Bis(3-allyl-4-hydroxyphenyl)sulfone synthesis

Yield: 84.4%

Reaction Conditions:

with sodium carbonate;sodium hydroxide in water at 95 - 100; for 5 h;Autoclave;Large scale;Solvent;Reagent/catalyst;Temperature;

Steps:

1 Example 1
An autoclave equipped with a stirrer, were mixed charged with ethylene glycol monobutyl ether 3800g and water 500g, 4,4'- dihydroxydiphenyl sulfone (hereinafter, bisphenol S) 1000g (4.0 moles) of sodium hydroxide 288g (7. 2 mol) and sequential I sodium carbonate was added 170g (1.6 mol). Then added allyl chloride 670g (8.8 moles), and sealed, and allowed to react for 5 hours under heating and stirred at 95 ~ 100 . After completion of the reaction, depressurized, Further, the reaction mixture was heated, I was distilled off and unreacted allyl chloride. The distillate was separated into an upper and lower layers. The top layer (recovered solvent A), contained ethylene glycol monobutyl ether 165g. After the bottoms reaction solution after described above reservoir it was cooled to 100 , water 1300g was charged to dissolve the by stirring byproduct inorganic salt was extracted lower layer was separated (the aqueous layer). The lower layer was 1900g, inorganic salts (the sodium chloride) and contains about 30% by weight as the main component, an ethylene glycol monobutyl ether was an aqueous solution containing 0.3% by weight. 'S From the lower layer, 4,4'-allyloxy diphenyl sulfone (hereinafter referred to as bisphenol S diallyl ether) was not detected. S%Nappm Upper (organic layer), ethylene glycol monobutyl ether solution of bisphenol S diallyl ether, the water is about 5%, Na content of about 1000ppm. HPLCS%S %'S% Also, HPLC the composition ratio (area percentage) is 97.1% bisphenol S diallyl ether, bisphenol S 0.2%, 4- hydroxyphenyl-4'-allyloxy-phenyl sulfone (hereinafter, bisphenol S monoallyl ether) 0. It was 7%. To the upper (organic layer), 35% hydrochloric acid 19g of (0.2mol) was added, and after stirring 1 hour, distilled at normal pressure to remove a distillate of 393g. g The distillate (collected solvent B) is contained ethylene glycol monobutyl ether 45g. The bottoms reaction solution after the distillation was filtered hot to remove insolubles. S During hot filtration after the reaction mixture (filtrate), Na content is included 30ppm, the yield was calculated from the content of bisphenol-S diallyl ether was 97%. a Reaction solution after the heat and filtration (filtrate), N, N- dimethyl aniline 0.13g, hydroquinone monomethyl ether 0.13g, was charged in an autoclave, 205 in a closed state (0.2MPaG) ~ 215 in the 7 time, it was subjected to a heat rearrangement reaction. HPLC HPLC composition ratio of the reaction solution after heating rearrangement reaction (area percentage), bis (3-allyl-4-hydroxyphenyl) sulfone 92.0%, monoallyl body 2.9%, mono dislocation body 0.9%, other It was 4.2%. Ethylene glycol monobutyl ether as a solvent in this reaction solution was cooled by distilled off at atmospheric pressure and reduced pressure to recover a 3420g. The recovered distillate (recovered solvent C) is, GC composition ratio (area percentage) 99.5% were ethylene glycol monobutyl ether. When the bottoms reaction solution after described above reservoir became about 100 , and stirred by adding water 3500g and 13 wt% aqueous solution of sodium hydroxide 1766g to the reaction solution, followed by heating distilled under atmospheric pressure, the residual ethylene glycol mono-butyl ether to was removed by azeotrope with water. Distillate by azeotropic is 1300g (recovered solvent D), it had to contain 170g of ethylene glycol mono-butyl ether. Transfer the pot residual reaction solution after the distillation in the four-necked flask, after which additional water was added, and treated with activated carbon and acid precipitation of the desired compound with 25 wt% sulfuric acid. S The resulting crystals were filtered off, washed with water and dried, bis (3-allyl-4-hydroxyphenyl) sulfone purified product 1114g (yield based on bisphenol S: 84.4%) was obtained. HPLC The resulting bis (3-allyl-4-hydroxyphenyl) HPLC composition ratio of the sulfonic purified product (area percentage) of 97.3% and a melting point of 154 ~ 155 .

References:

Konishi Kagaku Kogyo Co., Ltd.;Katayama, Naoki KR101597659, 2016, B1 Location in patent:Paragraph 0090-0101