CN103664630A - Method for using metalloporphyrin to catalyze and oxidize o-nitroethylbenzene to prepare alpha-o-nitrobenzene ethanol - Google Patents

Abstract

The invention relates to a method for preparing α-o-nitrophenylethanol by catalyzing the oxidation of o-nitroethylbenzene by metalloporphyrin. The method uses o-nitroethylbenzene as a raw material, oxygen as an oxidant, and under normal pressure and solvent-free conditions, selects 5-60 ppm of mononuclear metalloporphyrin or μ-oxygen-binuclear metalloporphyrin as a catalyst, and the temperature is 100-160 Reaction at ℃ for 1 to 12 hours to obtain α-o-nitrophenylethanol. This method uses the metal porphyrin compound which is environmentally friendly and uses a very small amount of metal porphyrin compound as a catalyst, which not only eliminates the problem of difficult treatment of salty wastewater and equipment corrosion caused by the use of acetate catalysts in other methods, but also makes α-o-nitrobenzene The selectivity of ethanol reaches 45.0%. The method does not use solvents and free radical initiators, which not only greatly reduces the cost of product preparation, but also avoids the problem of environmental pollution caused by the use of solvents and the problem of high energy consumption required for solvent recovery, so that it has industrial advantages Broad application prospects.

Description

Method for preparing α-o-nitrophenylethanol by metalloporphyrin catalyzed oxidation of o-nitroethylbenzene

technical field

The invention relates to a method for preparing aromatic alcohols, in particular to a method for preparing α-o-nitrophenylethanol by catalyzing the oxidation of o-nitroethylbenzene by metalloporphyrins.

Background technique

α-Nitrophenylethanol is an important intermediate in organic synthesis, widely used in the synthesis of medicines, spices, coatings, textile industry, photosensitive materials, etc. At present, the preparation methods of α-o-nitrophenylethanol mainly include the reduction method of acetophenone derivatives and the oxidation method of ethylbenzene derivatives. Oxygen oxidation of o-nitroethylbenzene to prepare α-o-nitrophenylethanol has the advantages of good atom economy, short process, simple operation, readily available raw materials, and simple separation. Compared with other synthetic methods, it has broader industrial application prospects.

Fatemeh Rajabi et al. (Catalysis Communication, 2011.12(6):4-4) reported a method for the selective oxidation of ethylbenzene derivatives using silica-supported Co(II) as a catalyst. The method uses o-nitroethylbenzene as a raw material, in an acetic acid solvent, uses silica-supported Co(II) as a catalyst, N-hydroxyphthalimide as a free radical initiator, and feeds 1 atm of oxygen. After reacting for 12 hours, α-o-nitrophenylethanol was obtained, wherein the molar ratio of reactant, catalyst and free radical initiator was 200:1:20. The selectivity of α-o-nitrophenylethanol was 12%, and the yield was 8.5%.

The main disadvantages of this method are:

(1) The amount of catalyst used is very large (5000ppm), and a large amount of saline wastewater will be produced, which not only seriously pollutes the environment, but also corrodes the equipment;

(2) Not only the activity of the catalyst used is low, but also the selectivity of alcohol is low, only 12%;

(3) This method must use N-hydroxyphthalimide as a free radical initiator and acetic acid as a solvent, which not only corrodes the equipment, increases the cost of product preparation, but also causes serious environmental pollution and large separation energy. consumption.

Contents of the invention

The object of the present invention is to provide a method for preparing α-o-nitrophenylethanol by catalyzing the oxidation of o-nitroethylbenzene by metalloporphyrins with simple operation, low cost and environmental friendliness.

A kind of method that metalloporphyrin catalyzes oxidation o-nitroethylbenzene to prepare α-o-nitrophenylethanol provided by the present invention, its step is: take o-nitroethylbenzene as raw material, oxygen as oxidant, under normal pressure, no Under the condition of the solvent, the mononuclear metalloporphyrin represented by formula (I), formula (II) or the μ-oxygen-binuclear metalloporphyrin represented by formula (III) is selected as the catalyst, and the amount of catalyst is 5-60ppm. React at 160°C for 1 to 12 hours to obtain α-o-nitrophenylethanol,

Among them, M ₁ is iron, manganese, cobalt, copper or zinc, M ₂ is iron, manganese or cobalt, M ₃ and M ₄ are the same or different, when they are the same, they are all iron, manganese or cobalt, and when they are different, M ₃ is iron , M ₄ is manganese, M ₃ is iron, M ₄ is cobalt or M ₃ is manganese, M ₄ is cobalt, R ₁₁ , R ₁₂ , R ₁₃ , R 21 , R ₂₂ , R ₂₃ , _{R 31 ,} R ₃₂ or R ₃₃ is hydrogen, halogen, nitro, hydroxyl, methyl, methoxy or carboxyl, and ligand X is halogen.

Preferably _M1 is iron, manganese or cobalt.

Preferably _M2 is iron or manganese.

Preferably, M ₃ and M ₄ are iron, manganese or cobalt, and M ₃ and M ₄ are the same.

Preferably X is chlorine.

The preferred amount of catalyst used is 10 ppm.

The preferred reaction temperature is 120-140°C.

The preferred reaction time is 2 to 4 hours.

The oxygen flow rate is 20-60mL/min.

Compared with existing methods, the inventive method has the following beneficial effects:

(1) This method uses the metalloporphyrin compound which is environmentally friendly and used in a very small amount (5-60ppm) as a catalyst, which not only avoids the difficult treatment of saline wastewater and equipment corrosion caused by the large-scale use of acetate catalysts in other methods, And it can be degraded naturally in the environment without secondary pollution;

(2) This method uses metalloporphyrin as a catalyst, which has the characteristics of high activity and high selectivity similar to enzymes. The selectivity of α-o-nitrophenylethanol can reach 45.0%;

(3) This method does not use solvents and free radical initiators, which not only greatly reduces the cost of product preparation, but also avoids the problem of environmental pollution caused by the use of solvents and the problem of high energy consumption required for solvent recovery, so that it is widely used in industry has broad application prospects.

Detailed ways

Example 1

In a 100mL three-necked flask, add 15.4g of o-nitroethylbenzene, 1.0×10 ^-3 g of tetraphenylcobalt porphyrin chloride (i.e. in general formula (II), R ₂₁ is H, R ₂₂ is H, R ₂₃ is H, M ₂ is Co, X is Cl), at a flow rate of 40mL/min, 1atm oxygen is introduced, and the reaction is carried out at 150°C for 12h. After the reaction mixture was distilled under reduced pressure and ethanol recrystallized, the filtrate was taken to obtain α-o-nitrophenylethanol. According to liquid chromatography analysis, the selectivity of α-o-nitrophenylethanol was 31.6%, and the yield was 9.6%.

Example 2

In a 100mL three-necked flask, add 15.4g of o-nitroethylbenzene and 1.0×10 ^-3 g of tetrakis-(p-methylphenyl)iron porphyrin chloride (that is, R ₂₁ in general formula (II) is H, R ₂₂ is H, R ₂₃ is CH ₃ , M ₂ is Fe, X is Cl), at a flow rate of 40 mL/min, 1 atm of oxygen is introduced, and the reaction is carried out at 140°C for 10 h. After the reaction mixture was distilled under reduced pressure and ethanol recrystallized, the filtrate was taken to obtain α-o-nitrophenylethanol. Through liquid chromatography analysis, the selectivity of α-o-nitrophenylethanol was 32.3%, and the yield was 9.1%.

Example 3

In a 100mL three-necked flask, add 15.4g o-nitroethylbenzene and 1.0× ^{10 -3} g tetrakis-(p-methylphenyl)manganese porphyrin chloride (i.e. R ₂₁ in general formula (II) is H, R ₂₂ is H, R ₂₃ is CH ₃ , M ₂ is Mn, X is Cl), at a flow rate of 60 mL/min, 1 atm of oxygen is introduced, and the reaction is carried out at 140°C for 12 hours. After the reaction mixture was distilled under reduced pressure and ethanol recrystallized, the filtrate was taken to obtain α-o-nitrophenylethanol. According to liquid chromatography analysis, the selectivity of α-o-nitrophenylethanol was 37.8%, and the yield was 12.0%.

Example 4

In a 100mL three-necked flask, add 15.4g o-nitroethylbenzene, 1.0×10 ^-3 g tetrakis-(p-methoxyphenyl)copper porphyrin (that is, R ₁₁ in general formula (I) is H, R ₁₂ is H, R ₁₃ is OCH ₃ , M ₁ is Cu), feed 1 atm of oxygen at a flow rate of 40 mL/min, and react at 150°C for 12 hours. After the reaction mixture was distilled under reduced pressure and ethanol recrystallized, the filtrate was taken to obtain α-o-nitrophenylethanol. According to liquid chromatography analysis, the selectivity of α-o-nitrophenylethanol was 28.2%, and the yield was 10.4%.

Example 5

In a 100mL three-necked flask, add 15.4g of o-nitroethylbenzene, 1.0×10 ^-3 g of tetrakis-(p-methylphenyl) zinc porphyrin (that is, R ₁₁ in general formula (I) is H, R ₁₂ is H, R ₁₃ is CH ₃ , M ₁ is Zn), at a flow rate of 20mL/min, 1atm oxygen is introduced, and the reaction is carried out at 140°C for 12h. After the reaction mixture was distilled under reduced pressure and ethanol recrystallized, the filtrate was taken to obtain α-o-nitrophenylethanol. According to liquid chromatography analysis, the selectivity of α-o-nitrophenylethanol was 25.8%, and the yield was 2.9%.

Example 6

In a 100mL three-necked flask, add 15.4g of o-nitroethylbenzene and 1.0×10 ^-3 g of tetrakis-(p-nitrophenyl)manganese porphyrin (that is, R ₁₁ in general formula (I) is H, R ₁₂ is H, R ₁₃ is NO ₂ , M ₁ is Mn), feed 1 atm oxygen at a flow rate of 40 mL/min, and react at 140°C for 3 hours. After the reaction mixture was distilled under reduced pressure and ethanol recrystallized, the filtrate was taken to obtain α-o-nitrophenylethanol. According to liquid chromatography analysis, the selectivity of α-o-nitrophenylethanol was 45.0%, and the yield was 7.4%.

Example 7

In a 100mL three-necked flask, add 15.4g of o-nitroethylbenzene, 0.5×10 ^-3 g of tetrakis-(o-hydroxyphenyl)cobalt porphyrin chloride (that is, R ₂₁ in general formula (II) is OH, R ₂₂ is H, R ₂₃ is H, M ₂ is Co, X is Cl), feed 1 atm oxygen at a flow rate of 60 mL/min, and react at 150 °C for 12 h. After the reaction mixture was distilled under reduced pressure and ethanol recrystallized, the filtrate was taken to obtain α-o-nitrophenylethanol. According to liquid chromatography analysis, the selectivity of α-o-nitrophenylethanol was 29.3%, and the yield was 9.1%.

Example 8

In a 100mL three-necked flask, add 15.4g of o-nitroethylbenzene, 4.0×10 ^-3 g of tetrakis-(p-methoxyphenyl)cobalt porphyrin chloride (that is, R ₂₁ in general formula (II) is H , R ₂₂ is H, R ₂₃ is OCH ₃ , M ₂ is Co, X is Cl), at a flow rate of 40 mL/min, 1 atm of oxygen was introduced, and the reaction was carried out at 150°C for 12 hours. After the reaction mixture was distilled under reduced pressure and ethanol recrystallized, the filtrate was taken to obtain α-o-nitrophenylethanol. According to liquid chromatography analysis, the selectivity of α-o-nitrophenylethanol was 30.7%, and the yield was 7.7%.

Example 9

In a 100mL three-necked flask, add 15.4g o-nitroethylbenzene, 6.0×10 ^-3 g tetrakis-(p-carboxyphenyl)cobalt porphyrin chloride (i.e. R ₂₁ in general formula (II) is H, R ₂₂ is H, R ₂₃ is COOH, M ₂ is Co, X is Cl), feed 1 atm oxygen at a flow rate of 40 mL/min, and react at 150 °C for 12 h. After the reaction mixture was distilled under reduced pressure and ethanol recrystallized, the filtrate was taken to obtain α-o-nitrophenylethanol. According to liquid chromatography analysis, the selectivity of α-o-nitrophenylethanol was 27.7%, and the yield was 6.0%.

Example 10

In a 100mL three-necked flask, add 15.4g o-nitroethylbenzene, 1.0×10 ^-3 g tetrakis-(p-methoxyphenyl) manganese porphyrin (that is, R ₁₁ in general formula (I) is H, R ₁₂ is H, R ₁₃ is OCH ₃ , M ₁ is Mn), at a flow rate of 40 mL/min, 1 atm of oxygen is introduced, and the reaction is carried out at 150°C for 12 hours. After the reaction mixture was distilled under reduced pressure and ethanol recrystallized, the filtrate was taken to obtain α-o-nitrophenylethanol. Through liquid chromatography analysis, the selectivity of α-o-nitrophenylethanol was 37.9%, and the yield was 12.5%.

Example 11

In a 100mL three-necked flask, add 15.4g of o-nitroethylbenzene, 1.0×10 ^-3 g of tetraphenylmanganese porphyrin (that is, in general formula (I), R ₁₁ is H, R ₁₂ is H, R ₁₃ is H , M ₁ is Mn), 1atm oxygen was introduced at a flow rate of 60mL/min, and the reaction was carried out at 140°C for 4h. After the reaction mixture was distilled under reduced pressure and ethanol recrystallized, the filtrate was taken to obtain α-o-nitrophenylethanol. Through liquid chromatography analysis, the selectivity of α-o-nitrophenylethanol was 43.6%, and the yield was 8.4%.

Example 12

In a 100mL three-necked flask, add 15.4g of o-nitroethylbenzene, 1.0×10 ^-3 g of tetraphenylmanganese porphyrin (that is, in general formula (I), R ₁₁ is H, R ₁₂ is H, R ₁₃ is H , M ₁ is Mn), 1atm oxygen was introduced at a flow rate of 40mL/min, and the reaction was carried out at 140°C for 12h. After the reaction mixture was distilled under reduced pressure and ethanol recrystallized, the filtrate was taken to obtain α-o-nitrophenylethanol. Through liquid chromatography analysis, the selectivity of α-o-nitrophenylethanol was 36.7%, and the yield was 12.7%.

Example 13

In a 100mL three-necked flask, add 15.4g o-nitroethylbenzene, 1.0×10 ^-3 g tetrakis-(p-chlorophenyl)copper porphyrin (that is, in the general formula (I), R ₁₁ is H, R ₁₂ is H, R ₁₃ is Cl, M ₁ is Cu), feed 1 atm oxygen at a flow rate of 60 mL/min, and react at 140 °C for 6 h. After the reaction mixture was distilled under reduced pressure and ethanol recrystallized, the filtrate was taken to obtain α-o-nitrophenylethanol. Through liquid chromatography analysis, the selectivity of α-o-nitrophenylethanol is 27.7%, and the yield is 5.9%

Example 14

In a 100mL three-necked flask, add 15.4g of o-nitroethylbenzene, 1.0×10 ^-3 g of tetrakis-(p-hydroxyphenyl)manganese porphyrin chloride (i.e. R ₂₁ in general formula (II) is H, R ₂₂ is H, R ₂₃ is OH, M ₂ is Mn, X is Cl), at a flow rate of 40 mL/min, 1 atm of oxygen is introduced, and the reaction is carried out at 90°C for 12 hours. After the reaction mixture was distilled under reduced pressure and ethanol recrystallized, the filtrate was taken to obtain α-o-nitrophenylethanol. According to liquid chromatography analysis, the selectivity of α-o-nitrophenylethanol was 40.6%, and the yield was 7.8%.

Example 15

In a 100mL three-necked flask, add 15.4g o-nitroethylbenzene, 1.0×10 ^-3 g tetrakis-(p-carboxyphenyl)cobalt porphyrin chloride (i.e. R ₂₁ in general formula (II) is H, R ₂₂ is H, R ₂₃ is COOH, M ₂ is Co, X is Cl), feed 1 atm oxygen at a flow rate of 60 mL/min, and react at 160 °C for 12 h. After the reaction mixture was distilled under reduced pressure and ethanol recrystallized, the filtrate was taken to obtain α-o-nitrophenylethanol. According to liquid chromatography analysis, the selectivity of α-o-nitrophenylethanol was 33.6%, and the yield was 10.1%.

Example 16

In a 100mL three-necked flask, add 15.4g of o-nitroethylbenzene and 1.0×10 ^-3 g of tetrakis-(p-nitrophenyl)manganese porphyrin (that is, R ₁₁ in general formula (I) is H, R ₁₂ is H, R ₁₃ is NO ₂ , M ₁ is Mn), feed 1 atm oxygen at a flow rate of 40 mL/min, and react at 140°C for 1 h. After the reaction mixture was distilled under reduced pressure and ethanol recrystallized, the filtrate was taken to obtain α-o-nitrophenylethanol. Through liquid chromatography analysis, the selectivity of α-o-nitrophenylethanol is 39.8%, and the yield is 2.8%

Example 17

In a 100mL three-necked flask, add 15.4g o-nitroethylbenzene, 0.5×10 ^-3 g μ-oxygen-binuclear tetrakis-(p-nitrophenyl) manganese porphyrin (that is, R ₃₁ in general formula (Ⅲ) is H , R ₃₂ is H, R ₃₃ is NO ₂ , M ₃ and M ₄ are both Mn), and 1 atm of oxygen is introduced at a flow rate of 60 mL/min, and the reaction is carried out at 140°C for 8 hours. After the reaction mixture was distilled under reduced pressure and ethanol recrystallized, the filtrate was taken to obtain α-o-nitrophenylethanol. Through liquid chromatography analysis, the selectivity of α-o-nitrophenylethanol was 36.2%, and the yield was 9.3%.

Example 18

In a 100mL three-necked flask, add 15.4g o-nitroethylbenzene, 2.0×10 ^-3 gμ-oxygen-binuclear tetra-(m-nitrophenyl)iron-cobalt porphyrin (that is, R ₃₁ in general formula (Ⅲ) is H, R ₃₂ is NO ₂ , R ₃₃ is H, M ₃ is Fe, M ₄ is Co), feed 1 atm of oxygen at a flow rate of 40 mL/min, and react at 130°C for 12 hours. After the reaction mixture was distilled under reduced pressure and ethanol recrystallized, the filtrate was taken to obtain α-o-nitrophenylethanol. According to liquid chromatography analysis, the selectivity of α-o-nitrophenylethanol was 33.6%, and the yield was 8.9%.

Claims (8)

1. a catalysis of metalloporphyrin is oxidized the method that o-nitroethylbenzene is prepared α-o-nitrophenylethanol, the steps include: take that o-nitroethylbenzene is as raw material, oxygen is oxygenant, under normal pressure, condition of no solvent, select the monokaryon metalloporphyrin of formula (I), formula (II) expression or the μ-oxygen-dinuclear metalloporphyrin of formula (III) expression as catalyzer, catalyst levels is 5～60ppm, at 100～160 ℃, reacts 1～12h, obtain α-o-nitrophenylethanol

Wherein, M ₁for iron, manganese, cobalt, copper or zinc, M ₂for iron, manganese or cobalt, M ₃and M ₄identical or different, when identical, be iron, manganese or cobalt, when different, M ₃for iron, M ₄for manganese, M ₃for iron, M ₄for cobalt or M ₃for manganese, M ₄for cobalt, R ₁₁, R ₁₂, R ₁₃, R ₂₁, R ₂₂, R ₂₃, R ₃₁, R ₃₂, R ₃₃for hydrogen, halogen, nitro, hydroxyl, methyl, methoxyl group or carboxyl, dentate X is halogen.

2. according to the method for claim 1, it is characterized in that M ₁for iron, manganese or cobalt.

3. according to the method for claim 1, it is characterized in that M ₂for iron or manganese.

4. according to the method for claim 1, it is characterized in that M ₃, M ₄for iron, manganese or cobalt, M ₃and M ₄identical.

5. according to the method for claim 1, it is characterized in that X is chlorine.

6. according to the method for claim 1, it is characterized in that catalyst levels is 10ppm.

7. according to the method for claim 1, it is characterized in that temperature of reaction is 120～140 ℃.

8. according to the method for claim 1, it is characterized in that the reaction times is 2～4h.