JP2000038360A - Production of alicyclic alcohols and their separation - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for efficiently separating monools and diols from a mixture comprising alicyclic monools and alicyclic diols. SOLUTION: This method for separating alicyclic alcohols comprises (l) (b) the first extraction process, wherein, a mixture comprising alicyclic monools and alicyclic diols is subjected to extraction operation using an aqueous solvent and an organic solvent, such as an aromatic organic solvent, so as to partition the alicyclic monools into the organic solvent layer and the alicyclic diols into the aqueous solvent layer and (c) the second extraction process, wherein, an organic solvent, such as an alcohol having a carbon number of >=4, is added to the aqueous solvent layer for extraction so as to partition the alicyclic diols into the organic solvent layer, or (2) (d) a crystallization process, wherein, the mixture is subjected to crystallization operation to crystallize the alicyclic monools and (e) an extraction process, wherein, an organic solvent such as an alcohol having a carbon number of >=4 is added to the remaining liquid after recovering the alicyclic monools for extraction so as to partition the alicyclic diols to the organic solvent layer.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a method for producing alicyclic alcohols such as adamantanols and the like which are useful as raw materials for highly functional materials and pharmaceutical and agricultural chemicals, and a method for separating the same.

[0002]

2. Description of the Related Art Although alicyclic compounds have a cyclic structure, their properties are similar to those of aliphatic compounds. Therefore, utilization of these structures and properties in various applications has been studied. I have. In particular, various polymers having enhanced functionality can be obtained by deriving an alicyclic alcohol having a hydroxyl group bonded to a ring into an acrylic acid derivative or a carbonate. Such polymers are used in optical materials such as optical fibers, optical elements, optical lenses, holograms, optical disks, and contact lenses, transparent resin coatings for organic glass, conductive polymers, photographic photosensitive materials, and fluorescent materials. Use is expected.

For example, polymers derived from adamantanols have a conventional property in terms of optical properties such as light-guiding loss, refractive index and birefringence, moisture resistance, heat resistance and thermal expansion coefficient. Have high levels that cannot be achieved with polymers. Amino derivatives derived from adamantanols are useful for deriving various pharmaceuticals and pesticides exhibiting high pharmacological activity, and are used, for example, as a therapeutic drug for Parkinson's disease "Symmetrel".

As a method for producing alicyclic alcohols, JP-A-9-327626 discloses a method of oxidizing alicyclic hydrocarbons such as adamantane with oxygen using an imide compound having a specific structure as a catalyst. ing. According to this method, the corresponding monool, diol, and polyols such as triol and tetraol can be obtained in good yield under mild conditions. However, the alicyclic alcohols such as the monool form and the diol form have similar chemical and physical properties, and also have similar properties to by-products such as ketone bodies and ketool forms which are by-produced in the reaction. Therefore, it is extremely difficult to efficiently separate them.

[0005]

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide a method for efficiently separating monools and / or diols from a mixture containing alicyclic monols and alicyclic diols. Is to provide. Another object of the present invention is to provide a method for efficiently producing a corresponding alicyclic alcohol from alicyclic hydrocarbons or alicyclic monools corresponding to the alicyclic hydrocarbons. It is in.

[0006]

Means for Solving the Problems As a result of intensive studies to achieve the above object, the present inventors have found that two extraction steps using a specific solvent or a crystallization step using a specific solvent. The present inventors have found that alicyclic monools and / or alicyclic diols can be efficiently separated by selecting a specific separation operation such as a combination of the above and an extraction step, and completed the present invention.

That is, the present invention relates to a method for separating a monool and a diol from a mixture containing the alicyclic monol and an alicyclic diol, wherein (b) the method comprises the step of: An extraction operation using an aqueous solvent containing water and at least one organic solvent selected from an aromatic organic solvent and an alcohol having 4 or more carbon atoms converts the alicyclic monools to an organic solvent layer. A first extraction step of distributing alicyclic diols to an aqueous solvent layer, and (c) adding at least one organic solvent selected from alcohols, esters and amines having 4 or more carbon atoms to the aqueous solvent layer. And extracting the alicyclic diols and distributing the alicyclic diols to an organic solvent layer.

The present invention also provides a method for separating alicyclic monools from a mixture containing alicyclic monools and alicyclic diols, wherein (f) separating the alicyclic monools Provided is a method for separating alicyclic monools, which comprises a distillation step of separating by distillation.

The present invention further relates to a method for separating alicyclic diols from a mixture containing an alicyclic monool and an alicyclic diol, and (g) using the mixture with an organic solvent. Provided is a method for separating alicyclic diols, which comprises a crystallization step of crystallizing alicyclic diols by performing a crystallization operation.

The present invention still further relates to a method for separating monools and diols from a mixture containing alicyclic monools and alicyclic diols, wherein (d) the mixture comprises: A crystallization step using an aqueous solvent containing at least water to crystallize alicyclic monols; and (e) a residual liquid having 4 carbon atoms in the residual liquid obtained by collecting the alicyclic monols. An extraction step of adding and extracting at least one organic solvent selected from the above alcohols and amines and distributing the alicyclic diols to an organic solvent layer, thereby providing a method for separating alicyclic alcohols.

[0011] The present invention also relates to (a) oxidizing at least one substrate selected from alicyclic hydrocarbons and alicyclic monools corresponding to the alicyclic hydrocarbons, An oxidation step of obtaining a mixture containing alicyclic monools and alicyclic diols, and (b) converting the mixture into an aqueous solvent containing at least water, an aromatic organic solvent and a carbon number of 4
An extraction operation using at least one organic solvent selected from the above alcohols is performed, and an alicyclic monool is distributed to an organic solvent layer, and an alicyclic diol is distributed to an aqueous solvent layer. An extraction step, and (c) extracting by adding at least one organic solvent selected from alcohols, esters and amines having 4 or more carbon atoms to the aqueous solvent layer, and distributing the alicyclic diols to the organic solvent layer. A method for producing alicyclic alcohols, comprising a second extraction step.

The present invention further comprises the step of oxidizing (a) at least one substrate selected from alicyclic hydrocarbons and alicyclic monools corresponding to the alicyclic hydrocarbons, (A) an oxidation step of obtaining a mixture containing alicyclic monools and alicyclic diols, and (f) a distillation step of separating alicyclic monools from the mixture by distillation. A manufacturing method is provided.

The present invention further provides (a) oxidizing at least one substrate selected from alicyclic hydrocarbons and alicyclic monools corresponding to the alicyclic hydrocarbons, An oxidation step of obtaining a mixture containing the corresponding alicyclic monol and alicyclic diol, and (g) crystallizing the alicyclic diol by subjecting the mixture to a crystallization operation using an organic solvent. A method for producing alicyclic alcohols, comprising a crystallization step.

[0014] The present invention also relates to (a) oxidizing at least one substrate selected from alicyclic hydrocarbons and alicyclic monools corresponding to the alicyclic hydrocarbons, (D) subjecting the mixture to an crystallization operation using an aqueous solvent containing at least water to obtain a mixture containing an alicyclic monol and an alicyclic diol. (E) adding at least one organic solvent selected from alcohols and amines having 4 or more carbon atoms to the residual liquid obtained by collecting the alicyclic monools, and extracting the residue. And an extraction step of distributing the alicyclic diols to an organic solvent layer.

[0015]

DESCRIPTION OF THE PREFERRED EMBODIMENTS [Oxidation step (a)] In the oxidation step (a), at least one selected from alicyclic hydrocarbons and alicyclic monols corresponding to the alicyclic hydrocarbons is used. Oxidation of the species substrate provides a mixture comprising the corresponding cycloaliphatic monol and cycloaliphatic diol.

The alicyclic hydrocarbon as the substrate may be any compound having a non-aromatic carbon ring, and the alicyclic hydrocarbon may be an alicyclic hydrocarbon and an alicyclic hydrocarbon having a substituent. Hydrocarbons. Examples of the substituent include various substituents, for example, a halogen atom (fluorine, chlorine, bromine, or iodine atom), an oxo group, a substituted oxy group (for example, a C _1-4 alkoxy group, an aryloxy group, an acyloxy group, and the like) ), Carboxyl group, substituted oxycarbonyl group (for example, C _1-4 alkoxy-carbonyl group and the like),
Substituted or unsubstituted carbamoyl group, cyano group, nitro group,
A substituted or unsubstituted amino group or an alkyl group (for example, C _1-4
Examples thereof include an alkyl group, a cycloalkyl group, an aryl group (for example, a phenyl and naphthyl group), a heterocyclic group and the like. The substituent also includes an aromatic or non-aromatic ring fused to a non-aromatic carbon ring.

The alicyclic hydrocarbons can be classified into monocyclic hydrocarbons having a monocyclic carbon ring and polycyclic hydrocarbons having a polycyclic carbon ring. As monocyclic hydrocarbons, for example,
C3-C20 such as cyclohexane, cyclooctane, cyclodecane, cyclododecane, and cyclopentadecane
Degree of cycloalkanes; cycloalkenes having about 3 to 20 carbon atoms such as cyclohexene, cyclooctene and cyclodecene;

The polycyclic hydrocarbons include (i) condensed ring hydrocarbons in which an aromatic carbon ring is condensed with a non-aromatic carbon ring;
i) Bridged cyclic hydrocarbons having about 2 to 4 rings are included.
Examples of the condensed ring hydrocarbons include indane, tetralin, fluorene, acenaphthene, and the like. Examples of the crosslinked cyclic hydrocarbons include, for example, decalin, bicyclo [2.2.0] hexane, bicyclo [2.2.2] octane, and bicyclo [3.2.1].
Octane, bicyclo [4.3.2] undecane, tuzeon, karan, pinan, pinene, bornane, bornylene,
Norbornane, norbornene, camphor, camphoric acid, camphene, tricyclene, tricyclo [4.3.
1.1 ^2,5 ] undecane, tricyclo [5.2.1.0
^3,8 ] decane, exotricyclo [5.2.1.0 ^2,6 ]
Decane, endotricyclo [5.2.1.0 ^2,6 ] decane, endotricyclo [5.2.2.0 ^2,6 ] undecane, adamantane, 1-chloroadamantane, 1-methyladamantane, 1, 3-dimethyladamantane, 1-
Methoxy adamantane, 1-carboxy adamantane,
1-methoxycarbonyladamantane, 1-nitroadamantane, tetracyclo [4.4.0.1 ^2,5 .
[ ^1,7,10 ] dodecane, perhydroacenaphthene, perhydroanthracene, perhydrofluorene, perhydrophenanthrene, perhydrophenalene, perhydroindene and the like.

The alicyclic monools as substrates corresponding to the alicyclic hydrocarbons include compounds having one hydroxyl group bonded to a non-aromatic carbon ring constituting the alicyclic hydrocarbons. The binding position is not particularly limited.

As a method for oxidizing the substrate, a method using chromic acid (see Japanese Patent Publication No. Sho 42-16621) and a method of oxidizing with oxygen in the presence of a cobalt salt catalyst (see Japanese Patent Publication No. Sho 4-16).
A method of oxidizing with oxygen in the presence of a specific imide compound (see JP-A-9-32762).
Any known or well-known oxidation method may be applied, but a method using the imide compound is preferable from the viewpoint of operability, economy, yield, and the like.

More specifically, the substrate is represented by the following formula (1)

Embedded image (Wherein R ¹ and R ² are the same or different and each represents a hydrogen atom,
A halogen atom, an alkyl group, an aryl group, a cycloalkyl group, a hydroxyl group, an alkoxy group, a carboxyl group, an alkoxycarbonyl group, or an acyl group; R ¹ and R ² are bonded to each other to form a double bond, or an aromatic or A non-aromatic ring may be formed. X represents an oxygen atom or a hydroxyl group. R ¹ , R ² , or R ¹ and R ²
Are bonded to each other to form a double bond or an aromatic or non-aromatic ring represented by the above formula (1).
(Substituted cyclic imide group may be further bonded to one or two).) Oxidation with oxygen in the presence of an imide compound represented by the formula (1) is preferable.

In the above formula (1), the substituents R ¹ and R ²
Among them, the halogen atom includes iodine, bromine, chlorine and fluorine atoms. Examples of the alkyl group include, for example, a C _1-10 alkyl group such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, s-butyl, t-butyl, pentyl, and hexyl, preferably a C _1-6 alkyl group, particularly A C _1-4 alkyl group. 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.

Examples of the alkoxy group include a C _1-10 alkoxy group such as methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, t-butoxy, pentyloxy and hexyloxy, preferably a C _1-6 alkoxy group. And especially C _1-4 alkoxy groups. The alkoxycarbonyl group includes, for example, a methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, isopropoxycarbonyl, butoxycarbonyl, isobutoxycarbonyl, t-butoxycarbonyl, pentyloxycarbonyl, hexyloxycarbonyl, etc.
Included are _1-10 alkoxy-carbonyl groups, preferably C _1-6 alkoxy-carbonyl groups, especially C _1-4 alkoxy-carbonyl groups. Examples of the acyl group include, for example, C, such as formyl, acetyl, propionyl, butyryl, isobutyryl, valeryl, isovaleryl, and bivaloyl groups.
An example is a _1-6 acyl group.

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 have about 5 to 12 membered rings, especially about 6 to 10 membered rings, and may be heterocycles or fused heterocycles, but are often carbon rings. Such a ring includes, for example, a non-aromatic carbon ring (a cycloalkane ring which may have a substituent such as a cyclohexane ring, a cycloalkene ring which may have a substituent such as a cyclohexene ring, and the like) ), A non-aromatic bridged ring (eg, a bridged carbon ring optionally having a substituent such as a 5-norbornene ring), a benzene ring, an aromatic optionally having a substituent such as a naphthalene ring Including aromatic rings. The ring is often composed of an aromatic ring. The ring is an alkyl group, a haloalkyl group,
Hydroxyl group, alkoxy group, carboxyl group, alkoxycarbonyl group, acyl group, nitro group, cyano group,
It may have a substituent such as an amino group or a halogen atom. In the formula (1), X represents an oxygen atom or a hydroxyl group, and the bond between the nitrogen atom N and X is a single bond or a double bond.

R ¹ , R ² , or a double bond or an aromatic or non-aromatic ring formed by bonding R ¹ and R ² to each other are represented by the above formula (1). One or two N-substituted cyclic imide groups may be further bonded. For example, when R ¹ or R ² is an alkyl group having 2 or more carbon atoms, the N-substituted cyclic imide group may be formed to include two adjacent carbon atoms constituting the alkyl group. When R ¹ and R ² are bonded to each other to form a double bond, the N-substituted cyclic imide group may be formed to include the double bond. Further, when R ¹ and R ² are bonded to each other to form an aromatic or non-aromatic ring, the N-substituted cyclic imide group is formed to include two adjacent carbon atoms constituting the ring. It may be.

Preferred imide compounds include those represented by the following formula:

Embedded image (Wherein, R ^{3 to} R ⁶ are the same or different and each represents a hydrogen atom, an alkyl group, a haloalkyl group, a hydroxyl group, an alkoxy group, a carboxyl group, an alkoxycarbonyl group, an acyl group, a nitro group, a cyano group, an amino group, R ^{3 to} R ⁶ may be mutually adjacent groups to form an aromatic or non-aromatic ring, and in formula (1f), A represents a methylene group or Represents an oxygen atom, R ¹ ,
R ² is the same as above. The benzene ring of the formula (1c) has the formula (1
c) One or two N-substituted cyclic imide groups shown in the above may be further bonded.) In the substituents R ^{3 to} R ⁶ , an alkyl group, an alkoxy group,
Examples of the alkoxycarbonyl group, the acyl group, and the halogen atom include the substituents or atoms exemplified in the above-described R ¹ and R ² . Examples of the haloalkyl group include a C _1-4 haloalkyl group such as a trifluoromethyl group. The substituents R ^{3 to} R ⁶ are usually a hydrogen atom,
It is often about 4 to about 4 alkyl groups, carboxyl groups, nitro groups, and halogen atoms. The ring formed by combining R ^{3 to} R ⁶ with each other is the same as the ring formed by combining R ¹ and R ² with each other, and in particular, an aromatic or non-aromatic 5- to 12-membered ring Is preferred.

The imide compound is prepared by a conventional imidization reaction, for example, by reacting the corresponding acid anhydride with hydroxylamine N
It can be prepared by a method of reacting with H ₂ OH and imidizing via ring opening and ring closing of an acid anhydride group.

Preferred imide compounds include, for example,
An imide compound derived from an aliphatic polycarboxylic anhydride (for example, 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.). These imide compounds have high oxidation catalytic activity. Particularly preferred imide compounds include alicyclic polycarboxylic anhydrides or aromatic polycarboxylic anhydrides,
Among them, N derived from aromatic polycarboxylic anhydrides
-Hydroxyimide compounds such as N-hydroxyphthalimide.

The imide compound represented by the formula (1) can be used alone or in combination of two or more in the oxidation reaction.

The oxidation catalyst may be composed of an imide compound represented by the formula (1) and a co-catalyst. Co-catalysts include transfer metal compounds (eg, oxides, organic acid salts, inorganic acid salts, halides, complexes, and heteropoly acids or salts thereof),
Boron compounds, quaternary ammonium salts and the like are included.
As the transition metal element in the transition metal compound, for example, an element belonging to Groups 3 to 11 of the periodic table, in particular, Ce, V, Nb,
Cr, Mo, W, Mn, Fe, Ru, Co, Rh, N
i, Cu and the like. The cocatalysts can be used alone or in combination of two or more.

The amount of the imide compound represented by the above formula (1) can be selected in a wide range, for example, 0.0001 to 1 mol, preferably 0.001 to 1 mol, per mol of the substrate.
It is about 0.5 mol, more preferably about 0.01 to 0.3 mol. The amount of the co-catalyst to be used can be appropriately selected within a range that does not reduce the reactivity and the selectivity. For example, the amount is 0.0001 to 0.7 mol, preferably 0.0001 to 0.5 mol per 1 mol of the substrate. Mole, more preferably 0.00
It is about 01 to 0.3 mol, and often about 0.0005 to 0.1 mol.

The oxygen used for the oxidation reaction using the imide compound represented by the formula (1) may be active oxygen, but it is advantageous to use molecular oxygen. The molecular oxygen is not particularly limited, and pure oxygen may be used, or oxygen diluted with an inert gas such as nitrogen, helium, argon, or carbon dioxide may be used. It is preferable to use air from the viewpoint of economic efficiency as well as operability and safety.

The amount of oxygen to be used is, for example, 0.5 mol or more (for example, 1 mol / mol of substrate) depending on the type of the substrate.
Mol or more), preferably 1 to 100 mol, more preferably about 2 to 50 mol.

The oxidation reaction is usually performed in a solvent inert to the reaction. Examples of the solvent include organic acids such as acetic acid and propionic acid; nitriles such as acetonitrile, propionitrile and benzonitrile; amides such as formamide and N, N-dimethylformamide;
Alcohols such as butanol, t-amyl alcohol;
Aliphatic hydrocarbons such as hexane and octane; benzene,
Aromatic hydrocarbons such as toluene; halogenated hydrocarbons such as chloroform, dichloromethane, dichloroethane, fluorobenzene, chlorobenzene, bromobenzene, and trifluoromethylbenzene; nitro compounds such as nitromethane and nitrobenzene; methyl acetate, ethyl acetate;
Esters such as methyl benzoate and ethyl benzoate; ethers such as diethyl ether and diisopropyl ether; and mixed solvents thereof. As the solvent, an organic acid, a nitrile, a halogenated hydrocarbon, or the like is often used.

The reaction temperature can be appropriately selected according to the type of the imide compound and the substrate, and is, for example, 0 to 300.
° C, preferably 30 to 250 ° C, more preferably 40 ° C.
To about 150 ° C., and usually reacts at about 60 to 120 ° C. in many cases. The reaction can be carried out under normal pressure or under pressure.
１００100 atm (for example, 1.5 to 80 atm), preferably 2 to 70 atm, more preferably 5 to 50 atm
m. The reaction time can be appropriately selected depending on the reaction temperature and pressure, for example, from a range of 30 minutes to 48 hours, preferably 1 to 36 hours, more preferably 2 to 24 hours. The reaction can be carried out by a conventional method such as a batch system, a semi-batch system, or a continuous system in the presence of molecular oxygen or in the flow of molecular oxygen.

When the alicyclic hydrocarbons and the corresponding alicyclic monols are oxidized with oxygen using the oxidation catalyst, the corresponding alicyclic monols and alicyclic diols are mainly produced. Depending on the reaction conditions, alicyclic polyols such as alicyclic triols, and cyclic ketones and cyclic ketools in which the methylene group constituting the ring is oxidized are by-produced. Therefore, by the above oxidation reaction, alicyclic monools, alicyclic diols and catalysts, and, depending on conditions, alicyclic polyols, cyclic ketones, cyclic ketools, unreacted alicyclic hydrocarbons And the like.

In the above-mentioned oxidation reaction, a compound having a methine carbon atom [for example, a bridge having a methine group at a bridgehead position (or a junction position)] is used as an alicyclic hydrocarbon or alicyclic monol as a substrate. , Alicyclic monools and / or diols in which a hydroxyl group is introduced into the methine carbon atom are mainly produced. .

For example, oxidation with adamantane and / or 1-adamantanol as a substrate gives 1-adamantanol, 1,3-adamantanediol and, depending on the conditions, 1,3,5-adamantanetriol, 1,3,3
A mixture containing 5,7-adamantantetraol, 2-adamantanone, unreacted adamantane and the like is obtained.
Oxidation using 1,3-dimethyladamantane and / or 1,3-dimethyl-5-adamantanol as a substrate,
1,3-dimethyl-5-adamantanol, 1,3-dimethyl-5,7-adamantanediol and, depending on conditions, 1,3-dimethyladamantanone, 1,3-dimethyl-5-hydroxyadamantanone, unreacted A mixture containing 1,3-dimethyladamantane and the like is obtained. Also, endotricyclo [5.2.1.0 ^2,6 ] decane and / or 2-hydroxyendotricyclo [5.2.
Oxidation of 1.0 ^2,6 ] decane mainly yields ² -hydroxyendotricyclo [5.2.1.0 ^2,6 ] decane and 2,6-dihydroxyendotricyclo [5.2.
1.0 ^2,6 ] decane is produced. Furthermore, when oxidizing decalin and / or 4a-hydroxydecalin, 4a
-Hydroxydecalin, 4a, 8a-dihydroxydecalin and the like are produced. When norbornane and / or 1-hydroxynorbornane is used as a substrate, 1-hydroxynorbornane and / or 1,4-dihydroxynorbornane and the like are generated.

When cyclic ketones are by-produced in the oxidation reaction, the cyclic ketones may be alicyclic hydrocarbons before the first extraction step (b) or crystallization step (d) described below. Alternatively, a reduction step for reducing to alicyclic monools may be provided. Examples of the reduction method include a catalytic reduction method using hydrogen, a metal, a metal hydride, a metal hydride complex compound, borane,
A reduction method using a reducing agent such as hydrazine is exemplified.

[First Extraction Step (b)] In the first extraction step (b), a mixture containing an alicyclic monol and an alicyclic diol is mixed with an aqueous solvent containing at least water and an aromatic solvent. An extraction operation using an organic solvent and at least one organic solvent selected from alcohols having 4 or more carbon atoms is performed, and alicyclic monools are used as an organic solvent layer, and alicyclic diols are used as an aqueous solvent layer. Respectively.

The mixture containing the alicyclic monools and the alicyclic diols to be subjected to the extraction operation is not limited to the reaction product obtained in the oxidation step, but may also be used to hydrolyze the corresponding halide or ester. The reaction product obtained by the above may be used. When the reaction mixture obtained by the oxidation reaction or the like is subjected to the extraction operation, pretreatment such as distillation of the reaction solvent may be performed in advance.

The aqueous solvent includes an aqueous solvent containing water as a main component. Such aqueous solvents include water alone or water and a water-soluble organic solvent (for example, aliphatic monohydric alcohols having 1 to 3 carbon atoms such as methanol, ethanol and isopropanol; alicyclic monohydric alcohols such as cyclohexanol) Polyhydric alcohols such as ethylene glycol, propylene glycol and glycerin; carboxylic acids such as formic acid, acetic acid, propionic acid, hexanoic acid and decanoic acid;
Ketones such as acetone and cyclohexanone; aliphatic nitriles such as acetonitrile and propionitrile; glycol ethers such as ethylene glycol dimethyl ether; cyclic ethers such as tetrahydrofuran and dioxane; aprotic such as N, N-dimethylformamide, dimethylsulfoxide and pyridine Polar solvents). The concentration of water in the aqueous solvent is, for example, 75 to 100% by weight, preferably 90 to 100% by weight,
More preferably, it is about 95 to 100% by weight. Water is particularly preferred as the aqueous solvent.

Examples of the aromatic organic solvent include solvents which can be separated from the aqueous solvent, for example, aromatic carboxylic acid esters (eg, methyl benzoate, ethyl benzoate, butyl benzoate, dimethyl phthalate, phthalate) diethyl, such as C _7-8 aryl mono- or dicarboxylic acids -C _1-6 alkyl esters, such as dibutyl phthalate), aliphatic carboxylic acid aryl esters (e.g., phenyl acetate, C _1-6 aliphatic, phenyl propionic acid Carboxylic acid phenyl ester, etc.), aliphatic carboxylic acid aralkyl ester (for example, C _1-6 aliphatic carboxylic acid-C such as benzyl acetate, etc.)
Aromatic esters such as _7-9 aralkyl esters);
Aryl halides (eg, halobenzenes such as fluorobenzene, chlorobenzene, bromobenzene, dichlorobenzene, dibromobenzene, etc.); haloalkyl-substituted benzenes (eg, trifluoromethylbenzene, etc.); aromatic nitriles (eg, benzonitrile, etc.); Aromatic ketones (such as acetophenone);
Aromatic ethers (for example, benzyl ether and the like) are included. Among these, aromatic esters such as aromatic carboxylic acid esters (such as benzoic acid esters) and aryl halides are preferable.

Alcohols having 4 or more carbon atoms include butanol, isobutyl alcohol, s-butyl alcohol, pentanol, isopentyl alcohol, hexanol,
Isohexyl alcohol, 3,3-dimethylbutanol, heptanol, isoheptyl alcohol, octanol, isooctyl alcohol, 2-ethylhexanol, decanol, dodecanol, cyclopentanol,
Examples thereof include aliphatic or alicyclic alcohols having about 4 to 14 carbon atoms such as cyclohexanol and methylcyclohexanol; and aromatic alcohols having about 7 to 10 carbon atoms such as benzyl alcohol and 2-phenethyl alcohol.
Among them, C6 to C12 (particularly C6 to C12) can suppress the transfer of the alicyclic monol to the aqueous layer.
About 8) aliphatic or cycloaliphatic alcohols are preferred.

The amount of each extraction solvent depends on the type and amount of the extract,
The ratio can be appropriately selected in consideration of the ratio of the alicyclic monol to the alicyclic diol. For example, the amount of the aqueous solvent is 0.1 to 10 with respect to 1 part by weight of the alicyclic diol.
0 parts by weight, preferably about 5 to 50 parts by weight. The amount of the aqueous solvent is, for example, 0.05 to 10 parts by weight, preferably 0 to 10 parts by weight, based on 1 part by weight of at least one organic solvent selected from an aromatic organic solvent and an alcohol having 4 or more carbon atoms. About 1 to 1 part by weight.

The extraction operation can be performed in a conventional manner,
Any of a batch system, a semi-batch system, and a continuous system may be used. The extraction operation may be repeated a plurality of times (for example, about 2 to 10 times). The extraction temperature can be appropriately selected in consideration of operability, solubility, and the like.
The temperature is 50 ° C, more preferably about 10 to 35 ° C. In addition, 1,3-dimethyl-5-adamantanol and 1,3
The extraction temperature when separating -dimethyl-5,7-adamantanediol is often about 25 to 45 ° C.

The alicyclic monools distributed to the organic solvent layer by the above extraction are separated by a conventional separation means such as concentration,
It can be separated and purified by crystallization, extraction, recrystallization, column chromatography, or a combination thereof.
For example, alicyclic monools can be separated and purified by a distillation step (f) described below.

The alicyclic monol may be used as it is in the organic solvent layer obtained in the first extraction step (b) or, if necessary, by diluting, concentrating, dehydrating, or exchanging the solvent. Or isolated as crystals by distillation, crystallization, etc., and then recycled to the reaction system (for example, the oxidation step (a)).

[Second extraction step (c)] In the second extraction step (c), (i) an alcohol having 4 or more carbon atoms is added to the aqueous solvent layer obtained in the first extraction step (b). ) At least one organic solvent selected from esters and (iii) amines is added and extracted, and the alicyclic diols are distributed to the organic solvent layer. Depending on the type of alicyclic diol, the alicyclic diol can be crystallized by cooling or concentrating the aqueous solvent layer obtained in the first extraction step (b).

The alcohol having 4 or more carbon atoms includes
Those exemplified as the alcohol having 4 or more carbon atoms in the first extraction step can be used. Among them, aliphatic or alicyclic alcohols having about 4 to 10 carbon atoms, such as butanol, hexanol, and 2-ethylhexanol, in order to suppress the transfer of polyols such as alicyclic triol to the organic solvent layer; benzyl alcohol 7 to 12 carbon atoms such as
A degree of aromatic alcohol is preferred.

The above-mentioned ester comprises the above-mentioned aqueous solvent layer.
Esters that can be separated into aqueous solvents
Aliphatic carboxylic acid esters (eg, methyl acetate,
Chill, propyl acetate, isopropyl acetate, butyl acetate,
Isobutyl acetate, s-butyl acetate, t-butyl acetate, vinegar
Hexyl acid, 2-ethylhexyl acetate, propionate
Chill, ethyl propionate, isobutyl propionate,
Hexyl propionate, methyl butyrate, ethyl pentanoate
, Ethyl hexanoate, ethyl decanoate, etc. _2-10Fat
Aliphatic carboxylic acid-C_1-10Alkyl esters, especially C_2-3
Aliphatic carboxylic acid-C_1-4Alkyl ester;
And aliphatic carboxylic acids such as phenyl and phenyl propionate.
Reel ester, etc.), aromatic carboxylic acid ester (example)
For example, methyl benzoate, ethyl benzoate, phthalic acid
Chill, diethyl phthalate, diethyl phthalate, phthalic acid
C such as dibutyl_7-8Aryl mono- or dicarboxylic acid-
C_1-6Alkyl esters, etc.). these
Of these, aliphatic carboxylic acid esters such as ethyl acetate
preferable.

Examples of the amine include amines which can be separated from the aqueous solvent constituting the aqueous solvent layer, for example, aliphatic amines such as triethylamine, tripropylamine and hexylamine; N, N-dimethylcyclohexylamine and the like. Alicyclic amines; aromatic amines such as aniline, N-methylaniline, N, N-dimethylaniline and toluidine; and cyclic amines such as N-ethylpiperidine.

The amount of the organic solvent to be used can be appropriately selected in consideration of the amount of the aqueous solvent layer, the type and amount of the alicyclic diol contained in the aqueous solvent layer, and the like. For example, the amount of the organic solvent used is, for example, about 0.05 to 10 parts by weight, and preferably about 0.1 to 1 part by weight, based on 1 part by weight of the aqueous solvent layer.

The extraction operation can be performed by a conventional method,
Any of a batch system, a semi-batch system, and a continuous system may be used. The extraction operation may be repeated a plurality of times (for example, about 2 to 10 times). The extraction temperature is, for example, 0 to 100.
° C, preferably 5 to 50 ° C, more preferably 10 to 3 ° C.
It is about 5 ° C.

The alicyclic diols distributed to the organic solvent layer by the above extraction may be separated and purified by conventional separation means, for example, concentration, crystallization, extraction, recrystallization, column chromatography, or a combination thereof. Can be. For example, alicyclic diols can be separated and purified by the crystallization step (g) described below.

The alicyclic polyols such as alicyclic triols can be separated from the aqueous solvent layer obtained by the above extraction, if necessary, by the conventional separation means.

[Crystallization Step (d)] In the crystallization step (d),
The mixture containing the alicyclic monol and the alicyclic diol is subjected to a crystallization operation using an aqueous solvent containing at least water to crystallize the alicyclic monol.

The mixture containing an alicyclic monool and an alicyclic diol to be subjected to the crystallization operation is not limited to the reaction product obtained in the oxidation step, but may be a mixture of a corresponding halide or ester. It may be a reaction product obtained by decomposition. When the reaction mixture obtained by the oxidation reaction or the like is subjected to the crystallization operation, a pretreatment such as distillation of the reaction solvent may be performed in advance.

As the aqueous solvent, water alone or a mixed solvent of water and a water-soluble organic solvent can be used.
Examples of the water-soluble organic solvent include the solvents exemplified as the water-soluble organic solvent in the first extraction step (a). These organic solvents can be used alone or in combination of two or more. Preferred water-soluble organic solvents include carboxylic acids having about 1 to 10 carbon atoms (particularly, about 2 to 5 carbon atoms),
Acetone, acetonitrile, aliphatic monohydric alcohols having 1 to 3 carbon atoms, cyclic ethers and the like are included. When a water-soluble solvent (for example, a carboxylic acid such as acetic acid) is used as a reaction solvent in the reaction step such as the oxidation step (a), after the reaction is completed, the reaction mixture is concentrated to an appropriate degree, The alicyclic monools can be crystallized by a simple operation of adding

In a preferred aqueous solvent, the ratio (weight ratio) between the water-soluble organic solvent and water is the former / the latter = 0 / 100-5.
0/50, especially 0/100 to 40/60, especially 5 /
It is about 950-30 / 70.

The crystallization operation can be performed by a conventional method, for example, by cooling or concentrating a mixture containing an alicyclic monol and an alicyclic diol in the aqueous solvent. it can.

In this crystallization operation, the temperature at which the mixture containing the alicyclic monol and the alicyclic diol is dissolved is, for example, 10 to 180 ° C., preferably 10 to 180 ° C.
0 ° C, more preferably about 15 to 60 ° C. If the dissolution temperature is too high, the alicyclic diols are liable to deteriorate, and if the dissolution temperature is too low, the solubility is reduced and the crystallization efficiency is reduced. When a mixed solvent of a water-soluble organic solvent (eg, carboxylic acid) and water is used as the aqueous solvent, a solution of the mixed solvent containing a mixture of alicyclic monools and alicyclic diols is cooled. Alternatively, alicyclic monools may be precipitated by concentration, and water is added to a solution of the water-soluble organic solvent (or the mixed solvent) containing the mixture and heated as necessary. By doing so, alicyclic monools may be precipitated.

The precipitated alicyclic monol can be separated and recovered by a conventional separation method, for example, a method such as filtration or centrifugation. These alicyclic monols can be further refined by recrystallization. The alicyclic monol can be recycled to the reaction step (for example, the oxidation step (a)).

[Extraction Step (e)] In the extraction step (e),
The residual liquid containing alicyclic diols after collecting the alicyclic monools precipitated in the crystallization step (d),
(I) adding at least one organic solvent selected from an alcohol having 4 or more carbon atoms and (ii) an amine and extracting the mixture;
Partition the alicyclic diols into the organic solvent layer.

As the alcohol or amine having 4 or more carbon atoms, the same alcohols and amines as those exemplified in the second extraction step (c) can be used. The extraction operation and method, the method for separating and recovering alicyclic diols, and the like can also be performed according to the second extraction step (c).

In the present invention, by combining the first extraction step (b) and the second extraction step (c) or the crystallization step (d) and the extraction step (e), alicyclic monools can be The alicyclic diols can be efficiently separated from the alicyclic diols, and the separated alicyclic monools can be recycled to the reaction system as needed. It can be obtained easily.

[Distillation Step (f)] In the distillation step (f),
A mixture containing at least an alicyclic monol is subjected to distillation to distill an alicyclic monol.

The mixture containing alicyclic monools to be subjected to the distillation step (f) includes the reaction product obtained in the reaction step such as the oxidation step and the organic solvent obtained in the first extraction step (b). And the like.

The distillation method is not particularly limited, and a conventional method can be employed. For example, any of a tray column and a packed column may be used, and either continuous distillation or batch distillation may be used. The pressure and temperature during distillation are appropriately selected depending on the type of alicyclic monol. In the distillation, a suitable solvent (for example, an organic solvent for extraction used in the first extraction step (b); an azeotropic solvent for the alicyclic monool, etc.) is used in order to increase the recovery rate of the alicyclic monol. It may be carried out by continuously or intermittently adding to the concentrated residue (bottom liquid).

The alicyclic monools distilled off by distillation can be further purified, if necessary. For example, cooling a fraction containing an alicyclic monol obtained by distillation, or crystallizing the alicyclic monol by adding an appropriate organic solvent to the fraction, filtering and drying. Thereby, a high-purity alicyclic monol can be obtained. As the organic solvent, for example, hydrocarbons such as aliphatic hydrocarbons (particularly, aliphatic hydrocarbons of about _C7-10 ) such as pentane, hexane, heptane, octane, nonane, decane, and dodecane are used. Further, a solvent higher than the melting point of the alicyclic monol is preferable as the organic solvent. By such a crystallization operation, cyclic ketones (for example, 1,3-dimethyladamantanone, etc.) by-produced in the reaction can be efficiently removed.

In the case where the fraction containing the alicyclic monools is cooled and crystallized and filtered, for example, pentane is used in order to efficiently remove the high-boiling solvent remaining in the wet crystals. It is preferable to carry out a rinsing treatment with a low-boiling organic solvent such as an aliphatic hydrocarbon such as hexane, heptane and the like (especially an aliphatic hydrocarbon of about C _5-7 ). When the alicyclic monol has sublimability (for example, 1,3
-Dimethyl-5-adamantanol, etc.) and drying to reduce loss due to sublimation, for example, at a temperature of 10-6.
About 5 ° C (preferably 15 to 62 ° C), pressure 15 Torr
It is preferable to carry out the reaction at about r to atmospheric pressure (preferably 18 Torr to atmospheric pressure).

In the distillation step (f), the ratio of alicyclic monools to alicyclic diols is the former / latter> 50/50
(Especially the former / the latter> 65/35)
It is particularly useful as a method for separating alicyclic monols. The ratio of alicyclic monools and alicyclic diols in the reaction product is determined by appropriately selecting the reaction time, reaction temperature, amount of catalyst, amount of oxygen supply, reaction pressure, type and amount of cocatalyst, and the like. Can be adjusted.

[Crystallization Step (g)] In the crystallization step (g),
A mixture containing at least an alicyclic diol is subjected to a crystallization operation using an organic solvent to crystallize the alicyclic diol.

The mixture containing the alicyclic diols to be subjected to the crystallization operation includes a reaction product obtained in a reaction step such as the oxidation step, an organic solvent layer obtained in the second extraction step (c), and the like. Is mentioned.

For crystallization, it is preferable to use at least one organic solvent selected from the aromatic organic solvents exemplified as the extraction solvent in the first extraction step (b) and alcohols having 4 or more carbon atoms. Among these organic solvents, aromatic esters such as aromatic carboxylic acid esters (such as benzoic acid esters), aryl halides, and aliphatic or alicyclic alcohols having about 4 to 12 (particularly 6 to 8) carbon atoms. Is particularly preferred.

The crystallization operation can be performed by a conventional method, for example, by cooling or concentrating a mixture containing an alicyclic diol in the organic solvent. Further, the alicyclic diols can be crystallized by concentrating the mixed solution to an appropriate amount as needed and then adding an appropriate solvent. In the crystallization operation, the temperature at which the mixture containing the alicyclic diol is dissolved in the organic solvent can be appropriately selected within a range where the alicyclic diol is not deteriorated. The temperature is, for example, about 10 to 180 ° C.

The precipitated alicyclic diols can be separated and recovered by a conventional separation method, for example, filtration, centrifugation, rinsing, drying and, if necessary, recrystallization. As the solvent used for the rinsing, for example, a chain ether such as methyl-t-butyl ether, an ester such as t-butyl acetate, an aromatic hydrocarbon such as toluene,
Aliphatic hydrocarbons such as hexane and octane, alicyclic hydrocarbons such as cyclohexane, halogenated hydrocarbons such as dichloroethane, and mixtures thereof, or a mixture of these solvents with the aromatic organic solvent and an alcohol having 4 or more carbon atoms At least one organic solvent selected from the group consisting of an aromatic ester such as an aromatic carboxylic acid ester (such as a benzoic acid ester), an aryl halide, and a fat having about 4 to 12 (particularly 6 to 8) carbon atoms. And alicyclic alcohols]. When the alicyclic monool corresponding to the alicyclic diol has sublimability (for example, 1,3-dimethyl-5-adamantanol or the like), the alicyclic monool is efficiently removed. The drying after crystallization is preferably performed, for example, under the conditions of a temperature of 60 ° C. or more (for example, about 60 to 80 ° C.) and a pressure of 20 Torr or less (for example, about 5 to 20 Torr).

When the filtrate obtained in the crystallization step (g) contains an alicyclic monol, the filtrate is subjected to an appropriate treatment (separation / purification treatment, etc.) if necessary, It can be recycled to the reaction step (for example, the oxidation step (a)).

In the crystallization step (g), the ratio of the alicyclic monol to the alicyclic diol is the former / the latter <60/40 (particularly, the former / the latter <45/55). It is particularly useful as a method for separating cyclic diols.

[0080]

According to the separation method of the present invention, a specific separation operation such as two extraction steps using a specific solvent or a combination of a crystallization step and an extraction step using a specific solvent is employed. Therefore, the monools and / or diols can be efficiently separated from the mixture containing the alicyclic monools and the alicyclic diols. Further, according to the production method of the present invention, a corresponding alicyclic alcohol can be efficiently produced from an alicyclic hydrocarbon or an alicyclic monool corresponding to the alicyclic hydrocarbon.

[0081]

EXAMPLES The present invention will be described below in detail with reference to examples, but the present invention is not limited to these examples.

Example 1 (Production of 1,3-adamantanediol) 50.00 g of adamantane, 12.00 g of N-hydroxyphthalimide, V (ACAC) ₃ (vanadium (III)
0.128 g of acetylacetonate) and 534 g of acetic acid
Was charged into an autoclave and reacted at a reaction temperature of 90 ° C. and a reaction pressure of 20 kgf / cm ² for 3 hours while supplying air from the lower part of the autoclave at a flow rate of 20 liter / hour. As a result, the conversion rate of adamantane was 98.8%.
With 1,3-adamantanediol (yield 29.6%;
18.3 g), 1-adamantanol (yield 19.0)
%; 10.6 g), 2-adamantanone (yield 10.2)
%; 5.6 g), and 1,3,5-adamantanetriol (yield 6.6%; 4.5 g). The obtained reaction mixture (585 g) was heated at a pressure of 110 Torr and heated at a temperature of 11 Torr.
After concentrating at 0 ° C., 468 g of acetic acid was distilled off (distillation rate: 80% by weight) to obtain 117 g of a concentrated liquid. There was no thermal aging of 1,3-adamantanediol during this operation. To the concentrated solution, 2925 g of methyl benzoate was added, and the pressure was increased to 20.
The mixture was concentrated under the conditions of Torr and a heating medium of 110 ° C. to distill 608 g of a mixture of acetic acid and methyl benzoate (distillation rate: 20).
2434 g of a concentrated liquid. During this operation,
There was no heat aging of 3-adamantanediol.

Next, 609 g of water was added to the concentrated solution (S / F = 0.25), and the mixture was stirred at 20 ° C. for 1 hour.
The mixture was allowed to stand at 0 ° C. for 1 hour to separate liquid. This operation is performed twice more on the organic layer obtained by liquid separation, and the aqueous layer 186 is formed.
4 g and 2397 g of a methyl benzoate layer were obtained. The aqueous layer contained 17.4 g of 1,3-adamantanediol and 0.9 g of the methyl benzoate layer. Also, 0.2 g of 1-adamantanol as an intermediate was distributed to the aqueous layer and 10.4 g to the methyl benzoate layer. 1864g of the above water layer
615 g of benzyl alcohol was added to the mixture (S / F = 0.3
3) After stirring at 30 ° C. for 1 hour, the mixture was allowed to stand at 30 ° C. for 1 hour and liquid was separated. This operation was further performed twice on the organic layer obtained by liquid separation to obtain 1706 g of an aqueous layer and 2003 g of a benzyl alcohol layer. 1,3-adamantanediol contained 0.9 g in the aqueous layer and 1 g in the benzyl alcohol layer.
6.5 g was contained. Above benzyl alcohol layer 2
003 g was concentrated under the conditions of a pressure of 30 to 5 Torr and a heating medium of 120 ° C., and 1863 g of a mixture of benzyl alcohol and a small amount of water was distilled (distillation rate: 93% by weight).
40 g were obtained. During this operation, there was no heat aging of 1,3-adamantanediol. While stirring the above concentrate, 2
After cooling to 0 ° C, methyl-t-butyl ether 42
0 g was added dropwise over 30 minutes. The resulting mixture was then stirred in an ice bath (2-3 ° C) for 30 minutes. The precipitate was suction-filtered under reduced pressure, rinsed twice with 60 g of methyl-t-butyl ether, and dried under the conditions of a pressure of 10 Torr and a heating medium of 120 ° C. for 4 hours to obtain 12.5 g of a dried product.

The dried product was subjected to gas chromatography (G
C), the purity of 1,3-adamantanediol was 92.7% by weight and 1,3,5-adamantanetriol was 3.1 as an impurity.
% By weight, 1.9% by weight of benzyl alcohol, and trace amounts of 1-adamantanol. In the above steps, the yield of 1,3-adamantanediol based on the charged adamantane was 29.6% for the reaction yield and 63.3 for the purification yield.
% And a consistent yield of 18.7%.

Example 2 (Production of 1,3-adamantanediol) The reaction was carried out in the same manner as in Example 1. The purification process was performed in the same manner as in Example 1, except that 2-ethylhexanol was used instead of benzyl alcohol. When the obtained dried product was subjected to a GC analysis (internal standard method), the purity of 1,3-adamantanediol was 94.3% by weight, and 1,3,7-adamantanetriol was 1.9% by weight as an impurity. , 2-ethylhexanol and trace amounts of 1-adamantanol. In the above steps, the yield of 1,3-adamantanediol based on the charged adamantane was 29.6% for the reaction yield and 52.0% for the purification yield.
6%, consistent yield 15.6%.

Example 3 (Production of 1,3-adamantanediol) The reaction was carried out in the same manner as in Example 1. The purification step was performed in the same manner as in Example 1, except that n-butanol was used instead of benzyl alcohol. G
According to C analysis (internal standard method), the purity of 1,3-adamantanediol was 87.3% by weight, and the impurity content was:
6.1% by weight of 1,3,5-adamantanetriol, n
-Butanol 2.4% by weight, trace amount of 1-adamantanol. In the above steps, the yield of 1,3-adamantanediol based on the charged adamantane was 29.6% for the reaction yield, 60.8% for the purification yield, and 18.0% for the consistent yield.
Met.

Example 4 (Production of 1,3-adamantanediol) The reaction was carried out in the same manner as in Example 1. The purification step was performed in the same manner as in Example 1, except that triethylamine was used instead of benzyl alcohol. G
According to C analysis (internal standard method), the purity of 1,3-adamantanediol was 94.0% by weight, and the impurity content was:
1,3,5-adamantanetriol 2.4% by weight, triethylamine 1.6% by weight, 1-adamantanol trace amount. In the above steps, the yield of 1,3-adamantanediol based on the charged adamantane was 29.6% for the reaction yield, 50.0% for the purification yield, and 14.8 for the consistent yield.
%Met.

Example 5 (Production of 1,3-adamantanediol) 2397 g of the methyl benzoate layer obtained in Example 1
Was concentrated under the conditions of a pressure of 20 Torr and a heating medium of 120 ° C. to distill 2277 g of a mixture of methyl benzoate and a small amount of water (distillation rate: 95% by weight) to obtain 120 g of a concentrated liquid. This concentrated solution was charged into an autoclave, and acetic acid 400
g, N-hydroxyphthalimide 11.2 g, V (AC
AC) ₃ 0.120 g was added, and the reaction pressure was 20 kgf / c.
The reaction was carried out for 4 hours under the conditions of m ² and a reaction temperature of 80 ° C. while supplying air from the lower part of the autoclave at a flow rate of 10 liter / hour. As a result, the yield of 1,3-adamantanediol was 45.1% (based on charged 1-adamantanol).
Was generated by By subjecting the obtained reaction mixture to a separation and purification method according to Example 1, 1,3-adamantanediol having the same quality as that of Example 1 was obtained.

Example 6 (Production of 1,3-adamantanediol) 585 g of a reaction mixture obtained by reacting in the same manner as in Example 1 was concentrated under the conditions of a pressure of 110 Torr and a heating medium of 110 ° C., and 468 g of acetic acid. Was distilled out (distillation rate: 80% by weight) to obtain 117 g of a concentrated liquid. 2925 g of chlorobenzene was added to this concentrated solution, the pressure was 110 Torr, and the heat medium 11
The mixture was concentrated at 0 ° C. to distill 304 g of a mixture of acetic acid and chlorobenzene (distillation rate: 10% by weight).
38 g were obtained. During this operation, there was no thermal aging of the product, 1,3-adamantanediol.

Next, 685 g of water was added to this concentrated liquid (S / F = 0.25), and the mixture was stirred at 20 ° C. for 1 hour.
The mixture was allowed to stand at 0 ° C. for 1 hour to separate liquid. This operation was further performed twice on the obtained organic layer to obtain 2074 g of an aqueous layer and 2719 g of a chlorobenzene layer. The aqueous layer contained 17.3 g of 1,3-adamantanediol, and the chlorobenzene layer contained 1.0 g. The intermediate, 1-adamantanol, contained 0.1 g in the aqueous layer and 1 g in the chlorobenzene layer.
0.5g was contained. The chlorobenzene layer 2719
g was concentrated under the conditions of a pressure of 100 Torr and a heating medium of 110 ° C., and 2501 g was distilled (distillation rate: 92% by weight) to obtain 218 g of a concentrated liquid. This concentrated solution was charged into an autoclave, 250 g of acetic acid, N-hydroxyphthalimide.
2 g and 0.120 g of V (ACAC) ₃ were added, and the reaction was carried out for 8 hours under the conditions of a reaction pressure of 20 kgf / cm ² and a reaction temperature of 75 ° C. while supplying air from the lower part of the autoclave at a flow rate of 10 liter / hour. As a result, 1,3-adamantanediol was produced in a yield of 48.5% (based on the charged 1-adamantanol). By subjecting the obtained reaction mixture to a separation and purification method according to Example 1, 1,3-adamantanediol having the same quality as that of Example 1 was obtained.

Example 7 (Production of 1,3-adamantanediol) 585 g of a reaction mixture obtained by reacting in the same manner as in Example 1 was concentrated under the conditions of a pressure of 110 Torr and a heating medium of 110 ° C., and 468 g of acetic acid. Was distilled out (distillation rate: 80% by weight) to obtain 117 g of a concentrated liquid. Add 543 water to this concentrate.
g was added and cooled to room temperature. The precipitated solid was filtered and dried until the water content became 1% by weight or less to obtain 1-adamantanol (recovery rate 90%). The obtained 1-adamantanol was used as a raw material to carry out a reaction according to Example 5, and the reaction mixture was subjected to a separation and purification method according to Example 1 to obtain a reaction mixture.
1,3-Adamantanediol having the same quality as that of Example 1 was obtained.

On the other hand, the filtrate obtained by the filtration
After adding 330 g of butanol and stirring at 30 ° C. for 1 hour, the mixture was allowed to stand at 30 ° C. for 1 hour and liquid was separated. This operation
The separation was performed twice more on the obtained organic layer to obtain 700 g of an aqueous layer and 620 g of an n-butanol layer. The extraction rate (partition rate) of 1,3-adamantanediol into the n-butanol layer was 90%. The n-butanol layer was concentrated to about 1/6, and methyl-t-butyl ether 31 was concentrated.
0 g was added and cooled to room temperature. The precipitated solid is filtered,
After drying, 1,3-adamantanediol having a purity of 97% was obtained. The crystallization yield was 76%. As impurities, 1-adamantanol was contained in a trace amount and 1,3,5-adamantanetriol was contained in 2% by weight. The purification yield of 1,3-adamantanediol in the above step was 68%.

Example 8 (Production of 1,3-dimethyl-5-adamantanol) 1000.0 g of 1,3-dimethyladamantane, 198.6 g of N-hydroxyphthalimide, V (ACAC) ₃
(Vanadium (III) acetylacetonate) 2.12
g, and 7132 g of acetic acid were charged into an autoclave, and the reaction temperature was 90 ° C. and the reaction pressure was 20 kgf / cm ² .
The reaction was carried out for 90 minutes while supplying air from the lower part of the autoclave at a flow rate of 370 normal liters / hour. As a result, the conversion of 1,3-dimethyladamantane was 86.0%.
To give 1,3-dimethyl-5-adamantanol (yield 5
4.4%, 597 g), 1,3-dimethyl-5,7-adamantanediol (12.6% yield, 151 g),
1,3-dimethyladamantanone (yield 10.0%, 1
09g) and 1,3-dimethyladamantanketool (1.7% yield, 20g). The obtained reaction mixture (8500 g) was concentrated under the conditions of a pressure of 80 Torr and a heating medium of 140 ° C. to distill 7000 g of acetic acid (distillation rate: 8
2% by weight) and 1500 g of a concentrated liquid.

The above concentrated solution (1500 g) was distilled under reduced pressure using a 30 cm-high Raschig-packed packed column to obtain a main fraction 39
6 g (pressure 10 Torr, overhead temperature 120 ° C.) were obtained.
The main fraction is solid at normal temperature, and after pulverization to remove acetic acid mixed in the main fraction, the temperature is 60 ° C. and the pressure is 20 Torr.
It was dried for 8 hours under the conditions of r. As a result, the purity was 99.3%.
376 g of 1,3-dimethyl-5-adamantanol was obtained. In the above steps, the production results of 1,3-dimethyl-5-adamantanol were a reaction yield of 54.4%, a purification yield of 62.5%, and a consistent yield of 34.0%.

Example 9 (Production of 1,3-dimethyl-5,7-adamantanediol) 1000.0 g of 1,3-dimethyladamantane, 198.6 g of N-hydroxyphthalimide, V (ACAC) ₃
(Vanadium (III) acetylacetonate) 2.12
g, and 7132 g of acetic acid were charged into an autoclave, and the reaction temperature was 90 ° C. and the reaction pressure was 20 kgf / cm ² .
The reaction was carried out for 20 hours while supplying air at a flow rate of 370 normal liters / hour from the lower part of the autoclave. As a result, at a conversion of 1,3-dimethyladamantane of 100%,
1,3-dimethyl-5-adamantanol (yield 0.5
%, 5 g), 1,3-dimethyl-5,7-adamantanediol (yield 65.8%, 786 g), 1,3-dimethyladamantanone (yield 10.1%, 110 g),
1,3-dimethyladamantanketool (7.1 yield)
%, 84 g), and 1,3-dimethyladamantanketodiol (0.7% yield, 9 g).

8640 g of the obtained reaction mixture was subjected to pressure 8
The solution was concentrated under the conditions of 0 Torr and 140 ° C.
g of acetic acid was distilled off (distillation rate: 75% by weight), and concentrated solution 214
0 g was obtained. After adding 2675 g of methyl benzoate thereto, the mixture was concentrated under the conditions of a pressure of 60 to 40 Torr and a heating medium of 140 ° C., and a mixture of 1200 g of acetic acid and methyl benzoate was distilled off (distillation rate: 25%). 3615 g were obtained. This liquid was cooled to 20 ° C. while stirring, and the precipitated crystals were subjected to suction filtration under reduced pressure to obtain 1512 g of wet crystals. 500 g of n-butanol and methyl-
2250 g of t-butyl ether was added, and the liquid temperature was 2 to 3 ° C.
And stirred for 1 hour. The above slurry liquid was subjected to suction filtration under reduced pressure to obtain 945 g of wet crystals. The wet crystals were dried at 80 ° C. and 20 Torr for 8 hours. As a result, 93.1% pure 1,3-dimethyl-5,7-
659 g of adamantanediol was obtained. In the above steps, the production results of 1,3-dimethyl-5,7-adamantanediol were 65.8% for the reaction yield and 7 for the purification yield.
8.1%, consistent yield 51.4%.

Example 10 (Co-production of 1,3-dimethyl-5-adamantanol and 1,3-dimethyl-5,7-adamantanediol) 1000.0 g of 1,3-dimethyladamantane, 198. N-hydroxyphthalimide 6g, V (ACAC) ₃
(Vanadium (III) acetylacetonate) 2.12
g, and 7132 g of acetic acid were charged into an autoclave, and under the conditions of a reaction temperature of 90 ° C and a reaction pressure of 20 kgf / cm ² ,
The reaction was carried out for 3 hours while supplying air at a flow rate of 370 normal liters / hour from the lower part of the autoclave. As a result, the conversion of 1,3-dimethyladamantane was 98.5%.
To give 1,3-dimethyl-5-adamantanol (yield 4
1.7%, 458 g), 1,3-dimethyl-5,7-adamantanediol (yield 29.2%, 349 g),
1,3-dimethyladamantanone (9.3% yield, 10
1g) and 1,3-dimethyladamantanketool (4.3% yield, 51g).

8470 g of the resulting reaction mixture was crushed at a pressure of 8
The solution was concentrated under the conditions of 0 Torr and 140 ° C.
g of acetic acid was distilled off (distillation rate: 75% by weight).
7 g were obtained. To this concentrate, 3000 g of methyl benzoate was added, and the mixture was concentrated under the conditions of a pressure of 60 Torr and a heating medium of 140 ° C., and a mixture of 1000 g of acetic acid and methyl benzoate was distilled off (distillation rate: 20% by weight). 4117 g of a liquid was obtained. 4000 g of methyl benzoate was added to this concentrate.

To the above liquid, 6500 g of water (S / F =
0.80), and the mixture was stirred at a liquid temperature of 30 to 40 ° C. for 10 minutes, allowed to stand for 1 hour, and separated. This operation was repeated 10 times for the organic layer obtained by liquid separation. By this extraction operation, 72.7 kg of an aqueous layer and 6.9 kg of an organic layer were obtained. The amount of 1,3-dimethyl-5,7-adamantanediol in this aqueous layer was 328 g. In addition, 1 in this organic layer
The amount of 3-dimethyl-5-adamantanol was 360 g. When the aqueous layer was allowed to stand at a liquid temperature of 20 ° C. for 15 hours, crystals precipitated. The crystals are filtered under reduced pressure with suction to obtain wet crystals 4.
95 g were obtained. 1,3-dimethyl-5 in this wet crystal
The amount of 7-adamantanediol was 141 g. Also,
23.8 kg for 72.2 kg of filtrate (S / F = 0.
33) n-Butanol was added, the mixture was stirred at a liquid temperature of 20 ° C. for 10 minutes, and allowed to stand for 1 hour. After liquid separation, the obtained organic layer weighed 24.0 kg and the aqueous layer weighed 72.0 kg.
The amount of 1,3-dimethyl-5,7-adamantanediol in this organic layer was 170 g. To the organic layer was added 495 g of the wet crystals obtained from the aqueous layer,
Stir for minutes to dissolve. 24.5 kg of the obtained organic layer was concentrated under the conditions of a pressure of 400 Torr and a heating medium of 140 ° C.
A mixture of 3.0 kg of n-butanol and water was distilled off (distillation rate: 94% by weight) to obtain 1.5 kg of a concentrate. When this concentrate was cooled to 20 ° C., crystals precipitated. To this, 4.5 kg of methyl-t-butyl ether was added over 1 hour, and the mixture was stirred at a liquid temperature of 2 to 3 ° C. for 1 hour. The slurry was vacuum filtered under reduced pressure to obtain 346 g of wet crystals. The wet crystals were dried at a temperature of 80 ° C. and a pressure of 20 Torr. In the above steps, 1,3-dimethyl-5,
The production results of 7-adamantanediol were as follows.
9.2%, purification yield was 79.1%, and consistent yield was 23.1%.

[0100] 1,3-Dimethyl-5- contained in the organic layer obtained by extraction with the above-mentioned methyl benzoate and water.
Adamantanol was purified by the following method. A 2 liter separable flask was equipped with a stirrer, a packed tower of 30 cm in height, a bottom liquid thermometer and a top thermometer.
Under a condition of 0 Torr and a heating medium of 140 ° C., 6.9 kg of the organic layer is used.
Is continuously concentrated, and a distillate having an overhead temperature of 70 to 80 ° C (1)
6.2 kg and 0.7 kg of the concentrate were obtained. The concentrated liquid was further distilled at a pressure of 10 Torr, and the overhead temperature was 112 to 12
269 g of a distillate (2) at 2 ° C. was obtained. In distillate (1), 1,3-dimethyl-5-adamantanol contains 176
g of distillate (2), and 184 g of 1,3-dimethyl-5-adamantanol. Here, in order to remove 1,3-dimethyladamantanone contained in the distillate (2), n was added to the distillate (2).
-Heptane (200 g) was added and dissolved by stirring at reflux at a pressure of 760 Torr. Then, the solution was cooled to 20 ° C. while stirring to precipitate crystals. The precipitated crystals were subjected to suction filtration under reduced pressure, and dried at a pressure of 20 Torr and a temperature of 60 ° C. for 8 hours. As a result, the purity was 96.0%.
125 g of 1,3-dimethyl-5-adamantanol
Obtained. In the above steps, the production results of 1,3-dimethyl-5-adamantanol were a reaction yield of 41.7%, a purification yield of 26.2%, and a consistent yield of 10.9%.

Example 11 (Co-production of 1,3-dimethyl-5-adamantanol and 1,3-dimethyl-5,7-adamantanediol) In the same manner as in Example 3, the oxidation reaction and methyl benzoate were removed. An extraction operation using water was performed to separate 1,3-dimethyl-5,7-adamantanediol from the aqueous layer. on the other hand,
From the organic layer obtained by the extraction operation, 1,3-dimethyl-5-adamantanol was obtained by the following method. 6.9 kg of the water-extracted organic layer obtained in Example 3 was subjected to pressure 1
Distillation was carried out under the conditions of 0 Torr and a heating medium of 140 ° C. to distill 5.5 kg of a mixture of methyl benzoate and 1,3-dimethyl-5-adamantanol (distillation rate: 80% by weight).
5.5 kg of methyl benzoate was added to this concentrated liquid, and 5.5 kg of a mixture of methyl benzoate and 1,3-dimethyl-5-adamantanol was distilled under the same conditions (distillation rate 80% by weight). ). Further, 4.7 kg of methyl benzoate was added to this concentrated solution, and a mixture of methyl benzoate and 1,3-dimethyl-5-adamantanol was added under the same conditions.
5 kg was distilled (distillation rate 90% by weight). The total amount of the mixture (distillate) of the above-mentioned methyl benzoate and 1,3-dimethyl-5-adamantanol was 16.5 kg, and the amount of 1,3-dimethyl-5-adamantanol contained therein was 299 g. there were.

A 2 liter separable flask was equipped with a stirrer, a packed tower of 30 cm in height, a bottom liquid thermometer and a top thermometer. The distillate was charged, and the pressure was 10 to 20 Torr.
r, continuous concentration under the condition of a heating medium at 140 ° C.
15.0 kg of a distillate at 80 ° C. and 1.5 kg of a concentrate were obtained. This concentration solution was cooled to 20 ° C., and the precipitated crystals were subjected to suction filtration under reduced pressure. After rinsing with 100 g of n-hexane, 313 g of wet crystals were obtained. This wet crystal is subjected to a pressure of 20 Torr,
It was dried at a temperature of 60 ° C. for 8 hours. As a result, the purity was 95.
0% of 1,3-dimethyl-5-adamantanol is added to 15
5 g were obtained. In the above steps, 1,3-dimethyl-5
-The production performance of adamantanol was a reaction yield of 41.7.
%, The purification yield was 32.1%, and the consistent yield was 13.4%.

Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat II (reference) // C07B 61/00 300 C07B 61/00 300

Claims (14)

[Claims] 1. A method of separating a monool and a diol from a mixture containing an alicyclic monol and an alicyclic diol, wherein (b) separating the mixture from an aqueous solution containing at least water. A solvent, and an extraction operation using at least one organic solvent selected from an aromatic organic solvent and an alcohol having 4 or more carbon atoms, and alicyclic monools are added to the organic solvent layer to form an alicyclic monool. A first extraction step of distributing the diols to the aqueous solvent layer, and (c) extracting the aqueous solvent layer by adding at least one organic solvent selected from alcohols, esters and amines having 4 or more carbon atoms, A second extraction step of distributing the alicyclic diols to the organic solvent layer, and a method for separating alicyclic alcohols. 2. The alicyclic alcohols according to claim 1, further comprising a distillation step of separating alicyclic monools contained in the organic solvent layer obtained in the first extraction step (b) by distillation. Separation method. 3. The alicyclic diols contained in the organic solvent layer obtained in the second extraction step (c) are subjected to a crystallization operation using an organic solvent to convert the alicyclic diols into crystals. The method for separating alicyclic alcohols according to claim 1 or 2, comprising a crystallization step of precipitating. 4. A method for separating alicyclic monols from a mixture containing an alicyclic monool and an alicyclic diol, wherein (f) separating the alicyclic monool by distillation. A method for separating alicyclic monols including a distillation step. 5. A method for separating alicyclic diols from a mixture containing an alicyclic monol and an alicyclic diol, comprising: (g) subjecting the mixture to a crystallization operation using an organic solvent. A method for separating alicyclic diols, the method comprising a crystallization step of crystallizing the alicyclic diols upon application. 6. A method for separating a monool and a diol from a mixture containing an alicyclic monol and an alicyclic diol, the method comprising: (d) separating the mixture from an aqueous solution containing at least water. A crystallization step of subjecting to a crystallization operation using a solvent to crystallize alicyclic monools, and (e) alcohol and amine having 4 or more carbon atoms in the residual liquid obtained by collecting the alicyclic monools And extracting the mixture with at least one organic solvent selected from the group consisting of: and extracting the alicyclic diols to the organic solvent layer. 7. Oxidation of at least one substrate selected from (a) alicyclic hydrocarbons and alicyclic monools corresponding to the alicyclic hydrocarbons to form a corresponding alicyclic hydrocarbon An oxidation step of obtaining a mixture containing monools and alicyclic diols; and (b) selecting the mixture from an aqueous solvent containing at least water, an aromatic organic solvent and an alcohol having 4 or more carbon atoms. An extraction operation using at least one organic solvent is performed, and the alicyclic monol is added to the organic solvent layer.
First to distribute alicyclic diols to the aqueous solvent layer, respectively
An extraction step, and (c) extracting by adding at least one organic solvent selected from alcohols, esters and amines having 4 or more carbon atoms to the aqueous solvent layer, and distributing the alicyclic diols to the organic solvent layer. A method for producing alicyclic alcohols, comprising a second extraction step. 8. The alicyclic alcohols according to claim 7, further comprising a distillation step of separating alicyclic monools contained in the organic solvent layer obtained in the first extraction step (b) by distillation. Manufacturing method. 9. The alicyclic diols contained in the organic solvent layer obtained in the second extraction step (c) are subjected to a crystallization operation using an organic solvent to form alicyclic diols. The method for producing alicyclic alcohols according to claim 7 or 8, comprising a crystallization step of precipitating. 10. A method comprising oxidizing (a) at least one substrate selected from alicyclic hydrocarbons and alicyclic monools corresponding to the alicyclic hydrocarbons to form a corresponding alicyclic hydrocarbon; A method for producing alicyclic alcohols, comprising: an oxidation step of obtaining a mixture containing monools and alicyclic diols; and (f) a distillation step of separating alicyclic monools from the mixture by distillation. (A) oxidizing at least one substrate selected from alicyclic hydrocarbons and alicyclic monools corresponding to the alicyclic hydrocarbons to form a corresponding alicyclic hydrocarbon; An oxidation step of obtaining a mixture containing monools and alicyclic diols; and (g) a crystallization step of subjecting the mixture to a crystallization operation using an organic solvent to crystallize the alicyclic diols. A process for producing an alicyclic alcohol containing: (A) oxidizing at least one substrate selected from alicyclic hydrocarbons and alicyclic monools corresponding to the alicyclic hydrocarbons to form a corresponding alicyclic hydrocarbon; An oxidation step of obtaining a mixture containing monools and alicyclic diols, and (d) subjecting the mixture to a crystallization operation using an aqueous solvent containing at least water to form alicyclic monools. A crystallization step of precipitating, and (e) adding at least one organic solvent selected from alcohols and amines having 4 or more carbon atoms to the remaining liquid from which the alicyclic monools have been recovered, and extracting the residual liquid. An extraction step of distributing the diols to the organic solvent layer. A substrate is represented by the following formula (1): (Wherein R ¹ and R ² are the same or different and each represents a hydrogen atom,
A halogen atom, an alkyl group, an aryl group, a cycloalkyl group, a hydroxyl group, an alkoxy group, a carboxyl group, an alkoxycarbonyl group, or an acyl group; R ¹ and R ² are bonded to each other to form a double bond, or an aromatic or A non-aromatic ring may be formed. X represents an oxygen atom or a hydroxyl group. R ¹ , R ² , or R ¹ and R ²
Are bonded to each other to form a double bond or an aromatic or non-aromatic ring represented by the above formula (1).
The alicyclic alcohol according to any one of claims 7 to 12, wherein the alicyclic alcohol is oxidized by oxygen in the presence of an imide compound represented by the formula (1) wherein the substituted cyclic imide group may further have one or two substituents. Manufacturing method. 14. The process for producing alicyclic alcohols according to claim 7, wherein the separated alicyclic monools are recycled to the oxidation step.