JP3500674B2 - Method for producing alkenyl phenyl ethers - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [0001] The present invention relates to an alkenyl phenyl ether
Manufacturing methods that can obtain high yields of
You. Alkenyl phenyl ether obtained by the present invention
Are organic intermediates of various fine chemicals,
Useful as raw materials for polymer production, polymer modifiers, etc.
Compound. [0002] BACKGROUND OF THE INVENTION Phenols and alkenyl halides
Reaction in the presence of alkali, alkenyl phenyl
The reactions for synthesizing ters are known (eg, organic
Reactions (Org.Reactions),2, 26 etc.] However, phenols and alkenyl halides
Can be obtained simply by reacting in the presence of alkali.
Is low, and unreacted phenols remain in the reaction system.
After completion of the reaction, a purification step such as distillation or alkali extraction is performed.
It is necessary to use an industrial method to produce the desired product at low cost.
Is disadvantageous. Also, phenols and alkenylhalas
When reacting with
Use methane in the presence of a phase transfer catalyst
There is a known method for synthesizing nyl ethers.
For example, Tetrahedron, vol. 30, 13
P. 79), this method also uses alkenyl phenyl ether
The problem of low yields of compounds (about 50% of theoretical)
Have. [0003] SUMMARY OF THE INVENTION The present invention relates to a phenol
And alkenyl halides in high yield
To provide a method for producing phenyl ethers.
You. [0004] Means for Solving the Problems The present inventors have proposed such an eye.
As a result of various studies to achieve the target, phenols and
Reaction with kenyl halide in the presence of alkali
When producing kenyl phenyl ethers,
Using a water-ketone mixed solvent and the presence of a phase transfer catalyst
Unreacted phenols remain by reacting under
Alkenyl phenyl ethers can be obtained in high yield
The inventors have found that the present invention has been completed. That is, the book
The present invention provides a water-ke
Phenols and alkenyl halides in a mixed solvent
Alkenyl phenyl ether characterized by reacting
The present invention relates to a method for producing ethers. Hereinafter, the present invention will be described in detail. ○ Phenols Phenols used in the present invention are phenolic
There is no particular limitation as long as it is a compound having a hydroxyl group, for example,
A monovalent phenol represented by the following general formula [1];
A dihydric phenol represented by the general formula [2] or [3] and
Trivalent or higher polyhydric phenols can be used. [0006] Embedded image [Wherein, R¹, R^Two, R^Three, R^FourAnd R^Five
Are each independently a hydrogen atom, a halogen atom, an alkyl group,
Alkoxy, nitro, amino, alkenyl,
Represents a phenyl group or a substituted phenyl group] [0008] Embedded image [Where R⁶, R⁷, R⁸And R⁹Is German
First, hydrogen atom, halogen atom, alkyl group, alkoxy
Si group, nitro group, amino group, alkenyl group, phenyl group
Or represents a substituted phenyl group] [0010] Embedded image [Where R^Ten, R¹¹, R¹²And R¹³Is German
Hydrogen atom, halogen atom, alkyl group, alkoxy
Group, nitro group, amino group, alkenyl group, phenyl group or
Is a substituted phenyl group, m is 0 or 1, and X is
S, SO_Two, O, [0012] Embedded image Or [0014] Embedded image And R¹⁴And R¹⁵Is a hydrogen atom,
Phenyl group, substituted phenyl group, trifluoromethyl
And trichloromethyl groups, which are the same as each other.
May be different) A monohydric phenol represented by the general formula [1]
Preferable specific examples include phenol and o-cresol.
M-cresol, p-cresol, 4-ethylphen
Knol, 2-ethylphenol, 6-ethylphenol
, 4-propylphenol, 4-n-butylphenol
, 4-tert-butylphenol, 2,4-dimethyl
Phenol, 2,6-dimethylphenol, 2-chloro
Rophenol, 4-chlorophenol, 6-chlorophen
Knol, 4-bromophenol, 4-fluorophenol
, 4-methoxyphenol, 2-methoxyphenol
, 4-ethoxyphenol, 4-propyloxyphen
Knol, 4-amyloxyphenol, 4-nitrophen
Knol, 3-nitrophenol, 2-nitrophenol
4-aminophenol, 3-aminophenol, 2
-Allylphenol, 4-allylphenol, 2,4-
Diallyl phenol, 2-methallyl phenol, 4-methyl
Tallyl phenol, 2,4-dimethallyl phenol, 2
-Phenylphenol, 3-phenylphenol and 4
-Phenylphenol and the like. A dihydric phenol represented by the general formula [2]
Preferred examples of o-dihydroxybenze
, M-dihydroxybenzene, p-dihydroxyben
Then, 2,4-dihydroxy-1-chlorobenzene,
1,4-dihydroxy-2-chlorobenzene, 3,4-
Dihydroxy-1-chlorobenzene, 1,2-dihydro
Xy-4-methylbenzene, 1,3-dihydroxy-5
-Methylbenzene, 3,4-dihydroxy-1-methyl
Benzene, 1,2-dihydroxy-3-methoxybenze
1,4-dihydroxy-2-methoxybenzene,
1,4-dihydroxy-2-nitrobenzene, 3,4-
Dihydroxy-1-aminobenzene and 1,3-dihydride
Roxy-5-phenylbenzene and the like. A dihydric phenol represented by the general formula [3]
Preferred specific examples of 2,2-bis [4-hydro
Xy-phenyl] propane, 2,2-bis [4-hydro
[Xy-5-methyl-phenyl] propane, 2,2-bis
[4-hydroxy-3-methoxy-phenyl] propa
2,2-bis [4-hydroxy-3-chloro-phene
Nil] propane, 3,3-bis [4-hydroxy-
Nyl] pentane, 1,1,1,3,3,3-hexafur
Oro-2,2-bis [4-hydroxy-phenyl] pro
Bread, 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'-dihi
Droxy-biphenyl, bis [4-hydroxy-phenyl
Thioether, bis [4-hydroxy-phenyl]
Ether, bis [4-hydroxy-phenyl] sulfo
And 2,2-bis [3-hydroxy-phenyl] p
There are lopan and the like. Specific examples of trihydric or higher polyhydric phenol
For example, 2,2-bis [3,5-dihydroxy-phenyl
Enyl] propane, 4- {4- [1,1-bis (4-h
Droxyphenyl) ethyl] -α, α-dimethylbenzyl
Ruphenol, 1,1,1-tris (4-hydroxy
Phenyl) ethane, and cresol and novolak types
Phenol resins and the like can be mentioned. ○ Alkenyl halide The alkenyl halide in the present invention has 2 to 1 carbon atoms.
Those having 0 alkenyl groups are preferred, and specific examples thereof
Allyl chloride, allyl bromide, allyl
Iodide, methallyl chloride, methallyl bromide,
Methallyl iodide, crotyl chloride, crotyl broma
, Vinyl chloride, vinyl bromide, etc.
Can be ○ Alkali Further, the alkali in the present invention is dissolved in a polar solvent
Those are preferred, and there are organic compounds or inorganic compounds. Yes
Specific examples of organic compounds include ethylamine and diethylamido.
Aliphatic amines such as aniline and triethylamine; aniline, diamine
Aromatic amines such as methylaniline; pyridine, quinori
Organic bases such as benzene and piperidine; phenylhydrazine
Hydrazine derivatives; quaternary ammonium hydroxide;
There is a honium base and the like, as a specific example of the inorganic compound, water
Sodium oxide, potassium hydroxide, lithium hydroxide, etc.
Alkali metal hydroxide; magnesium hydroxide, potassium hydroxide
Alkaline earth metal hydroxides such as lucium; sodium carbonate
Alkali metal carbonates such as potassium carbonate and potassium carbonate;
Alkaline earth metal carbonate such as gnesium and calcium carbonate
There are salts and the like. If necessary, two or more kinds of the alkalis
May be used. Also, the above alkali is added to the reaction system.
At this time, even if the alkali is a solid, it is a solution such as an aqueous solution.
May be. ○ Reaction solvent Anti-phenols and alkalis used in the present invention
Since the reaction material has poor compatibility, the reaction proceeds smoothly,
To obtain the desired product in high yield, a water-ketone mixed solvent is used.
Need to be Ketone in the present invention is used as a reaction solvent.
There is no particular limitation as long as it can be used.
There are the following compounds: That is, acetone, diethyl keto
, Methyl ethyl ketone, methyl isobutyl ketone,
Tyl-n-butyl ketone, methyl-n-amyl ketone,
Methyl-n-hexyl ketone, ethyl-n-butyl keto
, Di-n-propyl ketone, diisobutyl ketone,
Cytyl oxide, holon, isophorone, cyclohexano
, Methylcyclohexanone, acetonylacetone, di
Acetone alcohol, acetophenone, dipnon, etc.
is there. Among the above ketones, represented by the following general formula [4]
The compounds are the preferred ketones in the present invention. R¹⁶CO (YCO)_nR¹⁷        [4] (In the above formula, R¹⁶And R¹⁷Each has 1 carbon atom
From 6 to 6 saturated or unsaturated hydrocarbons;¹⁶And R¹⁷Is
A ring may be formed by a carbon-carbon bond.
1 to 3 hydrocarbons, and n is 0 or 1. )the above
In the ketone represented by the general formula [4], R¹⁶And R¹⁷But charcoal
Compounds that are saturated or unsaturated hydrocarbons having a prime number of 1 to 4 are preferred.
It is a more preferable compound, and the reaction can be completed in a short time.
Particularly preferred compounds that can be
Tyl ketone, methyl ethyl ketone and methyl isobutyl
There are ketones and the like. Among these, acetone increases yield.
And the reaction time can be shortened.
It is a new compound. Mixing of water-ketone mixed solvent in the present invention
Although the ratio is not particularly limited, it is necessary to complete the reaction in a short time.
Water / ketone mixing ratio (volume
Ratio) is from 1/9 to 9/1, more preferably from 3/7 to 9/1.
7/3. ○ Phase transfer catalyst Phase transfer catalysts facilitate reactions between substrates in different phases
Is a catalyst having a function to perform phase transfer in the present invention.
Quaternary ammonium salts, quaternary phosphonium salts,
Conventionally known, such as crown ether and cryptand
Any of these can be used. In the present invention
A preferred phase transfer catalyst is phenoxy ion.
Quaternary ammonium suitable for nucleophilic substitution of halogen ions
Transfer between organic salts such as chromium salts and quaternary phosphonium salts
There is a catalyst. As a specific example of the quaternary ammonium salt,
Ra-n-butylammonium fluoride, tetraethyl
Luammonium fluoride, tetramethylammonium
Muchloride, tetraethylammonium chloride,
Tetrapropylammonium chloride, tetra-n-
Butyl ammonium chloride, tetra-n-amylua
Ammonium chloride, trimethylethylammonium
Chloride, trimethylbenzylammonium chloride
, Triethylbenzyl ammonium chloride, tri
Octylmethylammonium chloride, dimethyldi-
n-butylammonium chloride, dimethylbenzyl
Phenylammonium chloride, distearyl dimethyl
Luammonium chloride, benzyl tri-n-butyl
Ammonium bromide, cetyl dimethyl ethyl ammonium
Ium bromide, n-decyltrimethylammonium
Bromide, distearyl dimethyl ammonium broma
Id, n-hexadecyltrimethylammonium bromide
, Phenyltrimethylammonium bromide, te
Tra-n-butylammonium bromide, tetraethyl
Luammonium bromide, tetramethylammonium
Bromide, tetra-n-propyl ammonium bromide
Id, trimethylvinylammonium bromide, ethyl
Rutrimethylammonium iodide, ethyltri-n-
Propyl ammonium iodide, phenyl triethyl alcohol
Nmonium iodide, phenyltrimethylammonium
Iodide, tetra-n-amyl ammonium iodide,
Tetra-n-butylammonium iodide, tetraethyl
Luammonium iodide, tetra-n-hexylammonium
Ammonium iodide, tetramethylammonium iodide,
Triethylbenzyl ammonium iodide, benzyl
Limethylammonium hydroxide, n-hexadec
Rutrimethylammonium hydroxide, phenylt
Limethylammonium hydroxide, tetra-n-butyl
Thilammonium hydroxide, tetra-n-decyl
Ammonium hydroxide, tetra-ethyl ammonium
Hydroxide, tetramethylammonium hydroxide
Oxide, tetra-n-propyl ammonium hydroxide
Side, trimethylbenzylammonium hydroxy
, Benzyltrimethylammonium tribromide,
Tra-n-butylammonium bromoiodide, tetra
Ethyl ammonium perchlorate and tetramethyl alcohol
And ammonium sulfate. As a specific example of the quaternary phosphonium salt,
Rutriphenylphosphonium bromide, allyltrife
Nylphosphonium chloride, benzyltriphenylphos
Honium chloride, n-butyltriphenylphosphonium
Mubromide, chloromethyltriphenylphosphonium chloride
Loride, 4-ethoxybenzyltriphenylphosphonium
Mubromide, ethyltriphenylphosphonium bromide
, N-hexyltriphenylphosphonium bromide,
Methyltriphenylphosphonium iodide, tetra-n
-Butylphosphonium bromide, tetraphenylphospho
Chloride and tetraphenylphosphonium tetra
Phenyl borate and the like. Preferred examples of these phase transfer catalysts
Is a quaternary ammonium salt because of ease of purification after the reaction, etc.
Especially tetramethylammonium bromide, tetraethyl
Ammonium bromide, tetra-n-propyl ammonium
Um chloride, tetra-n-propylammonium bromide
Amide, tetra-n-butylammonium chloride, tet
Ra-n-butylammonium bromide, tributylben
Diammonium chloride and tributylbenzylan
Monium bromide and the like are preferred. The preferred use of the phase transfer catalyst in the present invention
Dosage is based on the phenolic hydroxyl groups of the raw phenols
It is 0.01 to 50 mol% with respect to 1 mol, more preferably.
More preferably, it is 1 to 20 mol%. Amount of phase transfer catalyst used
Is less than 0.01 mol%, the reaction time is long,
Even if it is used more than 50 mol%, the effect is not much different, and it is economical
May be disadvantageous. The method for preparing the phase transfer catalyst is a commercially available phase transfer catalyst.
The kinetic catalyst may be used as it is,
Reaction of sphine and acid such as halide in the system, 4
Used as quaternary ammonium salt or quaternary phosphonium salt
Is also good. Further, the method of adding the phase transfer catalyst is particularly limited.
But not enough to accelerate the reaction after the start of the reaction
Before the reaction, add a predetermined amount of the total amount to the reaction solution in advance.
May be added or not added before the reaction or
May be added in advance, and the remainder may be added during the reaction. ○ Reaction conditions The phenols and alkenyl halides of the present invention
The preferred reaction charge ratio is based on the alkenyl halide species.
It is not possible to set uniform conditions depending on the type and reactivity
However, one mole of phenolic hydroxyl group of phenols
And alkenyl halide is 1 to 3 mol, more preferably
Or 1 to 1.5 mol. In addition, phenols and alcohol in the reaction system
The preferred charging ratio of potassium is phenol phenol
1 to 3 moles of alkali relative to 1 mole of acidic hydroxyl groups,
More preferably, it is 1 to 1.5 mol. The reaction temperature and reaction time depend on the type of ketone used.
, The type and amount of the phase transfer catalyst, the alkenyl halide
Since it differs depending on the type and amount, setting uniformly
Although it is not possible, it is usually 0.5 to 2 at room temperature to 150 ° C.
It may be set within the range of 4 hours, more preferably 40
The reaction is carried out at a temperature of １００100 ° C. for 1 to 12 hours. The reaction is carried out under reduced pressure, normal pressure or under pressure.
It can be performed under these conditions. The reaction atmosphere is not particularly limited
Inert, such as nitrogen, argon etc.
Under the atmosphere. ○ Separation and purification As described above, alkenyl phenyl ethers were produced.
After the production, the product is extracted by a standard method and
It can be used as various synthetic raw materials, but if necessary, water
The extract may be purified by a general purification method such as washing.
No. [0035] Examples and Comparative Examples Next, according to Examples and Comparative Examples,
The present invention will be described more specifically. Example 1 A stirrer, a reflux tube, a thermometer and a dropping funnel were used.
4-into the attached 300 ml glass four-necked flask
30.0 g of tert-butylphenol (0.20 mol
9.2 g of 96% sodium hydroxide (0.22
), Tetra-n-butylammonium bromide 3.2
g (0.01 mol) and a mixed solvent of acetone and water [A
Seton: water = 1: 1 (volume ratio)]
Hot stirring was performed. After the internal temperature reaches 60 ° C,
Slowly drop 21.7 g (0.24 mol) of chloride
After completion of the dropwise addition, the reaction was further performed at an internal temperature of 60 ± 3 ° C. for 2 hours.
Was. After completion of the reaction, the aqueous layer was neutralized with hydrochloric acid,
Extract with dichloromethane and separate the dichloromethane layer with gas chromatography.
As a result of analysis by luffy, the raw material 4-tert
-Butylphenol had completely disappeared. As above
And the 4-tert-butylphenyl used as the reaction raw material
Based on the amount produced when all of the enol is converted,
4-tert-butylphenyl methallyl
Was obtained in a yield of 98.3%. (Hereinafter,
Generated when all the phenols used in the conversion are converted
The yield of the target compound is shown on the basis of. ) [0036] Example 2 A stirrer, a reflux tube, a thermometer and a dropping funnel were used.
Screw into the attached 300ml glass four-necked flask
Phenol A 29.7 g (0.13 mol), 96% hydroxyl
12.1 g (0.29 mol) of sodium chloride, tetra-n
-Butyl ammonium bromide 4.2 g (0.013 m
) And a mixed solvent of acetone and water [acetone: water =
1: 1 (volume ratio)], and heat and stir.
Was. After the internal temperature reaches 60 ° C, methallyl chloride 2
9.0 g (0.32 mol) is slowly dropped, and the dropping is completed.
Thereafter, the reaction was further performed at an internal temperature of 60 ± 3 ° C. for 2 hours. End of reaction
After that, neutralize the aqueous layer with hydrochloric acid and extract with dichloromethane.
And separate the dichloromethane layer by gas chromatography.
As a result of the analysis, the raw materials bisphenol A and bisphenol A
No enol A monomethallyl ether present
Was. As described above, the desired product, bisphenol A
Dimethallyl ether was obtained in 98.7% yield. [0037] Example 3 Of the charged amounts of Example 2, tetra-n-butyl
2.1 g (0.0066)
Mol) and the reaction time was 4.5 hours.
Perform the reaction in the same manner as in 2, and the treatment after the reaction is completed.
I went to. As a result of analysis by gas chromatography,
Bisphenol A and bispheno intermediate
All A monomethallyl ether had completely disappeared. Up
As described above, bisphenol A dimeth
The lyl ether was obtained in a yield of 97.4%. [0038] Example 4 In the preparation of Example 2, tetra-n-butyl
2.1 g of ammonium bromide (0.0066
), The reaction solvent is a mixed solvent of methyl ethyl ketone and water
[Methyl ethyl ketone: water = 1: 1 (volume ratio)]
In the same manner as in Example 2, except that the reaction time was set to 6 hours.
The reaction was performed, and the treatment after the completion of the reaction was similarly performed. Gask
As a result of chromatographic analysis,
Nol A and bisphenol A monometallic intermediate
The ruether had completely disappeared. As above,
9 bisphenol A dimethallyl ether
Obtained in a yield of 7.2%. [0039] Example 5 In the preparation of Example 2, tetra-n-butyl was used.
2.1 g of ammonium bromide (0.0066
), The reaction solvent is a mixed solvent of diethyl ketone and water [di-
Ethyl ketone: water = 1: 1 (volume ratio)] and the reaction time
The reaction was carried out in the same manner as in Example 2 except that the reaction time was changed to 8 hours.
The treatment after the completion of the reaction was performed in the same manner. Gas chromatog
As a result of analysis by raffy, the raw material bisphenol A
And bisphenol A monomethallylate as an intermediate
Le had completely disappeared. As described above,
97.0% of a certain bisphenol A dimethallyl ether
In a yield of [0040] Example 6 Of the preparations of Example 2, tetra-n-butyl
2.1 g of ammonium bromide (0.0066
), The reaction solvent is a mixture of methyl isobutyl ketone and water
Solvent [methyl isobutyl ketone: water = 1: 1 (volume
Example 2 except that the reaction time was 10 hours.
The reaction is performed in the same manner as described above.
went. As a result of gas chromatography analysis,
Is bisphenol A and bisphenol is an intermediate
The ru-A monomethallyl ether had completely disappeared. the above
The desired product, bisphenol A dimethary
The ether was obtained in a yield of 96.5%. [0041] Embodiment 7 Of the preparations in Embodiment 2, the type of phase transfer catalyst
And the amount of tetra-n-butylammonium chloride
1.8 g (0.0066 mol), reaction time is 6 hours
Except that the reaction was carried out in the same manner as in Example 2.
Was similarly performed. Analyze by gas chromatography
As a result, the raw material bisphenol A and intermediate
Bisphenol A monomethallyl ether completely disappears
Was. As described above, the desired product, bispheno
A dimethallyl ether was obtained in a yield of 97.7%. [0042] [Embodiment 8] Among the preparations in Embodiment 2, the type of phase transfer catalyst
And the amount of tributylbenzylammonium chloride
2.1 g (0.0066 mol) and the reaction time was 7 hours
The reaction was completed in the same manner as in Example 2 except that
Subsequent processing was performed similarly. Minutes by gas chromatography
As a result of the analysis, the raw material bisphenol A and intermediate
Some bisphenol A monomethallyl ethers completely disappear
Had lost. As described above,
N-A dimethallyl ether was obtained in a yield of 97.3%.
Was. [0043] Example 9 Of the preparations of Example 2, tetra-n-butyl
2.1 g of ammonium bromide (0.0066
), The reaction solvent was a mixed solvent of acetone and water
: Water = 7: 3 (volume ratio)], and the reaction time is 12 hours.
The reaction was carried out in the same manner as in Example 2 except that
The processing after the completion of the reaction was similarly performed. Gas chromatography
As a result of analysis in
Bisphenol A monomethallyl ether, which is an intermediate, is complete
It had completely disappeared. As described above,
Sphenol A dimethallyl ether yield of 99.1%
I got it. [0044] Example 10 Of the preparations in Example 2, tetra-n-butyl
2.1 g (0.0066)
Mol), and the reaction solvent was a mixed solvent of acetone and water [acetone
: Water = 4: 6 (volume ratio)], and the reaction time is 6 hours.
Reaction was carried out in the same manner as in Example 2 except that
The processing after the end was performed in the same manner. Gas chromatography
As a result of the analysis, the raw material bisphenol A and intermediate
Bisphenol A monomethallyl ether is complete
Had disappeared. As described above, the target screw
Phenol A dimethallyl ether in 96.4% yield
Obtained. [0045] Example 11 Of the preparations in Example 2, the starting phenol
Type and amount of bisphenol F 26.0 g (0.13
The reaction was carried out in the same manner as in Example 2 except that
The treatment after the completion of the reaction was similarly performed. Gas chromatograph
As a result of the analysis, the raw material bisphenol F and
The intermediate bisphenol F monomethallyl ether is complete
It had completely disappeared. As described above,
Sphenol F dimethallyl ether yield of 98.2%
I got it. [0046] Example 12 Of the preparations in Example 2, alkenylhalai
The type and amount of chloride were 24.5 g (0.3
2 mol) and the reaction temperature was 50 ± 3 ° C.
The reaction was carried out in the same manner as in Example 2, and the treatment after completion of the dropping was also
Performed similarly. Results analyzed by gas chromatography
As a result, the raw material bisphenol A and the intermediate bis
Phenol A monoallyl ether has completely disappeared.
Was. As described above, the desired product, bisphenol A
The diallyl ether was obtained in a yield of 97.2%. [0047] Example 13 Among the preparations of Example 1, species of phase transfer catalyst
2. the amount and type of tetra-n-butylphosphonium bromide;
4 g (0.01 mol) and the reaction time was 3 hours.
The reaction was carried out in the same manner as in Example 1 except for the
The processing was performed similarly. Analyzed by gas chromatography
As a result, the raw material 4-tert-butylphenol is
It had completely disappeared. As described above
4-tert-butylphenyl methallyl ether
Obtained in 8.1% yield. [0048] COMPARATIVE EXAMPLE 1 Among the preparations of Example 1, tetra-n-butyl
Same as Example 1 except that ammonium bromide was omitted
The reaction was carried out by the same method, and the treatment after completion of the reaction was carried out in the same manner.
As a result of analysis by gas chromatography, 4
-Tert-butylphenol remaining 12.3%
And 4-tert-butylphenylmetal
The yield of the ether was only 78.1%.Comparative Example 2 Of the preparations in Example 1, the reaction solvent was toluene.
Mixed solvent of water and water [toluene: water = 1: 1 (volume ratio)]
The reaction was carried out in the same manner as in Example 1 except that
The processing after the completion was performed in the same manner. By gas chromatography
As a result of analysis, it was found that the starting material 4-tert-butylpheno
-Tert- is the target substance with 45% remaining
The yield of butyl-phenylmethallyl ether is limited to 46%.
wait. Comparative Example 3 The reaction solvent of Example 2 was mixed with xylene and water.
Except that the mixed solvent [xylene: water = 1: 1 (volume ratio)]
Performs a reaction in the same manner as in Example 2, and performs a treatment after completion of the reaction.
The same went for the same. Analyzed by gas chromatography
As a result, 28% of bisphenol A as a raw material was used as an intermediate.
Some bisphenol A monomethallyl ether is 48% each
Bisphenol A dimetalli
The yield of luether was only 20%. [0049] According to the production method of the present invention, phenols and
Alkenyl phenyl ether is reacted with kenyl halide.
To produce higher yields of
It is extremely valuable as an industrial manufacturing method.
It is a thing.

────────────────────────────────────────────────── ─── Continuation of the front page (56) References JP-A-57-81418 (JP, A) JP-A-6-100487 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) C07C 43/00 C07C 41/00

Claims (1)

(57) [Claim 1] In the presence of a phase transfer catalyst and an alkali,
OH groups are bonded to aromatic carbon atoms in a water-ketone mixed solvent.
A method for producing alkenyl phenyl ethers, comprising reacting phenols and alkenyl halide in combination.