CN1166620C - Green nitration process of utilizing rare earth metal salt of perfluoro alkyl sulfonic acid to catalyze aromatic compound - Google Patents
Green nitration process of utilizing rare earth metal salt of perfluoro alkyl sulfonic acid to catalyze aromatic compound Download PDFInfo
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Abstract
The present invention relates to novel rare earth metal salt of perfluothane sulfonic acid of catalysts of which the molecular formula is Ln (OSO2CnFn+1)3, wherein n=7 to 10, and Ln= rare earth elements. An environmentally friendly synthetic method of nitro-substitution aromatic compounds is obtained by the nitration reaction of catalytic aromatic compounds. The method of the present invention is an economical green nitrification method which has the advantages of no pollution to environment and is suitable for industrial production.
Description
The present invention is to use the nitrated of a kind of novel rare earth Louis acid catalysis aromatics, obtains the eco-friendly synthetic method of nitro substituted aromatic compound.
Nitro-compound is mainly used in explosive, gunpowder, propelling agent, industrial chemicals, medicine and agricultural chemicals etc., concerning the national economy and national defence of a country, has special significance.
The nitration reaction of aromatics is very important reaction in chemical industry.But industrial nitrated production at present also mainly relies on early stage use nitration mixture technology.Use the nitrification of nitration mixture to have many weak points.1. the product of mixed acid nitrification, the position of substitution selectivity of nitro is bad.2. the corrodibility of nitration mixture is very strong, and production security is poor.3. have only nitric acid to be consumed in the mixed acid nitrification process, and a large amount of sulfuric acid discharge, and environment is had very big pollution as spent acid.4. use mixed acid nitrification to produce nitration product or oxidation products through regular meeting.
Since more than, now each state all in the new nitrated technology of active research to replace the nitration mixture technology, for example use the lewis acid catalyst catalytic nitration.Some lewis acid catalyst such as boron trifluoride are a kind of good nitrated catalyzer, m-nitrobenzaldehyde can be converted into dinitrobenzal-dehyde [F.J.Waller fully under the effect of nitric acid and boron trifluoride catalyst, A.G.M.Barrett and G.F.Hennion Ind.Eng.Chem.1940,32,408; G.F.Hennion US Pat., 2314212,1943.].Another utilizes the nitrifying process of lewis acid catalyst to be to use the aluminum chloride that is added in the metal nitrate.But using Lewis acid at present or using lewis acidic mixture is highstrung to water as the nitrifying process of catalyzer.This mainly is because nitrated employed Lewis acid itself is highstrung to water at present.
Simple perfluoro alkyl sulfonic acid is the strongest acid known to up to now, since Forsberg in 1987 introduces trifluoromethanesulfonic acid rare-earth salts [Ln (OTf)
3] since, [J.H.forsberg, V.T.Spaziano, T.M.Balasubramanian, G.K.Liu, S.A.Kinsley, C.A.Duckworth, J.J.Poteruca, P.S.Brown and J.L.Miller; J.Org.Chem., 1987,52,1017] various rare earth perfluorinated sulfonates become the focus of numerous catalyzed reaction researchs as Lewis acid.Kobayshi has developed the recyclable water-proof Lewis acid [S.kobayashi, Synlett, 1994,689] that uses repeatedly, and these rare-earth saltss have replaced traditional Lewis acid in many reactions.The successful Application of rare-earth salts is given and is used the classical inverse of strong lewis acid should bring hope, react as Diels-Alder, [I.E.Marko and G.R.Evans, Tetrahedron Lett., 1994,35,277] Michael addition reaction, [S.kobayashi, I.Hachiya, T.Takakori, M.Akida and H.Ishitani, Tetrahedron Lett., 1992,33,6815] Friedel-Crafts reaction [A.Kawada, S.Mitamura and S.kobayashi, Chem.Commun., 1996,183] etc.These catalyzer can be usually can recycling, and keep good catalytic activity.These use the catalytic reaction of rare-earth saltss, much can be in water or protonic solvent gratifying carrying out.These advantages make the trifluoromethanesulfonic acid rare-earth salts substitute sulfuric acid use in aromatic hydrocarbons electrophilic nitrated to have had certain possibility.
People such as Waller and Barrett in systematic research in 1998 the trifluoromethanesulfonic acid rare-earth salts be the nitrated reaction of catalyst bromobenzene.[F.J.Waller, A.G.M.Barrett, D.C.Braddock, R.M.McKinnelland D.Ramprasad J.Chem.Soc., Perkin Trans.7,1999,867] its reaction system is with 1, the 2-ethylene dichloride is a solvent, only uses 96% concentrated nitric acid, with the trifluoromethanesulfonic acid rare-earth salts catalysis of 10%mol.The best result that they obtain is with Lu (OTf)
3Obtain 68% productive rate during catalysis, other rare-earth saltss such as La (OTf)
3Productive rate 34%, Eu (OTf)
3Productive rate 57%, Yb (OTf)
3Productive rate 62%.
Kobayashi has mentioned use Sc (OSO in nearest report
2CF
3)
3[Sc (OTf)
3], Sc (OSO
2C
4F
9)
3And Sc (OSO
2C
8F
17)
3[Sc (OPf)
3] as catalyst Diels-Alder and Aze Diels-Alder reaction.[S.kobayashi，J.Matsuo，T.Tsuchiya，K.Odashima，Chem.Lett.，2000，178]。So people are expected to further improve the nitration reaction that above-mentioned rare earth Lewis acid can find a kind of more effective catalyst aromatics.
The object of the invention provides a kind of improved rare earth Lewis acid, adopts the green nitration method of the aromatics of this novel rare-earth Louis acid catalysis, has more effective catalytic nitration response capacity.
The green nitration method of the aromatics of a kind of rare earth Louis acid catalysis provided by the invention, the rare earth lewis acid catalyst molecular formula of using is Ln (OSO
2C
nF
2n+1)
3The rare earth metal salt of perfluoro alkyl sulfonic acid, n=7-10 wherein, Ln=rare earth element.Rare earth element can be Sc, Y and lanthanon etc.
Above-mentioned rare earth Lewis acid provided by the invention can more effective catalytic nitration reaction.Aromatic hydrocarbons is generally organic phase or is soluble in organic phase, and nitric acid is water, and both do not dissolve each other.High-grade perfluoro alkyl sulfonic acid and derivative thereof have high surfactivity, are suitable for two phase reaction.Fluorocarbon chain is too short, and then to reduce capillary ability in solvent relatively poor, long its solubleness in water that then influences of fluorocarbon chain.The fluorocarbon chain of senior perfluoro alkyl sulfonic acid is with C
7-10The most suitable.
In the methods of the invention, in organic solvent or organic solvent-free, the mol ratio of the rare earth metal salt of nitric acid, aromatics and perfluoro alkyl sulfonic acid is 1: 1-5: 0.00005-0.005, recommending mol ratio is 1: 1-2: 0.0001-0.0005.Temperature of reaction is 20-100 ℃, and the reaction times is 10-100 hour.The recommendation response temperature is 50-100 ℃, and the reaction times is 20-50 hour.
Above-mentioned aromatics molecular formula is RR
1Z, wherein, R=H, C
1-5Alkyl, halogen, C
6H
5Or C
1-5Alkoxyl group etc., R
1=H or C
1-5Alkyl, Z=phenyl, naphthyl, tetralyl, anthryl or fluorenyl etc.
Adopt method of the present invention, with the rare earth metal salt [Ln (OPf) of perfluorooctane sulfonate
3] for nitrated catalyzer and toluene are that reaction raw materials is an example, the nitric acid with 65% is the nitro carrier, uses 0.02% perfluorooctane sulfonate ytterbium salt to be catalyzer, reaction is 48 hours under 50-70 ℃ condition, isolated yield is 60%, and through stratographic analysis, para-nitrotoluene accounts for 80%.
The rare earth metal salt La (OPf) of four kinds of and for example following perfluorooctane sulfonates
3, Yb (OPf)
3, Eu (OPf)
3And Sc (OPf)
3, and a kind of perfluor sulfonic acid in last of the ten Heavenly stems La (OSO
2C
10F
21)
3Be example, its catalytic effect is as follows.
Sequence number catalyzer time/hour temperature/℃ productive rate %
1 La(OPf)
3 48 70 50
2 La(OSO
2C
10F
21)
3?96 70 40
3 Yb(OPf)
3 48 70 60
4 Yb(OTf)
3 96 70 32
5 Yb
2O
3 96 70 10
6 Eu(OPf)
3 48 70 60
7 Sc(OPf)
3 48 70 65
By contrasting the catalytic capability of several rare earth metal salts, La (OPf)
3Catalytic capability than Yb (OTf)
3Exceed nearly one times.In the perfluorooctane sulfonate rare-earth salts, the catalytic capability of perfluorooctane sulfonate scandium salts is higher than other catalyzer, but the catalytic effect of several rare-earth saltss is close, from the angle of economy, uses La salt or Yb salt for well.
Adopt method of the present invention, compare, have following advantage with the nitrifying method of having reported:
1. the present invention does not need solvent, thereby the pollution problem that does not exist solvent to bring, and has reduced production cost simultaneously yet.
2. the present invention does not need to add other acid, and help to produce the nitryl positive ion, thereby do not have the pollution of spent acid, be a kind of nitrated method of green.
3. catalyst consumption is 0.02% among the present invention, and consumption is few, and can reuse after suitably adding, thereby the present invention is a kind of nitrifying method of economy.
4. the present invention carries out the nitrated of aromatic hydrocarbons, and its product has only nitration product and water, does not have other discharge, environmentally safe.It is a kind of industrial method that is fit to.
So method of the present invention is the nitrifying method of a kind of economy, pollution-free green, following examples help to understand the present invention, but are not limited to content of the present invention
Embodiment 1
With toluene (0.4ml, 5mmol) and 65% concentrated nitric acid (0.25g 2.5mmol) adds reactor and mixes, and adds catalyzer Yb (OPf)
3(2.1mg .0.05%mol), reflux stirs, and temperature of reaction is controlled at 70 ℃.React and stop heating after 48 hours, dichloromethane extraction use in mixture washing back, is spin-dried on Rotary Evaporators, the mistake post.Obtain yellow oily liquid 206mg, productive rate 60%.The 2-nitrotoluene:
1H-NMR (CDCl
3, TMS) δ 2.61 (3H, s, CH
3); 7.20-7.45 (2H, m, Ar); 7.48 (1H, d, J=7.5Hz, Ar); 7.96 (1H, d, J=7.5Hz, Ar) 3-nitrotoluene:
1H-NMR (CDCl
3, TMS) δ 2.48 (3H, s, CH
3) 7.49 (2H, Ar) 8.04 (2H, Ar) 4-nitrotoluene:
1H-NMR (CDCl
3, TMS) δ 2.48 (3H, s, CH
3) 7.33 (2H, d, J=8.4Hz, Ar) 8.13 (2H, d, J=8.4Hz, Ar) MS (EI) m/z 137 (M
+) [Calc.for C
7H
8NO
2(137.1360) requires M, 137.0477, Found:M
+137.0464]
Embodiment 2
With toluene (0.4ml, 5mmol) and 65% concentrated nitric acid (0.25g 2.5mmol) adds reactor and mixes, and adds catalyzer La (OPf)
3(2.0mg, 0.05%mol), reflux stirs, and temperature of reaction is controlled at 70 ℃.React and stop heating after 48 hours, dichloromethane extraction use in mixture washing back, is spin-dried on Rotary Evaporators, the mistake post.Obtain yellow oily liquid 172mg, productive rate 50%.
Embodiment 3
With toluene (0.4ml, 5mmol) and 65% concentrated nitric acid (0.25g 2.5mmol) adds reactor and mixes, and adds catalyzer Eu (OPf)
3(2.1mg, 0.05%mol), reflux stirs, and temperature of reaction is controlled at 70 ℃.React and stop heating after 48 hours, dichloromethane extraction use in mixture washing back, is spin-dried on Rotary Evaporators, the mistake post.Obtain yellow oily liquid 200mg, productive rate 60%.
Embodiment 4
With toluene (0.4ml, 5mmol) and 65% concentrated nitric acid (0.25g 2.5mmol) adds reactor and mixes, and adds catalyst S c (OPf)
3(1.9mg, 0.05%mol), reflux stirs, and temperature of reaction is controlled at 70 ℃.React and stop heating after 48 hours, dichloromethane extraction use in mixture washing back, is spin-dried on Rotary Evaporators, the mistake post.Obtain yellow oily liquid 222mg, productive rate 65%.
Embodiment 5
With toluene (0.4ml, 5mmol) and 65% concentrated nitric acid (0.25g 2.5mmol) adds reactor and mixes, and adds catalyzer La (OSO
2C
10F
21)
3(2.4mg, 0.05%mol), reflux stirs, and temperature of reaction is controlled at 70 ℃.React and stop heating after 48 hours, dichloromethane extraction use in mixture washing back, is spin-dried on Rotary Evaporators, the mistake post.Obtain yellow oily liquid 135mg, productive rate 40%.
Embodiment 6
With methyl-phenoxide (0.6ml, 5mmol) and 65% concentrated nitric acid (0.25g 2.5mmol) adds reactor and mixes, and adds catalyzer Yb (OPf)
3(2.1mg, 0.05%mol), reflux stirs, and temperature of reaction is controlled at 70 ℃.React and stop heating after 48 hours, dichloromethane extraction use in mixture washing back, is spin-dried on Rotary Evaporators, the mistake post.Obtain yellow oily liquid 75mg, productive rate 30%.The 2-Nitroanisole
1H-NMR (CDCl
3, TMS) δ 3.96 (3H, s, CH
3) 7.03-7.09 (2H, m, Ar) 7.56 (1H, t, J=7.8Hz, Ar) 7.85 (1H, d, J=7.9Hz, Ar) 4-Nitroanisoles
1H-NMR (CDCl
3, TMS) δ 3.92 (3H, s, CH
3) 6.96 (2H, d, J=8.2Hz, Ar) 8.22 (2H, d, J=8.1Hz, Ar) MS (EI) m/z 153 (M
+) [Calc.for C
7H
7NO
3(153.1354) requires M, 153.0426, Found:M
+153.0432]
Embodiment 7
With chlorobenzene (0.5ml, 5mmol) and 65% concentrated nitric acid (0.25g 2.5mmol) adds reactor and mixes, and adds catalyzer Yb (OPf)
3(2.1mg, 0.05%mol), reflux stirs, and temperature of reaction is controlled at 70 ℃.React and stop heating after 48 hours, dichloromethane extraction use in mixture washing back, is spin-dried on Rotary Evaporators, the mistake post.Obtain yellow oily liquid 215mg, productive rate 55%.The 4-nitro-chlorobenzene
1H-NMR (CDCl
3, TMS) δ 7.62 (2H, d, J=8.2Hz, Ar) 8.06 (2H, d, J=8.2Hz, Ar) 2-nitro-chlorobenzenes
1H-NMR (CDCl
3, TMS) δ 7.30-7.36 (3H, m, Ar) 7.75 (1H, d, J=7.8Hz, Ar) MS (EI) m/z 158 (M
+) [Calc.for C
6H
4ClNO
2(157.5542) requires M, 156.9931, Found:M
+156.9915]
Embodiment 8
With bromobenzene (0.53ml, 5mmol) and 65% concentrated nitric acid (0.25g 2.5mmol) adds reactor and mixes, and adds catalyzer Yb (OPf)
3(2.1mg .0.05%mol), reflux stirs, and temperature of reaction is controlled at 70 ℃.React and stop heating after 48 hours, dichloromethane extraction use in mixture washing back, is spin-dried on Rotary Evaporators, the mistake post.Obtain yellow crystals 278mg, productive rate 55%.M.p.:96-110 ℃ of 4-nitro bromobenzene
1H-NMR (CDCl
3, TMS) δ 7.59 (2H, d, J=8.5Hz, Ar) 8.00 (2H, d, J=8.5Hz, Ar) 2-nitro bromobenzenes
1H-NMR (CDCl
3, TMS) δ 7.27-7.33 (3H, m, Ar) 7.70 (1H, d, J=7.8Hz, Ar) MS (EI) m/z 202 (M
+) [Calc.for C
6H
4BrNO
2(202.0055) requires M, 200.9425, Found:M
+200.9410]
Embodiment 9
With benzene (0.4ml, 5mmol) and 65% concentrated nitric acid (0.25g 2.5mmol) adds reactor and mixes, and adds catalyzer Yb (OPf)
3(2.1mg .0.05%mol), reflux stirs, and temperature of reaction is controlled at 70 ℃.React and stop heating after 48 hours, dichloromethane extraction use in mixture washing back, is spin-dried on Rotary Evaporators, the mistake post.Obtain yellow oily liquid 36mg, productive rate 15%.
1H-NMR(CDCl
3，TMS)δ7.71(2H，t，J＝7.7Hz，Ar)7.52-7.58(1H，m，Ar)8.24(2H，d，J＝7.8Hz，Ar)MS(EI)m/z123(M
+)[Calc.for?C
6H
5NO
2(123.1094)requires?M，123.0320，Found：M
+123.0333]
Embodiment 10
With dimethylbenzene (0.6ml, 5mmol) and 65% concentrated nitric acid (0.25g 2.5mmol) adds reactor and mixes, and adds catalyzer Yb (OPf)
3(2.1mg .0.05%mol), reflux stirs, and temperature of reaction is controlled at 70 ℃.React and stop heating after 48 hours, dichloromethane extraction use in mixture washing back, is spin-dried on Rotary Evaporators, the mistake post.Obtain yellow oily liquid 190mg, productive rate 50%.1,2-dimethyl 4-oil of mirbane
1H-NMR (CDCl
3, TMS) δ 2.38 (6H, s, CH
3) 7.25 (1H, d, J=8.0Hz, Ar) 7.94-8.00 (2H, m, Ar) 1,3-dimethyl 5-oil of mirbane
1H-NMR (CDCl
3, TMS) δ 2.42 (6H, s, CH
3) 7.30 (1H, s, Ar) 7.83 (2H, s, Ar) 1,4-dimethyl 2-oil of mirbane
1H-NMR (CDCl
3, TMS) δ 2.40 (3H, s, CH
3) 2.55 (3H, s, CH
3) 7.20-7.33 (2H, m, Ar) 7.78 (1H, s, Ar) 2,3-dimethyl 1-oil of mirbane
1H-NMR (CDCl
3, TMS) δ 2.37 (6H, s, CH
3) 7.08-7.45 (2H, m, Ar) 7.58 (1H, d, J=7.8Hz, Ar) 2,4-dimethyl 1-oil of mirbane
1H-NMR (CDCl
3, TMS) δ 2.40 (3H, s, CH
3) 2.60 (3H, s, CH
3) 7.11-7.16 (2H, m, Ar) 7.92 (1H, d, J=7.9Hz, Ar) 2,6-dimethyl 1-oil of mirbane
1H-NMR (CDCl
3, TMS) δ 2.30 (6H, s, CH
3) 7.11-7.28 (3H, m, Ar) MS (EI) m/z 151 (M
+) [Calc.for C
8H
9NO
2(151.1626) requires M, 151.0633, Found:M
+151.0630]
Embodiment 11
(0.75g, (0.25g 2.5mmol) adds reactor and mixes, and adds catalyzer Yb (OPf) 5mmol) to be dissolved in the concentrated nitric acid of chloroform (1ml) and 65% with biphenyl
3(2.1mg .0.05%mol), reflux stirs, and temperature of reaction is controlled at 70 ℃.React and stop heating after 48 hours, dichloromethane extraction use in mixture washing back, is spin-dried on Rotary Evaporators, the mistake post.Obtain yellow solid 150mg, productive rate 30%.M.p.:45-50 ℃ of nitrobiphenyl:
1H-NMR (CDCl
3, TMS) δ 7.27-8.28 (9H, m, Ar) MS (EI) m/z 199 (M
+) [Calc.for C
12H
9NO
2(199.2054) requires M, 199.0633, Found:M
+199.0630]
Embodiment 12
(0.70g, (0.25g 2.5mmol) adds reactor and mixes, and adds catalyzer Yb (OPf) 5mmol) to be dissolved in the concentrated nitric acid of chloroform (1ml) and 65% with the 2-methylnaphthalene
3(2.1mg .0.05%mol), reflux stirs, and temperature of reaction is controlled at 70 ℃.React and stop heating after 48 hours, dichloromethane extraction use in mixture washing back, is spin-dried on Rotary Evaporators, the mistake post.Obtain yellow solid 283mg, productive rate 60%.m.p.：38-42℃
1H-NMR(CDCl
3，TMS)δ2.49(s，CH
3)2.53(s，CH
3)2.57(s，CH
3)7.34(d，J＝8.5Hz，Ar)7.42-7.62(m，Ar)7.67(d，J＝8.3Hz，Ar)7.85(d，J＝8.3Hz，Ar)8.05(d，J＝8.2Hz，Ar)8.18(d，J＝8.0Hz，Ar)8.33(s，Ar)MS(EI)m/z?187(M
+)[Calc.forC
11H
9NO
2(187.1947)requires?M，187.0633，Found：M
+?187.0625]
Embodiment 13
With 1,2,3, the 4-naphthane (1.3ml, 5mmol) and 65% concentrated nitric acid (0.25g 2.5mmol) adds reactor and mixes, and adds catalyzer Yb (OPf)
3(2.1mg, 0.05%mol), reflux stirs, and temperature of reaction is controlled at 70 ℃.React and stop heating after 48 hours, dichloromethane extraction use in mixture washing back, is spin-dried on Rotary Evaporators, the mistake post.Obtain yellow oily liquid 225mg, productive rate 50%.
1H-NMR(CDCl
3，TMS)δ1.95-2.02(1H，m，CH
2)2.07-2.16(2H，m，CH
2)2.63(2H，t，J＝6.6Hz，CH
2)2.94(2H，t，J＝6.3Hz，CH
2)3.02-3.60(1H，m，CH
2)7.22-8.01(3H，m，Ar)MS(EI)m/z177(M
+)[Calc.for?C
10H
11NO
2(177.1999)requires?M，177.0790，Found：M
+177.0785]
Embodiment 14
(0.89g, (0.5g 5mmol) adds reactor and mixes, and adds catalyzer Yb (OPf) 5mmol) to be dissolved in the concentrated nitric acid of chloroform (1ml) and 65% with anthracene
3(2.1mg, 0.05%mol), reflux stirs, and temperature of reaction is controlled at 70 ℃.React and stop heating after 48 hours, dichloromethane extraction use in mixture washing back, is spin-dried on Rotary Evaporators, the mistake post.Obtain yellow solid 240mg, m.p.:144-148 ℃ of productive rate 43%.
1H-NMR(CDCl
3，TMS)δ7.00-7.28(4H，m，Ar)7.41-7.64(4H，m，Ar)8.49(1H，s，Ar) MS(EI)m/z?223(M
+)[Calc.for?C
14H
9NO
2(223.2268)requires?M，223.0633，Found：M
+223.0637]
Embodiment 15
With ethylbenzene (0.61ml, 5mmol) and 65% concentrated nitric acid (0.25g 2.5mmol) adds reactor and mixes, and adds catalyzer Yb (OPf)
3(2.1mg, 0.05%mol), reflux stirs, and temperature of reaction is controlled at 70 ℃.React and stop heating after 48 hours, dichloromethane extraction use in mixture washing back, is spin-dried on Rotary Evaporators, the mistake post.Obtain yellow oily liquid 226mg, productive rate 60%.2-nitro ethylbenzene
1H-NMR (CDCl
3, TMS) δ 1.26 (3H, t, J=7.2Hz, CH
3) 2.88 (2H, q, J=7.2Hz, CH
2) 7.10-7.60 (3H, m, Ar) 7.75 (1H, d, J=8.0Hz, Ar) 4-nitro ethylbenzene
1H-NMR (CDCl
3, TMS) δ 1.27 (3H, t, J=7.2Hz, CH
3) 2.74 (2H, q, J=7.2Hz, CH
2) 7.30 (2H, d, J=8.0Hz, Ar) 8.03 (2H, d, J=8.0Hz, Ar) MS (EI) m/z 151 (M
+) [Calc.for C
8H
9NO
2(151.1626) requires M, 151.0633, Found:M
+151.0623]
Embodiment 16
With isopropyl benzene (0.70ml, 5mmol) and 65% concentrated nitric acid (0.15g 1.5mmol) adds reactor and mixes, and adds catalyzer Yb (OPf)
3(2.1mg, 0.05%mol), reflux stirs, and temperature of reaction is controlled at 70 ℃.React and stop heating after 48 hours, dichloromethane extraction use in mixture washing back, is spin-dried on Rotary Evaporators, the mistake post.Obtain yellow oily liquid 245mg, productive rate 60%.The 2-nitrocumene
1H-NMR (CDCl
3, TMS) δ 1.30 (6H, d, CH
3) 3.25-3.57 (1H, m, CH) 7.15-7.65 (4H, m, Ar) 4-nitrocumene
1H-NMR (CDCl
3, TMS) δ 1.29 (6H, d, J=7.8Hz, CH
3) 3.25-3.56 (1H, m, CH) 7.35 (2H, d, J=7.8Hz, Ar) 8.10 (2H, d, J=7.8Hz, Ar) MS (EI) m/z 165 (M
+) [Calc.for C
9H
11NO
2(165.1892) requires M, 165.0790, Found:M
+165.0805]
Embodiment 17
(0.83g, (0.5g 5mmol) adds reactor and mixes, and adds catalyzer Yb (OPf) 5mmol) to be dissolved in the concentrated nitric acid of chloroform (1ml) and 65% with fluorenes
3(2.1mg, 0.05%mol), reflux stirs, and temperature of reaction is controlled at 70 ℃.React and stop heating after 48 hours, dichloromethane extraction use in mixture washing back, is spin-dried on Rotary Evaporators, the mistake post.Obtain yellow solid 160mg, m.p.:156-160 ℃ of productive rate 30%.
1H-NMR(CDCl
3，TMS)δ4.01(2H，s，CH
2)7.30-8.36(7H，m，Ar) MS(EI)m/z?211(M
+)[Calc.for?C
13H
9NO
2(211.2161)requires?M，211.0633，Found：M
+?211.0637]
Claims (7)
1, a kind of nitrifying method of rare earth metal salt catalyze aromatic compound of perfluoro alkyl sulfonic acid, it is characterized in that in organic solvent or organic solvent-free, the mol ratio of the rare earth metal salt of nitric acid, aromatics and perfluoro alkyl sulfonic acid is 1: 1-5: 0.00005-0.005, temperature of reaction is 20-100 ℃, reaction times is 10-100 hour, and the rare earth metal salt of described perfluoro alkyl sulfonic acid has following molecular formula: Ln (SO
2C
nF
2n+1)
3, n=7-10 wherein, the Ln=rare earth element, above-mentioned aromatics molecular formula is RR
1Z, wherein R=H, C
1-5Alkyl, halogen, C
6H
5Or C
1-5Alkoxyl group, R
1=H or C
1-5Alkyl, Z=phenyl, naphthyl, tetralyl, anthryl or fluorenyl.
2, a kind of nitrifying method as claimed in claim 1, the mol ratio that it is characterized in that the rare earth metal salt of described nitric acid, aromatics and perfluoro alkyl sulfonic acid is 1: 1-2: 0.0001-0.0005.
3, a kind of nitrifying method as claimed in claim 1 is characterized in that described temperature of reaction is 50-100 ℃.
4, a kind of nitrifying method as claimed in claim 1 is characterized in that described reaction times 20-50 hour.
5, a kind of nitrifying method as claimed in claim 1 is characterized in that described rare earth element is Sc, Y or lanthanon.
6, a kind of nitrifying method as claimed in claim 1 is characterized in that described rare earth element is the Yb element.
7, a kind of nitrifying method as claimed in claim 1 is characterized in that reacting in the system of organic solvent-free.
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| CN100378067C (en) * | 2005-07-15 | 2008-04-02 | 中国科学院上海有机化学研究所 | Environmental nitration method of trimethylbenzene catalyzed by sulfonate substituted by alkane containing fluorine |
| CN102557988B (en) * | 2011-12-28 | 2014-05-21 | 河北化工医药职业技术学院 | Preparation method of 4-nitro phthalonitrile |
| CN104418752B (en) * | 2013-08-30 | 2017-02-08 | 南京理工大学 | Method for synthesizing single nitro-o-xylene employing catalytic nitration in micro-reactor |
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