JP3089772B2 - Method for producing diol compound having cyclohexane ring - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a cyclohexane ring having a benzene ring having a benzene ring represented by the following general formula (1), which is reduced to hydrogen to form a diol compound having a cyclohexane ring represented by the following general formula (2). The present invention relates to a method for producing a diol compound having:

[0002]

(However, R ₁ and R ₂ are the same or different groups selected from H and CH ₃ groups.)

The diol compound having a cyclohexane ring represented by the general formula (2) obtained in the present invention includes a polymer, a polymer modifier, a surfactant, various stabilizers,
It is useful as a raw material for manufacturing peroxides and the like.

[0005]

2. Description of the Related Art A diol compound having a cyclohexane ring represented by the general formula (2) is a method which can be carried out industrially, though it is a useful compound as described above, and has a hydroxyl group. No excellent production method has been found in which a high yield can be obtained without undesirable side reactions such as a hydrogenation reaction, that is, a hydrocracking reaction.

[0006]

In view of such circumstances, an object of the present invention is to provide a method for producing a diol compound having a cyclohexane ring represented by the general formula (2),
It is an object of the present invention to provide an excellent production method which can be carried out industrially and can obtain a high yield without an undesirable side reaction.

[0007]

Means for Solving the Problems The inventors of the present invention have made intensive studies to achieve the above object, and have reached the present invention. That is, the present invention provides a diol compound having a cyclohexane ring having a cyclohexane ring represented by the following general formula (2) by hydrogen-reducing a diol compound having a benzene ring represented by the following general formula (1). The present invention relates to a method for producing a diol compound having a cyclohexane ring, which is hydrogen-reduced in the presence of an organic solvent, a rhodium catalyst as a reducing catalyst , and an alkali metal hydroxide.

[0008]

(However, R ₁ and R ₂ are the same or different groups selected from H and CH ₃ groups.)

The details will be described below. The compound represented by the general formula (1) of the present invention is, specifically, 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.

The method for producing the compound represented by the general formula (1) is not particularly limited, but can be obtained by subjecting the compound represented by the following general formula (3) to air oxidation, or obtained by the following general formula (4) or ( The compound represented by 5) can be obtained by subjecting it to a reduction reaction with sodium sulfite, hydrogen or the like in the presence of a catalyst.

[0012]

(However, R ₁ and R ₂ are the same or different groups selected from H and CH ₃ groups.)

The compound represented by the general formula (2) of the present invention is, specifically, 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 organic solvent in the present invention is not particularly limited as long as it dissolves the compound of the general formula (1) and is inert to the hydrogen reduction reaction. Specific examples include ethylene glycol monomethyl ether and ethylene glycol. Glycol monoethyl ether, ethylene glycol dimethyl ether, diethylene glycol monomethyl ether, dioxane, dipropyl ether, ethers such as diphenyl ether, methanol, ethanol, isopropanol, cyclohexanol, ethylene glycol, alcohols such as diethylene glycol can be exemplified, Among them, methanol, ethanol, isopropanol and cyclohexanol are preferred. The amount of the organic solvent to be used is generally 0.5 to 20 parts by weight per 1 part by weight of the compound of the general formula (1).

[0016] The reduction catalyst used in the method of the present invention includes rhodium oxide, rhodium / activated carbon, rhodium.
Rhodium catalyst such as aluminum / alumina is used, especially active
Rhodium catalysts supported on charcoal or alumina are preferred. Each of these catalysts can be used alone or as a multi-component catalyst of two or more types, and those obtained by adding a small amount of other metals to these catalysts may be used.

The amount of the reducing catalyst used is as follows: 1 part by weight of the compound represented by the general formula (1),
0.005 to 0.2 parts by weight is preferred.

The reaction temperature of the hydrogen reduction of the present invention is 30 to 2
The reaction temperature is 50 ° C., preferably 50 to 200 ° C., and the reaction pressure is 1 to 50 kg / cm ² G, preferably 5 to 30 k.
g / cm ² G.

As described above, the reasons for determining the preferable ranges for the amount of the catalyst, the reaction temperature and the reaction pressure are as follows. That is, when the amount of the catalyst is too large, the reaction temperature is too high, or the reaction pressure is too high, a side reaction other than the target reaction, for example, a hydrocracking reaction or the like may occur, and the by-products may increase. On the other hand, if the amount of the catalyst is too small, the reaction temperature is too low, or the reaction pressure is too low, the reaction rate of the target reaction may be reduced. If the amount of the organic solvent is too small, in terms of controlling heat removal,
If it is too large, it is not preferable in terms of energy consumption.

In the present invention, an alkali metal hydroxide is used. Examples of the alkali metal hydroxide include, for example, lithium hydroxide, sodium hydroxide, calcium hydroxide and the like, with lithium hydroxide being preferred.

The amount of the alkali metal hydroxide used is 0.000 per part by weight of the compound represented by the general formula (1).
05 parts by weight or more, preferably 0.0001 to 0.005
Parts by weight. If the amount of the alkali metal hydroxide used is too small, undesirable side reactions such as hydrogenation side decomposition occur, and the yield of the target compound represented by the general formula (2) decreases. When using an alkali metal hydroxide, it may be added to the reaction system in a solid state or a solution state. The reaction is usually carried out by a slurry reaction in an autoclave or a flow reaction in a fixed bed.

A preferred method for separating and recovering the desired compound (2) from the reaction mixture thus obtained is as follows. That is, after completion of the reaction, the catalyst is separated by filtration,
Subsequently, the organic solvent is removed by distillation, and subsequently, the product is distilled off and solidified to obtain the desired compound (2), or the bottom liquid or the bottom after removing the organic solvent by distillation The target compound (2) can be obtained by crystallizing the distillate obtained by distillation from the distillate with a solvent containing hexane, toluene, chlorobenzene, water or the like alone or as a mixture.

[0023]

Next, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples. Example 1 In a SUS 200 cc autoclave with a stirring machine,
48.6 g (0.25 mol) of 1,3-di (2-hydroxy-2-propyl) benzene, 48.6 g of ethanol,
2.43 g of a 5% rhodium-carbon catalyst (manufactured by NE Chem Cat Co.) and 0.5 g of a 5 wt% lithium hydroxide aqueous solution were charged, and a reduction reaction was performed at 75 ° C. under a constant hydrogen pressure of 15 kg / cm ² G. Was carried out. After the reaction for 2 hours, absorption of a predetermined amount of hydrogen was recognized. The reaction was stopped, and the catalyst was filtered off to obtain a reaction solution. As a result of gas chromatography analysis, the conversion of 1,3-di (2-hydroxy-2-propyl) benzene was 100%, and the selectivity of 1,3-di (2-hydroxy-2-propyl) cyclohexane was 100%. Was 96.5%.

Comparative Example 1 The same procedure as in Example 1 was carried out except that no aqueous lithium hydroxide solution was used. 1,3-di (2-hydroxy-2
The conversion of (-propyl) benzene was 99.6%, and the selectivity for 1,3-di (2-hydroxy-2-propyl) cyclohexane was 85.3%. Examples 2 to 6 and Comparative Example 2 The same procedure was performed as in Example 1 except that the conditions in Tables 1 and 2 were used. The results are shown in Tables 1 and 2.

[0025]

TABLE 1 --------------------------------- implementation Example Comparative Example 1 2 3 2 starting compound * 1 m-DKA ← ← ← Reduction catalyst * 2 5% Rh / C ← ← 5% Ru / C Reduction catalyst / raw compound Weight ratio 0.05 / 1 ← ← ← Alkali metal hydroxide type * 3 5% LiOH ← 10% LiOH 5% LiOH Usage g 0.5 0.2 0.5 ← Alkali metal hydroxide / raw compound weight ratio 0.0005 / 1 0.0002 / 1 0.001 / 1 0.0005 / 1 Reaction temperature ℃ 75 ← ← 80 Reaction pressure kg / cm ² 15 ← ← 20 Raw material conversion rate 100 100 99.3 99.6 Selectivity% * 4 96.5 95.8 95.1 93.4 −−−−−−−−−−−−−−−−−−−−−−−−−−−−−− −−−

[0026]

TABLE 2 --------------------------------- implementation Example Comparative Example 4 5 6 1 starting compound m- DKA p-DKA m-DHEB m-DKA Reduction catalyst 5% Rh / C ← ← 5% Rh / C Reduction catalyst / raw compound Weight ratio 0.05 / 1 ← ← ← Alkali metal hydroxide Type 5% NaOH 5 % LiOH ←-Amount used g 0.5 ← ←-Alkali metal hydroxide / raw material weight ratio 0.0005 / 1 ← 0.0006 / 1-Reaction temperature ℃ 80 ← ← 75 Reaction pressure kg / cm ² 20 ← ← 15 Raw material conversion % 99.0 100 100 99.6 Selectivity% 92.6 94.2 95.4 85.3 -----------------------------

* 1 m-DKA: 1,3-di (2-hydroxy-2-propyl) benzene p-DKA: 1,4-di (2-hydroxy-2-propyl) benzene m-DHEB: 1,3 -Di (1-hydroxyethyl) benzene * 2% indicates wt%. * 3% indicates wt%, and an aqueous solution was used. * 4 Selectivity indicates the conversion ratio (on a molar basis) of the reacted starting material to the target compound. The target compounds are as follows. Examples 1-4 and Comparative Examples 1-2 : 1,3-di (2-hydroxy-2-propyl) cyclohexane Example 5 : 1,4-di (2-hydroxy-2-propyl) cyclohexane Example 6 : 1,3-di (1-hydroxyethyl) cyclohexane

[0028]

As described above, according to the present invention,
A method for producing a diol compound having a cyclohexane ring represented by the general formula (2), which is industrially feasible, and is excellent in that a high yield is obtained without undesirable side reactions. To be able to provide.

Continuation of the front page (56) References JP-A-53-149950 (JP, A) JP-A-1-85939 (JP, A) JP-B-45-35300 (JP, B2) Wolinsky, Joseph. et al. "Reaction of methylmagnesium iodide and diethyl 1,2-cyclohexanedic arboxylates." Or g. Chem. , 1968, Vol. 33 (10), p. 3950-3953. Marshall, James A. et al. "Synthesis and stereochemistry of 5-substituted 2-methylcyclo-hept anones." Org. Chem. , 1968, Vol. 33 (11), pp. 4090-4097. Liberman, A .; L. et al. "Sequence of melting points of steoisomeric 1,4-disubstituted cycloh xanes (new regularity)." Dokl. Akad. Nauk SSSR, 1971, Vol. 201 (1), p. 115-116. (58) Field surveyed (Int. Cl. ⁷ , DB name) C07C 31/27 B01J 23/46 C07C 29/19-29/20 CA (STN) REGISTRY (STN)

Claims (2)

(57) [Claims] 1. Production of a diol compound having a cyclohexane ring having a benzene ring represented by the following general formula (1) by hydrogen reduction to obtain a diol compound having a cyclohexane ring represented by the following general formula (2): A method comprising the steps of:
A method for producing a diol compound having a cyclohexane ring, which is hydrogen-reduced in the presence of a platinum catalyst and an alkali metal hydroxide. (However, R ₁ and R ₂ are the same or different groups selected from H and CH ₃ groups.) 2. The method according to claim 1, wherein the alkali metal hydroxide is lithium hydroxide.