JPH01233253A - Production of arylozxyallene compound - Google Patents

Abstract

PURPOSE:To obtain a compound useful as a polymerizable monomer by reduced processes, by processing propargyl alcohol into a propargyl aryl ether and then allenylating. CONSTITUTION:Propargyl alcohol is reacted with a phenol shown by the formula R-OX (R is aromatic hydrocarbon residue; X is H or alkali metal) in the presence of a dehydrating agent in a solvent such as THF at room temperature -120 deg.C to give a propargyl aryl ether shown by the formula R-O-CH2-C=CH. Triphenylphosphine-carbon tetrachloride, dicyclohexylcarbodiimide-cupric chloride, etc., may be used as the dehydrating agent. Then the propargyl aryl ether is isomerized in the presence of a base (e.g., potassium alcoholate of t-butyl alcohol) to give an aryloxyallene compound shown by the formula R-O-CH=C= CH2.

Description

Detailed Description of the Invention Technical Field The present invention relates to a novel method for producing aryloxyarene compounds useful as polymerizable monomers, and a novel method for producing intermediate propargyl aryl ethers used in the production method. This relates to a manufacturing method.

BACKGROUND OF THE INVENTION Among compounds having so-called arene bonds in which three carbon atoms are bonded to each other through two double bonds, homoradical polymerization of a phenoxyarene compound represented by the formula % is known as Polymer Preprints.

Japan, 35(2), 133 (1986), etc., interest in such phenoxyarene compounds and polymers has been increasing. This is because such phenoxyarene compounds can not only be radically polymerized in the same way as vinyl monomers, but also, by radical polymerization, a polymer containing a structural unit represented by e6)1° in the main chain can be obtained, and the molecule Because it contains ionic or radically polymerizable vinyl ether groups, allyl groups, or reactive phenoxy groups, it opens the door to the synthesis of new substances based on these, and is expected to have a wide range of applications in coating materials and other various fields. This is because it will be done.

Conventionally, such phenoxyarene compounds and their phenyl-substituted products were generally synthesized by a method in which a phenol and a propargyl bromide phenyl ether compound were obtained, and this was subjected to an isomerization reaction under the action of potassium alcoholade of t-butyl alcohol. .

H2 H, C-C-0 and H3 However, since the propargyl bromide used in the above method is relatively expensive, there is a need for a more industrially advantageous method for producing arene compounds.

Problems to be Solved by the Invention Therefore, if propargyl phenyl ether compounds can be produced directly from cheaper propargyl alcohol without using propargyl bromide, an industrial process for producing aryloxyarene compounds useful as polymerizable monomers will be established. It is the main objective of the present invention to find a manufacturing method that will lead to the process.

Means for Solving the Problems According to the present invention, the above object is achieved by combining propargyl alcohol with the general formula % [] (wherein R is an aromatic hydrocarbon group with or without a substituent; (hydrogen atom or alkali metal), dicyclohexylcarbodiimide-cupric chloride system, azodicarboxylic acid ester-triphenylphosphine system, triphenylphosphine-carbon tetrachloride system, or hexamethylphosphite triad. - Maximum R-0-CH2-C=CH...[■] (in the formula R
(as described above) is a step of obtaining a propargyl aryl ether represented by
This can be achieved by a process for producing an aryloxyarene compound represented by the general formula %[[] (wherein R is as described above), which comprises a step of allenylating the propargyl aryl ether under basic conditions.

By dissolving sodium phenolate and triphenylphosphine in benzene, removing trace amounts of water from the system as an azeotrope, adding alcohol and carbon tetrachloride, and heating under reflux, Furukawa et al. succeeded in directly 0-alkylating with alcohol,
As a method for alkylating phenols, Journal of the Chemical Society of Japan 19
83(7), 1099-1101. The same report shows examples of reacting phenols with various saturated alcohols, benzyl alcohol, and allyl alcohol, but how does propargyl alcohol behave? There is no suggestion as to whether similar O-alkylation proceeds with respect to phenols.

The present inventors paid attention to the above method and found that when propargyl alcohol was selected as the alcohol, the desired propargyl phenyl ether could be obtained in high yield, and that various aromatic compounds could be used as the phenols. Instead of using propargyl bromide, we were able to establish a method for producing aryloxyarene compounds easily and in high yield from cheaper 10 pargyl alcohol. They also discovered that the dehydration reaction between aromatic phenols and propargyl alcohol can be carried out in the presence of several dehydrating agents other than the triphenylphosphine-carbon tetrachloride system, which is also an important basis for the present invention. It is.

The phenols reacted with propargyl alcohol in the method of the present invention are compounds represented by the formula (wherein R is an aromatic hydrocarbon residue with or without a substituent; X is a hydrogen atom or an alkali metal). be. Examples of aromatic hydrocarbon residues include polyphenyl compounds in which 2 to 10 benzene rings are assembled, such as benzene, naphthalene, anthracene, phenanthrene, triphenylene, naphthacene, perylene, pentacene, and hexacene, and residues of bisphenols. The aromatic ring may have any substituent other than a halogen, an alkyl group, a cyano group, an alkoxy group, or any other substituent having an active hydrogen atom.

Those found to be particularly useful as dehydrating agents are:
In addition to the above-mentioned triphenylphosphine-carbon tetrachloride, a combination of dicyclohexylcarbodiimide-cupric chloride,
It is a combination of azodicarboxylic acid ester and triphenylphosphine, and a phosphonium salt of hexamethylphosphite triamide.

Among the above dehydrating agents, the present inventors used free phenols in the case of dicyclohexylcarbodiimide-cupric chloride, and in the case of other dehydrating agents, in the form of alkali metal salts. It has been found that the reaction can proceed conveniently using the following phenols.

In the reaction, the above-mentioned phenols, propargyl alcohol, and dehydrating agent are reacted in a suitable inert solvent such as tetrahydrofuran, benzene, toluene, xylene, ester, etc. at a temperature of room temperature to 120°C, preferably 50 to 100°C. By doing so, the reaction proceeds extremely easily and the desired propargyl ether can be obtained.

The propargyl aryl ether obtained by the method of the present invention can then be converted into the corresponding arene compound in an extremely high yield by reacting it with potassium alcoholade of t-butyl alcohol under salinizing conditions, for example.

As described above, in the method of the present invention, propargyl halide is usually obtained by halogenation from propargyl alcohol, and this is reacted with phenols to obtain propargyl phenyl ether. can be used to synthesize propargyl phenyl ether, which is then led to the corresponding arene compound through an isomerization reaction, which not only requires a single step compared to the conventional method, but also allows the use of inexpensive propargyl alcohol. Since this method is possible, it is an industrially extremely useful method for producing aryloxyarene compounds. Furthermore, an industrially advantageous method for producing propargyl phenyl ether, which is an intermediate for producing the aryloxyarene compound, is provided.

The present invention will be explained below with reference to Examples. Parts and percentages are by weight unless otherwise specified.

Example 1 Synthesis of propargyl phenyl ether 500m13 equipped with a thermometer, stirrer, cooling tube, and decanter
100 ml of benzene, 23.2 g (0.2 mol) of sodium phenolate, and 57.8 g (0.22 mol) of triphenylphosphine were added to a flask and heated.

After refluxing benzene for 30 minutes to remove water contained in the system, 56.06 g (1,000 ml) of propargyl alcohol was added.
ol) and 30 mol of carbon tetrachloride were added thereto, and the mixture was heated under reflux for 3 hours. After cooling, the generated sodium chloride was filtered, and excess alcohol and carbon tetrachloride were removed from the filtrate using an evaporator. Hexane was added to the concentrated solution to filter out insoluble materials. The filtrate was washed with a sodium hydroxide solution, and then sulfuric acid dried with magnesium. By concentrating the hexane solution, 11.8 g of propargyl phenyl ether was obtained (crude yield: 44.
7%). The structure was confirmed by LH-NMR.

IH-NMR (ppm>J12.49 (IHS, CI)
4.65 (211S, CH2-0) 6.89-7j
4 (5H1pb-1f) Example 2 Synthesis of allenyl phenyl ether 50m1 equipped with a thermometer, rotor, and cooling pipe
30 flasks with t-BuOKl, 06g, t-B
5.49 g of uOH was added and completely dissolved. From the dropping funnel, a mixed solution of t-BuOHIIg and 5.0 g of propargyl phenyl ether was added dropwise at room temperature over 1 hour. Thereafter, it was heated to 60°C, kept warm for 15 minutes, and then cooled.

Pure water 201 was added to the reaction mixture to stop the reaction, and the mixture was extracted with ether. By concentrating the ether layer with an evaporator, 3.58 g of allenyl phenyl ether (
Yield = 71.6%>. The structure was confirmed by H-NMR.

H-NMR (ppm) J 5j8-5.40 (IH,
t, C=CI+-0) 6.78-6.80 (2H, d,
H2C=C= )7.0-7.28 (58, m, ph-
11) Example 3 Synthesis of 4.4'-diprobargyloxybiphenyl 500 m equipped with a thermometer, stirrer, cooling tube, and decanter
Benzene lθOwl, 18.6 g (0.1 mol) of sodium phenolate, and 57.8 g (0.22 mol) of triphenylphosphine were added to a 130-liter plastic bottle and heated. After refluxing benzene for 30 minutes and removing water contained in the system, 56.06 g of propargyl alcohol (
1, Omol) and 301 carbon tetrachloride were added, and the mixture was heated under reflux for 3 hours. After cooling, the generated sodium chloride was filtered, and excess alcohol and carbon tetrachloride were removed from the filtrate using an evaporator. Hexane was added to the concentrated solution, insoluble matter was filtered, and the filtrate was washed with a sodium hydroxide solution. and dried over magnesium sulfate. By concentrating the hexane solution, 11
．． 0 g (crude yield 42.θ%) was obtained. The structure is IH-NMR
I confirmed it.

IH-NMR (ppm) δ 2.54 (28
,S,CI! == )4.72 (4H,S,-
CH2-0) 6.90-7.60 (8H, Ill, p
h-H) Example 4 Synthesis of 4.4'-sialenyloxybiphenyl 1.06 g of t-BuOK, 5.5 g of t-BuOH in a 50 ml 30 flask equipped with a thermometer, rotor, and cooling tube.
0g was added and completely dissolved. From the dripping funnel, t-Bu
A mixed solution of 5.42 g (0.02 mol) of OH'fig and 4.4'-dipropargyloxybiphenyl was added dropwise at room temperature over 1 hour. Then, heat to 60℃ and
After being kept warm for 5 minutes, it was cooled.

20 ml of pure water was added to the reaction mixture to stop the reaction, and the mixture was extracted with ether. By concentrating the ether layer with an evaporator, 4,4'-sialenyloxybiphenol 3
．． 4g (yield: 65%) of W was obtained. The structure is 1) f-NM
Confirmed with R.

Claims (2)

[Claims] (1) Propargyl alcohol and the general formula R-OX...[I] (wherein R is an aromatic hydrocarbon residue with or without a substituent; X is a hydrogen atom or an alkali metal) Phenols are reacted in the presence of a dehydrating agent such as dicyclohexylcarbodiimide-cupric chloride system, azodicarboxylic acid ester-triphenylphosphine system, triphenylphosphine-carbon tetrachloride system, or hexamethylphosphite triamide phosphonium base. , a step of obtaining propargyl aryl ether represented by the general formula R-O-CH_2-C≡CH...[II] (wherein R is as described above),
and an aryloxyarene compound represented by the general formula R-O-CH=C=CH_2...[III] (wherein R is as described above), which comprises a step of allenylating the propargyl aryl ether under basic conditions. manufacturing method. (2) Propargyl alcohol and the general formula R-OX... [I] (wherein R is an aromatic hydrocarbon residue with or without a substituent; X is a hydrogen atom or an alkali metal) Reacting phenols in the presence of a dehydrating agent such as dicyclohexylcarbodiimide-cupric chloride type, azodicarboxylic acid ester-triphenylphosphine type, triphenylphosphine-carbon tetrachloride type or hexamethylphosphite triamide phosphonium salt type. A method for producing propargyl aryl ether represented by the general formula R-O-CH_2≡CH... [II] (wherein R is as described above), characterized by: