JPH0769950A - Production of aromatic hydroxy compound - Google Patents

Abstract

PURPOSE:To obtain an aromatic hydroxy compound such as phenol from an aromatic compound such as benzene in a single step. CONSTITUTION:In the presence of at least one compound selected from a group composed of polyhydroxy aromatic compounds and their dehydrogenated compounds as a catalyst, an aromatic compound such as benzene is reacted with an oxidizing agent such as oxygen, etc. A reaction vessel is charged with an aromatic compound such as benzene and oxygen as raw materials, and a reaction is conducted in the presence of at least one compound selected from polyhydroxy aromatic compounds and their dehydrogenated compounds, and the objective aromatic hydroxy compound such as phenol is produced.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel process for producing an aromatic hydroxy compound, which comprises producing at least one aromatic hydroxy compound from an aromatic compound in one step.

[0002]

2. Description of the Related Art Conventionally, as a method for producing phenol from benzene and oxygen in one step, a method of reacting benzene and oxygen in a gas phase or a liquid phase in the presence of a catalyst is known.
However, in the case of a gas phase reaction, complete oxidation of benzene occurs and the selectivity of phenol is very low (Japanese Patent Laid-Open No. 56-87).
527). In the case of the liquid phase reaction, there is a method of oxidizing benzene using copper salt and oxygen, but the conversion rate of benzene is low and the yield of phenol is low (organic synthetic chemistry 41,
839 (1983)).

Further, using a palladium-based catalyst, 1,1
Although there is a method of oxidizing benzene in the presence of 0-phenanthroline and carbon monoxide, the yield of phenol is low (JP-A-2-19809). Therefore, a method for producing phenol by direct oxidation of benzene has been desired,
It has not been industrialized yet.

Further, Japanese patent, Japanese Patent Laid-Open No. Hei 3-23633.
No. 8 discloses a method for producing phenol from benzene using a metal phosphate catalyst. According to this method, the yield of phenol is about 6%, which is an unprecedentedly high yield, but the reaction temperature is as high as about 500 ° C., and a sufficiently economical production method has not yet been reached.

[0005]

Therefore, an object of the present invention is to obtain a high yield of aromatic hydroxy compounds represented by phenols from aromatic compounds represented by benzene and benzene derivatives under mild and low corrosive conditions. It is to provide a method of manufacturing at a rate.

[0006]

Means for Solving the Problems As a result of intensive studies on the above problems, the present inventors have shown that aromatic compounds represented by benzene and benzene derivatives are represented by phenols and the like in the presence of an oxidizing agent such as oxygen. The present invention has been completed by finding a method for producing an aromatic hydroxy compound according to the present invention in a high yield under mild and low corrosive conditions. That is, the present invention relates to an aromatic hydroxy compound characterized by reacting an aromatic compound with an oxidant in the presence of at least one selected from the group consisting of polyhydroxy aromatic compounds and dehydrogenated compounds thereof. It is a manufacturing method. Further, the present invention is preferably the method for producing an aromatic hydroxy compound, which comprises reacting the aromatic compound with an oxidizing agent in the presence of the aromatic dihydroxy compound. Also,
The present invention is more preferably a method for producing an aromatic hydroxy compound, which comprises reacting an aromatic compound with an oxidizing agent in the presence of hydroquinones or quinones. As a result, by carrying out the present invention, a method for producing an aromatic hydroxy compound, which is excellent in terms of economy with extremely high efficiency and low corrosiveness, is provided.

The aromatic compound used in the present invention is a 6-carbon ring condensed compound such as benzene, substituted benzenes, naphthalene, substituted naphthalene, anthracene, substituted anthracenes, durene and substituted durenes, thiophene,
Substituted thiophenes, furans, substituted furans, pyridine,
Heteroaromatic compounds such as substituted pyridines, quinolines, and substituted quinolines. Substituents which these aromatic compounds have include alkyl groups such as methyl, ethyl, propyl and butyl groups, carboxyl groups, nitro groups, amino groups, cyano groups, acetyl groups, alkoxy groups, hydroxyl groups, acetoxy groups, halogens. Examples include elements and thioalkoxy groups. These are used alone or in combination of two or more.
Specific examples of the substituted benzenes include toluene, ethylbenzene, xylene, propylbenzene, butylbenzene, benzoic acid, nitrobenzene, aniline, benzonitrile, acetophenone, anisole, phenol, catechol, resorcin, hydroquinone, phenyl acetate,
Fluorobenzene, chlorobenzene, bromobenzene,
Examples include iodobenzene and thioanisole.

The aromatic hydroxy compound defined in the present invention is a compound in which at least one hydroxyl group is directly bonded to the carbon forming the aromatic ring of the above aromatic compound, and more specifically, the above aromatic compound. The carbon-hydrogen bond at the carbon forming the aromatic ring is converted to at least one carbon-hydroxy bond. For example, from benzene, phenol, catechol,
Hydroquinone, resorcin, etc. are produced, naphthols, dihydroxynaphthalenes, etc. are produced from naphthalene, mono- and polyhydroxytoluenes are produced from toluene, and methoxyphenol, methoxyresorcin, etc. are produced from anisole. Similarly, a compound having one or more hydroxyl groups directly bonded to aromatic carbon is produced from the aromatic compound. Depending on the reaction conditions, quinones such as benzoquinone, naphthoquinone or anthraquinone are simultaneously formed together with the aromatic hydroxy compound.

The polyhydroxy aromatic compound used in the present invention is a compound in which at least two or more hydroxyl groups are directly bonded to the carbons forming the aromatic ring, and specific examples thereof include hydroquinone (p-dihydroxybenzene). ), O-dihydroxybenzene, m-dihydroxybenzene, 1,2,3-trihydroxybenzene, 1,2,4-trihydroxybenzene, 1,3,5
-Trihydroxybenzene, p, p'-diphenol,
o, p'-diphenol, o, o'-diphenol,
1,2-dihydroxynaphthalene, 1,3-dihydroxynaphthalene, 1,4-dihydroxynaphthalene, 1,
5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 1,7-dihydroxynaphthalene, 1,8-
Dihydroxynaphthalene, 2,3-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, 2,7-dihydroxynaphthalene, 1,5-dihydroxyanthracene, 1,8-dihydroxyanthracene, α-ethyl-
9,10-dihydroxyanthracene, anthrahydroquinone (9,10-dihydroxyanthracene), 3,
4-dihydroxy-9-anthranol, 1,8-dihydroxy-9-anthranol, 1,2-dihydroxyanthraquinone, 1,3-dihydroxyanthraquinone, 1,4-dihydroxyanthraquinone, 1,5-dihydroxyanthraquinone, 1, 8-dihydroxyanthraquinone, 2,3-dihydroxyanthraquinone,
2,6-dihydroxyanthraquinone, 2,7-dihydroxyanthraquinone, 1,2,3-trihydroxyanthraquinone, 1,2,4-trihydroxyanthraquinone, 1,2,6-trihydroxyanthraquinone,
1,2,7-trihydroxyanthraquinone, bisphenol A, bisphenol B, bisphenol S, bisphenol F, tetramethylbisphenol S, methylhydroquinone, 2,5-dimethylhydroquinone, trimethylhydroquinone, ethylhydroquinone, n-propylhydroquinone, i- Propylhydroquinone, t-butylhydroquinone, 2,5-di-t-butylhydroquinone,
2,5-dihydroxyhydroquinone, methoxyhydroquinone, 2,3-dihydroxytoluene, 2,4-dihydroxytoluene, 2,5-dihydroxytoluene, 2,
6-dihydroxytoluene, 3,4-dihydroxytoluene, 3,5-dihydroxy-o-xylene, 3,6-
Dihydroxy-o-xylene, 2,4-dihydroxy-
m-xylene, 2,5-dihydroxy-m-xylene,
2,6-dihydroxy-p-xylene, 2,3-dihydroxybenzoic acid, 2,4-dihydroxybenzoic acid, 2,
There are 6-dihydroxybenzoic acid, 3,4-dihydroxybenzoic acid, 3,5-dihydroxybenzoic acid, 4,4′-dihydroxydiphenyl ether and the like. Preferably,
Hydroquinones or hydroquinones such as hydroquinone having a substituent such as an alkyl group in the benzene nucleus. The dehydrogenated compound of the polyhydroxy aromatic compound used in the present invention means a compound in which hydrogen of at least one hydroxyl group of the polyhydroxy compound is dehydrogenated and converted into a ketone group. Preferred are compounds or quinones in which all hydroxyl groups have been dehydrogenated to ketone groups. Specific examples thereof include dehydrogenation compounds of dihydroxybenzenes such as p-benzoquinone and o-benzoquinone, dehydrogenation compounds of diphenols such as diphenoquinone, 1,4-naphthoquinone, 1,2-naphthoquinone and 2,6- Dehydrogenation compounds of dihydroxynaphthalene such as naphthoquinone, 9,10-anthraquinone, 1,2-
Examples thereof include dehydrogenated compounds of dihydroxyanthracenes such as anthraquinone, 1,4-anthraquinone, 2-methylanthraquinone and 2-ethylanthraquinone.
In the present invention, the amount of the polyhydroxy aromatic compound or its dehydrogenation compound used is not particularly limited, but in the case of hydroquinone, benzene 100 g used in the batch reaction can be used, as an example of an easily practicable amount. To 0.001 to 500 g, more preferably 0.1 to 5 g
The amount is 0 g.

The oxidant used in the present invention is a substance capable of supplying oxygen molecules, oxygen atoms, oxygen ions or oxygen radicals in the reaction state in the reaction system. Specific examples include oxygen gas, oxygen gas diluted with an inert gas, air, diluted air, hydrogen peroxide, organic peroxide, inorganic peroxide and the like. Preferred is oxygen gas, oxygen gas diluted with an inert gas, or air. Use one or more of these.

In the present invention, the yield of an aromatic hydroxy compound such as phenol can be improved by adding water to the reaction system in a gas or liquid state. Further, the reaction system is preferably acidic. This acidity is achieved by adding an acidic substance to the reaction system. Examples of the acidic substance added to the reaction system include Bronsted acid and Lewis acid. As the Bronsted acid, for example, mineral acids such as heteropoly acid, hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, boric acid, acetic acid, benzoic acid, formic acid, trichloroacetic acid,
Examples thereof include organic acids such as trifluoromethanesulfonic acid and sulfonic acid, and inorganic acids such as zeolites and mixed oxides. As the Lewis acid, aluminum chloride, ferric chloride, boron chloride compound, antimony chloride compound,
Examples include stannic chloride, antimony fluoride, zeolites, mixed oxides, and the like. Furthermore, inorganic and organic acid salts are also used as the acidic substance. Preferably heteropolyacid is added to the reaction system.

The heteropolyacid referred to in the present invention is generally a composite metal oxide acid composed of two or more different metal oxide composites and those in which some or all of the protons of these acids are replaced with metal cations. is there. As a preferred heteropoly acid, a heteropoly acid containing vanadium as a metal as a hetero atom is recommended, and as a more easily available heteropoly acid, a general formula H _{(3 + n)} PV _n Mo _(12-n) O ₄₀ , H _{( 4 + n)} SiV _n Mo
_(12-n) O ₄₀ , H _{(3 + n)} PV _n W _(12-n) O ₄₀ , H _{(4 + n)} SiV _n W _(12-n) O
₄₀ (where n is a positive integer of 0 or 6 or less,
H is a hydrogen atom, P is a phosphorus atom, Si is a silicon atom, V is a vanadium atom, Mo is a molybdenum atom, W is a tungsten atom, and O is an oxygen atom. ) And heteropoly acids obtained by exchanging a part or all of the protons of these heteropoly acids with metal ions are exemplified as being easily available.

The metal to be exchanged with the proton of the heteropolyacid in the present invention may be a metal ion of a typical metal or a transition metal, but is preferably an ion of a typical metal, more preferably an alkali metal or an alkaline earth metal. It is a heteropoly acid that has been exchanged for at least one type of ion. The method for exchanging a proton with a metal ion is not particularly limited in the present invention, and any method may be used as long as a substantially metal ion-exchanged form is obtained, but as a method that is easy to carry out As an example, a method of stirring and mixing an aqueous solution of a metal hydroxide, a metal carbonate, a metal acetate and the like and an aqueous solution of a heteropolyacid, and then isolating by evaporating to dryness and the like can be mentioned.

Specific examples of the heteropolyacid in the present invention
If shown, H can be expressed as a molecular formula or a rational formula._FourPVMo₁₁O
₄₀, H_FivePV₂Mo_TenO₄₀, H₆PV₃Mo₉O₄₀, H₇PV_FourMo₈O₄₀, H₈PV_FiveM
o₇O₄₀, NaH₃PVMo₁₁O₄₀, Na₂H₂PVMo₁₁O₄₀, Na₃HPVMo₁₁O
₄₀, Na_FourPVMo₁₁O₄₀, KH₃PVMo₁₁O₄₀, K₂H₂PVMo₁₁O₄₀, K₃H
PVMo₁₁O₄₀, K_FourPVMo₁₁O₄₀, LiH₃PVMo₁₁O₄₀, Li₂H₂PVMo₁₁
O₄₀, Li₃HPVMo₁₁O₄₀, Li_FourPVMo₁₁O₄₀, RbH₃PVMo₁₁O₄₀, R
b₂H₂PVMo₁₁O₄₀, Rb₃HPVMo₁₁O₄₀, Rb_FourPVMo₁₁O₄₀, CsH₃PV
Mo₁₁O₄₀, Cs₂H₂PVMo₁₁O₄₀, Cs₃HPVMo₁₁O₄₀, Cs_FourPVMo₁₁O
₄₀, MgH₃PVMo₁₁O₄₀, Mg₂H₂PVMo₁₁O₄₀, Mg₃HPVMo₁₁O₄₀,
Mg_FourPVMo₁₁O₄₀, CaH₃PVMo₁₁O₄₀, Ca₂H₂PVMo₁₁O₄₀, Ca₃HP
VMo₁₁O₄₀, Ca_FourPVMo₁₁O₄₀, NaH_FourPV₂Mo_TenO₄₀, Na₂H₃PV₂Mo
_TenO₄₀, Na₂H₃PV₂Mo_TenO₄₀, Na₃H₂PV₂Mo_TenO₄₀, Na_FourHPV₂Mo
_TenO₄₀, Na_FivePV₂Mo_TenO₄₀, KH_FourPV₂Mo_TenO₄₀, K₂H₃PV₂Mo_TenO
₄₀, K₂H₃PV₂Mo_TenO₄₀, K₃H₂PV₂Mo_TenO₄₀, K_FourHPV₂Mo
_TenO₄₀, K_FivePV₂Mo_TenO₄₀, LiH_FourPV₂Mo_TenO₄₀, Li₂H₃PV₂Mo_TenO
₄₀, Li₂H₃PV₂Mo_TenO₄₀, Li₃H₂PV₂Mo_TenO₄₀, Li_FourHPV₂Mo_TenO
₄₀, Li_FivePV₂Mo_TenO₄₀, RbH_FourPV₂Mo_TenO₄₀, Rb₂H₃PV₂Mo
_TenO₄₀, Rb₂H₃PV₂Mo_TenO₄₀, Rb₃H₂PV₂Mo_TenO₄₀, Rb_FourHPV₂Mo
_TenO₄₀, Rb_FivePV₂Mo_TenO₄₀, CsH_FourPV₂Mo_TenO₄₀, Cs₂H₃PV₂Mo_Ten
O₄₀, CsRb₂H₃PV₂Mo_TenO₄₀, Cs₃H₂PV₂Mo_TenO₄₀, Cs_FourHPV₂Mo
_TenO₄₀, Cs_FivePV₂Mo_TenO₄₀, H_FourPVW₁₁O₄₀, H_FivePV2W_TenO₄₀, H₆P
V₃W₉O₄₀, H₇PV_FourW₈O₄₀, H₈PV_FiveW₇O₄₀, NaH₃PVW₁₁O₄₀, Na₂
H₂PVW₁₁O₄₀, Na₃HPV2W₁₁O₄₀, Na_FourPVW₁₁O₄₀, KH₃PV2W₁₁O
₄₀, K₂H₂PVW₁₁O₄₀, K₃HPVW₁₁O₄₀, K_FourPVW₁₁O₄₀, LiH₃PVW
₁₁O₄₀, Li₂H₂PVW₁₁O₄₀, Li₃HPVW₁₁O₄₀, Li_FourPVW₁₁O₄₀, R
bH₃PVW₁₁O₄₀, Rb₂H₂PVW₁₁O₄₀, Rb₃HPVW₁₁O₄₀, Rb_FourPVW₁₁
O₄₀, CsH₃PVW₁₁O₄₀, Cs₂H₂PVW₁₁O₄₀, Cs₃HPVW₁₁O₄₀, Cs_Four
PVW₁₁O₄₀, MgH₂PVW₁₁O40, Mg₂PVW₁₁O₄₀, CaH₂PVW₁₁O₄₀,
Ca₂PVW₁₁O₄₀, NaH₂PV₂W_TenO₄₀, Na₂H₃PV₂W_TenO₄₀, Na₃H₂P
V₂W_TenO₄₀, Na_FourHPV₂W_TenO₄₀, Na_FivePV2W_TenO₄₀, KH_FourPV₂W_TenO
₄₀, K₂H₃PV₂W_TenO₄₀, K₃H₂PV₂W_TenO₄₀, K_FourHPV₂W_TenO₄₀, K_Five
PV₂W_TenO₄₀, LiH_FourPV₂W_TenO₄₀, Li₂H₃PV₂W_TenO₄₀, Li₃H₂PV₂
W_TenO₄₀, Li_FourHPV₂W_TenO₄₀, Li_FivePV₂W_TenO₄₀, RbH_FourPV₂W
_TenO₄₀, Rb₂H₃PV₂W_TenO₄₀, Rb₃H₂PV₂W_TenO₄₀, Rb_FourHPV₂W_TenO
₄₀, Rb_FivePV₂W_TenO₄₀, CsH_FourPV₂W_TenO₄₀, Cs₂H₃PV₂W_TenO₄₀, C
s₃H₂PV₂W_TenO₄₀, Cs_FourHPV₂W_TenO₄₀, Cs_FivePV₂W_TenO₄₀, MgH₃PV
₂W_TenO₄₀, Mg₂HPV₃W_TenO₄₀, Mg_2.5PV₂W_TenO₄₀, CaH₃PVW_TenO
₄₀, Ca₂HPV₂W_TenO₄₀, Ca_2.5PV₂W_TenO₄₀, NaH_FivePV₃W₉O₄₀, N
a₂H_FourPV₃W₉O₄₀, Na₃H₃PV₃W₉O₄₀, Na_FourH₂PV₃W₉O₄₀, Na_FiveHPV
₃W₉O₄₀, Na₆PV₃W₉O₄₀, KH_FivePV₃W₉O₄₀, K₂H_FourPV₃W₉O₄₀, K₃
H₃PV₂W₉O₄₀, K_FourH₂PV₃W₉O₄₀, K_FiveHPV₃W₉O₄₀, K₆HPV₃W
₉O₄₀, LiH_FivePV₃W₉O₄₀, Li₂H_FourPV₃W₉O₄₀, Li₃H₃PV₃W₉O₄₀,
Li_FourH₂PV₃W₉O₄₀, Li_FiveHPV₃W₉O₄₀, Li₆PV₃W₉O₄₀, RbH_FivePV₃W
₉O₄₀, Rb₂H_FourPV₃W₉O₄₀, Rb₃H₃PV₃W₉O₄₀, Rb_FourH₂PV₃W
₉O₄₀, Rb_FiveHPV₃W₉O₄₀, Rb₆PV₃W₉O₄₀, CsH_FivePV₃W₉O₄₀, C
s₂H_FourPV₃W₉O₄₀, Cs₃H₃PV₃W₉O_{Four 0}, Cs_FourH₂PV₃W₉O₄₀, Cs_FiveHPV
₃W₉O₄₀, Cs₆PV₃W₉O₄₀, MgH_FourPV₃W₉O₄₀, Mg₂H₂PV₃W₉O₄₀,
Mg₃PV₃W₉O₄₀, CaH_FourPV₃W₉O₄₀, Ca₂H₂PV₃W₉O₄₀, Ca₃PV₃W₉
O₄₀, NaH₆PV_FourW₈O₄₀, Na₂H_FivePV_FourW₈O₄₀, Na₃H_FourPV_FourW₈O₄₀, N
a_FourH₃PV_FourW₈O₄₀, Na_FiveH₂PV_FourW₈O₄₀, Na₆HPV_FourW₈O₄₀, Na₇PV_FourW
₈O₄₀, KH₆PV_FourW₈O₄₀, K₂H_FivePV_FourW₈O₄₀, K₃H_FourPV_FourW₈O₄₀, K_FourH
₃PV_FourW₈O₄₀, K_FiveH₂PV_FourW₈O₄₀, K₆HPV_FourW₈O₄₀, K₇PV_FourW₈O₄₀,
LiH₆PV_FourW₈O₄₀, Li₂H_FivePV_FourW₈O₄₀, Li₃H_FourPV_FourW₈O₄₀, Li_FourH₃P
V_FourW₈O₄₀, Li_FiveH₂PV_FourW₈O₄₀, Li₆HPV_FourW₈O₄₀, Li₇PV_FourW
₈O₄₀, RbH₆PV_FourW₈O₄₀, Rb₂H_FivePV_FourW₈O₄₀, Rb₃H_FourPV_FourW₈O₄₀,
Rb_FourH₃PV_FourW₈O₄₀, Rb_FiveH₂PV_FourW₈O₄₀, Rb₆HPV_FourW₈O₄₀, Rb₇PV_Four
W₈O₄₀, CsH₆PV_FourW₈O₄₀, Cs₂H_FivePV_FourW₈O₄₀, Cs₃H_FourPV_FourW
₈O₄₀, Cs_FourH₃PV_FourW₈O₄₀, Cs_FiveH₂PV_FourW₈O₄₀, Cs₆HPV_FourW₈O₄₀,
Cs₇PV_FourW₈O₄₀, MgH_FivePV_FourW₈O₄₀, Mg₂H₃PV_FourW₈O₄₀, Mg₃HPV_FourW
₈O₄₀, Mg_3.5PV_FourW₈O₄₀, CaH_FivePV_FourW₈O₄₀, Ca₂H₃PV_FourW₈O_{Four 0},
Ca₃HPV_FourW₈O₄₀, Cs_3.5PV_FourW₈O₄₀, NaH₇PV_FiveW₇O₄₀, Na₂H₆PV
_FiveW₇O₄₀, Na₃H_FivePV_FiveW₇O ₄₀, Na_FourH_FourPV_FiveW₇O₄₀, Na_FiveH₃PV_FiveW₇O
₄₀, Na₆H₂PV_FiveW₇O₄₀, Na₇HPV_FiveW₇O₄₀, Na₈PV_FiveW₇O ₄₀, KH₇P
V_FiveW₇O₄₀, K₂H₆PV_FiveW₇O₄₀, K₃H_FivePV_FiveW₇O₄₀, K_FourH_FourPV_FiveW
₇O₄₀, K_FiveH₃PV_FiveW₇O₄₀, K₆H₂PV_FiveW₇O₄₀, K₇HPV_FiveW₇O₄₀, K₈P
V_FiveW₇O₄₀, LiH₇PV_FiveW₇O₄₀, Li₂H₆PV_FiveW₇O₄₀, Li₃H_FivePV_FiveW₇O
₄₀, Li_FourH_FourPV_FiveW₇O₄₀, Li_FiveH₃PV_FiveW₇O₄₀, Li₆H₂PV_FiveW₇O₄₀, L
i₇HPV_FiveW₇O₄₀, Li₈PV_FiveW₇O₄₀, RbH₇PV_FiveW₇O₄₀, Rb₂H₆PV_FiveW₇
O₄₀, Rb₃H_FivePV_FiveW₇O₄₀, Rb_FourH_FourPV_FiveW₇O₄₀, Rb_FiveH₃PV_FiveW₇O₄₀,
Rb₆H₂PV_FiveW₇O₄₀, Rb₇HPV_FiveW₇O₄₀, Rb₈PV_FiveW₇O₄₀, CsH₇PV_FiveW
₇O₄₀, Cs₂H₆PV_FiveW₇O₄₀, Cs₃H_FivePV_FiveW₇O₄₀, Cs_FourH_FourPV_FiveW
₇O₄₀, Cs_FiveH₃PV_FiveW₇O₄₀, Cs₆H₂PV_FiveW₇O₄₀, Cs₇HPV_FiveW₇O₄₀,
Cs₈PV_FiveW₇O₄₀, MgH₆PV_FiveW₇O₄₀, Mg₂H_FourPV_FiveW₇O₄₀, Mg₃H₂PV_Five
W₇O₄₀, Mg_FourPV_FiveW₇O₄₀, CaH₆PV_FiveW₇O₄₀, Ca₂H_FourPV_FiveW₇O₄₀, C
a₃H₂PV_FiveW₇O₄₀, Ca_FourPV_FiveW₇O₄₀ Etc.

When the present invention is carried out in the liquid phase, the reaction solution is usually used in the range of PH7 or less, preferably PH5 or less. However, the present invention is not necessarily limited to these ranges.

In carrying out the present invention, polyhydroxyaromatic compounds, their dehydrogenated compounds and acids (the compounds and acids are hereinafter abbreviated as catalyst) and inert to aromatic compounds in the reaction system. It is also possible to add a solvent or gas and dilute it. Specifically, methane, ethane, propane, butane,
Aliphatic saturated hydrocarbons such as hexane and cyclohexane,
Inert gases such as nitrogen, argon and helium are exemplified.

The reaction temperature is not particularly limited, but is preferably 0 ° to 400 ° C, more preferably 10 ° to 300 ° C.
Is the range. If the reaction temperature is extremely low, the conversion rate of the aromatic compound is low, in other words, the reaction rate is extremely low, and the productivity of the reaction product is low. On the other hand, if the reaction temperature is 400 ° C. or higher, undesirable side reactions and the like progress and increase in by-products, aromatic compounds as raw materials,
Further, the stability of the aromatic hydroxy compound as a product is not preferable, and the selectivity of the reaction is lowered, which is not economical.

The reaction can be carried out under any of reduced pressure, increased pressure and normal pressure. From the viewpoint of reaction efficiency (reaction efficiency per unit volume), it is not preferable to carry out at a too low pressure. In addition, it is not preferable to carry out the reaction at an excessively high pressure from the viewpoint of the economical efficiency of the equipment such as a reactor.
Usually the preferred operating pressure range is 0.05-300 kg / cm ² G
And more preferably 0.5 to 200 kg / cm ² G. However, the invention is not limited to only these pressure ranges.

The reaction can be carried out in any of a liquid phase, a gas-liquid phase and a gas phase. Furthermore, the catalyst can be used in either a uniform or non-uniform form. These catalysts can be used in any of a solution state, a two-layer separated state, a two-layer mixed layer state, a slurry state, a fixed bed, a moving bed, a fluidized bed and the like.

The present invention can be carried out in any reaction method of a normal batch reaction, a semi-batch reaction in which a part of raw materials or a catalyst is continuously supplied, or a continuous flow reaction. In addition, the addition order and addition method of each component such as the aromatic compound, the oxidizing agent, and the catalyst are not particularly limited.

Furthermore, it is also possible to carry out in a semi-batch form, such as adding an oxidizing agent such as oxygen continuously or sequentially or intermittently over several steps depending on the consumption thereof. The yield of aromatic hydroxy compound is improved.

The reaction time (residence time or catalyst contact time in flow reaction) is not particularly limited, but is usually 0.
It is 1 second to 30 hours, preferably 0.5 seconds to 15 hours. After the reaction, if necessary, the reaction product can be separated and recovered from the catalyst or the like by a method such as filtration separation, extraction, and distillation. The aromatic hydroxy compound which is the target product is a sequential treatment method such as solvent extraction, distillation, alkali treatment, acid treatment or the like from the separated and recovered material, or a usual separation or purification method such as an operation in which these are appropriately combined. Can be separated, purified, and obtained. Further, the unreacted raw material can be recovered and recycled to the reaction system for use.

In the case of a batch reaction, the catalyst recovered by separating the reaction product after the reaction can be used as it is, or after regenerating a part or all thereof, it can be repeatedly used as a catalyst in the reaction again. When the reaction is carried out in a fixed-bed or fluidized-bed continuous reaction system, the catalyst partially or wholly inactivated or reduced in activity by subjecting it to the reaction can be regenerated after interruption of the reaction and then used in the reaction. Then
In addition, a part of the catalyst is continuously or intermittently withdrawn,
After regeneration, it can be recycled to the reactor and reused. Further, fresh catalyst can be continuously or intermittently fed to the reactor. When the reaction is carried out in a moving bed flow continuous reaction or a homogeneous catalyst flow reaction system, the catalyst can be separated, regenerated and reused as in the batch reaction.

[0024]

EXAMPLES The present invention will be described in more detail below with reference to examples. However, the invention is not limited to only these examples. In addition, the yield of the hydroxy compound which is the product described in each of the examples and the table was based on the aromatic compound which was the raw material for the charging.

Example 1 Benzene was added to 50 ml of Hastelloy C autoclave.
After charging 15.0 g, water 10.0 g, hydroquinone, 0.22 g,
The inside of this autoclave was replaced with a mixed gas of oxygen 9% and nitrogen 91%, and then pressure was further increased to 110 kg / cm ² G. Reaction temperature 150 ℃
After reacting for 1.0 hour with stirring, the reaction liquid was cooled and analyzed by gas chromatography. As a result, it was confirmed that phenol was produced in a yield of 1.7% based on the charged benzene.

Example 2 In the method carried out in Example 1, H ₇ PV ₄ M was added to the reaction solution.
o ₈ O ₄₀ · 30H ₂ O, all under the same conditions and methods as in Example 1 except that 0.42 g was added. As a result, the phenol yield was 4.2%.

Example 3 The reaction and analysis were carried out under the same conditions and methods as in Example 2 except that the heteropolyacid was replaced by H ₆ PV ₃ Mo ₉ O ₄₀ · 30H ₂ O, 0.43 g. As a result, the yield of phenol was 4.3%.

Comparative Example 1 The reaction and analysis were carried out under the same conditions as in Example 3 except that hydroquinone was not added by the method carried out in Example 3. As a result, the yield of phenol was 1.5%.

Example 4 The reaction and analysis were carried out under the same conditions as in Example 2 except that the heteropolyacid was replaced by H ₅ PV ₂ Mo ₁₀ O ₄₀ · 30H ₂ O, 0.44 g. As a result, the yield of phenol was 3.8%.

Example 5 The reaction and analysis were carried out under the same conditions as in Example 2 except that the heteropolyacid was replaced by H ₄ PVMo ₁₁ O ₄₀ .30H ₂ 0, 0.45 g.
The result was a phenol yield of 3.1%.

Example 6 The reaction and analysis were carried out under the same conditions as in Example 2 except that the heteropolyacid was replaced with H ₅ PV ₂ W ₁₀ O ₄₀ · 30H ₂ O (0.61 g). As a result, the yield of phenol was 3.0%.

Example 7 The reaction and analysis were carried out under the same conditions as in Example 2, except that H ₇ PV ₄ W ₈ O ₄₀ · 29H ₂ O (0.55 g) was used in place of the heteropolyacid. As a result, the yield of phenol was 3.5%.

Example 8 The reaction and analysis were carried out under the same conditions as in Example 2 except that the heteropolyacid was Na ₃ H ₃ PV ₃ Mo ₉ O ₄₀ · 29H ₂ O, 0.42 g. As a result, the yield of phenol was 3.6%.

Example 9 The reaction and analysis were carried out under the same conditions as in Example 1 except that 10.0 g of 0.1N sulfuric acid was used in place of water in the method carried out in Example 1. As a result, the yield of phenol is 2.
It was 7%.

Example 10 The procedure of Example 1 was repeated except that 0.1N phosphoric acid 1 was used instead of water.
The reaction and analysis were carried out under the same conditions as in Example 1 except that 0.0 g was used. As a result, the yield of phenol was 2.8%.

Example 11 The procedure of Example 3 was repeated except that m was used instead of hydroquinone.
The reaction and analysis were carried out under the same conditions as in Example 3, except that 0.25 g of dihydroxybenzene was used. As a result,
The yield of phenol was 3.3%.

Example 12 The reaction and analysis were carried out in the same manner as in Example 3 except that 0.46 g of bisphenol A was used instead of hydroquinone in the method carried out in Example 3. As a result, the yield of phenol was 3.3%.

Example 13 Instead of hydroquinone in the method carried out in Example 3, 1,
The reaction and analysis were carried out under the same conditions as in Example 3, except that 0.25 g of 3,5-trihydroxybenzene was used. As a result, the yield of phenol was 3.7%.

Example 14 The reaction and analysis were carried out in the same manner as in Example 3 except that 0.32 g of 1,4-dihydroxynaphthalene was used instead of hydroquinone in the method carried out in Example 3. As a result, the yield of phenol was 3.2%.

Example 15 The procedure of Example 3 was repeated except that 0.42 g of anthrahydroquinone was used in place of hydroquinone.
Reaction and analysis were performed under the same conditions as above. As a result, the yield of phenol was 3.7%.

Example 16 The procedure of Example 3 was repeated except that hydroquinone was replaced by p
Reaction and analysis were carried out under the same conditions as in Example 3, except that 0.22 g of benzoquinone was used. As a result, the yield of phenol was 3.6%.

Example 17 In the same manner as in Example 3, instead of hydroquinone, 1,
The reaction and analysis were carried out under the same conditions as in Example 3 except that 0.32 g of 4-naphthoquinone was used. As a result, the yield of phenol was 3.1%.

Example 18 Instead of hydroquinone in the method carried out in Example 3, 9,
The reaction and analysis were carried out under the same conditions as in Example 3, except that 0.42 g of 10-anthraquinone was used. As a result, the yield of phenol was 3.5%.

Examples 19 to 21 The results of the same procedures and methods as in Example 3 were carried out except that the reaction temperatures were changed to 110 °, 130 ° and 170 ° C., respectively. Listed in Table 1. The results of Example 3 are also shown.

[0045]

[Table 1] Table 1 ──────────────────────────────────── Reaction temperature (℃) Phenol yield (%) ──────────────────────────────────── Example 19 110 1.2 Example 20 130 3.0 Example 3 150 4.3 Example 21 170 3.6 ────────────────────────────────── ───

Examples 22 to 26 In Example 3, instead of benzene, toluene, naphthalene, β-naphthol, anisole and p- were used.
The reaction and analysis were carried out under the same conditions and methods as in Example 3, except that the amount of each xylene was changed to 15.0 g. Result is,
As shown in Table 2, the production of aromatic hydroxy compounds was observed in good yield. The aromatic dihydroxy compound in the product is shown as the total of all isomers.

[0047]

[Table 2] Table 2 ──────────────────────────────────── Aromatic compound Yield (%) Hydroxy Compound Dihydroxy Compound ──────────────────────────────────── Example 22 Toluene 2.5 0.1 Example 23 Naphthalene 1.8 0.1 Example 24 β-naphthol (raw material) 0.2 Example 25 Anisole 1.5 Trace amount Example 26 p-xylene 2.7 Trace amount ─────────── ──────────────────────────

Example 27 Instead of hydroquinone, 0.25 g of methylhydroquinone (2 mmo
Reaction and analysis were conducted under the same conditions as in Example 3 except that l) was used. As a result, the yield of phenol is 4.5%
Met.

Example 28 0.34 g of t-butylhydroquinone instead of hydroquinone
Reaction and analysis were conducted under the same conditions as in Example 3 except that (2 mmol) was used. As a result, the yield of phenol was 3.8%.

Example 29 The reaction and analysis were carried out under the same conditions as in Example 3 except that 0.45 g (2 mmol) of 2,5-di-t-butylhydroquinone was used instead of hydroquinone. As a result, the yield of phenol was 4.0%.

Example 30 0.28 g (2 m of methoxyhydroquinone instead of hydroquinone
The reaction and analysis were carried out under the same conditions as in Example 3 except that (mol) was used. As a result, the yield of phenol is 4.1.
%Met.

Example 31 2,4 dihydroxytoluene in place of hydroquinone
Reaction and analysis were carried out under the same conditions as in Example 3, except that 25 g (2 mmol) was used. As a result, the yield of phenol was 3.9%.

Example 32 3,4 dihydroxybenzoic acid in place of hydroquinone
Reaction and analysis were carried out under the same conditions as in Example 3, except that 31 g (2 mmol) was used. As a result, the yield of phenol was 3.8%.

Example 33 The reaction and analysis were carried out under the same conditions as in Example 3 except that 0.34 g (2 mmol) of 2,4,6-trihydroxybenzoic acid was used instead of hydroquinone. As a result, the yield of phenol was 4.2%.

Example 34 All Example 3 except that 0.34 g (2 mmol) of 4,4'-dihydroxydiphenyl ether was used instead of hydroquinone.
Reaction and analysis were performed under the same conditions as above. As a result, the yield of phenol was 3.9%.

[0056]

According to the present invention, the following effects can be obtained. (1) Phenol can be produced with high selectivity by directly oxidizing benzene. (2) Phenol can be directly oxidized and produced under mild conditions of low temperature and low pressure as compared with the conventional method. In addition, it can be carried out under the condition that the reactor or the like is hardly corroded. (3) In terms of safety, process, and phenol, which are industrially important,
It is possible to produce a significant economic advantage. As described above, the present invention can provide a novel industrially excellent method for producing phenol.

Claims (9)

[Claims] 1. A process for producing an aromatic hydroxy compound, which comprises reacting an aromatic compound with an oxidizing agent in the presence of at least one selected from the group consisting of polyhydroxy aromatic compounds and dehydrogenated compounds thereof. Method. 2. The method according to claim 1, wherein the polyhydroxy aromatic compound is an aromatic dihydroxy compound. 3. The method according to claim 1, wherein the polyhydroxy aromatic compound is a hydroquinone and the dehydrogenated compound thereof is a quinone. 4. The method according to claim 1, 2 or 3, wherein the oxidant is a substance capable of supplying an oxygen molecule, an oxygen atom, an oxygen ion or an oxygen radical. 5. The method according to claim 1, 2 or 3, wherein the oxidant is oxygen gas, oxygen gas diluted with an inert gas, or air. 6. The method according to claim 1, 2 or 3, wherein the reaction is carried out in the presence of water. 7. The method according to claim 1, 2 or 3, wherein the reaction is carried out in the presence of an acid. 8. The method according to claim 7, wherein the acid is a heteropoly acid. 9. The method according to claim 1, 2 or 3, wherein the oxidizing agent is continuously or intermittently inserted.