JPH0517383A - Production of 1-propenyl phenyl ethers - Google Patents

Abstract

PURPOSE:To produce a high-purity 1-propenyl ether by isomerization reaction of allyl phenyl ether in high selectivity and in high yield, industrially and advantageously. CONSTITUTION:Allyl phenyl ether is reacted with dichlorobisacetonitrile palladium (II) and chloroform in a nitrogen atmosphere at 60 deg.C for 7 hours. After the reaction is completed, chloroform is distilled away, petroleum ether is added to the reaction mixture, precipitated dichlorobisacetonitrile palladium (II) is filtered and recovered and the petroleum ether is distilled away from the filtrate to give 1-propenyl ether in 94% yield. The reaction is carried out under a milder condition than a conventional method and side reactions are suppressed to give 1-propenyl ether in high yield and in high selectivity.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a method for producing 1-propenylphenyl ethers, and more particularly to a method for producing 1-propenylphenyl ethers by an isomerization reaction of allylphenyl ethers. 1-Propenyl phenyl ether is useful as a polymer raw material such as a curing agent for maleimide resin.

[0002]

2. Description of the Related Art As a method for producing 1-propenyl phenyl ethers, a method of alkali isomerizing corresponding allyl phenyl ethers is known as the most general method [J. Amer. Chem. Soc. 83]. Volume 1701-1704 (1961
Year)]). This reaction is carried out in the presence of metal alcoholate,
It is carried out by heating in a high boiling polar solvent such as 1,2-dimethoxyethane, polypropylene glycol or dimethyl sulfoxide.

However, the above-mentioned reaction is a water washing step in which the polar solvent used is compatible with water and the metal alcoholate which is an isomerization catalyst is separated from the 1-propenyl ether produced, whereby the reaction solution forms an emulsion. Therefore, in order to avoid this, it is necessary to distill off the polar solvent in advance and add a new extraction solvent that is difficult to dissolve in water, such as ether, benzene, toluene, ethyl acetate, and methyl isobutyl ketone. It costs.

Further, since the above reaction is carried out at a high temperature of over 150 ° C. under strong basicity for several tens of hours, and in some cases for hundreds of tens of hours, allyl ether as a raw material or a product 1- Propenyl ether and the like have a drawback that they cause thermal polymerization and other side reactions to produce undesired by-products, which is not suitable for industrial use.

[0005]

DISCLOSURE OF THE INVENTION The present invention uses allyl phenyl ethers as a starting material, and suppresses side reactions, has high selectivity, high yield, and is industrially advantageous in high purity 1-propenyl phenyl ethers. Is intended to provide a method of manufacturing

[0006]

The method for producing 1-propenylphenyl ethers of the present invention, which achieves the above object, comprises:
The method is characterized by isomerizing allyl phenyl ethers in the presence of a divalent palladium compound.

The method for producing the allyl ether of phenols, which is the starting material of the present invention, is to dissolve phenols in acetone and then to prepare phenolate with an equimolar or slightly excess amount of potassium carbonate, and then add allyl bromide. The method of reacting in a molar amount is known as the most general method [J. Amer. Chem. Soc., Vol. 62, page 1863 (1941).
Year)〕.

The phenols used for producing the allyl phenyl ether used in the present invention may be phenols having a structure in which at least one of the ortho position and the para position is unsubstituted with respect to the phenolic hydroxyl group. Specific examples of the phenols include phenol, o
-, m-, p-cresol, chlorophenol, nitrophenol, aminophenol, methoxyphenol, acetoxyphenol, acetylphenol, 2,4-dimethylphenol, monohydric phenols such as 2,5-dimethylphenol, catechol, hydroquinone , Biphenol, 2,2-bis (4-hydroxyphenyl) propane [bisphenol
A], bis (4-hydroxyphenyl) methane [that is, bisphenol F]], 4,4-dihydroxybenzophenone, 4,4-dihydroxyphenyl sulfone, 3,9-bis (2-
Hydroxyphenyl) -2,4,8,10-tetraoxaspiro [5.5] undecane, 3,9-bis (4-hydroxyphenyl) -2,4,8,10-tetraoxaspiro [5.5] undecane, 1, Dihydric phenols such as 1,1,3,3,3-hexafluoro-2,2-bis (p-hydroxyphenyl) propane [ie hexafluorobisphenol A], phenol novolac, cresol novolac, salicylaldehyde and phenol Alternatively, polyphenol obtained by reacting cresol under an acid catalyst, polyphenol obtained by reacting p-hydroxybenzaldehyde and phenol or cresol under an acid catalyst, terephthalaldehyde and phenol or cresol or bromphenol are reacted under an acid catalyst. Polyhydric phenols such as polyphenols obtained by the above are mentioned.

The divalent palladium compound used as the isomerization catalyst in the present invention means that the oxidation state of the palladium atom of the compound is, for example, Pr by James P. Collman and Louis S. Hegedus.
inciples and Applications of Organotransition Meta
Chemistry, University Science Books, 1987
The method described on pages 21-56, i.e., removing all ligands from the metal atom while maintaining their closed shell state,
+2 by the method of counting the valences left in the metal later
Refers to all compounds containing a palladium atom classified as
It is not affected by the kind of atoms bonded to palladium, such as palladium (II) metal salt or organometallic palladium (II).

The divalent palladium compound used as the isomerization catalyst in the present invention has 1 to 2 ligands which increase the compatibility with the reaction system of the present invention comprising a solvent and allyl phenyl ether. Such compounds are preferable, and the isomerization rate is improved by using such a catalyst.

Examples of the ligand which increases the compatibility include aliphatic and aromatic nitriles such as acetonitrile, propionitrile and benzonitrile, and aliphatic and aromatic phosphines such as triphenylphosphine, tributylphosphine and triethylphosphine. , Acetylacetone,
Benzoylacetone, 3-methyl-2,4-pentadione, etc.
Aliphatic diamines such as 1,3-diketones, ethylenediamine, 1,2-diaminopropane, 1,3-diaminopropane, 1,
2-diphenylphosphinoethane, 1,3-diphenylphosphinopropane Aliphatic diphosphines such as 1,2-diphenylphosphinopropane, monoolefins such as ethylene, propylene and butene, 1,3-butadiene, 1,3 -Dienes such as pentadiene and 1,4-pentadiene, and diphosphine-substituted ferrocenes such as bis (diphenylphosphino) ferrocene, bis (dimethylphosphino) ferrocene, and bis (diethylphosphino) ferrocene. Among these, divalent palladium compounds having 1 to 2 nitriles, diketones and aliphatic diphosphines as ligands are particularly preferable because they have excellent compatibility with polar solvents.

Further, a divalent palladium compound which is not reduced to zero-valent palladium under the conditions of the present isomerization reaction is particularly preferable.

Specific examples of such a divalent palladium compound include palladium (II) chloride and palladium nitrate (I
I), palladium (II) sulfate, palladium (II) acetate, palladium (II) perchlorate, palladium (II) cyanide, palladium (II) trifluoroacetate, boron tetrafluoride palladium (I
I), palladium (II) oxide, palladium (II) bromide, palladium (II) iodide and to the extent that coordination supersaturation with these compounds does not occur, specifically, acetonitrile, benzonitrile, triphenylphosphine, ammonia, Coordination of 1 molecule or 2 molecules for monodentate ligands such as diphenylphosphinoferrocene and monoolefin, and 1 molecule for bidentate ligands such as (1,2-diphenylphosphino) ethane, ethylenediamine and dienes. Examples thereof include palladium (II) coordination complexes in which a child is coordinated, and further palladium (II) acetylacetonate, palladium (II) benzoylacetonate, and the like.

These palladium (II) compounds may be added alone or in combination of two or more. The amount added is 0.0001 to 0 per 1 mol of the allyl group of allyl phenyl ethers.
It is 1 mol, preferably 0.001 to 0.05 mol. If the amount of the palladium (II) compound added is too small, the isomerization rate will be slow and it will take a long time to complete the reaction. Further, if the amount is too large, not only does the isomerization rate not be improved so much, but it becomes difficult to completely separate the palladium (II) compound from the reaction product after the reaction is completed.

The solvent used in this reaction includes ketones such as acetone, methyl ethyl ketone and 2-pentanone, aliphatic alcohols such as methanol, ethanol and propanol, and fatty acids such as ethyl acetate, methyl acetate, methyl formate and ethyl formate. Examples include so-called polar organic solvents such as group esters, chloroform, dichloromethane, dibromomethane, and aliphatic halogen compounds such as carbon tetrachloride.

Of these, the catalyst used is palladium (I
I) An aliphatic halogen compound having a small complexing ability with a compound, that is, a solvent having no oxygen atom in the molecule is desirable, and particularly, dichloromethane, chloroform, 1,1,1-
Chlorine-containing organic solvents such as trichloroethane, 1,1,2-trichloroethane and carbon tetrachloride impart high compatibility with allylphenyl ethers as reaction substrates and divalent palladium compounds as catalysts, and It is preferable because the catalyst is not deactivated under the chemical reaction conditions.

The amount of solvent used varies depending on the type and structure of the allyl phenyl ethers used and is not specified unconditionally, but it should be such that it can be smoothly stirred and mixed by a normal stirring method at a predetermined temperature. Yes, substrate concentration 30-80
It is added in an amount of about 40% by weight, preferably about 40 to 60% by weight.

However, if the substrate concentration is less than 30% by weight, the amount of 1-propenylphenyl ethers obtained from one reaction tank is small and it is not economical, and if it exceeds 80% by weight, allyl phenyl ethers insoluble in the solvent are obtained. Remains, the reaction effect is significantly reduced, and the viscosity of the reaction solution itself is increased to lower the stirring efficiency, which is not preferable.

The isomerization reaction of the present invention is carried out in the temperature range of 20 ° C to 80 ° C for 1 to 10 hours, preferably in the temperature range of 30 to 60 ° C.
~ 8 hours is recommended. When the reaction temperature is lower than 20 ° C, it takes a long time to complete the isomerization, and when it is higher than 80 ° C, the produced 1-propenylphenyl ethers are polymerized to produce an undesired by-product.

The reaction pressure is not particularly limited, and it can be carried out under reduced pressure, normal pressure or increased pressure. Further, the atmosphere of the reaction system is an inert gas which does not deactivate by causing a chemical reaction such as oxidation, reduction or insertion with respect to the divalent palladium compound which is the catalyst used, for example, nitrogen, helium, It is preferably performed in a stream of argon or the like.
From an economical point of view, it is particularly preferable to carry out in a nitrogen stream.

After the completion of the reaction, the reaction solution is passed through a column packed with silica gel, alumina, molecular sieves, synthetic zeolite, cellulose acetate, methyl cellulose or the like to easily adsorb the used divalent palladium catalyst on the column and easily remove it. It is possible to
It is also possible to blow a reducing gas such as hydrogen into the reaction solution for 1 to 2 hours to reduce the divalent palladium compound, and to filter it out as a zero-valent palladium compound insoluble in the reaction solvent called so-called palladium black. .

More economically, a solvent which does not dissolve the divalent palladium compound as a catalyst, for example, an aliphatic hydrocarbon solvent such as pentane, hexane, heptane, petroleum ether, etc. is added to the reaction solution to precipitate the catalyst. The method of removing by filtration can be reused without deactivating the catalyst.

[0023]

[Function] The isomerization reaction using a divalent palladium catalyst
Since the reaction temperature is low and the reaction proceeds under mild conditions, side reactions are unlikely to occur, the conversion is high, and the selectivity is high.
A high-purity target product can be easily obtained. Also, after the reaction is completed,
The catalyst can be separated in an active state by adding a solvent which does not dissolve the catalyst and can be reused.

[0024]

EXAMPLES The present invention will be described in more detail below with reference to examples and comparative examples.

Example 1 10.45 g (76.8 mmol) of allyl phenyl ether and 167 m of dichlorobisacetonitrile palladium (II) were placed in a four-necked flask equipped with a stirrer, a cooling tube, a thermometer and a gas introduction tube.
g (0.71 mmol) and 30 g of chloroform were charged, and the mixture was heated at 60 ° C. in a water bath under a nitrogen atmosphere and stirred for 7 hours to carry out an isomerization reaction.

After completion of the reaction, the reaction solution was transferred to an evaporator and heated under reduced pressure to recover chloroform. 40 ml of petroleum ether was added to the residue, and the orange precipitate of dichlorobis (acetonitrile) palladium (II) formed after stirring was recovered by vacuum filtration. Petroleum ether was recovered from the filtrate by heating under reduced pressure to obtain 9.86 g of a colorless transparent viscous liquid.

When this product was analyzed by liquid chromatography, the starting material allyl phenyl ether had disappeared.
The nuclear magnetic resonance spectrum was measured with a JEOLPMX60SI spectrometer using TMS in deuterated chloroform as a standard sample. As a result, δ1.73 (dd) 3H -O-CH = CH- CH ₃ δ4.78 (quintet) 1H -O-CH = CH -CH ₃ δ6.30 (d, d) 1H -OC H = CH- CH ₃ δ 6.73-7.46 (m) 5H phenol ring gave 1-propenylphenyl ether in 94% yield with a selectivity of 100%.

Examples 2-9, Comparative Examples 1-3 Using the isomerization catalyst dichlorobis (acetonitrile) palladium (II) or various isomerization catalysts used in Example 1,
With the addition amount, reaction temperature, reaction time and reaction solvent shown in Table 1,
Otherwise, the isomerization reaction of allyl phenyl ether was carried out in the same manner as in Example 1.

The isolated yield of the obtained 1-propenyl phenyl ether, the conversion rate of the raw material allyl phenyl ether and 1-
Table 1 shows the selectivity of propenyl phenyl ether (weight of 1-propenyl phenyl ether / weight of 1-propenyl phenyl ether + weight of by-product).

[0030]

[Table 1]

As is clear from Table 1, in the isomerization reaction system of the example, the desired product can be obtained in a high yield in a short time at a relatively low temperature, and its selectivity is also high. On the other hand, the reaction system of the comparative example requires a reaction at a high temperature for a long time, its yield and selectivity are low, and by-products are generated due to the thermal polymerization rate and the like.

Example 10 (Synthesis of bisphenol A diallyl ether) Thermometer,
In a 2 l-four-necked flask equipped with a stirrer, a condenser and a dropping funnel, bisphenol A (228 g), NaOH (82.5 g) and n-
Propanol (1 l) was charged and refluxed. After all the contents were dissolved, 200 ml of allyl chloride was slowly added through the dropping funnel. The reaction solution became almost neutral after 3 hours. After continuing refluxing for a further 3 hours, the mixture was cooled to room temperature, the precipitated NaCl was filtered, and n-propanol was distilled off.

The crude diallyl ether of crude bisphenol A (308 g) obtained was dissolved in methylene chloride and washed with water. After separating the aqueous layer, methylene chloride was distilled off. The structure of the obtained purified bisphenol A was identified by liquid chromatography analysis, nuclear magnetic resonance analysis and infrared absorption spectroscopy analysis.

(1-Propenyl etherification) 103 g (0.33 mol) of bisphenol A diallyl ether obtained above, 200 g of carbon tetrachloride and dichlorobis (acetonyl)
7.76 g (0.02 mol) of palladium (II) was charged in the same apparatus as described in Example 1 and stirred at 50 ° C. for 8 hours to carry out an isomerization reaction.

After completion of the reaction, dichlorobis (acetonitrile) palladium (II) was recovered by the same operation as in Example 1 to obtain 100 g of a colorless transparent viscous liquid. It was identified as bisphenol A di (1-propyl) ether (abbreviated as BADP) by liquid chromatography, gel filtration chromatography, nuclear magnetic resonance and infrared spectroscopy.

Reference Example 1 and Comparative Reference Examples 1 and 2 BADP, 0,0′-diallylbisphenol A (abbreviated as DABA)
And 0,0-di (1-dipropenyl) bisphenol A (DAPA
(Abbreviation) was examined for gel time with the formulation in Table 2.
It can be seen that BADP has a shorter curing time than DABA and a longer curing time than DAPA, and thus has appropriate workability.

[0037]

[Table 2]

[0038]

INDUSTRIAL APPLICABILITY The production method of the present invention suppresses side reactions under mild reaction conditions as compared with conventionally known methods, and produces 1-propenylphenyl ethers in high yield, high selectivity and high conversion rate. can do.

Claims (2)

[Claims] 1. A process for producing 1-propenyl phenyl ethers, which comprises isomerizing allyl phenyl ethers in the presence of a divalent palladium compound catalyst. 2. The method according to claim 2, wherein the isomerization reaction is carried out in an organic polar solvent.