殐 殐 27 1 Vol.27 No.1 2009 1 ImagingScienceandPhotochemistry Jan.,2009 檭檭檭檭檭檭檭檭檭檭檭檭檭檭殐 殐 *O! "# #B) 1,CDE 1, 2, 1 (1., 200092;2., 200092) $ %:3 J = 2J4 ',V T, _` * C?. + SU L 3 H4 E '.< 4 893?, V 9 P>?. & ' : J ; T ;4 ;592J :1674 0475(2009)01 0063 06 ()* :O64 +,-.:A < T4 01234 C 0,I0 L ) c UV [1 4]. ",2 G 5! 4 < T 34 /,? &' O ;3 (5 A G ) 2 < T C U 5,I?X. C?,. < TI0 > ) c UV, 0!", ^ C C 0 c 0 )+. 2 C 0 MHI 0 cl 3 @ [5 10].M!"I!"< T4 01 0. cl L : >, 2,,23 C 0 [11 14]. 1 E) 1.1 A 45 BrukerTensor27 9 A (KBr [ );Varian AM 300 8 C D E A (CDC13 DMSO d6 5,TMS GP);500 W [C ;Agilent6890/GC5973N MSD \A;KrussKSPⅡ ]Z? A. M # 45 \. 1.2 < T 0 M =! T :, 8,0, TB P 1(I 1). /01 :2008 07 31; 1 :2008 09 15. 3456:6 (1964 ),,, C 0 LC!", S,E mail:rhzhang@yahoo.cn. 63
64 27 (1 < T 0 Syntheticrouteforoxazolidinone 1.2.1 2 8 2! /(1) 0 I3 500mL 1 X,<Y12g(0.1mol)! T 150mL H2O 0.75g NaOH,Z [\,I70 <Y32gKMnO4, c 1h.R< / a] W /0. _,a] MnO2. _ " S3 =a] 6 c C 1.R< P/O ph=4.0,s,^.br< P/U ph=1, " S.@, _,Z[ ] " B 5.6g, >:37%. 1 HNMR(CDC13):δ7.5 8.4(m,5H); 13 CNMR(CDC13):δ128.91,130.89, 131.82,135.43,163.82,185.59;MS 犿 / 狕 :150[M] + ;IR(KBr)ν:1729,1686,1596, 1450,1220,1179,980,716,683cm -1.m.p.60 62( 62 64 [15] ). 1.2.2 2 8 2! (2) 0 I1 X <Y2 8 2! /3g(20mmo1),= 5.5 ml,<]^_6h, ] W,<Y ) Z[ a], B. 2 8 2!, 1 9: c. 1.2.3 1 (2 8 2! )< 2 /(3 犪 ) 0 4.5g(39mmol) L G/L3.1gNaOH 15mL, L R Y40mL2 8 2! (7.2g,43mmol),R ( c.]a, S3.R< P/U ph=2.0,s,@,z[ B V. 1, \("# =1 40), BbV.17.3g, >:76%. 1 HNMR(CDC13):δ7.4 8.2(m,5H),4.81 4.68(m,1H),3.7 3.5(m,2H), 2.44 2.16(m,2H),2.14 1.92 (m,2h); 13 CNMR (CDC13):δ25.19,28.88, 46.34,60.25,127.27,128.15,130.20,135.69,170.44,170.71,176.01;MS 犿 / 狕 : 247[M] + ;IR(KBr)ν:3438,2982,1740,1680,1643,1446,1240,1178,1047,1018, 979,835,720,666cm -1. 1.2.4 < T 01(4 犪,4 犫 ) 0 200mg(0.8mmol)1 (2 8 2! )< 2 /50mg(0.4mmol)
1 6 :< T4 01 0!" 65 K2CO3 20mL T (1 1),60 <]2min,b<Y40mL T (1 1),I 12h.Z[ ] T, /,S,@,Z[. 1 \( /, =1 1)B 4 犪,4 犫,5.$ > 85%. 4 犪 1 HNMR(CDC13):δ7.30 7.52(m,5H ),5.74 5.66(t, 犑 =5.1Hz,1H),5.38 (s,1h),3.86 3.72(m,1H),3.18 3.06(m,1H),2.24 2.06(m,2H),2.12 1.68(m,2H); 13 CNMR (CDC13):δ23.99,31.46,42.40,83.33,94.23,125.62, 128.36,128.67,136.10,173.60;MS 犿 / 狕 :203[M] + ;IR(KBr)ν:3413,2931,1715, 1417,1305,1246,1098,1016,708,652cm -1. 4 犫 1 HNMR(CDC13):δ7.22 7.36(m,5H),5.57 5.51(t, 犑 =5.1Hz,1H),5.39 (s,1h),3.76 3.65(m,1H),3.12 3.01(m,1H),2.21 1.76(m,4H); 13 CNMR (CDC13):δ24.28,31.63,42.99,83.27,92.53,126.83,128.41,128.55,135.81, 173.08;MS 犿 / 狕 :203[M] + ;IR(KBr)ν:3413,2972,1710,1414,1248,1092,1020, 709,647cm -1. 5 1 HNMR(CDC13):δ7.35 7.55(m,5H ),3.70 3.60(t, 犑 =6.9 Hz,2H),3. 48 3.38(t, 犑 =6.9Hz,2H),2.04 1.78(m,4H),2.14 1.92 (m,2h); 13 CNMR (CDC13):δ26.26,27.55,46.03,49.47,126.95,128.11,137.16,169.61;MS 犿 / 狕 : 175[M] + ;IR(KBr)ν:3353,2971,2879,1620,1574,1425,1161,793,706,660 cm -1. 2 < $R(PET)] c c 01 L < L (2 < T. Mechanismofsynthesisofoxazolidinone ] 3 = ^ L F [16 18]., 013 犪 I < $RL. 1 L, 3 CO2 B 1,4 ] L, ] L$
66 27 E 3. 1BC U F,] LBC c,e 3 TB < T 014 犪 L4 犫 ( 2)., 013 犪 I L Z B 4 犪 L4 犫 E 01, 2I c, 1 "a.!" T "# 3 5 c 1, \. 2.1 T c 1 = T c,a +4 犪 L4 犫 E 01=9, B 1(5). cd T, ' T?< $R c,i< $R Q 1! c, 1 + ( 1). T c 1 Efectofacetone watersolventsonyield(%) T c 4 犪 4 犫 5 100% 0 12h 22 19 59 90% 10% 12h 54 32 14 60% 40% 12h 44 25 31 30% 70% 12h 41 33 26 0% 100% 12h 59 41 0 2.2 "# c 1 ="# c, cb 4 犪 L4 犫 E 01, "#cd Z,4 犪 WI <( 2). 2 "# c 1 Efectofmethanol watersolventsonyield(%) "# c 4 犪 4 犫 100% 0 12h 0 0 90% 10% 12h 49 51 60% 40% 12h 51 49 30% 70% 12h 54 46 0% 100% 12h 59 41 2.3 c 1 = c, cb 4 犪 L4 犫 E 01, cd Z,4 犪 WI <( 3). 3 c 1 Efectofacetonitrile watersolventsonyield(%) c 4 犪 :4 犫 100% 0 12h 47:53 90% 10% 12h 47:53 60% 40% 12h 55:45 30% 70% 12h 57:43 0% 100% 12h 59:41
1 6 :< T4 01 0!" 67 3 0 < T4 014 犪 L4 犫, 5 Q 4 犪 L4 犫 E 01M. 5 <,4 犪 WC3J <, 8 5 < M. FG +: [1] KusP,JonesPG,CelinskiR.Structureelucidationof2 amino 5 phenyl 2 oxazolin 4 one(pemoline)andx raystructureofitshydrolysisproduct5 phenyl oxazolidi ne 2,4 dione[j]. 犣犲犻狋狊犮犺狉犻犳狋犳狌犲狉犖犪狋狌狉犳狅狉狊犮犺狌狀犵, 犅 : 犆犺犲犿犻犮犪犾犛犮犻犲狀犮犲狊,2005,60(8):853 857. [2] "[#.3 A 0 *+<T[J].,2001,32(3):237 238. WuRB.Synthesizingfurazoidonumbyone stepnitrosation[j]. 犑狅狌狉狀犪犾狅犳犆犺犻狀犪犘犺犪狉犿犪犮犲狌狋犻犮犪犾犝狀犻狏犲狉狊犻狋狔, 2001,32(3):237 238. [3] LebelH,HuardK,LectardS.N tosyloxycarbamatesasasourceofmetalnitrenes:rhodium catalyzedc Hin sertionandaziridinationreactions[j]. 犑. 犃犿. 犆犺犲犿. 犛狅犮.,2005,127(41):14198 14199. [4] CoumbaridesGS,EamesJ,FlinnA,NorthenJ,YohannesY.Probingtheresolutionof2 phenylpropanoyl chlorideusingquasi enantiomericevans'oxazolidinones[j]. 犜犲狋狉犪犺犲犱狉狅狀犔犲狋.,2005,46(5):849 853. [5] CayleyAN,CoxRJ,Ménard MoyonC,SchmidtJP,TaylorRJK.Deacetalisatio n bicyclisationroutesto novelpolycyclicheterocyclesusingstannouschloridedehydrate[j]. 犜犲狋狉犪犺犲犱狉狅狀犔犲狋.,2007,48(37):6556 6560. [6] KamimuraA,OmataY,TanakaK,ShiraiM.Oxyoxazolidinoneasanauxiliaryforheterocyclicsynthesis.En antioselectiveformationofn unprotected2 pyrrolid onesfromselenocarboxylateandalylaminesviaradicalcy clization[j]. 犜犲狋狉犪犺犲犱狉狅狀,2003,59(33):6291 6299. [7] OmataY,KakehiA,ShiraicM,KamimuraA.Stereoselectiveformationofopticalyactive2 oxy 1,3 oxazoli din 4 onesandaneficientsynthesisofopticalyactivesecondary2 pyrolidones[j]. 犜犲狋狉犪犺犲犱狉狅狀犔犲狋.,2002, 43(39):6911 6914. [8] PadwaA,PreinM.π Facialdiastereoselectionin[3+2] cycloadditionsofisomünchnonedipoles[j]. 犑. 犗狉犵. 犆犺犲犿.,1997,62(20):6842 6854. [9] GiraudL,RenaudP.Protecting/radicaltranslocatingchiralauxiliaries:anewconceptinradical mediatedasym metricsynthesis[j]. 犑. 犗狉犵. 犆犺犲犿.,1998,63(25):9162 9163. [10] NairV,SanthiV,SheelaKC,RadhakrishnanKV,RathNP.Chemoselective1,3 dipolarcycloadditionreac tionsofrhodium(i) generatedisomunchnoneswith1,4 quinones:synthesisofnovelazapolycycles[j]. 犛狔狀 狋犺犲狊犻狊,2003,10:1559 1564. [11] NatarajanA,RamamurthyV.Asymmetricinductionduringphotocyclizationofchiralandachiralα oxoamides withinachiralzeolites[j]. 犗狉犵. 犅犻狅犿狅犾. 犆犺犲犿.,2006,4(24):4533 4542. [12] GriesbeckAG,HofmannN,WarzechaKD.Photoinduced electron transferchemistry:fromstudiesonpet processestoapplicationsinnaturalproductsynthesis[j]. 犃犮犮. 犆犺犲犿. 犚犲狊.,2007,40(2):128 140. [13] GriesbeckAG,KramerW,LexJ.Diastereo andenantioselectivesynthesisofpyrrolo[1,4]benzodiazepines throughdecarboxylativephotocyclization[j]. 犃狀犵犲狑. 犆犺犲犿. 犐狀狋. 犈犱.,2001,40(3):577 579. [14] NatarajanA,WangK,RamamurthyV,ScheferJR,PatrickB.Controlofenantioselectivityinthephoto chemicalconversionofα oxoamidesintoβ lactamderivatives[j]. 犗狉犵. 犔犲狋.,2002,4(9):1443 1446. [15] CrichD,ZouYK.Catalyticoxidationadjacenttocarbonylgroupsandatbenzylicpositionswithafluorousse
68 27 leninicacidinthepresenceofiodoxybenzene[j]. 犑. 犗狉犵. 犆犺犲犿.,2005,70(8):3309 3311. [16] GriesbeckAG,HeinrichT,OelgemōlerM,MolisA,HeidtmannA.Synthesisofcyclicpeptidesbyphoto chemicaldecarboxylationofn phthaloylpeptidesinaqueoussolution[j]. 犎犲犾狏犲狋犻犮犪犆犺犻犿犻犮犪犃犮狋犪,2002,85 (12):4561 4578. [17] ChestatCA,WhitenDG.Photocyclizationofalpha ketoamidesinhomogeneo ussolutionandaqueouscyclo dextrinmedia.theroleofzwiterionsanddiradicalsinphotoinducedelectrontransferreactions[j]. 犑. 犃犿. 犆犺犲犿. 犛狅犮.,1992,114(6):2188 2197. [18] NatarajanA,MagueJT,RamamurthyV.AsymmetricInductionduringYangcyclizationofα oxoamides:the powerofacovalentlylinkedchiralauxiliaryisenhancedinthecrystalinestate[j]. 犑. 犃犿. 犆犺犲犿. 犛狅犮.,2005, 127(10):3568 3576. 犛狋狌犱狔狅狀狋犺犲犘犺狅狋狅狊狔狀狋犺犲狊犻狊狅犳犗狓犪狕狅犾犻犱犻狀狅狀犲 ZHANGRong hua 1,GUJia min 1,ZHUZhi liang 2,JIANGZhi qin 1 (1. 犇犲狆犪狉狋犿犲狀狋狅犳犆犺犲犿犻狊狋狉狔, 犜狅狀犵犼犻犝狀犻狏犲狉狊犻狋狔, 犛犺犪狀犵犺犪犻 200092, 犘. 犚. 犆犺犻狀犪 ; 2. 犆狅犾犲犵犲狅犳犈狀狏犻狉狅狀犿犲狀狋犪犾犛犮犻犲狀犮犲犪狀犱犈狀犵犻狀犲犲狉犻狀犵, 犜狅狀犵犼犻犝狀犻狏犲狉狊犻狋狔, 犛犺犪狀犵犺犪犻 200092, 犘. 犚. 犆犺犻狀犪 ) 犃犫狊狋狉犪犮狋 :Thephotochemicalmethodwasusedtoreplacethetraditionalmethod,suchasthe metalcatalyst,tosynthesizetheimportantdrugintermediateoxazolidinone.theadvantagesof thisprocedurewerehighyields,mildreactionconditions,simpleprotocol,andclean.atthe sametime,theefectsofthreediferentsolventsacetone,methanol,acetonitrileontheyields oftheproductswerestudied.thestereo selectivitywasincreasedwiththeenlargementofthe polarityofsolvents. 犓犲狔狑狅狉犱狊 :photochemistry;oxazolidinone;solventefect;chiralcatalyst Corespondingauthor:ZHANGRong hua