JPS5936977B2 - Method for producing 4,4'-bisphenolsulfone derivative - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention provides heat-resistant, flame-retardant polymer raw materials such as polycarbonate, epoxy, polyester, phenolic resin, etc., as well as 4, which are important as intermediates for crosslinking agents, agricultural chemicals, dyes, etc.
The present invention relates to a method for producing a 4'-bisphenolsulfone derivative.

More specifically, 4|4'-bisphenol sulfides or 4,4'-bisphenol sulfoxides are oxidized with hydrogen peroxide in the presence of equimolar or more alkali in water and/or an organic solvent that does not produce organic peracids. The present invention relates to a method for producing a corresponding 4,4'-bisphenolsulfone derivative.

In general, hydrogen peroxide is a typical oxidizing agent when producing sulfone derivatives from sulfides and sulfoxides, and oxidation using deoxidized hydrogen is usually performed under acidic conditions.

Conventionally, for 4,4'-diphenolsulfone, 4
, 4-diphenol sulfide is generally produced in an acidic aqueous solution in the presence of a metal catalyst such as molybdenum, vanadium, titanium or tungsten. A typical known technique involves heating and refluxing 4,4'-diphenol sulfide in an aqueous sulfuric acid solution in the presence of molybdenum while keeping the pH below 1, yielding 99.7% (purity 97%).
．． 6%) to obtain the desired product (U.S. Pat. No. 4, 08
9, 904 (1978)). Furthermore, a method for producing 4,4'-diphenolsulfone by oxidizing sulfoxide with hydrogen peroxide is carried out in glacial acetic acid (peracetic acid oxidation). For example, 4|4'-diphenol sulfoxide is oxidized in a large excess of glacial acetic acid at 85°C. The desired product is produced with a yield of 85% (L, N, Nik, Olenk
o et al., J. GsneralChem, of USSR, 3
3, 3731 (1963)).

However, the former method uses a relatively expensive metal catalyst, and since the catalyst is dissolved in an aqueous solution, recovery of the catalyst is complicated and there are many problems related to environmental protection. Moreover, the reaction conditions (particularly pH) significantly affect the yield and purity of the target product, and there are problems such as coloring of the product, making it uneconomical and difficult to call an industrially advantageous method. The latter is an oxidation reaction using a large excess of peracetic acid, so it must be handled with the risk of bumping and explosions in mind, and there are various economic and manufacturing issues involved in carrying out this reaction industrially. I have no choice but to think about the difficulties. The present inventors conducted extensive studies with the aim of providing an industrially advantageous method for producing 4|4'-bisphenolsulfone derivatives, and found that 4,4
By oxidizing '-bisphenolsulfides or 4,4'-bisphenolsulfoxides with hydrogen peroxide in the presence of an alkali, the corresponding 4,1-bisphenolsulfone derivatives can be produced with high purity and high purity. The present invention was achieved by discovering that it can be produced with extremely high yield and with ease.

That is, the present invention relates to the general formula (1) (where R and R2 are hydrogen, halogen, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, a hydroxyl group, an alkoxy group, an allyloxy group, a carboxyl group, or a carbalkoxy group) may be the same or different from each other.

4,4'-, where n is an integer of O or 1)
Bisphenol sulfides (in general formula (1),
n=0 compound) or 4,4'-bisphenol sulfoxides (n=1 compound in general formula (1))
is oxidized with hydrogen peroxide in the presence of equimolar or more alkali in water and/or an organic solvent that does not produce organic deoxidation to obtain the corresponding 4,41-bisphenolsulfone derivative (in general formula (1), n is 2 A method for producing a compound that is According to the present invention, 4,4'-bisphenol sulfide or sulfoxides form a solution by forming the corresponding phenolade in the presence of equimolar or more alkali in an aqueous solvent, and this is dissolved in a theoretical amount. When hydrogen oxide is reacted,
The oxidation proceeds smoothly, and the corresponding target product, 4,4'-bisphenolsulfone, is obtained by neutralization after the reaction is complete.

The amount of alkali to be used must be at least equimolar to the amount of bisphenol sulfide or sulfoxide.
In particular, when using 4,4'-bisphenol sulfide, if the mole is less than equimolar, sulfoxide, which is a primary oxidation product, will be mixed in, and sulfone will be produced in proportion to the amount of alkali added. The surprising fact was discovered that when sulfoxide is used, the sulfoxide disappears and all sulfone is formed.
According to the present invention, the reaction proceeds smoothly if the stoichiometric amount of hydrogen peroxide is used, but there is no problem even if a large excess of hydrogen peroxide is used, and no oxidized by-products are produced. It is industrially very advantageous that the corresponding 4,4'-bisphenolsulfone derivatives can be produced with extremely high purity and in almost quantitative yield. Further, according to the present invention, 14,
4. If the phenolade of bisphenol sulfide or sulfoxides is insoluble in water, it can be dissolved and reacted by using a small amount of hydrogen peroxide and an organic solvent that does not produce organic peracids; 2. Regardless of its solubility in water, organic solvents can be used instead of water, so the volumetric yield of the target product is significantly improved because the amount of organic solvent used is much smaller than that of water. This is also a feature of the present invention.

The 4,47-bisphenol sulfides and 4,4'-bisphenol sulfoxides used in the method of the present invention are compounds represented by the general formula (1).

For example, 4,4'-diphenol sulfide, 4,4'
-diphenol sulfoxide, 4,4'-bis(2-chlorophenono(he)sulfide, 4,4'-bis(3
-chlorophenolic sulfide, 4,4'-bis(2
-Methylphenono(ha)sulfide, 4,4'-bis(3-methylphenono(ha)sulfide, 4,4'
-bis(2,5-dimethylphenono(he)sulfide, 4,4'-bis(2,5-dimethylphenonolisulfoxide), 4,4-bis(2-isopropyl-5-methylphenol sulfide, 4,4'-bis(2-Tcr
t-butylphenol) sulfoxide, 4,4-bis(
2-Methyl-6-Tert-butylphenol) sulfide, 4,4-bis(2-cyclohexylphenol sulfoxide, 4,4'-bis(2,6-di-Tcrt)
-butylphenol) sulfide, 4,4'-bis(2
-Tcrt-butyl-5-methylphenol) sulfoxide, 4,4'-bis(2-benzylphenol)
Sulfoxide, 4,4'-bis(-2-hydroxyphenol) sulfide, 4,4'-bis(2-methoxyphenol) sulfoxide, 4,4'-bis(2-phenoxyphenol) sulfoxide, 4,4'-bis(
2-carboxyphenono(he)sulfide, 4,4'
-bis(2-carboxyphenono(he)sulfoxide), 4,4'-bis(2-carbomethoxyphenol) sulfide, 4,4-bis(2-carbomethoxyphenol) sulfoxide, and the like. Organic liquefiers used in the method include hydrocarbons such as hexane, cyclohexane, hebutane, benzene, toluene, xylene, and ethylbenzene, dichloromethane, chloroform, carbon tetrachloride, dichloroethane, trichloroethane,
Halogenated hydrocarbons such as chlorobenzene and 0-dichlorobenzene, methanol, ethanol, propanol,
Alcohols such as butanol, ethers such as diethyl ether, dibutyl ether, tetrahydrofuran, and dioxane, ketones such as acetone and methyl ethyl ketone, acetic acid esters, carbon disulfide, N,N-dimethylformamide, and organic solvents such as dimethyl sulfoxide. Examples include general organic solvents other than organic acids that produce hydrogen peroxide and organic peracids, such as acetic acid and phosphoric acid.

Further, there is no problem in using a mixture of these organic sludge agents, and there is also no problem in using a mixture with water. If a water-immiscible solvent such as benzene, toluene, xylene, chlorobenzene, dichloroethane, or carbon tetrachloride is used in the above-mentioned benzene, the solvent can be recovered by steam distillation after the reaction is completed, and the recovered solvent remains as is. It can be recycled and reused, if necessary, with purification treatment, for example by distillation. This is extremely advantageous industrially, not only because it helps save on scouring agents, which leads to lower costs, but also because it poses fewer problems related to cyclic protection. The alkali used in the present invention includes sodium hydroxide, potassium hydroxide,
Examples include lithium hydroxide.

Although the alkali may be used as a solid, it is generally used as an aqueous solution. The alkali is usually equimolar to 5
It is used in an amount of about mol, preferably about 1 mol to 2 mol. However, in the case of 4,4'-bisphenol sulfide or sulfoxide having a carboxyl group as a substituent, a considerable amount of alkali is added to the carboxyl group to form a carboxylic acid alkali metal salt, and then an equimolar or more alkali is added to the carboxyl group. It is necessary to adjust the amount of alkali used to produce the corresponding phenolade. Various concentrations of hydrogen peroxide can be used, but 30 to 35% hydrogen peroxide is preferred for handling reasons.

In the present invention, hydrogen peroxide is used in a small excess of the theoretically required amount relative to the raw material sulfides or sulfoxides, but there is no problem in the range of 1.5 to 5.0 times the amount. When hydrogen peroxide is reacted, it is added dropwise to the alkaline solution of the sulfide or sulfoxide, or it may be mixed in advance with the phosphorus solution. In the present invention, the reaction temperature is usually in the range of 30 to 110°C, but if it is lower than 30°C, the reaction will take a long time;
If the reaction temperature is higher than 110°C, the concentration of hydrogen peroxide will be extremely reduced and phenomena such as bubbling will occur, making it practically impossible.

A more preferable temperature is 50 to 100°C. In carrying out the process of the present invention, 4,41-bisphenol sulfide or sulfoxide and an equimolar amount of alkali are generally dissolved in water and/or an organic solvent.
Hydrogen peroxide solution is gradually added dropwise while maintaining the temperature at 10°C. After the dropwise addition is completed, the mixture is stirred at the same temperature for 30 minutes to 5 hours. Cool to room temperature and neutralize with acid to obtain a precipitate.
Alternatively, after neutralization, the reaction solution is diluted with water or the flocculating agent is distilled off by steam distillation to obtain a precipitate. In some cases, the alkaline solution is distilled off by steam distillation to remove the solvent and then neutralized to obtain a precipitate. The desired product is obtained by filtering, washing with water, and drying.
In all cases, 4,4'-bisphenolsulfone derivatives are obtained with a high yield of over 90%, and the purity of the products is extremely good.They can be used as polymer raw materials, crosslinking agents, pesticides, and dyes without any special operations. etc. or as intermediates thereof.

Hereinafter, the method of the present invention will be explained in more detail with reference to Examples. Example 1 '4,4-bisphenol sulfide 21.89 (0.1
mol), sodium hydroxide 59 (0.125 mol) and water 100ml1C! )? 30% hydrogen peroxide solution 28.39 (0.25
mol) dropwise over 30 minutes.

The mixture is further stirred at the same temperature for 2 hours, cooled to temperature, and then neutralized to form a precipitate. After filtration, washing with cold water, and drying, 4,4'-diphenolsulfone was obtained. Yield 23.5
g (yield 94%), melting point 245-246°C, was recrystallized from water to obtain pure white needle crystals. Melting point 247-248℃
. Examples 2 to 4 Corresponding sulfones were synthesized using 4,4'-bisphene nolsulfide as a raw material in exactly the same manner as in Example 1.

The results are shown below. Example 5 4,4'-bis(2-chlorophenono(ha)sulfide 27.79 (0.1 mol)
is dissolved in 80 ml of ethanol.

Add 59 (0.125 mol) of sodium hydroxide to this and 2 mol of water.
Add the solution dissolved in 0ml. While keeping the temperature at 70-75℃, add 30% hydrogen peroxide solution 28.39 (0.2
5 mol) was added dropwise over 30 minutes. The mixture was stirred for an additional 3 hours at the same temperature, cooled to room temperature, and then neutralized to form a precipitate.

After filtering, washing with water and drying, 4,4-bis(2-chlorophenol)sulfone was obtained. Yield 29.09 (yield 9.4%
), melting point 195-197°C. The product was recrystallized from a mixture of ethanol and water to obtain pure white needle-like crystals.

Melting point: 196-197 DEG C. Examples 6-7 The corresponding sulfones were synthesized in exactly the same manner as in Example 5 using 4,4-bisphenol sulfides as raw materials.

The results are shown below. Example 8 23.490,1 mol of 4,4'-diphenol sulfoxide was added to 7 mol of potassium hydroxide.
．． 09 (0.125 mol) and water 100w11, and 30% hydrogen peroxide solution 14.29 (0.125 mol) was added dropwise over 30 minutes while maintaining the concentration at 55 to 60°C.

After stirring for an additional 3 hours at the same temperature and cooling to room temperature, the mixture is neutralized to form a precipitate. After filtering, washing with cold water and drying, 4,4'-diphenolsulfone was obtained. Yield 23.
99 (yield 96%) Example 9 4,4 bis(2-Tert-phthal-5-methylphenol) sulfoxide 37.49 (0.1 mol) was dissolved in 150 ml of xylene, and 20% potassium hydroxide was added thereto. Add aqueous solution 36,59 (0.13 mol) to 75-8
While keeping the temperature at 0℃, add 30% hydrogen peroxide solution 14.29 (
0.125 mol) was added dropwise over 30 minutes.

The mixture was further stirred at the same temperature for 2 hours and then neutralized. When xylene is removed by steam distillation, a precipitate is formed. After cooling to room temperature, it was filtered, washed with water, and dried to obtain 4,4-nickel bis(2-Te).
rt-butyl-5-methylphenol)sulfone was obtained. Yield 38.0f1 (yield 98%), melting point 248-25
0℃. Recrystallization from ethanol yielded pure white needle-like crystals.

Melting point: 250-251°C. Examples 10 to 11 Using 4,4'-diphenol sulfoxides as raw materials,
The corresponding sulfone was synthesized in exactly the same manner as in Example 9.

The results are shown below. Example 12 32.29 (0.1 mol) of 4,4'-bis(2-carboxyphenono(he)sulfoxide) was dissolved in a solution of 13.29 (0.33 mol) of sodium hydroxide and 150 d0 of water. While maintaining the temperature at 50 to 60°C, 14.29 (0.125 mol) of 30% hydrogen peroxide solution is added dropwise for 30 minutes.

The mixture is further wetted at the same temperature for 4 hours, cooled to room temperature, and then neutralized to form a precipitate. Finished, washed with water, dried and 4,4'-
Bis(2-carboxyphenol)sulfone was obtained. Yield 339 (yield 97.5%), melting point 301-303°C. Recrystallization from a mixture of acetic acid and water gave pure white needle crystals.

Claims (1)

[Claims] 1 4,4'-bisphenol sulfides or 4,
A 4,4'-bisphenol sulfone derivative characterized by oxidizing 4'-bisphenol sulfoxides with hydrogen peroxide in the presence of an equimolar or more alkali in water and/or an organic solvent that does not produce an organic peracid. manufacturing method.