JPH10101603A - Production of 1,2-indanediols - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for production with high safety by which the amount of an organic acid used is reduced and 1,2-indanediols are obtained in high yield in one stage in the method for producing the 1,2-indanediols by oxidizing indenes with an organic peracid. SOLUTION: An organic acid and water in an amount of 1-10 times (weight) based on the organic acid are added to indene or its benzene derivative and hydrogen peroxide is then dropped into the resultant mixture to oxidize the indene or its benzene derivative. A lower aliphatic carboxylic acid, e.g. formic acid or acetic acid is cited as the organic acid to be used. There is no problem in the concentration of the organic acid to be used if the amount of the organic acid is a prescribed one expressed in terms of the purity and the amount thereof used is 0.2-10 equiv., preferably 0.5-5 equiv. based on the indenes which are raw materials depending on the amount of the water used.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a method for producing 1,2-indanediols useful as raw materials for producing pharmaceuticals, agricultural chemicals, resin modification and the like on an industrial scale.

[0002]

2. Description of the Related Art As a method for producing 1,2-indanediols, for example, a method of reacting indene with bromine water to form a bromohydrin form, followed by hydrolysis in the presence of an alkali catalyst (hereinafter abbreviated as a promohydrin method; J Am.
Chem. Soc. , 57, 2022 (1935) and J.M. Org. Chem. , 37, 20, 3181 (1
972)), a method in which indene is oxidized as formic acid with hydrogen peroxide using a large excess of formic acid to form a formate ester, and then heated by adding water (hereinafter abbreviated as formate method; Japanese Patent Application Laid-Open No. HEI 8-1-119891); Method for hydrating 1,2-epoxyindane in the presence of an acid or alkali catalyst (JP-A-7-165647 and J. Org. Che.
m. , 39, 17, 2596 (1974)), a method for directly oxidizing indene, for example, a method for oxidizing indene with osmium oxide (J. Org. Chem., 37, 20, 3181).
(1972)), a method of oxidizing with a permanganate salt (Z. p.
hysik, Chem. , 113, 337 (192)
4)) and so on.

[0003]

However, the bromohydrin method has problems in terms of safety and health and waste / wastewater treatment because of the use of bromine water.

In the formate method, a large excess of formic acid is used as a solvent, so that after reacting indene and formic acid, formic acid must be distilled off to remove the formate ester as an intermediate. This has the disadvantage that the unreacted peroxide is concentrated, which entails the danger of explosion and the like. In addition, since the oxidation reaction temperature is as low as 30 to 40 ° C., in order to carry out the process on an industrial scale, special equipment capable of cooling to a low temperature is required in order to control the heat generated by the oxidation, and such equipment is not provided. In this case, there is a disadvantage that it takes a very long time to drop hydrogen peroxide and it is not economical.

The method of hydrating 1,2-epoxyindane has a problem in obtaining 1,2-epoxyindane as a raw material. 1,2-Epoxyindane is generally derived from a bromohydrin compound, but in that case, it has the above-mentioned problems and the number of steps increases, which is not desirable.

[0006] Furthermore, the method of directly oxidizing indene has problems in terms of economy and wastewater treatment.

[0007]

Means for Solving the Problems The present inventors have made intensive studies to solve the above-mentioned drawbacks. As a result, when oxidizing indene or its benzene ring-substituted product (hereinafter referred to as indene) with an organic peracid, An organic acid is added to the indene, and hydrogen peroxide is added dropwise to the indene to generate an organic peracid in the reaction system, and oxidize the indene with the organic peracid to obtain 1,2-indanediol. Are obtained in high yield,
Further, since the reaction solution is not concentrated after the completion of the oxidation reaction, the peroxide concentration does not increase, the safety is also improved, and it has been found that it is extremely useful industrially.

Further, when an oxidation reaction is carried out by dropping such hydrogen peroxide, the amount of organic acid used can be reduced by using a certain amount of water as a reaction solvent,
A reaction at a high temperature of 0 to 110 ° C. is possible, and 1,2-indanediols having a low content of organic acid ester can be obtained in one step in a high yield, which is an industrially very useful production method. The present invention has been completed.

That is, the present invention relates to an indene or a benzene ring-substituted product thereof, which contains an organic acid and 1 to 2
The present invention relates to a method for producing 1,2-indanediols, which comprises adding 0 times (weight) water and oxidizing the mixture by dripping hydrogen peroxide at 40 to 110 ° C.

[0010]

BEST MODE FOR CARRYING OUT THE INVENTION The starting materials used in the present invention are indenes, that is, indene or a benzene ring-substituted product thereof. The substituted benzene ring of indene means the benzene ring side of the indene skeleton, that is, the 4-, 5-, or 6-position.
A compound having a substituent at at least one of the 7th and 7th positions. Examples of the substituent include an alkyl group, an alkoxyl group, a hydroxyl group, a carboxyl group, a nitro group, an amino group, and a halogen.

The organic acids used in the present invention include lower aliphatic carboxylic acids such as formic acid and acetic acid. The concentration of the organic acid to be used is not a problem as long as the organic acid is in a predetermined amount as a pure component, and it depends on the amount of water used.
Preferably it is 0.5 to 5 equivalents. If the amount is too small, the reaction rate becomes slow and the reaction takes a long time, which is not preferable. Conversely, too much has no effect and is not economical.

In the present invention, the indene is oxidized using water as a solvent, but the water used may be any of industrial water, ion-exchanged water, pure water, distilled water and the like, and is not particularly limited. The amount used is 1 to 20 by weight with respect to the organic acid.
Times, preferably 1 to 10 times. If the amount is too large, the reaction rate becomes slow and the reaction takes a long time, which is not preferable. If the amount is too small, side reactions increase and the yield decreases.

The present invention relates to a method for producing 1,2-indanediols by oxidizing indene with an organic peracid, wherein hydrogen peroxide is added dropwise to a mixture of indene, water and an organic acid. And performing an oxidation reaction while generating an organic peracid.

As the hydrogen peroxide, 3 to 90% by weight of aqueous hydrogen peroxide can be used, and usually 30 to 35% by weight of aqueous hydrogen peroxide is used. The amount used is 0.5 to 5 equivalents, preferably 0.8 to 3 equivalents to the indene material.
Is equivalent. If the amount is too small, the conversion of the indene as a raw material becomes insufficient. However, since it is also possible to convert the entire amount by reducing the amount of hydrogen peroxide and to recover the indene as a raw material later, if such a method is adopted,
This is not the case. Conversely, if it is too large, unreacted hydrogen peroxide remains, which is not economical.

The dropping temperature and reaction temperature of hydrogen peroxide are 40 to 110 ° C. If the temperature is too low, the reaction rate becomes slow and the reaction takes a long time, which is not preferable. Further, in the present invention, by performing the oxidation reaction while generating an organic peracid by dropping hydrogen peroxide in the presence of water, it is possible to operate safely even at a higher temperature than the conventional method. If too high, peroxide decomposition will be severe and the risk of explosion will increase.

The time for dropping hydrogen peroxide is not particularly limited, and may be determined according to the cooling capacity.
It is about 4 hours. The oxidation reaction may be terminated immediately after the completion of the dropwise addition, but preferably the stirring is continued for 0.5 to 5 hours to complete the reaction.

When the oxidation reaction solution is cooled, crystals of 1,2-indanediols are precipitated. The cooling temperature is not particularly limited, but the lower temperature is 1,2-
The yield of indanediols is improved. The precipitated crystals are
For example, it is collected according to a conventional method such as centrifugal separation and filtration under reduced pressure. If high-purity 1,2-indanediols are required, the recovered crystals can be purified by means such as recrystallization or distillation.

Further, the filtrate after separation still contains some 1,2-indanediols and most of formic acid. These can be recycled next time to increase the yield of 1,2-indanediols and reduce the formic acid usage.

[0019]

EXAMPLES The method of the present invention will be specifically described below with reference to examples. [Example 1] Indene (98.1) was placed in a 200-ml flask equipped with a stirrer, thermometer and reflux condenser.
23.2 g (0.2 mol), 90% by weight formic acid 1
5.3 g (0.3 mol) and 30 g of water were charged, and 23.7 g (0.24 mol) of 34.5% by weight hydrogen peroxide solution was added dropwise at 70 ° C. over 0.4 hours. Stirring was continued at 2.6 ° C. for 2.6 hours.

After completion of the reaction, the reaction mixture was analyzed by gas chromatography. As a result, almost all indene was converted, and the 1,2-indanediol concentration was 23.0% by weight.
And the yield was 71.4 mol%. The 1,2-indanediol monoformate concentration in the reaction solution was 1.0%. Table 1 shows the results.

Example 2 Indene (98.6%) 1
1.6 g (0.1 mol), 15.3 g of 90% by weight formic acid
(0.3 mol), 45 g of water, and 34.5 at 70 ° C.
12.8 g (0.13 mol) of a 1% by weight aqueous hydrogen peroxide solution was added dropwise over 1 hour, and after completion of the addition, stirring was continued at 70 ° C. for 1 hour.

After the reaction was completed, the reaction mixture was analyzed by gas chromatography. As a result, almost all indene was converted, and the 1,2-indanediol concentration was 14.2% by weight.
And the yield was 81.3 mol%. The 1,2-indanediol monoformate concentration in the reaction solution was 0.4%. Table 1 shows the results.

Examples 3 to 6 The same operation as in Example 2 was carried out except that the amounts of indene, 90% by weight formic acid, water, 34.5% by weight of hydrogen peroxide and the reaction temperature were changed. Table 1 shows the results.

[0024]

[Table 1]

Example 7 Indene (9) was placed in a 2 liter flask equipped with a stirrer, thermometer and reflux condenser.
8.6%) 474 g (4 mol), 98% by weight formic acid 282
g (6 moles) and 682.5 g of water.
552.5 g (5.2 mol) of a weight-percent hydrogen peroxide solution was added to 2.
The mixture was added dropwise over 4 hours, and after the completion of the addition, stirring was continued at 70 ° C. for 1 hour.

After completion of the reaction, the reaction mixture was analyzed by gas chromatography. As a result, almost all the indene was converted, and the 1,2-indanediol concentration was 20.8% by weight.
And the yield was 71.2 mol%. The monoformate concentration of 1,2-indanediol in the reaction solution was 1.1%.

Example 8 Indene (98.6%) 23
7 g (2 mol), 282 g (6 mol) of 98% by weight formic acid,
625.2 g of water was charged, 262.2 g (2.6 mol) of 33.7% by weight of hydrogen peroxide solution was added dropwise at 70 ° C. over 1.2 hours, and after completion of the dropwise addition, the mixture was stirred at 70 ° C. for 0.8 hours. Continued.

After the reaction was completed, the reaction mixture was analyzed by gas chromatography. As a result, almost all indene was converted, and the concentration of 1,2-indanediol was 15.7% by weight.
And the yield was 75.1 mol%. The concentration of monoformate of 1,2-indanediol in the reaction solution was 1.2%.

Example 9 Indene (98.6%) 47
4 g (4 mol), 282 g (6 mol) of 98% by weight formic acid,
626.4 g of water was charged, and 433.5 g (4.4 mol) of 34.5% by weight aqueous hydrogen peroxide was added dropwise at 50 ° C. over 4 hours. After the addition was completed, stirring was continued at 50 ° C. for 5 hours.

After completion of the reaction, the reaction mixture was analyzed by gas chromatography. As a result, almost all the indene was converted, and the 1,2-indanediol concentration was 23.7% by weight.
And the yield was 72.7 mol%. The monoformate concentration of 1,2-indanediol in the reaction solution was 1.9%.

COMPARATIVE EXAMPLE 1 In a 100 ml flask equipped with a stirrer, thermometer and reflux condenser, 23.2 g (0.2 mol) of indene (98.6%) and 90% by weight of formic acid 30 were added. 5.7 g (0.6 mol), 25.5 g of a 32% by weight hydrogen peroxide solution at 70 ° C. without adding water.
(0.24 mol) was added dropwise over 1.7 hours, and after completion of the addition, stirring was continued at 70 ° C. for 1 hour.

After the completion of the reaction, the reaction mixture was analyzed by gas chromatography. As a result, almost all the indene was converted, but the 1,2-indanediol concentration was 12.8% by weight.
And the yield was 34.4 mol%. The concentration of the monoformate of 1,2-indanediol in the reaction solution was 4.0%. Table 2 shows the results.

Comparative Example 2 In a 200-ml flask equipped with a stirrer, thermometer and reflux condenser, 23.2 g (0.2 mol) of indene (98.6%) and 90% by weight of formic acid 15 0.3 g (0.3 mol) and 30.0 g of water were charged and 23.7 g of a 34.5% by weight hydrogen peroxide solution at 30 ° C.
(0.24 mol) was added dropwise over 1 hour.
Stirring was continued at 0 ° C. for 6 hours.

After completion of the reaction, the reaction mixture was analyzed by gas chromatography to find that the indene conversion was 86.5% and the 1,2-indanediol concentration was 15.4% by weight.
And the yield was 46.5 mol%. The monoformate concentration of 1,2-indanediol in the reaction solution was 2.2%. Table 2 shows the results.

[0035]

[Table 2]

Example 10 5-Methylindene
0 g (0.1 mol), 15.3 g of 90% by weight formic acid (0.
3 mol), 45 g of water, and 34.5% by weight at 70 ° C.
12.8 g (0.13 mol) of aqueous hydrogen peroxide was added dropwise over 1 hour, and after completion of the addition, stirring was continued at 70 ° C. for 1 hour.

After completion of the reaction, the reaction mixture was analyzed by gas chromatography. As a result, the concentration of 5-methyl-1,2-indanediol was 14.6% by weight, and the yield was 76.4% by mole.

[0038]

According to the present invention, the amount of the organic acid used can be reduced, the reaction can be performed at a higher temperature than in the conventional formate method, and 1,2-indanediols can be produced in one step. Obtained in yield. Further, after the oxidation reaction is completed, there is no step of concentrating the reaction solution to increase the peroxide concentration, so that it is highly safe and industrially extremely useful.

Claims (1)

[Claims] 1. An organic acid and water 1 to 20 times (by weight) the above organic acid are added to indene or its benzene ring-substituted product, and hydrogen peroxide is added dropwise to the mixture at 40 to 110 ° C. A method for producing 1,2-indanediols, which comprises oxidizing.