JPS61152635A - Production of 3,5-diisopropylphenol - Google Patents

Abstract

PURPOSE:To obtain the titled compound, by oxidizing 1,3,5-triisopropylbenzene with molecular oxygen to give a hydroperoxide concentration within a specific range in the presence of an aqueous solution of an alkali, followed by acid- decomposition of an oil phase in the presence of an acidic catalyst. CONSTITUTION:1,3,5-Triisopropylbenzene is oxidized with molecular oxygen in the presence of an aqueous solution of an alkali to give a hydroperoxide concentration in an oil phase within 10-110wt% range expressed in terms of triisopropylbenzene monohydroperoxide at 95-110 deg.C to obtain two phase consisting of the oil phase composed of oxidation reaction product and the aqueous solution phase of alkali, thereafter the oil phase is subjected to acid- decomposition treatment in the presence of an acidic catalyst, and the titled substance is separated therefrom. In obtaining the oil phase from the two phases, a water-insoluble solvent (example; benzene) is added to a mixture of the two phases and mixed with the oil phase, and the aqueous solution phase of alkali is separated and removed therefrom. EFFECT:The aimed substance is obtained in high purity. USE:A raw material for agricultural chemicals and medicines.

Description

DETAILED DESCRIPTION OF THE INVENTION [Technical Field of the Invention] The present invention relates to a method for producing 6,5-diisopropylphenol, which is a raw material for agricultural chemicals and medicines, from 1.3.5-)liisobrobylbenzene. For more details, see 1, 3.
5-triisopropylbenzene is oxidized to produce hydroperoxide, which is then decomposed with acid to produce 3-triisopropylbenzene.
, 5-diisopropylphenol.

[Conventional technology]

As a conventional technique for producing 6,5-diinpropylphenol, for example, a method of alkylating phenol with propylene is known. However, in this method,
In addition to the target 6,5-diisopropylphenol, a considerable amount of 2,4-diimpropylphenol, which is difficult to separate and remove, is produced as a by-product in the diisopropylphenol produced by the alkylation reaction. , a method of increasing the content of 3,5-diisopropylphenol by performing an isomerization reaction and then separating this 5,5-unit is carried out (for example, West German Patent Specification 20215).
No. 26). However, in this method, 2,
Since it is not possible to make all 4-units into 3.5-units, there is a drawback that it is difficult to increase the purity of the 3,5-units in the target object. , 5-Diisopropylphenol production method has such drawbacks, and 6.5-
A method for obtaining diisopropylphenol with high purity was investigated.

[Summary of the invention]

As a result, the inventors discovered that the above object could be achieved by employing the method described below, and completed the present invention.

That is, according to the method of the present invention, in producing 3,5-diisopropylphenol from 1,3.5-)lyisobrobylbenzene, the following steps (A) 1
, 3.5-) IJ isopropylbenzene is treated with molecular oxygen in the presence of an alkaline aqueous solution so that the hydroperoxide concentration in the oil phase ranges from 10 to 110% by weight in terms of triisopropylbenzene monohydroperoxide. A step of oxidizing triisopropylbenzene to obtain a two-liquid phase oxidation reaction mixture formed from an oil phase consisting of an oxidation reaction product of triisopropylbenzene and an alkaline aqueous solution phase; a step of obtaining an oil phase containing an oxidation reaction product by removing the alkaline aqueous solution phase from the mixture; a step of acid-decomposing the oil phase obtained in step 0 above in the presence of an acidic catalyst to obtain an acid-decomposed mixture; 0) A method for producing 6,5-diisopropylphenol comprising a combination of the following steps: separating 3,5-diisopropylphenol from the acid-decomposed mixture obtained in step ◎ above.

[Oxidation process]

In step (1) of the present invention, 1,3,5-triisopropylbenzene (hereinafter sometimes abbreviated as 1,3,5-TIPB) is oxidized by molecular oxygen in the presence of an alkaline aqueous solution to produce an oxidation reaction product. A two-liquid phase oxidation reaction mixture is formed, consisting of an oil phase and an alkaline aqueous phase.

1.3.5-TIPB may be oxidized with only one molecular oxygen, that is, pure oxygen gas, or a molecular oxygen-containing gas in which oxygen is diluted with an inert gas such as nitrogen. However, it is usually convenient and preferable to perform the oxidation using 9-Higashi.

In the method of the present invention, the degree of oxidation is usually determined based on the hydroperoxide concentration of the oil phase of the oxidation reaction product converted to triisopropylbenzene monohydroperoxide (hereinafter sometimes abbreviated as MHP). 10
It is carried out so that the amount is in the range of 40 to 110% by weight, preferably 40 to 90% by weight (calculated not including the alkaline aqueous solution).

For this purpose, it is necessary to maintain the pH of the aqueous phase and the reaction temperature during the oxidation reaction within an appropriate range. These are 1,3
．． Although it varies slightly depending on the concentration of 5-TIPB, the alkaline aqueous solution used, and other reaction conditions.

The pH of the aqueous phase is usually about 7 to about 10, and the reaction temperature is usually about 80 to about 120°C, preferably about 95°C to about 110°C.

Examples of alkaline aqueous solutions include sodium hydroxide,
Aqueous solutions of potassium hydroxide, sodium carbonate, potassium carbonate, etc. are used, and their alkaline concentrations are 20
Preferably, it is less than % by weight. The amount of the alkaline aqueous solution used is preferably about 5 to 60% by weight of the reaction system.

To start the oxidation reaction, a reaction initiator is added to the reaction system, and the reaction initiator is 1.3.5-TIP.
It is preferable to use the oxidation reaction product of B. In step (2) of the present invention, when oxidizing 1,3.5-TIPB, the hydroperoxide concentration of the oil phase in the oxidation reaction mixture is converted into MHP. If 1.3.5-TIPB f is oxidized to 10% by weight or less, the yield of the target product, 3,5-diisopropylphenol, will be low, which is not preferable. Also, the hydroperoxide concentration is M
1.3. so that it is 110% by weight or more in terms of HP.
When 5-TIPB is oxidized, in addition to triisopropylbenzene monohydroperoxide, triisopropylbenzene dihydroperoxide (D), which is not preferred in the method of the present invention, is produced! P ) and triisopropylbenzene trihydroperoxide (T)! The yield of 6,5-diinpropylphenol, which is the target product when the oxidation reaction product is subjected to acid decomposition treatment, is lower due to the increase in the amount of by-products of P) and the decrease in the amount of triisopropylbenzene monohydroperoxide produced. rate decreases and will be discussed later (D
In step J, the separation operation of 6,5-diisopropylphenol becomes complicated and the purity of the phenol decreases, which is not preferable.

The two-liquid phase oxidation reaction mixture obtained by the oxidation reaction step is formed from an oil phase consisting of the oxidation reaction product of 1,3.5-TIPB and an alkaline aqueous solution phase. Through this oxidation reaction, 1.3.5-TIPB becomes M)! P.

DHP, T)! P and unreacted 1.3.5-TIP
1, which is a mixture containing B etc. and whose main component is MHP;
3.5-TIPB is oxidized to the oxidation reaction product. The oxidation reaction product is contained in the oil phase of the two-liquid phase oxidation reaction mixture, and the oil phase is usually liquid.

[Step of removing alkaline aqueous solution phase]

The two-liquid phase oxidation reaction mixture obtained by the above-mentioned oxidation contains an alkaline aqueous solution phase, which will cause problems if it is directly subjected to the next acid decomposition step, so it is necessary to remove the alkaline aqueous solution phase.

Therefore, in step ◎ of the method of the present invention, the alkaline aqueous solution phase is separated and removed from the two-liquid phase oxidation reaction mixture obtained in the above-mentioned step, and the oil phase consisting of the oxidation reaction product of 1,3.5-TIPB is removed. get. The following two methods can be adopted for this purpose.

[1] The 92 liquid phase oxidation reaction mixture obtained in step (3) above is allowed to stand, and the separated alkaline aqueous phase is separated and removed to obtain an oxidation reaction product of 1.3.5-TIPB. How to obtain the oil phase.

[2] After adding a water-insoluble solvent to the two-liquid phase oxidation reaction mixture obtained in step (8) and mixing it with the oxidation reaction product, the alkali aqueous solution phase is separated and removed, thereby performing 1, 3. A method for obtaining an oil phase containing an oxidation reaction product of 5-TIPB.

Among these methods, it is preferable to adopt method [2] if necessary because the process is simple and most of the various impurities that have an adverse effect on the acid decomposition step can be removed. In this case, the water-insoluble solvent that can dissolve the 1.3.5-TIPB oxidation reaction product well is aromatic hydrocarbons such as benzene, toluene, xylene, ethylbenzene, cumene, chloroform, dichloroethane, trichloride, etc. Examples include norogenated hydrocarbons such as ethane, tricrene, perchlorobenzene, chlorobenzene, and dichlorobenzene, ketones such as methyl in butyl ketone, diisobutyl ketone, and inophorone, and ethers such as butyl ether and pentyl ether.

Among these, the use of aromatic hydrocarbons is most preferred. The amount of the water-insoluble solvent used varies depending on the temperature at the time of dissolution, the type of solvent, etc., but the amount of the above-mentioned solvent is usually used per 100 parts by weight of the oil phase of the oxidation reaction mixture.

10 to 1000 parts by weight, preferably 50 to 50 parts by weight
It is preferable to use 0 parts by weight. When the above method (2) is adopted, the temperature during mixing is arbitrary as long as the oxidation reaction mixture is completely dissolved, but it is usually 50 to 1
50°C is preferred. Furthermore, in both methods [1] and [2] above, the temperature during liquid separation of the alkaline aqueous solution phase is usually preferably 50 to 150°C. Said [
When using method 1), washing with water may be performed as necessary. Also, when the method [2] above is employed, washing with water may be performed as necessary after separating and removing the alkaline aqueous solution phase.

[Acid decomposition process]

The ◎ step of the method of the present invention includes the oxidation reaction product of 1,3.5-TIPB obtained in the 0 step.

An acid decomposition mixture is obtained by subjecting the oil phase to acid fractionation treatment in the presence of an acidic catalyst. In the method of the present invention, it is preferable to remove a small amount of water contained in the oil phase by distillation or the like prior to acid decomposition.

Further, when a water-insoluble solvent is used in the step ◎, part or all of the water-insoluble solvent contained in the oil phase may be removed by distillation or the like.

As the method for acid decomposition, for example, any method conventionally used for acid decomposition of oxidation reaction products of diisopropylbenzenes can be applied.

The acid decomposition method in the method of the present invention will be described in detail below.

Acidic catalysts used for acid decomposition of oxidation reaction products include inorganic acids such as sulfuric acid, hydrochloric acid, perchloric acid, and phosphoric acid; organic acids such as chloroacetic acid and para-toluenesulfonic acid; cation exchange resins, silica alumina , solid acids such as silica titania are used. When an inorganic acid or an organic acid is used as the acidic catalyst, it is preferable that the reaction system is homogeneous -C.

For this purpose, solvents that dissolve both the oxidation reaction product and the acidic catalyst are used as reaction solvents, for example ketones such as acetone, methyl ethyl ketone, diethyl ketone, methyl ibutyl ketone. These inorganic acids or organic acids are used in a proportion ranging from 0.01 to 15% by weight, preferably from 0.05 to 5% by weight, based on the oxidation reaction product;
C., preferably in the range of 70 to 90.degree. C. to obtain an acid decomposition mixture. Furthermore, when a solid acid is used among the acidic catalysts, the reaction system naturally becomes non-uniform. Even when a solid acid is used as an acidic catalyst, it is preferable to use the above-mentioned ketones as a reaction solvent.
It is used in a proportion ranging from 0% by weight, preferably from 5 to 80% by weight, and the acid decomposition reaction is usually carried out at a temperature ranging from 40 to 100°C, preferably from 70 to 90°C to obtain a step decomposition mixture. .

[Separation process]

In step ◎ of the method of the present invention, 3,5-diisopropylphenol is separated from the acid decomposed mixture obtained in step 0. When an inorganic acid or an organic acid is used as the acidic catalyst, the separation method is to neutralize the acidic catalyst by adding a base such as sodium carbonate to the acid decomposition mixture, and then remove the insoluble salt. , 3,5-
Diisopropylphenol is obtained.

Furthermore, when the solid acid is used as the acidic catalyst,
After removing the solid catalyst from the acid decomposition mixture by p-filtration or the like, 6,5-diisopropylphenol is obtained by the same method as described above.

〔Effect of the invention〕

According to the method of the present invention, the purity is higher than that of the conventional method.
-diisopropylphenol is obtained.

〔Example〕

The method of the present invention will be specifically explained below using examples.

Example 1 (1) In a reactor equipped with a stirrer, an air blowing sparger, and a reflux condenser, 1.3.5-triisopropylkene Jr. y (1,3,5-TIPB) 80009
．． 4.5 wt% NaOH aqueous solution 800I and air oxidation reaction product 8 of 1,6°5-TIPB as a reaction initiator.
After charging 0F and raising the temperature to 100℃, it was heated to 5.5 with air.
The pressure was increased to kg/dG. After that, the air was heated to 2.6Nrn.
The reaction was carried out at 100° C. for 6 hours with stirring while blowing at a rate of 1/hr. The obtained oxidation reaction product (oil layer) is 8
It was 400g. The hydroperoxide concentration in the oil layer was 59% in terms of MHP, and this included unreacted 1°3.5-TIPBll and 3.5-triisopropylbenzene monohydroperoxide (M)! P) and hei 1, 3
．． 5-triinpropylbenzene dihydroberoxide (DHP) was 44 wt%, 41 wt%, and 10 wt%, respectively.
% was included.

The MHP-equivalent hydroperoxide concentration in the oil layer was determined by adding methanol to a small sample taken from the two-component oxidation reaction mixture, in which the oil layer and water layer were uniformly mixed after the reaction, to make a homogeneous solution. The water concentration was determined by the method and expressed as the hydroperoxide concentration (measured by iodometry) in the oil layer remaining after the amount of water was removed from the homogeneous solution.

(2) Two-liquid phase oxidation reaction mixture obtained in (1) above (mixture of oil layer and water layer) 9200. ! i' toluene 40
00g was added and the aqueous layer separated for 1 minute was removed.

Next, the oil layer was washed with 1000 g of water, and toluene and mixed water were removed from the obtained oil layer by distillation to obtain a 1.3.5-TIPB solution 8400, li' containing MHP as a main component.

(3) The M) obtained in (2) above is placed in a reactor equipped with a stirrer, a reflux condenser, a raw material and catalyst supply port; and a reaction liquid outlet. 1.3.5-TIPB containing P as a main component
The solution was 100. ! At a speed of i'/hr, 3.8wt
% of sulfuric acid was fed at a rate of 100 g/hr, under stirring, at a reaction temperature of 67°C, and with an average residence time of 6.
The acid decomposition reaction was carried out while removing the reaction product so that the reaction time was 0 minutes. The concentration of 3,5-diisopropylphenol in the reaction product was 14.1 wt%, and the MH in the raw material
Based on P. The yield of 5,5-diisopropylphenol was 91 mo1%.

(4) Acid decomposition mixture obtained in the above (3) 1000. !
Add 15g of carbonic acid to V) and add IJum to catalyst (sulfuric acid)
After neutralizing the insoluble Na salts, acetone was distilled off from the P solution at normal pressure. As a result of fractional distillation of the obtained pot residue under reduced pressure using a 20-stage sheep tray distillation column, the raw material 1
, 3.5- 210g of TIPB (boiling point 108℃/1
1iIIIHg) is recovered and 6 with a purity of 996%
．． 5-diinpropylphenol (boiling point 117-b) was obtained.

The yield of 3,5-diisopropylphenol based on the charged 1.3.5-TIPB was 31.8 mo1%.

The amount of 1,3,5-TIPB consumed in the reaction (1,3,
5-1, 3.5- recovered from the TIPB charge
The yield of 3,5-diisopropylphenol was 56.8 mo1%, which was determined based on the amount of T and IPB).

Example 2 (1) Example 1 (1) except that the reaction time was 9 hours.
The pneumatic oxidation reaction of 1.3.5-TIPB was carried out in the same manner as described in ). Obtained oxidation reaction product (oil layer)
is 8,900 g, and the hydroperoxide concentration is 84% in terms of MHP, including unreacted 1.3.5-TIP.
B, M)! P and D)! P7% each 417. Owt%,
It contained 44.7 wt% and 17.8 wt%.

(2) Two-liquid phase oxidation reaction mixture (mixture of oil layer and water layer) obtained in (1) above: 10100. ! if MIBK 4
000. F was added and the separated aqueous layer was removed.

Next, the oil layer is washed with water iooog, and the mixed water is removed from the obtained oil layer by azeotroping with MIBK to obtain an MIBK solution of the 1.3.5-TTPB oxidation reaction product containing MHP as a main component. 12000.9 was obtained (M
)! P concentration 33.1 wt%).

(8) Add the above (2) to the reactor described in (8) of Example 1.
) The MrBK solution obtained in 100. 100 g/hr of acetone containing 0.2% perchloric acid at a rate of p/hr.
each at a rate of 1 hr and at a reaction temperature of 67° C. under stirring,
The 3,5-
The concentration of diisopropylphenol was 11.7 mo1%.

(4) Acid decomposition mixture obtained in (8) above 1000.9
Add 10I of carbonate to neutralize the catalyst,
After removing the insoluble Na salt from each house, acetone and MIBK were distilled off from the p liquid at normal pressure.

As a result of fractional distillation of the obtained pot residue under reduced pressure using a 40-stage sieve tray distillation column, the raw material 1,3.5-TIPB
62.5g of 3, with a purity of 994% was recovered.
107.6!9 of 5-diisopropylphenol was obtained.

3,5-TIPB based on the prepared 1.3.5-TIPB.

The yield of sopropylphenol is 37. The yield of 3,5-diinpropylphenol was 46.1 mo1% based on the amount of 1,3,5-TIPB consumed in the Ali reaction (same as defined in Example 1) at Q mo1%. Atsushi Example 3 (1) (1) of Example 1 except that the reaction time was 3 hours.
The air oxidation reaction of 1,3.5-TIPB was carried out in the same manner as described in . Obtained oxidation reaction product (oil W)
is 8230g, the hydroperoxide concentration is 30.5% in terms of MHP, and this includes unreacted 1.3.5-TI.
PB and MHP were 73.8 wt% and 22.5 w, respectively.
It contained t%.

(2) 10,030 g of the two-liquid phase oxidation reaction mixture (mixture of oil layer and aqueous layer) obtained in (1) above was allowed to stand at 60°C, and the separated aqueous layer was removed. Next, the oil layer was washed with 1000 g of water, and the water that had been mixed in was removed from the obtained oil layer by distillation. 1.3.5 containing P as a main component
-TIPB solution 823ON was obtained.

(8) Add the above (2) to the reactor described in (8) of Example 1.
) and containing 9MHP as the main component 1.3.5-
TIPB solution at a rate of 100.9/hr, Q, F3
Acetone containing wt% sulfuric acid was supplied at a rate of 100.9/hr, and the acid decomposition reaction was carried out under stirring at a reaction temperature of 67°C while extracting the reaction product so that the average residence time was 30 minutes. Ta. The concentration of 3,5-diisopropylphenol in the reaction product is 83wt%, and the yield of 3,5-diisopropylphenol is 92% based on MHP in the raw material.
．． It was 3mo1%.

(4) Acid decomposition mixture obtained in the above (3) 1000. F
159 sodium carbonate was added to neutralize the catalyst, and after removing insoluble Na salts, acetone was distilled off from the p liquid at normal pressure. As a result of fractional distillation of the obtained pot residue under reduced pressure using a 20-stage sheep tray distillation column, the raw material 1゜3.5-TI
PB is 365.3. V is recovered and the purity is 998.
75% of 6.5-diisopropylphenol was obtained.

The yield of 6,5-diisopropylphenol based on the charged 1.3.5-TIPB was 17.7 mo1%, and the amount of 1,3,5-TIPB consumed in the reaction (defined in Example 1) was 17.7 mo1%. The yield of 6,5-diinpropylphenol was 71.2m01% based on the same method as above).

Comparative Example 1 (1) Example 1 (1) except that the reaction time was 15 hours.
) The air oxidation reaction of 1.3.5-TIPB was carried out in the same manner as described in
) Ha9850,! i', the hydroperoxide concentration is M) (131% in terms of P, which includes unreacted 1
．． 3.5-TIPB and MHP were contained in 4.5 wt% and 31.9 wt%, respectively. MIBKloooo
g was added and the aqueous layer separated for 1 minute was removed. Then water 1000
The oil layer was washed with N, and the water mixed in with MIBK was removed from the obtained oil layer by azeotropy with MIBK.
- MIBK solution of TIPB oxidation reaction product 19650g
(MHP concentration i6.owt%) was obtained.

(8) Add the above (2) to the reactor described in (3) of Example 1.
) at a rate of 100 g/hr,
Acetone containing 0.8% sulfuric acid was supplied at a rate of 100 g/hr, and the acid decomposition reaction was carried out under stirring at a reaction temperature of 67° C. while extracting the reaction product so that the average residence time was 60 minutes. I did it. The concentration of 6,5-diinpropylphenol in the reaction product was 5.39 wt%, and the yield of 6,5-diisoflobylphenol based on MHP in the raw material was 89.3 mo1%.

(4) Acid decomposition mixture obtained in the above (8) 1000. !
Add sodium carbonate 159 to ii' to neutralize the catalyst,
After removing the insoluble Na salt from each house, acetone and MIBK were distilled off from the p liquid at normal pressure. Results of fractional distillation of the obtained pot residue under reduced pressure using a 40-stage sheep tray distillation column.

The raw material is 1,3.5-TIPB is 11. While IN was recovered, 3.5-diisopropylphenol with a purity of 94.6% was obtained as 4al'.

The yield of 6,5-diisopropylphenol based on the charged 1,3.5-TIPB is s 25.8rt+o
1% and 6,5 based on the amount of 1,3,5-TIPB consumed in the reaction (same as defined in Example 1).
-Yield of diisoflovirphenol is 27.3 mo
There was a 1% tear.

Claims (2)

[Claims] (1) 1,3,5-triisopropylbenzene to 3,
In producing 5-diisopropylphenol,
The following step: (A) 1,3,5-triisopropylbenzene is treated with molecular oxygen in the presence of an alkaline aqueous solution until the hydroperoxide concentration in the oil phase is 10 to 10% in terms of triisopropylbenzene monohydroperoxide. 110% by weight to obtain a two-liquid phase oxidation reaction mixture formed from an oil phase consisting of an oxidation reaction product of triisopropylbenzene and an alkaline aqueous solution phase, (B) the above (A) (C) obtaining an oil phase containing an oxidation reaction product by removing the alkaline aqueous phase from the two-liquid phase oxidation reaction mixture obtained in the step; (C) treating the oil phase obtained in step (B) above with an acidic catalyst; (D) obtaining an acid-decomposed mixture by performing acid decomposition treatment in the presence of 3,5-
A method for producing 3,5-diisopropylphenol, which comprises combining each step of separating diisopropylphenol. (2) When removing the alkaline aqueous solution phase from the two-liquid phase oxidation reaction mixture, a water-insoluble solvent is added to the two-liquid phase oxidation reaction mixture to mix the oil phase containing the oxidation reaction product with the water-insoluble solvent; The method according to claim (1), characterized in that the alkaline aqueous solution phase is separated and removed.