JPH0621106B2 - Aryloxy allene compound having polar group and method for producing the same - Google Patents

Description

TECHNICAL FIELD The present invention relates to a novel aryloxyarene compound having a polar group, which is 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. Radical Polymerization by Polymer Preprints, Japan,
Since it was announced in 35 (2), 133 (1986), etc.
There is increasing interest in such phenoxyarene compounds and polymers. 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 an object thereof is to provide a novel aryloxyallene compound useful as a polymerizable monomer. Is one. Further, conventional phenoxyarene compounds merely carry an ionic or radically polymerizable unsaturated bond, but by additionally carrying a functional functional period with these groups, a new application is cultivated. This is also one of the objects of the present invention. Further, it is one of the objects of the invention to establish an industrially advantageous production method of such a novel aryloxyallene compound.

Means for Solving the Problems According to the present invention, the above-mentioned object is represented by the general formula (HO-) nR- (A) m (wherein R is benzene, naphthalene, anthracene, bisphenols and benzene ring is 2 to 10). An aromatic hydrocarbon residue selected from the group consisting of individual linearly bonded p-polyphenyls and their halogen, alkyl, cyano, and alkoxy nucleus substitution products; A is -COOH or -SO
₃ H group; n is an integer of 1 to 10; m is an integer of 1 to 3), a step of reacting a hydroxyaryl compound having a polar group with propargyl halide to obtain an aryl propargyl ether, and the aryl propargyl formula by the method of the present invention comprising a step of allenyl of isomerization reaction under basic conditions with ether _{(CH 2 = C = CH-} O-) n-R- (a) m ( wherein R is benzene, An aromatic hydrocarbon residue selected from the group consisting of naphthalene, anthracene, bisphenols, p-polyphenyl having 2 to 10 linearly bonded benzene rings, and halogen, alkyl, cyano, or alkoxy nucleus substitution products thereof; A is -COOH or -SO
₃ H group; n is an integer of 1 to 10; m is an integer of 1 to 3) can be achieved by providing an aryloxyarene compound having a polar group.

A polar group (COOH or SO ₃ H group) represented by the general formula (HO-) nR- (A) m (wherein R, A, m and n are as described above) used as a starting material in the method of the present invention Are known per se, for example, O-hydroxybenzoic acid, m-hydroxybenzoic acid, p-hydroxybenzoic acid, p-hydroxybenzenesulfonic acid, O
-Cresolsulfonic acid, p-hydroxyacetic acid, p-hydroxyphenylpropionic acid, 1-naphthol-2-
Carboxylic acid, 2-naphthol-3-carboxylic acid, 2-naphthol-6-carboxylic acid, 1-naphthol-4-sulfonic acid, 1-naphthol-8-sulfonic acid, 2-naphthol-6-sulfonic acid, 1, 4-dihydroxy-2-naphthoic acid, 1-naphthol-3,6-disulfonic acid, 4'-
Hydroxybiphenyl-4-carboxylic acid, 2,2'-biphenol-3-carboxylic acid, 4-hydroxybiphenyl-3-carboxylic acid, 2-hydroxybiphenyl-3-carboxylic acid, 2- (4'-hydroxybenzeneazo) Benzoic acid, 2,2'-bis (4-hydroxyphenyl) -1-
Carboxyl-propane and the like are conveniently used. However, these are only examples of the starting hydroxyaryl used in the present invention, and include benzene, naphthalene, anthracene and bis (hydroxyphenyl) methane, 2,2'-bis (4-hydroxyphenyl) propane, 1,1 '. An aromatic hydrocarbon selected from bisphenols such as bis (4-hydroxyphenyl) cyclohexane and p-polyphenyl having 2 to 10 benzene rings, 1 to 10 hydroxyl groups and 1 to 3 Any aromatic phenol may be used as long as it has a carboxyl group or a sulfonic acid group.

In the present invention, a hydroxyaryl having a polar group as described above is reacted with a propargyl halide, preferably propargyl bromide, under alkaline conditions,
General formula (Wherein R, A, n, and m are as described above), an aryl propargyl ether is prepared.
In the reaction, it is convenient to use an inert solvent such as dioxane, benzene, toluene, xylene, or an ester, and to proceed the reaction by heating and stirring, and the target arylpropargyl ether can be obtained by distilling off the solvent.

In the present invention, the above aryl propargyl ether is then anylated under a basic condition, for example, by reacting with potassium aracholate of t-butanol in an isomerization reaction to obtain the target compound of the formula (CH ₂ = C ₂ = CH-O-) nR- (A) m (wherein R, A, m, and n are as described above), an aryloxyarene compound can be produced.

The aryloxyallene compounds thus obtained are all compounds not described in the literature, and since they have polar groups, they are all water-soluble and are extremely useful as polymer raw materials.

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

Example of Aryloxyallene Compound Having Polar Group Example 1 p-Hydroxybenzoic acid 19.276 in a flask equipped with a stirrer, thermometer, nitrogen inlet tube, and reflux condenser tube.
g, deionized water 50.242 g, NaOH 12.633 g, and citrabutylammonium bromide 0.011 g were added and dissolved. Then, 17.848 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 1N-HCl and then with ether / DIW to separate the ether layer. 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-propargyloxybenzene-4-carboxylic acid. Yield: 4
3.6 (%) Then, using the same reactor, t-BuOK 7.920
g, t-BuOH 44.882 g was weighed and 1-propargyloxybenzene-4-carboxylic acid 10.000 g and t-Bu
23.333 g of OH was added dropwise. Then, the mixture was reacted at 50 ° C for 60 minutes. Then, ion-exchanged water was added to stop the reaction. t-BuOH layer / water layer was t-Bu with an evaporator.
OH was distilled off. Then, 1N-HC1 was added, and the mixture was extracted with ether. The ether was distilled off with an evaporator, followed by column chromatography (silica gel).
The product was isolated and purified with a mesh (200) to give colorless and transparent oily 1-alkenyloxybenzene-4-carboxylic acid.

The structure was confirmed by FT-NMR (H) and IR.
Yield: 43.0 (%) Example 2 In a flask equipped with a stirrer, a thermometer, a nitrogen introduction tube, and a reflux condenser, 23.256 g of p-hydroxybenzenesulfonic acid, 48.065 g of ion-exchanged water, and NaOH 11.4.
82 g, tetrabutylammonium bromide 0.121 g
Was added and dissolved. Then, Provalgill bromide
17.075 g was added dropwise and reacted at 80 ° C. for 6 hours.

After the reaction was completed, the content was treated with 1N-HCl and then with ether / DIW to separate the ether layer. 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-propargyloxybenzene-4-sulfonic acid. Yield: 5
3.7 (%) Then, using the same reactor, t-BuCK 6.
580 g and t-BuOH 37.289 g were weighed, and 1-propargyloxybenzene-4-sulfonic acid 10.000 g and t-BuCH 23.333 g were added dropwise. After that, at 50 ℃
The reaction was carried out for 60 minutes. Then, ion-exchanged water was added to stop the reaction. The t-BuOH layer / water layer was evaporated to remove t-BuOH. Then, 1N-HCI was added, and the mixture was extracted with ether. The ether was distilled off with an evaporator, and then purified by column chromatography (silica gel mesh 2000).
Colorless and oily 1-allenyloxybenzene-4
-Sulfonic acid was obtained.

The structure was confirmed by FT-NMR (H) and IR.
Yield: 56.5 (%) Example 3 A flask equipped with a stirrer, a thermometer, a nitrogen inlet tube, and a reflux condenser was charged with p-hydroxybiphenyl-4.
-Carboxylic acid 26.989g, ion-exchanged water 45.360g, N
11.406 g of aOH and 0.129 g of tetrabutylammonium bromide were added and dissolved. Then, Propargil
16.114 g of bromide was added dropwise and reacted at 80 ° C. for 6 hours.

After the reaction was completed, the content was treated with 1N-HCL and then with ether / DIW to separate the ether layer. 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-propargyloxybiphenyl-4-carboxylic acid. Yield: 63.3 (%) Then, using the same reactor, t-BuOK 5.540 g,
After weighing 31.546 g of t-BuOH, 10.000 g of 1-propargyloxybiphenyl-4-carboxylic acid and t-B
23.333 g of uOH was added dropwise. Then, the mixture was reacted at 50 ° C for 60 minutes. Then, ion-exchanged water was added to stop the reaction.

The t-BuOH layer / water layer was t-BuOH by an evaporator.
Was distilled off. Then, 1N-HCI was added, and the mixture was extracted with ether. Ether was distilled off with an evaporator,
Then, it was isolated and purified by column chromatography (silica gel mesh 200) to give pale yellow crystals (mp = 122.5-
128.3c) of 1-allenyloxybiphenylcarboxylic acid was obtained. The structure was confirmed by FT-NMR (H) and IR. Yield: 43.0 (%).

Example 4 31.546 g of sodium 2-naphthol-6-sulfonate, 46.124 g of ion exchanged water, and N were placed in a flask equipped with a stirrer, a thermometer, a nitrogen introduction tube, and a reflux condenser.
5.799 g of aOH and 0.144 g of tetrabutylammonium bromide were added and dissolved. Then, Propargil
16.385 g of bromide was added dropwise and reacted at 80 ° C. for 6 hours.

After the reaction was completed, the content was treated with 1N-HCL and then with ether / DIW to separate the ether layer. 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-propargyloxynaphthalene-6-sulfonic acid. Yield: 33.6 (%) Then, using the same reaction procedure, t-BuOK 5.329
g, t-BuOH (30.199 g) was weighed, and 2-propargyloxynaphthalene-6-sulfonic acid (10.000 g) and t
-BuOH 23.333g was dripped. Then 60 at 50 ° C
Let react for minutes. Then, ion-exchanged water was added to stop the reaction.

The t-BuOH layer / water layer was t-BuOH by an evaporator.
Was distilled off. Then, 1N-HCL was added, and ether extraction was performed subsequently. The ether was removed by evaporation using an evaporator and then column chromatography (silica gel).
Isolation and purification with a mesh 200), white crystals (mp = 8
0.5-83.5 ° C) 2-Allenyloxynaphthalene-6-
Sulfonic acid was obtained.

The structure was confirmed by FT-NMR (H) and IR.
Yield: 45.3 (%).

Example 5 In a flask equipped with a stirrer, a thermometer, a nitrogen introduction tube, and a reflux condenser, 23.478 g of 4,4-bis (4-hydroxyphenyl) valeric acid and ion-exchanged water 4
4.279 g, 11.135 g of NaOH and 0.133 g of tetrabutylammonium bromide were added and dissolved. Then, 20.974 g of propargyl bromide was added dropwise and the mixture was heated at 80 ° C for 6 minutes.
Reacted for hours. After the reaction was completed, the content was treated with 1N-HCL and then with ether / DIW to separate the ether layer. Then, magnesium sulfate was added and the mixture was left standing overnight for dehydration. 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), and 4,4-bis (4-propargyloxyphenyl)
I got valeric acid. Yield 62.2 (%) Then, using the same reaction procedure, t-BuOK4.621
g, t-BuOH 26.183 g was weighed and 4,4-bis (4-propargyloxyphenyl) valeric acid 10.000 g
And t-BuOH (23.333 g) were added dropwise. After that, at 50 ℃
The reaction was carried out for 60 minutes. Then, ion-exchanged water was added to stop the reaction. The t-BuOH layer / water layer was evaporated to remove t-BuOH. Then, 1N-HCL was added, and ether extraction was performed subsequently. The ether was distilled off with an evaporator and then isolated and purified by column chromatography (silica gel mesh 200) to obtain a colorless and transparent oily 4,4-bis (4-arenyloxyphenyl) valeric acid.

The structure was confirmed by FT-NMR (H) and IR.
Yield: 45.3 (%).

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

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁵ Identification number Internal reference number FI Technical indication location C07C 309/43 7419-4H C08F 36/20 MPM 8416-4J (72) Inventor Keizo Ishii Osaka Neyagawa 19-17 Ikedanaka-cho, Ichi, Japan, Japan Paint Co., Ltd. (56) References JP-A-58-206590 (JP, A) J. Am. Chem. Soc. 105 [4], (1983), P838-844 J. Am. Chem. Soc. 104 [25], (1982), P7196-7204 Zashch. Met. 16 [5], (1980), (Russ), P620-622

Claims (2)

[Claims] 1. A compound represented by the general formula (CH ₂ ═C═CH—O—) n—R— (A) m (wherein R is benzene, naphthalene, anthracene, bisphenol, and 2 to 10 linear benzene rings) An aromatic hydrocarbon residue selected from the group consisting of p-polyphenyl bonded to and a halogen, alkyl, cyano, or alkoxy nucleus substitution product thereof; A is —COOH or —SO
₃ H group; n is an integer of 1 to 10; m is an integer of 1 to 3) 2. A general formula (HO-) nR- (A) m (wherein R is benzene, naphthalene, anthracene, bisphenol, and p-polyphenyl in which 2 to 10 benzene rings are linearly bonded). And an aromatic hydrocarbon residue selected from the group consisting of halogen, alkyl, cyano, and alkoxy nucleus substitution products thereof; A is —COOH or —SO.
₃ H group; n is an integer of 1 to 10; m is an integer of 1 to 3) and a hydroxyaryl compound having a polar group represented by the following formula is reacted with a propargyl halide to give a compound represented by the general formula (CH≡C-CH _2- ) n-R (A) m (wherein R, A, n, and m are as described above) to obtain an aryl propargyl ether having a polar group, and isomerization of the aryl propargyl ether under basic conditions. reaction comprises the step of allenyl of the general formula _{(CH 2 = C = CH-} O-) n-R- (A) m ( wherein R is benzene, naphthalene, anthracene, bisphenols and benzene rings 2-10 An aromatic hydrocarbon residue selected from the group consisting of individual linearly bonded p-polyphenyls and their halogen, alkyl, cyano, and alkoxy nucleus substitution products; A is -COOH The other is -SO
₃ H group; n is an integer of 1 to 10; m is an integer of 1 to 3) A process for producing an aryloxyarene compound having a polar group represented by