钝化芳环的硝化研究进展刘金强

　　:200812,:20091　＊(No.20776127),(No.2007BAI34B07)(No.Y4090045,R4090358)＊＊Correspondingauthor　e-mail:[e-mail]钝化芳环的硝化研究进展＊刘金强　钱　超　陈新志＊＊(浙江大学化工所　杭州310027)　　芳香族化合物的硝化反应是工业生产中重要的单元反应,钝化芳环的硝化反应在医药、农药、染料和炸药合成中有重要地位。本文从硝化试剂角度综述了近年来钝化芳环的硝化反应,包括硝酸盐硫酸、硝酸酯、硝酸、氮氧化物等硝化方法。简要评述了这些方法的特点,并展望了硝化方法的研究方向。其中,硝酸盐硫酸体系具有较强的硝化能力,对于钝化芳环,可以在温和条件下以高收率得到硝化产物,在实验室制备或工业应用中具有较高的应用价值;其他硝化方法由于各种原因暂时不能对钝化程度较高的芳环进行硝化,还需进一步研究具有较高活性的硝化体系。　硝化　钝化芳环　硝酸盐　硝酸酯　硝酸　氮氧化物:O621.25+5.4;O625.61　:A　:1005-281X(2009)12-2635-07NitrationofDeactivatedAromaticCompoundsLiuJinqiang　QianChao　ChenXinzhi＊＊(InstituteofChemicalEngineering,ZhejiangUniversity,Hangzhou310027,China)Abstract　Thenitrationofaromaticsisanimportantreactioninchemicalindustry,andthenitrationofdeactivatedaromaticsplaysakeyroleinthesynthesisofmedicines,pesticides,dyesandexplosives.Inthispaper,thelatestprogressofthenitrationofdeactivatedaromaticcompoundsisreviewedinthepointofviewofnitratingagents,includingnitrate-sulfuricacid,nitrateester,nitricacidandnitrogenoxides.Theirspecificfeatures,meritsanddemeritsareoutlinedandtheperspectivesofthenitrationareprospected.Amongthem,nitrate-sulfuricacidsystemwithhighernitratingactivitycangethighyieldsatmildconditioninthenitrationofdeactivatedaromaticcompoundsandcouldbeusedinthelaboratoryandindustrialapplications.Andforothernitratingmethods,thenitrationofhighdegreedeactivatedaromaticsis,sofar,notsatisfyingfordifferentreasonsandmoreeffortsareneededfordevelopingnewagentswithhighernitratingactivity.Keywords　nitration;deactivatedaromaticcompounds;nitrates;nitrateesters;nitricacid;nitrogenoxidesContents1　Introduction2　Nitratesulfuricacidasnitrationagent2.1　Nitratesulfuricacidasnitrationagent2.2　Supportednitrateasnitrationagent3　Nitrateesterasnitrationagent3.1　Ethyleneglycoldinitrateasnitrationagent3.2　Trifluoroacetylnitrateasnitrationagent3.3　Nitrationwithacetylnitratecatalyzedbyionicliquid4　Nitricacidasnitrationagent4.1　Catalyzedbysolidacid4.2　CatalyzedbyBrφnstedacidionicliquid4.3　CatalyzedbyLnperfluorooctanesulfonateandperfluorooctanesulfonicacid2112200912化　学　进　展PROGRESSINCHEMISTRYVol.21No.12　Dec.,20094.4　CatalyzedbyLewisacid5　Nitrogenoxidesasnitrationagent5.1　NO2O2asnitrationagent5.2　N2O5asnitrationagent5.3　NO2O3asnitrationagent5.4　N2O4asnitrationagent6　Conclusion1　,、、。,,,、,。,-[1,2],;,,,,,,。,———,()。2　2.1　-,,,,,。Majumdar[3](UN),,[4]。Mundla[5]UN,,,(75%)。Almog[6]UN,(NU),UNNU,,1。,,,、,。1　[6]Table1　Nitrationyieldsofdeactivatedaromaticswithureanitrate(UN)andnitrourea(NU)[6]substrateproductdistributionofUNnitrationisolatedyield(%)productdistributionofNUnitrationisolatedyield(%)nitrobenzene1,3-dinitro(91%),1,2-dinitro(9%)931,3-dinitro(93%),1,2-dinitro(7%)68benzonitrile3-nitro(88%),2-nitro(12%)853-nitro(86%),2-nitro(14%)90benzoicacid3-nitro973-nitro71m-toluicacid3-methyl-6-nitro(58%),3-methyl-2-nitro(22%),3-methyl-4-nitro(12%)943-methyl-6-nitro(74%),3-methyl-2-nitro(23%),3-methyl-4-nitro(3%)75o-anisicacid2-methoxy-5-nitro932-methoxy-5-nitro1004(p)-NO2toluene2,4-dinitro992,4-dinitro992(o)-NO2toluene2,4-dinitro(70%),2,6-dinitro(30%)982,4-dinitro(70%);2,6-dinitro(30%)98　　Ramana[7](GN)85%,0—5℃,,、,79%、76%、88%;Oxley[8](NG),,,(AN)、、UNNU,2。2,UNGNNUNG　　　　　　　2　[8]Table2　Yieldswithdifferentnitratingagents[8]substrateyieldsbynitratingagents(%)EGDNGNNGUNNUANHNO3nitrobenzene93949193948194benzonitrile—7875768582—benzoicacid—7997———99m-toluicacid—84859989——4(p)-NO2toluene999390939795942(o)-NO2toluene91907396———o-toluicacid—8889——93—·2636·化　学　进　展21,,,,,,。,,,,,。2.2　Hajipour[9]SiO2,,,60%72%。,,,。,。Yadav[10](“clayan”),,70℃65%25%[11]。,,。Zolfigol[12]SiO2,,,80%()—85%(),。Shokrolahi[13]NaNO3、,97%92%。,,,。,,,,,,。3　3.1　Oxley[8](EGDN),,2。,,,。3.2　,,。Botvay[14](ANTFAA),。Smith[15](HNO3TFAA)、Hβ。,、,2,4-;HNO3Ac2O,,2h;HNO3TFAA2-2,4-,92%2,4-,2,4-2,6-25∶1。70∶1,。[16],。HNO3TFAA,TFAA,,HNO3Ac2O。3.3　Smith[17]ANTFAA,TFAA,。,HNO3Ac2O,,,。Dal[18][bmpy][OTf][bmpy][NTf2],3。,HNO3Ac2O,[bmpy][NTf2],[NO2][BF4],;,30%,。,。Wang[19]Cu(N(C4F9SO2)2)2[N4446][NTf2]In(NTf2)3[N4446][NTf2]、HNO3Ac2O,。2mol%,90.6%,,4.3—4.8,·2637·12　,,5。3　[bmpy][N(Tf)2][bmpy][OTf][NO2][BF4][18]Table3　Nitrationofaromaticsubstratesbyacetylnitratein[bmpy][N(Tf)2]and[bmpy][OTf]andacomparisonwithnitrationby[NO2][BF4]in[bmpy][N(Tf)2].Yieldsafter1hat25℃[18]substrateAc2OHNO3yield%[NO2][BF4]yield%[bmpy][NTf2][bmpy][OTf][bmpy][NTf2]Cl-64854Br-597572-NO2-tol30338nitro-111　　,。,,,。4　4.1　Bharadwaj[20]TiO2、70%,,,40%。,,。Hajipour[21]P2O5,65%,,、、、58%、82%、81%、80%78%,。Olah[22]2CF3SO3H-B(O3SCF3)3HNO3,、,。,99%,85%,78%。,[23]NO2Cl-3MXn,,,。,。、,,,,,。4.2　BrφnstedQiao[24]3--1-(4-)3--1-(4-)Brφnsted,,5%,42.5%、56.3%,1∶1。,。,,Brφnsted,。Fang[25]Brφnsted、。,,,。[26]Brφnsted([Hmim][CF3COO])([Hmim][HSO4]),,,。0℃,,40%—80%,。18℃8h,ANTFAA6.2,0℃8h,ANTFAA14.0,,98%。Brφnsted、,,。4.3　Yi[27]Yb(OSO2C8F17)3(),、、。,[28]、、。,,60℃(90—110℃),,,,。,,,70%—90%。·2638·化　学　进　展21,,,,6—10,。4.4　LewisLewis,、,,,。[29]。Frost[30]InX3、,X(Cl,OTf,NTf2),。,In(NTf2)3,(93%)(98%),,(31%),,1∶1.5—1.9,,5%。5　5.1　NO2O2Peng[31,32]NO2O2,,;,[33]、,,,。Cho[34]NO2,60℃0.37—0.79MPa,(FeCl3·6H2O)。,0.65MPa,、34∶66;0.79MPa,3o∶m∶p=12∶85∶3,。,,2.5NO2,4.5NO2,