JP3175487B2 - Process for producing cycloalkanol and cycloalkanone - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing cycloalkanol and cycloalkanone in a high yield by decomposing a cycloalkyl hydroperoxide in the presence of a catalyst. Cycloalkanols and cycloalkanones are very useful compounds as raw materials for the production of monomers for polyamide polymers such as nylon, synthetic intermediates for chemicals, organic solvents and the like.

[0002]

2. Description of the Related Art As a method for producing cycloalkanol and cycloalkanone by decomposing a cycloalkyl hydroperoxide in the presence of a metal catalyst, there are known industrial chemical journals.
73, 2388 (1970) The method of using a naphthenate such as cobalt, molybdenum, or manganese to decompose cyclohexyl hydroperoxide in cyclohexane or another solvent according to the description is known, but in order to obtain a sufficient reaction rate. Since the reaction temperature needs to be kept high, cyclohexanol and cyclohexanone are lost due to thermal side reactions, which is not a satisfactory method. JP 2-1648
JP 36-156735 discloses a method using an organometallic complex in which a metal selected from cobalt, manganese, chromium, iron or vanadium is bonded to a phthalocyanine or porphyrin structure immobilized on a carrier substance, and JP-A-63-156735. The publication describes a method using a metal complex consisting of cobalt, manganese, chromium or iron and a certain isoindoline, but in each case, a large amount of a catalyst must be used, and the ligand must be used. There is a problem that it is not necessarily thermally stable and is expensive. Japanese Patent Application Laid-Open No. 58-219132 describes a method using cobalt oxide supported on zeolite, but this method requires an extremely large amount of catalyst to obtain a sufficient reaction rate.

[0003]

SUMMARY OF THE INVENTION An object of the present invention is to decompose a cycloalkyl hydroperoxide in the presence of a small amount of a highly active metal catalyst in a reaction system to obtain a cycloalkanol and a cycloalkanone at a high decomposition rate and a high yield. It is an object of the present invention to provide an industrially suitable method for producing cycloalkanol and cycloalkanone, which is capable of producing a compound.

[0004]

An object of the present invention According to an aspect of the cycloalkyl hydroperoxide, the general formula _{(I) [MCl n (PR} 1 R 2 R 3) m] (I) ( wherein, M is iron, Cobalt, nickel or copper, R
¹ , R ² and R ³ represent an aryl group. n is 1 or 2,
m shows the integer of 1-3. ) Is achieved by a method for producing cycloalkanol and cycloalkanone, which is decomposed in the presence of a metal complex represented by the formula (1).

Hereinafter, the present invention will be described in detail. As the cycloalkyl hydroperoxide used in the present invention, for example, cyclopentane, cyclohexane, cycloheptane, cyclooctane, cyclononane, cyclodecane, cyclododecane, cyclopentadecane, cyclohexadecane, etc. Peroxides.

The above cycloalkyl hydroperoxide is generally used at a reaction temperature of 120 to 180 ° C. and a reaction pressure of 1 to 20 atm in the absence of a substance which promotes the decomposition of cycloalkyl hydroperoxide such as a transition metal. The cycloalkane can be obtained by a liquid phase contact reaction with molecular oxygen such as air. In the present invention, not only cycloalkyl hydroperoxide separated from the cycloalkane oxidation reaction solution thus obtained by distillation or extraction, but also unpurified cycloalkyl hydroperoxide (that is, the oxidation reaction solution) is used as it is. Even if it is used, it can be decomposed efficiently to produce cycloalkanol and cycloalkanone.

When a cycloalkane oxidation reaction solution is used, a considerable amount of remaining unreacted cycloalkane reacts with the cycloalkyl hydroperoxide in addition to the direct production of the desired product from the cycloalkyl hydroperoxide. As a result, cycloalkanone and cycloalkanol are produced, so that there is an advantage that the yield of the target product is increased. When the oxidation reaction solution is used, it is preferable to remove contained acid by washing the oxidation reaction solution with water or alkali as needed before decomposing the cycloalkyl hydroperoxide. At this time, as the alkali, for example, a hydroxide or a carbonate of an alkali metal or an alkaline earth metal such as sodium hydroxide, potassium hydroxide, calcium hydroxide, sodium carbonate, potassium carbonate, and calcium carbonate is used.

The compound represented by the general formula (I) used in the present invention
The central metal M of the complex catalyst is iron, cobalt, nickel
Or copper, but preferably cobalt.
R in the ligand¹, R^Two, R^ThreeAre various aryl groups
But these are the same, but different
It may be something. n is 1 or 2. m is 1
It is an integer up to 3. For example, [CoCl_Two(PR¹R
^TwoR^Three)_Two], [CoCl (PR¹R^TwoR^Three)_Three], [FeCl_Two(PR¹R^Two
R^Three)_Two], [NiCl_Two(PR¹R^TwoR^Three)_Two], [CuCl (PR¹R^Two
R^Three)_Three], [CuCl (PR ¹R^TwoR^Three)]_FourAnd the like. What
In addition, these complexes are known ones, and most correspond.
Can be easily synthesized using metal chlorides as starting materials.
You.

The aryl groups include phenyl, benzyl, o-tolyl, m-tolyl, p-tolyl, o-methoxyphenyl, m-methoxyphenyl, p-methoxyphenyl, mesityl , O-fluorophenyl group, m-fluorophenyl group, p-fluorophenyl group, o-chlorophenyl group, m-chlorophenyl group, p-chlorophenyl group,
A substituted or unsubstituted aryl group such as a 2,3,4,5,6-pentafluorophenyl group is exemplified. These phosphine ligands containing an aryl group include triphenylphosphine, benzyldiphenylphosphine, dibenzylphenylphosphine, tribenzylphosphine, tri (o-
(Tolyl) phosphine, tri (m-tolyl) phosphine, tri
(p-tolyl) phosphine, diphenyl (o-tolyl) phosphine, diphenyl (p-tolyl) phosphine, tris (p-methoxyphenyl) phosphine, o-methoxyphenyldiphenylphosphine, p-methoxyphenyldiphenylphosphine, tri (mesityl) Phosphine, mesityldiphenylphosphine, tris (o-fluorophenyl) phosphine,
Tris (m-fluorophenyl) phosphine, tris (p-fluorophenyl) phosphine, m-fluorophenyldiphenylphosphine, p-fluorophenyldiphenylphosphine, tris (o-chlorophenyl) phosphine, tris (m
-Chlorophenyl) phosphine, tris (p-chlorophenyl) phosphine, tris (pentafluorophenyl) phosphine, bis (pentafluorophenyl) phenylphosphine, pentafluorophenyldiphenylphosphine. Preferably, it is triphenylphosphine.

In the decomposition of cycloalkyl hydroperoxide, usually, the above metal complex is added to the reaction mixture in an amount of 0.01 to 0.01% in terms of metal.
~ 250 wtppm, preferably 0.1 ~ 150 wtp
pm, the reaction temperature is 25 to 180 ° C, preferably 80 to 160 ° C, and the reaction pressure is 1 to 30 atm. When the reaction temperature is lower than 25 ° C., the reaction rate becomes slow, and when the reaction temperature is higher than 180 ° C., the yield of the target product is undesirably reduced. The above range is preferable because no special effect is observed even when the concentration of the catalyst is increased.

The decomposition reaction is carried out, for example, in a reactor equipped with a reflux condenser and a stirrer in order to release heat generated during the reaction and appropriately control the reaction temperature.

As described above, cyclopentanone, cyclohexanone, cycloheptanone, cyclooctanone, cyclononanone, cyclodecanone, cyclododecanone, cyclopentadecanone, cyclohexadecanone, and cyclopentanol, cyclohexanol, cycloheptanone The reaction solution for the decomposition of cycloalkyl hydroperoxide containing cycloalkanone and cycloalkanol such as phenol, cyclooctanol, cyclononanol, cyclodecanol, cyclododecanol, cyclopentadecanol and cyclohexadecanol is obtained. Alkanone and cycloalkanol are separated and purified by distillation or the like, if necessary, after removing the acid by washing the decomposition reaction solution with water or alkaline water. When a cycloalkane oxidation reaction solution is used, unreacted cycloalkane is separated by distillation and recycled for the oxidation reaction.

[0013]

Next, the present invention will be specifically described with reference to examples and comparative examples. The conversion of cyclohexyl hydroperoxide (CHP), the yield of cyclohexanone and cyclohexanol (KA) are determined by analyzing gaseous chromatographic analysis of cyclohexyl hydroperoxide (CHP), cyclohexanone (K) and cyclohexanol (A) according to the following formula. I asked.

[0014]

(Equation 1)

[0015]

(Equation 2)

Example 1 (Air oxidation of cyclohexane) 300 g of cyclohexane was charged into a pressure-resistant glass autoclave having a capacity of 500 ml, and air (pressure 10 k
g / cm ² ), and per 1 g of the reaction solution, 0.2770 mmol of cyclohexyl hydroperoxide (CHP), 0.1236 mmol of cyclohexanol (A), and 0.0901 mmol of cyclohexanone (K)
An oxidized solution of cyclohexane containing l was obtained.

(Decomposition of Cyclohexyl Peroxide) In a 50 ml pressure-resistant glass autoclave equipped with a reflux condenser, a thermometer, a stirrer, and a reaction solution outlet, 10 g of the above cyclohexane oxidizing solution and dichlorobis (triphenylphosphine) cobalt were added. [CoCl ₂ (PPh ₃ ) ₂ ] with a metal content of 7.5
It was added so as to be ppm by weight. Then, the mixture was heated to 120 ° C. with stirring to decompose cyclohexyl hydroperoxide (CHP) for 45 minutes. After the completion of the reaction, the reaction solution was analyzed by gas chromatography.
As a result, the CHP conversion was completely decomposed and the KA yield was 10
At 5.9%, the K / A ratio (molar ratio) was 0.49.

Comparative Example 1 In Example 1, the catalyst was changed to cobalt octylate [Co (C ₇ H
₁₅ CO ₂ ) ₂ ], and the metal solution was added in an amount such that the metal concentration became 7.5 ppm by weight. The decomposition of cyclohexyl hydroperoxide (CHP) was carried out for 45 minutes in the same manner as in Example 1, and the reaction solution was analyzed. . As a result, the CHP conversion was 44% and the KA yield was 99.
At 8%, the K / A ratio (molar ratio) was 0.44.

Example 2 The procedure of Example 1 was repeated, except that the catalyst was changed to chlorotris (triphenylphosphine) copper [CuCl (PPh ₃ ) ₃ ] in an amount such that the metal concentration became 7.5 ppm by weight. Was subjected to decomposition of cyclohexyl hydroperoxide (CHP) for 90 minutes, and the reaction solution was analyzed. As a result, the CHP conversion was completely decomposed, the KA yield was 107.9%, and the K / A ratio (molar ratio) was 0.53.

Comparative Example 2 In Example 1, the catalyst was changed to copper chloride [CuCl] and added in such an amount that the metal concentration became 7.5 ppm by weight, and the decomposition of cyclohexyl hydroperoxide (CHP) was carried out in the same manner as in Example 1.
The reaction was analyzed for 90 minutes. As a result, CH
The P conversion was 48%, the KA yield was 102.5%, and the K / A ratio (molar ratio) was 0.87.

Examples 3 to 6 Cyclohexyl hydroperoxide (CHP) was decomposed in the same manner as in Example 1 except that the metal catalyst, its concentration and the reaction time were changed. Analysis was carried out. The results are summarized in Table 1.

[0022]

[Table 1]

[0023]

According to the present invention, cycloalkanol and cycloalkanone can be produced from cycloalkyl hydroperoxide with a high decomposition rate and a high yield by using a small amount of a highly active catalyst in the reaction system.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification code FI C07C 35/20 C07C 35/20 35/205 35/205 45/53 45/53 49/385 49/385 A 49/395 49 / 395 49/403 49/403 A 49/413 49/413 // C07B 61/00 300 C07B 61/00 300 (56) References JP-A-5-112486 (JP, A) JP-A 2-164836 (JP) JP-A-63-156735 (JP, A) JP-A-60-215639 (JP, A) JP-A-60-126237 (JP, A) JP-A-58-219132 (JP, A) 56-115729 (JP, A) JP-A-62-120337 (JP, A) JP-A-4-71646 (JP, A) U.S. Pat. No. 4,910,349 (US, A) (58) Fields investigated (Int. Cl. ⁷⁾ , DB name) C07C 27/00 310 C07C 35/02 C07C 35/06 C07C 35/08 C07C 35/20 C07C 35/205 C07C 45/53 C07C 49/385 C07C 49/395 C07C 49/403 C07C 49/413 C07B 61/00 30 0

Claims (1)

(57) [Claims] (1) a cycloalkyl hydroperoxide,
General formula _{(I) [MCl n (PR} 1 R 2 R 3) m] (I) ( wherein, M represents iron, cobalt, nickel or copper, R
¹ , R ² and R ³ represent an aryl group. n is 1 or 2,
m shows the integer of 1-3. A method for producing cycloalkanol and cycloalkanone, which is decomposed in the presence of a metal complex represented by the formula (1).