CN1247522C - Green nitration method of phenol type compound - Google Patents

Green nitration method of phenol type compound Download PDF

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CN1247522C
CN1247522C CN 02145268 CN02145268A CN1247522C CN 1247522 C CN1247522 C CN 1247522C CN 02145268 CN02145268 CN 02145268 CN 02145268 A CN02145268 A CN 02145268A CN 1247522 C CN1247522 C CN 1247522C
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phenol compound
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nitric acid
ksf
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CN1410415A (en
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施敏
崔世聪
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Shanghai Institute of Organic Chemistry of CAS
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Abstract

The present invention relates to a green nitration method for a phenol compound. Nitric acid and a phenol compound of which the molecular formula is RR1Z react for 0.5 to 20 hours at the temperature of 0 to 70 DEG C in an organic solvent when metal salt or a metal oxide load catalyst exists, wherein the molar ratio of the metal salt, the nitric acid and the phenol compound is 0.05 to 0.5: 1 to 2: 1. In the metal salt load catalyst, metal is oxide, halide or inorganic acid salt of the metal in the fourth, fifth or sixth main group. Montmorillonite KSF, a molecular sieve, silicon oxide, aluminum oxide or a mixture of two kinds of the oxide is used as a carrier, wherein R represents H, the alkyl of C1-5, halogen, or C6H5, R1 represents hydroxybenzene or a hydroxyl group, and Z represents phenyl, naphthyl, tetralyl, anthryl and flourenyl.

Description

The nitrifying method of phenol compound
Technical field
The present invention relates to a kind of organic chemistry synthetic method, specifically the green nitration method of phenol compound is the nitrifying method of the compound loaded type catalyst of a kind of fourth, fifth, six main group elements phenol compound.
Background technology
The nitration reaction of aromatics is the crucial chemical reaction of a class, and wherein the nitrated of phenol compound has important effect in fields such as industrial production and medicine are synthetic.For example, nitrophenol is a class carbon steel corrosion inhibitor, is the intermediate of medicine chlorzoxazone to the chlorine o-NP.The reduzate p-aminophenol of p-NP is the intermediate of medicines such as Paracetamol and clofibrate, also is applied to aspects such as photographic developer, antioxidant, the poly-agent of vinyl monomer group simultaneously.
Phenol compound is that a class is highly susceptible to nitrated compound, but that phenol compound itself is easy to again is oxidized, so certain difficulty is arranged in the selection of nitrifying method.As in industrial production, nitrophenols is generally all produced by indirect method, and mainly to be that phenol is direct oxidizing reaction easily takes place when nitrated for this, and the yield of nitration product is very low, and the oxidation products that generates is oily matter, makes product separation, the purifying difficulty that becomes.
In order to solve the nitrated problem of phenol compound, many research reports about this respect there is this year.Use AgNO 3/ BF 3Be nitrating agent, at CH 3Carry out nitration reaction (Olah, G.A. among the CN; Narang, S.C.; Olah, J.A.; Lammertsma, K.; Proc.Nal.Aacad.Sci., U.S.A 1982,4487).Use NaNO 3And HNO 3In aromatic solvent, carry out nitrated (Thompson, M.J. as nitrating agent; Zeeger, J.; Tetrahedron, 1991,47,8787).Use nitrocalcite to be nitrating agent, with nitrated (Bisarya, the S.C. of sulphuric acid catalysis phenol compound; Joshi, S.K.; Holker, A.G.; Synth.Commun., 1993,23 (8) 1125-1137).Use 100%HNO 3In acetic anhydride, with Cu (NO 3) 2/ K10 is that catalyzer carries out nitration reaction (Gigante, B.; Prozeres, A.O.; Marcelo-Curto, M.J.; Cornelis, A.; Laszlo, P.; J.Org.Chem., 1995,3445-3447).Use Fe (NO 3) 31.5N 2O 4, Cr (NO 3) 32N 2O 4And Cu (NO 3) 2N 2O 4For nitrating agent carries out nitrated (Firouzabadi, H.; Iranpoor, N.; Zolfigol, M.A.; Synth.Commun., 1997,27 (19), 3301-3312 and Iranpoor, N.; Firouzabadi, H.; Zolfigol, M.A.; Synth.Commun., 1998,28 (15), 2773-2781).Use N 2O 4Be nitrating agent, in 18-hat-6 solvents, carry out nitrated (Iranpoor, N.; Firouzabadi, H.; Heydari, R.; Synth.Commun., 1999,29 (19), 3295-3302).Use Bismuth trinitrate to be nitrating agent, covering the native KSF of holder is that catalyzer carries out nitrated (Susanta, S. in the THF solvent; Frederick, F.B.; Bimal, K.B.; Tetrahedron, 2000,41,8017-8020).
Summary of the invention
The green nitration method that the purpose of this invention is to provide a kind of phenol compound, the nitrifying method of the compound loaded type catalyst of specifically a kind of fourth, fifth, six main group elements phenol compound.
In the presence of the compound loaded type catalyzer of organic solvent neutralization fourth, fifth, six main group elements, nitric acid and molecular formula are RR 1The phenol compound of Z is 0.5-20 hour 0-70 ℃ of reaction, fourth, fifth, six main group element compounds wherein, nitric acid, phenol compound mol ratio are 0.05-0.5: 1-2: 1, with fourth, fifth, six main group element compounds, nitric acid, phenol compound mol ratio are 0.05-0.5: 1-2: 1 for good.The compound loaded type catalyzer of described wherein fourth, fifth, six main group elements is that fourth, fifth, six main group element compound 0.1mmol are carried on the carrier 500-2000mg R=H, C 1-5Alkyl, halogen, C 6H 5, R 1=phenolic hydroxyl group, Z=phenyl, naphthyl, tetralyl, anthryl, fluorenyl.
In research, find Bi (NO to nitration reaction 3) 3The native KSF of/illiteracy holder is a kind of good nitrated catalyzer.With Bi (NO 3) 3The native KSF of/illiteracy holder is nitrated catalyzer, with concentration is that 65% nitric acid is nitrating agent, used different solvents in the present invention, especially good with ether organic solvent, as reacting preferably in ether, glycol dimethyl ether, dioxane, tetrahydrofuran (THF) (THF) equal solvent, in ether solvent, Resorcinol is carried out nitratedly, obtained the nitrated productive rate more than 60%, reaction formula, reaction conditions and the results are shown in reaction formula 1 and table 1.
Reaction formula 1
Figure C0214526800041
Table 1 different organic solvents RightThe influence of Bi (NO3) 3/KSF catalysis Resorcinol nitration reaction
Sequence number Solvent Hour Productive rate (%)
1 2 3 4 5 6 7 Et 2O Et 2O THF THF dimethyl formamide sherwood oil EtOH 1.0 16 1.0 16 16 16 16 50 61 52 70 68 do not react
Under the identical in the present invention reaction conditions, concentration of nitric acid is 10-100%, and when concentration of nitric acid was reduced to 20%, this nitration reaction still can be carried out, and needs to amplify nitrated productive rate about about 50% but carrier covers the usage quantity of the native KSF of holder.When concentration of nitric acid brought up to 95%, when reacting down for 0 ℃, productive rate was 75%, and reaction at room temperature is comparatively violent, and by product is more, reaction formula, reaction conditions and partial results such as reaction formula 2 and table 2.
Reaction formula 2
Figure C0214526800051
Table 2. concentration of nitric acid is to B i(NO3) nitration reaction of 3/KSF catalysis Resorcinol influence
Sequence number Concentration of nitric acid, % The KSF consumption Productive rate (%)
1 2 3 4 5 60％ 60％ 60％ 20％ 20％ 500mg 500mg 500mg 1000mg 1500mg 61 60 71 53 50
On the other hand, be carried on the Bismuth trinitrate that covers on the native KSF of holder and can repeatedly reclaim repeated use, still have catalytic activity, and its recovery is very convenient, only need to filter the post-heating activation, promptly reusable.As in the table 2, sequence number 2-5 reclaims reusable catalyzer to carry out catalyzed reaction, through four recovery repeated experiments, has all obtained result preferably.
The compound loaded type catalyzer of fourth, fifth, six main group elements among the present invention, the oxide compound of described fourth, fifth, six main group elements or inorganic acid salt, as Ge, Sn, Pb, As, Sb, Bi, Se or Te, be catalyzer preferably with the oxide compound of bismuth and its inorganic acid salt wherein, its nitrated productive rate can reach more than 70%, and reaction formula, reaction conditions and result are as described in reaction formula 3 and the table 3.
Reaction formula 3
Figure C0214526800061
The nitration reaction influence of table 3. different metal/KSF catalysis Resorcinol
Sequence number Catalyzer Productive rate (%)
1 2 3 4 5 6 7 8 9 10 - Bi(NO 3) 3 Bi 2O 3 BiCl 3 SeO 2 Sb 2O 3 GeO 2 Sn(NO 3) 4 As 2O 3 PbCl 2 27 71 73 58 52 60 60 51 53 45
Different carriers affect is as described in reaction formula 4 and the table 4, wherein Bi (NO 3) 3/ SiO 2Under higher temperature, can react by catalytic nitration, but Bi (NO 3) 3/ cover and ask native KSF catalyzer at room temperature to have best effect.
Reaction formula 4
Figure C0214526800071
Table 4. nitration reaction of benzene diformazan between Bi (NO3) 3/ carrier catalysis that contains different carriers
Sequence number Carrier Temperature (℃) Productive rate (%)
1 2 3 4 5 6 7 8 - - KSF KSF KSF SiO 2 SiO 2The 4A molecular sieve Room temperature 70 room temperatures 50 70 room temperatures 50 50 Do not react 51 71 70 62 and do not react 75 10
Also tested its catalytic effect among the present invention to multiple substrate.Most of substrate all obtains nitration product with yield preferably, and wherein the nitrated productive rate of para-chlorophenol and p-tert-butylphenol reaches more than 95%, and partial results is seen reaction formula 5 and table 5.
Reaction formula 5
Table 5. Bi (NO 3) 3/KSF catalysis is to the influence of the nitration reaction of various substituted anilines
1) product: 2-nitrophenols (31%) and4-nitrophenols (35%).
2) product is 1,4-dimethoxy-2-nitro-benzene.
The nitrifying method of this phenol compound has many advantages.At first, this nitrifying method is to use the nitric acid of low concentration as nitrating agent, with respect to nitrosonitric acid and other nitrating agents comparatively economy and safety on producing.Simultaneously, Bismuth trinitrate and Meng Tuo soil KSF are common Chemicals, and reusable in nitration reaction, and it is convenient to reclaim.On the other hand, as solvent, its hazardness to environment is significantly less than halogenated alkane or nitroparaffins to this nitrifying method with ethers such as ether or tetrahydrofuran (THF)s.The most important thing is that the nitrated catalyzer environmentally safe that this digestion reaction uses is a kind of economy, green nitrated catalyzer.
So method of the present invention is the nitrifying method of a kind of economy, pollution-free green,
Embodiment
Following examples help to understand the present invention, but are not limited to content of the present invention.
Embodiment 1
To cover the native KSF of holder (500mg) and add reactor, heat the activation of bleeding.(solvent, 5mL), (165mg, 1.5mmol), (39mg 0.1mmol) adds reactor to Bismuth trinitrate to Resorcinol to tetrahydrofuran (THF), mixes.(0.15mL 2.1mmol), stirs 16h under the room temperature to the concentrated nitric acid of dropping 65%.Dichloromethane extraction is used in reaction mixture washing back, is spin-dried for, crosses post on Rotary Evaporators.Obtain yellow solid 170mg, productive rate 73%.4-nitro-resorcinol IR (KCl) ν 1532,1397cm -1(NO 2), 1255cm -1(ArOH); 1H-NMR (CDCl 3, TMS) δ 6.47 (1H, dd, J=9.2Hz, 3.4Hz, Ar), 6.52 (1H, d, J=3.4Hz, Ar), 8.05 (1H, d, J=9.2Hz, Ar), 10.97 (1H, s, ArOH); MS (EI) m/z 155 (M +) analytical value: 155.1082; Ultimate analysis C 6H 5NO 4, measured value: C, 46.48; H, 3.44; N, 9.02%.Calculated value: C, 46.46; H, 3.25; N, 9.03%.
Embodiment 2
To cover the native KSF of holder (1000mg) and add reactor, heat the activation of bleeding.(solvent, 5mL), (165mg, 1.5mmol), (39mg 0.1mmol) adds reactor to Bismuth trinitrate to Resorcinol to tetrahydrofuran (THF), mixes.(0.40mL 1.8mmol), stirs 16h under the room temperature to the concentrated nitric acid of dropping 20%.Dichloromethane extraction is used in reaction mixture washing back, is spin-dried for, crosses post on Rotary Evaporators.Obtain yellow solid 170mg, productive rate 56%.
Embodiment 3
To cover the native KSF of holder (500mg) and add reactor, heat the activation of bleeding.(solvent, 5mL), (165mg, 1.5mmol), (23mg 0.05mmol) adds reactor to bismuth oxide to Resorcinol to tetrahydrofuran (THF), mixes.(0.15mL 2.1mmol), stirs 16h under the room temperature to the concentrated nitric acid of dropping 65%.Dichloromethane extraction is used in reaction mixture washing back, is spin-dried for, crosses post on Rotary Evaporators.Obtain yellow solid 170mg, productive rate 73%.
Embodiment 4
To cover the native KSF of holder (500mg) and add reactor, heat the activation of bleeding.(solvent, 5mL), (165mg, 1.5mmol), (11mg 0.1mmol) adds reactor to selenium oxide to Resorcinol to tetrahydrofuran (THF), mixes.(0.15mL 2.1mmol), stirs 16h under the room temperature to the concentrated nitric acid of dropping 65%.Dichloromethane extraction is used in reaction mixture washing back, is spin-dried for, crosses post on Rotary Evaporators.Obtain yellow solid 120mg, productive rate 52%.
Embodiment 5
To cover the native KSF of holder (500mg) and add reactor, heat the activation of bleeding.(solvent, 5mL), (165mg, 1.5mmol), (30mg 0.1mmol) adds reactor to weisspiessglanz to Resorcinol to tetrahydrofuran (THF), mixes.(0.15mL 2.1mmol), stirs 16h under the room temperature to the concentrated nitric acid of dropping 65%.Dichloromethane extraction is used in reaction mixture washing back, is spin-dried for, crosses post on Rotary Evaporators.Obtain yellow solid 140mg, productive rate 60%.
Embodiment 6
To cover the native KSF of holder (500mg) and add reactor, heat the activation of bleeding.(solvent, 5mL), (165mg, 1.5mmol), (10mg 0.1mmol) adds reactor to germanium oxide to Resorcinol to tetrahydrofuran (THF), mixes.(0.15mL 2.1mmol), stirs 16h under the room temperature to the concentrated nitric acid of dropping 65%.Dichloromethane extraction is used in reaction mixture washing back, is spin-dried for, crosses post on Rotary Evaporators.Obtain yellow solid 139mg, productive rate 60%.
Embodiment 7
With SiO 2(500mg) add reactor.(solvent, 5mL), (165mg, 1.5mmol) (39mg 0.1mmol) adds reactor to Bismuth trinitrate to Resorcinol to tetrahydrofuran (THF), mixes.(0.15mL, 2.1mmol) oil bath is heated to 50 ℃ to the concentrated nitric acid of dropping 65%, stirs 16h.Dichloromethane extraction is used in reaction mixture washing back, is spin-dried for post on Rotary Evaporators.Obtain yellow solid 174mg, productive rate 75%.
Embodiment 8
To cover the native KSF of holder (500mg) and add reactor, heat the activation of bleeding.(solvent, 5mL), (0.13mL, 1.5mmol), (39mg 0.1mmol) adds reactor to Bismuth trinitrate to phenol to tetrahydrofuran (THF), mixes.(0.15mL 2.1mmol), stirs 30min under the room temperature to the concentrated nitric acid of dropping 65%.Dichloromethane extraction is used in reaction mixture washing back, is spin-dried for, crosses post on Rotary Evaporators.Obtain yellow liquid 65mg, productive rate 31%, 2-nitrophenols and faint yellow solid 102mg, productive rate 49%, 4-nitrophenols.2-nitrophenols: IR (KCl) ν 1522,1416cm -1(NO 2), 1240cm -1(ArOH); 1H-NMR (CDCl 3, TMS) δ 7.00 (1H, dt, J=7.5Hz, 1.5Hz, Ar), 7.16 (1H, d, J=7.4Hz, Ar), 7.59 (1H, dt, J=7.5Hz, 1.5Hz, Ar), 8.12 (1H, dd, J=7.5Hz, 1.5Hz, Ar), 10.60 (1H, s, ArOH); MS (EI) m/z 139 (M +) analytical value: 139.1088; 4-nitrophenols: IR (KCl) ν 1522,1416cm -1(NO 2), 1240cm -1(ArOH); 1H-NMR (CDCl 3, TMS) δ 6.08 (1H, s, ArOH), 6.92 (1H, dd, J=7.1Hz, 2.1Hz, Ar), 8.18 (1H, dd, J=7.1Hz, 2.0Hz, Ar); MS (EI) m/z 139 (M +) analytical value: 139.1088; Ultimate analysis C 6H 5NO 3, measured value: C, 51.73; H, 3.73; N, 10.04%, calculate: C, 51.80; H, 3.62; N, 10.07%.
Embodiment 9
To cover the native KSF of holder (500mg) and add reactor, heat the activation of bleeding.(solvent, 5mL), (1.0mL, 1.0mmol), (39mg 0.1mmol) adds reactor to Bismuth trinitrate to para-chlorophenol to tetrahydrofuran (THF), mixes.(0.1mL 1.4mmol), stirs 16h under the room temperature to the concentrated nitric acid of dropping 65%.Dichloromethane extraction is used in reaction mixture washing back, is spin-dried for, crosses post on Rotary Evaporators.Obtain yellow solid 170mg, productive rate 98%.2-nitro para-chlorophenol IR (KCl) ν 1522,1416cm -1(NO 2), 1240cm -1(ArOH); 1H-NMR (CDCl 3, TMS) δ 7.14 (1H, d, J=9.4Hz, Ar), 7.54 (1H, dd, J=9.4Hz, 2.5Hz, Ar), 8.11 (1H, d, J=2.5Hz, Ar), 10.48 (1H, s, ArOH); MS (EI) m/z 173 (M +) calculated value: 173.5536; Ultimate analysis C 6H 4ClNO 3, actual measurement: C, 41.58; H, 2.36; N, 8.10%, calculated value: C, 41.52; H, 2.32; N, 8.07%.
Embodiment 10
To cover the native KSF of holder (500mg) and add reactor, heat the activation of bleeding.(solvent, 5mL), (173mg, 1.0mmol), (39mg 0.1mmol) adds reactor to Bismuth trinitrate to p bromophenol to tetrahydrofuran (THF), mixes.(0.1mL 1.4mmol), stirs 16h under the room temperature to the concentrated nitric acid of dropping 65%.Dichloromethane extraction is used in reaction mixture washing back, is spin-dried for, crosses post on Rotary Evaporators.Obtain yellow solid 150mg, productive rate 70%.2-nitro p bromophenol IR (KCl) ν 1532,1412cm -1(NO 2), 1249cm -1(ArOH); 1H-NMR (CDCl 3, TMS) δ 7.08 (1H, d, J=9.2Hz, Ar), 7.67 (1H, dd, J=9.2Hz, 2.5Hz, Ar), 8.26 (1H, d, J=2.5Hz, Ar), 10.49 (1H, s, ArOH); MS (EI) m/z 219 (M +), calculated value: 218.0049; Ultimate analysis C 6H 4BrNO 3, measured value: C, 33.34; H, 2.08; N, 6.35%, calculated value: C, 33.06; H, 1.85; N, 6.42%.
Embodiment 11
To cover the native KSF of holder (500mg) and add reactor, heat the activation of bleeding.(solvent, 5mL), (150mg, 1.0mmol), (39mg 0.1mmol) adds reactor to Bismuth trinitrate to p-tert-butylphenol to tetrahydrofuran (THF), mixes.(0.15mL 2.1mmol), stirs 16h under the room temperature to the concentrated nitric acid of dropping 65%.Dichloromethane extraction is used in reaction mixture washing back, is spin-dried for, crosses post on Rotary Evaporators.Obtain yellow solid 90mg, productive rate 38%, 2,6-dinitrobenzene p-tert-butylphenol and yellow liquid 110mg, productive rate 56%, 2-nitro p-tert-butylphenol.2,6-dinitrobenzene p-tert-butylphenol IR (KCl) ν 1532,1367cm -1(NO 2), 1265cm -1(ArOH); 1H-NMR (CDCl 3, TMS) δ 1.37 (9H, s, CH 3), 8.32 (2H, s, Ar), 11.29 (1H, s, ArOH); MS (EI) m/z 240 (M +), calculated value: C 10H 12N 2O 5(240.2128)]; Ultimate analysis C 10H 12N 2O 5, measured value: C, 50.07; H, 5.06; N, 11.59%, calculated value: C, 50.00; H, 5.04; N, 11.66%.2-nitro p-tert-butylphenol IR (KCl) ν 1532,1397cm -1(NO 2), 1255cm -1(ArOH); 1H-NMR (CDCl 3, TMS) δ 1.33 (9H, s, CH 3), 7.11 (1H, d, J=9.8Hz, Ar), 7.65 (1H, dd, J=9.8Hz, 3.4Hz, Ar), 8.08 (1H, d, J=3.4Hz, Ar), 10.47 (1H, s, ArOH); MS (EI) m/z 195 (M +) analytical value: C 10H 13NO 3(195.2152); High resolution mass spectrum, calculated value: M, 195.0895, measured value: M +195.0899.
Embodiment 12
To cover the native KSF of holder (500mg) and add reactor, heat the activation of bleeding.(solvent, 5mL), (124mg, 1.0mmol), (39mg 0.1mmol) adds reactor to Bismuth trinitrate to p methoxy phenol to tetrahydrofuran (THF), mixes.(0.15mL 2.1mmol), stirs 16h under the room temperature to the concentrated nitric acid of dropping 65%.Dichloromethane extraction is used in reaction mixture washing back, is spin-dried for, crosses post on Rotary Evaporators.Obtain yellow solid 130mg, productive rate 71%.2,6-dinitrobenzene p methoxy phenol IR (KCl) ν 1537,1358cm -1(NO 2), 1243cm -1(ArOH); 1H-NMR (CDCl 3, TMS) δ 3.91 (3H, s, OCH 3), 7.86 (2H, s, Ar), 11.00 (1H, s, ArOH); MS (EI) m/z 214 (M +) analytical value: 214.1324; Ultimate analysis C 7H 6N 2O 6, calculated value: C, 39.26; H, 2.82; N, 13.08%, measured value: C, 39.38; H, 2.69; N, 12.87%.
Embodiment 13
To cover the native KSF of holder (500mg) and add reactor, heat the activation of bleeding.(solvent, 5mL), (138mg, 1.0mmol), (39mg 0.1mmol) adds reactor to Bismuth trinitrate to tetrahydrofuran (THF), mixes to the anisole methyl ether.(0.15mL 2.1mmol), stirs 16h under the room temperature to the concentrated nitric acid of dropping 65%.Dichloromethane extraction is used in reaction mixture washing back, is spin-dried for, crosses post on Rotary Evaporators.Obtain yellow solid 140mg, productive rate 76%.The 2-nitro is to anisole methyl ether IR (KCl) ν 1527,1354cm -1(NO 2); 1H-NMR (CDCl 3, TMS) δ 3.71 (3H, s, OCH 3), 3.81 (3H, s, OCH 3), 6.91 (1H, d, J=9.6Hz, Ar), 7.01 (1H, dd, J=9.6Hz, 3.1Hz, Ar), 7.28 (1H, d, J=9.6Hz, Ar); MS (EI) m/z 183 (M +) analytical value: 183.1614, ultimate analysis C 8H 9NO 4, measured value: C, 52.49; H, 4.95; N, 7.62%, calculated value: C, 52.46; H, 4.95; N, 7.65%.

Claims (6)

1, a kind of nitrifying method of phenol compound is characterized in that nitric acid and molecular formula are RR in the presence of the compound loaded type catalyzer of organic solvent neutralization fourth, fifth, six main group elements 1The phenol compound of Z was 0-70 ℃ of reaction 0.5-20 hour, wherein fourth, fifth, six main group element compounds, nitric acid, phenol compound mol ratio are 0.05-0.5: 1-2: 1, fourth, fifth, six main group element compounds are the oxide compound of fourth, fifth or six main group elements or their inorganic acid salt in the compound loaded type catalyzer of described fourth, fifth, six main group elements, R=H, C 1-5Alkyl, halogen or C 6H 5, R 1=phenolic hydroxyl group, Z=phenyl, naphthyl, tetralyl, anthryl or fluorenyl.
2, the nitrifying method of a kind of phenol compound as claimed in claim 1 is characterized in that fourth, fifth, six main group elements are Ge in the compound loaded type catalyzer of described fourth, fifth, six main group elements, Sn, Pb, As, Sb, Bi, Se or Te.
3, the nitrifying method of a kind of phenol compound as claimed in claim 1 is characterized in that described temperature of reaction is 0 a ℃-room temperature.
4, the nitrifying method of a kind of phenol compound as claimed in claim 1 is characterized in that described carrier is to cover holder native KSF, molecular sieve or SiO 2
5, the nitrifying method of a kind of phenol compound as claimed in claim 1 is characterized in that every 0.1mmol metal-salt is carried on the 500-2000mg carrier in the compound loaded type catalyzer of described fourth, fifth, six main group elements.
6, the nitrifying method of a kind of phenol compound as claimed in claim 1 is characterized in that described organic solvent is an ether organic solvent.
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