JPH11228481A - Bicyclo(3.3.1)nonane derivative and its production - Google Patents

Abstract

PROBLEM TO BE SOLVED: To simply obtain a new bicyclo[3.3.1] nonane derivative having hydroxymethyl or acyloxymethyl group at the 3 position and having oxo group at the 7 position and useful as a raw material for acrylic resin monomers, etc. SOLUTION: This bicyclo[3.3.1]nonane derivative is represented by formula I (R<1> is H or an acyl; carbon atom constituting bicyclo[3.3.1]nonane ring may have a substituent group), e.g.3-acetoxymethy1-7-oxo-bicyclo[3.3.1]nonane. The derivative is obtained by reacting an adamantane derivative of formula III (R<b> is H, hydroxyl or an acyloxy) with a compound of the formula R<a> -OH and molecular oxygen in the presence of an imide compound of formula II [R<1> and R<2> are each independently H, a halogen, an acyl, an alkyl, an aryl, a cycloalkyl, hydroxyl, an alkoxy, etc.; X is 0 or hydroxyl; (n) is 1, 2 or 3] and hydrochloric acid.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a novel bicyclo [3.3.1] nonane derivative and a method for producing the same.
This compound is expected to be used as a raw material for acrylic resin monomers for resists.

[0002]

2. Description of the Related Art Hydroxyl and hydroxymethyl groups,
Alternatively, a non-aromatic polycyclic hydrocarbon having a substituent such as an oxo group or an acyloxymethyl group, which is a precursor thereof, is a raw material (alcohol component) of a (meth) acrylate ester which is a monomer of an acrylic resin for a resist. ), Which has recently attracted attention. But,
Conventionally, a bicyclo [3.3.1] nonane derivative having a hydroxymethyl group or an acyloxymethyl group at the 3-position and an oxo group at the 7-position has not been known. In addition,
JP-A-8-38909 and JP-A-9-32762
No. 6 discloses a method similar to the present invention, that is, a method of oxidizing an adamantane derivative with molecular oxygen in the presence of a specific imide compound. But,
According to this method, the bicyclo [3.3.1] nonane derivative has not been obtained.

[0003]

Accordingly, an object of the present invention is to provide a bicyclo [3. having a hydroxymethyl group or an acyloxymethyl group at the 3-position and an oxo group at the 7-position.
3.1] A nonane derivative is provided. Another object of the present invention is to provide a method for producing a bicyclo [3.3.1] nonane derivative having a hydroxymethyl group or an acyloxymethyl group at the 3-position and an oxo group at the 7-position. is there.

[0004]

As a result of repeated studies on the oxidation reaction of adamantane derivatives, when the adamantane derivative is oxidized with molecular oxygen under specific reaction conditions, a novel bicyclo [3.3] is obtained. .1] Nonane derivatives were obtained, and the present invention was completed.

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

Embedded image (Wherein ^Ra represents a hydrogen atom or an acyl group, and the carbon atom constituting the bicyclo [3.3.1] nonane ring may have a substituent). .1]
A nonane derivative is provided.

The present invention also provides (A) the following formula (2)

Embedded image (Wherein R ¹ and R ² are the same or different and each represents a hydrogen atom,
A halogen atom, an alkyl group, an aryl group, a cycloalkyl group, a hydroxyl group, an alkoxy group, a carboxyl group, an alkoxycarbonyl group, or an acyl group; R ¹ and R ² are bonded to each other to form a double bond, or A non-aromatic ring may be formed. X represents an oxygen atom or a hydroxyl group, and n represents an integer of 1 to 3), and (B) a strong acid, in the presence of the following formula (3):

Embedded image (In the formula, R ^b represents a hydrogen atom, a hydroxyl group, or an acyloxy group. The carbon atoms constituting the adamantane skeleton are substituted except for one carbon atom adjacent to the bridgehead carbon atom to which R ^b is bonded. An adamantane derivative represented by the following formula (4): ^a compound represented by the following formula (4): R ^a —OH (where R ^a represents a hydrogen atom or an acyl group); By reacting with oxygen, the above formula (1)
The production method of the bicyclo [3.3.1] nonane derivative which produces | generates the bicyclo [3.3.1] nonane derivative represented by these is provided.

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION [Bicyclo [3.3.1] nonane derivative] In the bicyclo [3.3.1] nonane derivative represented by the formula (1), the acyl group represented by ^Ra is formyl. Or saturated or unsaturated aliphatic carboxylic acid acyl groups such as acetyl, propionyl, butyryl, butyryl, isobutyryl, valeryl, isovaleryl, hexanoyl, palmitoyl, acryloyl, oxalyl, malonyl groups; cycloaliphatic carboxylic acids such as cycloheptanecarbonyl and cyclohexanecarbonyl groups Acyl groups; aromatic carboxylic acyl groups such as benzoyl, toluyl, phthaloyl, and naphthoyl groups; heterocyclic carboxylic acid acyl groups such as nicotinoyl and furoyl groups; sulfones such as methanesulfonyl, ethanesulfonyl, benzenesulfonyl, and p-toluenesulfonyl groups. Acid acyl group Murrell. These acyl groups include a halogen atom (such as a fluorine or chlorine atom), an alkyl group (such as a C _1-4 alkyl group such as a methyl group), an alkoxy group (such as a C _1-4 alkoxy group such as a methoxy group), and an aryl group. It may have a substituent such as a phenyl or naphthyl group, a nitro group, a cyano group, or a haloalkyl group (such as a trifluoromethyl group). Preferred acyl groups include an aliphatic carboxylic acid acyl group and an aromatic carboxylic acid acyl group. Particularly, C _1-5 such as acetyl group
An aliphatic carboxylic acid acyl group is preferred.

The bicyclo [3.3.
1] In the nonane derivative, examples of the substituent that may be possessed by the carbon atom constituting the bicyclo [3.3.1] nonane ring include a halogen atom (eg, chlorine or bromine atom) and an alkyl group (eg, methyl group). C _1-4 alkyl group), such as a hydroxyl group, such as C _1-4 alkoxy group such as alkoxy group (methoxy group), an acyloxy group (e.g., acyloxy corresponding to the exemplified acyl group as the acyl group in R ^a Group), a hydroxymethyl group, a substituted or unsubstituted amino group (amino, mono- or di-C
_1-4 alkylamino, _C1-5 aliphatic acylamino, aromatic acylamino group, etc.), carboxyl group, substituted oxycarbonyl group ( _C1-4 alkoxycarbonyl group such as methoxycarbonyl, ethoxycarbonyl group, etc.), substituted or unsubstituted Substituted carbamoyl groups (carbamoyl, mono- or di-
C _1-4 alkylcarbamoyl group), nitro group, acyl group (eg, the acyl group exemplified as the acyl group for R ^a ), and oxo group. The hydroxyl group, hydroxymethyl group, amino group, and carboxyl group may be protected with a conventional protecting group.

As typical examples of the compound represented by the formula (1), 3-acetoxymethyl-7-oxo-bicyclo [3.3.1] nonane, 3-acetoxymethyl-7-oxo-1-methyl -Bicyclo [3.3.1] nonane, 3
-Acetoxymethyl-7-oxo-5-methyl-bicyclo [3.3.1] nonane, 3-acetoxymethyl-7-
Oxo-1,5-dimethyl-bicyclo [3.3.1] nonane, 3-acetoxymethyl-1-hydroxy-7-oxo-bicyclo [3.3.1] nonane, 3-acetoxymethyl-5-hydroxy- 7-oxo-bicyclo [3.
3.1] Nonane, 3-acetoxymethyl-7-oxo-
1-methoxy-bicyclo [3.3.1] nonane, 3-acetoxymethyl-7-oxo-5-methoxy-bicyclo [3.3.1] nonane, 3-acetoxymethyl-1-hydroxymethyl-7-oxo -Bicyclo [3.3.1]
Nonane, 3-acetoxymethyl-5-hydroxymethyl-7-oxo-bicyclo [3.3.1] nonane, 3-acetoxymethyl-1-amino-7-oxo-bicyclo [3.3.1] nonane, -Acetoxymethyl-5-amino-7-oxo-bicyclo [3.3.1] nonane, 3
-Acetoxymethyl-7-oxo-1- (N, N-dimethylamino) -bicyclo [3.3.1] nonane, 3-acetoxymethyl-7-oxo-5- (N, N-dimethylamino) -bicyclo [3.3.1] nonane, 3-acetoxymethyl-1-carboxy-7-oxo-bicyclo [3.3.1] nonane, 3-acetoxymethyl-5-carboxy-7-oxo-bicyclo [3.3 .1] nonane, 3-acetoxymethyl-7-oxo-1-methoxycarbonyl-bicyclo [3.3.1] nonane, 3-acetoxymethyl-7-oxo-5-methoxycarbonyl-
Bicyclo [3.3.1] nonane, 3-acetoxymethyl-7-oxo-1-nitro-bicyclo [3.3.1] nonane, 3-acetoxymethyl-7-oxo-5-nitro-bicyclo [3. 3.1] Nonane, 3-acetoxymethyl-1-acetyl-7-oxo-bicyclo [3.3.
1] Nonane, 3-acetoxymethyl-5-acetyl-7
-Oxo-bicyclo [3.3.1] nonane, 3-hydroxymethyl-7-oxo-bicyclo [3.3.1] nonane, 3-hydroxymethyl-7-oxo-1-methyl-
Bicyclo [3.3.1] nonane, 3-hydroxymethyl-7-oxo-5-methyl-bicyclo [3.3.1] nonane and the like can be mentioned. The compound represented by the formula (1) is expected to be used as a monomer material of a functional polymer such as an acrylic resin for a resist.

[Production of Bicyclo [3.3.1] nonane Derivative] In the imide compound (A) represented by the above formula (2) used in the production method of the present invention, halogen among the substituents R ¹ and R ² is used. Atoms include iodine, bromine, chlorine and fluorine. Examples of the alkyl group include methyl, ethyl,
1 carbon atom such as propyl, isopropyl, butyl, isobutyl, s-butyl, t-butyl, hexyl, decyl group, etc.
It contains about 10 to about 10 linear or branched alkyl groups. Preferred alkyl groups include, for example, those having 1 to 1 carbon atoms.
A lower alkyl group having about 6, particularly about 1 to 4 carbon atoms is exemplified.

The aryl group includes phenyl and naphthyl groups, and the cycloalkyl group includes cyclopentyl and
And a cyclohexyl group. The alkoxy group includes
For example, methoxy, ethoxy, isopropoxy, butoxy, t-butoxy, hexyloxy groups and other C1-C1
About 10 carbon atoms, preferably about 1 to 6 carbon atoms, particularly 1 carbon atom
About 4 lower alkoxy groups are included.

The alkoxycarbonyl group includes, for example, an alkoxycarbonyl group having about 1 to 10 carbon atoms in the alkoxy moiety such as methoxycarbonyl, ethoxycarbonyl, isopropoxycarbonyl, butoxycarbonyl, t-butoxycarbonyl, hexyloxycarbonyl and the like. included. Preferred alkoxycarbonyl groups include lower alkoxycarbonyl groups having about 1 to 6, particularly about 1 to 4, carbon atoms in the alkoxy moiety. Examples of the acyl group include acyl groups having about 1 to 6 carbon atoms, such as formyl, acetyl, propionyl, butyryl, isobutyryl, valeryl, isovaleryl, and pivaloyl groups.

The substituents R ¹ and R ² may be the same or different. In the formula (2), R ¹ and R ² may be bonded to each other to form a double bond or a ring having an aromatic or non-aromatic attribute. The preferred aromatic or non-aromatic ring is a 5- to 12-membered ring, particularly a 6- to 10-membered ring, and may be a heterocyclic ring or a fused heterocyclic ring, but is often a hydrocarbon ring. Such rings include, for example,
Non-aromatic alicyclic ring (cycloalkane ring optionally having a substituent such as cyclohexane ring, cycloalkene ring optionally having a substituent such as cyclohexene ring), non-aromatic bridge A bridged ring (eg, a bridged hydrocarbon ring which may have a substituent such as a 5-norbornene ring),
An aromatic ring (including a condensed ring) which may have a substituent such as a benzene ring and a naphthalene ring is included. The ring is
Often composed of aromatic rings. The ring is an alkyl group, a haloalkyl group, a hydroxyl group, an alkoxy group,
Carboxyl group, alkoxycarbonyl group, acyl group,
It may have a substituent such as a nitro group, a cyano group, an amino group, and a halogen atom.

Preferred imide compounds (A) include compounds represented by the following formula.

Embedded image (Wherein, R ^{3 to} R ⁶ are the same or different and each represents a hydrogen atom, an alkyl group, a haloalkyl group, a hydroxyl group, an alkoxy group, a carboxyl group, an alkoxycarbonyl group, an acyl group, a nitro group, a cyano group, an amino group, R ^{3 to} R ⁶ may be a group in which adjacent groups are bonded to each other to form an aromatic or non-aromatic ring.
R ¹ , R ² and n are the same as described above) In the substituents R ^{3 to} R ⁶ , the alkyl group includes the same alkyl group as the above-described alkyl group, particularly an alkyl group having about 1 to 6 carbon atoms. A haloalkyl group having about 1 to 4 carbon atoms such as a trifluoromethyl group; an alkoxy group having the same alkoxy group as described above, particularly a lower alkoxy group having about 1 to 4 carbon atoms and an alkoxycarbonyl group; Includes the same alkoxycarbonyl group as described above, particularly a lower alkoxycarbonyl group having about 1 to 4 carbon atoms in the alkoxy moiety. Examples of the acyl group include the same acyl groups as described above, particularly an acyl group having about 1 to 6 carbon atoms. Examples of the halogen atom include fluorine,
Chlorine and bromine atoms can be exemplified. The substituents R ^{3 to} R ⁶ are usually a hydrogen atom, a lower alkyl group having about 1 to 4 carbon atoms, a carboxyl group, a nitro group, or a halogen atom in many cases. The ring formed by combining R ^{3 to} R ⁶ with each other is the same as the ring formed by combining R ¹ and R ² with each other, and in particular, an aromatic or non-aromatic 5- to 12-membered ring Is preferred.

In the formula (2), X represents an oxygen atom or a hydroxyl group, and the bond between the nitrogen atom N and X is a single bond or a double bond. n is usually about 1 to 3, preferably 1 or 2. The imide compound (A) represented by the formula (2) can be used alone or in combination of two or more.

The acid anhydride corresponding to the imide compound (A) represented by the formula (2) includes, for example, a saturated or unsaturated aliphatic dicarboxylic anhydride such as succinic anhydride and maleic anhydride, and tetrahydroanhydride. Saturated or unsaturated non-aromatic cyclic polyvalent such as phthalic acid, hexahydrophthalic anhydride (1,2-cyclohexanedicarboxylic anhydride), 1,2,3,4-cyclohexanetetracarboxylic acid 1,2-anhydride Crosslinked cyclic polycarboxylic anhydrides (alicyclic polycarboxylic anhydrides) such as carboxylic anhydrides (alicyclic polycarboxylic anhydrides), heptonic anhydride, hymic anhydride, and phthalic anhydride , Tetrabromophthalic anhydride, tetrachlorophthalic anhydride, nitrophthalic anhydride, trimetic anhydride, methylcyclohexenetricarboxylic anhydride, pyromellitic anhydride, none Mellitic acid, 1,8; 4,
Aromatic polycarboxylic anhydrides such as 5-naphthalenetetracarboxylic dianhydride are included.

Preferred imide compounds include, for example,
N-hydroxysuccinimide, N-hydroxymaleimide, N-hydroxyhexahydrophthalimide, N, N'-dihydroxycyclohexanetetracarboxylic imide, N-hydroxyphthalimide, N-hydroxytetrabromophthalimide N-hydroxytetrachlorophthalic imide, N-hydroxyhetic imide, N-hydroxyhymic imide, N-hydroxytrimellitic imide, N, N'-dihydroxypyromellitic imide, N, N'-dihydroxy And naphthalenetetracarboxylic imide. Particularly preferred compounds are alicyclic polycarboxylic anhydrides or aromatic polycarboxylic anhydrides, especially N-hydroxyimide compounds derived from aromatic polycarboxylic anhydrides,
For example, N-hydroxyphthalimide is included.

The imide compound (A) is prepared by a conventional imidization reaction, for example, a reaction between a corresponding acid anhydride and hydroxylamine NH ₂ OH, followed by ring opening and ring closing of the acid anhydride group. Can be prepared.

The strong acid (B) used in the method of the present invention includes an inorganic acid and an organic acid. As the inorganic acid, for example,
Sulfuric acid, nitric acid, hydrogen halide (hydrogen fluoride, hydrogen chloride,
Hydrogen bromide, hydrogen iodide, and the corresponding hydrohalic acids), phosphoric acid, heteropolyacids (eg, phosphomolybdic acid, phosphotungstic acid, phosphovanadomolybdic acid, silicomolybdic acid, silicotungstic acid, and the like) and the like. Can be Examples of the organic acid include alkylsulfonic acids (e.g., methanesulfonic acid, ethanesulfonic acid, etc.), haloalkylsulfonic acids (e.g., trifluoromethanesulfonic acid, etc.), arylsulfonic acids (e.g., benzenesulfonic acid, p-toluenesulfonic acid, Sulfonic acids such as naphthalenesulfonic acid); phosphonic acids such as alkylphosphonic acid and arylphosphonic acid. As the strong acid (B), a strongly acidic cation exchange resin (exchanger) such as a sulfonic acid type cation exchange resin and a phosphonic acid type cation exchange resin (exchanger) can also be used.

The pKa in the aqueous solution of the strong acid (B) at 25 ° C. is preferably 3 or less (for example, about -14 to 3), more preferably 0 or less (for example, about -14 to 0), and particularly preferably. -2 or less (for example, -14 to -2
Degree). Preferred strong acids (B) include sulfonic acids such as alkylsulfonic acids such as methanesulfonic acid. The strong acid (B) may be used alone or in combination of two or more.

[0021] In adamantane derivative represented by the formula (3), an acyloxy group (and preferably acyloxy group) represented by R ^b as, the exemplified acyl group as the acyl group in R ^a (and, preferably acyl groups ), That is, an acyloxy group of aliphatic carboxylic acid, an acyloxy group of alicyclic carboxylic acid, an acyloxy group of aromatic carboxylic acid, an acyloxy group of heterocyclic carboxylic acid and an acyloxy group of sulfonic acid. In addition, as the substituent which may be possessed by the carbon atom constituting the adamantane skeleton, in the bicyclo [3.3.1] nonane derivative represented by the above formula (1),
The same substituents as those exemplified as the substituent which the carbon atom constituting the bicyclo [3.3.1] nonane ring may have may be mentioned.

Specific examples of the adamantane derivative represented by the formula (3) include, for example, adamantane, 1-methyladamantane, 1,3-dimethyladamantane, 1-adamantanol, 1,3-adamantanediol, 1-methoxyadamantane , 1-acetoxyadamantane, 1-
Hydroxymethyl adamantane, 1-amino adamantane, 1- (N, N-dimethylamino) adamantane, 1
-Carboxyadamantane, 1-methoxycarbonyladamantane, 1-nitroadamantane, 1-acetyladamantane, and the like.

In the compound represented by the formula (4),
Examples of the acyl group represented by R ^a, include the same acyl groups as those exemplified as the acyl group in the R ^a. Representative examples of the compound represented by the formula (4) include, for example, water; and organic acids such as formic acid, acetic acid, propionic acid, acrylic acid, malonic acid, and benzoic acid. Water and an organic acid may coexist in the system.

The molecular oxygen is not particularly limited, and pure oxygen may be used, or oxygen or air diluted with an inert gas such as nitrogen, helium, argon or carbon dioxide may be used.

In the method of the present invention, the amount of the imide compound (A) represented by the formula (2) is, for example, 0.001 mol per mol of the adamantane derivative represented by the formula (3).
001 to 1 mol, preferably 0.001 to 0.7 mol,
More preferably, it is about 0.01 to 0.5 mol. The amount of the strong acid (B) used may be a small amount, and for example, per 1 mol of the adamantane derivative represented by the formula (3),
It is about 0.00001 to 2 mol, preferably about 0.001 to 1 mol, and more preferably about 0.01 to 0.7 mol.

The amount of the compound represented by the formula (4) is based on 1 mol of the adamantane derivative represented by the formula (3).
For example, it is about 0.8 to 500 mol, preferably about 1 to 200 mol, and more preferably about 1 to 100 mol. The compound represented by the formula (4) can be used as a reaction solvent.

The amount of oxygen used is usually 0.5 mol or more (for example, 1 mol or more), preferably 1 to 100 mol, per 1 mol of the adamantane derivative represented by the formula (3).
More preferably, it is about 2 to 50 mol. Often, an excess of molecular oxygen is used relative to the substrate.

In the method of the present invention, a metal compound may be used as a promoter. The metal element constituting the metal compound is not particularly limited, and may be any of the metal elements of Groups 1 to 15 of the periodic table. Note that, in this specification, boron B is also included in the metal element. For example, as the metal elements, Group 1 elements (such as Li, Na, and K), Group 2 elements (such as Mg, Ca, Sr, and Ba), Group 3 elements (such as Sc, lanthanoid elements, and actinoid elements), Group 5 elements (Ti, Zr, Hf, etc.), Group 5 elements (V, etc.), Group 6 elements (Cr, Mo, W, etc.), Group 7 elements (Mn, etc.), Group 8 elements (Fe, Ru, etc.), 9 Group elements (Co, Rh, etc.), Group 10 elements (Ni, Pd, Pt)
), Group 11 elements (such as Zn), Group 13 elements (such as B, Al, In), Group 14 elements (such as Sn and Pb), and Group 15 elements (such as Sb and Bi). And the like. Preferred metal elements include transition metal elements (groups 3 to 12 of the periodic table). Above all, elements of Groups 5 to 11 of the periodic table are preferable. The valence of the metal element is not particularly limited, and may be about 1 to 6, but often about 2 or 3.

Examples of the metal compound include simple substances, hydroxides, oxides (including complex oxides), halides (fluoride, chloride, bromide, iodide), oxo acid salts (for example, nitrate) , Sulfate, phosphate, borate,
Inorganic compounds such as carbonates), oxo acids, and isopoly acids; organic compounds such as organic acid salts (eg, acetate, propionate, cyanate, naphthenate, stearate), and complexes. The ligands constituting the complex include OH (hydroxo), alkoxy (methoxy,
Ethoxy, propoxy, butoxy, etc.), acyl (acetyl, propionyl, etc.), alkoxycarbonyl (methoxycarbonyl, ethoxycarbonyl, etc.), acetylacetonato, cyclopentadienyl group, halogen atom (chlorine, bromine, etc.), CO, CN, Oxygen atom, H ₂ O
(Aquo), phosphorus compound of phosphine (triarylphosphine such as triphenylphosphine), NH
_And nitrogen-containing compounds such as ₃ (ammine), NO, NO ₂ (nitro), NO ₃ (nitrat), ethylenediamine, diethylenetriamine, pyridine and phenanthroline.

The amount of the metal compound used is, for example, based on 1 mol of the adamantane derivative represented by the formula (3).
0.00001-1 mol, preferably 0.0001-
It is about 0.1 mol, more preferably about 0.001 to 0.05 mol.

The method of the present invention is usually carried out in an organic solvent. Examples of the organic solvent include nitriles such as acetonitrile, propionitrile, and benzonitrile; formamide, acetamide, dimethylformamide (D
Amides such as MF) and dimethylacetamide; alcohols such as t-butanol and t-amyl alcohol;
Aliphatic hydrocarbons such as hexane and octane; benzene,
Aromatic hydrocarbons such as toluene; halogenated hydrocarbons such as chloroform, dichloromethane, dichloroethane, carbon tetrachloride, chlorobenzene and trifluoromethylbenzene; nitro compounds such as nitrobenzene, nitromethane and nitroethane; esters such as ethyl acetate and butyl acetate Ethers such as diethyl ether and diisopropyl ether; and mixed solvents thereof.

The reaction temperature is, for example, 0 to 300 ° C., preferably 30 to 250 ° C., and more preferably 40 to 200 ° C.
° C, and usually reacts at about 40 to 150 ° C in many cases. The reaction can be carried out under normal pressure or under pressure. When the reaction is carried out under pressure, usually 1 to 100a
tm (for example, 1.5 to 80 atm), preferably 2 to
It is about 70 atm. The reaction time can be appropriately selected, for example, from a range of about 30 minutes to 48 hours depending on the reaction temperature and pressure.

The reaction is carried out in the presence of oxygen or in the flow of oxygen.
It can be carried out by a conventional method such as a batch system, a semi-batch system, and a continuous system. By the reaction, the adamantane skeleton of the adamantane derivative represented by the formula (3) is cleaved to produce the bicyclo [3.3.1] nonane derivative represented by the formula (1).

After completion of the reaction, the reaction product is subjected to a conventional method,
For example, separation and purification can be easily performed by separation means such as filtration, concentration, distillation, extraction, crystallization, recrystallization, and column chromatography, or a separation means in which these are combined. In addition,
In the formula (1), the compound (ester) in which R ^a is an acyl group can be easily converted into R by a conventional hydrolysis method (acid hydrolysis method, neutral hydrolysis method or alkali hydrolysis method).
can be converted to a compound (alcohol) in which ^a is a hydrogen atom.

[0035]

According to the present invention, there is provided a novel bicyclo [3.3.1] nonane derivative having a hydroxymethyl group or an acyloxymethyl group at the 3-position and an oxo group at the 7-position. . Further, according to the production method of the present invention, the novel bicyclo [3.3.1] nonane derivative can be efficiently obtained by a simple operation.

[0036]

The present invention will be described in more detail with reference to the following Examples, which should not be construed as limiting the invention thereto.

EXAMPLE 1 2 mmol of adamantane, 0.2 mmol of N-hydroxyphthalimide, 2 drops of methanesulfonic acid and 6 m of acetic acid
The mixture was stirred at 100 ° C. for 6 hours under an oxygen atmosphere (1 atm). The product in the reaction solution was isolated by using high performance liquid chromatography to obtain 3-acetoxymethyl-7-oxo-bicyclo [3.3.1] nonane (yield: 12%). The spectrum data of this compound is shown below. ¹ H-NMR (CDCl ₃ ) δ: 0.93 (t, 2H),
1.60-1.68 (m, 1H), 1.85-2.12.
(M, 4H), 2.03 (s, 3H), 2.22-2.
50 (m, 4H), 2.49 to 2.58 (m, 2H),
3.81 (d, 2H) ¹³ C-NMR (CDCl ₃ ) δ: 20.89 (1C),
28.13 (2C), 28.39 (1C), 28.68
(2C), 30.84 (2C), 50.28 (1C),
68.78 (1C), 170.96 (1C), 212.
26 (1C)

Continued on the front page (51) Int.Cl. ⁶ Identification code FI C07C 67/035 C07C 67/035 69/14 69/14 // C07B 61/00 300 C07B 61/00 300

Claims (4)

[Claims] [Claim 1] The following formula (1) (Wherein ^Ra represents a hydrogen atom or an acyl group, and the carbon atom constituting the bicyclo [3.3.1] nonane ring may have a substituent). .1]
Nonane derivatives. (A) The following formula (2): (Wherein R ¹ and R ² are the same or different and each represents a hydrogen atom,
A halogen atom, an alkyl group, an aryl group, a cycloalkyl group, a hydroxyl group, an alkoxy group, a carboxyl group, an alkoxycarbonyl group, or an acyl group; R ¹ and R ² are bonded to each other to form a double bond, or A non-aromatic ring may be formed. X represents an oxygen atom or a hydroxyl group, and n represents an integer of 1 to 3), and (B) a strong acid and in the presence of a strong acid, the following formula (3): (In the formula, R ^b represents a hydrogen atom, a hydroxyl group, or an acyloxy group. The carbon atoms constituting the adamantane skeleton are substituted except for one carbon atom adjacent to the bridgehead carbon atom to which R ^b is bonded. An adamantane derivative represented by the following formula (4): ^a compound represented by the following formula (4): R ^a —OH (where R ^a represents a hydrogen atom or an acyl group); By reacting with oxygen, the following formula (1) (Wherein R ^a is the same as described above, and bicyclo [3.3.
1] A process for producing a bicyclo [3.3.1] nonane derivative which produces a bicyclo [3.3.1] nonane derivative represented by the formula (1) wherein the carbon atom constituting the nonane ring may have a substituent: . 3. The method for producing a bicyclo [3.3.1] nonane derivative according to claim 2, wherein a protonic acid having a pKa of 3 or less in an aqueous solution at 25 ° C. is used as the strong acid (B). 4. The process for producing a bicyclo [3.3.1] nonane derivative according to claim 2, wherein a sulfonic acid is used as the strong acid (B).