JPH10316601A - Oxidation of polycyclic hydrocarbon - Google Patents

Abstract

PROBLEM TO BE SOLVED: To carry out oxidation reaction effectively at high conversion rate on an industrial scale while suppressing the adhesion of a sublimable polycyclic hydrocarbon on a reactor and on the internal walls of tubes by using a specific mixed solvent as a reaction solvent on the oxidation of the polycyclic hydrocarbon. SOLUTION: A sublimable polycyclic hydrocarbon (e.g. a bridged cyclic hydrocarbon having a methylidyne group, especially an adamantane) is oxidized in the presence of an oxidizing catalyst consisting of an imide compound expressed by the formula [R<1> and R<2> are each H, a halogen, an alkyl, etc., and they may be bonded to each other to form a double bond or a ring; X is oxygen or hydroxyl; (n)=1-3] in a mixed solvent consisting of (A) a non- sublimable aromatic compound (e.g. a benzene derivative) and (B) at least one compound (e.g. an organic compound such as a 1-4C aliphatic hydrocarbon) selected from acidic compounds and non-aromatic nitrile compounds [the component A/the component B=(25/75) to (95/5) by weight] under contact with oxygen to produce a polycyclic hydrocarbon which has a hydroxyl or oxo group.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to an oxidation method useful for producing a corresponding oxide from a polycyclic hydrocarbon having sublimability, and a method for producing a hydroxyl- or oxo-group-containing polycyclic compound. About.

[0002]

2. Description of the Related Art Polycyclic hydrocarbons have a unique function because they have a three-dimensional symmetric structure or a structure in which each ring is stabilized. Therefore, by introducing a hydroxyl group into the polycyclic hydrocarbons and, if necessary, deriving the acrylic acid derivative or carbonate, etc.,
Various copolymers with enhanced functionality can be obtained. For example, in a bridged cyclic hydrocarbon having a methine carbon atom at the bridgehead position, a method for producing a polyester from an adamantane derivative into which a functional group (eg, a hydroxyl group, an amino group, a carboxyl group, etc.) is introduced (Japanese Patent Laid-Open No. −
No. 21090), a method for obtaining a polycarbonate (eg, US Pat. No. 3,594,427), a method for obtaining a polyamide or polyimide (eg, US Pat. No. 3,832,332), and a method for obtaining a polyurethane (Japanese Patent Publication No. 44-1).
No. 2891), a method for obtaining polysulfone and polysulfonate (US Pat. No. 3,753,950) and a method for obtaining a vinyl polymer (JP-B-46-2).
No. 8419) has been proposed. Also, a homopolymer using a polycyclic hydrocarbon as a monomer has been proposed (US Pat. No. 3,649,702). Polymers obtained from such polycyclic hydrocarbons are generally
Functionality is high, for example, light guide loss, refractive index, optical properties such as birefringence, moisture resistance, heat resistance, properties such as thermal expansion, have a high level that can not be achieved with conventional polymers I have. Accordingly, the polymer is used as an optical fiber, an optical element, an optical lens, a hologram, an optical disk, an optical material such as a contact lens, a transparent resin coating agent for an organic glass, a conductive polymer, a photographic photosensitive material, a fluorescent material, and the like. Use is being considered. In addition, amino derivatives derived from alcoholic or ketone bodies of bridged cyclic hydrocarbons such as adamantane,
It is useful for inducing various medicines and pesticides that exhibit high pharmacological activity, as represented by the therapeutic drug “Symmetrel” for Parkinson's disease. Thus, polycyclic hydrocarbons having a functional group such as a hydroxyl group or an oxo group are:
Used for a wide range of applications.

[0003] As a method for producing an alcohol compound of a polycyclic hydrocarbon such as adamantane, a polycyclic hydrocarbon is brominated with an excessive amount of bromine, and the resulting bromide is hydrolyzed with an excess of silver nitrate or silver sulfate. Decomposition method (JP-A-2-196)
No. 744), polycyclic hydrocarbons are dissolved in a concentrated acetic acid solution,
Oxidation using chromic acid (Japanese Patent Publication No. Sho 42-1662)
No. 1), a method of oxidizing molten adamantane by oxygen using a cobalt salt as a catalyst (Japanese Patent Publication No. 42-26792).
Publication). JP-A-8-38909
Japanese Patent Application Laid-Open Publication No. H11-15083 proposes a method of oxidizing a substrate with oxygen using an imide compound as a catalyst. When this oxidation method is applied to adamantane, an alcohol form of adamantane can be obtained. The 67th Annual Meeting of the Chemical Society of Japan, 19
In 1994, "Lecture Proceedings II", it was reported that when adamantane was oxidized with N-hydroxyphthalimide using oxygen, the corresponding alcohols and ketones were formed.

[0004] However, among the polycyclic hydrocarbons, sublimable compounds such as adamantane, norbornane, camphor and the like may be dissolved in a solvent or heated.
When a gas is supplied, it has the property of being easily volatilized.
Therefore, when such a compound is oxidized as a substrate, a problem arises in that the substrate is volatilized during the reaction operation and adheres in a solid state to the gas phase portion of the reactor and the inner wall of the pipe, thereby blocking the pipe and the like. . Therefore, it is particularly difficult to produce the target oxide in a continuous manner.

[0005]

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide a method which can suppress the sublimable polycyclic hydrocarbons from adhering to the inner wall of a reactor or a pipe and can carry out a reaction operation smoothly. An object of the present invention is to provide a method for oxidizing cyclic hydrocarbons. Another object of the present invention is to provide a method capable of oxidizing polycyclic hydrocarbons at a high conversion while suppressing the adhesion of sublimable polycyclic hydrocarbons to inner walls such as pipes. Still another object of the present invention is to provide a method capable of oxidizing sublimable polycyclic hydrocarbons with good operability under mild conditions. Another object of the present invention is to oxidize sublimable polycyclic hydrocarbons having a methylidyne group at the bridgehead position under mild conditions to produce a corresponding oxide having a hydroxyl group or oxo group introduced industrially. It is an object of the present invention to provide a method for efficiently producing the same.

[0006]

Means for Solving the Problems The inventors of the present invention have made intensive studies to achieve the above object, and as a result, have found that sublimable polycyclic hydrocarbons are oxidized in a reaction system having a space. When a specific mixed solvent is used as a reaction solvent,
The inventors have found that the polycyclic hydrocarbons can be remarkably suppressed from adhering to the reactor and the inner wall of the pipe, and have completed the present invention. That is, the present invention relates to a method for producing a sublimable polycyclic hydrocarbon by using at least one selected from (A) a non-sublimable aromatic compound and (B) an acidic compound and a non-aromatic nitrile.
Provided is a method for oxidizing polycyclic hydrocarbons, which is oxidized by oxygen in a mixed solvent composed of a compound of any kind. Polycyclic hydrocarbons include bridged cyclic hydrocarbons and the like. The aromatic compound (A) as one component of the mixed solvent contains a benzene derivative and the like, and the compound (B) as the other component includes an organic acid such as an aliphatic carboxylic acid having 1 to 4 carbon atoms. And so on. The ratio between the aromatic compound (A) and the compound (B) in the mixed solvent is, for example, about the former / the latter (weight ratio) = about 25/75 to 95/5.

In the above method, the following formula (1) is used as an oxidation catalyst.

[0008]

Embedded image (Wherein R ¹ and R ² are the same or different and each represent 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, an acyl group; R ¹
And R ² may combine with each other to form a double bond or an aromatic or non-aromatic ring. X represents an oxygen atom or a hydroxyl group, and n represents an integer of 1 to 3.) may be used.

According to another aspect of the present invention, there is provided a sublimable polycyclic hydrocarbon having a methylidyne group at a bridgehead position or a bonding position in the presence of an oxidation catalyst comprising the imide compound represented by the above formula (1). And (A) a non-sublimable aromatic compound;
(B) contacting with oxygen in a mixed solvent composed of an acidic compound and at least one compound selected from non-aromatic nitriles to form a hydroxyl group at a bridgehead or a junction or a hydroxyl group at a bridgehead or a junction; An oxo group is introduced into an adjacent site to produce a hydroxyl or oxo group-containing polycyclic compound. In the present specification, “sublimation” means not only the property that a solid evaporates directly from a solid state, but also the property that a solid volatilizes in a state of being dissolved in a solvent.

[0010]

BEST MODE FOR CARRYING OUT THE INVENTION

[Sublimable Polycyclic Hydrocarbons] The substrate to be subjected to the oxidation reaction is not particularly limited as long as it is a polycyclic hydrocarbon having sublimability, and a wide variety of compounds can be used. Such polycyclic hydrocarbons have an oxidizable group such as a methyl group, a methylene group, a methine group [methylidyne group (-CH <)], a hydroxymethylene group [-CH (OH)-], and the like. It includes polycyclic hydrocarbons, such as bridged cyclic hydrocarbons and fused polycyclic hydrocarbons. These polycyclic hydrocarbons may have an aromatic ring.

As the crosslinked cyclic hydrocarbons, for example,
Bicyclic to tetracyclic hydrocarbons having about 7 to 16 carbon atoms constituting the ring, for example, compounds having a carbon-hydrogen bond at a bridgehead position or a junction position, and the like, in particular, norbornane, camphor (camphor) , And bicyclic hydrocarbons such as pinene, pinane, camphene and bornene; tricyclic hydrocarbons such as adamantane; and derivatives thereof. Examples of the condensed polycyclic hydrocarbon include a condensed polycyclic hydrocarbon in which a 5- to 8-membered ring is condensed by about 2 to 8 and a derivative thereof. In fused polycyclic hydrocarbons, for example,
5- or 6-membered ring is 2 to 2 like naphthalene derivative
In many cases, about 6 condensation occurs.

These polycyclic hydrocarbons include various substituents such as halogen atoms (iodine, bromine, chlorine and fluorine atoms) and alkyl groups (for example, depending on the type of polycyclic hydrocarbons). Methyl, ethyl, propyl, isopropyl, butyl, isobutyl, s-butyl, t-butyl,
An alkyl group having about 1 to 6 carbon atoms such as a hexyl group, particularly a lower alkyl group having about 1 to 4 carbon atoms), an oxo group,
Hydroxyl group, alkoxy group (for example, methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, t-butoxy, hexyloxy group and the like about 1 to 6 carbon atoms, particularly about 1 to 4 alkoxy groups, etc.),
Hydroxyalkyl groups (eg, hydroxymethyl, 2
A hydroxy C _1-4 alkyl group such as a hydroxyethyl group, an acyl group (for example, an acyl group having about 1 to 6 carbon atoms such as a formyl, acetyl, propionyl, butyryl, valeryl, pivaloyl group), an amino group, and a substituent It may be substituted by an amino group, a cyano group, a nitro group or the like.

Preferred polycyclic hydrocarbons include polycyclic hydrocarbons having a methylidyne group (particularly, bridged cyclic hydrocarbons), and polycyclic hydrocarbons having a methyl group or a methylene group at an allylic or benzylic position. Including the formula hydrocarbons,
Adamantanes (adamantane; adamantane derivatives having substituents such as halogen atoms, alkyl groups, hydroxyl groups and oxo groups), norbornanes (norbornanes; norbornane derivatives having substituents such as halogen atoms and alkyl groups), camphors (camphor Or a derivative thereof), and in particular, adamantane such as adamantane is often used.

When the polycyclic hydrocarbons are oxidized, the corresponding oxides (alcohols, aldehydes, ketones,
(Carboxylic acids). Products vary depending on the type of substrate, oxidation method, reaction conditions, and the like. For example, in polycyclic hydrocarbons having a methylidyne group (bridged cyclic hydrocarbons having a methylidyne group at a bridgehead position, condensed polycyclic hydrocarbons having a methylidyne group at a junction position, etc.), A hydroxyl group is introduced at a tertiary carbon atom constituting the group. Also, for example, by appropriately selecting the catalyst system or adjusting the reaction temperature and reaction time,
An oxo group can be introduced at a site (secondary carbon atom) adjacent to the methylidine group. More specifically, for example, when adamantane or a derivative thereof is oxidized, usually, adamantanol having a hydroxyl group introduced at the bridgehead position (1-adamantanol; 1,3-adamantanediol,
Adamantane polyols such as 3,5-adamantanetriol), adamantanones having an oxo group introduced at a secondary carbon atom adjacent to the bridgehead (such as 2-adamantanone), hydroxyl groups introduced at the bridgehead and bridgehead positions To form a hydroxyadamantanone (for example, 1-hydroxy-2-adamantanone) in which an oxo group is introduced at a site adjacent to. Oxidation of an adamantane derivative having one or two hydroxyl groups also produces a more highly hydroxylated adamantane polyol.

On the other hand, in polycyclic hydrocarbons having a methyl group or a methylene group at the allylic or benzylic position, a hydroxyl group, oxo group or carboxyl group (which may be cleaved in some cases) at the allylic or benzylic position by oxidation. ) Is introduced. In a compound having a cycloalkane ring, the cycloalkane ring is cleaved by oxidation,
The corresponding dicarboxylic acid may be formed.

[Solvent] In the method of the present invention, as a reaction solvent, at least one selected from (A) a non-sublimable aromatic compound and (B) an acidic compound and a non-aromatic nitrile is used.
It is characterized in that a mixed solvent composed of the above compounds is used.

The non-sublimable aromatic compound (A) includes:
Various compounds which have an aromatic ring such as a benzene ring and a naphthalene ring, are non-sublimable, and inert to the reaction can be used.
The aromatic ring of the aromatic compound (A) has various substituents, for example, a halogen atom (fluorine, chlorine, bromine or iodine atom), a cyano group, a nitro group, a hydroxyl group, an alkoxy group (for example, methoxy, ethoxy, Propoxy, isopropoxy, butoxy, isobutoxy, t-butoxy,
A C _1-10 alkoxy group such as a hexyloxy group, preferably a C _1-6 alkoxy group, more preferably a C _1-4 alkoxy group, and an alkoxycarbonyl group (for example, methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, isopropoxycarbonyl) , A butoxycarbonyl group or other alkoxy moiety having 1 to 10 carbon atoms, preferably about 1 to 6 carbon atoms, and more preferably about 1 to 4 alkoxycarbonyl groups). 6).

The aromatic compound (A) includes, for example, an aromatic hydrocarbon (eg, benzene), an aromatic hydrocarbon substituted with a halogen atom (eg, fluorobenzene, chlorobenzene, 1,2-dichlorobenzene). , 1,
3-dichlorobenzene, bromobenzene, etc.), an aromatic hydrocarbon substituted with a cyano group (eg, benzonitrile), an aromatic hydrocarbon substituted with a nitro group (eg, nitrobenzene), substituted with an alkoxy group Aromatic hydrocarbons (eg, anisole, phenetole, etc.), aromatic hydrocarbons substituted with alkoxycarbonyl groups (eg, methyl benzoate, ethyl benzoate, etc.)
And so on. The aromatic compounds (A) may be used alone or in combination of two or more. Aromatic compound (A)
In order to increase the solubility of the substrate, the solubility (10 ° C.) of the substrate is about 3 (g / 100 g) or more [for example, 3
１００100 (g / 100 g)], preferably 5 (g / 100 g).
100 g) or more [for example, 5 to 50 (g / 100
g)).
Further, the solubility parameter δ of the aromatic compound (A)
[(Cal / cc) ^1/2 ] is, for example, about 7.8 to 12.5,
It is preferably about 8 to 11, more preferably about 8 to 10 (for example, about 8 to 9). Preferred aromatic compounds (A) include aromatic hydrocarbons substituted with a halogen atom such as chlorobenzene (δ = about 8.4), and aromatic hydrocarbons substituted with a cyano group such as benzonitrile (δ = 8.4). Group hydrocarbons and the like. In particular, a benzene derivative is often used as the aromatic compound (A).

Among the compounds (B), as the acidic compound, an organic acid is usually used. Examples of organic acids include carboxylic acids such as formic acid, acetic acid, propionic acid, butyric acid, trifluoroacetic acid, and benzoic acid; oxycarboxylic acids such as glycolic acid, lactic acid, and hydroxybutyric acid; and sulfonic acids such as methanesulfonic acid and ethanesulfonic acid. Is mentioned. Preferred organic acids include, for example, carboxylic acids. Among the compounds (B), examples of the non-aromatic nitrile include aliphatic nitriles having about 2 to 6 carbon atoms such as acetonitrile, propionitrile, and butyronitrile;
An alicyclic nitrile having about 5 to 10 carbon atoms, such as cyclohexanenitrile, is included. The compound (B) can be used alone or in combination of two or more. Preferred compounds (B) include organic acids, for example, aliphatic carboxylic acids, among which those having 1 to 4 carbon atoms such as acetic acid and propionic acid.
Aliphatic carboxylic acids (particularly acetic acid and the like). The ratio between the aromatic compound (A) and the compound (B) is
You can choose from a wide range, for example, the former / the latter (weight ratio)
= 10 / 90-95 / 5, preferably 25 / 75-95
/ 5, more preferably about 25/75 to 90/10.

The reaction solvent includes the aromatic compound (A) and the compound (B) as long as the reaction and reaction operability are not impaired.
A third solvent component other than the above may be added. In the present invention, the aromatic compound (A) and the compound (B) are used as reaction solvents.
Because the former is excellent in solubility of the substrate and suppresses the volatilization of the substrate, and the latter is to improve the reactivity of the substrate or to suppress the adhesion of the substrate on the inner wall of the pipe, etc. It can be oxidized at a conversion rate. Therefore, the target oxide can be efficiently produced. In particular, even if the reaction is performed in a continuous manner, troubles such as clogging of pipes do not occur, so that stable operation can be performed for a long period of time.
When an acidic compound such as acetic acid is used alone as a reaction solvent, the substrate is remarkably adhered to the inner wall of the pipe, and the pipe is easily blocked. Further, when an aromatic compound such as chlorobenzene is used alone as a reaction solvent, the reaction rate is low, and a sufficient conversion cannot be obtained.

[Oxidation Catalyst] A wide range of substances that catalyze the oxidation of the substrate can be used as the oxidation catalyst used for oxidizing the substrate with oxygen. Among such oxidation catalysts, when the imide compound represented by the formula (1) is used as a catalyst,
Substrate can be oxidized efficiently under mild conditions.

In the imide compound represented by the formula (1), the halogen atom among the substituents R ¹ and R ² includes iodine, bromine, chlorine and fluorine atoms. Examples of the alkyl group include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, s-butyl, t-butyl,
It includes a linear or branched alkyl group having about 1 to 10 carbon atoms, such as pentyl, hexyl, heptyl, octyl, and decyl groups. Preferred alkyl groups include, for example,
A lower alkyl group having about 1 to 6 carbon atoms, particularly about 1 to 4 carbon atoms is exemplified.

The aryl group includes a phenyl group, a naphthyl group and the like, and the cycloalkyl group includes a cyclopentyl, cyclohexyl, cyclooctyl group and the like. Alkoxy groups include, for example, methoxy, ethoxy,
Propoxy, isopropoxy, butoxy, isobutoxy, t-butoxy, pentyloxy, hexyloxy groups and the like, preferably containing a lower alkoxy group having about 1 to 10 carbon atoms, preferably about 1 to 6 carbon atoms, particularly about 1 to 4 carbon atoms. It is.

The alkoxycarbonyl group includes, for example, a carbon atom of an alkoxy moiety such as methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, isopropoxycarbonyl, butoxycarbonyl, isobutoxycarbonyl, t-butoxycarbonyl, pentyloxycarbonyl and hexyloxycarbonyl. The number includes about 1 to 10 alkoxycarbonyl groups. Preferred alkoxycarbonyl groups have 1 to 6 carbon atoms in the alkoxy moiety.
About, especially about 1 to about 4 lower alkoxycarbonyl groups. 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 (1), R ¹ and R ² may be bonded to each other to form a double bond or an aromatic or non-aromatic ring. Preferred aromatic or non-aromatic rings are about 5 to 12 membered rings, especially about 6 to 10 membered rings, and may be a heterocyclic ring or a fused heterocyclic ring,
Often it is a hydrocarbon ring. Examples of such a ring include a non-aromatic alicyclic ring (a cycloalkene ring which may have a substituent such as a cyclohexane ring and a cycloalkene which may have a substituent such as a cyclohexene ring). Ring), a non-aromatic bridged ring (eg, a bridged hydrocarbon ring which may have a substituent such as a 5-norbornene ring), a benzene ring, a naphthalene ring or the like. And aromatic rings. The ring is often composed of an aromatic ring.

Preferred imide compounds include the following formula (1a)
To (1f).

[0027]

Embedded image (Wherein, R ^{3 to} R ⁶ are the same or different and are each a hydrogen atom,
It represents an alkyl 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, and a halogen atom. 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, and an alkoxy group Include the same alkoxy group as described above, particularly a lower alkoxy group having about 1 to 4 carbon atoms, and the alkoxycarbonyl group includes the same alkoxycarbonyl group as described above, particularly a lower alkoxy group having about 1 to 4 carbon atoms in the alkoxy moiety. Includes carbonyl groups.
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. 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. In the above formula (1), X represents an oxygen atom or a hydroxyl group, and n is usually 1 to 3.
Degree, preferably 1 or 2. One or more imide compounds represented by the formula (1) can be used in the carboxylation reaction.

The acid anhydride corresponding to the imide compound represented by the formula (1) includes, for example, saturated or unsaturated aliphatic polycarboxylic anhydrides such as succinic anhydride and maleic anhydride, and tetrahydrophthalic anhydride. Acid, hexahydrophthalic anhydride (1,2-cyclohexanedicarboxylic anhydride),
1,2,3,4-cyclohexanetetracarboxylic acid 1,
Saturated or unsaturated non-aromatic cyclic polycarboxylic acid anhydrides (alicyclic polycarboxylic acid anhydrides) such as 2-anhydrides, and bridged cyclic polycarboxylic acids such as hetic acid anhydride and hymic acid anhydride Anhydrides (alicyclic polycarboxylic anhydrides), phthalic anhydride, tetrabromophthalic anhydride, tetrachlorophthalic anhydride, nitrophthalic anhydride, trimellitic anhydride,
Aromatic polycarboxylic anhydrides such as methylcyclohexenetricarboxylic anhydride, pyromellitic anhydride, mellitic anhydride, 1,8; 4,5-naphthalenetetracarboxylic dianhydride are included.

Preferred imide compounds include, for example,
An imide compound derived from an aliphatic polycarboxylic anhydride (eg, N-hydroxysuccinimide, N-hydroxymaleimide, etc.), an alicyclic polycarboxylic anhydride, or an aromatic polycarboxylic anhydride Compounds derived from the product (for example, 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'-dihydroxynaphthalenetetracarboxylic imide, etc.). Particularly preferred imide compounds include N-hydroxyimide compounds derived from alicyclic polycarboxylic anhydrides, especially aromatic polycarboxylic anhydrides, such as N-hydroxyphthalimide.

The imide compound is prepared by a conventional imidation reaction, for example, by reacting the corresponding acid anhydride with hydroxylamine N
It can be prepared by reacting with H ₂ OH to open the acid anhydride group and then closing the ring to imidize the ring. The amount of the imide compound used may be in a wide range, for example, 0.001 mol (0.1 mol%) to 1 mol (100 mol%), preferably 0.001 mol (0.1 mol), per 1 mol of the substrate. %) ~
0.5 mol (50 mol%), more preferably 0.01 mol
To 0.3 mol, and can be selected from the range of 0.01 to 0.1 mol.
It is often about 25 mol.

[Co-catalyst] The oxidation catalyst may be composed of the imide compound represented by the above formula (1) and a co-catalyst. The co-catalyst includes a metal compound, for example, a compound containing a Group 2A element (such as magnesium, calcium, strontium, or barium), a transition metal compound, or a compound containing a Group 3B element (such as boron B or aluminum Al) in the periodic table. .
The cocatalyst can be used alone or in combination of two or more.

Examples of the elements of the transition metal include Group 3A elements of the periodic table (for example, lanthanide elements such as lanthanum La, cerium Ce and samarium Sm, actinoid elements such as actinoid Ac, in addition to scandium Sc and yttrium Y). Group 4A element (titanium Ti, zirconium Zr, hafnium Hf, etc.), group 5A element (vanadium V, niobium Nb, tantalum Ta, etc.), group 6A element (chromium Cr, molybdenum Mo, tungsten W, etc.), group 7A element (manganese) Mn, technetium Tc,
Group 8 elements (iron Fe, ruthenium R, etc.)
u, osmium Os, cobalt Co, rhodium Rh, iridium Ir, nickel Ni, palladium Pd, platinum P
t), group 1B elements (copper Cu, silver Ag, gold Au, etc.) and group 2A elements (zinc Zn, cadmium Cd, etc.).

Preferred co-catalysts include transition metal elements (for example, lanthanoid elements such as Ce, Group 3A elements such as actinoid elements, Group 4A elements such as Ti and Zr, V, Nb, etc.). Group 5A element, Cr, M
Group 6A elements such as o and W, and 7A such as Mn, Tc and Re
Group 8 elements such as Fe, Ru, Co, Rh, and Ni; Group 1B elements such as Cu;
Group B elements are included. In particular, when combined with the imide compound represented by the above formula (1), a group 4A element such as Ti and Zr, a group 5A element such as V, a group 6A element such as Cr, Mo, W, Mn, Tc, Re Group 7A elements such as Fe, R
Group 8 element such as u, Co, Rh, Ni, 1B such as Cu
The use of a compound containing a group III element increases the conversion of polycyclic hydrocarbons (eg, adamantanes), and increases the hydroxyl group-containing polycyclic hydrocarbons (eg, adamantanol, etc.) and oxo group-containing polycyclic hydrocarbons. Hydrogens (for example,
Adamantanone) can be obtained in high yield.
In particular, when a compound containing a Group 5A element (such as V) is used as a cocatalyst, a plurality of sites of a substrate (eg, a bridgehead position or a bonding position of polycyclic hydrocarbons) can be efficiently oxidized, and a plurality of hydroxyl groups can be oxidized. (Adamantane polyol and the like) into which is introduced can be obtained in good yield. In addition, group 4A elements (Ti, Zr, etc.) and group 6A elements (Cr,
Use of a compound containing a group 7A element (such as Mn) or a group 7A element (such as Mn) as a cocatalyst has the advantage that the deactivation of the imide compound can be greatly suppressed even under severe reaction conditions.
Further, when a compound containing a Group 1B element (such as Cu) in the periodic table and the imide compound are combined, the selectivity in the oxidation reaction can be improved and the imide compound can be prevented from being deactivated, which is industrially advantageous. . The oxidation number of the metal element constituting the co-catalyst is not particularly limited, and may be, for example, 0, +2, +3, +4, +5, +6, etc., depending on the type of the element. When a divalent transition metal compound (for example, a divalent cobalt compound, a divalent manganese compound, or the like) is used as a cocatalyst, the oxidation activity can often be improved as compared with, for example, a trivalent transition metal compound. Further, when the adamantane component is oxidized with a catalyst system in which a divalent transition metal compound (for example, a divalent cobalt compound) is combined with the imide compound, under mild conditions, a polyol body such as adamantanediol can have a high selectivity and a high selectivity. It can be obtained in a yield, and there is almost no by-product of a ketone body.

The co-catalyst may be a simple metal, a hydroxide, or the like, but is usually a metal oxide (including a double oxide or an oxyacid salt), an organic acid salt, or an inorganic acid salt containing the above element. It is often a halide, a coordination compound (complex) containing the metal element, a polyacid (heteropolyacid or isopolyacid) or a salt thereof.

Examples of the boron compound containing boron (B) include boron hydroxide (for example, borane, diborane, tetraborane, pentaborane, decaborane, etc.),
Boric acid (eg, orthoboric acid, metaboric acid, tetraboric acid, etc.), borate (eg, nickel borate, magnesium borate, manganese borate, etc.), boron oxide such as B ₂ O ₃ , borazane, borazene , Borazine, boron amide, boron imide and other nitrogen compounds, BF ₃ , BCl
₃ , halides such as tetrafluoroborate, and borate esters (eg, methyl borate, phenyl borate, etc.). Preferred boron compounds include boric acid such as borohydride and orthoboric acid or salts thereof, especially boric acid.

The hydroxide includes, for example, Mn (OH)_Two,
MnO (OH), Fe (OH)_Two, Fe (OH)_ThreeSuch
Is included. Metal oxides include, for example, Sm_TwoO_Three, T
iO _Two, ZrO_Two, V_TwoO_Three, V_TwoO_Five, CrO, Cr
_TwoO_Three, MoO_Three, MnO, Mn_ThreeO_Four, Mn_TwoO_Three,
MnO_Two, Mn_TwoO₇, FeO, Fe_TwoO_Three, Fe_ThreeO
_Four, RuO_Two, RuO_Four, CoO, CoO_Two, Co_TwoO
_Three, RhO_Two, Rh_TwoO_Three, Cu_TwoO_ThreeEtc. are included,
As the double oxide or oxyacid salt, for example, MnAl_Two
O_Four, MnTiO_Three, LaMnO_Three, K_TwoMn_TwoO_Five,
CaO xMnO_Two(X = 0.5, 1, 2, 3, 5),
Manganates [eg, Na_ThreeMnO_Four, Ba_Three(Mn
O_Four)_TwoManganese (V) acid salts, such as K_TwoMnO_Four, Na
_TwoMnO _Four, BaMnO_FourManganese (VI) salts, such as K
MnO_Four, NaMnO_Four, LiMnO_Four, NH_FourMnO
_Four, CsMnO_Four, AgMnO_Four, Ca (Mn
O_Four)_Two, Zn (MnO_Four)_Two, Ba (MnO_Four)_Two,
Mg (MnO_Four)_Two, Cd (MnO _Four)_TwoSuch as overman
Ganates] and the like.

Examples of the organic acid salt include C _2-20 fatty acid salts such as cobalt acetate, manganese acetate, cobalt propionate, manganese propionate, cobalt naphthenate, manganese naphthenate, cobalt stearate, and manganese stearate; Manganese acid and corresponding C
e salt, Ti salt, Zr salt, V salt, Cr salt, Mo salt, Fe
Salts, Ru salts, Ni salts, Pd salts, Cu salts, Zn salts and the like are exemplified. As the inorganic acid salts, for example, nitrates such as cobalt nitrate, iron nitrate, manganese nitrate, nickel nitrate, copper nitrate and the like are used. Sulfates, phosphates and carbonates (eg, cobalt sulfate, iron sulfate, manganese sulfate, cobalt phosphate, iron phosphate, manganese phosphate, iron carbonate, manganese carbonate, iron perchlorate, etc.). As the halide, for example, SmCl ₃ , SmCl ₂ ,
TiCl ₂ , ZrCl ₂ , ZrOCl ₂ , VCl ₃ , V
OCl ₂ , MnCl ₂ , MnCl ₃ , FeCl ₂ , Fe
Cl ₃ , RuCl ₃ , CoCl ₂ , RhCl ₂ , RhC
l ₃ , NiCl ₂ , PdCl ₂ , PtCl ₂ , CuC
1, chlorides such as CuCl ₂ , and corresponding fluorides, bromides and iodides (eg, MnF ₂ , MnB
r ₂ , MnF ₃ , FeF ₂ , FeF ₃ , FeBr ₂ , F
eBr _3, FeI _2, CuBr, halides such as CuBr, etc. ^{_{2), M 1 MnCl 3,}} M 1 2 MnCl 4, M
^{_{1 2 MnCl 5, M 1 2}} MnCl 6 (M 1 represents a monovalent metal), and the like double halides such.

Examples of ligands forming a complex include alkoxy groups such as OH (hydroxo), methoxy, ethoxy, propoxy and butoxy groups, acyl groups such as acetyl (OAc) and propionyl, methoxycarbonyl (acetato), ethoxycarbonyl and the like. Alkoxycarbonyl group, acetylacetonato (AA), cyclopentadienyl group, halogen atom such as chlorine, bromine, CO, CN, oxygen atom, H ₂ O (aquo), phosphine (eg, triphenylphosphine, etc.) Phosphorus compounds such as triarylphosphine); and nitrogen-containing compounds such as NH ₃ (ammine), NO, NO ₂ (nitro), NO ₃ (nitrat), ethylenediamine, diethylenetriamine, pyridine, and phenanthroline. In the complex or complex salt, the same or different ligands may be coordinated by one kind or two or more kinds. Preferred ligands include, for example, phosphorus compounds such as OH, alkoxy group, acyl group, alkoxycarbonyl group, acetylacetonate, halogen atom, CO, CN, H ₂ O (aquo) and triphenylphosphine;
Nitrogen-containing compounds are included, including H ₃ , NO ₂ , and NO ₃ .

Preferred complexes include the preferred transition metals
Complexes containing elements are included. Suitable transition metal elements and ligands
Complexes can be combined in this case.
Cetyl acetonato complex (for example, Ce, Sm, Ti, Z
r, V, Cr, Mo, Mn, Fe, Ru, Co, Ni,
Acetylacetonato complexes such as Cu and Zn, and titanyl
Acetylacetonate complex TiO (AA)_Two, Zirconyl
Acetylacetonate complex ZrO (AA)_Two, Vanadilla
Cetylacetonato complex VO (AA)_TwoEtc.), Carbo
Nyl complexes and cyclopentadienyl complexes (for example, trica
Rubonyl cyclopentadienyl manganese (I), bis
Clopentadienyl manganese (II), biscyclopenta
Dienyl iron (II), Fe (CO)_Five, Fe_Two(C
O)₉, Fe_Three(CO)₁₂), Nitrosyl compounds
(For example, Fe (NO)_Four, Fe (CO) _Two(NO)_Two
Thiocyanato complex (eg, cobalt thiocyanate)
Nato, manganese thiocyanato, iron thiocyanato, etc.),
Acetyl complexes (eg, cobalt acetate, manganese acetate,
Iron acetate, copper acetate, zirconyl acetate ZrO (OAc)_Two,
Titanyl acetate TiO (OAc)_Two, Vanadyl acetate VO
(OAc)_TwoEtc.).

The polyacid constituting the heteropolyacid is often at least one of Group 5 or 6 elements of the periodic table, for example, V (vanadic acid), Mo (molybdic acid) and W (tungstic acid). The central atom is not particularly limited. For example, Be, B, Al, Si, Ge,
Sn, Ti, Zr, Th, N, P, As, Sb, V, N
b, Ta, Cr, Mo, W, S, Se, Te, Mn,
I, Fe, Co, Ni, Rh, Os, Ir, Pt, Cu
And so on. Specific examples of heteropoly acids include:
For example, cobalt molybdate, cobalt tungstate, molybdenum tungstate, manganese molybdate, manganese tungstate, manganese molybdenum tungstate, vanadomolybdophosphate, manganese vanadium molybdate, manganese vanadomolybdophosphate, vanadium molybdate, vanadium Tungstic acid, silicomolybdic acid, silicotungstic acid, phosphomolybdic acid, phosphotungstic acid, phosphovanadomolybdate, phosphovanadotungstic acid, and the like.

The amount of the cocatalyst to be used is in a wide range, for example, 0.0001 mol (0.01 mol%) per 1 mol of the substrate.
To 0.7 mol (70 mol%), preferably 0.0001
To 0.5 mol, more preferably in the range of about 0.001 to 0.3 mol, and often about 0.0005 to 0.1 mol (for example, 0.005 to 0.1 mol). . The ratio of the co-catalyst to the imide compound represented by the formula (1) can be selected within a range that does not impair the reaction rate and the selectivity.
001 to 10 mol, preferably about 0.005 to 5 mol, more preferably about 0.01 to 3 mol,
It is often about 5 to 5 mol (particularly 0.001 to 1 mol). The activity of the imide compound may decrease as the amount of the cocatalyst increases. Therefore, in order to maintain a high activity of the oxidation catalyst system, the ratio of the co-catalyst is more than an effective amount of 0.1 mol per 1 mol of the imide compound.
Mol or less (e.g., 0.001 to 0.1 mol, preferably 0.005 to 0.08 mol, more preferably 0.0
(About 1 to 0.07 mol).

The imide compound represented by the formula (1), or the catalyst composed of the imide compound and the cocatalyst, may be a homogeneous system or a heterogeneous system.
Further, the catalyst may be a solid catalyst in which a catalyst component is supported on a carrier. As the carrier, a porous carrier such as activated carbon, zeolite, silica, silica-alumina and bentonite is often used. The supported amount of the catalyst component in the solid catalyst is 0.1 to 50 parts by weight, preferably 0.5 to 30 parts by weight, more preferably 0.5 to 30 parts by weight, based on 100 parts by weight of the carrier. It is about 1 to 20 parts by weight. The amount of the cocatalyst supported is 0.1 to 30 parts by weight, preferably 0.5 to 30 parts by weight, per 100 parts by weight of the carrier.
It is about 25 parts by weight, more preferably about 1 to 20 parts by weight.

[Oxygen] The oxygen used as the oxidizing agent may be pure oxygen, or may be diluted with an inert gas (eg, nitrogen, helium, argon, carbon dioxide, etc.) before use. Note that the oxygen source may be air. The amount of oxygen used can be selected according to the type of the substrate.
0.5 mol or more (for example, 1 mol or more), preferably 1 to 100 mol, more preferably 2 mol
About 50 mol. In many cases, an excess molar amount of oxygen relative to the substrate is used, and it is particularly advantageous to carry out the reaction under an atmosphere containing molecular oxygen such as air or oxygen.

[Oxidation reaction] The reaction temperature can be appropriately selected according to the oxidation method and the type of the substrate.
0 ° C., preferably 30 to 250 ° C., more preferably 5 ° C.
It is about 0 to 200 ° C, and usually reacts at about 70 to 150 ° C in many cases. The reaction can be carried out under normal pressure or under pressure.
1 to 100 atm (for example, 1.5 to 80 atm), preferably 2 to 70 atm, more preferably 5 to 50 atm
tm in many cases. The reaction time can be selected from the range of, for example, 30 minutes to 48 hours, preferably 1 to 36 hours, and more preferably 2 to 24 hours, depending on the reaction temperature and reaction pressure.

The reaction can be carried out by a conventional method such as a batch system, a semi-batch system, and a continuous system. In the method of the present invention, oxidation can be performed while suppressing the adhesion of sublimable polycyclic hydrocarbons to pipes and the like, so that troubles due to clogging hardly occur even in a continuous method. Therefore, the target compound can be produced with high production efficiency, which is extremely industrially advantageous. After the completion of the reaction, the reaction product is easily separated and purified by a conventional method, for example, separation means such as filtration, concentration, distillation, extraction, crystallization, recrystallization, column chromatography, or a combination thereof. it can.

The compound produced by the method of the present invention is
Optical fiber, optical element, optical lens, hologram,
It is suitably used as an optical material such as an optical disc and a contact lens, a transparent resin coating agent for organic glass, a conductive polymer, a photographic photosensitive material, a fluorescent material, and an intermediate material for various medicines and agricultural chemicals.

[0047]

According to the present invention, the oxidation of sublimable polycyclic hydrocarbons is carried out in a mixed solvent composed of specific components, so that the polycyclic hydrocarbons adhere to the inner wall of the reactor or pipe. Can be suppressed, and the reaction can proceed smoothly. In addition, a corresponding oxide can be generated at a high conversion rate from a sublimable polycyclic hydrocarbon. When a specific imide compound is used as an oxidation catalyst, polycyclic hydrocarbons can be oxidized under mild conditions. In addition, sublimable polycyclic hydrocarbons having a methylidyne group at the bridgehead can be oxidized under mild conditions, and the corresponding oxide having a hydroxyl group or oxo group introduced can be industrially efficiently produced.

[0048]

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 A mixed solvent 3 in which chlorobenzene and acetic acid were mixed in a glass reactor at a ratio of the former / the latter (weight ratio) = 50/50.
0 mL, and add 2.725 g of adamantane (2
0 mmol), N-hydroxyphthalimide 0.326
g (2 mmol) and vanadium oxide V ₂ O ₅ 0.01
8 g (0.1 mmol) was added and dissolved, and the mixture was stirred at 85 ° C. for 3 hours under an oxygen atmosphere. As a result of analyzing the reaction mixture by high performance liquid chromatography and gas chromatography, the conversion of adamantane was 87.9%, and 1-adamantanol (yield 46.4%), 1,3
-Adamantanediol (20% yield), 2-adamantanone (8% yield), and 1,3,5-adamantanetriol (1.4% yield) were produced. No solid deposit was found on the inner wall of the gas phase of the reactor.

Example 2 The former / the latter (weight ratio) = 80 with chlorobenzene and acetic acid
The same operation as in Example 1 was performed except that a mixed solvent mixed at a ratio of / 20 was used. As a result, the conversion of adamantane was 77.2%, and 1-adamantanol (yield 46.7%) and 1,3-adamantanediol (yield 1
2.9%) and 2-adamantanone (8.1% yield). No solid deposit was found on the inner wall of the gas phase of the reactor.

Comparative Example 1 The same operation as in Example 1 was performed except that acetic acid was used alone as a solvent. At the start of the reaction, the reaction system was heterogeneous. Further, shortly after the start of the reaction, a large amount of solid substance adhered to the inner wall of the gas phase of the reactor, and the system was closed, so the reaction was stopped.

Comparative Example 2 The same operation as in Example 1 was performed except that chlorobenzene was used alone as a solvent, and the conversion of adamantane was only 60%.

Example 3 A mixed solvent 5 in which chlorobenzene and acetic acid were mixed in a glass reactor at a ratio of the former / the latter (weight ratio) = 20/80.
00 mL, and add 13.6 g of adamantane
(0.1 mol), 1.6 g of N-hydroxyphthalimide
(0.01 mol) and 0.17 g (0.0005 mol) of vanadium acetylacetonate V (AA) ₃ were added and dissolved.
), And stirred at 75 ° C for 1 hour. As a result of analyzing the reaction mixture by high performance liquid chromatography and gas chromatography, the conversion of adamantane was 99%,
Mainly, 1-adamantanol, 1,3-adamantanediol and 2-adamantanone were formed. The solid substance was only slightly adhered to the inner wall of the gas phase of the reactor, and did not hinder the progress of the reaction.

Example 4 The former / latter (weight ratio) = 50 with chlorobenzene and acetic acid
The same operation as in Example 3 was performed except that a mixed solvent mixed at a ratio of / 50 was used. As a result, the conversion of adamantane was 95%, mainly 1-adamantanol, 1,
3-Adamantanediol and 2-adamantanone were produced. No solid deposit was found on the inner wall of the gas phase of the reactor.

Example 5 Benzonitrile and acetic acid were mixed in the former / the latter (weight ratio) = 50.
The same operation as in Example 3 was performed except that a mixed solvent mixed at a ratio of / 50 was used. As a result, the conversion of adamantane was 85%, mainly 1-adamantanol,
1,3-Adamantanediol and 2-adamantanone were produced. No solid deposit was found on the inner wall of the gas phase of the reactor.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁶ Identification code FI C07B 41/02 C07B 41/02 Z 41/06 41/06 Z 61/00 300 61/00 300

Claims (9)

[Claims] 1. A sublimable polycyclic hydrocarbon comprising (A) a non-sublimable aromatic compound and (B) at least one compound selected from an acidic compound and a non-aromatic nitrile. For oxidizing polycyclic hydrocarbons in a mixed solvent by oxygen oxidation. 2. The oxidation method according to claim 1, wherein the polycyclic hydrocarbon is a bridged cyclic hydrocarbon. 3. The oxidation method according to claim 1, wherein the aromatic compound (A) is a benzene derivative. 4. The method according to claim 1, wherein the compound (B) is an organic acid. 5. The oxidation method according to claim 4, wherein the organic acid is an aliphatic carboxylic acid having 1 to 4 carbon atoms. 6. An aromatic compound (A) in a mixed solvent
And the ratio of the compound (B) to the former / the latter (weight ratio) = 2
The oxidation method according to claim 1, wherein the ratio is from 5/75 to 95/5. 7. The following formula (1) (Wherein R ¹ and R ² are the same or different and each represent 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, an acyl group; R ¹
And R ² may combine with each other to form a double bond or an aromatic or non-aromatic ring. X represents an oxygen atom or a hydroxyl group, and n represents an integer of 1 to 3), and is oxidized in the presence of an oxidation catalyst composed of an imide compound represented by the following formula: 8. A sublimable polycyclic hydrocarbon having a methylidyne group at a bridgehead position or a junction position in the presence of an oxidation catalyst composed of the imide compound represented by the formula (1),
Contacting with oxygen in a mixed solvent composed of (A) a non-sublimable aromatic compound and (B) at least one compound selected from an acidic compound and a non-aromatic nitrile to form a bridgehead position or a junction position A method for producing a hydroxyl- or oxo-group-containing polycyclic compound, wherein a hydroxyl group is introduced into the compound, or an oxo group is introduced into a site adjacent to the bridgehead or junction position. 9. The hydroxyl group or oxo group-containing polysaccharide according to claim 8, wherein adamantane or a derivative thereof is brought into contact with oxygen in a mixed solvent composed of a benzene derivative and an organic acid to produce adamantanol or adamantanone. A method for producing a cyclic compound.