JPS5825667B2 - Method for producing 2,2′↓-bisphenolsulfone derivative - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing 2,2'-bisphenolsulfone derivatives.

More specifically, the general formula (I) (wherein R1, R2 and R3 represent hydrogen, halogen, alkyl group, cycloalkyl group, aryl group or aralkyl group).

However, R1 excludes hydrogen.

Furthermore, R1, R2, and R3 may be combined to form a ring) and sulfur dichloride are reacted in a hydrocarbon solvent to synthesize the corresponding 2,2'-bisphenol sulfide. General formula (I[) (wherein R1, R2, R3 have the same meanings as general formula (I)), characterized in that it is oxidized with hydrogen peroxide in the presence of an equimolar or more alkali without isolating the sulfide. The present invention relates to a method for producing a 2,2'-bisphenol sulfone derivative represented by

2,2'-bisphenol sulfone derivatives, which are oxidation products of 2,2'-bisphenol sulfides, are important as light stabilizers, polyolefin modifiers, lubricating oil additives, agricultural chemicals, and intermediates thereof.

It is generally known that the 2,2'-bisphenol sulfides used as raw materials are produced by reacting substituted phenols and sulfur dichloride in a hydrocarbon-based inert organic solvent.

In addition, hydrogen peroxide is used as an oxidizing agent in the oxidation reaction of sulfides, but in hydrogen peroxide oxidation, glacial acetic acid is used as a solvent.
Isolation of sulfides is essential for producing sulfone derivatives by hydrogen peroxide oxidation since the process is carried out in a water-miscible organic solvent such as acetone or alcohols.

However, 2,2'-bisphenol sulfides are often obtained as resinous substances, and isolation and purification are generally complicated. Since the isolation yield is lower due to the relative solubility of
- Performing an isolation operation to subject bisphenol sulfides to an oxidation reaction cannot be said to be an industrially advantageous method from the viewpoint of manufacturing operations and economic efficiency.

For example, in the phenol of general formula (I), R1 is ter
t-C8H17, 4-te where R2 and R3 are H
Isolated yield of 2,2'-bis(4-tert-octylphenol)-sulfide obtained by reacting rt-octyl-phenol and sulfur dichloride in carbon tetrachloride and diluting with a large amount of petroleum ether. The rate is 40% [US Pat. No. 2,971,968 (1961): Chemic
alAbstracts, vol, 55.14
385 (1961)).

Based on the state of the art regarding cholera, it is an industrially desired problem to produce 2,2'-bisphenol sulfone derivatives by directly oxidizing 2,2'-bisphenol sulfide without isolating it.

On the other hand, when producing sulfones from sulfides, hydrogen peroxide is a typical oxidizing agent, and although it is usually carried out in glacial acetic acid (peracetic acid oxidation), it is known that it also proceeds in organic solvents such as acetone. It is being

Conventionally, oxidation of 2,2'-bisphenol sulfides with hydrogen peroxide was similarly carried out in glacial acetic acid.
Methods for preparing the corresponding 2,2'-bisphenolsulfone derivatives are known.

C.J. Am, Chem, Soc,, Ze, 238 (1
966)).

However, since the above method involves an oxidation reaction using a large excess of peracetic acid, the risk of bumping and explosion must be taken into consideration when handling the method.Furthermore, a large amount of glacial acetic acid is used, and a large amount of water is used after the reaction is completed. A large amount of expense is required, including waste liquid treatment, and various difficulties must be considered in order to carry out this reaction industrially.

The present inventors discovered that the oxidizing agent is inexpensive, easy to handle, and furthermore, it is easy to perform post-treatment of the reaction.
As a result of studying the oxidation reaction of 2,2'-bisphenol sulfides using hydrogen peroxide, we found that when hydrogen peroxide is oxidized in the presence of an alkali in a hydrocarbon solvent, the corresponding 2,2'-bisphenol sulfone derivative It was discovered that it is possible to produce

Here, the amount of alkali used must be at least equimolar to 2,2'-bisphenol sulfide, and if it is less than equimolar, sulfoxide will be mixed.

That is, sulfone is produced in proportion to the amount of alkali added, and when an equimolar amount of alkali is used, sulfoxide disappears and all sulfone is produced.

Therefore, the present inventors developed an industrially advantageous 2,2'-bisphenol sulfone derivative represented by the general formula (6) by converting the phenol represented by the general formula (I) into sulfide and then continuously carrying out an oxidation reaction. As a result of extensive research aimed at providing a production method, the corresponding 2,2'-bisphenol sulfide was produced by reacting the phenol represented by the general formula (I) with sulfur dichloride in a hydrocarbon solvent. The present inventors have discovered that 2,2'-bisphenolsulfone derivatives can be produced in good yields by oxidizing them with hydrogen peroxide in the same solvent in the presence of equimolar or more alkali without isolating the sulfide, and have thus arrived at the present invention. .

That is, the present invention involves reacting a phenol represented by general formula (I) with sulfur dichloride in a hydrocarbon solvent,
A compound represented by the general formula (6) characterized by synthesizing the corresponding 2,2'-bisphenol sulfide and oxidizing it with hydrogen peroxide in the presence of an equimolar or more alkali without isolating the sulfide. This is a method for producing 2,2'-bisphenol sulfone derivatives.

In carrying out the present invention, the substituted phenol represented by general formula (I) is usually dissolved in a hydrocarbon solvent, maintained at a temperature of -10 to 40°C without a catalyst or in the presence of a catalyst, and then dichlorinated. Gradually drip in the sulfur.

After the dropwise addition is completed, the mixture is stirred at the same temperature for 1 to 5 hours, and then the hydrogen chloride dissolved in the solvent is driven out by blowing air, or the organic layer is separated after thoroughly washing with water.

The hydrocarbon solvents used here include aliphatic saturated hydrocarbons such as hexane, cyclohexane, and heptane, aliphatic halogenated hydrocarbons such as dichloromethane, chloroform, carbon tetrachloride, dichloroethane, trichloroethane, benzene, toluene, xylene, etc. Aromatic hydrocarbons such as ethylbenzene, chlorobenzene, and 0-dichlorobenzene are mentioned.

These hydrocarbon solvents can be recovered by steam distillation after the completion of the reaction, and can be reused, if necessary, with purification treatment, for example, by distillation.

This not only leads to lower costs (helping to save on solvents), but also poses fewer environmental protection problems, which is of great industrial advantage.

The amount of sulfur dichloride used in the synthesis of 2.goo bisphenol sulfides may be used in an amount of 1 mole per 2 moles of phenol as a raw material, but it may be in the range of 1.0 to 1.1 moles.

Furthermore, the sulfidation reaction proceeds more smoothly when a Lewis acid is used as a catalyst.

The Lewis acids used include aluminum chloride, zinc chloride, stannic chloride, and ferric chloride, with zinc chloride being particularly preferred.

The reaction temperature for sulfidation is preferably in the range of -10 to 40°C.

If the reaction temperature is lower than 110°C, the reaction will take a long time;
At temperatures above 0°C, side reactions occur and the purity of 2,2'-bisphenol sulfides is extremely reduced.

A more preferred temperature is 0 to 20°C.

The end point of the sulfidation reaction can be determined quickly and simply by, for example, gas chromatography, thin layer chromatography or high performance liquid chromatography.

After the completion of the sulfidation reaction, an aqueous alkali solution of equimolar or more is then added, and hydrogen peroxide solution is added dropwise while maintaining the temperature at 30 to 110°C.

After completion of the dropwise addition, the mixture is stirred at the same temperature for 30 minutes to 5 hours, neutralized, and the solvent 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.

It is filtered, washed with water, and dried to obtain the target 2-gu bisphenol sulfone derivative.

Examples of the alkali used in this oxidation reaction include sodium hydroxide, potassium hydroxide, and lithium hydroxide.

Alkali is generally used as an aqueous solution.

The alkali is usually used in an amount of about 1 to 5 moles relative to the sulfide, preferably about 1 to 2 moles.

As the hydrogen peroxide, various concentrations of hydrogen peroxide are used, but 30 to 35% hydrogen peroxide is preferable for handling reasons.

In the present invention, hydrogen peroxide is used in a small excess of the theoretically necessary amount relative to 2,2'-bisphenol sulfides, but it may be in a range of 1.5 to 5.0 times the amount.

The reaction temperature of the oxidation reaction is usually carried out in the range of 30 to 110°C, but if it is lower than 30°C, the reaction will take a long time, and if the reaction temperature is higher than 11.0°C, the concentration of hydrogen peroxide will decrease. The amount decreases extremely and phenomena such as bubbling occur, making it practically impossible.

A more preferable temperature is 50 to 100°C.

The method of the invention will be explained in further detail by the following examples.

Example 1 21.61 (0.2 mol) of p-cresol was dissolved in 50 ml of 1,2-dichloroethane, and 10.8 f (0.105 mol) of sulfur dichloride was added to the solution while maintaining the temperature between 0 and 10°C. Allow to drip for 1.5 hours.

After stirring at the same temperature for 3 hours, air was blown to drive out hydrogen chloride.

Next, add 30% sodium hydroxide aqueous solution 14.7S'(0
, 11 mol), the temperature is raised to 50 to 60°C, and at the same temperature, 27.2 fI (o, 24 mol) of 30% hydrogen peroxide solution is added dropwise over 20 minutes.

After further stirring at the same temperature for 2 hours, the mixture is neutralized.

Dichloroethane was removed by steam distillation and a precipitate formed.

After filtration, washing with water, and drying, 2,2'-bis(p-cresol)sulfone was obtained.

Yield 24. my (yield 88%).

Melting point: 203-204°C. Recrystallization from glacial acetic acid-water gave pure white needle crystals.

Melting point: 207-208°C.

Elemental analysis C (to) H (to) 8% calculated value 60
．． 4 5.07 11.5 Measured value 60.1 5.12 11.1 Example 2 2,2-bis(p-chlorophenol) sulfone was prepared in exactly the same manner as in Example 1 using p-chlorophenol. Obtained.

Yield 86%. Melting point: 187-188°C.

Recrystallization from glacial acetic acid gave pure white needle crystals.

Melting point 191-192℃ Elemental analysis Ce/9 H(he) C1% 8% Calculated value 45.2 2.52 22.2 10.0 Measured value
45.8 2.47 22.7 10.3 Example 3 p-bromophenol 34.6 f? (0.2 mol) was dissolved in 65 ml of carbon tetrachloride, and 0.52 mol of zinc chloride was added to it.
Add.

10.8f of sulfur dichloride while keeping the temperature between 0 and 10℃
I (0.105 mol) is added dropwise over about 1.5 hours.

After that, stir at the same temperature for about 1 hour (after stirring, blow in air to drive out hydrogen chloride.

Next, 24f of 20% sodium hydroxide aqueous solution (0,12
After adding mol), the temperature was raised to 60-70℃, and at the same temperature 30
% hydrogen peroxide solution (0.25 mol) was added dropwise over 20 minutes.

After further stirring at the same temperature for 2 hours, the mixture is neutralized.

When carbon tetrachloride is removed by steam distillation, a precipitate forms.

After filtration, washing with water, and drying, 2·/-bis(p-7''romophenol)sulfone was obtained.

Yield: 32.6P (yield: 80%). Melting point 203-205
Recrystallization from glacial acetic acid at 0.degree. C. gave pure white needle crystals.

Melting point: 209-210°C.

Elemental analysis C (C) H (H) Br (C) 8% Calculated value 35.3 1.97 39.2 7.85 Measured value 35.6 2.01 39.8 7.89 Example 4 2.4 2,2-bis(4,6-dichlorophenol)sulfone was obtained in exactly the same manner as in Example 3 using -dichlorophenol.

Yield 82%.

Melting point: 165-166°C. Recrystallization from ethanol yielded pure white needle-like crystals.

, 1 melting point 169-170°C.

Elemental analysis C (to) H (to) CI (to) S (to) 1 Calculated value 37.1 1.56 36.5 8.2
6 Measured value 37.6 1.52 36.9 8.36 Example 5 p-tert-octylphenol 41.27 (0,
10.8 f (2 mol) of sulfur dichloride (0,105
mol) dropwise over about 2 hours.

After further stirring at the same temperature for 1 hour, air was blown to drive out hydrogen chloride.

Next, 44f of 10% sodium hydroxide aqueous solution (0,11
After adding mol), the temperature was raised to 50-60℃, and at the same temperature 30
% hydrogen peroxide solution (28.3 f (0.25 mol)) was added dropwise over 20 minutes.

After stirring for another 2 hours at the same temperature, the n
- Distillation of hexane and neutralization produces a precipitate.

Filter, wash with water and dry to obtain 2,2'-bis(p-tert).
-, tmethylphenol) sulfone was obtained.

Yield 45f? (Yield 95%).

Melting point: 142-143°C. Recrystallization from glacial acetic acid gave pure white needle crystals.

Melting point 144-145°C.

Elemental analysis Ce/eH (c) S (h) Calculated value 70
．． 9 8.92 6.75 Measured value 71.3 8.87 6.71 Example 6 2-tert-butyl-4-methylphenol 32.
8? (0.2 mol) was dissolved in 70 TrL of benzene, and while keeping the temperature at 20-30°C, 10 mol of sulfur dichloride was added.
．． 8S' (0,105 mol) is added dropwise over about 1 hour.

Thereafter, the mixture was stirred at the same temperature for 3 hours, and then thoroughly washed with water until neutral.

Next, add 30% sodium hydroxide aqueous solution 17.3P (0,
After adding 13 mol), the temperature was raised to 70-80°C, and at the same temperature, 28.3 f? of 30% hydrogen peroxide solution was added. (0.25 mol) to 2
Drop in 0 minutes.

After stirring at the same temperature for an additional 2 hours, the mixture is neutralized. When benzene is removed by steam distillation, a precipitate forms.

Filter, wash with water, dry and prepare 2.2-bis(4-)f-6-
tert-7' tylphenol) sulfone was obtained.

Yield: 35.5S' (yield: 91%). Melting point 128-130
℃.

Recrystallization from ethanol yielded pure white needle-like crystals.

Melting point 132-133°C.

Elemental analysis C (to) H (to) S (to) Calculated value
67.6 7.74 8.21 Measured value 67.2 7.81 8.26 Example 7 p-tert-amylphenol 32.82 (0,2
2,2'-bis(p-tert-amylphenol) sulfone was obtained by the same procedure as in Example 6 except that 0.51 mol of zinc chloride was used.

Revenue ”$9o, 5%.

Melting point: 117-118°C. Recrystallization from n-hexane yielded pure white prismatic crystals.

Melting point 122-123°C. Elemental analysis 6% H%
S (to) Calculated value 67.6 7.74 8.21 Measured value 67.9 7.75 8.18 Example 8 p-tert-butylphenol 30P (0.2 mol)
Dissolve chlorobenzene in 801,711, and add 0.51 of aluminum chloride to it.

Sulfur dichloride 11.3P while keeping the temperature between 0 and 10℃
(0.11 mol) was added dropwise over about 2 hours.

After further stirring at the same temperature for 3 hours, the mixture was thoroughly washed with water until neutral.

Next, 20% potassium hydroxide aqueous solution 36.5P (0,1
After adding 3 mol), the temperature was raised to 80-90℃, and at the same temperature
28.31 (0.25 mol) of 0% hydrogen peroxide solution was added dropwise over 20 minutes.

After stirring for another 2 hours at the same temperature, chlorobenzene is distilled off by steam distillation, and upon neutralization a precipitate is produced.

After filtering, washing with water and drying, 2,2-bis(p-tert-
Butylphenol) sulfone was obtained.

Yield: 33.7P (yield: 93%). Melting point 127-129
℃.

Recrystallization from n-hexane yields pure white needle crystals.

Melting point: 131-132°C. Elemental analysis C (c) H%
S (to) Calculated value 66.3 7.23 8.85 Measured value 66.2 7.41 8.78 Examples 9 to 13 P-cresol in Example 1 was replaced with various phenols, and otherwise in exactly the same manner, Various 2,2-bisphenol sulfone derivatives were obtained.

The results are shown in Table-1.

Claims (1)

[Scope of Claims] 1 General formula (I) (wherein R1, R2 and R3 represent hydrogen, halogen, alkyl group, cycloalkyl group, -aryl group or aralkyl group. However, R1 excludes hydrogen. Furthermore, R1, R2, and R3 may be combined to form a ring) and sulfur dichloride are reacted in a hydrocarbon solvent to synthesize the corresponding 2,2'-bisphenol sulfide. General formula (6) - (wherein R1, R2 and R3 are the same as general formula (I), characterized in that it is oxidized with hydrogen peroxide in the presence of an equimolar or more alkali without isolating the sulfide. A method for producing a 2,2-bisphenolsulfone derivative represented by (indicating meaning).