JP3367058B2 - Method for removing aromatic primary hydroperoxides - Google Patents

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to an aromatic primary hydroperoxide by-produced in the production of aromatic tertiary hydroperoxides [2] useful as an intermediate for aromatic alcohols such as alkylphenols and alkylnaphthols. It relates to a method of removing the class [1].

[0002]

BACKGROUND OF THE INVENTION Aromatic tertiary hydroperoxides [2] are commonly used as intermediates for aromatic alcohols such as alkylphenols and alkylnaphthols. Aromatic tertiary hydroperoxides are usually obtained by oxygen-oxidizing an aromatic hydrocarbon compound substituted with a corresponding secondary alkyl group such as isopropyl group or sec-butyl group. Decomposition leads to aromatic alcohols and ketones. However, in oxygen oxidation,
In the aromatic hydrocarbon compound, an isopropyl group, sec-
When it has a methyl group in addition to a butyl group and the like, in addition to the desired aromatic tertiary hydroperoxides [2], an aromatic primary hydroperoxides [1] in which a methyl group, which is a non-target compound, is oxidized [1] ]] Is generated. When the aromatic primary hydroperoxides [1] are contained in the aromatic tertiary hydroperoxides [2], the aromatic primary hydroperoxides [1] are converted to secondary alkyl group-substituted aromatic alcohols by acid decomposition. And formaldehyde are formed, and this formaldehyde becomes a factor to inhibit the formation of methyl group-substituted aromatic alcohols in acid decomposition. Therefore, it is necessary to remove the aromatic primary hydroperoxides [1] prior to acid decomposition. The inventors of the present invention have conducted extensive studies on a method for removing aromatic primary hydroperoxides [1], and as a result, have found that hydroperoxides containing aromatic primary hydroperoxides [1] and aromatic tertiary hydroperoxides [2]. The inventors have found that the purpose can be achieved by contacting the mixture with an organic quaternary ammonium hydroxide, and completed the present invention.

[0003]

That is, the present invention is based on the general formula [1] (In the formula, Ar represents an aromatic group which may have a substituent, R ₁ and R ₂ each independently represent a lower alkyl group, and m and n each independently represent 1 or 2).
Represents ) Aromatic primary hydroperoxides and general formula [2] (In the formula, Ar, R ₁ , R ₂ , m and n have the same meanings as described above.) A hydroperoxide mixture containing an aromatic tertiary hydroperoxide is represented by the following formula: The present invention relates to a method for removing aromatic primary hydroperoxides, which is characterized by bringing them into contact with each other. Hereinafter, the present invention will be described in detail.

Examples of the aromatic group of the hydroperoxide mixture containing the aromatic primary hydroperoxides [1] and the aromatic tertiary hydroperoxides [2] include (substituted) phenyl group and (substituted) naphthyl group. be able to. Examples of aromatic primary hydroperoxides include: And the like, and the compound may be a mixture of isomers. Examples of aromatic tertiary hydroperoxides [2] include: And the like, and the compound may be a mixture of isomers. As the aromatic primary hydroperoxides [1] and the aromatic tertiary hydroperoxides [2], primary and tertiary hydroperoxides of cymene are preferably used.

Hydroperoxide mixtures containing aromatic primary hydroperoxides [1] and aromatic tertiary hydroperoxides [2] are, for example, those of the general formula [3] (In the formula, Ar, R ₁ , R ₂ , m and n have the same meanings as described above.) The aromatic compound shown in the liquid phase is contacted with oxygen or an oxygen-containing gas to oxidize it, and then concentrated if necessary. You can get it. The oxidation may be performed in a non-aqueous state or may be performed in the coexistence of an alkaline aqueous solution. Examples of the aromatic compound [3] include benzenes having a methyl group and a secondary alkyl group such as cymene, methyl sec-butylbenzenes, dimethylisopropylbenzenes, methyldiisopropylbenzenes and dimethyldiisopropylbenzene, and methylisopropyl. Examples include naphthalene, methyl sec-butylnaphthalene, dimethylisopropylnaphthalene, dimethyldiisopropylnaphthalene and the like, and naphthalene having a methyl group and a secondary alkyl group. The compound may be a mixture of isomers. .

The hydroperoxide mixture containing the aromatic primary hydroperoxides [1] and the aromatic tertiary hydroperoxides [2] may be a solution of the aromatic compound [3] or another solvent. Examples of such a solvent include hydrocarbons such as benzene, toluene, ethylbenzene, cumene, xylene and diisopropylbenzene, and ketones such as acetone, methyl ethyl ketone and methyl isobutyl ketone. The hydroperoxide concentration in the hydroperoxide mixture (the concentration of the aromatic primary hydroperoxides [1] and the aromatic tertiary hydroperoxides [2] combined) is usually 1 to 9
It is 5%, preferably 5 to 95%.

The ratio of the aromatic primary hydroperoxides [1] and the aromatic tertiary hydroperoxides [2] in the hydroperoxide mixture is usually the aromatic primary hydroperoxides [1] / aromatic tertiary hydroperoxides. Peroxides [2] = 3-30 / 97-70 (weight / weight),
It is preferably 5 to 25/95 to 75.

The organic quaternary ammonium hydroxide used is represented by the general formula [4] (In the formula, R ₃ and R ₄ each represent an alkyl group which may have a substituent or an aralkyl group which may have a substituent, and R ₅ and R ₆ each represent an alkyl group. ) Or a compound represented by the general formula [5] (In the formula, R ₇ represents an alkyl group which may have a substituent, and R ₈ represents a hydrogen atom or an alkyl group.). Examples of the compound [4] and the compound [5] include tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetra-n-propylammonium hydroxide,
Tetra-n-butylammonium hydroxide, benzyltrimethylammonium hydroxide, benzyltriethylammonium hydroxide, stearyltrimethylammonium hydroxide, trimethyloctadecylammonium hydroxide, lauryltrimethylammonium hydroxide, trimethylhexadecylammonium hydroxide, distearyldimethylammonium Hydroxide, dicetyl dimethyl ammonium hydroxide, tricapryl methyl ammonium hydroxide,
o, m or p-methoxybenzyltriethylammonium hydroxide, o, m or p-phenoxybenzyltriethylammonium hydroxide, trimethyldodecylammonium hydroxide, trimethyldecylammonium hydroxide, trioctylmethylammonium hydroxide, N-butylpyridinium hydroxy , N-laurylpyridinium hydroxide, N-laurylpicolinium hydroxide, triethylpropylammonium hydroxide, diethylpropylbenzylammonium hydroxide, o, m or p-chlorobenzyltriethylammonium hydroxide, methylethylpropylbenzylammonium hydroxide , Diethylbutylbenzylammonium hydroxide, methyldiethylbenzylammonium Monium hydroxide, dimethylethylbenzylammonium hydroxide, tripropylbenzylammonium hydroxide, ethyldipropylbenzylammonium hydroxide, diethyldibenzylammonium hydroxide, dimethyllaurylbenzylammonium hydroxide, dimethylstearylbenzylammonium hydroxide, dimethyloctylbenzyl Ammonium hydroxide, dimethyl myristyl benzyl ammonium hydroxide can be mentioned,
These can be used alone or in combination. The organic quaternary ammonium hydroxide is usually used as a solution of water, methanol, ethanol or the like.

The amount used is usually 0.001 to 5 mol times that of the aromatic primary hydroperoxides [1]. The combined use of organic quaternary ammonium hydroxide and alkali can reduce the amount of organic quaternary ammonium hydroxide. In this case, the amount of the organic quaternary ammonium hydroxide is usually 0.0 with respect to the aromatic primary hydroperoxide [1].
The amount is 01 to 1 mol times, preferably 0.001 to 0.5 mol times. When an alkali is not used in combination, it is usually 0.1 to 5 mol times, preferably 0.3 to 3 mol times, relative to the aromatic hydroperoxides [1]. When the alkali is used in combination, examples of the alkali include alkali metal hydroxides such as sodium hydroxide, potassium hydroxide, lithium hydroxide, calcium hydroxide, barium hydroxide, magnesium hydroxide and strontium hydroxide, and alkaline earth metals. A hydroxide etc. can be mentioned. The amount used is usually 0.1 to 20 relative to the aromatic primary hydroperoxides [1].
It is a molar ratio, preferably 0.5 to 10 molar times.
The present invention is usually carried out in the coexistence of a polar solvent such as water, methanol or ethanol. Water is preferably used. The reaction temperature is usually 30 to 150 ° C., preferably 70 to 110.
℃.

The removal of the aromatic primary hydroperoxides [1] of the present invention is usually carried out by adjusting the content of the primary hydroperoxides [1] to the aromatic tertiary hydroperoxides [2].
On the other hand, it is usually 1/25 (weight / weight) or less, preferably 1/50 (weight / weight) or less, more preferably 1/1.
00 (weight / weight) or less, and at that time,
Decomposition rate of aromatic tertiary hydroperoxides [2] is 30
% Or less, preferably 20% or less, more preferably 10% or less.
It is advantageous to carry out the treatment so that it is less than or equal to%. In the present invention, the decomposition treatment liquid can be analyzed by liquid chromatography or the like to check the reaction rates of the aromatic primary hydroperoxides [1] and the aromatic tertiary hydroperoxides [2]. The end point of the reaction can also be determined by. After the reaction, if necessary, for example, liquid separation and washing may be performed. Thus, the obtained aromatic tertiary hydroperoxides [2] liquid can be led to the corresponding aromatic alcohols in a high yield by performing, for example, acid decomposition treatment.

[0011]

EFFECT OF THE INVENTION According to the method of the present invention, aromatic primary hydroperoxides can be easily and highly concentrated in a hydroperoxide mixture containing aromatic primary hydroperoxides and aromatic tertiary hydroperoxides. It can be selectively removed.

[0012]

EXAMPLES The present invention will now be described in more detail with reference to examples, but the present invention is not limited to the examples.
The abbreviations of the compounds used in the examples have the following structures.

Example 1 An oxidation product (LC) of m- and p-mixed cymene (LC
Analytical value: Simene 84.4%, 3HPO 8.85%, 1HPO 1.
61%) 50 g, 10% benzyltriethylammonium hydroxide aqueous solution 0.51 g, and 8% sodium hydroxide aqueous solution 5.0 g were added, and the mixture was kept warm at 80 ° C. for 2 hours, and the oil phase 5
0.2 g (LC analysis: cymene 85.2%, 3HPO 8.87
%, 1 HPO 0.02%) and an aqueous phase 5.2 g (LC analysis value: 3 HPO 0.61%, 1 HPO 0%) were obtained (Cymene 1
Hydroperoxide decomposition rate 98.7%, cymene tertiary hydroperoxide recovery rate 100%).

Example 2 In a four-necked flask equipped with a stir bar equipped with a thermometer and a reflux condenser, an oxidation product (LC) of m- and p-mixed cymene (LC) was mixed.
Analysis value: Simene 81.3%, 3HPO 11.4%, 1HPO 2.
09%) 50 g, 40% benzyltrimethylammonium hydroxide aqueous solution 0.126 g, and 8% sodium hydroxide aqueous solution 5.0 g were added, and the mixture was kept warm at 80 ° C. for 2 hours, and oil phase 48.3 g (LC analysis value: cymene 81.7% , 3 HPO 1
2.0%, 1HPO 0.02%) and 5.0 g of water phase (LC analysis value: 3HPO 1.21%, 1HPO 0%) were obtained (Cymene primary hydroperoxide decomposition rate 98.9%, Cymene 3).
100% recovery of primary hydroperoxide).

Example 3 In a four-necked flask equipped with a stir bar equipped with a thermometer and a reflux condenser, an oxidation product (LC) of m- and p-mixed cymene was prepared.
Analytical value: Simene 84.7%, 3HPO 8.80%, 1HPO 1.
55%) 50 g, 10% benzyltriethylammonium hydroxide aqueous solution 0.25 g, and 8% sodium hydroxide aqueous solution 5.0 g were added, and the mixture was kept warm at 80 ° C. for 2 hours, and the oil phase 5
0.2 g (LC analysis: Simene 86.1%, 3HPO 8.50
%, 1HPO 0.05%) and an aqueous phase 5.0 g (LC analysis value: 3HPO 0.72%, 1HPO 0.03%) were obtained (cymene primary hydroperoxide decomposition rate 96.9%, cymene 3).
Recovery rate of primary hydroperoxide 97.0%).

Example 4 In a four-necked flask equipped with a stir bar equipped with a thermometer and a reflux condenser, an oxidation product (LC) of m- and p-mixed cymene was mixed.
Analytical value: Simene 84.4%, 3HPO 8.85%, 1HPO 1.
61%) 50 g, 40% benzyltriethylammonium hydroxide aqueous solution 0.63 g, and 8% sodium hydroxide aqueous solution 5.02 g were added, and the mixture was kept warm at 80 ° C. for 0.167 hours, and the oil phase was 50.0 g (LC analysis value: simene. 84.5%, 3H
PO 8.82%, 1HPO 0.04%) and aqueous phase 5.48g
(LC analysis value: 3HPO 1.08%, 1HPO 0.00%) was obtained (Cymene primary hydroperoxide decomposition rate 97.3).
%, Cymene tertiary hydroperoxide recovery rate 99.7
%).

Example 5 In a four-necked flask equipped with a stir bar equipped with a thermometer and a reflux condenser, an oxidation product (LC) of m- and p-mixed cymene was mixed.
Analytical value: Simene 84.4%, 3HPO 8.85%, 1HPO 1.
61%) 50 g, 40% benzyltriethylammonium hydroxide aqueous solution 1.25 g, and 8% sodium hydroxide aqueous solution 5.03 g were added, and the mixture was kept warm at 80 ° C. for 0.167 hours, and the oil phase was 49.9 g (LC analysis value: simene. 84.6%, 3H
PO 8.77%, 1HPO 0.00%) and water phase 6.20 g
(LC analysis value: 3HPO 1.35%, 1HPO 0.00%) was obtained (Cymene primary hydroperoxide decomposition rate 100%,
Cymene tertiary hydroperoxide recovery rate 99.0%).

Example 6 Oxidation products of m- and p-mixed cymene (LC analysis: cymene 87.2%, 3HPO 7.82%, 1HP) in a 500 ml separable flask equipped with a cooling tube, thermometer and baffle.
O 1.11%) 100.0g is charged and kept at 80 ° C. 2.46 g of a methanol solution of 40% benzyltrimethylammonium hydroxide was added, and the mixture was stirred at the same temperature for 0.5 hour, and 101.8 g of a reaction solution (LC analysis value: cymene 84.9%, 3HPO 7.11%, 1HPO <0.01% ) (Cymene primary hydroperoxide decomposition rate 99.7
%, Cymene tertiary hydroperoxide recovery rate 90.9
%).

Example 7 Oxidation product of m- and p-mixed cymene (LC analysis composition: cymene 87.2%, 3HPO 7.82%, 1HPO 1.11%) 85.
The reaction was performed in the same manner as in Example 6 except that 0 g and 40% benzyltriethylammonium hydroxide solution in methanol (3.37 g) were used, and the reaction solution was 87.1 g (LC analysis value: cymene 84.3%, 3HPO 6.60%, 1HPO 0%). ) (Cymene primary hydroperoxide decomposition rate 100
%, Cymene tertiary hydroperoxide recovery rate 87.7
%) Was obtained.

Example 8 In a four-necked flask equipped with a stir bar equipped with a thermometer and a reflux condenser, an oxidation product (LC) of m- and p-mixed cymene was prepared.
Analysis value: Simene 85.2%, 3HPO 8.44%, 1HPO 1.
38%) 50.1 g, 40% benzyltrimethylammonium hydroxide aqueous solution 2.5 g and water 3.5 g were added, and the mixture was kept warm at 80 ° C. for 2 hours, and oil phase 50.3 g (LC analysis value: cymene 85.1%, 3HPO 8.06). %, 1 HPO <0.01%
) And 5.7 g of aqueous phase (LC analysis: 3 HPO 0.17
%, 1HPO 0.03%) (cymene primary hydroperoxide decomposition rate 99.5%, cymene tertiary hydroperoxide recovery rate 96.0%).

Example 9 In a four-necked flask equipped with a stir bar equipped with a thermometer and a reflux condenser, an oxidation product (LC) of m- and p-mixed cymene was prepared.
Analysis value: Simene 81.3%, 3HPO11.4%, 1HPO2.09%)
30.0 g, 10% tetra-n-butylammonium hydroxide aqueous solution 9.0 g were added, and the mixture was kept warm at 80 ° C. for 2 hours, and the oil phase 30.7 g (LC analysis value: cymene 78.7%, 3HP
O 11.2%, 1HPO 0%) and an aqueous phase 8.1g (LC analysis value: 3HPO 0.23%, 1HPO 0%) were obtained (cymene primary hydroperoxide decomposition rate 100%, cymene tertiary hydroperoxide recovery rate 100%). ).

Examples 10 to 13 Similar to Example 9 except that the weight of the organic quaternary ammonium hydroxide solution shown in Table 1 shown in Table 1 was used in place of 9.0 g of 10% aqueous solution of tetra-n-butylammonium hydroxide. Was reacted. The results are shown in Table 1.

[Table 1]

Comparative Example 1 An oxidation product (LC) of m- and p-mixed cymene (LC
Analysis value: Simene 85.2%, 3HPO 8.44%, 1HPO 1.
38%), 50.0 g, benzyltriethylammonium chloride 1.5 g and water 5.0 g are added, and the mixture is stirred at 80 ° C for 2
After keeping the temperature for 5 hours, the oil phase was 50.3g (LC analysis value: Simene 8
5.1%, 3HPO 8.58%, 1HPO 1.43%) and water phase 5.9g (LC analysis: 3HPO 0.61%, 1HPO
0.05%) (decomposition rate of cymene primary hydroperoxide 0%, recovery rate of cymene tertiary hydroperoxide 100)
%).

Manufacturing Example 50A glass-lined bubble column equipped with a flow controller, feed pump and cyclone (inner diameter of 0.05 m,
Tower height 3.2 m, tower volume 6.0 liters, 5-stage perforated plate type, open area ratio 1
%) Was used to adjust the concentration of m, p-mixed cymene hydroperoxide (mixture of 3HPO and 1HPO) to 1%, m, p-mixed cymene solution (m / p = 57.4 / 42.
6) 1.24 kg / h and 0.238 kg / h of air were continuously injected, and the reaction was carried out at a reaction temperature of 130 ° C., a residence time of 3 hours and a pressure of 0.1 kg / cm ² -G to obtain an oxidation product (LC
Analysis value: Simene 79.9%, 3HPO 9.13%, 1HPO
1.60%) was obtained at 1.27 kg / h.

─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Issei Okamoto 2200 Tsurusaki, Oita City, Oita Prefecture Sumitomo Chemical Co., Ltd. (72) Inventor Toru Maru 2200 Tsurusaki, Oita City, Oita Prefecture Sumitomo Chemical Co., Ltd. In-company (72) Inventor Shigeo 2200 Tsurusaki, Oita City, Oita Prefecture Sumitomo Chemical Co., Ltd. (56) Reference JP-A-2-290845 (JP, A) JP-A-63-35558 (JP, A) JP 60-54357 (JP, A) JP 58-198468 (JP, A) JP 59-186958 (JP, A) JP 57-59861 (JP, A) JP 57 -38735 (JP, A) JP 62-34755 (JP, B1) (58) Fields investigated (Int.Cl. ⁷ , DB name) C07C 409/08 C07C 407/00

Claims (2)

(57) [Claims] 1. A general formula [1] (In the formula, Ar represents an aromatic group which may have a substituent, R ₁ and R ₂ each independently represent a lower alkyl group, and m and n each independently represent 1 or 2).
Represents ) Aromatic primary hydroperoxides and general formula [2] (In the formula, Ar, R ₁ , R ₂ , m and n have the same meanings as described above.) A hydroperoxide mixture containing an aromatic tertiary hydroperoxide is represented by the following formula: A method for removing aromatic primary hydroperoxides, which comprises contacting. 2. The aromatic primary hydroperoxides [1] are primary hydroperoxides of cymene, and the aromatic tertiary hydroperoxides [2] are tertiary hydroperoxides of cymene. Method.