JP2003034662A - Method for distilling oxystyrene derivative - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a new method for distilling an oxystyrene derivative that is free from a weak point of a conventional method. SOLUTION: The method for distilling the oxystyrene derivative shown by general formula (I) (wherein, R is an alkyl group, haloalkyl group, aryl group, particularly phenyl group, aralkyl group, particularly benzyl group, alkoxyalkyl group, alkanoyl group, alkoxycarbonyl group, aralkyloxycarbonyl group or alkylsilil group) is characterized by adding 1,2,3-triphenol or its derivative as a polymerization inhibitor to the oxystyrene derivative shown by general formula (I) and distilling the oxystyrene derivative in the presence of this polymerization inhibitor. By this method, a viscous polymer-like material is prevented from forming during a distillation step as well as the oxystyrene derivative distillate is recovered in high yield.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a method for distilling an oxystyrene derivative useful as a raw material for medicines and agricultural chemicals, functional polymers, polymer synthesis, etc. after the synthesis in the presence of a polymerization inhibitor for the purpose of purification. It is a thing.

[0002]

2. Description of the Related Art Among oxystyrene derivatives, for example, p
-Tert-Butoxystyrene (hereinafter abbreviated as "PTBST").
"PTBST" is a registered trademark of the applicant. ) Is known to be extremely useful as a resist raw material used in VLSI applications and the like (JP-A-59-199705 and JP-A-3-2).
77608), and m-tert-butoxystyrene (hereinafter abbreviated as “MTBST”) are known to be useful as intermediate raw materials for functional polymers, pharmaceuticals and agricultural chemicals (Japanese Patent Laid-Open No. Hei 10 (1999) -242242). 2-160739).

As a method for synthesizing an oxystyrene derivative,
The following methods are known. For example, PTBST and MTB
A tert-butoxystyrene such as ST is prepared by preparing a Grignard reagent from halogen-substituted styrene such as chlorostyrene, bromostyrene, and iodostyrene, and magnesium, and then reacting it with perbenzoic acid tert-butyl ester ( JP-A-59-199705) is known. Also, tert-butoxyphenyl chloride, tert-butoxyphenyl bromide, tert-butoxyphenyl halide such as tert-butoxyphenyl iodide and a Grignard reagent from magnesium, and then vinyl halide such as vinyl chloride and vinyl bromide. A method of synthesizing by coupling (Japanese Patent Publication No. 4-71896, Japanese Patent Laid-Open No. 160739/1990) is known.

In the method of synthesizing the oxystyrene derivative as described above, the synthesized target compound is usually separated and purified by distillation. However, since the oxystyrene derivative is generally polymerized by light or heat to form a highly viscous liquid polymeric substance, the product recovery rate during distillation may be significantly reduced. Furthermore, due to the produced polymeric substance, in the distillation column, in the distillation can, in the pipe, etc.,
Blockage of the distillation column or piping, abnormal pressure reduction inside the distillation column due to the above, difficulty in cleaning due to adhesion of polymeric substances,
It may cause troubles such as. Therefore, in order to avoid these troubles, it has been customary to add various polymerization inhibitors to the oxystyrene derivative and carry out the distillation operation in the presence of the polymerization inhibitor. As the method, for example, tert such as PTBST or MTBST
-In the distillation of butoxystyrene, a method of performing distillation in the presence of 4-tert-butylcatechol as a polymerization inhibitor (Japanese Patent Publication No. 4-71896, JP-A No. 2-160739).
Alternatively, a method of carrying out distillation in the presence of N-nitrosophenylhydroxylamine aluminum salt, N-nitrosophenylhydroxylamine ammonium salt, 2,4-dinitrophenol or the like as a polymerization inhibitor (JP 2000-327617 A).
Japanese patent publication).

However, the above-mentioned conventionally used polymerization inhibitors do not exhibit a sufficient inhibitory effect on the formation of a polymeric substance under the harsh conditions of long time and high temperature in the distillation step of the oxystyrene derivative, so that they are high in activity. As a viscous polymeric substance is formed, the distillation column or distillation can, etc. is clogged with the distillation column or piping as described above, abnormal decompression degree in the distillation column due to the above, adhesion of the polymeric substance It often causes troubles such as difficulty of cleaning. In addition, even if such trouble does not occur,
There is always the problem of reduced product yield after distillation. For these reasons, the conventional distillation methods for oxystyrene derivatives have not been satisfactory.

[0006]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a new distillation method for oxystyrene derivatives which can overcome the drawbacks of the conventional methods. In other words, there is almost no formation of a polymeric substance that occurs in the conventional method, and PTBS has a high product recovery rate even after a long distillation operation.
An object of the present invention is to provide a novel distillation method capable of purifying oxystyrene derivatives such as T and MTBST by distillation.

[0007]

[Means for Solving the Problems] The present inventors have conducted extensive studies and studied in order to solve the conventional problems. As a result, in the distillation step after synthesizing the oxystyrene derivative represented by the general formula (I) described below, 1,2,3-triphenol of the general formula (II) described below or a derivative thereof was used as a polymerization inhibitor. It was found that by adding and distilling in the presence thereof, the oxystyrene derivative of the general formula (I) can be distilled with a high recovery rate without generating a polymeric substance. The present invention has been completed based on this finding.

Therefore, in the present invention, 1,2,3-triphenol or a derivative thereof is used as a polymerization inhibitor and represented by the following general formula (I): (In the formula, R is an alkyl group, a haloalkyl group, an aryl group, especially a phenyl group, an aralkyl group, especially a benzyl group,
An alkoxyalkyl group, an alkanoyl group, an alkoxycarbonyl group, an aralkyloxycarbonyl group, or an alkylsilyl group) is added to the oxystyrene derivative, and the oxystyrene derivative is distilled in the presence of the polymerization inhibitor. Characterized by the general formula (I)
A method for distilling an oxystyrene derivative of the above is provided.

The method of the present invention will be described in detail below. The oxystyrene derivative distilled in the method of the present invention is a known compound and can be synthesized by a known synthesis method (for example, the method of Japanese Patent Publication No. 4-71896).

Specific examples of the oxystyrene derivative of the general formula (I) to be distilled in the method of the present invention include:
For example: That is, p-methoxystyrene, p-ethoxystyrene, p-n-propoxystyrene, p-iso-propoxystyrene, p-n-butoxystyrene, p-iso-butoxystyrene, p-sec-butoxystyrene, p-tert. -Butoxystyrene, pn-amyloxystyrene, p-iso-amyloxystyrene, p
-Sec-amyloxystyrene, p-tert-amyloxystyrene, p-cyclopropyloxystyrene, p-cyclopropylmethyloxystyrene, p-cyclobutyloxystyrene, p-cyclopentyloxystyrene, p-
Cyclohexyloxystyrene, p-trifluoromethoxystyrene, p-pentafluoroethoxystyrene, p
-Chloromethoxystyrene, p- (2-chloroethoxy) styrene, p-bromomethoxystyrene, p- (2-bromoethoxy) styrene, p-phenyloxystyrene, p- (4
-Methylphenyloxy) styrene, p- (4-fluorophenyloxy) styrene, p- (4-chlorophenyloxy) styrene, p- (4-bromophenyloxy) styrene, p- (4-methoxyphenyloxy) styrene, p− (4
-Ethoxyphenyloxy) styrene, p- (4-tert-butoxyphenyloxy) styrene, p- (4-nitrophenyloxy) styrene, p-benzyloxystyrene, p-
(4-methylbenzyloxy) styrene, p-methoxymethoxystyrene, p- (1-ethoxyethoxy) styrene, p
-(2-Tetrahydropyranyloxy) styrene, p-acetoxystyrene, p- (tert-butylcarbonyloxy)
Styrene, p-benzyloxycarbonyloxystyrene, p-methoxycarbonyloxystyrene, p- (tert
-Butoxycarbonyloxy) styrene, p-trimethylsilyloxystyrene, p- (tert-butyldimethylsilyloxy) styrene and the like. Further, instead of the oxystyrene derivative of the general formula (I) having a para-substituted phenyl group, an oxystyrene derivative having a corresponding meta-substituted phenyl group can be used.

The 1,2,3-triphenol or its derivative used as a polymerization inhibitor in the method of the present invention is
The following general formula (II) (In the formula, R ¹ , R ² and R ³ are each independently a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkynyl group, a substituted or unsubstituted aryl Groups, especially phenyl groups,
A substituted or unsubstituted aralkyl group, especially a benzyl group, a substituted or unsubstituted alkanoyl group, especially an acetyl group, a substituted or unsubstituted aroyl group, especially a benzoyl group, a cyano group,
It represents a carboxyl group, an alkoxycarbonyl group, a substituted or unsubstituted carbamoyl group, a nitro group, or a substituted or unsubstituted amino group, and R ⁴ , R ⁵ , and R ⁶ are each independently a hydrogen atom, a substituted or unsubstituted alkyl group. Group, substituted or unsubstituted alkenyl group, substituted or unsubstituted alkynyl group, substituted or unsubstituted aryl group, especially phenyl group, substituted or unsubstituted aralkyl group, especially benzyl group,
A substituted or unsubstituted alkanoyl group, especially an acetyl group, a substituted or unsubstituted aroyl group, especially a benzoyl group, a substituted or unsubstituted alkylsulfonyl group, a substituted or unsubstituted arylsulfonyl group, or a substituted or unsubstituted carbamoyl group, and also R ¹ and R ² , R ² and R ³ , R ³ and R ⁴ ,
R ⁴ and R ⁵ , R ⁵ and R ⁶ , or R ⁶ and R ¹ may be bonded to each other to form a substituted or unsubstituted carbocyclic group having a cyclic structure. The carbon atom constituting the ring group may be replaced by an oxygen, sulfur or nitrogen atom, and a double bond may be present in the carbon ring group), which is a pyrogallol or a pyrogallol derivative. be able to.

The 1,2,3-tris of the general formula (II) are
Among phenol and its derivatives, the following general formula
(IIa) (In the formula, R¹, R^Two, R^ThreeAre independent hydrogen
Child, halogen atom, alkyl group, alkenyl group, alk
Nyl group, haloalkyl group, haloalkenyl group, haloal
Quinyl group, hydroxyalkyl group, alkoxyalkyl
Groups, haloalkoxyalkyl groups, aryl groups, especially
Nyl group, aralkyl group, especially benzyl group, alkanoyl
Groups, especially acetyl groups, aroyl groups, especially benzoyl groups,
Aryloxyalkyl group, aralkyloxyalkyl
Group, aroyloxyalkyl group, alkanoyloxya
Alkyl group, cyano group, carboxyl group, alkoxycal
Bonyl group, carboxyalkyl group, alkoxy carbonyl group
Represents an alkyl group or a carbamoyl group, R^Four,
R⁵, R⁶Are each independently a hydrogen atom, an alkyl group,
Alkenyl group, alkynyl group, substituted or unsubstituted aryl
Groups, especially phenyl groups, substituted or unsubstituted aralkyl
Groups, especially benzyl groups, alkanoyl groups, especially acetyl
Groups, substituted or unsubstituted aroyl groups, especially benzoyl groups,
Alkylsulfonyl group, substituted or unsubstituted arylsulfo
Indicates a nyl group or a substituted or unsubstituted carbamoyl group.
Then R¹And R^Two, R^TwoAnd R^Three, R^ThreeAnd R^Four, R^FourAnd R⁵, R
⁵And R⁶, Or R ⁶And R¹Are bound together and replaced
Or a carbocyclic group having an unsubstituted cyclic structure may be constituted.
The carbon atom that constitutes the carbocyclic group of the cyclic structure is an acid
May replace atoms of elemental, sulfur or nitrogen,
A double bond may be present in the carbocyclic group)
More preferred are pyrogallol or pyrogallol derivatives
I found something wrong.

The 1,2,3-triphenol or its derivative is a known compound, which may be a substance produced by a known method (for example, Japanese Patent Laid-Open No. 52-068135), or may be commercially available. Goods may be used.

DETAILED DESCRIPTION OF THE INVENTION The method of the present invention is carried out as follows. That is, immediately after the oxystyrene derivative of general formula (I) to be distilled is produced, the polymerization inhibitor 1,2,3-triphenol or its derivative is added thereto. After this, a distillation operation may be performed.

Specific examples of the 1,2,3-triphenol of the general formula (II) or (IIa) or its derivative used as a polymerization inhibitor in the method of the present invention include the following. To be Ie pyrogallol and 4
-Fluoropyrogallol, 4-chloropyrogallol, 4-
Bromopyrogallol, 4-iodopyrogallol, 4-methylpyrogallol, 4-ethylpyrogallol, 4-n-propylpyrogallol, 4-iso-propylpyrogallol, 4
-N-butylpyrogallol, 4-iso-butylpyrogallol, 4-sec-butylpyrogallol, 4-tert-butylpyrogallol, 4-cyclopentylpyrogallol, 4-cyclohexylpyrogallol, 4-vinylpyrogallol, 4-
Allylpyrogallol, 4- (2-propynyl) pyrogallol, 4-trifluoromethylpyrogallol, 4-chloromethylpyrogallol, 4-bromomethylpyrogallol, 4-
Iodomethylpyrogallol, 4- (1-chloroethyl) pyrogallol, 4- (2-chloroethyl) pyrogallol, 4-
(1-bromoethyl) pyrogallol, 4- (2-bromoethyl) pyrogallol, 4-glycidylmethylpyrogallol,
4-hydroxymethylpyrogallol, 4- (2-hydroxyethyl) pyrogallol, 4- (1-hydroxyethyl) pyrogallol, 4-methoxymethylpyrogallol, 4- (2-methoxyethyl) pyrogallol, 4-ethoxymethylpyrogallol, 4- Chloromethoxymethylpyrogallol, 4-phenylpyrogallol, 4- (p-tolyl) pyrogallol, 4
-(M-tolyl) pyrogallol, 4- (o-tolyl) pyrogallol, 4- (p-chlorophenyl) pyrogallol, 4- (m-
(Chlorophenyl) pyrogallol, 4- (o-chlorophenyl) pyrogallol, 4- (p-nitrophenyl) pyrogallol, 4- (m-nitrophenyl) pyrogallol, 4- (o-nitrophenyl) pyrogallol, 4- (2-pyridyl) Pyrogallol, 4- (3-pyridyl) pyrogallol, 4- (4-pyridyl) pyrogallol, 4-benzylpyrogallol, 4- (p
-Chlorobenzyl) pyrogallol, 4- (m-chlorobenzyl) pyrogallol, 4- (o-chlorobenzyl) pyrogallol, 4- (p-methylbenzyl) pyrogallol, 4- (m-methylbenzyl) pyrogallol, 4- (o -Methylbenzyl)
Pyrogallol, 4- (p-hydroxybenzyl) pyrogallol, 4- (m-hydroxybenzyl) pyrogallol, 4- (o
-Hydroxybenzyl) pyrogallol, 4- (2,3-dihydroxybenzyl) pyrogallol, 4- (2,4-dihydroxybenzyl) pyrogallol, 4- (2,5-dihydroxybenzyl) pyrogallol, 4- (2,6-dihydroxy Benzyl) pyrogallol, 4- (3,4-dihydroxybenzyl) pyrogallol, 4- (3,5-dihydroxybenzyl) pyrogallol,
4- (2,3,4-trihydroxybenzyl) pyrogallol, 4
-(3,4,5-Trihydroxybenzyl) pyrogallol, 4-
(2,3,5-trihydroxybenzyl) pyrogallol, 4-
(2,3,6-trihydroxybenzyl) pyrogallol, 4-
(2,4,5-Trihydroxybenzyl) pyrogallol, 4-
(2,4,6-trihydroxybenzyl) pyrogallol, 4- (p
-Nitrobenzyl) pyrogallol, 4- (m-nitrobenzyl) pyrogallol, 4- (o-nitrobenzyl) pyrogallol, 4- (2-pyridylmethyl) pyrogallol, 4- (3-pyridylmethyl) pyrogallol, 4- (4 -Pyridylmethyl)
Pyrogallol, 4-formylpyrogallol, 4-acetylpyrogallol, 4-propionylpyrogallol, 4-benzoylpyrogallol, 4- (p-chlorobenzoyl) pyrogallol, 4- (m-chlorobenzoyl) pyrogallol, 4-
(o-chlorobenzoyl) pyrogallol, 4- (p-methylbenzoyl) pyrogallol, 4- (m-methylbenzoyl) pyrogallol, 4- (o-methylbenzoyl) pyrogallol,
4- (2,3-dihydroxybenzoyl) pyrogallol, 4-
(2,4-dihydroxybenzoyl) pyrogallol, 4- (2,5
-Dihydroxybenzoyl) pyrogallol, 4- (2,6-dihydroxybenzoyl) pyrogallol, 4- (3,4-dihydroxybenzoyl) pyrogallol, 4- (3,5-dihydroxybenzoyl) pyrogallol, 4- (2,3,4 -Trihydroxybenzoyl) pyrogallol, 4- (3,4,5-trihydroxybenzoyl) pyrogallol, 4- (2,3,5-trihydroxybenzoyl) pyrogallol, 4- (2,3,6-trihydroxybenzoyl) Pyrogallol, 4- (2,4,5-trihydroxybenzoyl) pyrogallol, 4- (2,4,6-trihydroxybenzoyl) pyrogallol, 4- (p-nitrobenzoyl) pyrogallol, 4- (m-nitrobenzoyl) Pyrogallol, 4- (o-nitrobenzoyl) pyrogallol, 4-phenoxymethylpyrogallol, 4-benzyloxymethylpyrogallol, 4-benzoyloxymethylpyrogallol , 4-acetyloxymethylpyrogallol, 4-cyanopyrogallol, 4-nitropyrogallol, 4-carboxypyrogallol (i.e. gallic acid), 4-methoxycarbonylpyrogallol, 4-ethoxycarbonylpyrogallol, 4- (iso-amyloxycarbonyl) ) Pyrogallol, 4- (n-butoxycarbonyl) pyrogallol (i.e. gallic acid n-butyl ester), 4- (iso-butyloxycarbonyl) pyrogallol, 4- (n-hexadecyloxycarbonyl) pyrogallol, 4- (n- Dodecyloxycarbonyl) pyrogallol, 4- (n-octyloxycarbonyl) pyrogallol, 4- (n-propyloxycarbonyl) pyrogallol, 4-stearyloxycarbonylpyrogallol, 4-carboxymethylpyrogallol, 4-methoxycarbonylmethylpyrogallol, 4- Mosquito Ba moil pyrogallol, 4-dimethylaminocarbonyl pyrogallol, there is pyrogallol derivatives such as like. Substituents on the pyrogallol derivative include not only the above 4-position substituents on the benzene nucleus but also 5-position substituents, 4,5-di-substituted products, 4,6-di-substituted products and 4,5,6-tri-substituted products. It may be in the eggplant position,
In the case of a di-substituted product or a tri-substituted product, the substituting two or three functional groups may be the same or different.

Further, 1, of the general formula (II) or (IIa)
Examples of 2,3-triphenol or its derivatives also include the following. That is, 1,2,3-trimethoxybenzene, 1,2,3-triallyloxybenzene, 1,2,3-tris (2-propynyloxy) benzene, 1,2,3-tricyclohexyloxybenzene, 1 1,2,3-triacetoxybenzene, 1,2,3-triphenoxybenzene, 1,2,3-tris (4-chlorophenoxy) benzene, 1,2,3-tris (3
-Chlorophenoxy) benzene, 1,2,3-tris (2-chlorophenoxy) benzene, 1,2,3-tris (4-tolyloxy) benzene, 1,2,3-tris (3-tolyloxy) benzene, 1 , 2,3-Tris (2-tolyloxy) benzene, 1,2,3
-Tris (4-hydroxyphenoxy) benzene, 1,2,3-
Tris (3-hydroxyphenoxy) benzene, 1,2,3-tris (2-hydroxyphenoxy) benzene, 1,2,3-tris (4-methoxyphenoxy) benzene, 1,2,3-tris (3
-Methoxyphenoxy) benzene, 1,2,3-tris (2-methoxyphenoxy) benzene, 1,2,3-tribenzyloxybenzene, 1,2,3-tris (4-methylbenzyloxy)
Benzene, 1,2,3-tris (3-methylbenzyloxy) benzene, 1,2,3-tris (2-methylbenzyloxy) benzene, 1,2,3-tris (4-chlorobenzyloxy) benzene, 1,2,3-Tris (3-chlorobenzyloxy) benzene, 1,2,3-tris (2-chlorobenzyloxy) benzene, 1,2,3-tris (4-hydroxybenzyloxy) benzene, 1, 2,3-Tris (3-hydroxybenzyloxy) benzene, 1,2,3-Tris (2-hydroxybenzyloxy)
Benzene, 1,2,3-tris (4-nitrobenzyloxy) benzene, 1,2,3-tris (3-nitrobenzyloxy) benzene, 1,2,3-tris (2-nitrobenzyloxy) benzene Included.

Further, the 1,2,3-triphenol of the general formula (II) or its derivative used as the polymerization inhibitor in the present invention includes the catechol derivative or the resorcinol derivative of the specific examples shown below or 2, Also included are 3-disubstituted hydroxyphenols or 2,6-disubstituted hydroxyphenols or 1,2,3-tribenzoyloxybenzene or other benzene derivatives.

That is, 1,2,3-triphenol or its derivative as a polymerization inhibitor includes 3-
Methoxycatechol, 3-allyloxycatechol, 3-
(2-propynyloxy) catechol, 3-cyclohexyloxycatechol, 3-acetoxycatechol, 3-phenoxycatechol, 3- (4-chlorophenoxy) catechol, 3- (3-chlorophenoxy) catechol, 3- (2-chloro) Phenoxy) catechol, 3- (4-tolyloxy) catechol, 3- (3-tolyloxy) catechol, 3- (2-
Trilyloxy) catechol, 3- (4-hydroxyphenoxy) catechol, 3- (3-hydroxyphenoxy) catechol, 3- (2-hydroxyphenoxy) catechol, 3-
(4-Methoxyphenoxy) catechol, 3- (3-methoxyphenoxy) catechol, 3- (2-methoxyphenoxy)
Catechol, 3-benzyloxycatechol, 3- (4-methylbenzyloxy) catechol, 3- (3-methylbenzyloxy) catechol, 3- (2-methylbenzyloxy)
Catechol, 3- (4-chlorobenzyloxy) catechol, 3- (3-chlorobenzyloxy) catechol, 3- (2
-Chlorobenzyloxy) catechol, 3- (4-hydroxybenzyloxy) catechol, 3- (3-hydroxybenzyloxy) catechol, 3- (2-hydroxybenzyloxy) catechol, 3- (4-nitrobenzyloxy) catechol , 3- (3-nitrobenzyloxy) catechol, 3
-(2-Nitrobenzyloxy) catechol, 3-benzoyloxycatechol, 3- (4-methylbenzoyloxy)
Catechol, 3- (3-methylbenzoyloxy) catechol, 3- (2-methylbenzoyloxy) catechol, 3-
(4-chlorobenzoyloxy) catechol, 3- (3-chlorobenzoyloxy) catechol, 3- (2-chlorobenzoyloxy) catechol, 3- (4-methoxybenzoyloxy) catechol, 3- (3-methoxybenzoyloxy )
Catechol, 3- (2-methoxybenzoyloxy) catechol, 3- (4-nitrobenzoyloxy) catechol, 3
-(3-Nitrobenzoyloxy) catechol, 3- (2-nitrobenzoyloxy) catechol, 3- (2-pyridyloxy) catechol, 3- (3-pyridyloxy) catechol, 3- (4-pyridyloxy) catechol ; Or 2-
Methoxyresorcinol, 2-allyloxyresorcinol, 2- (2-propynyloxy) resorcinol, 2-
Cyclohexyloxyresorcinol, 2-acetoxyresorcinol, 2-phenoxyresorcinol, 2- (4
-Chlorophenoxy) resorcinol, 2- (3-chlorophenoxy) resorcinol, 2- (2-chlorophenoxy)
Resorcinol, 2- (4-tolyloxy) resorcinol, 2- (3-tolyloxy) resorcinol, 2- (2-tolyloxy) resorcinol, 2- (4-hydroxyphenoxy) resorcinol, 2- (3-hydroxyphenoxy)
Resorcinol, 2- (2-hydroxyphenoxy) resorcinol, 2- (4-methoxyphenoxy) resorcinol, 2- (3-methoxyphenoxy) resorcinol, 2-
(2-Methoxyphenoxy) resorcinol, 2-benzyloxyresorcinol, 2- (4-methylbenzyloxy)
Resorcinol, 2- (3-methylbenzyloxy) resorcinol, 2- (2-methylbenzyloxy) resorcinol, 2- (4-chlorobenzyloxy) resorcinol, 2
-(3-Chlorobenzyloxy) resorcinol, 2- (2-
(Chlorobenzyloxy) resorcinol, 2- (4-hydroxybenzyloxy) resorcinol, 2- (3-hydroxybenzyloxy) resorcinol, 2- (2-hydroxybenzyloxy) resorcinol, 2- (4-nitrobenzyloxy) resorcinol, 2- (3-nitrobenzyloxy) resorcinol, 2- (2-nitrobenzyloxy) resorcinol, 2-benzoyloxyresorcinol, 2
-(4-methylbenzoyloxy) resorcinol, 2- (3
-Methylbenzoyloxy) resorcinol, 2- (2-methylbenzoyloxy) resorcinol, 2- (4-chlorobenzoyloxy) resorcinol, 2- (3-chlorobenzoyloxy) resorcinol, 2- (2-chlorobenzoyloxy) resorcinol 2- (4-methoxybenzoyloxy) resorcinol, 2- (3-methoxybenzoyloxy) resorcinol, 2- (2-methoxybenzoyloxy) resorcinol, 2- (4-nitrobenzoyloxy)
Resorcinol, 2- (3-nitrobenzoyloxy) resorcinol, 2- (2-nitrobenzoyloxy) resorcinol, 2- (2-pyridyloxy) resorcinol, 2-
(3-pyridyloxy) resorcinol, 2- (4-pyridyloxy) resorcinol; or 2,3-dimethoxyphenol, 2,3-diallyloxyphenol, 2,3-bis (2
-Propynyloxy) phenol, 2,3-dicyclohexyloxyphenol, 2,3-diacetoxyphenol,
2,3-diphenoxyphenol, 2,3-bis (4-chlorophenoxy) phenol, 2,3-bis (3-chlorophenoxy) phenol, 2,3-bis (2-chlorophenoxy) phenol, 2,3 -Bis (4-tolyloxy) phenol, 2,3
-Bis (3-tolyloxy) phenol, 2,3-bis (2-tolyloxy) phenol, 2,3-bis (4-hydroxyphenoxy) phenol, 2,3-bis (3-hydroxyphenoxy) phenol, 2,3 -Bis (2-hydroxyphenoxy)
Phenol, 2,3-bis (4-methoxyphenoxy) phenol, 2,3-bis (3-methoxyphenoxy) phenol,
2,3-bis (2-methoxyphenoxy) phenol, 2,3-
Dibenzyloxyphenol, 2,3-bis (4-methylbenzyloxy) phenol, 2,3-bis (3-methylbenzyloxy) phenol, 2,3-bis (2-methylbenzyloxy) phenol, 2,3 -Bis (4-chlorobenzyloxy) phenol, 2,3-bis (3-chlorobenzyloxy)
Phenol, 2,3-bis (2-chlorobenzyloxy) phenol, 2,3-bis (4-hydroxybenzyloxy) phenol, 2,3-bis (3-hydroxybenzyloxy) phenol, 2,3-bis ( 2-hydroxybenzyloxy) phenol, 2,3-bis (4-nitrobenzyloxy) phenol, 2,3-bis (3-nitrobenzyloxy) phenol,
2,3-bis (2-nitrobenzyloxy) phenol, 2,3
-Dibenzoyloxyphenol, 2,3-bis (4-methylbenzoyloxy) phenol, 2,3-bis (3-methylbenzoyloxy) phenol, 2,3-bis (2-methylbenzoyloxy) phenol, 2, 3-bis (4-chlorobenzoyloxy) phenol, 2,3-bis (3-chlorobenzoyloxy) phenol, 2,3-bis (2-chlorobenzoyloxy) phenol, 2,3-bis (4-methoxybenzoyl) (Oxy) phenol, 2,3-bis (3-methoxybenzoyloxy) phenol, 2,3-bis (2-methoxybenzoyloxy) phenol, 2,3-bis (4-nitrobenzoyloxy) phenol, 2,3- Bis (3-nitrobenzoyloxy) phenol, 2,3-bis (2-nitrobenzoyloxy) phenol, 2,3-bis (2-pyridyloxy) phenol, 2,3-bis (3-pyridyloxy) phenol, 2,
3-bis (4-pyridyloxy) phenol, 2,3-methylenedioxyphenol, 2-acetoxy-3-methoxyphenol, 3-acetoxy-2-methoxyphenol, 2
-Benzyloxy-3-methoxyphenol, 3-benzyloxy-2-methoxyphenol, 2-benzoyloxy-3-methoxyphenol, 3-benzoyloxy-2
-Methoxyphenol; or 2,6-dimethoxyphenol, 2,6-diallyloxyphenol, 2,6-bis
(2-propynyloxy) phenol, 2,6-dicyclohexyloxyphenol, 2,6-diacetoxyphenol, 2,6-diphenoxyphenol, 2,6-bis (4-chlorophenoxy) phenol, 2,6-bis (3-chlorophenoxy) phenol, 2,6-bis (2-chlorophenoxy) phenol, 2,6-bis (4-tolyloxy) phenol, 2,
6-bis (3-tolyloxy) phenol, 2,6-bis (2-
Tolyloxy) phenol, 2,6-bis (4-hydroxyphenoxy) phenol, 2,6-bis (3-hydroxyphenoxy) phenol, 2,6-bis (2-hydroxyphenoxy) phenol, 2,6-bis (4 -Methoxyphenoxy) phenol, 2,6-bis (3-methoxyphenoxy) phenol, 2,6-bis (2-methoxyphenoxy) phenol, 2,
6-dibenzyloxyphenol, 2,6-bis (4-methylbenzyloxy) phenol, 2,6-bis (3-methylbenzyloxy) phenol, 2,6-bis (2-methylbenzyloxy) phenol, 2 , 6-bis (4-chlorobenzyloxy) phenol, 2,6-bis (3-chlorobenzyloxy)
Phenol, 2,6-bis (2-chlorobenzyloxy) phenol, 2,6-bis (4-hydroxybenzyloxy) phenol, 2,6-bis (3-hydroxybenzyloxy) phenol, 2,6-bis ( 2-hydroxybenzyloxy) phenol, 2,6-bis (4-nitrobenzyloxy) phenol, 2,6-bis (3-nitrobenzyloxy) phenol,
2,6-bis (2-nitrobenzyloxy) phenol, 2,6
-Dibenzoyloxyphenol, 2,6-bis (4-methylbenzoyloxy) phenol, 2,6-bis (3-methylbenzoyloxy) phenol, 2,6-bis (2-methylbenzoyloxy) phenol, 2, 6-bis (4-chlorobenzoyloxy) phenol, 2,6-bis (3-chlorobenzoyloxy) phenol, 2,6-bis (2-chlorobenzoyloxy) phenol, 2,6-bis (4-methoxybenzoyl) (Oxy) phenol, 2,6-bis (3-methoxybenzoyloxy) phenol, 2,6-bis (2-methoxybenzoyloxy) phenol, 2,6-bis (4-nitrobenzoyloxy) phenol, 2,6- Bis (3-nitrobenzoyloxy) phenol, 2,6-bis (2-nitrobenzoyloxy) phenol, 2,6-bis (2-pyridyloxy) phenol, 2,6-bis (3-pyridyloxy) phenol, 2 , 6
-Bis (4-pyridyloxy) phenol, 2-acetoxy-6-methoxyphenol, 2-benzyloxy-6-methoxyphenol, 2-benzoyloxy-6-methoxyphenol; or 1,2,3-tribenzoyloxybenzene 1,2,3-tris (4-methylbenzoyloxy) benzene, 1,2,3-tris (3-methylbenzoyloxy) benzene, 1,2,3-tris (2-methylbenzoyloxy) benzene, 1 , 2,3-Tris (4-chlorobenzoyloxy) benzene, 1,2,3-tris (3-chlorobenzoyloxy) benzene, 1,2,3-tris (2-chlorobenzoyloxy) benzene, 1,2 , 3-Tris (4-methoxybenzoyloxy)
Benzene, 1,2,3-tris (3-methoxybenzoyloxy) benzene, 1,2,3-tris (2-methoxybenzoyloxy) benzene, 1,2,3-tris (4-nitrobenzoyloxy) benzene, 1,2,3-Tris (3-nitrobenzoyloxy) benzene, 1,2,3-tris (2-nitrobenzoyloxy) benzene, 1,2,3-tris (2-pyridyloxy) benzene, 1,2 , 3-tris (3-pyridyloxy) benzene,
1,2,3-Tris (4-pyridyloxy) benzene, 1-methoxy-2,3-methylenedioxybenzene, 1-benzyloxy-2,3-methylenedioxybenzene, 1-benzoyloxy-2,3 -Methylenedioxybenzene, 2-acetoxy-1,3-dimethoxybenzene, 1-acetoxy-2,3-
Dimethoxybenzene, 2-benzyloxy-1,3-dimethoxybenzene, 3-benzyloxy-1,2-dimethoxybenzene, 2-benzoyloxy-1,3-dimethoxybenzene, 3-benzoyloxy-1,2-dimethoxybenzene , Purpurogallin, ellagic acid, hematein, hematoxylin are also included.

The addition amount of 1,2,3-triphenol or its derivative used in the method of the present invention depends on the kind of the substituent R of the oxystyrene derivative of the formula (I) to be distilled, distillation temperature and distillation pressure. However, in general, 10 to 100,000 p are available for the oxystyrene derivative of the formula (I) to be distilled.
pm, preferably in the concentration range of 100-10,000 ppm.
The distillation temperature is usually 20 to 200 ° C, preferably 40 to 150 ° C. The oxystyrene derivative of the formula (I) is usually distilled under reduced pressure, usually 0.0001 to 50
It is carried out under a pressure of 0 mmHg, preferably 0.0001-10 mmHg.

[0019]

The present invention will be described in more detail based on the following examples, but the invention is not intended to be limited by these examples.

Example 1 100 g of PTBST (p-tert-butoxystyrene) immediately after being synthesized by the method of Japanese Patent Publication No. 4-71896 in a four-necked flask equipped with a distillation condenser, a thermometer and a stirrer.
Then, a mixture prepared by adding 0.05 g (concentration of 500 ppm) of pyrogallol as a polymerization inhibitor was charged. This mixed solution was distilled in a flask at 130 ° C. under a reduced pressure of 5 mmHg for 48 hours while stirring. 95.1 g from the flask by this distillation process
Was able to distill PTBST. At the bottom of the flask, about 4.9 g of highly viscous liquid substance remained without being distilled. The recovery rate (%) of PTBST that could be recovered by distilling from the flask was calculated by the following formula. Recovery rate (%) = [(weight of PTBST distilled from the flask by distillation) / (weight of PTBST charged in the flask before distillation)] x 100 The measured recovery rate (%) obtained is shown below. Is shown in Table 1.

[0020]

Example 2 The same distillation step as in Example 1 was operated except that 5-methylpyrogallol was used instead of pyrogallol as the polymerization inhibitor used in Example 1. The results are shown in Table 1 below.

Example 3 The same distillation step as in Example 1 was operated except that 4- (p-hydroxybenzyl) pyrogallol was used instead of pyrogallol as the polymerization inhibitor used in Example 1. The results are shown in Table 1 below.

Example 4 Example 1 was repeated except that 4- (n-dodecylcarbonyl) pigrol (that is, n-dodecyl gallate) was used in place of pyrogallol as the polymerization inhibitor used in Example 1. A similar distillation process was operated. The results are shown in Table 1 below.

[0021]

Example 5 The same distillation step as in Example 1 was operated except that 4,6-dinitropyrogallol was used instead of pyrogallol as the polymerization inhibitor used in Example 1. The results are shown in Table 1 below.

Example 6 The same distillation as in Example 1 except that MTBST (synthesized by the method described in JP-A-2-160739) was used in place of the PTBST to be distilled used in Example 1. The process was operated. The results are shown in Table 1 below.

[Example 7] The same distillation as in Example 2 except that MTBST (synthesized by the method described in JP-A-2-160739) was used in place of the PTBST to be distilled used in Example 2. The process was operated. The results are shown in Table 1 below.

Example 8 The same distillation as in Example 3 except that MTBST (synthesized by the method described in JP-A-2-160739) was used in place of the PTBST to be distilled used in Example 3. The process was operated. The results are shown in Table 1 below.

[Example 9] The same procedure as in Example 1 except that MTBST (synthesized by the method described in JP-A-2-160739) was used in place of the distilled PTBST used in Example 4. The MTBST distillation process was operated in the presence of n-dodecyl gallate. The results are shown in Table 1 below.

[Example 10] The same distillation as in Example 3 except that MTBST (synthesized by the method described in JP-A-2-160739) was used in place of the PTBST to be distilled used in Example 5. The process was operated. The results are shown in Table 1 below.

[0022]

Comparative Example 1 PTBST was prepared in the same manner as in Example 1 except that a known polymerization inhibitor, N-nitrosophenylhydroxylamine aluminum salt, was used in place of the pigallol used as the polymerization inhibitor in Example 1. The distillation process was operated. The results are shown in Table 1 below.

Comparative Example 2 MTBST was performed in the same manner as in Example 6 except that a known polymerization inhibitor, p-tert-butylcatechol, was used in place of the pigallol used as the polymerization inhibitor in Example 6.
The distillation process was operated. The results are shown in Table 1 below.

The results obtained in Examples 1-10 and Comparative Examples 1-2 above are summarized in Table 1 below.

[Table 1]

When the method of the present invention is carried out, the following effects are brought about. That is, formation of a highly viscous polymeric substance is prevented during the distillation step, and the recovery rate of the distilled oxystyrene derivative is high. Therefore, the method for distilling an oxystyrene derivative according to the present invention solves the problems of the conventional distilling method and is highly useful as an industrial method.

Claims (4)

[Claims] 1. A compound represented by the following general formula (I) using 1,2,3-triphenol or a derivative thereof as a polymerization inhibitor. (In the formula, R is an alkyl group, a haloalkyl group, an aryl group, especially a phenyl group, an aralkyl group, especially a benzyl group,
An alkoxyalkyl group, an alkanoyl group, an alkoxycarbonyl group, an aralkyloxycarbonyl group, or an alkylsilyl group) is added to the oxystyrene derivative, and the oxystyrene derivative is distilled in the presence of the polymerization inhibitor. Characterized by the general formula (I)
Method for distilling oxystyrene derivative of. 2. The 1,2,3-triphenol or its derivative used as a polymerization inhibitor is represented by the following general formula (II): (In the formula, R ¹ , R ² and R ³ are each independently a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkynyl group,
A substituted or unsubstituted aryl group, especially a phenyl group, a substituted or unsubstituted aralkyl group, especially a benzyl group, a substituted or unsubstituted alkanoyl group, especially an acetyl group, a substituted or unsubstituted aroyl group, especially a benzoyl group, a cyano group, a carboxyl group, An alkoxycarbonyl group, a substituted or unsubstituted carbamoyl group, a nitro group, or a substituted or unsubstituted amino group, and R ⁴ , R ⁵ , and R ⁶ are each independently
Hydrogen atom, substituted or unsubstituted alkyl group, substituted or unsubstituted alkenyl group, substituted or unsubstituted alkynyl group, substituted or unsubstituted aryl group, especially phenyl group, substituted or unsubstituted aralkyl group, especially benzyl group, substituted or unsubstituted An alkanoyl group, especially an acetyl group, a substituted or unsubstituted aroyl group, especially a benzoyl group, a substituted or unsubstituted alkylsulfonyl group, a substituted or unsubstituted arylsulfonyl group, or a substituted or unsubstituted carbamoyl group, and R ¹ and R ² , R ² and R ³ , R ³ and R ⁴ , R ⁴ and R ⁵ , R ⁵ and R ⁶ ,
Alternatively, R ⁶ and R ¹ may be bonded to each other to form a substituted or unsubstituted carbocyclic group having a cyclic structure, and the carbon atom constituting the carbocyclic group of the cyclic structure is oxygen or sulfur. The method according to claim 1, which is a pyrogallol or a pyrogallol derivative represented by the formula (1) or a nitrogen atom which may replace a nitrogen atom and a double bond may be present in the carbocyclic group. 3. 1,2,3-Triphenol or its derivative is represented by the following general formula (IIa): (In the formula, R ¹ , R ² and R ³ are each independently a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group, an alkynyl group, a haloalkyl group, a haloalkenyl group, a haloalkynyl group, a hydroxyalkyl group, an alkoxyalkyl. Base,
Haloalkoxyalkyl groups, aryl groups, especially phenyl groups, aralkyl groups, especially benzyl groups, alkanoyl groups,
In particular, acetyl group, aroyl group, especially benzoyl group, aryloxyalkyl group, aralkyloxyalkyl group,
Represents an aroyloxyalkyl group, an alkanoyloxyalkyl group, a cyano group, a carboxyl group, an alkoxycarbonyl group, a carboxyalkyl group, an alkoxycarbonylalkyl group or a carbamoyl group, and R ⁴ , R ⁵ and R ⁶ are each independently hydrogen. Atoms, alkyl groups, alkenyl groups, alkynyl groups, substituted or unsubstituted aryl groups, especially phenyl groups, substituted or unsubstituted aralkyl groups, especially benzyl groups, alkanoyl groups, especially acetyl groups, substituted or unsubstituted aroyl groups, especially benzoyl groups , An alkylsulfonyl group, a substituted or unsubstituted arylsulfonyl group, or a substituted or unsubstituted carbamoyl group, and R ¹ and
R ² , R ² and R ³ , R ³ and R ⁴ , R ⁴ and R ⁵ , R ⁵ and R ⁶ , or R ⁶ and R ¹ are bonded to each other to form a substituted or unsubstituted cyclic structure. The carbocyclic group may be constituted, and the carbon atom constituting the carbocyclic group of the cyclic structure may be replaced with an atom of oxygen, sulfur or nitrogen, and a double bond may be present in the carbocyclic group. The method according to claim 1, which is a pyrogallol or a pyrogallol derivative represented by (may be present). 4. The oxystyrene derivative to be distilled is tert.
-The method according to claim 1, 2 or 3, which is butoxystyrene.