JP2532271B2 - Polyfunctional phenoxyarene compounds and their preparation - Google Patents

Description

TECHNICAL FIELD The present invention relates to a novel polyfunctional phenoxyarene compound and an industrially advantageous production method thereof.

Among the compounds prior art three carbon atoms have a so-called allene bond attached at two double bonds with each other, phenoxy allene compound represented by the formula _{CH 2 = C = CH-O} -C 6 H 5 Since the publication of homo-radical polymerization of phenoxyallene compound in Polymer Preprints, Japan, 35 (2), 133 (1986) and the like, interest in such phenoxyarene compounds and polymers has been increasing. This is because not only are such phenoxyarene compounds capable of radical polymerization in the same way as vinyl monomers, but they are also radically polymerized into the main chain. A polymer containing a structural unit represented by is obtained, and since it has an ionically polymerizable or radically polymerizable vinyl ether group, an allyl group, or a reactive phenoxy group in the molecule, a new substance based on these is further developed. This is because it is expected to have a wide range of applications in various fields such as coating materials and the way of synthesizing.

The present inventors (In the formula, X is an alkoxy group having 1 to 4 carbon atoms, and 1 to 4 carbon atoms.
An alkyl group, a halogen or a cyano group of), a propargyl ether derived from a reaction of a substituted phenol represented by (Wherein X is as described above), a large number of substituted phenoxyarene compounds represented by
By its homo-radical polymerization or copolymerization with other α, β ethylenically unsaturated compounds, a reactive polymer having a vinyl ether group, an allyl group, and a substituted phenoxy group was obtained, and a patent application was filed. (Japanese Patent Application No. 62-146370) Problems to be Solved by the Invention The present invention is a further development of these studies, and is a novel allene compound as a raw material of a reactive polymer, especially a new type of polyfunctional allene compound. Is one of the main purposes. It is also an object of the invention to establish an industrially advantageous method for producing such a polyfunctional allene compound.

According to the present invention, according to the present invention, the above-mentioned objects are represented by the general formula: HO-ph-R-ph-OH (where ph is a phenyl group, a halogenated phenyl group, a cyano-substituted phenyl group, or an alkoxy-substituted phenyl group). Represents a group, and R represents a polyphenol compound represented by an aliphatic hydrocarbon having 1 to 6 carbon atoms, an alicyclic hydrocarbon or an aliphatic or alicyclic hydrocarbon residue containing an ether bond) and a propargyl halide. And a step of obtaining a phenylpropargyl ether represented by the general formula HC≡C-CH ₂ -O-ph-RO-CH ₂ -C≡CH (wherein ph and Rh are as described above),
And a phenylpropargyl ether which is allenylated under basic conditions.

Formula _{CH 2 = C = CH-O} -ph-R-ph-O-CH = C = CH 2 ( wherein ph represents a phenyl group, halogenated phenyl group, an alkyl-substituted phenyl group, a cyano-substituted phenyl group or an alkoxy-substituted Represents a phenyl group, and R represents an aliphatic hydrocarbon having 1 to 6 carbon atoms, an alicyclic hydrocarbon, or an aliphatic or alicyclic hydrocarbon residue containing an ether bond).

Formula HO-ph-R-ph-OH used as a starting material in the method of the present invention (wherein ph represents a phenyl group, a halogenated phenyl group, an alkyl-substituted phenyl group, a cyano-substituted phenyl group or an alkoxy-substituted phenyl group) , R is 1 to 6 aliphatic hydrocarbon, alicyclic hydrocarbon or an aliphatic or alicyclic hydrocarbon residue containing an ether bond), and polyphenol compounds represented by bisphenol A are various ones. Is known, and can be easily synthesized by condensation dehydration of a suitable ketone compound and carboxylic acid. Specifically, for example, bis (2-hydroxyphenyl) methane bis (3-hydroxyphenyl) methane bis (4-hydroxyphenyl) methane bis (2-hydroxy-4-methylphenyl) methane bis (2-hydroxy-5-). Methylphenyl) methane Bis (2-hydroxy-6-methylphenyl) methane Bis (4-hydroxy-2-methylphenyl) methane Bis (4-hydroxy-3-methylphenyl) methane Bis (3-hydroxy-2,4, 6-trimethylphenyl)
Methane Bis (2-hydroxy-4-propylphenyl) methane Bis (4-hydroxy-2-propylphenyl) methane Bis (4-hydroxy-2-methyl-6-ethylphenyl) methane Bis (4-hydroxy-2,3 , 5,6-Tetramethylphenyl) methane bis (2-hydroxy-4-tert-butylphenyl) methane bis (4-hydroxy-2-methyl-5-isopropylphenyl) methane bis (4-hydroxy-3-methyl- 6-isopropylphenyl) methane bis (4-hydroxy-2-tert-butyl-5-methylphenyl) methane bis (4-hydroxy-2,6-di-tert-butylphenyl) methane bis (4-hydroxy- 2-chlorophenyl) methane bis (4-hydroxy-2,6-dichlorophenyl) methane bis (2-hydroxy-4-brom Mophenyl) methane bis (3-hydroxy-2,4,6-trichlorophenyl)
Methane bis (4-hydroxy-2-methoxyphenyl) methane 2,2-bis (4-hydroxyphenyl) propane 2,2-bis (4-hydroxy-2-methylphenyl) propane 2,2-bis (4-hydroxy) -2,6-dibromophenyl)
Examples include propane 1,1-bis (4-hydroxyphenyl) cyclohexane.

The first step of the method of the present invention is the reaction of the above polyphenol compound with a propargyl halide, for example propargyl bromide, of the formula HC≡C-CH ₂ -O-ph-R-ph-O-CH ₂ -C≡CH (ph And R are the steps for obtaining the phenylpropargyl ether represented by the above), but the above reaction is carried out in a high yield in accordance with the Williamson method of synthesizing an alkylaryl ether by reacting phenol and an alkyl halide under alkaline conditions. The desired ether can be obtained with.

In the present invention, further, the obtained phenylpropargyl ether is allenylated under basicity to obtain the final polyfunctional phenoxyarene compound.

This allenylation usually proceeds with a potassium alcoholate of t-butyl alcohol to carry out an isomerization reaction, which leads to an extremely high yield. Thus obtained general formula CH ₂ ═C═CH—O-ph-R— The phenoxyarene compound represented by the formula: ph-O-CH = C = CH ₂ (wherein ph and R are as described above) is a compound not described in the literature, either alone or in other α, β-ethylenic compounds. It can be radically polymerized in the presence of an unsaturated compound and is useful as a raw material for producing a novel polymer.

When the above exemplified polyphenol compounds are used, the following allene compounds can be obtained.

Bis (2-arenyloxyphenyl) methane Bis (3-arenyloxyphenyl) methane Bis (4-arenyloxyphenyl) methane Bis (2-arenyloxy-4-methylphenyl) methane Bis (2-arenyloxy-5-) Methylphenyl) methane Bis (2-arenyloxy-6-methylphenyl) methane Bis (4-arenyloxy-2-methylphenyl) methane Bis (4-arenyloxy-3-methylphenyl) methane Bis (4-arenyloxy-2,4, 6-Trimethylphenyl) methane Bis (2-allenyloxy-4-propylphenyl) methane Bis (4-allenyloxy-2-propylphenyl) methane Bis (4-allenyloxy-2-methyl-6-ethylphenyl) methane Bis (3- Allenyloxy-2,3,5,6-tetramethylphene ) Methane bis (2-allenyloxy-4-tert-butylphenyl) methane bis (4-allenyloxy-2-methyl-5-isopropylphenyl) methane bis (4-allenyloxy-3-methyl-6-isopropylphenyl) methane bis (4-Allenyloxy-2-tert-butyl-5-methylphenyl) methane Bis (4-allenyloxy-2,6-di-tert-butylphenyl) methane Bis (4-arenyloxy-2-chlorophenyl) methane Bis (4- Allenyloxy-2,6-dichlorophenyl)
Methane Bis (2-allenyloxy-4-bronophenyl) methane Bis (3-allenyloxy-2,4,6-trichlorophenyl) methane Bis (4-arenyloxy-2-methoxyphenyl) methane 2,2′-bis (4-arene Nyloxyphenyl) propane 2,2′-bis (4-arenyloxy-2-methylphenyl) propane 2,2′-bis (4-arenyloxy-2,6-dibromophenyl) propane 1,1′-bis (4- Allenyloxyphenyl) cyclohexane The present invention will be described below with reference to Examples. Unless otherwise specified, all parts and percentages are by weight.

Example 1 A flask equipped with a stirrer, a thermometer, a nitrogen inlet tube, and a reflux condenser was charged with 2.206 (2.2-bis (4-hydroxyphenyl) propane) propane, 2.39 g of deionized water, and NaOH7.18.
g, tetrabutylammonium bromide 0.162 g, and dioxane 78.65 g were added and dissolved. Then, 21.36 g of propargyl bromide was added dropwise and reacted at 80 ° C. for 4 hours. After completion of the reaction, dioxane was distilled off with an evaporator, the content was treated with ether / DIW and a 1N-NaOH aqueous solution, and the ether layer was separated. Then, magnesium sulfate was added and left overnight to dehydrate. Magnesium sulfate was filtered off, and the ether was distilled off with an evaporator to obtain 2,2'-bis (4-propargyloxyphenyl) propane in crystalline form (melting point: 76.5 ° C). Yield: 43.6 (%) Then, using the same reactor, t-BuOK0.92
g, t-BuOH 4.76 g was weighed and completely dissolved.
A solution of 5.00 g of 2'-bis (4-propargyloxyphenyl) propane dissolved in 10.99 g of t-BuOH was added dropwise.
Then, the mixture was reacted at a temperature of 60 ° C for 30 minutes. Thereafter, ion-exchanged water was added to stop the reaction.

The t-BuOH layer / water layer was separated, and the water layer was further subjected to ether extraction. Then, both the t-BuOH layer and the ether layer were distilled off with an evaporator to obtain a brown liquid.

The liquid was isolated and purified by column chromatography (silica gel mesh 200) to obtain colorless transparent oily 2,2′-bis (4-arenyloxyphenyl) propane.

The structure was confirmed by FT-NMR (H) and IR. yield:
43.0 (%) Example 2 34.18 g of bis (4-hydroxyphenyl) methane, 30.72 g of ion-exchanged water, and NaOH 1 were placed in a flask equipped with a stirrer, a thermometer, a nitrogen introduction tube, and a reflux condenser.
5.45 g and tetrabutylammonium bromide 0.31 g were added and dissolved, and then propargyl bromide 6
9.34 g was added dropwise and reacted at 80 ° C. for 6 hours.

After the reaction was completed, the content was treated with ether / DIW and 1N-NaOH aqueous solution, and the ether layer was separated. Thereafter, magnesium sulfate was added, and the mixture was allowed to stand overnight to be dehydrated. After filtering magnesium sulfate, the ether was distilled off with an evaporator,
An oily substance was obtained. After that, it was isolated and purified by column chromatography (silica gel mesh 200),
Bis (4-propargyloxyphenyl) methane was obtained.
Yield: 63.2 (%) Then, using the same reactor, t-BuOH0.532
g and t-BuOH 8.02 g were weighed and completely dissolved, and 7.94 g of bis (4-propargylphenyl) methane was added to t-BuOH1.
What was melt | dissolved in 8.58g was dripped. Then, the reaction was carried out at a temperature of 60 ° C. for 30 minutes, ion-exchanged water was added to stop the reaction.

The t-BuOH layer / water layer was separated, and the water layer was further subjected to ether extraction, and both the t-BuOH layer and the ether layer were distilled off with an evaporator to obtain a brown oily substance.

Using ethyl acetate / hexane as a developing solvent,
Column chromatography (silica gel mesh 20
0) isolated and purified with colorless transparent oily bis (4
-Allenyloxyphenyl) methane was obtained.

The structure was confirmed by FT-NMR (H) and IR. yield:
It was 53.0 (%).

Example 3 27.478 g of 1,1′-bis (4-hydroxyphenyl) cyclohexane and 36.88 of ion-exchanged water were placed in a flask equipped with a stirrer, a thermometer, a nitrogen introduction tube, and a reflux condenser.
2g, NaOH 9.270g, tetrabutylammonium bromide
0.161 g was added and dissolved, and then 26.205 g of propargyl bromide was added dropwise and reacted at 80 ° C. for 6 hours.

After the reaction was completed, the contents were converted into ether / DIW and 1N-Na.
It was treated with an aqueous OH solution and the ether layer was separated. Thereafter, magnesium sulfate was added, and the mixture was allowed to stand overnight to be dehydrated. After filtering magnesium sulfate, ether was distilled off by an evaporator to obtain an oily substance. After that, it was purified by column chromatography (silica gel mesh 200) to obtain 1,1'-bis (4-propargyloxyphenyl).
Cyclohexane was obtained. Yield: 53.1 (%) Then, using the same reactor, t-BuOK1.620
g, t-BuOH 9.185 g, and weighed 1,1'-bis (4-propargyloxyphenyl) cyclohexane 10.00 g to t-Bu
After dropping 23.333 g of OH, the reaction was carried out at a temperature of 50 ° C. for 60 minutes, and ion-exchanged water was added to stop the reaction. t-BuOH
The layers / water layer were separated, and the hydrogen was further extracted with ether, and both the t-BuOH layer and the ether layer were distilled off with an evaporator to obtain a brown oily substance.

Then, it was isolated and purified by column chromatography (silica gel mesh 200) to obtain colorless and transparent oily 1,1-bis (4-arenyloxyphenyl) cyclohexane.

The structure was confirmed by FT-NMR (H) and IR. yield:
43.5 (%) Example 4 A flask equipped with a stirrer, a thermometer, a nitrogen introduction tube, and a reflux condenser was charged with 1,1-bis (2-methyl-4-).
(Hydroxy-5-butylphenyl) butane 35.070 g Ion-exchanged water 36.880 g, NaOH 9.270 g, tetraftyammonium bromide 0.161 g were added, and then propargyl.
23.4506 g of bromide was added dropwise, and the mixture was reacted at 80 ° C. for 6 hours.

After the reaction was completed, the content was treated with ether / DIW and 1N-NaOH aqueous solution, and the ether layer was separated. Then, magnesium sulfate was added and left overnight to dehydrate. After filtering magnesium sulfate, the ether was distilled off with an evaporator to obtain an oily substance. Then column chromatography 1,
1-Bis (2-methyl-4-propaloxy-5-butylphenyl) butane was obtained. Yield: 43.2 (%) Then, using the same reactor, t-BuOK1.219gt-B
uOH 6.904 g was weighed and 1,1-bis (2-methyl 4-propargyloxy-5-butylphenyl) butane 10.00 g and t
-BuOH 23,332g was dripped. Then, the mixture was reacted at 50 ° C. for 60 minutes, ion-exchanged water was added to stop the reaction. t-Bu
The OH / water layer is separated, and the water layer is further extracted with ether,
Both the t-BuOH layer and the ether layer were distilled off by an evaporator to obtain a brown oily substance.

Then, it was isolated and purified by color chromatography (silica gel mesh 200) to obtain colorless and transparent oily 1,1-bis (2-methyl-4-arenyloxy-5-butylphenyl) butane.

The structure was confirmed by FT-NMR (H) and IR. yield:
55.0 (%) 1,1-Bis (2-methyl-4-allenyloxy-5-butylphenyl) butane The following compounds were obtained by the same method.

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁶ Identification code Internal reference number FI Technical display area C07C 255/54 C07C 255/54 // C08F 36/02 MPM C08F 36/02 MPM (72) Inventor Keizo Ishii 19-17 Ikedanaka-cho, Neyagawa-shi, Osaka Japan Paint Co., Ltd. (72) Inventor Kei Aoki 19-17 Ikedanaka-cho, Neyagawa-shi, Osaka Japan Paint Co., Ltd.

Claims (2)

(57) [Claims] 1. A general formula CH ₂ = C = CH-O-ph-R-ph-O-CH = C = CH ₂ (wherein ph is a phenyl group, a halogenated phenyl group, an alkyl-substituted phenyl group, a cyano group). Represents a substituted phenyl group or an alkoxy-substituted phenyl group, and R represents an aliphatic hydrocarbon having 1 to 6 carbon atoms, an alicyclic hydrocarbon or an aliphatic or alicyclic hydrocarbon residue containing an ether bond) A polyfunctional phenoxyarene compound. 2. A general formula HO-pH-R-ph-OH (wherein ph is a phenyl group, a halogenated phenyl group, an alkyl-substituted phenyl group, a cyano-substituted phenyl group, or
A polyphenol compound represented by an alkoxy-substituted phenyl group, R is an aliphatic hydrocarbon having 1 to 6 carbon atoms, an alicyclic hydrocarbon, or an aliphatic or alicyclic hydrocarbon residue containing an ether bond, and a halogenated propargyl group. To obtain the general formula HC≡C-CH ₂ -O-ph-R-ph-O-CH ₂ -C-≡CH (wherein ph and R are as described above), and The method for producing a polyfunctional phenoxyarene compound according to claim 1, which comprises a step of allenylating phenylpropargyl ether under basic conditions.