JPWO2013183591A1 - Method for producing adamantanetriols - Google Patents

Abstract

The present invention relates to a method for producing adamantanetriols, in which adamantanes represented by the following general formula (1) are reacted with hydrogen peroxide in a solvent in the presence of a metal complex. Wherein R is a halogen atom, a hydroxyl group, an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, or the number of carbon atoms. Represents a 3-10 cycloalkoxy group, an acyl group having 2-10 carbon atoms, an acyloxy group having 2-10 carbon atoms, an aryl group, an aryloxy group; n represents an integer of 0-13; Is 2 or less)

Description

  The present invention relates to a method for producing adamantanetriols from adamantanes with high selectivity and high yield.

  Adamantanols in which an adamantane skeleton is substituted with a hydroxyl group are useful compounds as intermediates for highly functional polymers, electronic materials, synthetic lubricating oils, medicines and agricultural chemicals.

  As a method for producing adamantanols, a method of hydrolyzing bromoadamantane in the presence of a tertiary amine compound (see, for example, Patent Document 1), an adamantane and hypochlorite in the presence of a catalytic amount of a ruthenium compound, In a two-phase system of water / organic solvent (for example, see Patent Document 2), a method in which N-hydroxyphthalimide is used as a catalyst to oxidize adamantane with oxygen (for example, see Patent Document 3), and adamantane is trioxided A method of oxidizing with chromium (see, for example, Patent Document 4) is known.

  However, in Patent Document 1, a high temperature condition of 150 ° C. to 280 ° C. is required, a pre-process for synthesizing a bromide as a starting material is required, and further, a bromide derived from a raw material is mixed in and purification thereof is difficult. is there. In Patent Document 2, it is necessary to control the pH in the reaction system within a certain range, and the resulting product is adamantanediol. Moreover, in patent document 3, the selectivity of a product is low and requires complicated operation for isolation | separation of the obtained adamantanol. Furthermore, in Patent Document 4, it is necessary to use a large amount of highly toxic hexavalent chromium, and there is a problem with respect to environmental load.

  On the other hand, a method is also known in which adamantanes are converted to adamantanols by an oxidation reaction using hydrogen peroxide having a lower environmental load. For example, in Non-Patent Document 1, adamantane is used at 60 ° C. using a rhenium catalyst and hydrogen peroxide. Is undergoing oxidation reaction. However, the products obtained are only adamantane monool and a small amount of adamantane diol.

Japanese Unexamined Patent Publication No. 2-196744 Japanese Unexamined Patent Publication No. 2002-167342 Japanese Unexamined Patent Publication No. 10-286467 Japanese Unexamined Patent Publication No. 2003-321408

Tetrahedron Letters, 36, 6415 (1995) Science, 318, 783 (2007) Inorganic Chemistry, 44, 8125 (2005)

  Thus, although many methods for producing adamantanols are known, there are few examples using hydrogen peroxide as an oxidizing agent, and in particular, the number of hydroxyl groups introduced into the adamantane ring is controlled, and adamantanetriols are produced. There is no known method for obtaining the compound with high selectivity and high yield. The present invention provides a production method capable of reducing an energy cost and an environmental load by performing an oxidation reaction using hydrogen peroxide, and further obtaining adamantanetriols with high selectivity and high yield. With the goal.

  As a result of intensive studies to achieve the above object, the inventors of the present invention oxidize adamantane with hydrogen peroxide in the presence of a metal complex in a solvent. It was found to be obtained in a yield. That is, the gist of the present invention is as follows.

1. A method for producing an adamantanetriol, comprising reacting an adamantane represented by the following general formula (1) with hydrogen peroxide in a solvent in the presence of a metal complex.

  In the formula, R is a halogen atom, a hydroxyl group, a linear or branched alkyl group having 1 to 10 carbon atoms which may have a substituent, and a carbon atom having 3 substituents which may have a substituent. -10 cycloalkyl group, a linear or branched alkoxy group having 1 to 10 carbon atoms which may have a substituent, and a cyclocarbon having 3 to 10 carbon atoms which may have a substituent. An alkoxy group, an optionally substituted acyl group having 2 to 10 carbon atoms, an optionally substituted acyl group having 2 to 10 carbon atoms, a substituted or unsubstituted aryl group, substituted Or an unsubstituted aryloxy group is represented. n represents an integer of 0 to 13. When n is 2 or more, the plurality of R may be the same as or different from each other. However, the number of hydroxyl groups shall be 2 or less.

2. 2. The method for producing adamantanetriol according to 1 above, wherein the adamantane represented by the general formula (1) is reacted with hydrogen peroxide in a solvent in the presence of a metal complex and an organic acid.

3. 3. The method for producing an adamantanetriol according to 1 or 2, wherein the adamantanetriol is a 1,3,5-adamantanetriol derivative.

4). 4. The method for producing adamantanetriol according to any one of 1 to 3, wherein the solvent is a mixed solution of water / organic solvent.

5. 5. The method for producing adamantanetriols according to 4, wherein the organic solvent is one or more organic solvents selected from water-soluble alcohols or nitriles.

6). 5. The method for producing adamantanetriols according to 4 above, wherein the organic solvent is acetonitrile.

7). In the metal complex, at least one of the ligands has 4 to 8 nitrogen atoms, of which a plurality of nitrogen atoms are linked via two consecutive carbon atoms. The manufacturing method of adamantanetriol as described in any one of these.

8). 8. The method for producing adamantanetriol according to 7, wherein at least one of the ligands in the metal complex is a nitrogen-containing compound represented by the following general formula (2) or (3).

In the formula, R ^{1 to} R ⁴ may be the same or different and each represents a hydrogen atom or a linear or branched alkyl group having 1 to 10 carbon atoms which may have a substituent. Ar ¹ and Ar ² may be the same or different and each represents a substituted or unsubstituted nitrogen-containing aromatic heterocyclic group.

In the formula, Ar ^{3 to} Ar ⁵ may be the same or different and each represents a substituted or unsubstituted nitrogen-containing aromatic heterocyclic group.

9. In the metal complex, of the formula (2) in adjacent pairs of R ¹ to R ^4, at least one pair, via a single bond linked to form a ring, according to the 8 A method for producing adamantanetriols.

10. In the metal complex, among the adjacent pairs of R ^{1 to} R ⁴ in the general formula (2), R ¹ and R ² , and R ³ and R ⁴ are linked to form a ring via a single bond, respectively. 10. The method for producing an adamantanetriol according to 9 above.

11. The method for producing adamantanetriols according to any one of 1 to 10, wherein a central metal of the metal complex is a metal selected from transition metals.

12 12. The method for producing adamantanetriols according to 11 above, wherein a central metal of the metal complex is iron.

13. 3. The method for producing adamantanetriol according to 2, wherein the organic acid is an aliphatic carboxylic acid or an aromatic carboxylic acid.

14 14. The method for producing adamantanetriols according to 13, wherein the organic acid is acetic acid.

  According to the present invention, adamantanetriols can be produced with high selectivity and high yield by an inexpensive and low environmental impact method using adamantanes as a starting material.

  Hereinafter, embodiments of the present invention will be described in detail. The adamantane used as a starting material in the present invention is represented by the following general formula (1).

  In the formula, R is a halogen atom, a hydroxyl group, a linear or branched alkyl group having 1 to 10 carbon atoms which may have a substituent, and a carbon atom having 3 substituents which may have a substituent. -10 cycloalkyl group, a linear or branched alkoxy group having 1 to 10 carbon atoms which may have a substituent, and a cyclocarbon having 3 to 10 carbon atoms which may have a substituent. An alkoxy group, an optionally substituted acyl group having 2 to 10 carbon atoms, an optionally substituted acyl group having 2 to 10 carbon atoms, a substituted or unsubstituted aryl group, substituted Or an unsubstituted aryloxy group is represented. n represents an integer of 0 to 13. When n is 2 or more, the plurality of R may be the same as or different from each other. However, the number of hydroxyl groups shall be 2 or less.

  The “halogen atom” represented by R in the general formula (1), “a linear or branched alkyl group having 1 to 10 carbon atoms which may have a substituent”, “substituent An optionally substituted cycloalkyl group having 3 to 10 carbon atoms ", an" optionally substituted linear or branched alkoxy group having 1 to 10 carbon atoms ", An optionally substituted cycloalkoxy group having 3 to 10 carbon atoms ", an" optionally substituted linear or branched acyl group having 2 to 10 carbon atoms "and" a substituent group. "Halogen atom", "alkyl group having 1 to 10 carbon atoms", "cycloalkyl group having 3 to 10 carbon atoms", "carbon atom" in "acyloxy group having 2 to 10 carbon atoms" C 1-10 alkoxy group ”,“ C 3-10 cycloa Specific examples of the “coxy group”, “acyl group having 2 to 10 carbon atoms” and “acyloxy group having 2 to 10 carbon atoms” include halogen atoms such as fluorine atom, chlorine atom, bromine atom and iodine atom; Group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group and other linear alkyl groups; isopropyl group, isobutyl group, sec-butyl group, tert-butyl Group, branched alkyl group such as isooctyl group; cycloalkyl group such as cyclopropyl group, cyclopentyl group, cyclohexyl group, cyclooctyl group; methoxy group, ethoxy group, propoxy group, butoxy group, pentyloxy group, hexyloxy group, Straight chain such as heptyloxy group, octyloxy group, nonyloxy group, decyloxy group Lucoxy group; branched alkoxy group such as isopropoxy group, isobutoxy group, sec-butoxy group, tert-butoxy group, isooctyloxy group; cyclopropoxy group, cyclopentyloxy group, cyclohexyloxy group, cyclopropylmethyloxy group, etc. Cycloalkoxy group; linear or branched acyl group such as acetyl group, propanoyl group, butanoyl group, isobutanoyl group, pentanoyl group, hexanoyl group, heptanoyl group, octanoyl group benzoyl group, heptanoyl group, cyclohexanecarbonyl group; and acetyl And acyloxy groups such as an oxy group, a propionyloxy group, a butanoyloxy group, a heptanoyloxy group, and a hexanoyloxy group.

  Represented by R in the general formula (1), “which may have a linear or branched alkyl group having 1 to 10 carbon atoms”, “which may have a substituent; A good cycloalkyl group having 3 to 10 carbon atoms ”,“ a linear or branched alkoxy group having 1 to 10 carbon atoms which may have a substituent ”,“ may have a substituent Good C3-C10 cycloalkoxy group "," optionally substituted linear or branched acyl group with 2-10 carbon atoms "and" optionally substituted " Specific examples of the “substituent” in the “acyloxy group having 2 to 10 carbon atoms” specifically include a halogen atom, a linear or branched alkyl group having 1 to 10 carbon atoms, and a cyclohexane having 3 to 10 carbon atoms. An alkyl group, linear or branched having 1 to 10 carbon atoms An alkoxy group having 3 to 10 carbon atoms, a cycloalkoxy group having 3 to 10 carbon atoms, a haloalkyl group having 1 to 10 carbon atoms, a linear or branched haloalkoxy group having 1 to 10 carbon atoms, and the like. . Specifically, halogen atoms such as fluorine atom, chlorine atom, bromine atom, iodine atom; methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group Linear alkyl groups such as; branched alkyl groups such as isopropyl, isobutyl, sec-butyl, tert-butyl, and isooctyl; cycloalkyl such as cyclopropyl, cyclopentyl, cyclohexyl, and cyclooctyl Group: linear alkoxy group such as methoxy group, ethoxy group, propoxy group, butoxy group, pentyloxy group, hexyloxy group, heptyloxy group, octyloxy group, nonyloxy group, decyloxy group; isopropoxy group, isobutoxy group, sec-butoxy group, tert-butoxy group, iso-io Branched alkoxy groups such as tiloxy group; cycloalkoxy groups such as cyclopropoxy group, cyclopentyloxy group, cyclohexyloxy group, cyclopropylmethyloxy group; trifluoromethyl group, pentafluoroethyl group, nonafluorobutyl group, trifluoromethoxy And a haloalkyl group such as a group or a haloalkoxy group.

  Specific examples of the “aryl group” and “aryloxy group” in the “substituted or unsubstituted aryl group” and “substituted or unsubstituted aryloxy group” represented by R in the general formula (1) include: An aromatic hydrocarbon group having 6 to 20 carbon atoms, such as a phenyl group, a naphthyl group, a biphenyl group, an azulenyl group, an anthracenyl group, a terphenyl group, a pyrenyl group, or a phenanthryl group; or a condensed polycyclic aromatic group; An aryloxy group.

  Specific examples of the “substituent” in the “substituted aryl group” and “substituted aryloxy group” represented by R in the general formula (1) include a halogen atom, a straight chain having 1 to 10 carbon atoms or Branched alkyl group, cycloalkyl group having 3 to 10 carbon atoms, linear or branched alkoxy group having 1 to 10 carbon atoms, cycloalkoxy group having 3 to 10 carbon atoms, 1 to 1 carbon atoms Examples thereof include 10 haloalkyl groups, straight-chain or branched haloalkoxy groups having 1 to 10 carbon atoms, and the like. Specifically, halogen atoms such as fluorine atom, chlorine atom, bromine atom, iodine atom; methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group Linear alkyl groups such as; branched alkyl groups such as isopropyl, isobutyl, sec-butyl, tert-butyl, and isooctyl; cycloalkyl such as cyclopropyl, cyclopentyl, cyclohexyl, and cyclooctyl Group: linear alkoxy group such as methoxy group, ethoxy group, propoxy group, butoxy group, pentyloxy group, hexyloxy group, heptyloxy group, octyloxy group, nonyloxy group, decyloxy group; isopropoxy group, isobutoxy group, sec-butoxy group, tert-butoxy group, iso-io Branched alkoxy groups such as tiloxy group; cycloalkoxy groups such as cyclopropoxy group, cyclopentyloxy group, cyclohexyloxy group, cyclopropylmethyloxy group; trifluoromethyl group, pentafluoroethyl group, nonafluorobutyl group, trifluoromethoxy And a haloalkyl group such as a group or a haloalkoxy group.

  Although n in General formula (1) represents the integer of 0-13, it is especially preferable that it is an integer of 0-3 from reactivity, availability, etc.

  Specific examples of the adamantane represented by the general formula (1) include adamantane, 1-adamantanol, 2-adamantanol, 1,3-adamantanediol, 1-fluoroadamantane, 2-fluoroadamantane, 1,3- Difluoroadamantane, 1,3,5-trifluoroadamantane, 1-chloroadamantane, 2-chloroadamantane, 1,3-dichloroadamantane, 1,3,5-trichloroadamantane, 1-bromoadamantane, 2-bromoadamantane, 1 , 3-Dibromoadamantane, 1,3,5-tribromoadamantane, 1-methyladamantane, 2-methyladamantane, 1,3-dimethyladamantane, 1,3,5-trimethyladamantane, 1-ethyladamantane, 2-ethyl Adamantane, 1,3-die Ruadamantane, 1,3,5-triethyladamantane, 1-propyladamantane, 2-propyladamantane, 1,3-dipropyladamantane, 1,3,5-tripropyladamantane, 1-phenyladamantane, 2-phenyladamantane, 1,3-diphenyladamantane, 1,3,5-triphenyladamantane, 1-acetyloxyadamantane, 2-acetyloxyadamantane, 1,3-diacetyloxyadamantane, 1,3,5-triacetyloxyadamantane, 1- Methoxyadamantane, 2-methoxyadamantane, 1,3-dimethoxyadamantane, 1,3,5-trimethoxyadamantane, and the like can be mentioned. From the viewpoint of reactivity and availability, adamantane, 1-adamantanol, 2 -Adama Ethanol, 1,3-adamantane-diol is particularly preferable.

  The adamantane triols obtained by the present invention are compounds in which three hydroxyl groups are substituted on the adamantane skeleton. The substitution position of the three hydroxyl groups is not particularly limited. When an adamantane substituted with a hydroxyl group is used as a starting material, the resulting product has three hydroxyl groups in the adamantane skeleton regardless of the substitution position. It has been replaced. When four tertiary carbons (bridgehead carbons) on the adamantane skeleton are unsubstituted, the position is preferentially oxidized. Therefore, in the present invention, the 1,3,5-adamantane triol derivative is the most selective. And high yield.

  The metal complex used for this invention may be used independently, and 2 or more types may be mixed and used for it. The metal complex is not particularly limited, but a metal complex having a transition metal such as titanium, vanadium, manganese, iron, cobalt, nickel, copper, molybdenum, ruthenium, palladium, tungsten, rhenium, iridium as a central metal. preferable. Among these, a metal complex having a first transition metal such as titanium, vanadium, manganese, iron, cobalt, nickel, or copper as a central metal is more preferable, and an iron complex is particularly preferable.

  The ligand forming the metal complex used in the present invention may be a neutral molecule or an anion, and the number of ligands may be one or two or more. It may be the same or different. Specific examples of the ligand include halide ions such as chloride ions and bromide ions; hydroxide ions; cyanide ions; carboxylate ions such as acetate ions and propionate ions; nitrate ions; nitrite ions; Ion; β-diketon anion such as 2,4-pentanedionate, 2,4-hexanedionate; oxygen molecule; carbon monoxide; water; hydroxy compound; alkoxy compound such as methoxy compound, ethoxy compound, propoxy compound, butoxy compound Alkene such as ethylene, propylene, styrene, cyclopentadiene and cyclooctadiene; ether such as dimethyl ether and diethyl ether; nitrile compound such as acetonitrile and benzonitrile; phosphorus such as tri-tert-butylphosphine and triphenylphosphine Compound; ammonia, can be mentioned trimethylamine, triethylamine, ethylenediamine, pyridine, phenanthroline, and other amine compounds.

  The metal complex preferably used in the present invention contains at least one amine compound as a ligand. The amine compound is preferably a compound having 4 to 8 nitrogen atoms, and having a structure in which a plurality of nitrogen atoms are linked via two continuous carbon atoms. The number of nitrogen atoms in the compound having a structure having 4 to 8 nitrogen atoms, in which a plurality of nitrogen atoms are linked via two consecutive carbon atoms, is more preferably 4 to 6. 4 or 5 is particularly preferred. The number of nitrogen atoms linked via two consecutive carbon atoms is preferably 3 or more, more preferably 4 or 5, and particularly preferably 4. Specific examples of the compound having a structure having 4 to 8 nitrogen atoms, in which a plurality of nitrogen atoms are connected via two consecutive carbon atoms, include the following general formula (2) or (3 ) Can be mentioned.

In the formula, R ^{1 to} R ⁴ may be the same or different and each represents a hydrogen atom or a linear or branched alkyl group having 1 to 10 carbon atoms which may have a substituent. R ¹ and R ² , R ² and R ³ , R ³ and R ⁴ may be bonded to each other to form a ring. Ar ¹ and Ar ² may be the same or different and each represents a substituted or unsubstituted nitrogen-containing aromatic heterocyclic group.

In the formula, Ar ^{3 to} Ar ⁵ may be the same or different and each represents a substituted or unsubstituted nitrogen-containing aromatic heterocyclic group.

“1 carbon atom number” in “a linear or branched alkyl group having 1 to 10 carbon atoms which may have a substituent” represented by R ^{1 to} R ⁴ in the general formula (2) Specific examples of the “-10 to 10 linear or branched alkyl group” include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, and a decyl group. Linear alkyl groups; branched alkyl groups such as isopropyl group, isobutyl group, sec-butyl group, tert-butyl group, and isooctyl group can be exemplified.
Formula pairs ^{R 1} adjacent the (2) in the ^R 1 to R ⁴ and ^R 2, ^{R 2} and ^R 3, ^{R 3} and ^{R 4,} which may be linked to each other to form a ring, in which case Those linked via a single bond are preferred. The ring to be formed is preferably a cycloalkyl ring such as a cyclopentyl ring, a cyclohexyl ring or a cyclooctyl ring, or a heterocyclic ring such as a pyrrolidine ring or a piperidine ring. That is, it is preferable that at least one pair of R ^{1 to} R ^{4 in} the general formula (2) is connected so as to form a ring via a single bond, and R ¹ and R ² And R ³ and R ⁴ are particularly preferably connected to form a ring via a single bond.

As a “substituent” in “an optionally substituted linear or branched alkyl group having 1 to 10 carbon atoms” represented by R ^{1 to} R ⁴ in the general formula (2) Specifically, a halogen atom, a linear or branched alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, a linear or branched group having 1 to 10 carbon atoms Alkoxy group, cycloalkoxy group having 3 to 10 carbon atoms, linear or branched haloalkyl group having 1 to 10 carbon atoms, linear or branched haloalkoxy group having 1 to 10 carbon atoms, alkoxy Examples thereof include a carbonyl group and a nitro group. Specifically, halogen atoms such as fluorine atom, chlorine atom, bromine atom, iodine atom; methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group Linear alkyl groups such as; branched alkyl groups such as isopropyl, isobutyl, sec-butyl, tert-butyl, and isooctyl; cycloalkyl such as cyclopropyl, cyclopentyl, cyclohexyl, and cyclooctyl Group: linear alkoxy group such as methoxy group, ethoxy group, propoxy group, butoxy group, pentyloxy group, hexyloxy group, heptyloxy group, octyloxy group, nonyloxy group, decyloxy group; isopropoxy group, isobutoxy group, sec-butoxy group, tert-butoxy group, iso-io Branched alkoxy groups such as tiloxy group; cycloalkoxy groups such as cyclopropoxy group, cyclopentyloxy group, cyclohexyloxy group, cyclopropylmethyloxy group; trifluoromethyl group, pentafluoroethyl group, nonafluorobutyl group, trifluoromethoxy A haloalkyl group such as a group or a haloalkoxy group; an alkoxycarbonyl group such as a methoxycarbonyl group, an ethoxycarbonyl group or a propoxycarbonyl group; a nitro group; Among these, a halogen atom, a linear or branched alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, a linear or branched alkoxy group having 1 to 10 carbon atoms. Group, a cycloalkoxy group having 3 to 10 carbon atoms is preferable, a halogen atom, a linear or branched alkyl group having 1 to 5 carbon atoms, a linear or branched alkoxy group having 1 to 5 carbon atoms The group is particularly preferred.

R ^{1 to} R ⁴ are particularly preferably a hydrogen atom or a linear or branched alkyl group having 1 to 5 carbon atoms which may have a substituent.

As the “nitrogen-containing aromatic heterocycle” in the “substituted or unsubstituted nitrogen-containing aromatic heterocyclic group” represented by Ar ^{1 to} Ar ⁵ in the general formulas (2) and (3), specifically, Examples include pyrrole ring, imidazole ring, pyrazole ring, pyridine ring, pyrimidine ring, pyrazine ring, oxazole ring, thiazole ring, quinoline ring, isoquinoline ring, quinoxaline ring, cinnoline ring, indole ring, isoindole ring, benzimidazole ring, etc. Can do.
The nitrogen atoms contained in the compounds represented by the general formulas (2) and (3) are preferably bonded via two consecutive carbon atoms, and are represented by Ar ^{1 to} Ar ^5. The binding position of the nitrogen-containing aromatic heterocyclic group is preferably a carbon atom adjacent to the nitrogen atom in the nitrogen-containing aromatic heterocyclic ring.

The “substituent” in the “substituted or unsubstituted nitrogen-containing aromatic heterocyclic group” represented by Ar ^{1 to} Ar ⁵ in the general formulas (2) and (3) is a halogen atom or a carbon atom number of 1 -10 linear or branched alkyl group, cycloalkyl group having 3 to 10 carbon atoms, linear or branched alkoxy group having 1 to 10 carbon atoms, cycloalkoxy having 3 to 10 carbon atoms Group, a linear or branched haloalkyl group having 1 to 10 carbon atoms, a linear or branched haloalkoxy group having 1 to 10 carbon atoms, an alkoxycarbonyl group, and the like. Specifically, halogen atoms such as fluorine atom, chlorine atom, bromine atom, iodine atom; methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group Linear alkyl groups such as: branched alkyl groups such as isopropyl group, isobutyl group, sec-butyl group, tert-butyl group, isooctyl group, cycloalkyl such as cyclopropyl group, cyclopentyl group, cyclohexyl group, cyclooctyl group Group: linear alkoxy group such as methoxy group, ethoxy group, propoxy group, butoxy group, pentyloxy group, hexyloxy group, heptyloxy group, octyloxy group, nonyloxy group, decyloxy group; isopropoxy group, isobutoxy group, sec-butoxy group, tert-butoxy group, iso-io Branched alkoxy groups such as tiloxy group; cycloalkoxy groups such as cyclopropoxy group, cyclopentyloxy group, cyclohexyloxy group, cyclopropylmethyloxy group; trifluoromethyl group, pentafluoroethyl group, nonafluorobutyl group, trifluoromethoxy And a haloalkyl group such as a group or a haloalkoxy group; an alkoxycarbonyl group such as a methoxycarbonyl group, an ethoxycarbonyl group, or a propoxycarbonyl group. Among these, a halogen atom, a linear or branched alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, a linear or branched alkoxy group having 1 to 10 carbon atoms. Group, a cycloalkoxy group having 3 to 10 carbon atoms is preferable, a halogen atom, a linear or branched alkyl group having 1 to 5 carbon atoms, a linear or branched alkoxy group having 1 to 5 carbon atoms The group is particularly preferred.

  The number of nitrogen atoms contained in the nitrogen-containing compounds represented by the general formulas (2) and (3) is preferably 4 to 8, more preferably 4 to 6, and 4 or 5 It is particularly preferred that In the metal complex preferably used in the present invention, the nitrogen-containing compound represented by the general formulas (2) and (3) is arranged on the central metal via three or more nitrogen atoms among the nitrogen atoms of the compound. Are preferably tetradentate or pentadentate coordinated via 4 or 5 nitrogen atoms.

  Specific examples of preferable compounds among the nitrogen-containing compounds represented by the general formulas (2) and (3) are shown below, but the present invention is not limited to these compounds. In addition, even when a stereoisomer exists, the planar structural formula is described.

  As the ligand forming the metal complex used in the present invention, a commercially available ligand may be used, or a ligand synthesized by a known method (for example, see Non-Patent Documents 2 and 3) may be used.

  The metal complex used for this invention may contain the anion which makes this metal complex electrically neutral as a whole. The anion is not particularly limited, but halide ions such as fluoride ion, chloride ion, bromide ion, iodide ion; sulfide ion, oxide ion, hydroxide ion, hydride ion, Inorganic acid ions such as sulfite ion, phosphate ion, cyanide ion, carbonate ion, hydrogen carbonate ion, sulfate ion, nitrate ion, thiocyanate ion, tetrafluoroborate ion, hexafluorophosphate ion, hexafluoroantimonate ion And organic acid ions such as acetate ion, trifluoroacetate ion, trifluoromethanesulfonate ion, tetraphenylborate ion, phenoxide ion, picolinic acid and derivatives thereof. Among these, tetrafluoroborate ions, hexafluorophosphate ions, and hexafluoroantimonate ions are preferable, and hexafluoroantimonate ions are particularly preferable. These anions may be two or more mixed anions.

  Although the synthesis method of the metal complex used for this invention is not specifically limited, It can synthesize | combine by a well-known method (for example, refer nonpatent literature 2). Specifically, it can be synthesized by reacting a corresponding ligand with a corresponding metal salt such as ferrous chloride in a solvent.

  The amount of the metal complex used in the present invention is usually 0.001 to 2.0 times mol with respect to the starting adamantane, but preferably 0.005 to 0.5 times mol, 0.01 to 0 More preferably in the range of 1 mole. When the amount used is small, the reaction rate decreases, which is not preferable. When the amount used is large, a large amount of metal complex is used, which is not preferable from an industrial standpoint such as cost and reaction time.

  The hydrogen peroxide used in the present invention is not particularly limited as long as it is available as a reagent or industrial use, and it is preferable to use a 5 to 60% by weight aqueous solution (hydrogen peroxide solution). When the concentration of hydrogen peroxide in the hydrogen peroxide water is low, the amount of water in the reaction solution increases, so that the solubility of the starting material adamantane is reduced, leading to a decrease in reactivity. On the other hand, when the concentration of hydrogen peroxide is high, the risk of explosion increases, which is not preferable.

  The addition amount of hydrogen peroxide used in the present invention is usually 0.5 to 20 times mol, preferably 1.0 to 15 times mol, and 1.2 to 12 times mol of the starting adamantane. A range is more preferable. When the amount of hydrogen peroxide added is small, a large amount of unreacted raw materials and reaction intermediates, adamantane monools and adamantane diols, remain, and the selectivity and yield of adamantane triols decrease. On the other hand, when the amount of hydrogen peroxide added is large, adamantane polyols such as adamantanetetraols in which a hydroxyl group is further introduced into the target adamantanetriol are by-produced, and the selectivity and yield of adamantanetriols are also increased. descend.

  In the present invention, when the adamantane represented by the general formula (1) is reacted with hydrogen peroxide in the presence of a metal complex in a solvent, an organic acid is preferably further present. As will be described later, when the pH of the reaction system is greater than 6, hydrogen peroxide may be decomposed, and the presence of an organic acid in the reaction system can adjust the pH of the reaction system to 6 or less. . The organic acid used in the present invention is not particularly limited as long as it has high compatibility with water and is inactive under the reaction conditions of the present invention. Examples of such organic acids include aliphatic carboxylic acids such as formic acid, acetic acid, propionic acid, oxalic acid and succinic acid; aromatic carboxylic acids such as benzoic acid, phthalic acid and isophthalic acid; lactic acid, citric acid and salicylic acid. Hydroxy acid; and the like. Among these, an aliphatic carboxylic acid or an aromatic carboxylic acid is preferable, and acetic acid is particularly preferable from the viewpoint of availability and cost. These organic acids may be used alone or in combination of two or more. The amount of the organic acid used is usually 0.1 to 10 times mol with respect to the starting material adamantane, but preferably 0.3 to 8.0 times mol, and 0.5 to 6.0 times mol. It is more preferable that

  As the solvent used in the present invention, water or an organic solvent can be used alone or in combination, but a water / organic solvent mixed solution is preferable. The organic solvent is not particularly limited as long as it is an inert solvent for the oxidation reaction of the present invention, but is preferably a solvent having high compatibility with water and high solubility of the metal complex. When the compatibility with water is low, the reaction solution is separated into two phases, resulting in a decrease in the reaction rate. Moreover, when the solubility of a metal complex is low, the reaction rate will fall. Examples of the organic solvent preferably used in the present invention include alcohols such as methanol, ethanol, propanol, and isopropanol; nitrile compounds such as acetonitrile and benzonitrile; tetrahydrofuran; water-soluble organic solvents such as acetone. Among these, acetonitrile is particularly preferable. These organic solvents may be used alone, or two or more kinds of solvents may be mixed and used. The organic solvent is usually used in the range of 0.1 to 200 parts by weight with respect to 1 part by weight of the starting adamantane, but is preferably used in a proportion of 10 to 100 parts by weight. When used as a mixed solution of water / organic solvent, the mixing ratio of water (including water in hydrogen peroxide water) and the organic solvent is preferably used within a range of 1: 2 to 1: 100 by weight. .

  The reaction temperature of the oxidation reaction of the present invention is usually 0 to 100 ° C., preferably in the range of 0 to 80 ° C., more preferably 0 to 50 ° C., and particularly preferably in the range of 15 to 40 ° C. When the reaction temperature is low, the reaction rate decreases. When the reaction temperature is high, the selectivity and yield of adamantanetriols decrease due to decomposition of hydrogen peroxide and side reactions.

  The reaction time of the oxidation reaction of the present invention is usually 1 minute to 50 hours.

  Although the pH of the reaction solution is not particularly limited, it is preferably carried out under acidic to neutral conditions because decomposition of hydrogen peroxide is accelerated under basic conditions and neutralization of organic acids occurs. It is more preferable to carry out under acidic conditions, and it is particularly preferable to carry out at pH 6 or lower.

  The reaction vessel used in the present invention is not particularly limited and can be carried out using a reaction vessel equipped with a known stirrer. The order of addition of the reagent is not particularly limited, but adamantane as a starting material and a metal complex (and preferably an organic acid) as a catalyst are first dissolved in a solvent, and then hydrogen peroxide (peroxidized) is dissolved therein. Hydrogen water) is preferably added. The method of adding hydrogen peroxide (hydrogen peroxide solution) is not particularly limited, but in order to prevent a rapid temperature rise due to reaction heat, the addition rate is reduced by dropwise addition after dilution with a solvent as necessary. It is preferable to add while adjusting.

  The metal complex (and preferably an organic acid) and hydrogen peroxide (hydrogen peroxide solution) may be added all at once, or may be added in multiple portions in small portions. Even when the entire amount is added at a time, it is preferable to add the entire amount of hydrogen peroxide (hydrogen peroxide solution) dropwise. In addition, when adding a small amount in multiple portions, the addition amount and the number of additions are not particularly limited, and an appropriate amount may be added as many times as necessary while confirming the progress of the reaction by various instrumental analyses. preferable.

  Sampling when confirming the progress of the reaction can be performed by a known method, but if insoluble components (adamantanes, adamantanols, etc.) are present in the collected reaction solution, an appropriate solvent is added. It is preferable to analyze after dissolving insoluble matter. The solvent that can be used is not particularly limited as long as it is highly compatible with the reaction solution and has high solubility of various components contained therein. For example, water, methanol, ethanol, propanol, isopropanol, Examples include butanol, acetonitrile, tetrahydrofuran, acetone, ethyl acetate, chloroform and the like. Among these, water, butanol, acetonitrile, ethyl acetate, and chloroform are particularly preferable. These solvents may be used alone or in combination of two or more. When a solvent having low compatibility with the reaction solution is used, the sampling solution is separated into two phases and cannot be analyzed accurately. In addition, when a solvent having low solubility of various components contained in the reaction solution is used, a large amount of solvent is required to avoid precipitation of hardly soluble components, resulting in a decrease in the concentration of the entire sampling solution. Analysis becomes difficult.

  In the present invention, the analysis method for confirming the progress of the reaction is not particularly limited, and a known analysis method can be used. The analysis method is preferably a method that does not require any special pretreatment and enables qualitative and quantitative analysis. For example, instrumental analysis such as gas chromatography (GC) analysis and high performance liquid chromatography (HPLC) analysis. Is preferred. The column used for GC analysis or HPLC analysis is not particularly limited. However, since adamantanetriols, which are the object of the present invention, are highly polar and high-boiling compounds, columns corresponding to such compounds, for example, in the case of GC analysis Is preferably a G-250 column manufactured by Chemical Substance Evaluation Research Organization.

  After the oxidation reaction, decomposition of unreacted hydrogen peroxide with a reducing agent or neutralization with a base may be performed as necessary. Examples of the reducing agent include metal hydrides such as sodium borohydride and lithium aluminum hydride, sulfites such as potassium sulfite, ammonium sulfite, and sodium hydrogen sulfite, hydrazine, oxalic acid, and the like. preferable. The base used for neutralization includes metal hydroxides such as sodium hydroxide, potassium hydroxide, lithium hydroxide, and barium hydroxide, sodium carbonate, potassium carbonate, calcium carbonate, ammonium carbonate, magnesium carbonate, and sodium bicarbonate. And carbonates such as triethylamine and trimethylamine, and alkylammonium hydroxides such as tetramethylammonium hydroxide. Sodium carbonate and sodium hydrogen carbonate are particularly preferred. The reducing agent or base may be added as it is, or may be added as a solution.

  In the present invention, adamantanetriols can be obtained with high selectivity and high yield. In the solution after completion of the reaction, unreacted adamantanes, a small amount of adamantane monools and / or adamantanediols, etc. May exist. In such a case, adamantanetriols can be taken out from the solution after completion of the reaction using a known separation and purification method. Known separation and purification methods include filtration, concentration, distillation, extraction, crystallization, recrystallization, column chromatography and the like, and these may be used in combination.

  Specifically, separation and purification can be performed by the following method. The adamantanes and adamantane monools which are starting materials of the present invention are easily soluble in a water-insoluble organic solvent, and adamantanols having two or more hydroxyl groups (adamantanediols, adamantanetriols, etc.) are water or Easily soluble in water-soluble organic solvents. Using this difference in solubility, first, adamantanediols and / or adamantanetriols are separated from the reaction solution after completion of the reaction. That is, by performing a liquid separation operation by adding a water-insoluble organic solvent to the reaction solution, the starting material adamantanes and / or adamantane monools are added to the organic layer, and the adamantane diols and / or the water layer. Each adamantanetriol is extracted. Examples of the water-insoluble organic solvent used here include hexane, toluene, ethyl acetate, butanol, pentanol, hexanol, chloroform, and dichloromethane. From the viewpoint of polarity and separability from water, hexane Toluene is preferred. Subsequently, by concentrating the aqueous layer, a crude product of adamantanediols and / or adamantanetriols is obtained, but in some cases, an inorganic salt may be mixed. In that case, the inorganic salt can be removed by hot alcohol extraction or ion exchange treatment, if necessary. Furthermore, by recrystallizing the crude product of the obtained adamantanediols and / or adamantanetriols, the target adamantanetriols can be obtained with high purity. Solvents used for recrystallization include water, methanol, ethanol, propanol, 2-propanol, 1-butanol, 2-butanol, hexanol, acetonitrile, hexane, cyclohexane, acetone, ethyl acetate, tetrahydrofuran, chloroform, dichloromethane, toluene and the like. Among them, water, methanol, ethanol, acetone, ethyl acetate, and chloroform are particularly preferable. These solvents may be used alone or in combination of two or more.

  EXAMPLES Hereinafter, although an Example demonstrates this invention concretely, this invention is not limited to these Examples.

[Analysis conditions]
Confirmation of the oxidation reaction and confirmation of the product were performed by GC analysis. The analysis conditions are as follows. Column: G-250 manufactured by Chemicals Evaluation and Research Institute, 1.2 mm × 40 m × 1.0 μm, column temperature: held at 120 ° C. for 5 minutes, then heated to 200 ° C. at 10 ° C./min, and 15 minutes at 200 ° C. Holding, inlet temperature: 300 ° C., detector (hydrogen flame ionization detector) temperature: 280 ° C., carrier gas: helium, flow rate: 17 ml / min.

[Synthesis of Iron Complex (C-2)]
Under a nitrogen atmosphere, to a reaction vessel equipped with a stirrer, a thermometer, and a condenser, 1.07 g of (S, S) -2,2′-bipyrrolidine D-tartrate, 10 ml of water, and 10 ml of dichloromethane were added, and water-cooled. While stirring, 0.88 g of sodium hydroxide was added. Thereafter, 1.19 g of 2-chloromethylpyridine hydrochloride was added at room temperature and stirred for 8 hours. The reaction solution was separated, and the obtained organic layer was washed with 20 ml of saturated brine, dried over anhydrous magnesium sulfate, and the solvent was distilled off to obtain 1.03 g of a crude product. The crude product was purified by column chromatography (carrier: NH silica gel, eluent: toluene / ethyl acetate) to obtain 0.60 g (yield 59%) of the ligand (L-8).

  Under a nitrogen atmosphere, 1.41 g of ligand (L-8), 0.92 g of iron (II) chloride tetrahydrate and 30 ml of acetonitrile were added to the reaction vessel, and the mixture was stirred at room temperature for 7 hours. To the reaction solution, 20 ml of diisopropyl ether was added and stirred for 30 minutes to precipitate a metal complex. Crystals obtained by removing the solvent by decantation were washed twice with 20 ml of diisopropyl ether and dried to obtain 1.64 g of iron complex (C-1) (yield 71%).

  Under a nitrogen atmosphere, 1.64 g of iron complex (C-1), 2.55 g of silver hexafluoroantimonate (V) and 50 ml of acetonitrile were added to a light-shielding reaction vessel, followed by stirring at room temperature for 6 hours. The insoluble matter was removed by filtering the reaction solution using perlite. After the solvent was distilled off from the filtrate, the obtained solid was dissolved in acetonitrile, the insoluble matter was again filtered off using a syringe filter having a pore size of 0.2 μm, and the solvent was distilled off. By repeating this purification operation three times, 2.75 g (yield 96%) of an iron complex represented by the following structural formula (C-2) was obtained.

[Synthesis of Iron Complex (C-4)]
Under a nitrogen atmosphere, 9.02 g of pyridine-2-carboxaldehyde, 3.71 g of N, N′-dimethylethylene-1,2-diamine, and 300 ml of dichloromethane were added to a reaction vessel equipped with a stirrer, a thermometer, and a condenser. Stir at room temperature. Sodium triacetoxyborohydride (25.0 g) was added in 15 portions every 15 minutes, and then stirred at room temperature for 12 hours. To the reaction solution is added 100 ml of a saturated aqueous sodium hydrogen carbonate solution, and the mixture is separated. The obtained organic layer is washed with 100 ml of saturated brine, dried over anhydrous magnesium sulfate, and the solvent is distilled off to give crude product 9 .82 g was obtained. The crude product was purified by column chromatography (carrier: NH silica gel, eluent: chloroform / ethyl acetate) to obtain 4.63 g of ligand (L-1) (yield 41%).

  Under a nitrogen atmosphere, 4.63 g of ligand (L-1), 3.40 g of iron (II) chloride tetrahydrate and 100 ml of acetonitrile were added to the reaction vessel, and the mixture was stirred at room temperature for 7 hours. To the reaction solution, 100 ml of diisopropyl ether was added and stirred for 30 minutes to precipitate a metal complex. Crystals obtained by removing the solvent by decantation were washed twice with 50 ml of diisopropyl ether and dried to obtain 6.21 g of iron complex (C-3) (76% yield).

  Under a nitrogen atmosphere, 6.18 g of iron complex (C-3), 10.66 g of silver hexafluoroantimonate (V) and 200 ml of acetonitrile were added to a light-shielding reaction vessel, followed by stirring at room temperature for 6 hours. The insoluble matter was removed by filtering the reaction solution using perlite. After the solvent was distilled off from the filtrate, the obtained solid was dissolved in acetonitrile, the insoluble matter was again filtered off using a syringe filter having a pore size of 0.2 μm, and the solvent was distilled off. By repeating this purification operation three times, 10.39 g (yield 95%) of an iron complex represented by the following structural formula (C-4) was obtained.

[Synthesis of adamantanetriol]
To the reaction vessel, 4.00 g (29.4 mmol) of adamantane, 0.882 g (14.7 mmol) of acetic acid, 274 mg (0.294 mmol) of iron complex (C-2) synthesized in Example 1 as a catalyst, and 180 ml of acetonitrile were added. While stirring at room temperature, a mixed solution of 120 ml of acetonitrile and 4.00 g of 30% aqueous hydrogen peroxide (35.3 mmol as hydrogen peroxide) was dropped into the flask over 30 minutes. Thereafter, 274 mg (0.294 mmol) of iron complex, 0.882 g (14.7 mmol) of acetic acid, and 4.00 g of 30% hydrogen peroxide (35.3 mmol as hydrogen peroxide) were added every 30 minutes for a total of 9 times. . Meanwhile, the reaction was confirmed by GC analysis. Finally, the total amount used was 2.74 g of iron complex (0.1 times mol with respect to the substrate), 8.82 g of acetic acid (5.0 times mol with respect to the substrate), and 30% hydrogen peroxide solution 40. It was added until the amount became 0 g (12 moles as hydrogen peroxide with respect to the substrate), and the mixture was further stirred for 1 hour, and then the reaction was completed. As a result of GC analysis at the end of the reaction, the peak area ratios were adamantane monool: 0.0%, adamantanediol: 4.6%, 1,3,5-adamantanetriol: 72%. The results are summarized in Table 1.
After completion of the reaction, 500 ml of water was added to the reaction solution, 5% aqueous sodium hydrogen sulfite solution was added to decompose excess hydrogen peroxide, and the reaction solution was neutralized with a saturated aqueous sodium hydrogen carbonate solution. After performing a liquid separation operation by adding 300 ml of toluene, an aqueous layer was collected, and the collected aqueous layer was washed with 100 ml of toluene. The aqueous layer was concentrated and dried to obtain 121.07 g of a crude product of adamantanetriol. To the obtained crude product, 150 ml of methanol was added and heated. After stirring at 60 ° C., hot filtration was performed to remove insoluble matters. 100 ml of methanol was added to the crystals obtained by concentrating the filtrate, and the same operation was repeated to obtain crystals. The obtained crystals were dissolved in 150 ml of water, and the obtained solution was passed through a column packed with 100 ml of a strongly acidic cation exchange resin. The solution obtained by concentrating the solution after passing through was purified by recrystallization using methanol / chloroform to 4.22 g of the obtained crystal, and 2.38 g (yield 44%) of 1,3,5-adamantanetriol white crystal. (Purity 98%) was obtained.

  The reaction was performed under the same conditions as in Example 3, except that 1,3-adamantanediol was used instead of adamantane as a starting material. Finally, the total amount used was 1.34 g of catalyst (0.06 mol per mol), 4.28 g of acetic acid (3.0 mol per mol of substrate), and 19.4 g of 30% aqueous hydrogen peroxide. The mixture was added until the amount of hydrogen peroxide was 7.2 times as much as that of the substrate, and further stirred for 1 hour, and then the reaction was completed. As a result of GC analysis at the end of the reaction, the peak area ratios were adamantanediol: 9.0% and 1,3,5-adamantanetriol: 86%. The results are summarized in Table 1.

  To the reaction vessel was added 4.00 g (29.4 mmol) of adamantane, 0.882 g (14.7 mmol) of acetic acid, 822 mg (0.882 mmol) of iron complex (C-2) synthesized in Example 1 as a catalyst, and 150 ml of acetonitrile. While stirring at room temperature, a mixture of 150 ml of acetonitrile and 33.3 g of 30% aqueous hydrogen peroxide (294 mmol as hydrogen peroxide) was dropped into the flask over 120 minutes. Thereafter, the reaction was further completed by stirring for 1 hour. As a result of GC analysis at the end of the reaction, the peak area ratios were adamantane monool: 0.0%, adamantanediol: 5.9%, 1,3,5-adamantanetriol: 80%. The results are summarized in Table 1.

  The reaction was performed under the same conditions as in Example 3, except that the iron complex (C-4) synthesized in Example 2 was used instead of the iron complex (C-2). Finally, the total amount used was 2.94 g of catalyst (0.1 times mol with respect to the substrate), 8.82 g of acetic acid (5.0 times mol with respect to the substrate), and 40.0 g of 30% aqueous hydrogen peroxide. The mixture was added until the amount was 12 times as much as hydrogen peroxide with respect to the substrate, and further stirred for 1 hour, and then the reaction was completed. As a result of GC analysis at the end of the reaction, the peak area ratios were adamantane monool: 0.0%, adamantanediol: 9.8%, 1,3,5-adamantanetriol: 41%. The results are summarized in Table 1.

[Comparative Example 1]
As the oxidizing agent, sodium hypochlorite (10% aqueous solution) was used in place of hydrogen peroxide, and the oxidation reaction was performed under the same conditions as in Example 5 except that no organic acid (acetic acid) was used. . As a result of GC analysis at the end of the reaction, the peak area ratio was adamantane monool: 25%, adamantane diol: 4.7%, 1,3,5-adamantane triol: 1.9%. The results are summarized in Table 1.

[Comparative Example 2]
Sodium hypochlorite (10% aqueous solution) was used as the oxidizing agent, acetic acid was used as the organic acid, and the iron complex (C-4) synthesized in Example 2 was used as the catalyst. The oxidation reaction was carried out under the same conditions as in Example 3, except that the amount of the catalyst used was 1.2 times mol, 0.5 times mol, and 0.05 times mol, respectively. Since the progress of the reaction was slower than in Example 3, the reaction was terminated without adding the oxidant and the like after the second time. As a result of GC analysis at the end of the reaction, the peak area ratios were adamantane monool: 16%, adamantanediol: 3.3%, 1,3,5-adamantanetriol: 0.0%. The results are summarized in Table 1.

  As can be seen from the results in Table 1, in Examples 3 to 6 using hydrogen peroxide as the oxidant, the target adamantanetriol was obtained with high selectivity and high yield, while the following oxidant was used as the oxidant. In Comparative Examples 1 and 2 using sodium chlorite, adamantanetriol was hardly obtained. In addition, from the results of Example 3 and Example 5, adamantanetriol can be obtained with high selectivity and high yield when the catalyst, the organic acid and the oxidizing agent are added in portions, or when the total amount is added at once. I understood.

Although the present invention has been described in detail and with reference to specific embodiments, it will be apparent to those skilled in the art that various changes and modifications can be made without departing from the spirit and scope of the invention.
This application is based on the JP Patent application 2012-128899 of an application on June 6, 2012, The content is taken in here as a reference.

  According to the present invention, adamantane triols can be produced with high selectivity and high yield by an inexpensive and low environmental impact method using adamantanes as starting materials. The adamantanetriols obtained by the present invention are useful as intermediates for highly functional polymers, electronic materials, synthetic lubricants, medicines and agricultural chemicals.

Claims (14)

A method for producing an adamantanetriol, comprising reacting an adamantane represented by the following general formula (1) with hydrogen peroxide in a solvent in the presence of a metal complex.

(In the formula, R is a halogen atom, a hydroxyl group, a linear or branched alkyl group having 1 to 10 carbon atoms which may have a substituent, and the number of carbon atoms which may have a substituent. A cycloalkyl group having 3 to 10 carbon atoms, a linear or branched alkoxy group having 1 to 10 carbon atoms which may have a substituent, and a carbon atom having 3 to 10 carbon atoms which may have a substituent A cycloalkoxy group, an optionally substituted acyl group having 2 to 10 carbon atoms, an optionally substituted acyl group having 2 to 10 carbon atoms, a substituted or unsubstituted aryl group, Represents a substituted or unsubstituted aryloxy group; n represents an integer of 0 to 13, and when n is 2 or more, a plurality of Rs may be the same or different from each other; provided that the number of hydroxyl groups is 2 or less It shall be)   The method for producing an adamantanetriol according to claim 1, wherein the adamantane represented by the general formula (1) is reacted with hydrogen peroxide in a solvent in the presence of a metal complex and an organic acid.   The method for producing an adamantanetriol according to claim 1 or 2, wherein the adamantanetriol is a 1,3,5-adamantanetriol derivative.   The method for producing adamantanetriol according to any one of claims 1 to 3, wherein the solvent is a mixed solution of water / organic solvent.   The method for producing an adamantanetriol according to claim 4, wherein the organic solvent is one or more organic solvents selected from water-soluble alcohols or nitriles.   The method for producing adamantanetriols according to claim 4, wherein the organic solvent is acetonitrile.   In the metal complex, at least one of the ligands has 4 to 8 nitrogen atoms, of which a plurality of nitrogen atoms are linked via two consecutive carbon atoms. The manufacturing method of the adamantanetriol as described in any one of Claims 6. The method for producing an adamantanetriol according to claim 7, wherein in the metal complex, at least one of the ligands is a nitrogen-containing compound represented by the following general formula (2) or (3).

(Wherein R ^{1 to} R ⁴ may be the same or different and each represents a hydrogen atom or a linear or branched alkyl group having 1 to 10 carbon atoms which may have a substituent; Ar ¹ and Ar ² may be the same or different and each represents a substituted or unsubstituted nitrogen-containing aromatic heterocyclic group)

(In the formula, Ar ^{3 to} Ar ⁵ may be the same or different and each represents a substituted or unsubstituted nitrogen-containing aromatic heterocyclic group) In the metal complex, of the formula (2) in adjacent pairs of R ¹ to R ^4, at least one pair, via a single bond linked to form a ring, according to claim 8 Method for producing adamantanetriols. In the metal complex, among the adjacent pairs of R ^{1 to} R ⁴ in the general formula (2), R ¹ and R ² , and R ³ and R ⁴ are linked to form a ring via a single bond, respectively. The method for producing adamantanetriols according to claim 9.   The method for producing adamantanetriols according to any one of claims 1 to 10, wherein a central metal of the metal complex is a metal selected from transition metals.   The method for producing adamantanetriols according to claim 11, wherein the central metal of the metal complex is iron.   The method for producing an adamantanetriol according to claim 2, wherein the organic acid is an aliphatic carboxylic acid or an aromatic carboxylic acid. The method for producing adamantanetriols according to claim 13, wherein the organic acid is acetic acid.