oxatricyclo[4.2.1.04,8]nonan-3-one derivative useful e.g. as a raw material for resins for resist, etc. SOLUTION: The 2-oxatricyclo[4.2.1.04,8]nonan-3-one derivative is expressed by formula (1) (R is H or methyl; R1 is a hydrocarbon group or ORa; R2 is H, a hydrocarbon group, ORa or CO2Ra, R3 is H or a hydrocarbon group; R4 is H or a hydrocarbon group; and Ra is H or a hydrocarbon group).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a novel 2-oxatricyclo [4.2. Useful as a raw material of a functional polymer such as a photosensitive resin or a raw material of a pharmaceutical, an agricultural chemical or other fine chemicals. 1.0 ^{4, 8]} nonan-3-one derivatives and their preparation related.

[0002]

2. Description of the Related Art Positive photoresists used in a semiconductor manufacturing process have properties such as a property that an irradiated portion changes to alkali-soluble by light irradiation, adhesion to a silicon wafer, plasma etching resistance, and transparency to light used. Must have both. The positive photoresist is generally used as a solution containing a polymer as a main component, a photoacid generator, and several kinds of additives for adjusting the above properties. Is
It is extremely important that the polymer as the base agent has the above-mentioned properties in a well-balanced manner.

Exposure light sources for lithography used in the manufacture of semiconductors have become shorter in wavelength year by year, and an ArF excimer laser having a wavelength of 193 nm is expected as a next-generation exposure light source. It has been proposed to use a unit containing an alicyclic hydrocarbon skeleton having high transparency to the wavelength and etching resistance as a monomer unit of a resist polymer used in the ArF excimer laser exposure machine. However, although the alicyclic hydrocarbon skeleton is excellent in etching resistance, it has a drawback that adhesion to a substrate is low due to high hydrophobicity.
Therefore, for the purpose of improving this, copolymers incorporating a highly hydrophilic monomer unit having a carboxyl group or a lactone ring (adhesion imparting monomer unit) are being studied. For example, JP-A-2000-15
No. 9758 and JP-A-2000-26446 disclose a (meth) acrylate having a 2-oxatricyclo [4.2.1.0 ^4,8 ] nonan-3-one ring as a monomer component. Polymers have been proposed. However, these polymers have not always been sufficiently satisfactory in terms of adhesion to a substrate and a balance between the adhesion to the substrate and the etching resistance.

[0004]

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide a novel resin useful as a material for a resist resin or the like.
-Oxatricyclo [4.2.1.0 ^4,8 ] nonane-3
An object is to provide an -one derivative and a method for producing the same.

[0005]

Means for Solving the Problems The present inventors have conducted intensive studies in order to achieve the above object, and as a result, reacted a specific 5-norbornene-2-carboxylic acid derivative with a peracid or a peroxide. By reacting with (meth) acrylic acid or the like, a novel 2-oxatricyclo [4.2.1.0
^[4,8 ] Nonan-3-one derivative was obtained, thereby completing the present invention.

That is, the present invention provides the following formula (1)

Embedded image (Wherein, R represents a hydrogen atom or a methyl group, R ¹ represents a hydrocarbon group or an —OR ^a group, and R ² represents a hydrogen atom, a hydrocarbon group, an —OR ^a group, or a —CO ₂ ^Ra group. R ³ represents a hydrogen atom or a hydrocarbon group, R ⁴ represents a hydrogen atom or a hydrocarbon group, and R ^a represents a hydrogen atom or a hydrocarbon group. 2.2.1.0 ^4,8 ]
A nonan-3-one derivative is provided. The present invention also provides
The following equation (2)

Embedded image (Wherein, R ¹ represents a hydrocarbon group or an —OR ^a group, R ² represents a hydrogen atom, a hydrocarbon group, an —OR ^a group, or a —CO ₂ R ^a group, and R ³ represents a hydrogen atom or a hydrocarbon group. R ⁴ represents a hydrogen atom or a hydrocarbon group, and R ^a represents a hydrogen atom or a hydrocarbon group), and reacting the compound with (meth) acrylic acid or a reactive derivative thereof. , The above equation (1)
2-oxatricyclo [4.2.1.
0 ^4,8] nonane -3-one derivatives of 2-oxa-tricyclo [4.2.1.0 ^4,8] provides a method for producing nonan-3-one derivatives. The present invention further provides the above formula (2)
2-oxatricyclo [4.2.1.
[0 ^4,8 ] nonan-3-one derivatives. The present invention further provides the following formula (3)

Embedded image (Wherein, R ¹ represents a hydrocarbon group or an —OR ^a group, R ² represents a hydrogen atom, a hydrocarbon group, an —OR ^a group, or a —CO ₂ R ^a group, and R ³ represents a hydrogen atom or a hydrocarbon group. R ⁴ represents a hydrogen atom or a hydrocarbon group; R ^a represents a hydrogen atom or a hydrocarbon group), or a 5-norbornene-2-carboxylic acid derivative represented by By reacting with a peroxide, 2-oxatricyclo [4.2.1.0 ^4,8 ] nonan-3-one derivative represented by the above formula (2) is obtained. 2.1.0 ^4,8 ] nonane-3-one derivatives.

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION 2-oxo represented by the above formula (1)
Satricyclo [4.2.1.0^4,8] Nonan-3-one
In the derivative, R represents a hydrogen atom or a methyl group;
¹Is a hydrocarbon group or -OR^aA group represented by R^TwoIs a hydrogen atom,
Hydrocarbon group, -OR^aGroup or -CO_TwoR ^aA group represented by R^ThreePassing
And R^FourRepresents a hydrogen atom or a hydrocarbon group. The above R^a
Represents a hydrogen atom or a hydrocarbon group. Expression (1)
2-oxatricyclo [4.2.1.0^4,8Nonan-
The 3-one derivatives include endo-forms, exo-forms, and mixtures thereof.
Compounds are included.

[0008] hydrocarbon group in ^{R 1, R 2, R 3} , R 4, R a, aliphatic hydrocarbon group, alicyclic hydrocarbon group, aromatic hydrocarbon group and a plurality linked based on these Is included. Examples of the aliphatic hydrocarbon group include linear or branched such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, s-butyl, t-butyl, pentyl, t-amyl, hexyl, octyl, and decyl groups. Alkyl group (C _1-20 alkyl group, etc.); linear or branched alkenyl group such as vinyl, allyl, isopropenyl, 1-butenyl group (C _2-20 alkenyl group, etc.); 2-propynyl group, etc. Linear or branched alkynyl group (C
_2-20 alkynyl group) and the like.

The alicyclic hydrocarbon group includes, for example, a 3-20 membered alicyclic hydrocarbon group such as cyclopentyl, cyclohexyl, cyclohexenyl, cyclooctyl, cyclododecyl group (cycloalkyl group, cycloalkenyl group,
A cross-linked cyclic hydrocarbon group).

The aromatic hydrocarbon group includes, for example, C _6-20 aromatic hydrocarbon groups such as phenyl and naphthyl groups. Examples of a group in which a plurality of different hydrocarbon groups are linked include, for example, an aralkyl group of about C _7-21 such as benzyl and 2-phenylethyl; cyclopentylmethyl, 2-cyclopentylethyl, cyclohexylmethyl, 2-cyclohexylethyl And the like.

A halogen atom such as fluorine and chlorine, or a substituent such as an alkoxy group may be bonded to these hydrocarbon groups.

Among the above hydrocarbon groups, a C _1-15 alkyl group, a 3- to 15-membered cycloalkyl group and a group in which a plurality of these groups are linked (for example, a 5- to 6-membered cycloalkyl-C
_1-2 alkyl group and the like), particularly, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, and s.
Preferred are C _1-5 alkyl groups such as -butyl, t-butyl and t-amyl group (among others, C _1-4 alkyl groups).

The 2-oxatricyclo represented by the formula (1)
[4.2.1.0^4,8Representative of Nonan-3-one Derivatives
A typical example is 9- (meth) acryloyloxy-5-
Methyl-2-oxatricyclo [4.2.1.0^4,8]
Nonan-3-one (R = H or CH_Three, R¹= CH_Three, R^Two
= R^Three= R^Four= H), 9- (meth) acryloyloxy-
5-methoxy-2-oxatricyclo [4.2.1.0
^4,8] Nonan-3-one (R = H or CH_Three, R¹= OC
H_Three, R^Two= R^Three= R^Four= H), 9- (meth) acryloyl
Oxy-5,5-dimethyl-2-oxatricyclo
[4.2.1.0^{Four, 8}Nonan-3-one (R = H or
CH_Three, R¹= R^Two= CH_Three, R^Three= R^Four= H), 9- (me
TA) acryloyloxy-5,5-diethoxy-2-o
Xatricyclo [4.2.1.0^4,8Nonan-3-o
(R = H or CH_Three, R¹= R^Two= OCH _TwoCH_Three, R^Three=
R^Four= H), 9- (meth) acryloyloxy-5-ca
Rubox-5-methyl-2-oxatricyclo [4.
2.1.0^4,8] Nonan-3-one (R = H or CH_Three,
R¹= CH_Three, R^Two= COOH, R^Three= R^Four= H), 9-
(Meth) acryloyloxy-4,5-dimethyl-2-
Oxatricyclo [4.2.1.0^4,8Nonan-3-
ON (R = H or CH_Three, R¹= R^Three= CH_Three, R^Two= R^Four=
H) and the like.

The 2-oxatricyclo [4.2.1.0 ^4,8 ] nonan-3-one derivative represented by the formula (1) can be used as a raw material for a functional material such as a photosensitive resin, a drug, It can be used as a raw material for fine chemicals such as pesticides. In particular, 2-oxatricyclo [4.2.1.0 ^4,8 ] represented by the formula (1)
Among the nonan-3-one derivatives, compounds in which R ¹ is an —OR ^a group are useful as a monomer component for obtaining a resist polymer having high adhesion to a substrate, and compounds in which R ¹ is a hydrocarbon group. Is suitable as a monomer component for obtaining a resist polymer having an excellent balance between adhesion to a substrate and etching resistance by appropriately selecting R ² , R ³ and R ⁴ .

The 2-oxatricyclo [4.2.1.0 ^4,8 ] nonan-3-one derivative represented by the formula (1) is obtained by converting the corresponding compound represented by the formula (2) into It can be produced by reacting with (meth) acrylic acid or a reactive derivative thereof. More specifically, for example, (a) a compound represented by the formula (2) may be added to a (meth) acrylic halide such as (meth) acrylic chloride in the presence of a base such as triethylamine or pyridine if necessary. (B) reacting with an active reactive derivative of (meth) acrylic acid such as (meth) acrylic anhydride, or (b) a compound represented by the formula (2)
In the presence of a transesterification catalyst, a (meth) acrylate such as methyl (meth) acrylate is reacted,
(C) By reacting the compound represented by the formula (2) with (meth) acrylic acid in the presence of a strong acid, the corresponding 2-oxatricyclo [4.2.
1.0 ^4,8 ] nonan-3-one derivative can be obtained. The reaction conditions in these methods are the same as in the ordinary ester production method. At the time of the reaction, a polymerization inhibitor such as hydroquinone monomethyl ether or oxygen may be introduced in order to suppress the polymerization.

[0016] represented by formula (1) produced by the reaction of 2-oxatricyclo [4.2.1.0 ^{4, 8]} nonan-3-one derivatives, for example, filtration, concentration, distillation, extraction, Crystallization,
Separation and purification can be performed by separation means such as recrystallization, column chromatography, or a combination thereof.

A representative example of the 2-oxatricyclo [4.2.1.0 ^4,8 ] nonan-3-one derivative represented by the formula (2) is 9-hydroxy-5-methyl-2. - oxatricyclo [4.2.1.0 ^{4, 8]} nonan-3-one _{^{(R 1 = CH 3, R}} 2 = R 3 = R 4 = H), 9- hydroxy-5-methoxy-2- Oxatricyclo [4.2.1.
0 ^4,8 ] nonan-3-one (R ¹ ＯOCH ₃ , R ² ＲR ³ =
R ⁴ = H), 9-hydroxy-5,5-dimethyl-2-
Oxatricyclo [4.2.1.0 ^4,8 ] nonane-3-
ON (R ¹ = R ² = CH ₃ , R ³ = R ⁴ = H), 9-hydroxy-5,5-diethoxy-2-oxatricyclo [4.2.1.0 ^4,8 ] nonane-3 -On (R ¹ = R ² =
^{_{OCH 2 CH 3, R 3 =}} R 4 = H), 9- hydroxy-5-
Carboxy-5-methyl-2-oxatricyclo [4.
2.1.0 ^4,8 ] nonan-3-one (R ¹ = CH ₃ , R ² =
^{COOH, R 3 = R 4 =} H), 9- hydroxy-4,5
Dimethyl-2-oxatricyclo [4.2.1.
0 ^4,8 ] nonan-3-one (R ¹ ＲR ³ ＣＨCH ₃ , R ² ＲR ⁴
= H).

The 2-oxatricyclo [4.2.1.0 ^4,8 ] nonan-3-one derivative represented by the above formula (2) is represented by the corresponding 5- It can be obtained by reacting a norbornene-2-carboxylic acid derivative or an ester thereof with a peracid or peroxide.

5-norbornene-2 represented by the formula (3)
-As a typical example of the carboxylic acid derivative, 3-methyl-
5-norbornene-2-carboxylic acid (R¹= CH_Three, R^Two
= R^Three= R^Four= H), 3-methoxy-5-norbornene-
2-carboxylic acid (R¹= OCH _Three, R^Two= R^Three= R^Four=
H), 3,3-dimethyl-5-norbornene-2-cal
Bonic acid (R¹= R^Two= CH_Three, R^Three= R^Four= H), 3,3-
Diethoxy-5-norbornene-2-carboxylic acid (R¹
= R^Two= OCH_TwoCH_Three, R^Three= R^Four= H), 3-carboxy
Ci-3-methyl-5-norbornene-2-carboxylic acid
(R¹= CH_Three, R^Two= COOH, R^Three= R^Four= H), 2,
3-dimethyl-5-norbornene-2-carboxylic acid (R
¹= R^Three= CH_Three, R^Two= R^Four= H).

5-norbornene-2 represented by the formula (3)
Examples of the ester of the carboxylic acid derivative include alkyl esters such as methyl ester, ethyl ester, propyl ester, isopropyl ester, butyl ester, isobutyl ester, s-butyl ester, t-butyl ester (for example, C _1-4 alkyl). Esters); cycloalkyl esters such as cyclohexyl esters; aryl esters such as phenyl esters; aralkyl esters such as benzyl esters, and the like, but are not limited thereto.

The above-mentioned peracids include formic acid, peracetic acid, trifluoroperacetic acid, perbenzoic acid, m-chloroperbenzoic acid,
Organic peracids such as monoperoxyphthalic acid; and inorganic peracids such as permanganic acid. Peracids can also be used in salt form. The organic peracid may be an equilibrated peracid (eg, equilibrated formic acid, equilibrated peracetic acid, etc.). That is, for example, an organic acid such as formic acid or acetic acid may be used in combination with hydrogen peroxide to generate a corresponding organic peracid in the system. When using an equilibrium peracid, a small amount of a strong acid such as sulfuric acid may be added as a catalyst.

The amount of the peracid used is, for example, 0.8 to 2 moles, preferably 0.9 mole, per mole of the 5-norbornene-2-carboxylic acid derivative represented by the formula (3) or its ester. ~ 1.5 mol, more preferably 0.95-1.
It is about 2 mol.

Examples of the peroxide include hydrogen peroxide, peroxide, hydroperoxide, peroxoacid, and salts of peroxoacid.

As the hydrogen peroxide, pure hydrogen peroxide may be used.
For example, it is used in a form diluted with water (for example, 30% by weight hydrogen peroxide solution).

The amount of the peroxide such as hydrogen peroxide used is, for example, 0.9 to 0.9 mol per mol of the 5-norbornene-2-carboxylic acid derivative represented by the formula (3) or an ester thereof.
The amount is about 5 mol, preferably about 0.9 to 3 mol, and more preferably about 0.95 to 2 mol.

The above-mentioned hydrogen peroxide is often used together with a metal compound. Examples of the metal compound include W,
Oxides containing metal elements such as Mo, V, Mn, Re, oxo acids or salts thereof, sulfides, halides, oxyhalides, borides, carbides, silicides, nitrides, phosphides, peroxides, Complexes (inorganic complexes and organic complexes), organometallic compounds and the like. These metal compounds can be used alone or in combination of two or more.

As the oxide, for example, tungsten oxide (WO ₂ , WO _3, etc.), molybdenum oxide (MoO
₂ , MoO _3, etc.), vanadium oxide (VO, V ₂ O ₃ , V
O ₂ , V ₂ O _5, etc.), manganese oxide (MnO, Mn)
₂ O ₃ , Mn ₃ O ₄ , MnO ₂ , Mn ₂ O ₇ etc.), W, M
A composite oxide containing a metal element such as o, V, and Mn may be used.

The oxo acids include tungstic acid, molybdic acid, vanadic acid, manganic acid, etc., isopolyacids such as isopolytungstic acid, isopolymolybdic acid, isopolyvanadate; phosphotungstic acid, silicotungstic acid, and the like. Phosphomolybdenum sun, silico molybdic acid,
Heteropoly acids composed of the above-mentioned metal element such as limbanadomolybdic acid and other metal elements are included. As the other metal element in the heteropoly acid, phosphorus or silicon, particularly phosphorus is preferable.

Examples of the oxo acid salt include alkali metal salts such as sodium and potassium salts of the above oxo acid; alkaline earth metal salts such as magnesium salt, calcium salt and barium salt; ammonium salts; transition metal salts and the like. Can be The salt of an oxo acid (for example, a salt of a heteropoly acid) may be a salt in which a part of a hydrogen atom corresponding to a cation is substituted with another cation.

Examples of the peroxide containing a metal element include peroxo acids (eg, peroxotungstic acid, peroxomolybdate, peroxovanadate, etc.), and salts of peroxo acids (the alkali metal salts of the above peroxo acids, alkaline earths, etc.). Metal salts, ammonium salts, transition metal salts, etc.), peracids (permanganic acid, etc.), peracid salts (alkali metal salts of the above peracids, alkaline earth metal salts, ammonium salts, transition metal salts, etc.) and the like. No.

The amount of the metal compound used together with the hydrogen peroxide is, for example, 0.0001 to 2 mol per mol of the 5-norbornene-2-carboxylic acid derivative represented by the formula (3) or an ester thereof. Degree, preferably 0.0
About 005 to 0.5 mol, more preferably 0.001
About 0.2 mol.

5-norbornene-2 represented by the formula (3)
The reaction of the carboxylic acid derivative or its ester with the peracid or peroxide is carried out in the presence or absence of a solvent. Examples of the solvent include alcohols such as t-butyl alcohol; chloroform, dichloromethane, 1,2-
Halogenated hydrocarbons such as dichloroethane; aromatic hydrocarbons such as benzene; aliphatic hydrocarbons such as hexane, heptane and octane; alicyclic hydrocarbons such as cyclohexane; N, N-dimethylformamide, N, N-dimethylacetamide Amides such as acetonitrile, propionitrile, benzonitrile, etc .; linear or cyclic ethers such as ethyl ether and tetrahydrofuran; esters such as ethyl acetate; organic acids such as acetic acid; water and the like. These solvents may be used alone or as a mixture of two or more. When the reaction is performed in a heterogeneous system, water or a solvent containing water is often used as the solvent.

The reaction temperature can be appropriately selected in consideration of the reaction rate and the reaction selectivity.
Preferably it is about 10 to 80 ° C. The reaction is batch type,
It may be performed by any method such as a semi-batch type and a continuous type.

By the above reaction, 2-
Oxatricyclo [4.2.1.0 ^4,8Nonan-3-
An on derivative is formed. In this reaction, first, in equation (3)
A represented 5-norbornene-2-carboxylic acid derivative or
Epoxidation of the ester double bond occurs and continues
And the intramolecular cyclization reaction involving the opening of the epoxy ring proceeds
2-oxatricyclo [4.2.
1.0^4,8A nonan-3-one derivative is formed
Guessed.

[0035] represented by formula (2) produced by the reaction of 2-oxatricyclo [4.2.1.0 ^{4, 8]} nonan-3-one derivatives, for example, filtration, concentration, distillation, extraction, Crystallization,
Separation and purification can be performed by separation means such as recrystallization, column chromatography, or a combination thereof.

5-norbornene-2 represented by the formula (3)
-The carboxylic acid derivative or its ester can be obtained by utilizing the Diels-Alder reaction. For example, as shown in the following reaction step formula, a cyclopentadiene derivative represented by the formula (4) is reacted with an unsaturated compound represented by the formula (5) to thereby represent the compound represented by the formula (3). A 5-norbornene-2-carboxylic acid derivative can be produced.

Embedded image (Wherein R ¹ , R ² , R ³ and R ⁴ are the same as above)

Representative examples of the cyclopentadiene derivative represented by the formula (4) include cyclopentadiene, 2-methylcyclopentadiene, 2-ethylcyclopentadiene, 2-isopropylcyclopentadiene and the like. Representative examples of the unsaturated compound represented by the formula (5) include crotonic acid, 3-methoxypropenoic acid,
-Methyl-2-butenoic acid, 3,3-diethoxypropenoic acid, 3-carboxy-2-butenoic acid, 2-methyl-2-
Butenoic acid and the like.

The reaction between the cyclopentadiene derivative represented by the formula (4) and the unsaturated compound represented by the formula (5) is carried out in the presence or absence of a solvent. As the solvent,
For example, esters such as ethyl acetate; organic acids such as acetic acid; alcohols such as t-butyl alcohol; halogenated hydrocarbons such as chloroform, dichloromethane, and 1,2-dichloroethane; aromatic hydrocarbons such as benzene;
Aliphatic hydrocarbons such as hexane, heptane and octane;
Alicyclic hydrocarbons such as cyclohexane; amides such as N, N-dimethylformamide and N, N-dimethylacetamide; nitriles such as acetonitrile, propionitrile and benzonitrile; linear or cyclic ethers such as ethyl ether and tetrahydrofuran; Is mentioned.
These solvents are used alone or in combination of two or more.

Reaction rate and reaction selectivity (stereoselectivity, etc.)
Lewis acid may be added to the system in order to improve the viscosity.
Examples of the Lewis acid include AlCl ₃ , SnCl ₄ , T
Examples include, but are not limited to, iCl ₄ , BF _{3, and the} like.

The reaction temperature can be appropriately selected according to the type of the reaction raw material and the like, but is generally about -80 ° C to 300 ° C, preferably about -70 ° C to 250 ° C. The reaction is carried out under normal pressure or under pressure. The reaction may be performed by any method such as a batch system, a semi-batch system, and a continuous system.

The resulting 5-norbornene-2-carboxylic acid derivative represented by the formula (3) is, for example, filtered, concentrated,
Separation and purification can be performed by separation means such as distillation, extraction, crystallization, recrystallization, and column chromatography, or a combination thereof.

5-norbornene-2 represented by the formula (3)
An ester of a carboxylic acid derivative can be obtained by subjecting a 5-norbornene-2-carboxylic acid derivative represented by the formula (3) to a conventional esterification reaction. Also,
As the ester of the 5-norbornene-2-carboxylic acid derivative represented by the formula (3), the ester represented by the formula (3) is used instead of the compound represented by the formula (5).
It can also be produced in the same manner as the norbornene-2-carboxylic acid derivative.

[0043]

According to the method of the present invention, a novel 2-oxatricyclo [4.2.1.0 ^4,8 ] nonan-3-one derivative useful as a raw material for a resist resin or the like, and a derivative thereof. An efficient manufacturing method is provided.

[0044]

EXAMPLES The present invention will be described below in more detail with reference to Examples, but the present invention is not limited to these Examples. In addition, the 3-methyl-
The ratio between the endo form and the exo form of 5-norbornene-2-carboxylic acid was determined by gas chromatography.

Example 1 A flask equipped with a dropping funnel and a stirrer was charged with 3-methyl-
5-norbornene-2-carboxylic acid (endo-form 50%,
Exo body 50%) 228 g (1.5 mol), 27 g of tungstic acid and 650 g of water were added, and the temperature was raised to 50 ° C. while stirring, and 30% by weight from the dropping funnel while controlling the internal temperature at 50 to 60 ° C. 173 g (1.52 mol) of aqueous hydrogen peroxide was added dropwise over 2 hours. Thereafter, stirring was continued at 50 to 55 ° C for 5 hours. The reaction solution was cooled to room temperature, and after adding 500 g of a 10% by weight aqueous solution of sodium sulfite (Na ₂ SO ₃ ), 870 ml of water was added using a rotary evaporator.
Distillation was performed, and the concentrate was neutralized with a 10% by weight aqueous sodium carbonate solution. The neutralized solution was extracted twice with 1300 g of ethyl acetate, the ethyl acetate layers were combined, concentrated using a rotary evaporator, and mixed with 150 ml of n-hexane. The precipitated crystals are filtered and dried to obtain 9-
Hydroxy-5-methyl-2-oxatricyclo [4.
2.1.0 ^4,8 ] nonan-3-one (in the formula (2), a compound in which R ¹ ＣＨCH ₃ and R ² ＲR ³ ＲR ⁴ ＨH) were obtained in an amount of 76 g (045 mol). The yield was 30% based on the 3-methyl-5-norbornene-2-carboxylic acid used. [Spectral data of 9-hydroxy-5-methyl-2-oxatricyclo [4.2.1.0 ^4,8 ] nonan-3-one] MS (m / e): 168 (M ⁺ ), 15
0,140,122,84,57

Example 2 A flask equipped with a dropping funnel and a stirrer was charged with 9-hydroxy-5-methyl-2-oxatricyclo [4.2.
1.0 ^4,8 ] nonan-3-one (5.0 g, 30 mmol), triethylamine (4.6 g, 45 mmol), and 50 ml of dichloroethane as a solvent were dissolved therein. While controlling the reaction temperature to 0 ° C., 5.3 g (50 mmol) of methacrylic chloride was added dropwise. After dropping, 5
Stirring was continued at the same temperature for hours. The reaction solution was washed sequentially with an aqueous sodium hydrogen carbonate solution and brine, and then concentrated on a rotary evaporator, and the concentrated solution was subjected to silica gel column chromatography to give 9-methacryloyloxy-5-methyl-2-oxatricyclo. [4.2.
1.0 ^4,8 ] nonan-3-one (in the formula (1), R
= CH ₃ , R ¹ = CH ₃ , R ² = R ³ = R ⁴ = H) (5.0 g, 21 mmol). The yield is 70
%Met. [Spectral data of 9-methacryloyloxy-5-methyl-2-oxatricyclo [4.2.1.0 ^4,8 ] nonan-3-one] MS (m / e): 236 (M ^<+> ), 168 , 151, 69 ¹ H-NMR (CDCl ₃ ) δ: 6.01 (s, 1H), 5.
50 (s, 1H), 4.67 (d, 1H), 4.58
(D, 1H), 3.21 (m, 1H), 2.62-2.
55 (m, 2H), 2.14 (s, 3H), 2.10-
2.00 (m, 2H), 1.85-1.55 (m, 4
H)

Claims (4)

[Claims] [Claim 1] The following formula (1) (Wherein, R represents a hydrogen atom or a methyl group, R ¹ represents a hydrocarbon group or an —OR ^a group, and R ² represents a hydrogen atom, a hydrocarbon group, an —OR ^a group, or a —CO ₂ ^Ra group. R ³ represents a hydrogen atom or a hydrocarbon group, R ⁴ represents a hydrogen atom or a hydrocarbon group, and R ^a represents a hydrogen atom or a hydrocarbon group. 2.2.1.0 ^4,8 ]
Nonan-3-one derivatives. 2. The following formula (2): (Wherein, R ¹ represents a hydrocarbon group or an —OR ^a group, R ² represents a hydrogen atom, a hydrocarbon group, an —OR ^a group, or a —CO ₂ R ^a group, and R ³ represents a hydrogen atom or a hydrocarbon group. R ⁴ represents a hydrogen atom or a hydrocarbon group, and R ^a represents a hydrogen atom or a hydrocarbon group), and reacting the compound with (meth) acrylic acid or a reactive derivative thereof. And the following formula (1) (Wherein, R represents a hydrogen atom or a methyl group. R ¹ , R ² ,
R ³ and R ⁴ are the same as described above) to obtain a 2-oxatricyclo [4.2.1.0 ^4,8 ] nonan-3-one derivative represented by the following formula: 0.0 ^4,8 ] Nonan-3-one derivative. 3. The following formula (2): (Wherein, R ¹ represents a hydrocarbon group or an —OR ^a group, R ² represents a hydrogen atom, a hydrocarbon group, an —OR ^a group, or a —CO ₂ R ^a group, and R ³ represents a hydrogen atom or a hydrocarbon group. R ⁴ represents a hydrogen atom or a hydrocarbon group, and R ^a represents a hydrogen atom or a hydrocarbon group.) 2-oxatricyclo [4.2.1.0 ^4,8 ] Nonan-3-one derivatives. 4. The following formula (3): (Wherein, R ¹ represents a hydrocarbon group or an —OR ^a group, R ² represents a hydrogen atom, a hydrocarbon group, an —OR ^a group, or a —CO ₂ R ^a group, and R ³ represents a hydrogen atom or a hydrocarbon group. R ⁴ represents a hydrogen atom or a hydrocarbon group; R ^a represents a hydrogen atom or a hydrocarbon group), or a 5-norbornene-2-carboxylic acid derivative represented by By reacting with a peroxide, the following formula (2) (Wherein R ¹ , R ² , R ³ , and R ⁴ are the same as those described above). 2-oxatricyclo [4.2.1.0 ^4,8 ] nonane-
2-oxatricyclo [4.2.
1.0 ^4,8 ] Nonane-3-one derivative production method.