CN106045803A - Environment-friendly bionic catalytic nitration method for phenolic compound - Google Patents
Environment-friendly bionic catalytic nitration method for phenolic compound Download PDFInfo
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- CN106045803A CN106045803A CN201610352503.4A CN201610352503A CN106045803A CN 106045803 A CN106045803 A CN 106045803A CN 201610352503 A CN201610352503 A CN 201610352503A CN 106045803 A CN106045803 A CN 106045803A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
- C07B43/00—Formation or introduction of functional groups containing nitrogen
- C07B43/02—Formation or introduction of functional groups containing nitrogen of nitro or nitroso groups
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C201/00—Preparation of esters of nitric or nitrous acid or of compounds containing nitro or nitroso groups bound to a carbon skeleton
- C07C201/06—Preparation of nitro compounds
- C07C201/08—Preparation of nitro compounds by substitution of hydrogen atoms by nitro groups
Abstract
The invention discloses an environment-friendly bionic catalytic nitration method for a phenolic compound and belongs to the technical field of organic synthesis. The method provided by the invention comprises the steps of dissolving the phenolic compound, which serves as a raw material, in a solvent at normal temperature, adding sodium nitrite into the solution, then, dropwise adding hydrogen peroxide into the reaction solution, adding metal-doped Al-MCM-41 molecular sieves into the reaction solution at normal temperature so as to start a reaction, carrying out stirring so as to carry out a nitration reaction, and then, carrying out suction filtration, organic solvent extraction, depressurized concentration and column chromatography separation, thereby obtaining a target product. According to the nitration method disclosed by the invention, the reaction conditions are mild, heating is not required, the operation is convenient, and the product is easy to treat. The nitration method is applicable to an environment-friendly bionic catalytic nitration reaction for phenolic compounds.
Description
Technical field
The present invention relates to the green bionic catalysis nitration method of a kind of phenolic compound, belong to technical field of organic synthesis.
Background technology
The nitration product of phenolic compound is important fine-chemical intermediate, should in fields such as chemicals, medicine, reagent
With extensively, if nitrophenol is a kind of widely used acid-base indicator and analytical reagent, it is the important of synthetic dyestuffs, medicine etc.
Intermediate.At present, the nitration processes comparative maturity of phenolic compound, but all there is certain defect in various technique.
Traditional nitration method of phenolic compound is with the mixture of nitric acid or nitric acid and sulphuric acid as nitrating agent, typically
Phenols and nitrating agent are reacted the mixture obtaining nitrophenol by organic solvent, but the selectivity of reaction is poor, phenol hydroxyl
Base and phenyl ring are easily oxidized to quinones, thus cause technical process to be difficult to control to and phenol by-product after nitrification is explosive
Fried danger, the yield of nitrophenol is relatively low and causes serious environmental pollution and equipment corrosion.
In order to solve the nitrification problem of phenolic compound, there are many relevant reports about this respect in recent years.In the world
Report such as, AgNO3/BF3、NaNO3/HNO3、CaNO3/ dense H2SO4, 100%HNO3/Ac2O/Cu(NO3)2/K10、Fe
(NO3)3·1.5N2O4/Cr(NO3)3·2N2O4/Cu(NO3)2·N2O4、N2O4/ 18-crown-6, Bi (NO3)3The catalytic nitrations such as/KSF
System (Olah, G.A.；Narang,S.C.；Olah,J.A.；Lammertsma,K.Proc.Nal.Aacad.Sci.,U.S.A
1982,4487；Thompson,M.J.；Zeeger,P.J.Tetrahedron,1991,47,8787；Bisarya,S.C.；
Joshi,S.K.；Holker,A.G.Synth.Commmun,1993,23(8),1125-1137；Gigante,B.；Prozeres,
A.O.；Marcelo-Curto,M.J.；Cornelis,A.；Laszlo,P.J.Org.Chem.,1995,3445-3447；
Firouzabadi,H.；Iranpoor,N.；Zolfigol,M.A.Synth.Commun.,1997,27(19),3301-3312；
Iranpoor,N.；Firouzabadi,H.；Zolfigol,M.A.Synth.Commun.,1998,28(15),2773；
Iranpoor,N.；Firouzabadi,H.；Heydari,R.Synth.Commun.,1999,29(19),3295-3302；
Susanta,S.；Frederick,F.B.；Bimal,K.B.；Tetrahedron,2000,41,8017-8020).At home, phase
Closing patent report such as, use nitric acid is nitrating agent, and slaine or metal oxide supported type catalyst are with in machine solvent
Carry out nitrification (CN 1410415A, CN 1709856A).But these methods above-mentioned need to use large excess of strong acid more, deposit
In serious acid pollution and the shortcoming of equipment corrosion, and reaction dissolvent mostly to be the toxicity such as anhydride, nitrile, aromatic hydrocarbons, furan bigger
Organic solvent, toxic and contaminative are more serious.Along with the research of green nitration, recently occur in that use ionic liquid is
Catalyst carry out nitration reaction (Earle, M.J., Katdare, S.P.Aromatic nitration reactions [P] .EP:
1324973,2005-06-14).Using inorganic salt, strong-acid ion exchange resin is catalyst or under ultrasonic/microwave state
Carry out nitration reaction.But there is equipment corrosion in these green nitration methods, acid capacity is little, cost is high and it is extensive raw to be difficult to
The shortcoming produced.Although prior art also has (CN 104987293 A) using enzyme to carry out nitration reaction, but still suffer from sample
The problem that yield is low.Although prior art there is also the green gentle nitration method utilizing Catalyzed Synthesis By Peroxidase nitrification,
But relatively costly due to enzyme so that nitrification cost is the highest, simultaneously as the condition such as temperature and acid-base value is required relatively by enzyme
High so that the application of the method is restricted.
Summary of the invention
For solving above-mentioned technical problem, the invention provides the bionical nitration method of green of a kind of phenolic compound, overcome
Seriously polluted, shortcoming, the technical scheme taked such as etching apparatus, condition be violent and product yield is low in prior synthesizing method
As follows:
It is an object of the invention to provide the green bionic catalysis nitration method of a kind of phenolic compound, be chemical combination of classifying
Thing is raw material, is dissolved in solvent by phenolic compound at normal temperatures, reacts at dropping hydrogen peroxide, startup after adding sodium nitrite
Rear stirring carries out nitration reaction, then utilizes the extraction of sucking filtration, organic solvent, concentrating under reduced pressure and column chromatography for separation to obtain target and produces
Thing, it is characterised in that after adding hydrogen peroxide, add metal-doped Al-MCM-41 molecular sieve at normal temperatures to start reaction.
Preferably, described metal-doped Al-MCM-41 molecular sieve is that Fe-Al-MCM-41 molecular sieve, Mg-Al-MCM-41 divide
Son sieve or Cu-Al-MCM-41 molecular sieve.
It is highly preferred that described Fe-Al-MCM-41 molecular sieve, Mg-Al-MCM-41 molecular sieve or Cu-Al-MCM-41 molecule
Sieve, Qi Zhongtie, magnesium and copper load capacity over a molecular sieve is 2%.
Preferably, the silica alumina ratio of described metal-doped Al-MCM-41 molecular sieve is 50.
Preferably, the addition of described metal-doped Al-MCM-41 molecular sieve is that every 1mmol phenolic compound adds
0.05g-0.06g。
The step of described method is as follows:
1) at normal temperatures phenolic compound is dissolved in the phosphate buffer of pH=7, according to phenolic compound and nitrous acid
The ratio of the amount of the material of sodium is that 1:50-1:60 adds sodium nitrite, it is thus achieved that reactant liquor；
2) it is 1:3-1:4 according to the ratio of the amount of phenolic compound and the material of hydrogen peroxide, by hydrogen peroxide in 15min
Instill step 1) gained reactant liquor in；
3) to step 2 under room temperature) gained solution adds metal-doped Al-MCM-41 molecular sieve start reaction, stirring, obtain
Obtain nitration product solution；
4) organic solvent extraction 3 is utilized) gained nitration product solution, carry out column chromatography for separation after concentrating under reduced pressure, obtain
Obtain target product.
Preferably, step 3) described metal-doped Al-MCM-41 molecular sieve is Fe-Al-MCM-41 molecular sieve, Mg-Al-
MCM-41 molecular sieve or Cu-Al-MCM-41 molecular sieve, by sodium silicate, aluminum sulfate, cetyl trimethylammonium bromide, slaine,
Deionized water passes through hydrothermal synthesis method, is dried and obtained by roasting；Described slaine is the halogenide of ferrum, magnesium or copper, ferrum, magnesium or
Copper doping load capacity in Al-MCM-41 molecular sieve is 2%；The silica alumina ratio of described Al-MCM-41 molecular sieve is 50.
Preferably, step 3) addition of described metal-doped Al-MCM-41 molecular sieve is 0.05-0.06g, mixing time
For 80min.
Preferably, step 4) described organic solvent, for ethyl acetate, chloroform or dichloromethane；Described column chromatography divides
From, it is with unmodified packed column, with petroleum ether and acetone as leacheate, the volume ratio of leacheate is from 1/50-50/1 modulation.
Preferably, described phenolic compound, for phenol or p-methyl phenol or resorcinol.
Described either method can application in the nitration product preparation process of phenolic compound.
Metal-doped Al-MCM-41 molecular sieve described in the nitration method of the present invention, for Fe-Al-MCM-41 molecular sieve,
Mg-Al-MCM-41 molecular sieve or Cu-Al-MCM-41 molecular sieve.
The beneficial effect that the present invention obtains:
1. the nitration method of the present invention is compared with tradition nitric acid nitrating method, with gentle sodium nitrite-hydrogen peroxide body
System replaces nitric acid, and corrosivity is substantially reduced, and reduces environmental pollution, it is to avoid concentration and recovery nitric acid is dangerous；With existing phenols
Compounds green nitration method is compared, with metal-doped Al-MCM-41 molecular sieve as catalyst, it is achieved that can be anti-under room temperature
Nitrophenol should be generated, improve the safety of operation.
2. the nitration method of the present invention is easy and simple to handle, environmental protection, non-corrosiveness, reaction condition is gentle, overcomes tradition
In synthetic method, seriously polluted, etching apparatus, the condition shortcoming such as acutely, also overcomes enzyme catalysis nitrification to thermo-responsive, steady simultaneously
Qualitative difference and expensive shortcoming.
3. the present invention uses the active center of metal-doped Al-MCM-41 molecular sieve Mimetic enzyme, carries out bionical
Catalytic nitration, it is not necessary to use expensive, the enzyme of easy in inactivation to make catalyst, both overcome enzyme catalysis nitrification to thermo-responsive, stable
Property poor and expensive shortcoming, overcome again seriously polluted in prior synthesizing method, etching apparatus, condition simultaneously and acutely etc. lack
Point, it is achieved the green bionic catalysis nitrification of phenolic compound.
Specific implementation method
Below in conjunction with specific embodiment, the present invention will be further described, but the present invention should not be limited by the examples.
Following example material therefor, reagent, instrument and method, without specified otherwise, be this area conventional material, examination
Agent, instrument and method, those skilled in the art all can be obtained by commercial channel.
Embodiment 1
Under room temperature, 1mmol phenol is dissolved in the phosphate buffer of 40mL pH=7, adds the nitrous acid of 50mmol
Sodium, is dissolved in the hydrogen peroxide of 3mmol in 10mL phosphate buffer, instills in reactant liquor, add under room temperature in 15min
0.05g Fe-Al-MCM-41 molecular sieve starts reaction, stirring reaction 80min.Sucking filtration, filtrate extracts by ethyl acetate (2 × 80mL)
Take, concentrating under reduced pressure, and column chromatography for separation (with unmodified packed column, with petroleum ether and acetone as leacheate, petroleum ether and acetone volume ratio
For 3:1) i.e. obtain target product onitrophenol, yield 38.9% (1H NMR(600MHz,DMSO-d6)δ10.92(s,1H),
7.88(s,1H),7.53(s,1H),7.13(s,1H),6.98(s,1H)；13C NMR(150MHz,DMSO-d6)δ152.52(s),
137.31(s),135.71(s),125.59(s),119.77(s),119.54(s)；HR-ESI-MS m/z:Calcd for
C6H4NO3{[M-H]-}: 138.0197, found 138.0195), and paranitrophenol, yield 37.5% (1H NMR(600MHz,
DMSO-d6) δ 11.03 (s, 1H), 8.12 (d, J=9.2Hz, 2H), 6.93 (d, J=9.2Hz, 2H)；13C NMR(150MHz,
DMSO-d6)δ164.37(s),140.07(s),126.62(s),116.23(s)；HR-ESI-MS m/z:Calcd for
C6H4NO3{[M-H]-}: 138.0197, found 138.0197), total recovery 76.4%.Under the same conditions, do not using
Molecular sieve but 0.05g use water solublity four (to carboxyl phenyl) iron porphyrin to start reaction.Result obtains the receipts of onitrophenol
Rate is 23.7%, and the yield of paranitrophenol is 21.5%, and total recovery is 45.2%.
Embodiment 2
Under room temperature, 1mmol phenol is dissolved in the phosphate buffer of 40mL pH=7, adds the nitrous acid of 60mmol
Sodium, is dissolved in the hydrogen peroxide of 3mmol in 10mL phosphate buffer, instills in reactant liquor, add under room temperature in 15min
0.06g Fe-Al-MCM-41 molecular sieve starts reaction, stirring reaction 80min.Sucking filtration, filtrate extracts by ethyl acetate (2 × 80mL)
Take, concentrating under reduced pressure, and column chromatography for separation (with unmodified packed column, with petroleum ether and acetone as leacheate, petroleum ether and acetone volume ratio
For 3:1, i.e. obtain target product onitrophenol, yield 42.0%, and paranitrophenol, yield 39.8%, total recovery
81.8%.Under the same conditions, molecular sieve is not being used but 0.06g use water solublity four (p-sulfonic acid sodio phenyl) ferrum porphin
Quinoline starts reaction.It is 27.3% that result obtains the yield of onitrophenol, and the yield of paranitrophenol is 28.8%, and total recovery is
56.1%.
Embodiment 3
Under room temperature, 1mmol phenol is dissolved in the phosphate buffer of 40mL pH=7, adds the nitrous acid of 60mmol
Sodium, is dissolved in the hydrogen peroxide of 4mmol in 10mL phosphate buffer, instills in reactant liquor, add under room temperature in 15min
0.06g Fe-Al-MCM-41 molecular sieve starts reaction, stirring reaction 80min.Sucking filtration, filtrate extracts by ethyl acetate (2 × 80mL)
Take, concentrating under reduced pressure, and column chromatography for separation (with unmodified packed column, with petroleum ether and acetone as leacheate, petroleum ether and acetone volume ratio
For 3:1, i.e. obtain target product onitrophenol, yield 41.1%, and paranitrophenol, yield 39.4%, total recovery
80.5%.Under the same conditions, molecular sieve is not being used but 0.06g use water solublity four (p-sulfonic acid sodio phenyl) ferrum porphin
Quinoline starts reaction.It is 26.9% that result obtains the yield of onitrophenol, and the yield of paranitrophenol is 27.8%, and total recovery is
54.7%.
Embodiment 4
Under room temperature, 1mmol phenol is dissolved in the phosphate buffer of 40mL pH=7, adds the nitrous acid of 50mmol
Sodium, is dissolved in the hydrogen peroxide of 3mmol in 10mL phosphate buffer, instills in reactant liquor, add under room temperature in 15min
0.05g Mg-Al-MCM-41 molecular sieve starts reaction, stirring reaction 80min.Sucking filtration, filtrate extracts with chloroform (2 × 80mL)
Take, concentrating under reduced pressure, and column chromatography for separation (with unmodified packed column, with petroleum ether and acetone as leacheate, petroleum ether and acetone volume ratio
For 3:1, i.e. obtain target product onitrophenol, yield 22.7%, and paranitrophenol, yield 28.2%, total recovery
50.9%.Under the same conditions, molecular sieve is not being used but 0.05g use water solublity four (p-sulfonic acid sodio phenyl) ferrum porphin
Quinoline starts reaction.It is 23.5% that result obtains the yield of onitrophenol, and the yield of paranitrophenol is 24.2%, and total recovery is
47.9%.
Embodiment 5
Under room temperature, 1mmol phenol is dissolved in the phosphate buffer of 40mL pH=7, adds the nitrous acid of 50mmol
Sodium, is dissolved in the hydrogen peroxide of 3mmol in 10mL phosphate buffer, instills in reactant liquor, add under room temperature in 15min
0.05g Cu-Al-MCM-41 molecular sieve starts reaction, stirring reaction 80min.Sucking filtration, filtrate extracts with dichloromethane (2 × 80mL)
Take, concentrating under reduced pressure, and column chromatography for separation (with unmodified packed column, with petroleum ether and acetone as leacheate, petroleum ether and acetone volume ratio
For 3:1, i.e. obtain target product onitrophenol, yield 20.7%, and paranitrophenol, yield 21.9%, total recovery
42.6%.Under the same conditions, molecular sieve is not being used but 0.05g use water solublity four (p-sulfonic acid sodio phenyl) ferrum porphin
Quinoline starts reaction.It is 23.8% that result obtains the yield of onitrophenol, and the yield of paranitrophenol is 24%, and total recovery is
47.8%.
Embodiment 6
Under room temperature, 1mmol p-methyl phenol is dissolved in the phosphate buffer of 40mL pH=7, adds the Asia of 50mmol
Sodium nitrate, is dissolved in the hydrogen peroxide of 3mmol in 10mL phosphate buffer, instills in reactant liquor, add under room temperature in 15min
0.05g Fe-Al-MCM-41 molecular sieve starts reaction, stirring reaction 80min.Sucking filtration, filtrate extracts by ethyl acetate (2 × 80mL)
Take, concentrating under reduced pressure, and column chromatography for separation (with unmodified packed column, with petroleum ether and acetone as leacheate, petroleum ether and acetone volume ratio
For 3:1) i.e. obtain target product neighbour's nitro p-cresol, yield 69.4% (1H NMR(600MHz,DMSO-d6)δ10.65(s,
1H), 7.70 (d, J=1.5Hz, 1H), 7.37 (dd, J=8.5,2.0Hz, 1H), 7.04 (d, J=8.5Hz, 1H), 2.27 (s,
3H)；13C NMR(150MHz,DMSO-d6)δ150.53(s),136.66(s),129.11(s),125.08(s),119.46(s),
20.00(s)；HR-ESI-MS m/z:Calcd for C7H6NO3{[M-H]-}:152.0253,found 152.0351)。
Embodiment 7
Under room temperature, 1mmol p-methyl phenol is dissolved in the phosphate buffer of 40mL pH=7, adds the Asia of 60mmol
Sodium nitrate, is dissolved in the hydrogen peroxide of 4mmol in 10mL phosphate buffer, instills in reactant liquor, add under room temperature in 15min
0.06g Fe-Al-MCM-41 molecular sieve starts reaction, stirring reaction 80min.Sucking filtration, filtrate extracts by ethyl acetate (2 × 80mL)
Take, concentrating under reduced pressure, and column chromatography for separation (with unmodified packed column, with petroleum ether and acetone as leacheate, petroleum ether and acetone volume ratio
For 3:1) i.e. obtain target product neighbour's nitro p-cresol, yield 75.5%.Under the same conditions, not using molecular sieve and
It is that 0.06g uses water solublity four (p-sulfonic acid sodio phenyl) iron porphyrin to start reaction.Result obtains the yield of onitrophenol
27.3%, the yield of paranitrophenol is 28.8%, and total recovery is 56.1%.
Embodiment 8
Under room temperature, 1mmol resorcinol is dissolved in the phosphate buffer of 40mL pH=7, adds the nitrous of 50mmol
Acid sodium, is dissolved in the hydrogen peroxide of 3mmol in 10mL phosphate buffer, instills in reactant liquor, add under room temperature in 15min
0.05g Fe-Al-MCM-41 molecular sieve starts reaction, stirring reaction 80min.Sucking filtration, filtrate extracts by ethyl acetate (2 × 80mL)
Take, concentrating under reduced pressure, and column chromatography for separation (with unmodified packed column, with petroleum ether and acetone as leacheate, petroleum ether and acetone volume ratio
For 1:1, i.e. obtain target product 2-nitro-resorcinol, yield 18.2% (1H NMR(600MHz,CDCl3)δ10.65(s,
2H), 7.43 (t, J=9.2Hz, 1H), 6.62 (d, J=2.5Hz, 2H)；13C NMR(150MHz,DMSO-d6)δ156.40(s),
138.92(s),124.06(s),109.51(s)；HR-ESI-MS m/z:Calcd for C6H4NO4{[M-H]-}:
154.0146, found154.0141), and 4-nitro-resorcinol, yield 18.0% (1H NMR(600MHz,CDCl3)δ10.98
(s, 2H), 8.07 (d, J=9.3Hz, 1H), 6.54 (d, J=2.5Hz, 1H), 6.49 (dd, J=9.3,2.5Hz, 1H)；13C
NMR(150MHz,DMSO-d6)δ165.0(s),156.0(s),128.0(s),127.7(s),108.8(s),103.6(s)；HR-
ESI-MS m/z:Calcd for C6H4NO4{[M-H]-}: 154.0146, found 154.0146), total recovery 36.2%.
Embodiment 9
Under room temperature, 1mmol resorcinol is dissolved in the phosphate buffer of 40mL pH=7, adds the nitrous of 60mmol
Acid sodium, is dissolved in the hydrogen peroxide of 4mmol in 10mL phosphate buffer, instills in reactant liquor, add under room temperature in 15min
0.06g Fe-Al-MCM-41 molecular sieve starts reaction, stirring reaction 80min.Sucking filtration, filtrate extracts by ethyl acetate (2 × 80mL)
Take, concentrating under reduced pressure, and column chromatography for separation (with unmodified packed column, with petroleum ether and acetone as leacheate, petroleum ether and acetone volume ratio
For 1:1, i.e. obtain target product 2-nitro-resorcinol, yield 27.4%, and 4-nitro-resorcinol, yield 23.5%, always
Yield 50.9%.Under the same conditions, molecular sieve is not being used but 0.06g use water solublity four (p-sulfonic acid sodio phenyl)
Iron porphyrin starts reaction.It is 9.9% that result obtains the yield of 2-nitro-resorcinol, and the yield of 4-nitro-resorcinol is
11.8%, total recovery is 21.7%.
Embodiment 10
In the present embodiment, inventor uses and compares experiment without aluminum, the MCM-41 molecular sieve of ferrum.Experiment process and
Result is as follows:
Under room temperature, 1mmol phenol is dissolved in the phosphate buffer of 40mL pH=7, adds the nitrous acid of 60mmol
Sodium, is dissolved in the hydrogen peroxide of 3mmol in 10mL phosphate buffer, instills in reactant liquor, add under room temperature in 15min
0.06g MCM-41 molecular sieve starts reaction, stirring reaction 80min.Sucking filtration, filtrate extracts by ethyl acetate (2 × 80mL), subtracts
Pressure concentrates, column chromatography for separation (with unmodified packed column, with petroleum ether and acetone as leacheate, petroleum ether and acetone volume ratio are 3:
1, do not obtain target product onitrophenol and paranitrophenol.
Embodiment 11
In the present embodiment, inventor uses nonferrous Al-MCM-41 molecular sieve to compare experiment, the sial of molecular sieve
Ratio is 50.Process and the result of experiment are as follows:
Under room temperature, 1mmol phenol is dissolved in the phosphate buffer of 40mL pH=7, adds the nitrous acid of 60mmol
Sodium, is dissolved in the hydrogen peroxide of 3mmol in 10mL phosphate buffer, instills in reactant liquor, add under room temperature in 15min
0.06g Al-MCM-41 molecular sieve starts reaction, stirring reaction 80min.Sucking filtration, filtrate extracts by ethyl acetate (2 × 80mL),
Concentrating under reduced pressure, (with unmodified packed column, with petroleum ether and acetone as leacheate, petroleum ether and acetone volume ratio are column chromatography for separation
3:1, i.e. obtains target product onitrophenol, yield 1.0%, and paranitrophenol, yield 1.9%, total recovery 2.9%.
Embodiment 12
In the present embodiment, inventor uses the Fe-MCM-41 molecular sieve without aluminum to compare experiment, and ferrum is in molecular sieve
Doping load capacity be 2%.Process and the result of experiment are as follows:
Under room temperature, 1mmol phenol is dissolved in the phosphate buffer of 40mL pH=7, adds the nitrous acid of 60mmol
Sodium, is dissolved in the hydrogen peroxide of 3mmol in 10mL phosphate buffer, instills in reactant liquor, add under room temperature in 15min
0.06g Fe-MCM-41 molecular sieve starts reaction, stirring reaction 80min.Sucking filtration, filtrate extracts by ethyl acetate (2 × 80mL),
Concentrating under reduced pressure, (with unmodified packed column, with petroleum ether and acetone as leacheate, petroleum ether and acetone volume ratio are column chromatography for separation
3:1, i.e. obtains target product onitrophenol, yield 15.0%, and paranitrophenol, yield 11.1%, total recovery 26.1%.
Embodiment 13
In the present embodiment, inventor uses Fe-Al-MMT molecular sieve to compare experiment, and ferrum doping in molecular sieve is born
Carrying capacity is 2%, and the silica alumina ratio of molecular sieve is 50.Process and the result of experiment are as follows:
Under room temperature, 1mmol phenol is dissolved in the phosphate buffer of 40mL pH=7, adds the nitrous acid of 60mmol
Sodium, is dissolved in the hydrogen peroxide of 3mmol in 10mL phosphate buffer, instills in reactant liquor, add under room temperature in 15min
0.06g Fe-Al-MMT molecular sieve starts reaction, stirring reaction 80min.Sucking filtration, filtrate extracts by ethyl acetate (2 × 80mL),
Concentrating under reduced pressure, (with unmodified packed column, with petroleum ether and acetone as leacheate, petroleum ether and acetone volume ratio are column chromatography for separation
3:1, i.e. obtains target product onitrophenol, yield 10.2%, and paranitrophenol, yield 9.4%, total recovery 19.6%.
Embodiment 14
In the present embodiment, inventor uses Fe-Al-SBA-15 molecular sieve to compare experiment, ferrum mixing in molecular sieve
Miscellaneous load capacity is 2%, and the silica alumina ratio of molecular sieve is 50.Process and the result of experiment are as follows:
Under room temperature, 1mmol phenol is dissolved in the phosphate buffer of 40mL pH=7, adds the nitrous acid of 60mmol
Sodium, is dissolved in the hydrogen peroxide of 3mmol in 10mL phosphate buffer, instills in reactant liquor, add under room temperature in 15min
0.06g Fe-Al-SBA-15 molecular sieve starts reaction, stirring reaction 80min.Sucking filtration, filtrate extracts by ethyl acetate (2 × 80mL)
Take, concentrating under reduced pressure, and column chromatography for separation (with unmodified packed column, with petroleum ether and acetone as leacheate, petroleum ether and acetone volume ratio
For 3:1, i.e. obtain target product onitrophenol, yield 11.7%, and paranitrophenol, yield 16.7%, total recovery
28.4%.
Although the present invention is open the most as above with preferred embodiment, but it is not limited to the present invention, any is familiar with this
The people of technology, without departing from the spirit and scope of the present invention, can do various change and modification, the therefore protection of the present invention
Scope should be with being as the criterion that claims are defined.
Claims (10)
1. a green bionic catalysis nitration method for phenolic compound, is with compound of classifying as raw material, at normal temperatures by phenol
Compounds is dissolved in solvent, and after adding sodium nitrite, after dropping hydrogen peroxide, startup reaction, stirring carries out nitration reaction, so
After utilize the extraction of sucking filtration, organic solvent, concentrating under reduced pressure and column chromatography for separation to obtain target product, it is characterised in that adding
After hydrogen oxide, add metal-doped Al-MCM-41 molecular sieve at normal temperatures to start reaction.
Method the most according to claim 1, it is characterised in that described metal-doped Al-MCM-41 molecular sieve is Fe-Al-
MCM-41 molecular sieve, Mg-Al-MCM-41 molecular sieve or Cu-Al-MCM-41 molecular sieve.
Method the most according to claim 2, it is characterised in that described Fe-Al-MCM-41 molecular sieve, Mg-Al-MCM-41
Molecular sieve or Cu-Al-MCM-41 molecular sieve, Qi Zhongtie, magnesium and copper load capacity over a molecular sieve is 2%.
Method the most according to claim 1, it is characterised in that the silica alumina ratio of described metal-doped Al-MCM-41 molecular sieve
It is 50.
Method the most according to claim 1, it is characterised in that the addition of described metal-doped Al-MCM-41 molecular sieve
0.05g-0.06g is added for every 1mmol phenolic compound.
Method the most according to claim 1, it is characterised in that step is as follows:
1) at normal temperatures phenolic compound is dissolved in the phosphate buffer of pH=7, according to phenolic compound and sodium nitrite
The ratio of the amount of material is that 1:50-1:60 adds sodium nitrite, it is thus achieved that reactant liquor；
2) it is 1:3-1:4 according to the ratio of the amount of phenolic compound and the material of hydrogen peroxide, hydrogen peroxide is instilled in 15min
Step 1) gained reactant liquor in；
3) to step 2 under room temperature) gained solution adds metal-doped Al-MCM-41 molecular sieve start reaction, stirring, it is thus achieved that nitre
Change reaction mixture；
4) organic solvent extraction 3 is utilized) gained nitration product solution, carry out column chromatography for separation after concentrating under reduced pressure, it is thus achieved that mesh
Mark product.
Method the most according to claim 1, it is characterised in that step 3) described metal-doped Al-MCM-41 molecular sieve is
Fe-Al-MCM-41 molecular sieve, Mg-Al-MCM-41 molecular sieve or Cu-Al-MCM-41 molecular sieve, by sodium silicate, aluminum sulfate, ten
Six alkyl trimethyl ammonium bromides, slaine, deionized water pass through hydrothermal synthesis method, are dried and obtained by roasting；Described slaine
For the halogenide of ferrum, magnesium or copper, ferrum, magnesium or the copper doping load capacity in Al-MCM-41 molecular sieve is 2%；Described Al-MCM-
The silica alumina ratio of 41 molecular sieves is 50.
Method the most according to claim 1, it is characterised in that step 3) described metal-doped Al-MCM-41 molecular sieve
Addition is every 1mmol phenolic compound 0.05-0.06g, and mixing time is 80min.
Method the most according to claim 1, it is characterised in that step 4) described organic solvent, for ethyl acetate, three chloromethanes
Alkane or dichloromethane；Described column chromatography for separation, is with unmodified packed column, with petroleum ether and acetone as leacheate, and the body of leacheate
Long-pending ratio is from 1/50-50/1 modulation.
10. the application in the nitration product preparation process of phenolic compound of the either method described in claim 1-9.
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| CN112094182A (en) * | 2020-09-22 | 2020-12-18 | 中国海洋大学 | Green synthesis method of medical intermediate benzocyclohexanone compound |
| CN117865811A (en) * | 2024-03-11 | 2024-04-12 | 山东道可化学有限公司 | Method for preparing nitrobenzotrifluoride by continuously nitrifying benzotrifluoride |
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