CN100358859C - Nitrofication method for catalysis of phenol and diphenyl ether compounds using metal salt - Google Patents
Nitrofication method for catalysis of phenol and diphenyl ether compounds using metal salt Download PDFInfo
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Abstract
The present invention relates to a nitration method of phenol and phenylate compounds of which the molecular formula is RR<1>R<2>R<3>Z. In the method, metal salt is used as catalysts; in organic solvents, nitric acid is used as nitrating agents, and the phenol and phenylate compounds are nitrified, wherein R<1>, R<2> or R<3>=H, C1-5 alkyl, halogen, phenolic hydroxyl, C1-5 alkoxyl group or C6 H5; R= phenolic hydroxyl or C1-5 alkoxyl group; Z= phenyl, naphthyl, tetralyl, anthracyl or flourenyl. The metal salt is nitrate of transitional metal, the third main group metal, the fourth main group metal or the fifth main group metal, hydrochloride, acetate, phosphate, sulfate, sulphonate, cyanate or double salt containing the metal ions. The nitric acid with lower concentration is used as the nitrating agents, so that the present invention has the advantages of economy and security on production, the catalysts are cheap and are easy to get; simultaneously, the metal salt can be reused in nitration reaction, the recovery is convenient, and the used nitration catalysts have no pollution to environment and are economical green nitration catalysts.
Description
Technical field
The present invention relates to a class nitrifying method, particularly relate to the nitrifying method of metal-salt catalysis of phenol class and phenyl ether compound.
Background technology
The nitration reaction of aromatics is the crucial chemical reaction of a class, and wherein the nitrated of phenol and phenyl ether 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, vinyl monomer stopper simultaneously.
Phenol and phenyl ether compound are that a class is highly susceptible to nitrated compound, but that phenol and phenyl ether 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 and phenyl ether compound, many research reports about this respect are arranged in recent years.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, P.J.Tetrahedron, 1991,47,8787).Use nitrocalcite to be nitrating agent, with nitrated (Bisarya, the S.C. of sulphuric acid catalysis phenol and phenyl ether 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).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, KSF is that catalyzer carries out nitrated (Susanta, S. in the THF solvent; Frederick, F.B.; Bimal, K.B.Tetrahedron, 2000,41,8017-8020).
The contriver in research to nitration reaction, once with KSF as the nitrated catalyzer of phenolic compound, have preferably actively, in order to investigate the stability of KSF to water and acid, water and diluted acid are handled KSF respectively, embathe the unstable component among the KSF.KSF after the processing loses catalytic activity, and the KSF that filters out embathes liquid and obtains white solid through underpressure distillation, and KSF, the KSF that handled and KSF extract are done elementary composition analysis respectively, and it is not obvious to find that KSF handles the elementary composition variation in front and back, contain K in the extract, Ca, Mg, Al, Si, Sc, Ti, Zr, V, Cr, Mn, Fe, Co, Ni, metallic elements such as Cu.Based on above result, the contriver thinks that what play katalysis in the process of catalytic nitration is the salt compounds of these metallic elements, therefore attempts with the salt of these metals nitration reaction as the catalyst phenolic compound.Experimental result has confirmed contriver's conclusion, nearly all transition metal salt and III, IV or V main group metal salt can be as the catalyzer of phenolic compound nitration reaction, and most of metal is metal cheap and easy to get, wherein has only a few metals that certain toxicity is arranged.
Summary of the invention
The problem to be solved in the present invention provides the new nitrifying method of a kind of phenol and phenyl ether compound.
The present invention is the new nitrifying method of a kind of phenol and phenyl ether compound, adopts metal-salt directly to carry out nitrated as catalyzer.Specifically, in organic solvent, be nitrated catalyzer with the salt of metal, with nitric acid nitrating agent, Pyrogentisinic Acid's class and phenyl ether compound carry out nitrated.
Metal-salt described in the present invention is nitrate, hydrochloride, acetate, phosphoric acid salt, vitriol, sulfonate, the cyanate of transition metal, III, IV or V main group metal or the double salt that contains above metal ion.Above-mentioned metal-salt or double salt can be the salt or the double salt of metals such as Sc, Ce, Ti, Zr, V, Mo, Cr, Mn, Fe, Co, Ni, Cu, Zn, Al, In, Sn or Bi; Described organic solvent is recommended as ether, further is recommended as tetrahydrofuran (THF), ether etc.; Described nitric acid is 20～100% nitric acid, is recommended as 20～80% nitric acid, further is recommended as 30～70% nitric acid; Described phenol and phenyl ether compound molecular formula are RR
1R
2R
3Z, wherein, R=phenolic hydroxyl group or C
1-5Alkoxyl group, R
1, R
2Or R
3=H, C
1-5Alkyl, halogen, phenolic hydroxyl group, C
1-5Alkoxyl group or C
6H
5, Z=phenyl, naphthyl, tetralyl, anthryl or fluorenyl, described phenol and phenyl ether compound are recommended as phenol, Resorcinol, Resorcinol or p-tert-butylphenol etc.
Catalyst consumption is the metal ion metering mol ratio 1: 0.01～0.5 with phenol and phenyl ether compound and metal-salt or double salt in the inventive method, further be recommended as 1: 0.03～0.1, temperature range is at 0～100 ℃, further be recommended as 20～60 ℃, reaction times is 0.5～24 hour, further is recommended as 1～12 hour.The mol ratio of above-mentioned phenol and phenyl ether compound and nitric acid is recommended as 1: 0.1～and 10, further be recommended as 1: 1～2.
In experiment, used different solvents, especially at ether solvent, as reacting (Fig. 1 and form 1) preferably in ether, tetrahydrofuran (THF) (THF) equal solvent.And in methylene dichloride, Nitromethane 99Min. equal solvent, the productive rate of nitration reaction is very low.According to the difference of reaction substrate, the reaction times can be selected between 0.5-24 hour flexibly.
Fig. 1.
The nitration reaction of form 1. iron nitrate catalysis Resorcinos, the selection in solvent and reaction times.
| Sequence number | Solvent | Time (h) | Yield (%) a |
| 1 | |||
| 1 2 3 4 5 6 7 8 9 | Ether ether ether oxolane oxolane oxolane glycol dimethyl ether carrene nitromethane | 1 12 24 1 12 24 12 12 12 | 66 57 55 69 65 63 68 20 35 |
A)Separation yield.
Also investigated catalyst consumption in the experiment to the influence in yield and reaction times, comparatively the appropriate catalyst consumption is 1-10mol%.To using the concentration of nitric acid also to compare in the experiment, under identical reaction conditions, when concentration of nitric acid was reduced to 20%, this nitration reaction still can be carried out, and the usage quantity of catalyzer needs to amplify nitrated productive rate about about 54%.When concentration of nitric acid brought up to 95%, when reacting down for 0 ℃, productive rate was 69%, and reaction at room temperature is comparatively violent, by product more (Fig. 2 and form 2).
Fig. 2.
The nitration reaction of form 2. iron nitrate catalysis Resorcinos, the selection of concentration of nitric acid and catalyst levels.
| Sequence number | Nitric acid (%) | Iron nitrate (mol%) | Temperature (℃) | Time (h) | Yield (%) a |
| 1 | |||||
| 1 2 3 4 5 6 | 60 60 60 20 60 95 | 1 10 20 5 3 3 | r.t. r.t. r.t. 60 r.t. 0 | 24 2 1 4 2 1 | 57 66 65 54 65 69 |
A)Separation yield.
The hydrochloride Pyrogentisinic Acid of multiple metal and the catalytic activity of p-fluorophenol have been tested in the experiment.With the tetrahydrofuran (THF) is solvent, and 60% nitric acid is nitrating agent, and the consumption of metal-salt is 3% molar percentage (0.03 mmole), and the charging capacity of phenol or p-fluorophenol is 1 mmole, and the tetrahydrofuran (THF) usage quantity is 3 milliliters, 10 hours reaction times.In this nitrifying process, various salts all show good catalytic performance (Fig. 3 and form 3, Fig. 4 and form 4).
Fig. 3.
The nitration reaction of the hydrochloride catalysis of phenol of form 3. various metals
| Sequence number | Metal-salt | Yield (%) a | |
| 2 | 3 | ||
| 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 | ScCl 3 ZrCl 4 Mo 2O 3 CrCl 2 Mn(OAc) 2 FeCl 3 CoCl 2 NiCl 2 CuCl 2 ZnCl 2 SnCl 2 AlCl 3 InCl 3 BiCl 3 CeCl 3 | 40 42 39 41 41 41 42 40 40 44 42 42 40 41 41 | 50 45 44 50 45 46 50 48 49 49 47 49 48 49 47 |
A)Separation yield.
Fig. 4.
The nitration reaction of the hydrochloride catalysis p-fluorophenol of form 4. various metals
| Sequence number | Metal-salt | Yield (%) a |
| 4 | ||
| 1 2 3 4 5 6 7 8 9 10 11 | CrCl 2 Mn(OAc) 2 FeCl 3 CoCl 2 NiCl 2 CuCl 2 ZnCl 2 SnCl 2 AlCl 3 InCl 3 BiCl 3 | 88 85 90 89 87 87 90 87 87 87 88 |
A)Separation yield.
With phenol is that substrate is investigated the catalytic effect of different mantoquitas and molysite, with the tetrahydrofuran (THF) is solvent, 60% nitric acid is nitrating agent, the consumption of metal-salt is 3% molar percentage (0.03 mmole), the charging capacity of phenol is 1 mmole, the tetrahydrofuran (THF) usage quantity is 3 milliliters, 10 hours reaction times.In this nitrifying process, various mantoquitas and molysite all show good catalytic performance (Fig. 5 and form 5).
Fig. 5.
The nitration reaction of form 5. mantoquitas or molysite catalysis of phenol.
| Sequence number | Metal-salt | Yield (%) a | |
| 2 | 3 | ||
| 1 2 3 4 5 6 7 8 9 | CuSO 4 Cu(NO 3) 2 Cu(OAc) 2 CuBr 2 CuCl FeSO 4 (NH 4) 2Fe(SO 4) 2 K 3Fe(CN) 3 Fe(NO 3) 3 | 42 42 43 43 41 44 44 44 43 | 50 50 52 52 49 49 49 49 49 |
A)Separation yield.
The metal of using in above reaction is transition metal, III, IV or V main group metal, the metal-salt of using is cheap, be easy to get, and these metals and metal-salt toxicity thereof are all smaller, wherein the metal-salt with Fe, Co, Ni, Cu and Zn more cheaply is easy to get, chemical property is stable, and toxicity is very little, so we select for use iron nitrate as the catalyzer of nitration reaction the catalytic effect of multiple substrate to be investigated.The iron nitrate consumption is 3% molar percentage, and all the other conditions are the same.Most of substrate yield is all more than 80%, and wherein the nitrated productive rate of part substrate reaches (Fig. 6, Fig. 7 and form 6, Fig. 8 and form 7) more than 90%.
Fig. 6.
The nitration reaction of the various phenols of form 6. iron nitrate catalysis.
| Sequence number | R | Time (h) | Yield (%) a | |
| 5 | 6 | |||
| 1 2 b 3 4 5 6 7 8 9 d | F F Cl Br Me i-Pr t-Bu OMe OMe | 12 12 4 12 12 12 12 2 1 | 89 85-92 88 66 88 92 89 34 trace | 32 c 2 44 67 |
A)Separation yield.
B)Use the catalyzer that reclaims, reclaim and use five times, yield is at 85-92%.
C)Product comprises 2,4-two bromo-6-nitrophenolss, 2-bromo-4-nitrophenols and 4-nitrophenols.
D)The consumption of nitric acid is 2 equivalents.
Fig. 7.
2,4-two bromo-6-nitrophenols 2-bromo-4-nitrophenols 4-nitrophenolss
Scheme8.
The nitration reaction of the various phenols of Table 7. iron nitrate catalysis.
A)Separation yield.
B)60 ℃ of temperature of reaction.
C)80 ℃ of temperature of reaction
In the nitration reaction of iron nitrate catalysis p-fluorophenol, insolubles and residual water-content after the reaction mixture extraction heat under the condition of vacuumizing, remove moisture, the solid that obtains is once more as catalyzer, the nitration reaction that is used for the catalysis p-fluorophenol, reclaim to use so repeatedly 5 times, yield is all in (form 6, sequence number 2) more than 85%.All just remove moisture because of each the recovery, make metal-salt get back to the state of first use, so each catalytic activity that can not influence catalyzer that reclaims, what catalyzer can be unlimited recycles.Catalyst recovery method is easy, and cost is low, can not pollute in entire reaction course and removal process.
The nitrifying method of this phenol and phenyl ether 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, the metal-salt of using all is 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 nitration reaction is used is a kind of economy, green nitrated catalyzer.
Embodiment
Embodiment 1
With 12mg Fe (NO
3)
3* 9H
2O (3mol%), 3mL tetrahydrofuran (THF) and 94mg phenol (1.0mmol) add reactor, and (0.095mL, 1.2mmol), stirring reaction is 12 hours under the room temperature for the concentrated nitric acid of dropping 60% under stirring.The reaction mixture dichloromethane extraction, insolubles and residual water-content heat under the condition of vacuumizing, and remove moisture, and the solid that obtains is used for nitration reaction as catalyzer once more; Extraction liquid obtains yellow solid 60mg, productive rate 43%, 2-nitrophenols after being spin-dried on the Rotary Evaporators, crossing post; Faint yellow solid 68mg, productive rate 49%, 4-nitrophenols.2-nitrophenols: m.p.45-47 ℃, IR (KBr) v 1522,1416cm
-1(NO
2), 3250,1240cm
-1(OH);
1H NMR (CDCl
3, 300MHz, 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
+), 122 (M
+-17,6.46), 109 (M
+-30,22.97), 93 (M
+-46,8.40); HRMS (EI); C
6H
5NO
3, calculated value: M, 139.1088, measured value: 139.0272 (M
+); 4-nitrophenols: m.p.117-119 ℃, IR (KBr) v 1522,1416cm
-1(NO
2), 3253,1240cm
-1(OH);
1H NMR (CDCl
3, 300MHz, 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, 100), 123 (M
+-16,4.20), 109 (M
+-30,47.59), 93 (M
+-46,19.14); Ultimate analysis C
6H
5NO
3(%): calculated value: C, 51.80; H, 3.62; N, 10.07%. measured value: C, 51.73; H, 3.73; N, 10.04%.
Embodiment 2
With 10mg Cu (OAc)
2* H
2O (3mol%), 3mL tetrahydrofuran (THF) and 94mg phenol (1.0mmol) add reactor, and (0.095mL, 1.2mmol), stirring reaction is 12 hours under the room temperature for the concentrated nitric acid of dropping 60% under stirring.The reaction mixture dichloromethane extraction, insolubles and residual water-content heat under the condition of vacuumizing, and remove moisture, and the solid that obtains is used for nitration reaction as catalyzer once more; Extraction liquid obtains yellow solid 60mg, productive rate 43%, 2-nitrophenols after being spin-dried on the Rotary Evaporators, crossing post; Faint yellow solid 72mg, productive rate 52%, 4-nitrophenols.
Embodiment 3
With 12mg CoCl
2* 6H
2O (5mol%), 3mL tetrahydrofuran (THF) and 94mg phenol (1.0mmol) add reactor, and (0.095mL, 1.2mmol), stirring reaction is 12 hours under the room temperature for the concentrated nitric acid of dropping 60% under stirring.The reaction mixture dichloromethane extraction, insolubles and residual water-content heat under the condition of vacuumizing, and remove moisture, and the solid that obtains is used for nitration reaction as catalyzer once more; Extraction liquid obtains yellow solid 58mg, productive rate 42%, 2-nitrophenols after being spin-dried on the Rotary Evaporators, crossing post; Faint yellow solid 70mg, productive rate 50%, 4-nitrophenols.
Embodiment 4
With 8mg ZnCl
2(5mol%), 3mL tetrahydrofuran (THF) and 94mg p-fluorophenol (1.0mmol) add reactor, stir to drip 60% concentrated nitric acid down (0.095mL, 1.2mmol), stirring reaction is 12 hours under the room temperature.The reaction mixture dichloromethane extraction, insolubles and residual water-content heat under the condition of vacuumizing, and remove moisture, and the solid that obtains is used for nitration reaction as catalyzer once more; Extraction liquid obtains yellow solid 61mg, productive rate 44%, 2-nitrophenols after being spin-dried on the Rotary Evaporators, crossing post; Faint yellow solid 68mg, productive rate 49%, 4-nitrophenols.
Embodiment 5
With 8mg FeCl
3(5mol%), 3mL tetrahydrofuran (THF) and 112mg p-fluorophenol (1.0mmol) add reactor, stir to drip 60% concentrated nitric acid down (0.095mL, 1.2mmol), stirring reaction is 12 hours under the room temperature.The reaction mixture dichloromethane extraction, insolubles and residual water-content heat under the condition of vacuumizing, and remove moisture, and the solid that obtains is used for nitration reaction as catalyzer once more; Extraction liquid obtains yellow solid 141mg, productive rate 90%, 2-nitro p-fluorophenol: m.p.75-77 ℃ of IR (KBr) v 1526,1344cm after being spin-dried on the Rotary Evaporators, crossing post
-1(NO
2), 3265,1255cm
-1(OH);
1H NMR (CDCl
3, 300MHz, TMS) δ 7.17 (1H, dd, J=9.4Hz, 4.3Hz, Ar), 7.37 (1H, ddd, J=9.3Hz, 7.4Hz, 3.2Hz, Ar), 7.83 (1H, dd, J=8.1Hz, 3.0Hz, Ar), 10.38 (1H, s, ArOH); MS (EI) m/z 157 (M
+, 100), 140 (M
+-17,7.20), 127 (M
+-30,11.07), 111 (M
+-46,5.75); Ultimate analysis C
6H
4FNO
3(%): calculated value: C, 45.87; H, 2.57; N, 8.92%. measured value: C, 46.01; H, 2.58; N, 8.94%.
Embodiment 6
With 12mg Fe (NO
3)
3* 9H
2O (3mol%), 3mL tetrahydrofuran (THF) and 112mg p-fluorophenol (1.0mmol) add reactor, and (0.095mL, 1.2mmol), stirring reaction is 12 hours under the room temperature for the concentrated nitric acid of dropping 60% under stirring.The reaction mixture dichloromethane extraction, insolubles and residual water-content heat under the condition of vacuumizing, and remove moisture, and the solid that obtains is used for nitration reaction as catalyzer once more; Extraction liquid obtains yellow solid 140mg, productive rate 89%, 2-nitro p-fluorophenol after being spin-dried on the Rotary Evaporators, crossing post.
Embodiment 7
Insolubles and residual water-content after the reaction mixture extraction heat under the condition of vacuumizing, remove moisture, the solid that obtains is once more as catalyzer, add 3mL tetrahydrofuran (THF) and 112mg p-fluorophenol (1.0mmol), stir the concentrated nitric acid (0.095mL of dropping 60% down, 1.2mmol), stirring reaction is 12 hours under the room temperature.The reaction mixture dichloromethane extraction, insolubles and residual water-content heat under the condition of vacuumizing, and remove moisture, and the solid that obtains still can be used for nitration reaction as catalyzer once more; Extraction liquid obtains yellow solid 144mg, productive rate 92%, 2-nitro p-fluorophenol after being spin-dried on the Rotary Evaporators, crossing post.
Embodiment 8
With 12mg Fe (NO
3)
3* 9H
2O (3mol%), 3mL tetrahydrofuran (THF) and 129mg para-chlorophenol (1.0mmol) add reactor, and (0.095mL, 1.2mmol), stirring reaction is 4 hours under the room temperature for the concentrated nitric acid of dropping 60% under stirring.The reaction mixture dichloromethane extraction, insolubles and residual water-content heat under the condition of vacuumizing, and remove moisture, and the solid that obtains is used for nitration reaction as catalyzer once more; Extraction liquid obtains yellow solid 153mg, productive rate 88%, m.p.86-88 ℃ of 2-nitro para-chlorophenol, IR (KBr) v 1522,1416cm after being spin-dried on the Rotary Evaporators, crossing post
-1(NO
2), 3263,1240cm
-1(OH);
1H NMR (CDCl
3, 300MHz, 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
+, 100), 156 (M
+-17,9.26), 143 (M
+-30,9.73), 127 (M
+-46,15.36); Ultimate analysis C
6H
4ClNO
3(%): calculated value: C, 41.52; H, 2.32; N, 8.07%. measured value: C, 41.58; H, 2.36; N, 8.10%.
Embodiment 9
With 12mg Fe (NO
3)
3* 9H
2O (3mol%), 3mL tetrahydrofuran (THF) and 173mg p bromophenol (1.0mmol) add reactor, and (0.095mL, 1.2mmol), stirring reaction is 12 hours under the room temperature for the concentrated nitric acid of dropping 60% under stirring.The reaction mixture dichloromethane extraction, insolubles and residual water-content heat under the condition of vacuumizing, and remove moisture, and the solid that obtains is used for nitration reaction as catalyzer once more; Extraction liquid obtains yellow solid 143mg, productive rate 66%, 2-nitro p bromophenol after being spin-dried on the Rotary Evaporators, crossing post; 27mg, productive rate 9%, 2,4-two bromo-6-nitrophenolss; 18mg, productive rate 8%, 2-bromo-4-nitrophenols; 26mg, productive rate 19%, 4-nitrophenols.2-nitro p bromophenol: m.p.88-90 ℃, IR (KBr) v 1532,1412cm
-1(NO
2), 3266,1249cm
-1(OH);
1H NMR (CDCl
3, 300MHz, 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
+, 100), 202 (M
+-17,14.58), 189 (M
+-30,15.72), 173 (M
+-46,23.19); Ultimate analysis C
6H
4BrNO
3(%): calculated value: C, 33.06; H, 1.85; N, 6.42%. measured value: C, 33.34, H, 2.08; N, 6.35%.2,4-two bromo-6-nitrophenolss: m.p.114-116 ℃, IR (KBr) v 1531,1392cm
-1(NO
2), 3070,1242cm
-1(OH);
1H NMR (CDCl
3, 300MHz, TMS) δ 8.00 (1H, d, J=2.4Hz, Ar), 8.25 (1H, d, J=2.4Hz, Ar), 11.05 (1H, s, ArOH); MS (EI) m/z 297 (M
+, 100), 267 (M
+-30,18.37), 239 (M
+-58,19.23), 223 (M
+-74,12.92); Ultimate analysis C
6H
3Br
2NO
3(%): calculated value: C, 24.27; H, 1.02; N, 4.72%. measured value: C, 24.55; H, 1.11; N, 4.54%.2-bromo-4-nitrophenols: m.p.115-118 ℃, IR (KBr) v 1515,1337cm
-1(NO
2), 3390,1249cm
-1(OH);
1H NMR (CDCl
3, 300MHz, TMS) δ 6.21 (1H, s, ArOH), 7.13 (1H, d, J=9.0Hz, Ar), 8.16 (1H, dd, J=9.0Hz, 3.0Hz, Ar), 8.44 (1H, d, J=3.0Hz, Ar); MS (EI) m/z 219 (M
+, 100), 189 (M
+-30,85.62), 171 (M
+-46,12.50), 145 (M
+-74,31.51), 119 (M
+-100,8.76); Ultimate analysis C
6H
4BrNO
3(%): calculated value: C, 33.06; H, 1.85; N, 6.42%. measured value: C, 33.09; H, 1.92; N, 6.68%.
Embodiment 10
With 12mg Fe (NO
3)
3* 9H
2O (3mol%), 3mL tetrahydrofuran (THF) and 108mg p-methyl phenol (1.0mmol) add reactor, and (0.095mL, 1.2mmol), stirring reaction is 12 hours under the room temperature for the concentrated nitric acid of dropping 60% under stirring.The reaction mixture dichloromethane extraction, insolubles and residual water-content heat under the condition of vacuumizing, and remove moisture, and the solid that obtains is used for nitration reaction as catalyzer once more; Extraction liquid obtains yellow solid 135mg after being spin-dried on the Rotary Evaporators, crossing post, productive rate 88%, and 2-nitro p-methyl phenol: m.p.34-36 ℃, IR (KBr) v 1630,1370,3250,1245cm
-1 1H NMR (CDCl
3, 300MHz, TMS) δ 2.34 (3H, s, CH
3), 7.05 (1H, d, J=8.2Hz, Ar), 7.39 (1H, dd, J=2.0Hz, 8.2Hz, Ar), 7.90 (1H, d, J=2.0Hz, Ar), 10.44 (1H, s, ArOH); MS (EI) m/z 153 (M
+, 100), 136 (M
+-17,5.37), 123 (M
+-30,6.98), 77 (M
+-76,40.38); Ultimate analysis C
7H
7NO
3(%): calculated value: C, 54.90; H, 4.61; N, 9.15%. measured value: C, 54.77; H, 4.72; N, 9.30%.
Embodiment 11
With 12mg Fe (NO
3)
3* 9H
2O (3mol%), 3mL tetrahydrofuran (THF) and 136mg australol (1.0mmol) add reactor, and (0.095mL, 1.2mmol), stirring reaction is 12 hours under the room temperature for the concentrated nitric acid of dropping 60% under stirring.The reaction mixture dichloromethane extraction, insolubles and residual water-content heat under the condition of vacuumizing, and remove moisture, and the solid that obtains is used for nitration reaction as catalyzer once more; Extraction liquid obtains yellow solid 167mg after being spin-dried on the Rotary Evaporators, crossing post, productive rate 92%, and 2-nitro australol: m.p.54-56 ℃, IR (KBr) v 1543,1366cm
-1(NO
2), 3250,1251cm
-1(OH);
1H NMR (CDCl
3, 300MHz, TMS) δ 1.25 (6H, d, J=7.2Hz, CH
3), 2.89-2.99 (1H, m, CH), 7.09 (1H, d, J=8.7Hz, Ar), 7.37 (1H, dd, J=8.5Hz, 2.3Hz, Ar), 7.94 (1H, d, J=2.0Hz, Ar), 10.48 (1H, s, ArOH); MS (EI) m/z 181 (M
+, 23.76), 166 (M
++ 1-16,100), 77 (M
+-104,19.10), 43 (M
+-138,62.72); HRMS (EI) C
9H
11NO
3Calculated value: M, 181.0739, measured value: 181.0795 (M
+).
Embodiment 12
With 12mg Fe (NO
3)
3* 9H
2O (3mol%), 3mL tetrahydrofuran (THF) and 150mg p-tert-butylphenol (1.0mmol) add reactor, and (0.095mL, 1.2mmol), stirring reaction is 12 hours under the room temperature for the concentrated nitric acid of dropping 60% under stirring.The reaction mixture dichloromethane extraction, insolubles and residual water-content heat under the condition of vacuumizing, and remove moisture, and the solid that obtains is used for nitration reaction as catalyzer once more; Extraction liquid obtains yellow solid 174mg after being spin-dried on the Rotary Evaporators, crossing post, productive rate 89%, and 2-nitro p-tert-butylphenol: m.p.70-73 ℃, IR (KBr) v 1532,1397cm
-1(NO
2), 3249,1255cm
-1(OH);
1H NMR (CDCl
3, 300MHz, 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
+, 16.06), 180 (M
++ 1-16,100), 134 (M
+-61,17.32), 77 (M
+-118,9.29); HRMS (EI) C
10H
13NO
3Calculated value: M, 195.0895, measured value: 195.0899 (M
+).
Embodiment 13
With 12mg Fe (NO
3)
3* 9H
2O (3mol%), 3mL tetrahydrofuran (THF) and 124mg p methoxy phenol (1.0mmol) add reactor, and (0.095mL, 1.2mmol), stirring reaction is 2 hours under the room temperature for the concentrated nitric acid of dropping 60% under stirring.The reaction mixture dichloromethane extraction, insolubles and residual water-content heat under the condition of vacuumizing, and remove moisture, and the solid that obtains is used for nitration reaction as catalyzer once more; Extraction liquid obtains yellow solid 57mg, productive rate 34%, 2-nitro p methoxy phenol after being spin-dried on the Rotary Evaporators, crossing post; Yellow solid 94mg, productive rate 44%, 2,6-dinitrobenzene p methoxy phenol.2-nitro p methoxy phenol: m.p.80-81 ℃, IR (KBr) v 1534,1333cm
-1(NO
2), 3222,1249cm
-1(OH);
1H NMR (CDCl
3, 300MHz, TMS) δ 3.83 (3H, s, OCH
3), 7.09 (1H, d, J=9.0Hz, Ar), 7.22 (1H, dd, J=9.0Hz, 3.0Hz, Ar), 7.50 (1H, d, J=3.0Hz, Ar), 10.34 (1H, s, ArOH); MS (EI) m/z169 (M
+, 100), 139 (M
+-30,10.64), 111 (M
+-58,17.78), 107 (M
+-62,14.77), 95 (M
+-74,9.27); Ultimate analysis C
7H
7NO
4(%): calculated value: C, 49.71; H, 4.17; N, 8.28%. measured value: C, 49.69; H, 4.21; N, 8.27%.2,6-dinitrobenzene p methoxy phenol: m.p.77-79 ℃, IR (KCl) v1537,1358cm
-1(NO
2), 3251,1243cm
-1(OH);
1H NMR (CDCl
3, 300MHz, TMS) δ 3.91 (3H, s, OCH
3), 7.86 (2H, s, Ar), 11.00 (1H, s, ArOH); MS (EI) m/z 214 (M
+, 100), 184 (M
+-30,5.77), 77 (M
+-137,18.05), 51 (M
+-163,30.71); 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 14
With 12mg Fe (NO
3)
3* 9H
2O (3mol%), 3mL tetrahydrofuran (THF) and 124mg p methoxy phenol (1.0mmol) add reactor, and (0.16mL, 2.0mmol), stirring reaction is 1 hour under the room temperature for the concentrated nitric acid of dropping 60% under stirring.The reaction mixture dichloromethane extraction, insolubles and residual water-content heat under the condition of vacuumizing, and remove moisture, and the solid that obtains is used for nitration reaction as catalyzer once more; Extraction liquid obtains yellow solid 143mg, productive rate 67%, 2,6-dinitrobenzene p methoxy phenol after being spin-dried on the Rotary Evaporators, crossing post.
Embodiment 15
With 12mg Fe (NO
3)
3* 9H
2O (3mol%), 3mL tetrahydrofuran (THF) and 129mg ortho chloro phenol (1.0mmol) add reactor, and (0.095mL, 1.2mmol), stirring reaction is 4 hours under the room temperature for the concentrated nitric acid of dropping 60% under stirring.The reaction mixture dichloromethane extraction, insolubles and residual water-content heat under the condition of vacuumizing, and remove moisture, and the solid that obtains is used for nitration reaction as catalyzer once more; Extraction liquid obtains yellow solid 68mg, productive rate 39%, 2-chloro-6-nitrophenols after being spin-dried on the Rotary Evaporators, crossing post; Yellow solid 90mg, productive rate 52%, 2-chloro-4-nitrophenols.2-chloro-6-nitrophenols: m.p.70-71 ℃, IR (KBr) v1531,1324cm
-1(NO
2), 3469,1259cm
-1(OH);
1H NMR (CDCl
3, 300MHz, TMS) δ 6.97 (1H, dd, J=7.8Hz, 8.4Hz, Ar), 7.71 (1H, dd, J=7.8Hz, 1.5Hz, Ar), 8.06 (1H, dd, J=8.4Hz, 1.5Hz, Ar), 11.03 (1H, s, ArOH); MS (EI) m/z 173 (M
+, 91.92), 143 (M
+-30,51.06), 115 (M
+-58,34.80), 99 (M
+-74,51.49), 63 (M
+-110,100.00); Ultimate analysis C
6H
4ClNO
3(%): calculated value: C, 41.52; H, 2.32; N, 8.07%. measured value: C, 41.63; H, 2.28; N, 7.91%.2-chloro-4-nitrophenols: m.p.110-112 ℃, IR (KBr) v 1508,1335cm
-1(NO
2), 3370,1252cm
-1(OH);
1H NMR (CDCl
3, 300MHz, TMS) δ 7.14 (1H, d, J=9.3Hz, Ar), 8.12 (1H, dd, J=9.3Hz, 2.7Hz, Ar), 8.30 (1H, d, J=2.7Hz, Ar), 6.44 (1H, s, ArOH); MS (EI) m/z 173 (M
+, 100.00), 143 (M
+-30,75.68), 99 (M
+-74,64.08), 91 (M
+-82,35.11), 73 (M
+-100,34.53), 63 (M
+-110,64.71); Ultimate analysis C
6H
4ClNO
3(%): calculated value: C, 41.52; H, 2.32; N, 8.07%. measured value: C, 41.54; H, 2.36; N, 7.92%.
Embodiment 16
With 12mg Fe (NO
3)
3* 9H
2O (3mol%), 3mL tetrahydrofuran (THF) and 108mg ortho-methyl phenol (1.0mmol) add reactor, and (0.095mL, 1.2mmol), stirring reaction is 12 hours under the room temperature for the concentrated nitric acid of dropping 60% under stirring.The reaction mixture dichloromethane extraction, insolubles and residual water-content heat under the condition of vacuumizing, and remove moisture, and the solid that obtains is used for nitration reaction as catalyzer once more; Extraction liquid obtains yellow solid 55mg, productive rate 36%, 2-methyl-6-nitrophenols after being spin-dried on the Rotary Evaporators, crossing post; Yellow solid 90mg, productive rate 59%, 2-methyl-4-nitrophenols.2-methyl-6-nitrophenols: m.p.71-73 ℃, IR (KBr) v 1635,1344,3267,1236cm
-1 1H NMR (CDCl
3, 300MHz, TMS) δ 2.34 (3H, s, CH
3), 6.88 (1H, dd, J=9.0Hz, 7.3Hz, Ar), 7.45 (1H, d, J=7.3Hz, Ar), 7.69 (1H, d, J=9.0Hz, Ar), 10.92 (1H, s, ArOH); MS (EI) m/z 153 (M
+, 100), 136 (M
+-17,7.81), 123 (M
+-30,8.90), 77 (M
+-104,84.40); Ultimate analysis C
7H
7NO
3(%): calculated value: C, 54.90; H, 4.61; N, 9.15%.Found:C, 54.97; H, 4.69; N, 9.07%.2-methyl-4-nitrophenols: m.p.142-145 ℃, IR (KBr) v 1626,1374,3237,1286cm
-1 1H NMR (CDCl
3, 300MHz, TMS) δ 2.32 (3H, s, CH
3), 5.83 (1H, s, ArOH), 6.83 (1H, d, J=9.0Hz, Ar), 8.02 (1H, dd, J=9.0Hz, 2.8Hz, Ar), 8.07 (1H, d, J=2.8Hz, Ar); MS (EI) m/z 153 (M
+, 100), 137 (M
+-16,4.18), 123 (M
+-30,52.82), 77 (M
+-104,79.40); Ultimate analysis C
7H
7NO
3(%): calculated value: C, 54.90; H, 4.61; N, 9.15%. measured value: C, 54.68; H, 4.58; N, 9.24%.
Embodiment 17
With 12mg Fe (NO
3)
3* 9H
2O (3mol%), 3mL tetrahydrofuran (THF) and 138mg Pyrocatechol monoethyl ether (1.0mmol) add reactor, and (0.095mL, 1.2mmol), stirring reaction is 4 hours under the room temperature for the concentrated nitric acid of dropping 60% under stirring.The reaction mixture dichloromethane extraction, insolubles and residual water-content heat under the condition of vacuumizing, and remove moisture, and the solid that obtains is used for nitration reaction as catalyzer once more; Extraction liquid obtains yellow solid 64mg, productive rate 35%, 2-oxyethyl group-6-nitrophenols after being spin-dried on the Rotary Evaporators, crossing post; Yellow solid 104mg, productive rate 57%, 2-oxyethyl group-4-nitrophenols.2-oxyethyl group-6-nitrophenols: m.p.62-64 ℃, IR (KBr) v 1547,1328cm
-1(NO
2), 3170,1249cm
-1(OH);
1H NMR (CDCl
3, 300MHz, TMS) δ 1.51 (3H, t, CH
3), 4.15 (2H, q, CH
2), 6.89 (1H, dd, J=8.4Hz, 7.8Hz, Ar), 7.71 (1H, d, J=7.8Hz, Ar), 7.85 (1H, d, J=8.4Hz), 10.73 (1H, s, ArOH); MS (EI) m/z 183 (M
+, 39.15), 155 (M
+-28,29.51), 107 (M
+-76,100.00), 93 (M
+-90,22.30), 79 (M
+-104,28.93); Ultimate analysis C
8H
9NO
4(%): calculated value: C, 52.46; H, 4.95; N, 7.65%. measured value: C, 52.50; H, 4.91; N, 7.62%.2-oxyethyl group-4-nitrophenols: m.p.95-97 ℃, IR (KBr) v 1523,1338cm
-1(NO
2), 3458,1263cm
-1(OH);
1H NMR (CDCl
3, 300MHz, TMS) δ 1.50 (3H, t, CH
3), 4.21 (2H, q, CH
2), 6.97 (1H, d, J=8.7Hz, Ar), 7.71 (1H, d, J=2.7Hz, Ar), 7.85 (1H, dd, J=8.7Hz, 2.7Hz, Ar), 6.50 (1H, s, ArOH); MS (EI) m/z 183 (M
+, 94.89), 155 (M
+-28,100.00), 125 (M
+-58,59.82), 109 (M
+-74,28.60), 81 (M
+-102,23.68); Ultimate analysis C
8H
9NO
4(%): calculated value: C, 52.46; H, 4.95; N, 7.65%. measured value: C, 52.77; H, 4.94; N, 7.67%.
Embodiment 18
With 12mg Fe (NO
3)
3* 9H
2O (3mol%), 3mL tetrahydrofuran (THF) and 166mg 1,2-diethoxybenzene (1.0mmol) add reactor, stir drip down 60% concentrated nitric acid (0.095mL, 1.2mmol), 60 ℃ of following stirring reactions 24 hours.The reaction mixture dichloromethane extraction, insolubles and residual water-content heat under the condition of vacuumizing, and remove moisture, and the solid that obtains is used for nitration reaction as catalyzer once more; Extraction liquid obtains yellow solid 104mg, productive rate 50%, 1,2-diethoxy-4-nitrophenols: m.p.75-77 ℃, IR (KBr) v 1520,1327cm after being spin-dried on the Rotary Evaporators, crossing post
-1(NO
2);
1H NMR (CDCl
3, 300MHz, TMS) δ 1.50 (3H, t, CH
3), 1.51 (3H, t, CH
3), 4.16 (2H, q, CH
2), 4.19 (2H, q, CH
2), 6.89 (1H, d, J=9.0Hz, Ar), 7.71 (1H, d, J=2.4Hz, Ar), 7.85 (1H, dd, J=9.0Hz, 2.4Hz, Ar); MS (EI) m/z 211 (M
+, 70.49), 183 (M
+-28,31.04), 155 (M
+-56,100.00), 125 (M
+-86,45.36), 79 (M
+-132,18.17); Ultimate analysis C
10H
13NO
4(%): calculated value: C, 56.86; H, 6.20; N, 6.63%. measured value: C, 56.70; H, 6.20; N, 6.58%.
Embodiment 19
With 12mg Fe (NO
3)
3* 9H
2O (3mol%), 3mL tetrahydrofuran (THF) and 110mg Resorcinol (1.0mmol) add reactor, and (0.095mL, 1.2mmol), stirring reaction is 2 hours under the room temperature for the concentrated nitric acid of dropping 60% under stirring.The reaction mixture dichloromethane extraction, insolubles and residual water-content heat under the condition of vacuumizing, and remove moisture, and the solid that obtains is used for nitration reaction as catalyzer once more; Extraction liquid obtains yellow solid 107mg, productive rate 69%, m.p.117-119 ℃ of 4-nitro-resorcinol, IR (KBr) v 1532,1397cm after being spin-dried on the Rotary Evaporators, crossing post
-1(NO
2), 3354,1255cm
-1(OH);
1H NMR (CDCl
3, 300MHz, 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
+, 47.40), 125 (M
+-30,100), 97 (M
+-58,94.90), 77 (M
+-78,6.77) 51 (M
+-104,65.02); Ultimate analysis C
6H
5NO
4(%): calculated value: C, 46.46; H, 3.25; N, 9.03%. measured value: C, 46.48; H, 3.44; N, 9.02%.
Embodiment 20
With 12mg Fe (NO
3)
3* 9H
2O (3mol%), 3mL tetrahydrofuran (THF) and 108mg m-methyl phenol (1.0mmol) add reactor, and (0.095mL, 1.2mmol), stirring reaction is 12 hours under the room temperature for the concentrated nitric acid of dropping 60% under stirring.The reaction mixture dichloromethane extraction, insolubles and residual water-content heat under the condition of vacuumizing, and remove moisture, and the solid that obtains is used for nitration reaction as catalyzer once more; Extraction liquid obtains yellow solid 81mg, productive rate 53%, 3-methyl-4-nitrophenols after being spin-dried on the Rotary Evaporators, crossing post; Yellow solid 49mg, productive rate 32%, 5-methyl-2-nitrophenols; Yellow solid 21mg, productive rate 14%, 2-methyl-4-nitrophenols.3-methyl-4-nitrophenols: m.p.128-130 ℃, IR (KBr) v 1600,1410,3170,1230cm
-1 1H NMR (CDCl
3, 300MHz, TMS) δ 2.65 (3H, s, CH
3), 5.99 (1H, s, ArOH), 6.74-6.77 (2H, m, Ar), 8.03-8.07 (1H, m, Ar); MS (EI) m/z 153 (M
+, 55.90), 136 (M
+-17,100), 123 (M
+-30,6.24), 77 (M
+-76,77.06); Ultimate analysis C
7H
7NO
3(%): calculated value: C, 54.90; H, 4.61; N, 9.15%. measured value: C, 54.65; H, 4.49; N, 9.32%. 5-methyl-2-nitrophenols: m.p.56-58 ℃, IR (KBr) v 1590,1360,3277,1274cm
-1 1H NMR (CDCl
3, 300MHz, TMS) δ 2.40 (3H, s, CH
3), 6.79 (1H, dd, J=1.8Hz, 7.8Hz, Ar), 6.94 (1H, d, J=1.8Hz, Ar), 7.98 (1H, d, J=7.8Hz, Ar), 10.62 (1H, s, ArOH); MS (EI) m/z 153 (M
+, 100), 123 (M
+-30,24.42), 77 (M
+-76,49.13); Ultimate analysis C
7H
7NO
3(%): calculated value: C, 54.90; H, 4.61; N, 9.15%. measured value: C, 54.79; H, 4.66; N, 9.28%.3-methyl-2-nitrophenols: m.p.39-41 ℃, IR (KBr) v 1603,1340,1273cm
-1 1H NMR (CDCl
3, 300MHz, TMS) δ 2.63 (3H, s, CH
3), 6.83 (1H, d, J=7.2Hz, Ar), 7.01 (1H, d, J=7.8Hz, Ar), 7.38 (1H, dd, J=7.8Hz, 7.2Hz, Ar), 10.36 (1H, s, ArOH); MS (EI) m/z 153 (M
+, 55.82), 136 (M
+-17,100), 106 (M
+-47,28.68), 77 (M
+-104,84.40); Ultimate analysis C
7H
7NO
3(%): calculated value: C, 54.90; H, 4.61; N, 9.15%. measured value: C, 55.18; H, 4.77; N, 9.01%.
Embodiment 21
With 12mg Fe (NO
3)
3* 9H
2O (3mol%), 3mL tetrahydrofuran (THF) and 138mg add reactor to anisole methyl ether (1.0mmol), stir drip down 60% concentrated nitric acid (0.095mL, 1.2mmol), 80 ℃ of following stirring reactions 24 hours.The reaction mixture dichloromethane extraction, insolubles and residual water-content heat under the condition of vacuumizing, and remove moisture, and the solid that obtains is used for nitration reaction as catalyzer once more; Extraction liquid obtains yellow solid 146mg after being spin-dried on the Rotary Evaporators, crossing post, productive rate 80%, and the 2-nitro is to anisole methyl ether: m.p.:71-72 ℃; IR (KBr) v 1527,1354cm
-1(NO
2);
1H-NMR (CDCl
3, TMS, 300MHz) 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
+); 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%.
Embodiment 22
With 12mg Fe (NO
3)
3* 9H
2O (3mol%), 3mL tetrahydrofuran (THF) and 163mg 3,4-chlorophenesic acid (1.0mmol) adds reactor, and (0.095mL, 1.2mmol), stirring reaction is 12 hours under the room temperature for the concentrated nitric acid of dropping 60% under stirring.The reaction mixture dichloromethane extraction, insolubles and residual water-content heat under the condition of vacuumizing, and remove moisture, and the solid that obtains is used for nitration reaction as catalyzer once more; Extraction liquid obtains yellow solid 106mg, productive rate 51%, 2-nitro 4,5-chlorophenesic acid and yellow solid 62mg, productive rate 30%, 2-nitro 3,4-chlorophenesic acid after being spin-dried on the Rotary Evaporators, crossing post.2-nitro 4,5-chlorophenesic acid: m.p.:63-65 ℃; IR (KBr) v 1521,1364cm
-1(NO
2);
1H-NMR (CDCl
3, TMS, 300MHz) δ 7.34 (1H, s, ArH) 8.21 (1H, s, ArH) 10.45 (1H, s, OH); MS (EI) m/z 208 (M
+); Ultimate analysis C
6H
3Cl
2NO
3(%): measured value: C, 34.65; H, 1.45; N, 6.73%. calculated value: C, 34.52; H, 1.50; N, 6.68%.2-nitro 3,4-chlorophenesic acid: m.p.:76-78 ℃; IR (KBr) v 1522,1367cm
-1(NO
2);
1H-NMR (CDCl
3, TMS, 300MHz) δ 7.26 (1H, d, J=7.8Hz, ArH) 7.39 (1H, d, J=7.8Hz, ArH) 10.40 (1H, s, OH); MS (EI) m/z 208 (M
+); Ultimate analysis C
6H
3Cl
2NO
3(%): calculated value: C, 34.65; H, 1.45; N, 6.73%. measured value: C, 34.52; H, 1.50; N, 6.68%.
Embodiment 23
With 12mg Fe (NO
3)
3* 9H
2O (3mol%), 3mL tetrahydrofuran (THF) and 163mg 2,4,5-Trichlorophenol (1.0mmol) adds reactor, and (0.095mL, 1.2mmol), stirring reaction is 12 hours under the room temperature for the concentrated nitric acid of dropping 60% under stirring.The reaction mixture dichloromethane extraction, insolubles and residual water-content heat under the condition of vacuumizing, and remove moisture, and the solid that obtains is used for nitration reaction as catalyzer once more; Extraction liquid obtains yellow solid 167mg, productive rate 77% after being spin-dried on the Rotary Evaporators, crossing post.2-nitro 3,4,6-Trichlorophenol: m.p.:91-92 ℃; IR (KBr) v 1533,1358cm
-1(NO
2);
1H-NMR (CDCl
3, TMS, 300MHz) δ 7.65 7.56 (1H, s, OH) (1H, s, ArH); MS (EI) m/z 242 (M
+); Ultimate analysis C
6H
2Cl
3NO
3(%): measured value: C, 29.72; H, 0.83; N, 5.78%. calculated value: C, 29.57; H, 0.91; N.5.70%.
Embodiment 24
With 12mg Fe (NO
3)
3* 9H
2O (3mol%), 3mL tetrahydrofuran (THF) and 144mg beta naphthal (1.0mmol) add reactor, and (0.095mL, 1.2mmol), stirring reaction is 6 hours under the room temperature for the concentrated nitric acid of dropping 60% under stirring.The reaction mixture dichloromethane extraction, insolubles and residual water-content heat under the condition of vacuumizing, and remove moisture, and the solid that obtains is used for nitration reaction as catalyzer once more; Extraction liquid obtains yellow solid 82mg, productive rate 43% after being spin-dried on the Rotary Evaporators, crossing post.1-nitro beta naphthal: m.p.104_106 ℃ of .H NMR (300MHz, CDCl3): δ=7.27 (d, J=9.1Hz, 1H, Ar), 7.52 (m, J=7.5, J=1.1Hz, 1H, Ar), 7.75 (m, J=8.6, J=1.4Hz, 1H, Ar), 7.83 (d, J=8.0Hz, 1H, Ar), 8.02 (d, J=9.1Hz, 1H, Ar), 8.94 (d, J=8.6Hz, 1H, Ar), 12.20 (s, 1H, OH); MS (EI_): m/z (%)=189 (100) [M
+], 173 (12), 143 (25), 131 (37), 115 (51). ultimate analysis C
10H
7NO
3(%): calculated value: C 63.50, H3.73, and N 7.40, O 25.37. measured value: C63.55, H3.72, N7.39.
Claims (8)
1, the nitrifying method of a kind of catalysis phenols or phenyl ether compound, it is characterized in that in ether organic solvent and 0-100 ℃ under, as nitrated catalyzer, catalysis phenols or phenyl ether compound and nitric acid reaction 0.5-24 hour, described phenols and phenyl ether compound molecular formula were RR with metal-salt
1R
2R
3Z, wherein, R=hydroxyl or C
1-5Alkoxyl group, R
1, R
2Or R
3=H, C
1-5Alkyl, halogen, hydroxyl, C
1-5Alkoxyl group or C
6H
5, Z=phenyl, naphthyl, tetralyl, anthryl or fluorenyl, described metal salt catalyst, nitric acid and phenol or phenyl ether compound mol ratio are 0.01-0.5: 0.1-10: 1; Described metal-salt is nitrate, hydrochloride, acetate, phosphoric acid salt, vitriol, sulfonate, the cyanate of transition metal, III, IV or V main group metal or the double salt that contains above metal ion.
2, nitrifying method as claimed in claim 1 is characterized in that described metal is Sc, Ti, Zr, V, In, Sn, Al, Bi, Mo, Cr, Mn, Fe, Co, Ni, Cu or Zn.
3, nitrifying method as claimed in claim 1 is characterized in that described metal salt catalyst, nitric acid and phenol or phenyl ether compound mol ratio are 0.01-0.5: 1-2: 1.
4, nitrifying method as claimed in claim 1 is characterized in that described metal salt catalyst, nitric acid and phenol or phenyl ether compound mol ratio are 0.03-0.1: 1-2: 1.
5, nitrifying method as claimed in claim 1 is characterized in that described nitric acid is 20%～100% nitric acid.
6, nitrifying method as claimed in claim 5 is characterized in that described nitric acid is 30～70% nitric acid.
7, nitrifying method as claimed in claim 1 is characterized in that described temperature of reaction is 20-60 ℃.
8, nitrifying method as claimed in claim 1 is characterized in that the described reaction times is 1-12 hour.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
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| CN1850334B (en) * | 2006-05-26 | 2012-03-28 | 中国科学院上海有机化学研究所 | Use of Zr compound in catalyzing clean nitration of salicylic-acids compounds |
| CN101200429B (en) * | 2006-12-13 | 2012-08-22 | 上海睿智化学研究有限公司 | 2-nitro-4,5-dihalogenated phenol and 2-amino-4,5-dihalogenated phenol as well as its salt and method for synthesizing the same |
| CN102942487B (en) * | 2012-11-17 | 2014-04-09 | 聊城大学 | Method for preparing o-nitrophenol through phenol nitration selectivity |
| CN106748797B (en) * | 2017-01-17 | 2018-04-03 | 宁波大学 | A kind of preparation method of the naphthol derivative of 2 nitro 1 |
| CN106831435B (en) * | 2017-01-17 | 2018-06-12 | 宁波大学 | A kind of preparation method of 1- nitros-beta naphthal derivative |
| CN109535003B (en) * | 2018-12-06 | 2021-12-03 | 福建振新化学有限公司 | Process for nitration of para-alkylphenols |
| CN110590557B (en) * | 2019-08-28 | 2022-07-05 | 上海师范大学 | Nitration method of aryl phenol or aryl ether derivative |
| CN112661649B (en) * | 2020-12-25 | 2023-01-10 | 宁波龙欣精细化工有限公司 | 2,6-dinitro-4-tert-amylphenol and preparation method thereof |
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| 苯酚的固体酸催化选择性硝化. 彭新华.江苏化工，第24卷第3期. 1996 * |
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