三光气法合成取代苯异氰酸酯

37920089AppliedChemicalIndustryVol.37No.9Sep.2008:2008206227:2008207204:(20503):(1982-),,,,,:13647579212,E-mail:[e-mail]1,2,1,1(1.,570228;2.,716000):,10,,12,,1,22,3.55.5h,69.7%92.4%:;;;:O623.76+3:A:1671-3206(2008)09-1019-03Synthesisofsubstitutedphenylisocyanatesbybis(trichloromethyl)carbonatemethodWANGXiang2hui1,HEYong2ning2,PANMao2dong1,LINQiang1(1.KeyLaboratoryofTopicBiologicalResourcesofMinistryofEducation,HainanUniversity,Haikou570228,China;2.ShaanxiYanchangPetroleum(Group)Co.,Ltd.,Yanan716000,China)Abstract:Tensubstitutedphenylisocyanateswereobtainedwithbis(trichloromethyl)carbonateandsub2stitutedaniline.Factorssuchasmoleratioofrawmaterials,thesolventandtheinitiatorswerealsostud2ied.Theresultsshowthattheyieldofsubstitutedphenylisocyanatesare69.7%92.4%whenthereac2tionconditionsareasfollows:themoleratioofbis(trichloromethyl)carbonatetosubstitutedanilineis12,theinitiatoristriethylamine,thesolventistoluene,1,22dichloroethaneorethylacetate,thereactiontimeis3.55.5h.Keywords:bis(trichloromethyl)carbonate;substitutedaniline;phenylisocyanate;synthesis,,,[122],,,,,[324],,,,:R:H,oCl,mCl,pCl,mMe,pMe,oOCH3,pOCH3,mNO2,pNO211.11,22,;[()],99%,;;XT5;BioradFT401.20.0100.030mol,37,0.030mol,050.5h,36h,,,85.6%,b.p.8182/7.07kPa([5]:b.p.164)IR:=3060,2250,1602,1480cm-1,87.3%,b.p.8283/3.33kPa([5]:b.p.185)IR:=3060,2982,2925,2240,1602,1585,1468,750cm-1,85.2%,b.p.123124/4.67kPa([5]:b.p.98100/2.27kPa)IR:=3075,2950,2840,2250,1597,1465,1250,1040,892,765,675cm-1,70.4%,b.p.135140/5.60kPa([5]:b.p.106110/2.13kPa)IR:=3000,2930,2850,2280,1540,1470,1250,1050,820cm-1,77.1%,b.p.105110/6.00kPa([6]:b.p.7576/1.60kPa)IR:=3000,2920,2900,2270,1620,1600,1510,900,800,740,670cm-1,75.2%,b.p.9799/4.00kPa([5]:b.p.84/2.93kPa)IR:=3025,2980,2925,2250,1611,1525,809cm-1,92.4%,b.p.146148/6.67kPa([5]:b.p.9596/1.33kPa)IR:=3075,2975,2850,2245,1600,1470,1280,1043,750cm-1,72.5%,b.p.135140/5.60kPa([5]:b.p.106110/2.13kPa)IR:=3000,2930,2850,2280,1540,1470,1250,1050,820cm-1,65.2%,b.p.154156/4.67kPa([5]:b.p.130131/1.47kPa),m.p.4850([5]:m.p.5152)IR:=3100,2250,1613,1531,1350,1150,894,807,667cm-1,68.3%,b.p.161162/4.52kPa(:b.p.136137/1.47kPa),m.p.5456([5]:m.p.5557)IR:=3080,2230,1603,1490,1330,1140,870,800,665cm-122.1,,,,,,:2.2,,,,N,N2(DMF)3,,,;DMF,;,,,2.313,,,11Table1Effectofthemoleratioofbis(trichloromethyl)carbonatetosubstitutedanilineontheresults//%1355.31285.62385.81186.51,13,12,,122.41,2202019:4,,12,TLC,3.55.5h,42Table2Effectofsolventvolumeontheresults/mL/%/mL/%1,22/mL/%/mL/%1H2065.32068.92074.32075.62oCl2072.32078.62088.22087.33mCl2067.82082.32081.42085.24pCl3055.93065.73070.43069.45mMe2066.82072.42075.22077.16pMe3048.63061.53068.73075.27oOCH32070.82076.32078.52092.48pOCH33060.03056.73072.53071.09mNO27054.03565.26068.16569.710pNO27049.53568.26068.96571.21,1,22,,,,3,,;1,22,(8085),,,3,:12;;TLC,3.55.5h;18#1,22,9#,10#;69.7%92.4%:[1].[J].,2002,24(6):375.[2]WemtzJH.Fluofne2substitutedaromatlcisocyanate:US,2625561[P].1953201213.[3]RiveroIA,HerediaS,OehoaA.Etherificationcfaminoacidandmonoacidsusingtriphosgene[J].SynthCom2mun,2001,31(14):216922175.[4]SabrinaCastellano,GiorgioStefancioh.Synthesisoftrlcy2clietrlazepinonesrelatedtonevirapine[J].JHetercyclicChem,2000,37:15392l542.[5]ClintLane,JaiNagarkatti,DavidHarvey.Aldrich[M].US:PublishedbyAlidrichChemicalCompanyInc,1997.(CA)(AJ)(CSA)(JST)Ulrich(IC)(CJFD)(),16,10,660,2-328,BM4325,80():,:34,:030001,:0351-4085741,:0351-4128323,:[e-mail],:,:,:05021211090349066751201