JPH0565240A - Production of metharylphenol compounds - Google Patents

Abstract

PURPOSE:To obtain a metharylphenol compound useful as an organic synthetic intermediate for various fine chemicals, a raw material for producing polymers, a modifying agent for polymers, etc., in high selectivity and yield at a low cost without employing a high boiling point solvent. CONSTITUTION:When a metharylaryl ether having two or more benzene rings to each of which a metharyloxy group is directly bonded and in which at least one of the ortho and para positions to the metharyloxy group is non-substituted, such as bisphenol A dimetharyl ether, is subjected to a Claisen rearrangement to produce a metharyl phenol compound, e.g. 0,0'-dimetharyl bisphenol A, a base except aniline derivatives and saturated aliphatic bases not having polymerizable functional groups, e.g. 1-amino-2-methylnaphthalene, is added to the raw materials in an amount of 0.01-10mol.% based on the raw materials to advantageously obtain the objective compound, while largely reducing the thermal polymerization of the raw materials, the production of benzophenone derivatives, and the production of oligomers having double or triple bonds, etc.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a method for producing methallylphenols with a high selectivity and a high yield by Claisen rearrangement of a methallyl aryl ether having two or more benzene rings bonded to a methallyloxy group. Regarding The methallylphenols obtained by the present invention are compounds useful as organic synthetic intermediates for various fine chemicals, raw materials for polymer production, and modifiers for polymers.

[0002]

2. Description of the Related Art A reaction for rearrangement of methallyl phenyl ether to a phenol having a methallyl group at the ortho position by heating is known as a Claisen rearrangement reaction (hereinafter simply referred to as rearrangement reaction). When the ortho position is occluded by two substituents, the phenol has a methallyl group at the para position.

This rearrangement reaction is usually carried out with nitrobenzene, p
A high boiling solvent such as tolunitrile, N, N-dialkylaniline, tributylamine, tetralin or paraffin oil in an amount equivalent to methallyl phenyl ether;
Alternatively, it proceeds easily by heating at a high temperature of about 200 ° C. without being present [for example, organic.
Reactions vol. 2, pages 1-48, pages 29-47,
Journal of Organic Chemicals (J. Or
g. Chem.), vol. 28, 2468-2469 (19
63) etc.].

However, when such a high boiling point solvent is used, there are problems that thermal polymerization due to a methallyl group occurs and a benzofuran derivative is formed as a by-product, and since a large amount of solvent is generally used, After the rearrangement reaction,
Since it is necessary to separate and remove the solvent by a method such as distillation, it is disadvantageous as an industrial method for inexpensively producing the desired product.

Further, in order to obtain methallylphenols having high polymerizability, it is preferable to obtain methallylphenols having two or more methallyl groups at the molecular ends,
For that purpose, it is preferable to perform a Claisen transfer of a methallyl aryl ether having two or more benzene rings bonded to a methallyloxy group, but when a methallyl aryl ether having two or more benzene rings bonded to a methallyloxy group is heated, a by-product is produced. In addition to the above-mentioned benzofuran derivative, there is also a problem that oligomers such as dimers and trimers of methallyl aryl ether are produced.

On the other hand, there is known a method of carrying out the rearrangement reaction under reduced pressure or in the presence of an inert gas such as carbon dioxide or nitrogen (for example, Organic Reactions, vol.
(Page 2.24), it is hard to say that the effect of suppressing side reactions is sufficient.

[0007]

The object of the present invention is to carry out thermal polymerization, benzofuran, in Claisen rearrangement of a methallyl aryl ether having two or more benzene rings bonded to a methallyloxy group without using a high boiling solvent. A method for significantly suppressing the formation of derivatives and oligomers such as dimers and trimers of methallyl aryl ethers, and producing the target methallylphenols with high selectivity and high yield at low cost. To provide.

[0008]

[Constitution of the invention]

Means for Solving the Problems As a result of various studies aimed at achieving such an object, the inventors of the present invention have found that when a methallyl aryl ether having two or more benzene rings bonded to a methallyloxy group undergoes Claisen rearrangement, By allowing a specific base to coexist in the aryl aryl ether, the thermal polymerization, the formation of a benzofuran derivative, and the oligomer such as a dimer and trimer of the methallyl aryl ether can be significantly suppressed. It was found that methallyl phenols can be obtained with high selectivity and high yield,
The present invention has been completed.

That is, the present invention relates to a methallyl aryl ether having two or more benzene rings bonded to a methallyloxy group, wherein at least one ortho-position or para-position with respect to the methallyloxy group is unsubstituted. Performing Claisen rearrangement in the presence of 0.01 to 10 mol% of a base having no polymerizable functional group in the molecule and selected from a base other than an aniline derivative and a saturated aliphatic base. And a method for producing methallylphenols.

The present invention will be described in detail below. The methallyl aryl ether used in the present invention has two or more benzene rings in which at least one ortho-position or para-position is unsubstituted with respect to the methallyloxy group, and specific examples thereof include the following. Examples include methallyl ether of polyhydric phenol.

That is, the polyhydric phenol represented by the following general formula [1], 4- {4- [1,1-bis (4-hydroxyphenyl) ethyl] -α, α-dimethylbenzyl} phenol and 1,1 , Methallyl ethers of polyhydric phenols such as 1-tris (4-hydroxyphenyl) ethane.

[Chemical 1] [Wherein, m is 0 or 1, X is S, SO ₂ , O,

[Chemical 2] (Wherein R ³ and R ⁴ are hydrogen, an alkyl group, a phenyl group, a trifluoromethyl group or a trichloromethyl group, and may be the same as each other), and R ¹ and R ²
Is an alkyl group, an alkoxy group or a halogen group atom, a and b are each an integer of 1 or more and 2 or less, and c
And d are integers of 0 or more and 3 or less. ]

Preferred specific examples of the compound represented by the general formula [1] are 2,2-bis [4-hydroxy-phenyl] propane and 2,2-bis [4-hydroxy-5-].
Methyl-phenyl] propane, 2,2-bis [4-hydroxy-3-methoxy-phenyl] propane, 2,2-
Bis [4-hydroxy-3-chloro-phenyl] propane, 3,3-bis [4-hydroxy-phenyl] pentane, 1,1,1,3,3,3-hexafluoro-2,2
-Bis [4-hydroxy-phenyl] propane, 1,
1,1,3,3,3-hexachloro-2,2-bis [4
-Hydroxy-phenyl] propane, bis [4-hydroxy-phenyl] methane, 1,1-bis [4-hydroxy-phenyl] ethane, 4,4'-dihydroxy-biphenyl, bis [4-hydroxy-phenyl] thioether, Examples thereof include bis [4-hydroxy-phenyl] ether, bis [4-hydroxy-phenyl] sulfone and 2,2-bis [3,5-hydroxy-phenyl] propane.

These methallyl aryl ethers can be easily produced by a method of reacting the above polyhydric phenols with a methallyl halide in the presence of an alkali such as an alkali metal hydroxide. The methallyl allyl ether in which all ortho-positions and para-positions are substituted with respect to the methallyloxy group is excluded from the starting materials of the present invention because it cannot undergo a rearrangement reaction.

The base in the present invention is a base having no polymerizable functional group in the molecule and is a base selected from the group other than the aniline derivative and the saturated aliphatic base.

As the base, for example, 1-amino-4-phenylbutane, 3,3-diphenylpropylamine, o-
Benzene ring such as methoxybenzylamine, m-methoxybenzylamine, p-methoxybenzylamine, 2-phenylethylamine, N-phenylethylenediamine, 3-phenylpropylamine, m-xylenediamine, p-xylenediamine, N-phenylbenzylamine An aliphatic amine having: pyridine, acetylpyridine,
2-amino-5-chloropyridine, 2-amino-3-hydroxypyridine, 6-amino-2,4-lutidine, 2
-Amino-3-nitropyridine, 2-amino-3-picoline, 2-aminopyridine, 3-aminopyridine, 4-
Aminopyridine, 2-benzoylpyridine, 4-benzylpyridine, 2,2'-bi-4-picoline, 2,2'-
Bis (5-aminopyridyl) sulfide, 2-bromopyridine, 3-n-butylpyridine, 2- (p-chlorobenzyl) pyridine, 2-chloro-6-ethoxypyridine, 3-chloro-5-hydroxypyridine, 2 -Chloro-3-nitropyridine, 2-cyanopyridine, 2,6-
Diaminopyridine, 2,5-dichloropyridine, 4-dimethylaminopyridine, N, N-dimethylnicotinamide, 2,6-diphenylpyridine, 2,2′-dipyridyl, 2,2′-dipyridylamine, 4,4 ′ -Dipyridyl sulfide, 4- (ethylaminomethyl) pyridine,
2-ethylpyridine, 2-hydroxypyridine, 2,3
-Lutidine, 2- (3-pentyl) pyridine, 2-phenylpyridine, 2-picoline, 3-picolylamine, pyridine-4-aldehyde, 2,3-pyridinediol,
Pyridine derivatives such as 2,4,6-trimethylpyridine;
4-amino-1-benzylpiperidine, 4-amino-
2,2,6,6-tetramethylpiperidine, 4-benzylpiperidine, 2,6-dimethylpiperidine, 1,3-
Di-4-piperidyl propane, 1-ethyl piperidine,
3-hydroxypiperidine, 1-methyl-3-hydroxypiperidine, 1-methyl-2-piperidinemethanol, pipecoline, piperidine, piperidone, 2,2
Piperidine derivatives such as 6,6-tetramethylpiperidine; pyrrole derivatives such as pyrrole and 2-methylpyrrole; 1,2-dimethylindole, 2,3-dimethylindole, 4-hydroxyindole, indole, 5
-Indole derivatives such as methoxyindole, N-methylindole, 2-methylindole, 5-nitroindole, tryptamine, tryptophan; 8-aminoquinaldine, 2-aminoquinoline, 2,2'-biquinoline, 2-chloroquinoline, 5,7-dichloro-8-hydroxyquinoline, 2,4-dihydroxyquinoline, 2,
4-dimethylquinoline, leptidine, 2-methyl-6-
Quinoline derivatives such as ethoxyquinoline, 6-methylquinoline, 5-nitroquinoline, quinaldine, quinoline, isoquinoline, 1-methylisoquinoline; carbazole,
Carbazole derivatives such as 3,6-diaminocarbazole and N-ethylcarbazole; acridine derivatives such as acridine, acriflavine and N-methylacridone; 3-
Amino-5-methylpyrazole, 5-amino-1-phenylpyrazole, 4,4'-diantipyrmethane, 3
-Pyrazole derivatives such as methylpyrazole, pyrazole and 2-pyrazoline; N-benzyl-2-methylimidazole, N-tert-butoxycarbonylimidazole, 4,5-dichloroimidazole, 1,2-dimethylimidazole, N-ethylimidazole, Imidazole derivatives such as imidazole, 2-methylimidazole, 2-phenylimidazole, N-trimethylsilylimidazole; pyridazine derivatives such as 3-methylpyridazine, pyridazine; benzimidazole, 2-mercaptobenzimidazole, indazole, 5-aminoindazole and other benzines. Imidazole derivative or indazole derivative; 5-chloro-1,10-phenanthrene, 4,7
-Phenanthrene derivatives such as dimethyl-1,10-phenanthrene; 3-amino-1,2,4-triazole,
3-mercapto-1,2,4-triazole, 1,2,
Triazole derivatives such as 3-benzotriazole; 5,
6-diphenyl-3- (2-pyridyl) -1,2,4-
Triazine derivatives such as triazine and 2,4-diamino-6-methyl-s-triazine; tetrazole derivatives such as 5-amino-1H-tetrazole, 5-phenyltetrazole and 1H-tetrazole; 2-aminopurine, 6-
Purine derivatives such as chloropurine and adenine; imide compounds such as succinimide and maleimide; lactam derivatives such as ε-caprolactam and ω-heptalactam; furfurylamine, bases having a furan ring such as α-amino-γ-butyrolactone; 7- Amino-4-methylcoumarin, 7
A base having a coumarin ring such as diethylamino-4-methylcoumarin; a base having a xanthene ring such as 4-aminofluorescein and 5-aminofluorescein;
A base having a benzodioxolane ring such as methylenedioxyaniline; an oxazole derivative such as 3-benzoxazolidine, 2,4-diphenyloxazole, 5-aminoisoxazole; a benzoxazole derivative such as benzoxazole and 2-methylbenzoxazole;
Morpholine derivatives such as morpholine, N-ethylmorpholine and N-phenylmorpholine; 2-amino-5-nitrothiazole, 2-bromothiazole, 4-methylthiazole, thiazole, thiazole and other thiazole derivatives; 2-amino-4-chloro Benzothiazole derivatives such as benzothiazole and benzothiazole; 5-amino-
Bases having a naphthalene ring such as 1-naphthol and 1-amino-2-methylnaphthalene; bases having anthraquinone ring such as 1,5-diaminoanthraquinone and 1,2-diaminoanthraquinone; 2,7-diaminofluorene, 2- Examples include bases having a fluorene ring such as aminofluorene and alkoxide compounds such as sodium methoxide and sodium ethoxide. If desired, two or more kinds of these bases may be used in combination.

To carry out the rearrangement reaction in the presence of the above base,
For example, the base may be previously dissolved in methallyl aryl ether used as a starting material.

It is necessary to use the base in an amount of 0.01 to 10 mol%, preferably 0.05 to 5 mol%, based on the methallyl aryl ether. When the proportion of the base used is less than 0.01 mol%, it is difficult to exert the effect of the present invention that the target compound is obtained in a high purity by the rearrangement reaction, and 10 mol%
Even if it is used in a larger amount, there is no great difference in the above-mentioned effect, and since the step of removing the base by distillation after the reaction is increased, it is rather economically disadvantageous.

Since the reaction temperature and the reaction time vary depending on the type of methallyl aryl ether, the reactivity and the reaction scale, it is not possible to set uniform conditions.
It is suitable to carry out the reaction at a temperature of 50 to 300 ° C. for 0.5 to 20 hours, preferably at a temperature of 180 to 250 ° C. for about 1 to 10 hours.

The reaction can be carried out under reduced pressure, normal pressure or increased pressure.

The reaction atmosphere may be air or may be an atmosphere of an inert gas such as nitrogen or argon.

The following compounds are specific examples of methallylphenols that can be obtained as described above. That is, 2,2-bis [4-hydroxy-3- (2-methyl-2-propenyl) phenyl] propane, 2,2-bis [4-hydroxy-5-methyl-3- (2-methyl-2)
-Propenyl) phenyl] propane, 2,2-bis [4
-Hydroxy-5-ethoxy-3- (2-methyl-2-
Propenyl) phenyl] propane, 2,2-bis [4-
Hydroxy-5-chloro-3- (2-methyl-2-propenyl) phenyl] propane, 3,3-bis [4-hydroxy-3- (2-methyl-2-propenyl) phenyl] pentane, 1,1, 1,3,3,3-hexafluoro-2,2-bis [4-hydroxy-3- (2-methyl-2-propenyl) phenyl] propane, 1,1,1,
3,3,3-Hexachloro-2,2-bis [4-hydroxy-3- (2-methyl-2-propenyl) phenyl]
Propane, bis [4-hydroxy-3- (2-methyl-
2-propenyl) phenyl] methane, 1,1-bis [4
-Hydroxy-3- (2-methyl-2-propenyl) phenyl] ethane, 4,4'-dihydroxy-3,3'-
Bis (2-methyl-2-propenyl) biphenyl, 1,
1-bis (4-hydroxy-3-methallylphenyl) cyclohexane, [1,1-bis (4-hydroxy-3-)
Methallylphenyl) ethyl] benzene, bis [4-hydroxy-3- (2-methyl-2-propenyl) phenyl] thioether, bis [4-hydroxy-3- (2-
Methyl-2-propenyl) phenyl] ether, bis [4-hydroxy-3- (2-methyl-2-propenyl) phenyl] sulfone and 2,2-bis [4-hydroxy-3,5-di (2-methyl) 2-propenyl) phenyl] propane and the like.

In the method of the present invention, the content of methallylphenol which is a target product in the reaction product is extremely high. Therefore, the reaction product can be used as it is for many purposes, but it has a higher purity. When the product is required, it may be purified by a general method such as vacuum distillation.

[0023]

The present invention will be described in more detail with reference to the following examples. In addition, each of the following examples is a result of performing several times under the same conditions, there is a range in the composition of the reaction product,
Because of this.

Example 1 In a 200 ml glass three-necked flask equipped with a stirrer, a reflux tube and a thermometer, 50 g of bisphenol A dimethallyl ether and 1-amino-2-methylnaphthalene (2 parts with respect to bisphenol A dimethallyl ether). (Mol%) was charged and the rearrangement reaction was carried out at 195 ± 10 ° C. for 6 hours with stirring. After completion of the reaction, it was cooled to room temperature and ¹ H-NMR
As a result of analysis using a spectrum, the composition of the reaction product was 96.2 for o, o′-dimethallyl bisphenol A.
.About.98.8%, and unreacted bisphenol A dimethallyl ether was 0.9 to 2.7%. As a result of analysis by gel permeation chromatography (hereinafter abbreviated as GPC), the dimer [number average molecular weight 820 (styrene equivalent)] was 0.3 to 0.7%.

Example 2-6 A method similar to that of Example 1 except that 1-amino-2-methylnaphthalene used in Example 1 and 2 mol% of the used amount thereof were changed to various bases and used amounts. Rearrangement reaction was carried out.
Table 1 shows the ¹ H-NMR spectrum of the reaction product and the results of analysis by GPC.

[0026]

[Table 1] Note) * 1: Unit mol% * 2: o, o'-dimethallyl bisphenol A * 3: Bisphenol A dimethallyl ether * 4: 1-amino-2-methylnaphthalene

Example 8 Bisphenol F dimethallyl ether 3 was placed in a 200 ml glass three-necked flask equipped with a stirrer and a reflux tube.
0 g and 1-amino-2-methylnaphthalene (2 mol% based on bisphenol F dimethallyl ether) were charged, and the reaction was carried out at 195 ± 10 ° C. for 6 hours with stirring. After the reaction was completed, the reaction product was cooled to room temperature and analyzed using ¹ H-NMR spectrum. As a result, the composition of the reaction product was 0,0′-dimethallyl bisphenol F 95.8-98.5%, unreacted bisphenol. F dimethallyl ether is 0.6-
It was 2.8%. In addition, as a result of GPC analysis, the dimer [number average molecular weight 800 (styrene equivalent)] was 0.6 to
It was 1.2%.

Example 9 4,4'-Dimethallyloxybiphenyl 3 was placed in a 200 ml glass three-necked flask equipped with a stirrer and a reflux tube.
0 g and piperidine (4 mol% relative to 4,4′-dimethallyloxybiphenyl) were charged, and the mixture was stirred at 195 ±
The reaction was carried out at 10 ° C for 6 hours. After the reaction was completed, the mixture was cooled to room temperature and analyzed using ¹ H-NMR spectrum,
The composition of the reaction product was such that 4,4 ′-(3,3′-dimethallyl) biphenol was 96.2 to 98.4% and unreacted 4,4′-dimethallyloxybiphenyl was 0.7 to 2.
It was 9%. As a result of GPC analysis, the dimer [number average molecular weight 795 (styrene equivalent)] was 0.5 to
It was 1.1%.

Comparative Example 1 The rearrangement reaction was carried out in the same manner as in Example 1 except that only 50 g of bisphenol A dimethallyl ether was charged in the same three-necked flask as in Example 1. After completion of the reaction, the reaction product was cooled to room temperature and analyzed using ¹ H-NMR spectrum. As a result, the composition of the reaction product was found that 0,0′-dimethallylbisphenol A was 76.2 to 80.1% and was unreacted. Bisphenol A dimethallyl ether was 1.1 to 3.0%. As a result of GPC analysis, the dimer [number average molecular weight 820 (styrene equivalent)] was 9.5 to 10.6%, and the trimer [number average molecular weight 1150 (styrene equivalent)] was 0.8. Was 1.2%.

Example 10 In a 500 ml glass three-necked flask equipped with a stirrer and a reflux tube, 250 g of 1,1-bis (4-methallyloxyphenyl) cyclohexane and 1.9 g of 1H-tetrazole [1,1-bis]. (4 mol% relative to (4-methallyloxyphenyl) cyclohexane] was charged, and the reaction was carried out at 205 ± 10 ° C. for 2 hours with stirring. After the reaction,
The reaction product was cooled to room temperature and analyzed using ¹ H-NMR spectrum. As a result, the composition of the reaction product was 9,1-bis (4-hydroxy-3-methallylphenyl) cyclohexane.
6.5 to 98.4%, and unreacted raw material is 0.2 to
It was 2.2%. As a result of GPC analysis, the dimer [number average molecular weight 890 (styrene equivalent)] was 0.2 to
It was 1.3%.

Example 11 In a 500 ml glass three-necked flask equipped with a stirrer and a reflux tube, 250 g of [1,1-bis (4-methallyloxyphenyl) ethyl] benzene and 2.1 g of 2-methylimidazole {[ 4 mol%} with respect to 1,1-bis (4-methallyloxyphenyl) ethyl] benzene was charged, and the reaction was carried out at 205 ± 10 ° C. for 2 hours with stirring. After completion of the reaction, the mixture was cooled to room temperature and analyzed using ¹ H-NMR spectrum. As a result, the composition of the reaction product was [1,1-bis (4-hydroxy-3-methallylphenyl) ethyl].
The benzene content was 96.1 to 98.2% and the unreacted raw material content was 0.3 to 2.7%. As a result of GPC analysis, the dimer [number average molecular weight 905 (styrene equivalent)] was 0.2 to 1.2%.

[0032]

INDUSTRIAL APPLICABILITY According to the production method of the present invention, when a methallyl aryl ether having two or more benzene rings bonded to a methallyloxy group undergoes Claisen rearrangement, thermal polymerization, benzofuran, or the like, which could not be sufficiently suppressed by the conventional methods. Suppress side reactions such as formation of derivatives and oligomers such as dimers and trimers of methallyl aryl ethers,
This makes it possible to produce methallylphenols with high selectivity and high yield. Further, since it is not necessary to use a high boiling point solvent, a solvent removing step after the reaction is not necessary, and it is extremely useful as an industrial production method for obtaining an intended product at a low cost.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Yoshida ▲ 燇 ▼ Aichi Prefecture 1-chome, Funami-cho, Minato-ku, Nagoya-shi Toagosei Chemical Industry Co., Ltd. Nagoya Research Institute (72) Inventor Kaoru Kimura Aichi 1 Toa Synthetic Chemical Industry Co., Ltd. Nagoya Research Institute, 1 Funami-cho, Minato-ku, Nagoya

Claims (1)

[Claims] 1. A methallyloxy group is directly bonded,
In addition, a methallyl aryl ether having two or more benzene rings in which at least one ortho or para position is unsubstituted with respect to this group does not have a polymerizable functional group in the molecule. A method for producing methallylphenols, which comprises performing Claisen rearrangement in the presence of 0.01 to 10 mol% of a base that is a base other than an aniline derivative and a saturated aliphatic base. ..