JPH04257536A - Diol compound having cyclohexane ring and its production - Google Patents

Abstract

PURPOSE:To obtain a new industrially producible diol compound, extremely useful as a raw material for producing polymers, modifying agents for the polymers, surfactants, various stabilizers, peroxides, etc., and having cyclohexane ring. CONSTITUTION:A diol compound, expressed by formula I (R1 and R2 are H or CH3) and having cyclohexane rind, e.g. 1,3-(1-hydroxyethyl)cyclohexane. The aforementioned compound expressed by formula I is obtained by steps for reducing a diol compound, expressed by formula II and having benzene ring with hydrogen in the presence of an organic solvent and a reducing catalyst and providing a compound expressed by formula III. The above-mentioned method for production is industrially practicable and high conversion rate and selectivity can advantageously be achieved.

Description

[Detailed description of the invention]

0001

[Field of Industrial Application] The present invention relates to a novel diol compound having a cyclohexane ring represented by the above general formula (1), and a method for producing a diol compound having a cyclohexane ring represented by the above general formula (3). It is related to. The diol compound having a cyclohexane ring of the present invention is extremely useful as a raw material for producing polymers, polymer modifiers, surfactants, various stabilizers, peroxides, and the like.

0002

BACKGROUND OF THE INVENTION A diol compound having a cyclohexane ring represented by the general formula (1) is not known. Further, although the diol compound having a cyclohexane ring represented by the general formula (3) is a useful compound as described above, no excellent manufacturing method that is industrially practicable has been found.

0003

SUMMARY OF THE INVENTION In view of the current situation, an object of the present invention is to provide a novel diol compound having a cyclohexane ring represented by the above general formula (1), and to provide a diol compound having a novel cyclohexane ring represented by the above general formula (3). A method for producing a diol compound having a cyclohexane ring, which is industrially feasible and capable of achieving high conversion and high selectivity.
Our goal is to provide an excellent manufacturing method.

0004

[Means for Solving the Problems] In order to achieve the above object, the present inventors have arrived at the present invention as a result of intensive studies. That is, one aspect of the present invention relates to a diol compound having a cyclohexane ring represented by the general formula (1). Further, in another invention, a diol compound having a benzene ring represented by the general formula (2) is reduced with hydrogen in the presence of an organic solvent and a reduction catalyst, thereby producing cyclohexane represented by the general formula (3). The present invention relates to a method for producing a diol compound having a cyclohexane ring, which is a diol compound having a ring.

[0005] This will be explained in detail below. General formula of the present invention (
Specifically, the compound represented by 1) is 1,3-di(
1-hydroxyethyl)cyclohexane, 1,3-di(
2-hydroxy-2-propyl)cyclohexane, or 1-(1-hydroxyethyl)-3-(2-hydroxy-2-propyl)cyclohexane.

Specifically, the compound represented by the general formula (2) of the present invention is 1,2-di(1-hydroxyethyl)
Benzene, 1,2-di(2-hydroxy-2-propyl)benzene, 1-(1-hydroxyethyl)-2-(2
-hydroxy-2-propyl)benzene, 1,3-di(
1-hydroxyethyl)benzene, 1,3-di(2-hydroxy-2-propyl)benzene, 1-(1-hydroxyethyl)-3-(2-hydroxy-2-propyl)
Benzene, 1,4-di(1-hydroxyethyl)benzene, 1,4-di(2-hydroxy-2-propyl)benzene, or 1-(1-hydroxyethyl)-4-(2-
hydroxy-2-propyl)benzene.

Specifically, the compound represented by the general formula (3) of the present invention is 1,2-di(1-hydroxyethyl)
Cyclohexane, 1,2-di(2-hydroxy-2-propyl)cyclohexane, 1-(1-hydroxyethyl)-2-(2-hydroxy-2-propyl)cyclohexane, 1,3-di(1-hydroxyethyl) ) cyclohexane, 1,3-di(2-hydroxy-2-propyl)cyclohexane, 1-(1-hydroxyethyl)-3-(
2-hydroxy-2-propyl)cyclohexane, 1,
4-di(1-hydroxyethyl)cyclohexane, 1,
4-di(2-hydroxy-2-propyl)cyclohexane or 1-(1-hydroxyethyl)-4-(2-hydroxy-2-propyl)cyclohexane.

The method for producing the compound represented by the general formula (2) is not particularly limited, but it can be obtained by air oxidation of the compound represented by the following general formula (4), or the compound represented by the following general formula (5) or ( The compound represented by 6) can be obtained by subjecting it to a reduction reaction using sodium sulfite, hydrogen, etc. in the presence of a catalyst.

[0009]

(In the formula, R1 and R2 are the same or different groups selected from H and CH3 groups.)

00
11] Reduction catalysts used in the method of the present invention include palladium catalysts such as palladium black, palladium oxide, colloidal palladium, palladium/activated carbon, palladium/alumina, palladium/barium sulfate, palladium/barium carbonate, platinum black, Platinum catalysts such as colloidal platinum, platinum sponge, platinum oxide, platinum sulfide, platinum/activated carbon,
Rhenium catalysts such as rhenium/activated carbon, rhodium oxide,
Examples include rhodium catalysts such as rhodium/activated carbon and rhodium/alumina, ruthenium catalysts such as ruthenium oxide, ruthenium/activated carbon, and ruthenium/alumina. Furthermore, these catalysts may be modified by adding small amounts of other metals. Among these reduction catalysts, it is preferable to use a rhodium catalyst or a ruthenium catalyst, and it is particularly preferable to use a rhodium catalyst or a ruthenium catalyst supported on activated carbon or alumina.

The amount of the reduction catalyst used is 0 as the total weight of the catalyst per 1 part by weight of the compound represented by the general formula (2).
．． 0.05 to 0.2 parts by weight is preferred.

[0013] In the practice of this invention, organic solvents are used. The organic solvent is not particularly limited as long as it dissolves the compound of general formula (2) and is inert to the hydrogen reduction reaction, but specific examples include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, and ethylene. Examples include ethers such as glycol dimethyl ether, diethylene glycol monomethyl ether, dioxane, dipropyl ether, and diphenyl ether; alcohols such as methanol, ethanol, isopropanol, cyclohexanol, ethylene glycol, and diethylene glycol; among others,
Methanol, ethanol, isopropanol and cyclohexanol are preferred. The amount of organic solvent used is usually 0.5 to 20 parts by weight per 1 part by weight of the compound of general formula (2).

[0014] The reaction temperature of the present invention is 30 to 250°C;
Preferably the temperature is in the range of 50 to 200°C, and the reaction pressure is 1 to 50 kg/cm2G, preferably 5 to 30 kg/cm2G.
cm2G. The reaction usually takes the form of a slurry reaction using an autoclave or a fixed bed flow reaction. As mentioned above, the reason for determining the preferable ranges for the amount of catalyst, reaction temperature, and reaction pressure is as follows. That is, if the amount of catalyst is too large, the reaction temperature is too high, or the reaction pressure is too high, side reactions other than the desired reaction,
For example, hydrogenolysis reactions occur, resulting in an increase in by-products. On the other hand, if the amount of catalyst is too small, the reaction temperature is too low, or the reaction pressure is too low, the reaction rate of the desired reaction will be slow. Incidentally, if the amount of the organic solvent is too small, it is undesirable from the viewpoint of heat removal control, and when it is too large, it is undesirable from the viewpoint of energy consumption.

A preferred method for separating and recovering the target compound (3) from the reaction mixture thus obtained is as follows. That is, after the reaction is completed, the catalyst is separated by filtration,
Next, the organic solvent is removed by distillation, and the product is subsequently distilled off and solidified to obtain the target compound (3), or the bottoms or cans after removing the organic solvent by distillation are used. The target compound (3) can be obtained by crystallizing the distillate obtained by distillation from the extract using a solvent such as hexane, toluene, chlorobenzene, water, etc. alone or in combination.

[0016]

[Examples] Next, the present invention will be explained in more detail with reference to Examples, but the present invention is not limited thereto. Example 1 In a SUS 200cc autoclave with a stirrer,
1,3-di(2-hydroxy-2-propyl)benzene 48.6g (0.25 mol), ethanol 48.6
g, 2.43 g of 5% rhodium-supported activated carbon catalyst were charged, and 75 g was charged under a constant hydrogen pressure of 15 kg/cm2G.
The reduction reaction was carried out at °C. After 2 hours of reaction, a predetermined amount of H2 absorption was observed, so the reaction was stopped and the reaction solution was obtained after filtering the catalyst. As a result of gas chromatography analysis (hereinafter abbreviated as "GC analysis"), the reaction conversion rate of 1,3-di(2-hydroxy-2-propyl)benzene was 99.6%, and the reaction conversion rate of 1,3-di(2-hydroxy-2-propyl)benzene was 99.6%. 2-hydroxy-
The selectivity of 2-propyl)cyclohexane was 85.3%. Ethanol was removed from the reaction solution obtained above by distillation, and then 1,3-
A distillate containing di(2-hydroxy-2-propyl)cyclohexane as the main component was obtained, and this was recrystallized with toluene to obtain 1,000 g
3-di(2-hydroxy-2-propyl)cyclohexane was obtained. The above compound has a molecular weight of 2 by mass spectrum, NMR spectrum, and elemental analysis.
00 1,3-di(2-hydroxy-2-propyl)cyclohexane.

Example 2 Same as Example 1 except that 1,4-di(2-hydroxy-2-propyl)benzene was used instead of 1,3-di(2-hydroxy-2-propyl)benzene. The reaction was carried out. As a result of GC analysis, the reaction conversion rate of 1,4-di(2-hydroxy-2-propyl)benzene was 99.0.
%, the selectivity for 1,4-di(2-hydroxy-2-propyl)cyclohexane was 82.1%.

Example 3 A reaction was carried out in the same manner as in Example 1, except that a 5% ruthenium-supported activated carbon catalyst was used instead of the 5% rhodium-supported activated carbon catalyst. As a result of GC analysis, 1,3-di(2-
The reaction conversion rate of hydroxy-2-propyl)benzene is
The selectivity for 92.5% and 1,3-di(2-hydroxy-2-propyl)cyclohexane was 80.6%.

[0019]

[Effect of the invention] As explained above, according to the present invention,
Provided is a novel diol compound having a cyclohexane ring represented by the general formula (1), and a method for producing a diol compound having a cyclohexane ring represented by the general formula (3), which is also industrially practicable. We were able to provide an excellent manufacturing method that can achieve high conversion and high selectivity.

Claims (2)

[Claims] 1. A diol compound having a cyclohexane ring represented by the following general formula (1). (However, R1 and R2 are the same or different groups selected from H or CH3 groups.) [Claim 2] By reducing a diol compound having a benzene ring represented by the following general formula (2) with hydrogen in the presence of an organic solvent and a reducing catalyst, a cyclohexane ring represented by the following general formula (3) can be obtained. A method for producing a diol compound having a cyclohexane ring. (However, R1 and R2 are the same or different groups selected from H or CH3 groups.)