JPH0565239A - 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 selective 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 selected from aniline derivatives and saturated aliphatic bases which are soluble in the raw materials and which do not have polymerizable functional groups, e.g. N,N-dimethylaniline, 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 occupied by two co-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.
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 a derivative and an oligomer such as a dimer and trimer of a methallyl aryl ether, and producing a target methallylphenol at a high selectivity and a high yield at a 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, thermal polymerization, the formation of a benzofuran derivative, and the oligomers such as dimers and trimers of the methallyl aryl ether are significantly suppressed, and the target meta The inventors have found that rylphenols can be obtained with high selectivity and high yield, and have completed the present invention.

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. It has solubility with this and 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 selected from an aniline derivative and a saturated aliphatic base.

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 general formula [1], 4- {4- [1,1-bis (4-hydroxyphenyl) ethyl] -α, α-dimethylbenzyl} phenol and 1,1, 1-tris (4-hydroxyphenyl)
It is a methallyl ether of polyhydric phenols such as 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. ]

Specific examples of the compound represented by the general formula [1] include 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,
Examples include bis [4-hydroxy-phenyl] thioether, bis [4-hydroxy-phenyl] ether, bis [4-hydroxy-phenyl] sulfone, and 2,2-bis [3,5-hydroxy-phenyl] propane. You can

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 used in the present invention is a base which is soluble in the starting material methallyl aryl ether and has no polymerizable functional group in the molecule or an aniline derivative or a saturated aliphatic base.

As the base, for example, 1-aminodecane, 3
-Amino-2,2-dimethylbutane, 1-aminoheptadecane, 2-aminooctane, 1-aminopentadecane, 2-aminopentane, n-amylamine, n-butylamine, sec-butylamine, tert-butylamine, 1,4 -Diaminobutane, 1,10-diaminodecane, 1,7-diaminoheptane, 1,9-diaminononane, 1,8-diaminooctane, 1,2-diaminopropane, 1,3-diaminopropane, 1,3-dimethyl -N-butylamine, 1,5-dimethylhexylamine, 1,2-dimethylpropylamine, ethylamine,
Ethylenediamine, 2-ethylhexylamine, n-heptylamine, 2-heptylamine, 4-heptylamine, n-hexadecylamine, n-hexylamine, isoamylamine, isobutylamine, isopropylamine, laurylamine, methylamine, 2- Methylamine, 2-methylbutylamine, 2-methyl-1,5-diaminopentane, neopentylamine, n-nonylamine, n-octylamine, oleylamine, n-propylamine, stearylamine, n-tetradecylamine, 1 , 1,3,3-Tetramethylbutylamine, tridecylamine, trimethylhexamethylenediamine and other aliphatic primary amines; dimethylamine, diethylamine,
Di-n-propylamine, diisopropylamine, di-
n-butylamine, diisobutylamine, di-sec-
Butylamine, di-n-hexylamine, di-cyclohexylamine, N-methylethylamine, N-ethylisobutylamine, N-methyl-n-butylamine, N-
Aliphatic secondary amines such as methylisobutylamine; trimethylamine, triethylamine, tri-n-butylamine, triisobutylamine, tri-n-hexylamine, tri-cyclohexylamine, N, N-dimethylethylamine, N, N-dimethylpropyl. Amine, N, N
-Dimethyl-n-butylamine, N, N-dimethyl-n
-Propylamine, N, N-dimethylisopropylamine, N, N-dimethyl-n-dodecylamine, N, N-
Aliphatic tertiary amines such as dimethylmethylamine, N, N-diethylbutylamine, N-ethyl-N-methylbutylamine, N-ethyl-N-methylpropylamine, N-ethyl-N-butyl-propylamine; 2- Aminoethanol, 2-amino-1-butanol, 2-amino-
2-methyl-1-propanol, 2-amino-2-methyl-1,3-propanediol, 2-amino-2-ethyl-1,3-propanediol, 2- (ethylamino)
Ethanol, 2,2-iminodiethanol, 2- (dimethylamino) ethanol, 2- (diethylamino) ethanol, N-ethyl-2,2′-iminodiethanol,
Amino alcohols such as N-butyl-2,2'-iminodiethanol and 3-diethylamino-1,2-propanediol; aniline, 2,6-dimethylaniline, 2,
3-dimethylaniline, 3,4-dimethylaniline, o
-Aminobenzamide, m-aminobenzamide, p-
Aminobenzamide, m-aminobenzonitrile, o-
Aminobenzonitrile, 2-aminobenzophenone, 4
-Aminobenzophenone, o-aminobenzotrifluoride, m-aminobenzotrifluoride, p-aminobenzotrifluoride, 2-amino-5-chlorotoluene, 4-amino-m-cresol, 5-amino-o-cresol, m-aminodiphenyl, o-aminodiphenyl, p-aminodiphenyl, 2-aminodiphenyl ether, 4-aminodiphenyl ether, 4-aminofluorescein, 2-amino-4-methoxybiphenyl, 2
-Amino-4-nitrophenol, 4-amino-2-nitrophenol, o-aminophenol, m-aminophenol, p-aminophenol, 4-amino-2,3
-Xylenol, 6-amino-2,4-xylenol,
m-anisidine, o-anisidine, p-anisidine, benzidine, 2,2-bis (3-amino-4-methylphenyl) hexafluoropropane, 1,3-bis (m-aminophenoxy) benzene, 2,2- Screw (4
-Aminophenyl) hexafluoropropane, 3,3-
Bis (aminophenyl) sulfone, o-bromoaniline, m-bromoaniline, p-bromoaniline, 4-bromo-2,6-diethylaniline, pn-butoxyaniline, pn-butylaniline, p-sec. -Butylaniline, 6-tert-butyl-o-toluidine, o
-Chloroaniline, m-chloroaniline, p-chloroaniline, 4-chloro-2-nitroaniline, 2,4-diaminodiaminodiphenylamine, 4,4'-diaminodiphenyl ether, 4,4'-diaminodiphenylmethane, 3,3 '-Diaminodiphenylmethane, 3,4'
-Diaminodiphenylmethane, 2,5-dibromoaniline, 2,5-dichloroaniline, 2,4-dimethoxyaniline, 2,4-dinitroaniline, fluoroaniline, iodoaniline, 2-methyl-6-ethylaniline, 2-methyl -5-isopropylaniline, 3-nitro-4-aminotoluene, p-phenylazoaniline,
o-phenylenediamine, m-phenylenediamine, p
-Aniline derivatives such as phenylenediamine, primulin, sulfanilamide, o-toridin, o-toluidine, m-toluidine and p-toluidine.

Further, as the base, N-methylaniline, N-
Ethylaniline, N-n-propylaniline, N-is
o-propylaniline, Nn-butylaniline, N-
iso-butylaniline, Nn-hexylaniline,
N, N-dimethylaniline, N, N-diethylaniline, N, N-di-n-propylaniline, N, N-di-
n-butylaniline, N-ethyl-N-methylaniline, N-n-propyl-N-ethylaniline, N-methyltoluidine, N, N-dimethyltoluidine, N-ethyl-N-methyltoluidine, N-methyl- 2,6-diethylaniline, N, N-dimethyl-2,6-diethylaniline, N-ethyl-N-methyl-2,6-diethylaniline, N-methyldiphenylamine, N-methylphenylenediamine, N, N- Dimethylphenylenediamine, N-methyl-N'-ethylphenylenediamine,
Examples thereof include N- or N, N-alkyl-substituted aniline derivatives such as N, N-diethyl-N ′, N′-dimethylphenylenediamine. If desired, two or more kinds of the above bases may be used in combination.

To carry out the transfer 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 effect, and since the step of removing the base by distillation after the completion of the reaction is increased, it is rather economically disadvantageous.

The reaction temperature and the reaction time vary depending on the type of methallyl aryl ether, the reactivity, and the reaction scale, so that 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 an atmosphere of an inert gas such as nitrogen or argon.

The following compounds are specific examples of the 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, and therefore the reaction product can be used as it is for many purposes. When the product is required, it may be purified by a general method such as vacuum distillation.

[0024]

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 three-necked glass flask equipped with a stirrer, a reflux tube and a thermometer, 50 g of bisphenol A dimethallyl ether and N, N-dimethylaniline (4 mol% relative to bisphenol A dimethallyl ether). ) Was charged and the rearrangement reaction was performed at 195 ± 10 ° C. for 6 hours with stirring. After completion of the reaction, the reaction product was cooled to room temperature and analyzed using ¹ H-NMR spectrum.
o'-dimethallyl bisphenol A is 96.7-98.
7%, and unreacted bisphenol A dimethallyl ether was 1.0 to 2.5%. As a result of analysis by gel permeation chromatography (hereinafter abbreviated as GPC), the dimer [number average molecular weight 820 (styrene equivalent)] was 0.2 to 0.6%.

Example 2-6 Rearrangement was carried out in the same manner as in Example 1 except that N, N-dimethylaniline used in Example 1 and its used amount of 4 mol% were changed to various bases and used amounts. The reaction was carried out. Table 1 shows the ¹ H-NMR spectrum of the reaction product and the results of analysis by GPC.

[0027]

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

Example 7 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 pn-butylaniline (bisphenol F
(4 mol% relative to dimethallyl ether) was charged, and the reaction was carried out at 195 ± 10 ° C. for 6 hours with stirring. After the reaction,
After cooling to room temperature and analyzing using ¹ H-NMR spectrum, the composition of the reaction product was 0,0′-dimethallyl bisphenol F 96.0 to 98.3%, unreacted bisphenol F dimethallyl ether. Was 0.5 to 3.3%. As a result of GPC analysis, the dimer [number average molecular weight 800 (styrene equivalent)] was 0.4 to 1.1%.

Example 8 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 di-n-propylaniline (4 mol% based on 4,4′-dimethallyloxybiphenyl) were charged,
The reaction was carried out at 195 ± 10 ° C. for 6 hours with stirring. After completion of the reaction, the reaction product was cooled to room temperature and analyzed by using a ¹ H-NMR spectrum. As a result, the composition of the reaction product was 4,4 ′-(3.
3'-dimethallyl) biphenol is 96.1 to 98.5.
%, And unreacted 4,4′-dimethallyloxybiphenyl was 0.6 to 3.1%. As a result of GPC analysis, the dimer [number average molecular weight 795 (in terms of styrene)] was 0.3 to 1.0%.

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 9 In a 500 ml three-necked glass flask equipped with a stirrer and a reflux tube, 250 g of 1,1-bis (4-methallyloxyphenyl) cyclohexane and 5.3 g of 4,4'-diaminodiphenylmethane [1] , 1-Bis (4-methallyloxyphenyl) cyclohexane was added thereto and reacted at 205 ± 10 ° C. for 2 hours with stirring.
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 1,1-
Bis (4-hydroxy-3-methallylphenyl) cyclohexane was 96.2 to 98.7%, and unreacted raw materials were 0.3 to 2.7%. As a result of GPC analysis, the dimer [number average molecular weight 890 (converted to styrene)] was 0.2 to 1.1%.

Example 10 250 g of [1,1-bis (4-methallyloxyphenyl) ethyl] benzene and 4,4'-diaminodiphenylmethane were added to a 500 ml glass three-necked flask equipped with a stirrer and a reflux tube. 0 g {4 mol% relative 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 reaction product was cooled to room temperature and analyzed using ¹ H-NMR spectrum.
[1,1-bis (4-hydroxy-3-methallylphenyl) ethyl] benzene is 96.8 to 98.8%,
The unreacted raw material was 0.2 to 2.4%. Also, GPC
As a result of analysis by (1), the dimer [number average molecular weight 905 (converted to styrene)] was 0.1 to 1.3%.

Example 11 600 g of bisphenol A dimethallyl ether was placed in a 1-liter glass three-necked flask equipped with a stirrer and a reflux tube.
And 4,4'-diaminodiphenylmethane 14.2 g
[4 mol% relative to bisphenol A dimethallyl ether] was charged, and the reaction was carried out at 205 ± 10 ° C. for 2 hours with stirring. After completion of the reaction, the reaction product was cooled to room temperature and analyzed using ¹ H-NMR spectrum.
0,0'-dimethallyl bisphenol A is 96.4-9
8.8%, and the unreacted raw material was 0.8 to 2.3%. As a result of GPC analysis, the dimer [number average molecular weight 820 (styrene equivalent)] was 0.2 to 0.7%.

Example 12 The rearrangement reaction was carried out in the same manner as in Example 11 except that pn-butylaniline was used as the base in Example 11. 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 0. 0′-dimethallyl bisphenol A, 96.1 to 98.4%. The raw material for the reaction was 0.7 to 2.4%. Also, G
As a result of analysis by PC, the dimer [number average molecular weight 820 (converted to styrene)] was 0.3 to 0.8%.

[0035]

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, it has solubility in 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, Has no polymerizable functional group,
A method for producing methallylphenols, which comprises performing Claisen rearrangement in the presence of 0.01 to 10 mol% of a base selected from aniline derivatives and saturated aliphatic bases.