CN1230382C - Green nitrifying method by using Hf compound to catalyze compounds of phenols and aromatic ether - Google Patents
Green nitrifying method by using Hf compound to catalyze compounds of phenols and aromatic ether Download PDFInfo
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- CN1230382C CN1230382C CN 200310108236 CN200310108236A CN1230382C CN 1230382 C CN1230382 C CN 1230382C CN 200310108236 CN200310108236 CN 200310108236 CN 200310108236 A CN200310108236 A CN 200310108236A CN 1230382 C CN1230382 C CN 1230382C
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Abstract
The present invention relates to a new nitrating method for phenol and aromatic ether compounds. In the method, hafnium compound loading catalysts are used as catalysts and are formed by the way that hafnium compounds are loaded on KSF, SiO2 and other carriers. In organic solvents, the hafnium compounds are used as catalysts, nitric acid is used as nitrating agents, and the phenol and aromatic ether compounds are nitrified. The molecular formula of the phenol and aromatic ether compounds is RR<1>R<2>R<3>Z, wherein R, R<1>, R<2> and R<3> are equal to H, C1-5 alkyl, halogen, phenolic hydroxyl, C1-5 alkoxyl group and C6H5, R<1> is equal to phenolic hydroxyl and C1-5 alkoxyl group, and Z is equal to phenyl, naphthyl, tetralyl, anthracyl and flourenyl. 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 easy to get, KSF and other carriers can be reused in nitrating reaction, the recovery is convenient, and the nitrating catalysts used by the reaction method have no pollution to the environment and are economical green nitrating catalysts.
Description
Technical field
The present invention relates to a kind of Hf compound, preparation method and the application in green nitration method thereof, particularly relate to the green nitration method of phenols and aromatic oxide compounds.
Background technology
The nitration reaction of aromatics is the crucial chemical reaction of a class, and wherein the nitrated of phenols and aromatic oxide compounds 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.
Phenols and aromatic oxide compounds are that a class is highly susceptible to nitrated compound, but that phenols and aromatic oxide compounds are easy to again itself 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 phenols and aromatic oxide compounds, 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, 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 in the THF solvent nitrated (Susanta, S., Frederick, F.B., Bimal, K.B.Tetrahedron, 2000,41,8017-8020).
People such as Shi Min have tested multiple catalyzer in the research to nitration reaction, Bi (NO
3)
3And Bi
2O
3Be catalyzer preferably, its nitrated productive rate can reach more than 70%.
Hf is the metallic element of main group period 3, and itself and Ti, Zr are in same main group, have similar character.Recently a lot of to the research of the compound for catalysis organic reaction of Hf.With the oxide compound catalysis unsaturated carboxylic acid of Hf and epoxidation reaction (Han, the S. of unsaturated nitrile; Jacobs, B.A.; Bors, Daniel A.; Kaiser, F.W.; Klugherz, P.D.; Lin, M.; Cavalcanti, F.A.P.; Zolotorofe, and D.L. (Rohm and HaasCompany, USA) .Eur.Pat.Appl.EP 1193240 A1 3 Apr 2002,17pp.).Use Hf (OTf)
4With lithium perchlorate composite catalyst catalysis Friedel-Crafts acylation reaction (Hachiya, I.; Moriwaki, M.; Kobayashi, S.Tetrahedron Lett.1995,36 (3), 409-412).In the process of imines and aldolization synthesizing amino acid, use and contain Hf catalyzer (Wulff, W.D.; Xue, and S. (UOP Llc, USA) .PCT Int.Appl.WO 2000056448 A1 28 Sep 2000,33pp.).
Summary of the invention
The purpose of this invention is to provide a kind of hafnium compound.
The present invention also provides a kind of preparation method of above-mentioned hafnium compound.
Another object of the present invention provides a kind of application of hafnium compound, is used to provide the new nitrifying method of phenols and aromatic oxide compounds.
The invention provides new nitrifying method, the especially phenol of phenols and aromatic oxide compounds and the new nitrifying method of phenyl ether compound.This method is carried out nitrated as catalyzer to phenols or aromatic oxide compounds with carrier loaded hafnium compound.Recommend to carry out nitrated as catalyzer Pyrogentisinic Acid class or phenyl ether compound with carrier loaded hafnium compound.
Of the present inventionHafnium compound be with HfCl
4Hydrolysis, then at high temperature (be recommended as 100～200 ℃, further be recommended in 120 ℃) oven dry obtain, (through the ultimate analysis test, what obtain is not the oxide compound of Hf, but a kind of compound that contains Hf, Cl, O is called for short hafnium compound), the crystalline structure that obtains through the X-ray single crystal diffraction is as shown in Figure 1 and Figure 2.The molecular formula of this compound is [HfCl by analysis
2(OH)
2(H
2O)
2]
8, its molecular weight is 319.44.This compound is with reacting by good catalytic nitration after carrier loaded.
The application of hafnium compound of the present invention, be be used for catalysis phenols and aromatic oxide compounds nitrated, specifically, in organic solvent, with above-mentioned carrier loaded hafnium compound is nitrated catalyzer, with nitric acid is nitrating agent, carries out phenols and aromatic oxide compounds (being recommended as phenol or phenyl ether compound) nitrated.Described organic solvent is recommended as ether, further is recommended as tetrahydrofuran (THF), ether etc.Described carrier loaded hafnium compound is that foregoing hafnium compound is carried on KSF, SiO
2On carrier.Described nitric acid is recommended as 20～100% nitric acid.Described phenols and aromatic oxide compounds molecular formula are R (R
1) (R
2) (R
3) Z, wherein, R, R
2Or R
3=H, C
1-5Alkyl, halogen, phenolic hydroxyl group, C
1-5Alkoxyl group or C
6H
5, R
1=phenolic hydroxyl group or C
1-5Alkoxyl group, Z=phenyl, naphthyl, tetralyl, anthryl or fluorenyl.Recommendation Z is a phenyl, for example
Further recommending phenols and aromatic oxide compounds is phenol, Resorcinol, Resorcinol, p-tert-butylphenol etc.The product that obtains can be nitrated or two nitrated products, molecular formula such as RR
1R
1R
3Z (NO
2)
m, m=1 or 2.
Above-mentioned carrier loaded hafnium compound, load ratio are 0.01～1mmol/500mg, further are recommended as 0.1～0.5mmol/500mg.Catalyst consumption is a catalytic amount in the above-mentioned nitration reaction, it is 0.01～1mg Hf compound/mmol phenol or phenylate compound that consumption is recommended as with the Hf metering, further be recommended as with Hf metering 0.05～0.5mg Hf compound/mmol phenol or phenylate compound, range temperature is recommended in 30～100 ℃, further be recommended as 50～70 ℃, reaction times is recommended as 0.5～24 hour, further is recommended as 4～16 hours.The ratio of described hafnium compound loaded catalyst, nitric acid, phenol or phenyl ether compound is 0.01-1mg: 1-10mmol: 1mmol.The mole dosage ratio of above-mentioned phenol and phenyl ether compound and nitric acid is recommended as (0.1～1 molar percentage), further is recommended as 0.5～1 molar percentage.
In experiment, when having contrasted use and not used the Hf compound, the situation that nitration reaction is carried out.As seen from the figure, when the Hf compound for catalysis of use KSF load was nitrated, speed of response was obviously accelerated (Figure 1).
On the other hand, the hafnium compound that is carried on the KSF can repeatedly reclaim repeated use, still has catalytic activity, and its recovery is very convenient, only needs to filter the post-heating activation, and is promptly reusable.In experiment catalyzer has been carried out five times and reclaimed experiment, all obtained result preferably, best productive rate as a result can reach 87% (Table1).
In experiment, used different solvents, at ether solvent, as reacting (Table 2) preferably in ether, the THF equal solvent.And in methylene dichloride, Nitromethane 99Min. equal solvent, the productive rate of nitration reaction is very low.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, but the usage quantity of carrier KSF needs to amplify nitrated productive rate about about 66%.When concentration of nitric acid brought up to 95%, when reacting down for 0 ℃, productive rate was 80%, and reaction at room temperature is comparatively violent, by product more (Table 3).In experiment, tested its catalytic effect to multiple substrate.Most of substrate all obtains nitration product with yield preferably, wherein para-chlorophenol and to tert.-butylbenzene
The nitrated productive rate of phenol reaches (Table 4) more than 95%.
Reaction formula 1
Table 1. uses the nitration reaction of Hf compound/KSF catalysis Resorcinol.
Sequence number time/h productive rate (%)
1 16 84
2a 16 87
3a 16 86
4a 16 87
A) catalyzer is reused.
Table 2. uses the nitration reaction of Hf compound/KSF catalysis Resorcinol.
Sequence number solvent time/h productive rate (%)
1 ether 1.0 66
2 ether 16 80
3 tetrahydrofuran (THF)s 1.0 68
4 tetrahydrofuran (THF)s 16 87
5 ethylene glycol that methyl ether 16 82
6 methylene dichloride 16 20
7 Nitromethane 99Min.s 16 35
Reaction formula 3.
The nitration reaction of Table 3. under the effect of different concns nitric acid.
Sequence number nitric acid KSF productive rate %)
The percentage concentration amount
1 20％ 1000mg 66
2 60％ 500mg 84
3 95％ 500mg 80
Table 4. uses the nitration reaction of Hf compound/carrier catalysis Resorcinol.
The sequence number bed temperature (℃) productive rate (%)
1-room temperature is not reacted
2 - 70 54
3 KSF room temperatures 84
4 KSF 70 80
5 SiO
2 70 82
Reaction formula 5
Table 5. uses the nitration reaction of the different phenolic compounds of Hf compound/KSF catalysis.
Productive rate
Sequence number R
Time (h) 12
1 H 16 84
a
2 Cl 4 98 -
3 Br 16 84 -
4 t-Bu 16 40 57
5 OMe 16 - 73
6
4 84
b
7
16 81
c
8
16 77
A) product is 2-nitre cresylol (40%) and 4-nitrophenols (44%).
B) product is 1,4-dimethoxy-2-oil of mirbane.
C) product is 4,5-dichloro o-2-nitrophenols (51%) and 3,4-two chloro-2-nitrophenolss (30%).
The nitrifying method of this phenols and aromatic oxide compounds 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, KSF is common Chemicals, and reusable in nitration reaction, and it is convenient to reclaim.The oxide compound of bismuth is very easy to preparation again.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 this is nitrated anti-
The nitrated catalyzer environmentally safe that should use is a kind of economy, green nitrated catalyzer.
Description of drawings
Fig. 1, Fig. 2 are the crystalline structure that hafnium compound of the present invention obtains through the X-ray single crystal diffraction
Fig. 3 is to use the nitrated productive rate of para-chlorophenol under the different catalytic conditions (p-chlorophenol).
Embodiment
Embodiment 1
With HfCl
4(1.0g) add reactor, add water (2mL) its hydrolysis.With HfCl
4The aqueous solution of hydrolysate in down oven dry of high temperature (120 ℃), obtain faint yellow solid, promptly contain the catalyzer 3.6g of Hf, Cl, O, productive rate＞99% is called for short hafnium compound.This compound contains chlorine (Cl:22.16%.) through ultimate analysis.This compound recrystallization in water obtains light yellow crystal, obtains its crystalline structure as shown in Figure 1 and Figure 2 through the X-ray single crystal diffraction.
KSF (500mg) is added reactor, heat the activation of bleeding.(solvent, 5mL), (110mg, 1.0mmol), (32mg 0.1mmol) adds reactor to Resorcinol to tetrahydrofuran (THF), mixes with the hafnium compound of embodiment 1.(0.10mL 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 130mg, productive rate 84%.M.p.:117-119 ℃ of 4-nitro-resorcinol; IR (KCl) ν 1532,1397cm
-1(NO
2), 1255cm
-1(ArOH);
1H-NMR (CDCl
3, TMS, 300MHz) 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
+) [calculated value C
6H
5NO
4(155.1082)]; [measured value C, 46.48; H, 3.44; N, 9.02%.C
6H
5NO
4Calculated value C, 46.46; H, 3.25; N, 9.03%].
Embodiment 3
KSF (1000mg) is added reactor, heat the activation of bleeding.(solvent, 5mL), (110mg, 1.0mmol), (32mg 0.1mmol) adds reactor to Resorcinol to tetrahydrofuran (THF), mixes with the hafnium compound of embodiment 1.(0.30mL 1.4mmol), stirs 16h under the room temperature to the 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 102mg, productive rate 66%.
KSF (500mg) is added reactor, heat the activation of bleeding.(solvent, 5mL), (110mg, 1.0mmol), (32mg 0.1mmol) adds reactor to Resorcinol to tetrahydrofuran (THF), mixes with the hafnium compound of embodiment 1.(0.05mL, 1.4mmol), 0 ℃ is stirred 16h down to the concentrated nitric acid of dropping 95%.Dichloromethane extraction is used in reaction mixture washing back, is spin-dried for, crosses post on Rotary Evaporators.Obtain yellow solid 124mg, productive rate 80%.
Embodiment 5
With SiO
2(500mg) add reactor.(solvent, 5mL), (110mg, 1.0mmol), (39mg 0.1mmol) adds reactor to Resorcinol to tetrahydrofuran (THF), mixes with the hafnium compound of embodiment 1.(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, crosses post on Rotary Evaporators.Obtain yellow solid 127mg, productive rate 82%.
KSF (500mg) is added reactor, heat the activation of bleeding.(solvent, 5mL), (0.09mL, 1.0mmol), (32mg 0.1mmol) adds reactor to phenol to tetrahydrofuran (THF), mixes with the hafnium compound of embodiment 1.(0.10mL 1.4mmol), 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 55mg, productive rate 40%, 2-nitrophenols and faint yellow solid 61mg, productive rate 44%, 4-nitrophenols.M.p.:45-47 ℃ of 2-nitrophenols; Ir (KCl) ν 1522,1416cm
-1(NO
2), 1240cm
-1(ArOH);
1H-NMR (CDCl
3, TMS, 300MHz) 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
+) [calculated value C
6H
5NO
3(139.1088)]; M.p.:117-119 ℃ of 4-nitrophenols; IR (KCl) ν 1522,1416cm
-1(NO
2), 1240cm
-1(ArOH);
1H-NMR (CDCl
3, TMS, 300MHz) 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
+) [calculated value C
6H
5NO
3(139.1088)]; [measured value C, 51.73; H, 3.73; N, 10.04%.C
6H
5NO
3Calculated value C, 51.80; H, 3.62; N, 10.07%].
Embodiment 7
KSF (500mg) is added reactor, heat the activation of bleeding.(solvent, 5mL), (1.0mL, 1.0mmol), (32mg 0.1mmol) adds reactor to para-chlorophenol to tetrahydrofuran (THF), mixes with the hafnium compound of embodiment 1.(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%.M.p.:86-88 ℃ of 2-nitro para-chlorophenol; IR (KCl) ν 1522,1416cm
-1(NO
2), 1240cm
-1(ArOH);
1H-NMR (CDCl
3, TMS, 300MHz) 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 C
6H
4ClNO
3(173.5536)]; [measured value C, 41.58; H, 2.36; N, 8.10%.C
6H
4ClNO
3Calculated value C, 41.52; H, 2.32; N, 8.07%].
KSF (500mg) is added reactor, heat the activation of bleeding.(solvent, 5mL), (173mg, 1.0mmol), (32mg 0.1mmol) adds reactor to p bromophenol to tetrahydrofuran (THF), mixes with the hafnium compound of embodiment 1.(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 84%.M.p.:88-90 ℃ of 2-nitro p bromophenol; IR (KCl) ν 1532,1412cm
-1(NO
2), 1249cm
-1(ArOH);
1H-NMR (CDCl
3, TMS, 300MHz) 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 C
6H
4BrNO
3(218.0049)]; [measured value C, 33.34; H, 2.08; N, 6.35%.C
6H
4BrNO
3Calculated value C, 33.06; H, 1.85; N, 6.42%].
Embodiment 9
KSF (500mg) is added reactor, heat the activation of bleeding.(solvent, 5mL), (150mg, 1.0mmol), (32mg 0.1mmol) adds reactor to p-tert-butylphenol to tetrahydrofuran (THF), mixes with the hafnium compound of embodiment 1.(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 78mg, productive rate 40%, 2,6-dinitrobenzene p-tert-butylphenol and yellow liquid 137mg, productive rate 57%, 2-nitro p-tert-butylphenol.M.p.:70-73 ℃ of 2-nitro p-tert-butylphenol; IR (KCl) ν 1532,1397cm
-1(NO
2), 1255cm
-1(ArOH);
1H-NMR (CDCl
3, TMS, 300MHz) 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
+) [calculated value C
10H
13NO
3(195.2152); Calculated value M, 195.0895, measured value M
+195.0899].2, m.p.:96-98 ℃ of 6-dinitrobenzene p-tert-butylphenol; IR (KCl) ν 1532,1367cm
-1(NO
2), 1265cm
-1(ArOH);
1H-NMR (CDCl
3, TMS, 300MHz) 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)]; [measured value C, 50.07; H, 5.06; N, 11.59%.C
10H
12N
2O
5Calculated value C, 50.00; H, 5.04; N, 11.66%].
KSF (500mg) is added reactor, heat the activation of bleeding.(solvent, 5mL), (124mg, 1.0mmol), (32mg 0.1mmol) adds reactor to p methoxy phenol to tetrahydrofuran (THF), mixes with the hafnium compound of embodiment 1.(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 156mg, productive rate 73%.2, m.p.:77-79 ℃ of 6-dinitrobenzene p methoxy phenol; IR (KCl) ν 1537,1358cm
-1(NO
2), 1243cm
-1(ArOH);
1H-NMR (CDCl
3, TMS, 300MHz) δ 3.91 (3H, s, OCH
3) 7.86 (2H, s, Ar) 11.00 (1H, s, ArOH); MS (EI) m/z 214 (M
+) [calculated value C
7H
6N
2O
6(214.1324)]; [measured value C, 39.38; H, 2.69; N, 12.87%.C
7H
6N
2O
6Calculated value C, 39.26; H, 2.82; N, 13.08%].
Embodiment 11
KSF (500mg) is added reactor, heat the activation of bleeding.(solvent, 5mL), (138mg, 1.0mmol), (39mg 0.1mmol) adds reactor to tetrahydrofuran (THF), mixes with the hafnium compound of embodiment 1 to the anisole methyl ether.(0.10mL 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 154mg, productive rate 84%.The 2-nitro is to m.p.:71-72 ℃ of anisole methyl ether; IR (KCl) ν 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
+) [calculated value C
8H
9NO
4(183.1614)]; [measured value C, 52.49; H, 4.95; N, 7.62%.C
8H
9NO
4Calculated value C, 52.46; H, 4.95; N, 7.65%].
KSF (500mg) is added reactor, heat the activation of bleeding.Tetrahydrofuran (THF) (solvent, 5mL), 3, (163mg, 1.0mmol), (32mg 0.1mmol) adds reactor to the 4-chlorophenesic acid, mixes with the hafnium compound of embodiment 1.(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 106mg, productive rate 51%, 2-nitro 4,5-chlorophenesic acid and yellow solid 62mg, productive rate 30%, 2-nitro 3,4-chlorophenesic acid.2-nitro 4, m.p.:63-65 ℃ of 5-chlorophenesic acid; IR (KCl) ν 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
+) [calculated value C
8H
9NO
4(207.9984)]; [measured value C, 34.65; H, 1.45; N, 6.73%.C
6H
3Cl
2NO
3Calculated value C, 34.52; H, 1.50; N, 6.68%].2-nitro 3, m.p.:76-78 ℃ of 4-chlorophenesic acid; IR (KCl) ν 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
+) [calculated value C
8H
9NO
4(207.9984)]; [measured value C, 34.65; H, 1.45; N, 6.73%.C
6H
3Cl
2NO
3Calculated value C, 34.52; H, 1.50; N, 6.68%]
Embodiment 13
KSF (500mg) is added reactor, heat the activation of bleeding.Tetrahydrofuran (THF) (solvent, 5mL), 2,4, (197mg, 1.0mmol), (32mg 0.1mmol) adds reactor to the 5-Trichlorophenol, mixes with the hafnium compound of embodiment 1.(0.10mL 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 167mg, productive rate 77%.2-nitro 3,4, m.p.:91-92 ℃ of 6-Trichlorophenol; IR (KCl) ν 1533,1358cm
-1(NO
2);
1H-NMR (CDCl
3, TMS, 300MHz) δ 7.657.56 (1H, s, OH) (1H, s, ArH); MS (EI) m/z 242 (M
+) [calculated value C
8H
9NO
4(242.4431)]; [measured value C, 29.72; H, 0.83; N, 5.78%.C
6H
2Cl
3NO
3Calculated value C, 29.57; H, 0.91; N, 5.70%].
Claims (9)
1, a kind of hafnium compound, its molecular formula are [HfCl
2(OH)
2(H
2O)
2]
8
2, hafnium compound as claimed in claim 1 is characterized in that its molecular weight is 319.44.
3, the preparation method of hafnium compound as claimed in claim 1 is characterized in that HfCl
4Hydrolysate the aqueous solution 100 ℃～200 ℃ down oven dry obtain.
4, the preparation method of hafnium compound as claimed in claim 3 is characterized in that HfCl
4Hydrolysate the aqueous solution 120 ℃ down oven dry obtain.
5, the application of a kind of hafnium compound as claimed in claim 1, it is characterized in that in organic solvent, carrier loaded hafnium compound catalyzer, nitric acid and phenols or aromatic oxide compounds react, and described carrier loaded hafnium compound catalyzer is that the described hafnium compound of claim 1 is carried on KSF or SiO
2Carrier on, described phenols or aromatic oxide compounds molecular formula are R (R
1) (R
2) (R
3) Z, wherein, R, R
2Or R
3=H, C
1-5Alkyl, halogen, phenolic hydroxyl group, C
1-5Alkoxyl group or C
6H
5, R
1=phenolic hydroxyl group or C
1-5Alkoxyl group, Z=phenyl, naphthyl, tetralyl, anthryl or fluorenyl.
6, the application of a kind of hafnium compound as claimed in claim 6 is characterized in that described hafnium compound is carried on KSF or SiO
2Carrier on, the load ratio is 0.01～1mmol/500mg.
7, the application of a kind of hafnium compound as claimed in claim 6 is characterized in that described organic solvent is an ether organic solvent, and described nitric acid is 20%～100% nitric acid.
8, the application of a kind of hafnium compound as claimed in claim 6 is characterized in that the ratio of described carrier loaded hafnium compound loaded catalyst, nitric acid, phenols or aromatic oxide compounds is 0.01-1mg:1-10mmol:1mmol.
9, the application of a kind of hafnium compound as claimed in claim 6 is characterized in that described temperature of reaction is 30-100 ℃; The described reaction times is 0.5-24 hour.
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