JP2002173466A - Method for producing tertiary alcohol ester - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for easily and efficiently producing a tertiary alcohol ester compound from the corresponding tertiary alcohol having a ring in one of branched chains. SOLUTION: This method for producing a tertiary alcohol ester comprises reaction of a tertiary alcohol of formula (1) (wherein, the ring Z is a monocyclic or polycyclic nonaromatic or aromatic ring; and R1 and R2 are each same or different a hydrocarbon group or the like) with an organometallic compound of formula (2): R4-M [wherein, R4 is a hydrocarbon group; and M is a (ligand- bearing) metal atom or a group of formula (3): -MgY (wherein, Y is a halogen atom)] and a carboxylic acid halide of formula (4) (wherein, R3 is a hydrocarbon group or heterocyclic group; and X is a halogen atom) to obtain the objective tertiary alcohol ester of formula (5) (wherein, Z, R1, R2 and R3 are each the same as mentioned above).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a method for producing a tertiary alcohol ester, and more particularly, to a method for producing a functional polymer such as a photosensitive resin, which has a ring such as a non-aromatic ring. The present invention relates to a method for producing a tertiary alcohol ester.

[0002]

2. Description of the Related Art An ester of a tertiary alcohol containing a non-aromatic cyclic group such as an alicyclic hydrocarbon group and a polymerizable unsaturated carboxylic acid has an alcohol moiety eliminated by an acid,
Since a free carboxylic acid is formed and becomes alkali-soluble and functions as an acid-sensitive compound, it is a compound that has recently been attracting attention as a monomer of a functional polymer such as a photosensitive resin, particularly a resist.

Generally, a tertiary alcohol ester can be synthesized by reacting a corresponding tertiary alcohol with an acid or an acid halide. In addition, a general acid-sensitive tertiary alcohol ester is synthesized by reacting an acid halide with a corresponding tertiary alcohol in the presence of an amine such as triethylamine due to its acid sensitivity.

However, a tertiary alcohol ester containing a non-aromatic ring such as a bulky alicyclic hydrocarbon ring in one of its branched chains can be prepared from the corresponding tertiary alcohol by the above-mentioned method. It was difficult to synthesize efficiently. More specifically, an acrylate halide is allowed to act on a tertiary alcohol containing a non-aromatic ring such as a bulky alicyclic hydrocarbon ring in one of the branched chains in the presence of an amine such as triethylamine. If this is done, there will be problems such as the production of a large amount of the corresponding acrylate polymer or the inability to raise the substrate concentration due to the precipitation of a large amount of salt, making it difficult to obtain the corresponding acrylate efficiently. Met. Further, when a methacrylic halide is allowed to act on a tertiary alcohol containing a non-aromatic ring such as a bulky alicyclic hydrocarbon ring in one of the branched chains in the presence of an amine such as triethylamine. However, the target methacrylate is hardly produced due to its low reactivity.

[0005] As described above, a tertiary alcohol having a bulky non-aromatic ring such as an alicyclic hydrocarbon ring in one of its branched chains has a low reactivity due to its bulkiness and an acid-sensitive property. Efficient esterification was difficult due to the elimination of the ester moiety due to the property. Such a problem may occur not only when the carboxylic acid moiety is not limited to an unsaturated carboxylic acid but also when a saturated aliphatic carboxylic acid or an aromatic carboxylic acid is used. A third group having a non-aromatic ring in one of the branched chains;
The above problem can occur not only with the tertiary alcohol but also with the tertiary alcohol having an aromatic ring in one of the branched chains.

[0006]

Accordingly, an object of the present invention is to provide a method for easily and efficiently producing a corresponding tertiary alcohol ester compound from a tertiary alcohol having a ring in one of the branched chains. Is to provide.

[0007]

Means for Solving the Problems The inventors of the present invention have conducted intensive studies to achieve the above object, and as a result, when a specific organometallic compound and a carboxylic acid halide are used, one of the branched chains has a ring. The inventors have found that a corresponding tertiary alcohol ester can be easily and efficiently produced from a tertiary alcohol, and completed the present invention.

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

Embedded image (Wherein, ring Z represents a monocyclic or polycyclic non-aromatic or aromatic ring. R ¹ and R ² are the same or different and represent a hydrocarbon group. R ¹ and R ² are A tertiary alcohol represented by the following formula (2) R ⁴ -M (2) wherein R ⁴ is carbonized Shows a hydrogen group. M represents a metal atom which may have a ligand, or an organic metal represented by the following formula (3) -MgY (3) (wherein, Y represents a halogen atom). Compound and the following formula (4)

Embedded image (Wherein, R ³ represents a hydrocarbon group or a heterocyclic group; X represents a halogen atom), and reacted with a carboxylic acid halide represented by the following formula (5):

Embedded image (Wherein Z, R ¹ , R ² and R ³ are the same as above). A method for producing a tertiary alcohol ester is provided.

Ring Z is a norbornane ring, a bornane ring, an adamantane ring, a bicyclooctane ring, a tricyclo [5.
2.1.0 ^2,6 ] a bridged cyclic ring containing 2 to 4 rings such as a decane ring and a decalin ring. Ring Z is, for example,
It may have a substituent such as a halogen atom, an alkyl group, a hydroxyl group protected with a protecting group, or an amino group protected with a protecting group.

R ¹ and R ² include, for example, a C _1-6 alkyl group, a C _3-12 cycloalkyl group, a C _6-20 aryl group and the like. R ³ includes, for example, a hydrocarbon group having a polymerizable unsaturated group such as a vinyl group, a 1-propenyl group, and an isopropenyl group.

[0011]

BEST MODE FOR CARRYING OUT THE INVENTION [Tertiary alcohol] In the tertiary alcohol represented by the above formula (1), R ¹ , R ²
Examples of the hydrocarbon group represented by include an aliphatic hydrocarbon group, an alicyclic hydrocarbon group, an aromatic hydrocarbon group, and a group obtained by linking a plurality of these groups.

Examples of the aliphatic hydrocarbon group include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, s-butyl, t-butyl, pentyl, hexyl, octyl, decyl, vinyl, allyl and 2-propynyl. C _1-10 aliphatic hydrocarbon group (linear or branched alkyl group, alkenyl group and alkynyl group). Preferred aliphatic hydrocarbon groups are C
_1-6 (particularly C _1-4 ) is an aliphatic hydrocarbon group.

Examples of the alicyclic hydrocarbon group include a 3-12 membered alicyclic hydrocarbon group such as cyclopentyl and cyclohexyl (cycloalkyl group, cycloalkenyl group, etc.).

Examples of the aromatic hydrocarbon group include C _6-20 aromatic hydrocarbon groups (aryl groups) such as phenyl and naphthyl groups. Examples of a group in which a plurality of different types of hydrocarbon groups are linked to each other include, for example, an aralkyl group of about C _7-16 such as a benzyl or 2-phenylethyl group.

[0015] The hydrocarbon group may have a substituent. The substituent is not particularly limited as long as it does not inhibit the reaction, and examples thereof include a halogen atom, a substituted oxy (or thio) group (for example, methoxy, methylthio, methoxyethoxy, 2- (trimethylsilyl) ethoxy, benzyloxy group) And an acyl group (eg, a benzoyl group).

Examples of the alicyclic ring which R ¹ and R ² may combine with each other to form an alicyclic ring include a hydrocarbon ring corresponding to the alicyclic hydrocarbon group.

Preferred R ¹ and R ² include a C _1-6 alkyl group, a C _3-12 cycloalkyl group and a C _6-20 aryl group.
Particularly, a C _1-4 alkyl group, a C _5-6 cycloalkyl group, a phenyl group and the like are included.

Ring Z represents a monocyclic or polycyclic non-aromatic or aromatic ring. The non-aromatic ring includes an alicyclic hydrocarbon ring (non-aromatic hydrocarbon ring) and a non-aromatic hetero ring. The alicyclic hydrocarbon ring includes a monocyclic hydrocarbon ring and a polycyclic hydrocarbon ring [a spiro hydrocarbon ring, a ring assembly hydrocarbon ring, a bridged hydrocarbon ring (including a condensed hydrocarbon ring). And the non-aromatic heterocyclic ring includes a monocyclic heterocyclic ring and a polycyclic heterocyclic ring (such as a bridged cyclic heterocyclic ring).

Examples of the monocyclic hydrocarbon ring include a C _3-12 cycloalkane ring such as a cyclopentane, cyclohexane, cycloheptane and cyclooctane ring; and a C _3-12 cycloalkene ring such as a cyclohexene ring.
The spiro hydrocarbon ring includes, for example, C _5-16 spiro hydrocarbon rings such as spiro [4.4] nonane, spiro [4.5] decane, and spirobicyclohexane ring. Examples of the ring-assembled hydrocarbon ring include a ring-assembled hydrocarbon ring including a C _3-12 cycloalkane ring such as a bicyclohexane and a biperhydronaphthalene ring.

Examples of the bridged cyclic hydrocarbon ring include pinane, bornane, norpinane, norbornane, bicyclooctane ring (bicyclo [2.2.2] octane ring, bicyclo [3.2.1] octane ring, etc.). Bicyclic hydrocarbon ring; Homobredan, Adamantane, Tricyclo [5.
2.1.0 ^2,6] decane, tricyclo [4.3.1.1 ^{2
, 5} ] tricyclic hydrocarbon ring such as undecane ring; tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10] dodecane, etc. 4 ring and perhydro-1,4-methano-5,8 ring.

In the bridged cyclic hydrocarbon ring, a dimer hydrogenated product of a diene such as cyclopentadiene, cyclohexadiene or cycloheptadiene (for example, a dimerized hydrogenated product of dimer) Perhydro-
4,7-methanoindene), butadiene dimer (vinylcyclohexene) and hydrogenated products thereof].

The bridged cyclic hydrocarbon ring includes a condensed cyclic hydrocarbon ring such as perhydronaphthalene (decalin), perhydroanthracene, perhydrophenanthrene, perhydroacenaphthene, perhydrofluorene, perhydroindene. And a condensed ring obtained by condensing a plurality of 5- to 8-membered cycloalkane rings such as a perhydrophenalene ring.

Preferred examples of the bridged cyclic hydrocarbon ring include norbornane, bornane, adamantane, bicyclooctane, tricyclo [5.2.1.0 ^2,6 ] decane, decalin ring and the like.

As the monocyclic non-aromatic heterocyclic ring, for example,
Oxylan, oxane, oxepane, oxocan ring and other oxygen atom-containing heterocycles; and perhydroazepine ring and other nitrogen atom-containing heterocycles. Examples of the polycyclic non-aromatic heterocycle include a bridged cyclic heterocycle.

Further, the aromatic ring includes an aromatic hydrocarbon ring and an aromatic heterocyclic ring. Examples of the aromatic hydrocarbon ring include monocyclic or polycyclic aromatic hydrocarbon rings such as benzene, naphthalene, anthracene, phenanthrene, and phenalene rings. As the aromatic heterocyclic ring, for example, furan, thiophene, pyridine, pyridazine, pyrimidine, pyrazine, quinoline, isoquinoline, quinazoline, quinoxaline, acridine, heteroatom such as nitrogen atom, sulfur atom such as phenazine ring 1 or A monocyclic or polycyclic aromatic heterocyclic ring containing a plurality thereof is exemplified.

Preferred ring Z is a polycyclic non-aromatic ring (hydrocarbon ring or heterocyclic ring), particularly a bridged cyclic ring containing 2 to 4 rings such as an adamantane ring (bridged cyclic hydrocarbon). Ring or bridged cyclic heterocycle) is preferred.

Ring Z may have a substituent. The substituent is not particularly limited as long as it does not impair the reaction. Representative examples of the substituent include, for example, a halogen atom (eg, bromine, chlorine, fluorine atom), an alkyl group (eg, C _1-4 alkyl group such as methyl, ethyl, butyl, t-butyl group), and a protecting group. Examples include a protected hydroxyl group and an amino group protected with a protecting group.

Examples of the protecting group for the hydroxyl group include protecting groups commonly used in the field of organic synthesis, for example, an alkyl group (eg, a C _1-4 alkyl group such as a methyl or t-butyl group), a cycloalkyl group ( For example, a cyclohexyl group or the like, an aralkyl group (for example, a benzyl group), a substituted methyl group (for example, methoxymethyl, methoxythiomethyl, benzyloxymethyl, t-butoxymethyl, 2-
Methoxyethoxymethyl group, etc.), substituted ethyl group (eg, 1-ethoxyethyl, 1-methyl-1-methoxyethyl etc.), acyl group (eg, formyl, acetyl,
C _1-6 aliphatic acyl groups such as propionyl, butyryl, isobutyryl, valeryl and pivaloyl groups; acetoacetyl groups; aromatic acyl groups such as benzoyl and naphthoyl groups; and alkoxycarbonyl groups (eg, methoxycarbonyl, ethoxycarbonyl, Examples thereof include a C _1-4 alkoxycarbonyl group such as a t-butoxycarbonyl group and the like, and an aralkyloxycarbonyl group (eg, a benzyloxycarbonyl group and a p-methoxybenzyloxycarbonyl group). Preferred hydroxyl-protecting groups include C _1-4 alkyl groups, substituted methyl groups, substituted ethyl groups, acyl groups, C _1-4 alkoxycarbonyl groups and the like.

Examples of the amino-protecting group include the alkyl, cycloalkyl, aralkyl, acyl, alkoxycarbonyl, and aralkyloxycarbonyl groups exemplified as the hydroxyl-protecting group. Preferred amino-protecting groups include C _1-4 alkyl groups, C _1-6 aliphatic acyl groups, aromatic acyl groups, C _1-4 alkoxycarbonyl groups and the like.

[Organometallic Compound (Organometallic Reagent)] In the organometallic compound represented by the above formula (2), examples of the metal atom in M include alkali metals such as lithium, cerium, titanium, copper and the like. Transfer metal atoms and the like. The metal atom may have a ligand. Examples of the ligand include a halogen atom such as a chlorine atom, an alkoxy group such as an isopropoxy group, a dialkylamino group such as a diethylamino group, a cyano group, an alkyl group, and an alkali metal atom such as a lithium atom.

R ⁴ represents a hydrocarbon group, for example, a C _1-6 aliphatic hydrocarbon group such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, s-butyl, t-butyl (alkyl, Alkenyl group, alkynyl group); C _3-12 alicyclic hydrocarbon group such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclohexenyl, cyclooctyl, cyclododecyl group (cycloalkyl group, cycloalkenyl group, etc.); phenyl group And C _6-20 aromatic hydrocarbon groups (aryl groups).

R ⁴ may have a substituent. Examples of the substituent include the same substituents as those described above for R ¹ and R ² . Preferred R ⁴ includes a C _1-6 alkyl group, a C _3-12 cycloalkyl group, a C _6-20 aryl group and the like.
In particular, C _1-4 alkyl groups, C _{5 -6} cycloalkyl groups include a phenyl group.

In the above formula (3), examples of the halogen atom represented by Y include chlorine, bromine and iodine atoms.

Representative examples of the organometallic compounds represented by the above formula (2) include organic titanium compounds such as dimethyldiisopropoxytitanium (art complexes of organic titanium); methylmagnesium bromide, ethylmagnesium bromide, butyl Organic magnesium compounds such as magnesium bromide (such as Grignard reagent); and organic lithium compounds such as methyllithium and butyllithium. The organomagnesium compound can be used in combination with a copper halide.

The amount of the organometallic compound represented by the above formula (2) is limited to the tertiary alcohol 1 represented by the above formula (1).
For example, 1 to 3 mol, preferably 1 to 1.
It is about 5 mol.

[Carboxylic acid halide] In the carboxylic acid halide represented by the formula (4), R ³ represents a hydrocarbon group or a heterocyclic group.

The hydrocarbon group includes an aliphatic hydrocarbon group, an alicyclic hydrocarbon group, an aromatic hydrocarbon group, and a group obtained by linking a plurality of these groups. Examples of the aliphatic hydrocarbon group include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, s-butyl, t-butyl, pentyl,
Linear or branched alkyl groups such as hexyl, octyl, and decyl groups (such as C _1-20 alkyl groups); vinyl, allyl, isopropenyl, 1,2-dimethyl-1-propenyl, 1-butenyl, Linear or branched alkenyl groups such as hexenyl (eg, C _2-20 alkenyl groups);
Linear or branched alkynyl groups such as _-propynyl group (C _2-20 alkynyl group and the like);

As the alicyclic hydrocarbon group, 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).

Examples of the aromatic hydrocarbon group include a C _6-20 aromatic hydrocarbon group such as a phenyl and naphthyl group. Examples of a group in which a plurality of different types of hydrocarbon groups are linked to each other include, for example, an aralkyl group having about C _7-21 such as a benzyl or 2-phenylethyl group.

The heterocyclic group includes, for example, a 5- to 6-membered aromatic group containing about 1 to 4 heteroatoms selected from heteroatoms such as a nitrogen atom, an oxygen atom and a sulfur atom. Or a non-aromatic heterocyclic ring, and a condensed ring in which another aromatic or non-aromatic hydrocarbon ring or heterocyclic ring is fused to the heterocyclic ring.

These hydrocarbon groups and heterocyclic groups may have various substituents as long as the reaction is not impaired.

Preferred R ³ includes a hydrocarbon group having a polymerizable unsaturated group. Representative examples of the hydrocarbon group having a polymerizable unsaturated group include, for example, an alkenyl group such as a vinyl group, a 1-propenyl group and an isopropenyl group (particularly, a 1-alkenyl group). Examples of the halogen atom represented by X include a chlorine, bromine and iodine atom.

Representative examples of the carboxylic acid halide represented by the above formula (4) include acrylic acid halides such as acrylic acid chloride, methacrylic acid halides such as methacrylic acid chloride, and crotonic acid halides such as crotonic acid chloride. And unsaturated carboxylic acid halides.

The amount of the carboxylic acid halide represented by the formula (4) is, for example, 1 to 3 mol, preferably 1 to 3 mol, per mol of the tertiary alcohol represented by the formula (1).
It is about 1.5 mol.

[Reaction] In the method of the present invention, a tertiary alcohol represented by the formula (1) is first reacted with an organometallic compound represented by the formula (2) in an organic solvent. It is carried out by reacting the carboxylic acid halide represented by the formula (4) with the produced reaction intermediate (alkoxide).

The organic solvent may be any solvent which is inert to the reaction, for example, ethers such as diethyl ether, 1,2-dimethoxyethane and tetrahydrofuran;
Aliphatic hydrocarbons such as heptane, hexane and octane can be used.

The reaction temperature depends on the type of the reaction components and the like.
For example, it can be appropriately selected within a range of about -100 ° C to 150 ° C. For example, in the organometallic compound represented by the formula (2), when M is a metal atom (for example, lithium), the reaction temperature is, for example, -100 ° C to 30 ° C, preferably -10 ° C to 15 ° C. It is about. When a compound in which M represents a group represented by the formula (3) is used as the compound of the formula (2), the reaction temperature is, for example, about 0 ° C to 150 ° C, preferably about 20 ° C to 100 ° C. It is.

The reaction can be carried out by a conventional method such as a batch system, a semi-batch system, and a continuous system. Generally, an organometallic compound represented by the formula (3) (or a solution containing the same) is sequentially added to a solution containing a tertiary alcohol represented by the formula (1), A carboxylic acid halide represented by the following formula (or a solution containing the same) is sequentially added into the system.

After completion of the reaction, if necessary, after quenching with water or the like, for example, filtration, concentration, extraction, washing, distillation, crystallization,
By using separation and purification means such as recrystallization and column chromatography, the desired reaction product can be obtained.

The tertiary alcohol ester thus obtained is useful as a monomer of a functional polymer or an intermediate material for fine chemicals. In particular, a compound in which an alcohol moiety is eliminated by an acid to generate a free carboxylic acid,
It can be used as a monomer material for a photosensitive resin as an acid-sensitive compound.

[0051]

According to the method of the present invention, a corresponding tertiary alcohol ester compound can be easily and efficiently produced from a tertiary alcohol having a ring in one of the branched chains.

[0052]

The present invention will be described in more detail with reference to the following Examples, but it should not be construed that the invention is limited thereto.

Example 1 Synthesis of 1- (1'-adamantyl) -1-methylethyl acrylate from 1- (1'-adamantyl) -1-methylethanol (butyllithium method) 3 l flask equipped with stirrer and thermometer In addition, 1- (1'-
Adamantyl) -1-methylethanol (150 g / 7
72 mmol), tetrahydrofuran (THF; 120
0 ml) and stirred under a nitrogen stream. In a water bath, a 1.50 M solution of n-butyllithium in hexane (567 ml / 849 mmol) was added dropwise over 2 hours using a dropping funnel, followed by aging for 1 hour. To this, TH of acrylic acid chloride (76.9 g / 849 mmol) was added.
F (307 ml) solution was added dropwise over 1 hour.
Aged for hours. The reaction mixture was analyzed by high performance liquid chromatography to find that 1- represented by the formula (5a)
(1′-Adamantyl) -1-methylethyl acrylate (yield 79.2%) was produced. The reaction mixture was washed once with pure water, a 10% by weight aqueous solution of sodium carbonate and a 10% by weight aqueous solution of sodium chloride, and then the solvent was removed under reduced pressure, followed by purification by silica gel column chromatography. The target 1-
(1 ′ Adamantyl) -1-methylethyl acrylate (146 g / yield 75.9%) was obtained.

Embedded image

Example 2 Synthesis of 1- (1′-adamantyl) -1-methylethyl acrylate from 1- (1′-adamantyl) -1-methylethanol (butylmagnesium bromide method) 3 l equipped with a stirrer and a thermometer Add 1- (1'-
Adamantyl) -1-methylethanol (150 g / 7
72 mmol) and THF (600 g), and the mixture was stirred under a nitrogen stream. To this, a 2.51 mmol / g THF solution (338 g / 849 mmol) of n-butylmagnesium bromide prepared by a conventional method was added dropwise over 2 hours using a dropping funnel while controlling the liquid temperature at 50 ° C.
It was aged for an additional hour. To this, acrylic acid chloride (76.9 g / 849 mmol) in THF (307 m
l) The solution was added dropwise over 1 hour and aged for 1 hour. As a result of analyzing the reaction mixture by high performance liquid chromatography, 1- (1′-adamantyl) -1-methylethyl acrylate represented by the formula (5a) (yield: 76.
8%). This reaction mixture is mixed with pure water, 10
After washing once each with a 10% by weight aqueous solution of sodium carbonate and a 10% by weight aqueous solution of sodium chloride, the solvent was removed under reduced pressure, and the residue was purified by silica gel column chromatography to obtain 1- (1 ′ adamantyl) as a target substance. )
-1-methylethyl acrylate (139 g / yield 7
2.4%).

Example 3 Synthesis of 1- (1'-adamantyl) -1-methylethyl methacrylate from 1- (1'-adamantyl) -1-methylethanol (butyl lithium method) Methacrylic acid chloride was used instead of acrylic acid chloride The reaction was carried out in the same manner as in Example 1 except that The obtained reaction mixture was analyzed by high performance liquid chromatography, and as a result, 1- (1′-adamantyl) -1-methylethyl methacrylate represented by the following formula (5b) (yield 94.
1%). This reaction mixture is mixed with pure water, 10
After washing once each with a 10% by weight aqueous solution of sodium carbonate and a 10% by weight aqueous solution of sodium chloride, the solvent was removed under reduced pressure, and the residue was purified by silica gel column chromatography to obtain 1- (1 ′ adamantyl) as a target substance. )
-1-methylethyl methacrylate (183 g / yield 9
0.5%).

Embedded image

Example 4 Synthesis of 1- (1'-adamantyl) -1-methylethyl methacrylate from 1- (1'-adamantyl) -1-methylethanol (butylmagnesium bromide method) Methacrylic acid instead of acrylic acid chloride The reaction was carried out in the same manner as in Example 2 except that chloride was used. The obtained reaction mixture was analyzed by high performance liquid chromatography, and as a result, 1- (1 ′ adamantyl) -1-methylethyl methacrylate represented by the formula (5b) (yield: 87.4) was obtained.
%). The reaction mixture was washed once with pure water, a 10% by weight aqueous solution of sodium carbonate and a 10% by weight aqueous solution of sodium chloride, and then the solvent was removed under reduced pressure, followed by purification by silica gel column chromatography. 1- (1 ′ adamantyl) which is the target substance
1-methylethyl methacrylate (168 g / yield 8
3.1%).

Example 5 1- (1 '-(3'-methoxyethoxymethyloxyadamantyl) -1-methylethanol to 1- (1'-
(3 ′-(2 ″ -methoxyethoxymethyl) oxy)
Synthesis of adamantyl) -1-methylethyl acrylate (butyl lithium method) 1- (1 '-(3'-methoxyethoxymethyloxyadamantyl) -1-) instead of 1- (1'-adamantyl) -1-methylethanol The reaction was carried out in the same manner as in Example 1 except that methylethanol was used, and the obtained reaction mixture was analyzed by high performance liquid chromatography.
1- (1 ′-(3′-) represented by the following formula (5c)
(2 ″ -methoxyethoxymethyl) oxy) adamantyl) -1-methylethyl acrylate (70.3 yield)
%). The reaction mixture was washed once with pure water, a 10% by weight aqueous solution of sodium carbonate and a 10% by weight aqueous solution of sodium chloride, and then the solvent was removed under reduced pressure, followed by purification by silica gel column chromatography. 1- (1 ′-(3′-
(177% (yield: 65.2%) (2 ″ -methoxyethoxymethyl) oxy) adamantyl) -1-methylethyl acrylate was obtained.

Embedded image

Example 6 1- (1 '-(3'-methoxyethoxymethyloxyadamantyl) -1-methylethanol to 1- (1'-
(3 ′-(2 ″ -methoxyethoxymethyl) oxy)
Synthesis of adamantyl) -1-methylethyl methacrylate (butyl lithium method) 1- (1 '-(3'-methoxyethoxymethyloxyadamantyl) -1-) instead of 1- (1'-adamantyl) -1-methylethanol The reaction was carried out in the same manner as in Example 3 except that methylethanol was used, and the resulting reaction mixture was analyzed by high performance liquid chromatography.
1- (1 ′-(3′-) represented by the following formula (5d)
(2 ''-methoxyethoxymethyl) oxy) adamantyl) -1-methylethyl methacrylate (yield 91.3)
%). The reaction mixture was washed once with pure water, a 10% by weight aqueous solution of sodium carbonate and a 10% by weight aqueous solution of sodium chloride, and then the solvent was removed under reduced pressure, followed by purification by silica gel column chromatography. 1- (1 ′-(3′-
(2 "-methoxyethoxymethyl) oxy) adamantyl) -1-methylethyl methacrylate (241 g /
Yield 85.2%).

Embedded image

Comparative Example 1 Synthesis of 1- (1'-adamantyl) -1-methylethyl acrylate from 1- (1'-adamantyl) -1-methylethanol (triethylamine method) A 3 l flask equipped with a stirrer and a thermometer was used. , 1- (1′-
Adamantyl) -1-methylethanol (125 g / 6
43 mmol), methoxyphenol (0.125 g /
1.0 mmol), triethylamine (130 g / 12
90 mmol) and toluene (1750 ml), and the mixture was stirred under a nitrogen stream. In a water bath, acrylic chloride (87.3 g / 965 mmol) was added thereto using a dropping funnel.
Was added dropwise over 1 hour.
It was aged for an additional hour. As a result of analyzing the reaction mixture by high performance liquid chromatography, 1- (1′-adamantyl) -1-methylethyl acrylate (yield: 56.4%) represented by the formula (5a) was produced. Further analysis revealed that the starting material 1- (1′-adamantyl) -1-
Although almost no methyl ethanol remained, it was found that a large amount of a polymer of 1- (1′-adamantyl) -1-methylethyl acrylate as a product was formed.

Comparative Example 2 Synthesis of 1- (1'-adamantyl) -1-methylethyl acrylate from 1- (1'-adamantyl) -1-methylethanol (sodium hydride method) 300 ml equipped with a stirrer and a thermometer In a flask, sodium hydride (1.36 g / 56.61 mmol), TH
F (14 ml) was added and the mixture was stirred under a nitrogen stream. Using a dropping funnel, 1- (1′-adamantyl) -1-methylethanol (10 g / 51.46 mmol) in THF was added thereto.
(100 ml) The solution was added dropwise, and the mixture was further stirred under reflux for 3 hours. To this solution, a solution of acrylic acid chloride (5.12 g / 56.61 mmol) in THF (20 ml) was added dropwise over 1 hour using a dropping funnel in a water bath, and the mixture was further aged at room temperature for 5 hours. The reaction mixture was analyzed by high performance liquid chromatography to find that the starting material 1- (1′-
Most of adamantyl) -1-methylethanol remained, and the desired 1- (1′-adamantyl) -1-methylethyl acrylate was not produced.

Comparative Example 3 Synthesis of 1- (1'-adamantyl) -1-methylethyl acrylate from 1- (1'-adamantyl) -1-methylethanol (acrylic acid method) Stirrer, thermometer, dean-stark device 3 with
In a 00 ml flask, add 1- (1'-adamantyl) -1
-Methylethanol (10 g / 51.46 mmol),
Methoxyphenol (0.10 g / 0.8 mmol),
p-Toluenesulfonic acid monohydrate (0.489 g /
2.57 mmol), acrylic acid (5.56 g / 77.
19 mmol) and toluene (100 ml), and the mixture was stirred under reflux for 2 hours while blowing air. As a result of analyzing the reaction mixture by high performance liquid chromatography, isopropenyl adamantane represented by the following formula (6) was almost quantitatively produced, and the desired 1- (1′-
(Adamantly) -1-methylethyl acrylate was not produced.

Embedded image

Comparative Example 4 Synthesis of 1- (1'-adamantyl) -1-methylethyl methacrylate from 1- (1'-adamantyl) -1-methylethanol (triethylamine method) Methacrylic acid chloride was used instead of acrylic acid chloride. The reaction was carried out in the same manner as in Comparative Example 1, except for using. The reaction mixture was analyzed by high performance liquid chromatography. As a result, it was found that almost 1- (1′-adamantyl) -1-methylethanol as a raw material remained, and the desired 1- (1′-methylethanol) was obtained.
(Adamantyl) -1-methylethyl methacrylate was not produced.

Comparative Example 5 Synthesis of 1- (1′-adamantyl) -1-methylethyl methacrylate from 1- (1′-adamantyl) -1-methylethanol (sodium hydride method) Methacrylic acid instead of acrylic acid chloride The reaction was carried out in the same manner as in Comparative Example 2 except that chloride was used. The reaction mixture was analyzed by high performance liquid chromatography. As a result, it was found that almost 1- (1′-adamantyl) -1-methylethanol as a raw material remained, and the desired 1- (1′-methylethanol) was obtained.
(Adamantyl) -1-methylethyl methacrylate was not produced.

Claims (7)

[Claims] [Claim 1] The following formula (1) (Wherein, ring Z represents a monocyclic or polycyclic non-aromatic or aromatic ring. R ¹ and R ² are the same or different and represent a hydrocarbon group. R ¹ and R ² are A tertiary alcohol represented by the following formula (2) R ⁴ -M (2) wherein R ⁴ is carbonized Shows a hydrogen group. M represents a metal atom which may have a ligand, or an organic metal represented by the following formula (3) -MgY (3) (wherein, Y represents a halogen atom). Compound and the following formula (4): (Wherein, R ³ represents a hydrocarbon group or a heterocyclic group; X represents a halogen atom), and reacted with a carboxylic acid halide represented by the following formula (5): (Wherein Z, R ¹ , R ² , and R ³ are the same as described above). A method for producing a tertiary alcohol ester represented by the following formula: 2. The method for producing a tertiary alcohol ester according to claim 1, wherein the ring Z is a bridged cyclic ring containing 2 to 4 rings. 3. A ring Z is a norbornane ring, a bornane ring,
The method for producing a tertiary alcohol ester according to claim 1, which is an adamantane ring, a bicyclooctane ring, a tricyclo [5.2.1.0 ^2,6 ] decane ring or a decalin ring. 4. A monocyclic or polycyclic non-aromatic ring which may have a halogen atom, an alkyl group, a hydroxyl group protected by a protecting group or an amino group protected by a protecting group. The method for producing a tertiary alcohol ester according to claim 1, wherein 5. The method for producing a tertiary alcohol ester according to claim ¹ , wherein R ¹ and R ² are a C _1-6 alkyl group, a C _3-12 cycloalkyl group or a C _6-20 aryl group. 6. The method for producing a tertiary alcohol ester according to claim 1, wherein R ³ is a hydrocarbon group having a polymerizable unsaturated group. 7. The method for producing a tertiary alcohol ester according to claim 1, wherein R ³ is a vinyl group, a 1-propenyl group or an isopropenyl group.