JPH0745422B2 - Polycyclic phenoxyarene compound and process for producing the same - Google Patents

Description

TECHNICAL FIELD The present invention relates to a novel polycyclic phenoxyarene compound useful as a polymerizable monomer, and an industrially advantageous production method thereof.

Prior Art Among compounds having a so-called allene bond in which three carbon atoms are bonded to each other by two double bonds, a phenoxyarene compound represented by the formula CH ₂ ═C═CH—OC ₆ H ₅ alone. Since the radical polymerization was published in Polymer Preprints, Japan, 35 (2), 133 (1986), 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 the above-mentioned research, and provides a novel polycyclic phenoxyarene compound useful as a polymerizable monomer. It is one of the purposes. Further, it is one of the objects of the invention to establish an industrially advantageous production method of such a novel phenoxyarene compound.

Means for Solving the Problems According to the present invention, the above-mentioned objects are represented by the general formula (CH ₂ ═C═CH—O _n R (wherein R is a naphthalene, anthracene, or a benzen ring having 2 to 10 linear bonds). A polycyclic aromatic hydrocarbon residue selected from the group consisting of polyphenyl and azobenzene and their nuclear substituents; n is an integer of 1 to 3) and a polycyclic phenoxyarene compound represented by Sent.

Each of the novel polycyclic phenoxyarene compounds according to the present invention is a compound which is solid at room temperature and can be used as a paint or other useful polymer by ionic polymerization or radical polymerization in a molten state or a dissolved state.

The polycyclic phenoxyarene compound of the present invention has the general formula (HO _n R (wherein R is naphthalene, anthracene, benzene ring is 2
A polycyclic aromatic carbon-hydrogen residue selected from the group consisting of linearly bonded polyphenyls, azobenzenes, and nuclear substitution products thereof; n is an integer of 1 to 3) Can be industrially advantageously produced by the method of the present invention, which comprises a step of reacting with a propargyl halide to obtain a propargyloxy polycyclic phenyl compound, and a step of allenylating the compound under basic conditions.

In the above method, examples of the polycyclic phenol compound used as a starting material include α-naphthol, β-naphthol, 2,6-dihydroxynaphthalene, naphthresorcin, 2-oxyanthracene, 9-oxyanthracene, 1, 2-dioxyanthracene, 1,4-dioxyanthracene, 1,5-dioxylanthracene, 1,8-dioxyanthracene, 2,3-dioxyanthracene, 2,6-dioxyanthracene, 2,7- Dioxyanthracene, 1,9-dioxyanthracene, 9,10-dioxyanthracene, 0-phenylphenol, m-phenylphenol, p-phenylphenol, 4,4'-biphenol, 2,2'-biphenol, p
-Hydroxyazobenzene, polyphenyl dioxy derivatives in which 2 to 10 benzene rings are bonded in series, and the nuclear substitution products thereof, for example, halogen, alkyl, cyano, alkoxy, and acyl substitution derivatives. However, in addition to the above, various polycyclic phenols are known, and in the present invention, a poly (phenol having a formula (HO _n R) in which R is naphthalene, anthracene, or a benzene ring having 2 to 10 linear bonds is known. Polycyclic phenols represented by phenyl, azobenzene and halogen, alkyl, cyano, alkoxy or acyl substitution products thereof; n is an integer of 1 to 3) are conveniently used.

In the present invention, a polycyclic phenol is reacted with a propargyl halide in the presence of an alkali, and is represented by the formula (HC≡C = CH ₂ -O _n R (wherein R and n are as described above)). A propargyloxy polycyclic phenyl compound is then prepared which is then alenylated in an isomerization reaction under basic conditions, for example under the action of potassium alcoholate of t-butanol, to give the desired formula (CH ₂ C═C A polycyclic phenoxyarene compound represented by ═CH—O _n R is obtained.

The polycyclic phenoxyarene compounds thus obtained can be used as monofunctional or polyfunctional monomers for ionic polymerization or radical polymerization with compounds not described in any literature, and also show crystallinity and liquid crystallinity at room temperature solids. In addition, it can be used for the purpose of controlling the reaction temperature during melting, and is expected to have a wide range of uses.

The present invention will be described below with reference to examples.

Example 1 To a flask equipped with a stirrer, a thermometer, a nitrogen introduction tube, and a reflux condenser, 21.259 g of 1-naphthol, 53.086 g of ion-exchanged water, 6.675 g of NaOH, and 0.120 g of tetrabutylammonium bromide were added and dissolved. did. Then, 18.859 g of propargyl bromide was added dropwise and reacted at 80 ° C. for 6 hours.

After the reaction was completed, the content was treated with ether / DIW, and the ether layer was separated. Then, magnesium sulfate was added and left overnight to dehydrate. Magnesium sulfate was filtered off, and ether was distilled off with an evaporator. Then, it was isolated and purified by column chromatography (silica gel mesh 200) to obtain 1-propargyloxynaphthalene. Yield: 63.6 (%) Then, using the same reaction procedure, t-BuOK 1.532g,
6.186 g of t-BuOH was weighed out, and 10.000 g of 1-propargyloxynaphthalene and 23.333 g of t-BuOH were added dropwise. Then, the mixture was reacted at 50 ° C for 60 minutes. Then, ion-exchanged water was added to stop the reaction, and the t-BuOH layer / water layer was distilled off with an evaporator. Then, an aqueous NaOH solution was added, followed by ether extraction. The ether was distilled off with an evaporator, and then isolated and purified by column chromatography (silica gel mesh 200) to obtain colorless transparent oily 1-arenyloxynaphthalene.

The structure was confirmed by FT-NMR (H) and IR. Yield: 4
It was 3.0 (%).

Example 2 A flask equipped with a stirrer, thermometer, nitrogen inlet tube, and reflux condenser tube was charged with 2-hydrochianthracene 26.677.
g, ion-exchanged water 49.444 g, NaOH 6.217 g, and tetrabutylammonium bromide 0.096 g were added and dissolved. Then,
Add 18.859g of propargyl bromide and add 6 at 80 ℃.
Reacted for hours.

After the reaction was completed, the content was treated with ethyl acetate / DIW, and the ethyl acetate layer was separated. Then add magnesium sulfate,
It was left overnight and dehydrated. Magnesium sulfate was filtered off, and ethyl acetate was distilled off with an evaporator. Then, it was isolated and purified by column chromatography (silica gel mesh 200) to obtain 2-propargyloxyanthracene. Yield: 43.6 (%) Then, using the same reaction procedure, t-BuOK1.203g, TH
F6.816g was weighed and 2-propargyloxyanthracene 10.000g and THF23.333g were dripped.

Then, the mixture was reacted at 50 ° C for 60 minutes. Then, ion-exchanged water was added to stop the reaction. The THF layer / water layer was distilled off with an evaporator. Then, subsequently, it was isolated and purified by column chromatography (silica gel mesh 200) to obtain 2-allenyloxyanthracene as crystals (mp: 90.3-95.6c).

The structure was confirmed by FT-NMR (H) and IR. Yield: 5
It was 6.5 (%).

Example 3 In a flask equipped with a stirrer, a thermometer, a nitrogen introducing tube, and a reflux condenser, p-hydroxybiphenyl 24.140 was added.
g, ion-exchanged water 51.120 g, NaOH 6.427 g, and tetrabutylammonium bromide 0.127 g were added and dissolved. Then,
Add 18.161g of propargyl bromide and add 6 at 80 ℃.
Reacted for hours.

After the reaction was completed, it was treated with an aqueous solution of NaOH and separated with ethyl acetate. Then, magnesium sulfate was added and left overnight to dehydrate. Magnesium sulfate was filtered and ethyl acetate was distilled off with an evaporator. Then, it is isolated and purified by column chromatography (silica gel mesh 200), and 1-
Propargyloxybiphenyl was obtained. Yield: 53.1
(%) Then, using the same reaction measures, t-BuOK1.34
2 g and THF 7.607 g were weighed and 1-propargyloxybiphenyl 10.000 g and THF 23.333 g were added dropwise. After that, 50
The reaction was carried out at 60 ° C for 60 minutes. After that, add deionized water,
The reaction was stopped.

The THF layer / water layer was distilled off with an evaporator. After that, continue column chromatography (silica gel mesh)
200) for isolation and purification to give 4-allenyloxybiphenyl as a colorless oil.

The structure was confirmed by FT-NMR (H) and IR. Yield: 6
It was 3.2 (%).

Example 4 In a flask equipped with a stirrer, thermometer, nitrogen inlet tube, and reflux condenser, 2,7-dihydroxynaphthalene 21.
028 g, ion-exchanged water 46.103 g, NaOH 11.593 g, and tetrabutylammonium bromide 0.112 g were added and dissolved. Then, 32.756 g of propargyl bromide was added dropwise to 80 ° C.
And reacted for 6 hours.

After the reaction was completed, the content was treated with ether / DIW, and the ether layer was separated. Then, magnesium sulfate was added and left overnight to dehydrate. Magnesium sulfate was filtered off, and ether was distilled off with an evaporator. Then, it was isolated and purified by column chromatography (silica gel mesh 200) to obtain 2,7-dipropargyloxynaphthalene. Yield: 43.6 (%) Then, using the same reactor, t-BuOK2.316g,
13.108 g of THF was weighed and 10.000 g of 2,7-dipropargyloxynaphthalene and 23.333 g of THF were added dropwise. Then 6 at 50 ° C
The reaction was allowed for 0 minutes. Then, ion-exchanged water was added to stop the reaction.

The THF layer / water layer was distilled off with an evaporator. After that, continue column chromatography (silica gel mesh)
200) isolated and purified, white crystals (mp = 80.5-83.5c)
2,7-dialenenyloxynaphthalene was obtained.

The structure was confirmed by FT-NMR (H) and IR. Yield: 4
5.3 (%) Example 5 A flask equipped with a stirrer, a thermometer, a nitrogen introduction tube, and a reflux condenser was charged with 20,4-814 g of 4,4-biphenol, 40.285 g of deionized water, 10.131 g of NaOH, and 0.133 g of tetrabutylammonium bromide. Added and dissolved. Then, 28.623 g of propargyl bromide was added dropwise and reacted at 80 ° C. for 6 hours.

After the reaction was completed, the content was treated with ethyl acetate / DIW, and the ethyl acetate layer was separated. Then add magnesium sulfate,
It was left overnight and dehydrated. Magnesium sulfate was filtered off, and ethyl acetate was distilled off with an evaporator. Then, it was isolated and purified by column chromatography (silica gel mesh 200) to obtain 4,4-dipropargyloxybiphenyl. Yield: 42.2 '(%) Then, using the same reaction procedure, t-BuOK2.124g,
12.036 g of THF was weighed out, and 10.000 g of 4,4′-dipropayloxybiphenyl and 23.333 g of THF were added dropwise. Then 50
The reaction was carried out at a temperature of ° C for 60 minutes. Then, ion-exchanged water was added to stop the reaction.

The THF layer / water layer was distilled off with an evaporator. After that, continue column chromatography (silica gel mesh)
200) isolated and purified by pale yellow crystals (mp: 135.2-138.
5c) 4,4'-Diarenyloxy-biphenyl was obtained.

The structure was confirmed by FT-NMR (H) and IR. Yield: 3
It was 5.3 (%).

Examples 6 to 9 The following compounds were obtained by the same reaction.

Claims (3)

[Claims] 1. A compound represented by the general formula (CH ₂ ═C═CH—O _n R (wherein R is naphthalene, anthracene or benzene ring is 2
A polycyclic aromatic hydrocarbon residue selected from the group consisting of linearly bonded polyphenyl of 10 to 10 and azobenzene and their nuclear substituents; n is an integer of 1 to 3) Phenoxyarene compound. 2. The general formula (HO _n R (wherein R is naphthalene, anthracene, benzene ring is 2
~ 10 linearly bonded polyphenyl, azobenzene,
And a polycyclic aromatic hydrocarbon residue selected from the group consisting of their nuclear substituents; n is an integer of 1 to 3), and a polycyclic phenol compound represented by formula _{(HC≡C-CH 2 -O n R} ( step of allenyl step, and the compound under basic obtaining propargyloxy polycyclic phenyl compounds represented by each of the R and n formula as to above) The method for producing a polycyclic phenoxyarene compound according to claim 1, which comprises 3. A compound represented by the general formula (HC≡C—CH ₂ —O _n R (wherein R is naphthalene, anthracene or benzene ring is 2
To a polycyclic aromatic hydrocarbon residue selected from the group consisting of linearly bonded polyphenyl and azobenzene and their nuclear substituents; n is an integer of 1 to 3) Formula phenyl compound.