JP4248915B2 - Process for producing 3,3'-diallyl-4,4'-dihydroxydiphenylsulfone - Google Patents

Description

[0001]
[Field of the Invention]
The present invention relates to a method for producing 3,3′-diallyl-4,4′-dihydroxydiphenylsulfone, which is a substance useful as a color developer or polymer additive for heat-sensitive recording materials.
[0002]
[Prior art]
3,3′-diallyl-4,4′-dihydroxydiphenylsulfone is a substance useful as a color developer or polymer additive of a heat-sensitive recording material, and undergoes a Claisen rearrangement reaction with 4,4′-diallyloxydiphenylsulfone. A method for producing 3,3′-diallyl-4,4′-dihydroxydiphenylsulfone has been proposed. For example, 4,4′-diallyloxydiphenyl sulfone is reacted in a trichlorobenzene solvent at 216 to 219 ° C. for 10 hours to obtain mp 139 to 144 ° C. in a yield of 93.3% (Patent Document 1). In addition, 4,4′-diallyloxydiphenylsulfone having an alkali content of 50 ppm or less in terms of sodium hydroxide was reacted in a paraffinic solvent at 205 to 210 ° C. for 7 hours to obtain a purified yield of 70.9. % And purity (liquid chromatography) of 96.2% (Patent Documents 2 and 3). All of these methods have a disadvantage that they must be reacted at a high temperature of 200 ° C. or more for a long time.
[0003]
[Patent Document 1]
JP-A-60-169456
[Patent Document 2]
JP2002-30064
[Patent Document 3]
JP2002-30065
[0004]
[Problems to be solved by the invention]
An object of the present invention is to provide a method for producing 3,3′-diallyl-4,4′-dihydroxydiphenylsulfone with a short reaction time and high yield.
[0005]
[Means for Solving the Problems]
As a result of intensive studies to solve the above-mentioned problems, the present inventors have conducted a rearrangement reaction of 4,4′-diallyloxydiphenylsulfone under microwave irradiation to produce 3,3′-diallyl-4. , 4'-dihydroxydiphenylsulfone has been found to be able to be produced in a short time of several minutes to 30 minutes in a high yield in a reaction that conventionally took 7 to 10 hours, and the present invention has been completed. It was.
That is, the present invention is (1) Production of 3,3′-diallyl-4,4′-dihydroxydiphenylsulfone, wherein 4,4′-diallyloxydiphenylsulfone undergoes a rearrangement reaction under microwave irradiation. Method (2) The rearrangement reaction is carried out in a molten state. The method for producing 3,3′-diallyl-4,4′-dihydroxydiphenylsulfone as described in (1) (3) The rearrangement reaction is substantially free of oxygen. The present invention relates to a method for producing 3,3′-diallyl-4,4′-dihydroxydiphenylsulfone as described in (1) or (2) under an atmosphere.
[0006]
DETAILED DESCRIPTION OF THE INVENTION
The present invention is carried out by performing a rearrangement reaction of 4,4′-diallyloxydiphenyl sulfone under microwave irradiation.
[0007]
4,4'-diallyloxydiphenyl sulfone used as a raw material of the present invention includes 4,4'-dihydroxydiphenyl sulfone, allyl chloride and allyl bromide in an organic solvent, an alkali metal hydroxide, an alkaline earth metal hydroxide, and the like. It is produced by reacting in the presence of alkali (Japanese Patent Laid-Open No. 60-169456). The alkali contained in the raw material 4,4′-diallyloxydiphenylsulfone is converted to 3,3′-diallyl-4,2′-dihydroxydiphenylsulfone or 5- (3-allyl) during the rearrangement reaction in the present invention. There is a possibility of promoting the production of by-products such as -4-hydroxy) phenylsulfonyl-1-oxa-2-methylindane. These by-products are difficult to remove and cause deterioration in quality such as background fog when used as a color developer for heat-sensitive recording materials. Therefore, they are contained in 4,4′-diallyloxydiphenyl sulfone. It is preferable to use 4,4′-diallyloxydiphenyl sulfone having an alkali amount of several tens of ppm or less.
[0008]
The microwave used in the present invention is an electromagnetic wave having a frequency of usually 300 MHz to 30 GHz, and any of them may be used. Since 2450 MHz or 918 MHz is used for the industrial microwave irradiator, it may be normally used. The irradiation time varies depending on the amount charged, the wattage of the microwave irradiation apparatus, and so on, but it cannot be generally stated, but it is usually 1 to 60 minutes at 100 to 10 kW after reaching the reaction temperature. It is preferable that the reaction is completed in about 5 to 30 minutes because of easy control of the reaction. The reaction temperature is controlled in the range of 150 to 350 ° C., preferably 230 to 300 ° C., more preferably 240 to 290 ° C. by intermittent irradiation (on to off) of electromagnetic waves. The microwave irradiation experimental apparatus used in the present invention is manufactured and sold by, for example, Milestone, CEM, Micro Electronics Co., Ltd.
[0009]
In the present invention, the rearrangement reaction can be carried out either without a solvent or in the presence of a solvent. When a solvent is used, an inert and high boiling point solvent is preferable. For example, N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidinone, polar solvents such as dimethyl sulfoxide, chlorobenzenes such as o-dichlorobenzene and trichlorobenzene, high boiling aliphatic carbonization Hydrogen or the like can be used. When a solvent is used, 4,4′-diallyloxydiphenyl sulfone used as a raw material may be dissolved in the solvent and used, or a small amount so as to wet the raw material may be used.
When no solvent or a small amount of solvent that moistens the raw material is used, it is preferable to perform the transfer reaction by previously bringing the raw material into a molten state and irradiating the microweb in that state. In order to bring the raw material into a molten state in advance, the raw material may be irradiated with a micro-web to be in a molten state, or may be heated by another method, for example, a conventional electric heater or a heater using a heat medium, to be in a molten state.
In the present invention, it is preferable to carry out the transfer reaction without using a solvent since the equipment is charged efficiently and solvent recovery is unnecessary.
[0010]
In the present invention, in order to suppress side reactions and polymerization reactions, the reaction is preferably carried out in an atmosphere of an inert gas such as nitrogen or argon and substantially free of oxygen. Further, in order to suppress by-products, the reaction system may include antioxidants such as methoxyhydroquinone and butylhydroquinone and organic basic compounds such as N, N-dimethylaniline, N, N-diethylaniline, N, N such as dimethylaminopyridine. -Di-lower alkyl aromatic amines, hexamethylenetetramine, quinuclidine, quinoline, isoquinoline, quinaldine, phenanthroline such as 1,10-phenanthroline, nitrogen-containing cyclic compounds such as quinoxaline, etc. are added and the reaction is carried out in the presence thereof Is preferred. The lower alkyl group is preferably an alkyl group having 1 to 6 carbon atoms, preferably 1 to 3 carbon atoms. Examples of aromatic rings in aromatic amines include 5- to 6-membered aromatic rings, preferably 6-membered aromatic rings. The nitrogen-containing cyclic compound is preferably a nitrogen-containing cyclic compound having about 5 to 15 carbon atoms, more preferably about 6 to 12 carbon atoms (1 to 4 nitrogen atoms, preferably less than half of all atoms forming the ring). . The amount of these side reaction inhibitors to be added is not more than 1% by mass (hereinafter, unless otherwise specified) of 4,4′-diallyloxydiphenylsulfone, and is usually 0.01% to 0.5%. %.
[0011]
In the reaction, 4,4′-diallyloxydiphenylsulfone is continuously charged with 4,4′-diallyloxydiphenylsulfone in the reactor that is irradiated with microwaves, even if batchwise is used in which 4,4′-diallyloxydiphenylsulfone is charged into the reactor at once. The semi-batch method, which supplies the product in small or divided portions, or the flow-through method, in which 4,4'-diallyloxydiphenylsulfone is continuously supplied to the reactor irradiated with microwaves and the product is continuously discharged. Can be implemented.
[0012]
The reaction product can be confirmed by high-speed chromatography. After completion of the reaction, the content of 3,3′-diallyl-4,4′-dihydroxydiphenylsulfone in the obtained reaction product is 85% or more. This can be dissolved in an aqueous solution such as an alkaline solution and then acidified, or heated and dissolved in an organic solvent, and then cooled to precipitate crystals, isolated by filtration, or recrystallized from the organic solvent. It can be purified by a method such as combining both crystals. The purity of the purified 3,3′-diallyl-4,4′-dihydroxydiphenylsulfone thus obtained is usually 97% or more (area% in high-speed chromatography), and the yield is 80% or more.
[0013]
【Example】
The present invention will be described in more detail with reference to examples, but the present invention is not limited to the examples.
[0014]
Example 1
A quartz flask equipped with a temperature sensor and a magnetic stirrer was charged with 10.00 g of 4,4′-diallyloxydiphenylsulfone and 0.01 g of N, N-dimethylaniline and purged with nitrogen. Under nitrogen inflow, microwaves of 2450 MHz were irradiated at 100 W, melted at 160 ° C., and reacted for 5 minutes while maintaining the reaction temperature at 280 ° C. by on-off irradiation. The liquid reaction analysis value of the obtained reaction product was 3,3′-diallyl-4,4′-dihydroxydiphenylsulfone (hereinafter abbreviated as di-rearranged product) 89.5%, 3-allyl-4-hydroxy- 4'-allyloxydiphenyl sulfone (hereinafter abbreviated as mono-rearranged product) 1.4%, 5- (3-allyl-4-hydroxy) phenylsulfonyl 1-oxa-2-methylindane (hereinafter abbreviated as indane product) It was 1.1%, 3-allyl-4,4′-dihydroxydiphenylsulfone (hereinafter abbreviated as monoallyl form) 1.5%, isomer 0.8% and dimer 1.8%.
After dissolving this reaction product in a 10% by weight aqueous sodium hydroxide solution, a small amount of activated carbon was added, and the mixture was heated and stirred to decolorize, and the filtrate obtained by filtering off the activated carbon was neutralized by adding hydrochloric acid to precipitate crystals. Purified 3,3′-diallyl-4,4′-dihydroxydiphenyl sulfone having a purity of 96% to 98% can be obtained in a yield of 80% to 90%.
[0015]
Example 2
A quartz flask equipped with a temperature sensor and a magnetic stirrer was charged with 10.00 g of 4,4′-diallyloxydiphenylsulfone and 0.01 g of N, N-dimethylaniline and purged with nitrogen. Under nitrogen inflow, microwaves of 2450 MHz were irradiated at 100 W, melted at 160 ° C., and reacted for 20 minutes while maintaining the reaction temperature at 255 ° C. by on-off irradiation. The liquid chromatography analysis value of the obtained reaction product was as follows: di-rearranged 91.1%, mono-rearranged 1.6%, indane 1.0%, monoallyl 1.1%, isomer 0.6%, The dimer was 1.4%.
By purifying the reaction product by the method described in Example 1, 80% to 90% yield of purified 3,3′-diallyl-4,4′-dihydroxydiphenylsulfone having a purity of 96% to 98% is obtained. Can be obtained at
[0016]
Example 3
A quartz flask equipped with a temperature sensor and a magnetic stirrer was charged with 10.00 g of 4,4′-diallyloxydiphenylsulfone and purged with nitrogen. Under nitrogen inflow, microwaves of 2450 MHz were irradiated at 100 W, melted at 160 ° C., and reacted for 5 minutes while maintaining the reaction temperature at 280 ° C. by irradiation on-off. The liquid chromatographic analysis value of the obtained reaction product was as follows: di-rearrangement 87.4%, mono-rearrangement 1.9%, indane 1.7%, monoallyl 2.6%, isomer 1.7%, The dimer was 1.9%. By purifying the reaction product by the method described in Example 1, 80% to 90% yield of purified 3,3′-diallyl-4,4′-dihydroxydiphenylsulfone having a purity of 96% to 98% is obtained. Can be obtained at
[0017]
【The invention's effect】
The transfer reaction from 4,4′-diallyloxydiphenylsulfone to 3,3′-diallyl-4,4′-dihydroxydiphenylsulfone, which conventionally takes 7 to 10 hours, is carried out in a period of several minutes to 30 minutes. In addition, the yield of the target product is high, it is not inferior to the conventional method, and the reaction can be carried out even without solvent, which is very advantageous economically.

Claims (3)

3,3′-diallyl-4,4′-dihydroxydiphenyl is characterized in that 4,4′- diallyloxydiphenylsulfone undergoes a rearrangement reaction in the molten state at 240 to 290 ° C. under microwave irradiation. A method for producing sulfone. 4,4' row rearrangement reaction in the presence of 0.01-0.5% of an organic base compound against diallyl sulfone intends according to claim 1 3,3'-diallyl-4,4' -Manufacturing method of dihydroxy diphenyl sulfone. The method for producing 3,3'-diallyl-4,4'-dihydroxydiphenylsulfone according to claim 1 or 2, wherein the rearrangement reaction is carried out in an atmosphere substantially free of oxygen.