CN1944395A - Process for preparing P-nitro benzoic acid by bionically catalystically oxidizing P-nitro toluene with oxygen - Google Patents
Process for preparing P-nitro benzoic acid by bionically catalystically oxidizing P-nitro toluene with oxygen Download PDFInfo
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- CN1944395A CN1944395A CN 200610114075 CN200610114075A CN1944395A CN 1944395 A CN1944395 A CN 1944395A CN 200610114075 CN200610114075 CN 200610114075 CN 200610114075 A CN200610114075 A CN 200610114075A CN 1944395 A CN1944395 A CN 1944395A
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- oxygen
- nitrotoluene
- ethanol
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- ZPTVNYMJQHSSEA-UHFFFAOYSA-N 4-nitrotoluene Chemical compound CC1=CC=C([N+]([O-])=O)C=C1 ZPTVNYMJQHSSEA-UHFFFAOYSA-N 0.000 title claims abstract description 38
- OTLNPYWUJOZPPA-UHFFFAOYSA-N 4-nitrobenzoic acid Chemical compound OC(=O)C1=CC=C([N+]([O-])=O)C=C1 OTLNPYWUJOZPPA-UHFFFAOYSA-N 0.000 title claims abstract description 37
- 230000001590 oxidative effect Effects 0.000 title claims abstract description 8
- 239000001301 oxygen Substances 0.000 title claims description 27
- 229910052760 oxygen Inorganic materials 0.000 title claims description 27
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 title claims description 23
- 238000004519 manufacturing process Methods 0.000 title abstract 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 93
- 238000000034 method Methods 0.000 claims abstract description 18
- 239000003054 catalyst Substances 0.000 claims abstract description 7
- 229910052751 metal Inorganic materials 0.000 claims abstract description 7
- 239000002184 metal Substances 0.000 claims abstract description 7
- IEQIEDJGQAUEQZ-UHFFFAOYSA-N phthalocyanine Chemical compound N1C(N=C2C3=CC=CC=C3C(N=C3C4=CC=CC=C4C(=N4)N3)=N2)=C(C=CC=C2)C2=C1N=C1C2=CC=CC=C2C4=N1 IEQIEDJGQAUEQZ-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000000243 solution Substances 0.000 claims description 31
- 238000006243 chemical reaction Methods 0.000 claims description 30
- 239000002904 solvent Substances 0.000 claims description 19
- 239000000460 chlorine Substances 0.000 claims description 17
- 229910052742 iron Inorganic materials 0.000 claims description 10
- 229910052748 manganese Inorganic materials 0.000 claims description 10
- 239000007864 aqueous solution Substances 0.000 claims description 8
- 229910052725 zinc Inorganic materials 0.000 claims description 5
- 229910052802 copper Inorganic materials 0.000 claims description 4
- 239000001257 hydrogen Substances 0.000 claims description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims description 4
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims description 4
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 3
- 239000002994 raw material Substances 0.000 claims description 3
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 2
- 125000003545 alkoxy group Chemical group 0.000 claims description 2
- 229910052801 chlorine Inorganic materials 0.000 claims description 2
- 229910052736 halogen Inorganic materials 0.000 claims description 2
- 150000002367 halogens Chemical class 0.000 claims description 2
- -1 nitro, hydroxyl Chemical group 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 150000003624 transition metals Chemical group 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 26
- 239000000463 material Substances 0.000 abstract description 2
- 231100000053 low toxicity Toxicity 0.000 abstract 1
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 63
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 33
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 21
- 239000000047 product Substances 0.000 description 21
- 238000004587 chromatography analysis Methods 0.000 description 17
- 239000007788 liquid Substances 0.000 description 17
- 238000012856 packing Methods 0.000 description 17
- 238000012805 post-processing Methods 0.000 description 16
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 14
- 238000007254 oxidation reaction Methods 0.000 description 9
- 230000003647 oxidation Effects 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 5
- 238000002360 preparation method Methods 0.000 description 5
- 239000011701 zinc Substances 0.000 description 5
- 230000003197 catalytic effect Effects 0.000 description 4
- 239000010949 copper Substances 0.000 description 4
- BXRFQSNOROATLV-UHFFFAOYSA-N 4-nitrobenzaldehyde Chemical compound [O-][N+](=O)C1=CC=C(C=O)C=C1 BXRFQSNOROATLV-UHFFFAOYSA-N 0.000 description 3
- NVJHHSJKESILSZ-UHFFFAOYSA-N [Co].N1C(C=C2N=C(C=C3NC(=C4)C=C3)C=C2)=CC=C1C=C1C=CC4=N1 Chemical compound [Co].N1C(C=C2N=C(C=C3NC(=C4)C=C3)C=C2)=CC=C1C=C1C=CC4=N1 NVJHHSJKESILSZ-UHFFFAOYSA-N 0.000 description 3
- MPMSMUBQXQALQI-UHFFFAOYSA-N cobalt phthalocyanine Chemical compound [Co+2].C12=CC=CC=C2C(N=C2[N-]C(C3=CC=CC=C32)=N2)=NC1=NC([C]1C=CC=CC1=1)=NC=1N=C1[C]3C=CC=CC3=C2[N-]1 MPMSMUBQXQALQI-UHFFFAOYSA-N 0.000 description 3
- 238000004880 explosion Methods 0.000 description 3
- 239000011664 nicotinic acid Substances 0.000 description 3
- 150000003254 radicals Chemical class 0.000 description 3
- KMHSUNDEGHRBNV-UHFFFAOYSA-N 2,4-dichloropyrimidine-5-carbonitrile Chemical compound ClC1=NC=C(C#N)C(Cl)=N1 KMHSUNDEGHRBNV-UHFFFAOYSA-N 0.000 description 2
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 2
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 description 2
- JQRLYSGCPHSLJI-UHFFFAOYSA-N [Fe].N1C(C=C2N=C(C=C3NC(=C4)C=C3)C=C2)=CC=C1C=C1C=CC4=N1 Chemical compound [Fe].N1C(C=C2N=C(C=C3NC(=C4)C=C3)C=C2)=CC=C1C=C1C=CC4=N1 JQRLYSGCPHSLJI-UHFFFAOYSA-N 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000013067 intermediate product Substances 0.000 description 2
- 231100000252 nontoxic Toxicity 0.000 description 2
- 230000003000 nontoxic effect Effects 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 231100000419 toxicity Toxicity 0.000 description 2
- 230000001988 toxicity Effects 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- NUSORQHHEXCNQC-UHFFFAOYSA-N [Cu].N1C(C=C2N=C(C=C3NC(=C4)C=C3)C=C2)=CC=C1C=C1C=CC4=N1 Chemical compound [Cu].N1C(C=C2N=C(C=C3NC(=C4)C=C3)C=C2)=CC=C1C=C1C=CC4=N1 NUSORQHHEXCNQC-UHFFFAOYSA-N 0.000 description 1
- HGAHKUKYEGQDDR-UHFFFAOYSA-N [Fe].[Co].N1C(C=C2N=C(C=C3NC(=C4)C=C3)C=C2)=CC=C1C=C1C=CC4=N1 Chemical compound [Fe].[Co].N1C(C=C2N=C(C=C3NC(=C4)C=C3)C=C2)=CC=C1C=C1C=CC4=N1 HGAHKUKYEGQDDR-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000003905 agrochemical Substances 0.000 description 1
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 229910001882 dioxygen Inorganic materials 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- RBTKNAXYKSUFRK-UHFFFAOYSA-N heliogen blue Chemical compound [Cu].[N-]1C2=C(C=CC=C3)C3=C1N=C([N-]1)C3=CC=CC=C3C1=NC([N-]1)=C(C=CC=C3)C3=C1N=C([N-]1)C3=CC=CC=C3C1=N2 RBTKNAXYKSUFRK-UHFFFAOYSA-N 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 150000004032 porphyrins Chemical class 0.000 description 1
- 238000007348 radical reaction Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000012453 solvate Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- 125000006158 tetracarboxylic acid group Chemical group 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 239000000273 veterinary drug Substances 0.000 description 1
- FUTVBRXUIKZACV-UHFFFAOYSA-J zinc;3-[18-(2-carboxylatoethyl)-8,13-bis(ethenyl)-3,7,12,17-tetramethylporphyrin-21,24-diid-2-yl]propanoate Chemical compound [Zn+2].[N-]1C2=C(C)C(CCC([O-])=O)=C1C=C([N-]1)C(CCC([O-])=O)=C(C)C1=CC(C(C)=C1C=C)=NC1=CC(C(C)=C1C=C)=NC1=C2 FUTVBRXUIKZACV-UHFFFAOYSA-J 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The present invention is bionically catalyzed p-nitro toluene oxidizing process for preparing p-nitro benzoic acid. In the process, p-nitro toluene material is oxidized with introduced O2 of 0.8-3.0 MPa pressure inside water solution of alcohol at 35-55 deg.c in the presence of metal phthalocyanine, monocuclear metalloporphyrin or mu-oxybinuclear metalloporphyrin catalyst in the amount of 0.01-1.0 wt% of p-nitro toluene for 2-14 hr to obtain p-nitro benzoic acid. The process of the present invention is simple and has low toxicity, high operation safety, high product yield and low cost.
Description
Technical field
The present invention relates to a kind of preparation method of aromatic acid, specifically, relate to the method that a kind of bionically catalyzing and oxidizing para-nitrotoluene prepares p-nitrobenzoic acid.
Background technology
P-nitrobenzoic acid is the important intermediate of preparation medicine, dyestuff, veterinary drug, sensitive materials, agricultural chemicals and high strength fibre and resin.The method of the synthetic p-nitrobenzoic acid of bibliographical information mainly is the oxygen catalytic oxidation method that adopts in alkaline medium at present.It is that solvent is selected metal phthalocyanine (Org.Process Res.Dev.2005 for use that people such as She Yuanbin have successively reported in alkaline medium with the anhydrous methanol, 9:297～301) or metalloporphyrin (Org.Process Res.Dev.2006,10 (4), 757-761) be the method for the synthetic p-nitrobenzoic acid of bionic catalyst catalyzed oxidation para-nitrotoluene, this method has solved problem such as synthetic existing equipment corrosion of p-nitrobenzoic acid and environmental pollution in acidic medium.(Granted publication day: on August 23rd, 2006) disclose a kind of method of the prepared in reaction of controlled oxidation selectively intermediate product paranitrobenzaldehyde, this method is under alkaline condition to be that to select metal phthalocyanine or metalloporphyrin for use be that bionic catalyst oxygen catalytic oxidation para-nitrotoluene prepares paranitrobenzaldehyde to solvent with the anhydrous methanol to Chinese patent CN 1271040C.But its weak point is no matter to be that all to adopt anhydrous methanol be solvent for preparation p-nitrobenzoic acid or preparation intermediate product paranitrobenzaldehyde, not only operation under the pure oxygen condition of anhydrous methanol (reaction or distillation) has the potential explosion hazard, and laboratory or industrial operation personnel's health is also had the potential threat.
Summary of the invention
The purpose of this invention is to provide a kind ofly almost do not have toxicity, operational safety, yield height, cost is low and the simple bionically catalyzing and oxidizing para-nitrotoluene of technology prepares the method for p-nitrobenzoic acid.
The technical solution adopted in the present invention is: be raw material with the para-nitrotoluene, select any in the μ-oxygen dinuclear metalloporphyrin of the monokaryon metalloporphyrin of metal phthalocyanine, general formula (II), (III) structure of general formula (I) structure or general formula (IV) structure for use as catalyzer, in the formula, M
1, M
2, M
3, M
4, M
5Be transition metal atoms, M
1=Fe, Co, Cu, Zn, M
2=Fe, Mn, Co, Cu, Zn, M
3=Fe, Mn, Co, M
4And M
5Can be identical, also can be different, when identical, M
4=M
5=Fe, Mn, Co, not simultaneously, M
4=Fe, M
5=Mn or M
4=Fe, M
5=Co, R are carboxyl or hydrogen, R
1, R
2Be hydrogen, halogen, nitro, hydroxyl, alkoxyl group, dentate X are chlorine, and catalyst consumption is 0.01～1.0% of a para-nitrotoluene weight, to contain ethanol 40～95% volume of ethanol aqueous solution is solvent, in 1～6mol/L strong basicity aqueous ethanolic solution, feed the oxygen of 0.8～3.0MPa, control reaction temperature is 35～55 ℃, reaction times 2～14h obtains p-nitrobenzoic acid.
Preferably have the monokaryon metalloporphyrin of general formula (III) structure or the μ-oxygen-dinuclear metalloporphyrin of general formula (IV) structure and make catalyzer.
Be preferably M in the general formula (III) especially
3=Mn or Fe, R
1=NO
2Or Cl, R
2=H, the monokaryon metalloporphyrin of X=Cl; M in the general formula (IV)
4And M
5When identical, M
4=M
5=Fe, Mn or Co, M
4And M
5Not not simultaneously, M
4=Fe, M
5=Mn, R
1=NO
2Or Cl, R
2μ-oxygen of=H-dinuclear metalloporphyrin.
The starting point concentration of above-mentioned para-nitrotoluene is 0.2～1.2mol/L.
General formula (I)
General formula (II)
General formula (III)
General formula (IV)
The present invention uses aqueous ethanolic solution as solvent, and preferably containing ethanol 50～70% volume of ethanol aqueous solution is solvent, not only safe, almost non-toxic, and inexpensive, be easy to get, reduced the preparation cost of target product.
Nearly all chemical research person thinks that oxygen or air oxidation reaction are free radical reactions, and the consistent process of thinking that only the effective control of ability is reacted in organic solvent, the oxidizing reaction of free radical type then is difficult to carry out in the aqueous solution, buries in oblivion agent because water is the free radical of generally acknowledging.In addition, because water dissolving raw material para-nitrotoluene effectively also can cause reaction effectively not carry out.The para-nitrotoluene of prior art report prepares in the reaction of p-nitrobenzoic acid, and the methanol solvate of use can generate the stronger sodium methylate of alkalescence with sodium hydroxide, thereby more favourable to reaction, so think that methyl alcohol is indispensable for this reaction.But because methyl alcohol exists serious toxic side effect and potential explosive issue.So it is solvent that the present invention adopts aqueous ethanolic solution to replace anhydrous methanol, the many technical problems that in reactant aqueous solution, exist have been solved, realized that not only the bionically catalyzing and oxidizing para-nitrotoluene produces p-nitrobenzoic acid, and broken the free-radical oxidn reaction and generally be difficult for the rule of in water, carrying out, make the reaction medium of para-nitrotoluene oxidation realize the leap from the organic solvent to the aqueous solution.And adopt aqueous ethanolic solution all to be higher than the product yield that original anhydrous methanol is a solvent as the product yield of solvent gained.
Table 1 is the comparison of methyl alcohol, ethanol and water-based energy parameter.Data in the table 1 show that the toxicity of ethanol and water is far below methyl alcohol; Its flash-point is all far above methyl alcohol, and limits of explosion all far is narrower than methyl alcohol, illustrates that aqueous ethanolic solution is a kind of safer, almost non-toxic solvent; The boiling point of second alcohol and water illustrates that all far above methyl alcohol the volatility of aqueous ethanolic solution is low, the loss few.Therefore, use ethanol, the danger when particularly adopting its aqueous solution to reduce reaction process and solvent recuperation greatly, and to the harm of workman and environment.
Table 2 is comparisons of synthetic p-nitrobenzoic acid yield in the different solvents.Data from table 2 as can be seen, all adopt the oxidation style in aqueous ethanolic solution involved in the present invention, its product yield is all apparently higher than the data of prior art and bibliographical information.
The present invention be with metal phthalocyanine class or metal porphyrins as bionic catalyst, (35～55 ℃) have realized that the oxygen catalytic oxidation para-nitrotoluene prepares p-nitrobenzoic acid under mild conditions.Experimental results show that: these catalyzer all have good catalytic performance to the reaction that the dioxygen oxidation para-nitrotoluene prepares p-nitrobenzoic acid.
Embodiment
Embodiment 1
Get 2mg cobalt phthalocyanine (be R=H in the general formula (I), M
1=Co), 1.4g para-nitrotoluene and 2g sodium hydroxide are in the 200mL autoclave of packing into, add aqueous ethanolic solution (95% ethanol: 22mL that contains ethanol 55% (V/V), water: 16mL) 38mL, feeding pressure is the oxygen of 2.0MPa, temperature control reacts 14h down for 40 ℃ in water-bath.Take a sample in the reaction back, and the reaction mixture suction filtration is removed catalyzer, adds 15mL distilled water then, with the dilute hydrochloric acid neutralization, filters.Products therefrom detects with high pressure liquid chromatographic analysis, and the yield of p-nitrobenzoic acid is 96.2%.
Embodiment 2
Get the 22mg iron-phthalocyanine (be R=H in the general formula (I), M
1=Fe), 6.3g para-nitrotoluene and 9.0g sodium hydroxide, in the 200mL autoclave of packing into, add the aqueous ethanolic solution contain ethanol 70% (V/V) (95% ethanol: 28mL, water: 10mL) 38mL, reaction pressure is 3.0MPa, temperature control is 35 ℃ in the water-bath, reaction 8h.Post-processing step is with embodiment 1, and products therefrom detects with high pressure liquid chromatographic analysis, and the yield of p-nitrobenzoic acid is 96.4%.
Embodiment 3
Get the 10mg copper phthalocyanine (be R=H in the general formula (I), M
1=Cu), 1.0g para-nitrotoluene and 2.5g sodium hydroxide, in the 200mL autoclave of packing into, add the aqueous ethanolic solution contain ethanol 75% (V/V) (95% ethanol: 30mL, water: 8mL) 38mL, oxygen pressure is 2.5MPa, temperature control is 40 ℃ in the water-bath, reaction 10h.Post-processing step is with embodiment 1, and products therefrom detects with high pressure liquid chromatographic analysis, and the yield of p-nitrobenzoic acid is 93.2%.
Embodiment 4
Get 10mg zinc phthalocyanine (be R=H in the general formula (I), M
1=Zn), 3.6g para-nitrotoluene and 6.8g sodium hydroxide, in the 200mL autoclave of packing into, add the aqueous ethanolic solution contain alcohol 95 % (V/V) (95% ethanol: 38mL, water: 0mL) 38mL, oxygen pressure is 2.0MPa, temperature control is 45 ℃ in the water-bath, reaction 2h.Post-processing step is with embodiment 1, and products therefrom detects with high pressure liquid chromatographic analysis, and the yield of p-nitrobenzoic acid is 92.8%.
Embodiment 5
Get 5.2mg tetracarboxylic cobalt phthalocyanine (be R=COOH in the general formula (I), M
1=Co), 2.2g para-nitrotoluene and 4.8g potassium hydroxide, in the autoclave of packing into, add the aqueous ethanolic solution contain ethanol 65% (V/V) (95% ethanol: 26mL, water: 20mL) 46mL, oxygen pressure is 0.8MPa, temperature control is 55 ℃ in the water-bath, reaction 9h.Post-processing step is with embodiment 1, and products therefrom detects with high pressure liquid chromatographic analysis, and the yield of p-nitrobenzoic acid is 96.0%.
Embodiment 6
Getting 2.0mg four-(rubigan) cobalt porphyrin (is R in the general formula (II)
1=H, R
2=Cl, M
2=Co), and 4.0g para-nitrotoluene and 9.1g sodium hydroxide, in the 200mL autoclave of packing into, (95% ethanol: 28mL, water: 10mL) 38mL, oxygen pressure are 2.5MPa, 55 ℃ of water-bath temperature controls, reaction 8h to add the aqueous ethanolic solution that contains ethanol 70% (V/V).Post-processing step is with embodiment 1, and products therefrom detects with high pressure liquid chromatographic analysis, and the yield of p-nitrobenzoic acid is 96.4%.
Embodiment 7
Getting 1.1mg four-(rubigan) iron porphyrin (is R in the general formula (II)
1=H, R
2=Cl, M
2=Fe), 2.2g para-nitrotoluene and 1.5g sodium hydroxide, in the 200mL autoclave of packing into, add the aqueous ethanolic solution contain ethanol 65% (V/V) (95% ethanol: 26mL, water: 20mL) 46mL, oxygen pressure is 0.8MPa, temperature control is 45 ℃ in the water-bath, reaction 10h.Post-processing step is with embodiment 1, and products therefrom detects with high pressure liquid chromatographic analysis, and the yield of p-nitrobenzoic acid is 96.6%.
Embodiment 8
Getting 1.0mg four-(p-hydroxybenzene) copper porphyrin (is R in the general formula (II)
1=H, R
2=OH, M
2=Cu),, 2.8g para-nitrotoluene and 3.5g potassium hydroxide, in the 200mL autoclave of packing into, add the aqueous ethanolic solution contain ethanol 40% (V/V) (95% ethanol: 16mL, water: 22mL) 38mL, oxygen pressure is 2.0MPa, temperature control is 40 ℃ in the water-bath, reaction 14h.Post-processing step is with embodiment 1, and products therefrom detects with high pressure liquid chromatographic analysis, and the yield of p-nitrobenzoic acid is 92.8%.
Embodiment 9
Getting 0.3mg four-(rubigan) manganoporphyrin (is R in the general formula (II)
1=H, R
2=Cl, M
2=Mn), 3.0g para-nitrotoluene and 3.2g sodium hydroxide are in the 200mL autoclave of packing into, add the aqueous ethanolic solution contain ethanol 50% (V/V) (95% ethanol: 20mL, water: 18mL) 38mL, feeding pressure is the oxygen of 2.0MPa, temperature control is 45 ℃ in the water-bath, reaction 12h.Post-processing step is with embodiment 1, and products therefrom detects with high pressure liquid chromatographic analysis, and the yield of p-nitrobenzoic acid is 96.0%.
Embodiment 10
Getting 1.2mg four-(rubigan) zinc protoporphyrin (is R in the general formula (II)
1=H, R
2=Cl, M
2=Zn), 1.1g para-nitrotoluene and 2.8g sodium hydroxide, in the 200mL autoclave of packing into, add the aqueous ethanolic solution contain ethanol 70% (V/V) (95% ethanol: 28mL, water: 10mL) 38mL, oxygen pressure is 2.0MPa, temperature control is 50 ℃ in the water-bath, reaction 9h.Post-processing step is with embodiment 1, and products therefrom detects with high pressure liquid chromatographic analysis, and the yield of p-nitrobenzoic acid is 96.1%.
Embodiment 11
Getting 4.1mg μ-oxygen-double-core four-(Chloro-O-Phenyl) cobalt porphyrin (is R in the general formula (IV)
1=Cl, R
2=H, M
4=M
5=Co), 2.1g para-nitrotoluene and 3.5g potassium hydroxide, in the 200mL autoclave of packing into, add the aqueous ethanolic solution contain ethanol 85% (V/V) (95% ethanol: 34mL, water: 4mL) 38mL, oxygen pressure is 1.8MPa, temperature control is 35 ℃ in the water-bath, reaction 8h.Post-processing step is with embodiment 1, and products therefrom detects with high pressure liquid chromatographic analysis, and the yield of p-nitrobenzoic acid is 93.0%.
Embodiment 12
Getting 2.0mg μ-oxygen-double-core four-(ortho-nitrophenyl base) manganoporphyrin (is R in the general formula (IV)
1=NO
2, R
2=H, M
4=M
5=Mn), 2.1g para-nitrotoluene and 5g potassium hydroxide, in the 200mL autoclave of packing into, add the aqueous ethanolic solution contain ethanol 70% (V/V) (95% ethanol: 28mL, water: 10mL) 38mL, oxygen pressure 2.0MPa, temperature control is 55 ℃ in the water-bath, reaction 6h.Post-processing step is with embodiment 1, and products therefrom detects with high pressure liquid chromatographic analysis, and the yield of p-nitrobenzoic acid is 96.2%.
Embodiment 13
Getting 1mg μ-oxygen-double-core four-(Chloro-O-Phenyl) manganoporphyrin (is R in the general formula (IV)
1=Cl, R
2=H, M
4=M
5=Mn), 1.4g para-nitrotoluene and 2.5g sodium hydroxide, in the 200mL autoclave of packing into, add the aqueous ethanolic solution contain ethanol 75% (V/V) (95% ethanol: 30mL, water: 8mL) 38mL, oxygen pressure 2.5MPa, temperature control is 45 ℃ in the water-bath, reaction 10h.Post-processing step is with embodiment 1, and products therefrom detects with high pressure liquid chromatographic analysis, and the yield of p-nitrobenzoic acid is 93.1%.
Embodiment 14
Getting 10mg μ-oxygen-double-core four-(Chloro-O-Phenyl) iron-cobalt porphyrin (is R in the general formula (IV)
1=Cl, R
2=H, M
4=Fe, M
5=Co), 2.8g para-nitrotoluene and 3.5g potassium hydroxide, in the 200mL autoclave of packing into, add the aqueous ethanolic solution contain ethanol 80% (V/V) (95% ethanol: 32mL, water: 6mL) 38mL, oxygen pressure is 2.5MPa, temperature control is 50 ℃ in the water-bath, reaction 8h.Post-processing step is with embodiment 1, and products therefrom detects with high pressure liquid chromatographic analysis, and the yield of p-nitrobenzoic acid is 93.5%.
Embodiment 15
Getting 14mg μ-oxygen-double-core four-(ortho-nitrophenyl base) iron-manganoporphyrin (is R in the general formula (IV)
1=NO
2, R
2=H, M
4=Fe, M
5=Mn), 1.4g para-nitrotoluene and 2.6g potassium hydroxide, in the 200mL autoclave of packing into, add the aqueous ethanolic solution contain ethanol 90% (V/V) (95% ethanol: 36mL, water: 6mL) 42mL, oxygen pressure 3.0MPa, temperature control is 45 ℃ in the water-bath, reaction 6h.Post-processing step is with embodiment 1.Products therefrom detects with high pressure liquid chromatographic analysis, and the yield of p-nitrobenzoic acid is 93.0%.
Embodiment 16
Getting 12mg μ-oxygen-double-core four-(Chloro-O-Phenyl) iron-manganoporphyrin (is R in the general formula (IV)
1=Cl, R
2=H, M
4=Fe, M
5=Mn), 2.8g para-nitrotoluene and 4.5g potassium hydroxide, in the 200mL autoclave of packing into, add the aqueous ethanolic solution contain ethanol 65% (V/V) (95% ethanol: 26mL, water: 20mL) 46mL, oxygen pressure 2.0MPa, temperature control is 45 ℃ in the water-bath, reaction 10h.Post-processing step is with embodiment 1.Products therefrom detects with high pressure liquid chromatographic analysis, and the yield of p-nitrobenzoic acid is 96.8%.
Embodiment 17
Getting 2mg μ-oxygen-double-core four-(Chloro-O-Phenyl) iron-manganoporphyrin (is R in the general formula (IV)
1=Cl, R
2=H, M
4=Fe, M
5=Mn), 1.5g para-nitrotoluene and 3.5g sodium hydroxide, in the 200mL autoclave of packing into, add the aqueous ethanolic solution contain ethanol 70% (V/V) (95% ethanol: 28mL, water: 10mL) 38mL, oxygen pressure 0.8MPa, temperature control is 35 ℃ in the water-bath, reaction 14h.Post-processing step is with embodiment 1.Products therefrom detects with high pressure liquid chromatographic analysis, and the yield of p-nitrobenzoic acid is 96.7%.
The comparison of table 1 solvent nature
| Solvent | Limits of explosion (%) | Flash-point (℃) | Fusing point (℃) | Boiling point (℃) | LD 50 (mg·kg -1) |
| Methyl alcohol | 5.50～36.00 | 12.22 | -97.80 | 64.65 | 5628 |
| Ethanol | 4.30～19.00 | 14.00 | -117.30 | 78.40 | 7060 |
| Water | - | - | 0 | 100 | - |
The comparison of synthetic p-nitrobenzoic acid yield in table 2 different solvents
| For example | Catalyst system therefor | Solvent | Yield (%) |
| Comparative Examples 1 | The cobalt phthalocyanine | Anhydrous methanol | 89.6 |
| Embodiment 1 | Aqueous ethanolic solution | 96.2 | |
| Comparative Examples 2 | Iron-phthalocyanine | Anhydrous methanol | 89.5 |
| Embodiment 2 | Aqueous ethanolic solution | 96.4 | |
| Comparative Examples 3 | Four-(rubigan) cobalt porphyrins | Anhydrous methanol | 90.0 |
| Embodiment 6 | Aqueous ethanolic solution | 96.4 | |
| Comparative Examples 4 | Four-(rubigan) iron porphyrins | Anhydrous methanol | 90.2 |
| Embodiment 7 | Aqueous ethanolic solution | 96.6 | |
| Comparative Examples 5 | μ-oxygen-double-core four-(Chloro-O-Phenyl) iron-manganoporphyrin | Anhydrous methanol | 90.8 |
| Embodiment 16 | Aqueous ethanolic solution | 96.8 |
Ratio 1～5 is a solvent with the anhydrous methanol, and its add-on is 38mL, and other step is with corresponding embodiment.
Claims (4)
1. a bionically catalyzing and oxidizing para-nitrotoluene prepares the method for p-nitrobenzoic acid, it is characterized in that with the para-nitrotoluene being raw material, μ-oxygen dinuclear metalloporphyrin of selecting the monokaryon metalloporphyrin of metal phthalocyanine, general formula (II), (III) structure of general formula (I) structure or general formula (IV) structure for use is as catalyzer, in the formula, M
1, M
2, M
3, M
4, M
5Be transition metal atoms, M
1=Fe, Co, Cu, Zn, M
2=Fe, Mn, Co, Cu, Zn, M
3=Fe, Mn, Co, M
4And M
5Can be identical, also can be different, when identical, M
4=M
5=Fe, Mn, Co, not simultaneously, M
4=Fe, M
5=Mn or M
4=Fe, M
5=Co, R are carboxyl or hydrogen, R
1, R
2Be hydrogen, halogen, nitro, hydroxyl, alkoxyl group, dentate X are chlorine, and catalyst consumption is 0.01～1.0% of a para-nitrotoluene weight, to contain ethanol 40～95% volume of ethanol aqueous solution is solvent, in 1～6mol/L strong basicity aqueous ethanolic solution, feed the oxygen of 0.8～3.0MPa, control reaction temperature is 35～55 ℃, reaction times 2～14h obtains p-nitrobenzoic acid.
General formula (I)
General formula (II)
General formula (III)
General formula (IV)
2. according to the method for claim 1, it is characterized in that to contain ethanol 50～70% volume of ethanol aqueous solution be solvent.
3. according to the method for claim 1 or 2, it is characterized in that selecting for use the monokaryon metalloporphyrin with general formula (III) structure or the μ-oxygen-dinuclear metalloporphyrin of general formula (IV) structure to make catalyzer.
4. according to any method in the claim 1～3, it is characterized in that selecting for use M in the general formula (III)
3=Mn or Fe, R
1=NO
2Or Cl, R
2=H, the monokaryon metalloporphyrin of X=Cl; M in the general formula (IV)
4And M
5When identical, M
4=M
5=Fe, Mn or Co, M
4And M
5Not not simultaneously, M
4=Fe, M
5=Mn, R
1=NO
2Or Cl, R
2μ-oxygen of=H-dinuclear metalloporphyrin is made catalyzer.
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