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1、5#SupplementaryMaterial(ESI)forJournalofMaterialsChemistry#Thisjournalis©TheRoyalSocietyofChemistry2004Synthesis3-(2-cyanoethylsulfanyl)thiophene6a.Toasolutionof3-bromothiophene(3mL,32mmol)inanhydrousEt2O(25mL)underN2at–78°Cwasaddeddropwiseasolutionofn-BuLi2.5Minhexane(13.4mL,1.05equiv)in30min.
2、After15minofstirringat–78°C,thelithiatedsaltprecipitated,andelementalsulfur(1.05g,1.05equiv)wasaddedinoneportion.After30minofadditionalstirringat–78°C,themixturewasallowedtowarmtoroomtemperatureandstirredfor30min.Thesolutionwascooleddownto0°Cand3-bromopropionitrile(8.23g,5.1mL,2equiv)wasaddeddr
3、opwise.Themixturewasstirredfor1hatroomtemperature.Afteradditionofa0.5MaqueoussolutionofHCl(40mL),themixturewasextractedwithCH2Cl2(200mL).TheorganicphasesweredriedoverNa2SO4andevaporatedinvacuo.Theexcessof3-bromopropionitrilewasseparatedbydistillation(1mbar,78°C)usingaKugelrhorapparatus.Theresul
4、tingoilwaspurifiedbychromatographyonsilicagel(eluent:1:1CH2Cl2/petroleumether(PE))togivecompound6aasaslightlyyellowoil(4.5g,83%yield).1HNMR(CDCl3)d=2.57(t,2H,3J=7.2Hz),3.02(t,2H,3J=7.2Hz),7.08(dd,1H,3J=4.9Hz,4J=1.3Hz),7.37(dd,1H,4J=1.3Hz,4J=3.0Hz),7.38(dd,1H,4J=3.0Hz,3J=4.9Hz).13CNMR(CDCl3)d=18
5、.4,31.3,118.0,127.1,128.0,128.4,130.6.MS(70eV,EI)m/z(I%) :169(M+•,53),129(54),116(29),85(50),71(100).IR(neat)cm-1:2249(CN).Anal.CalcdforC7H7NS2:C,49.67;H,4.17;S,37.88;N,8.28,found:C,49.20;H,4.22;S,36.54;N,8.10.3-(2-Cyanoethyloxy)thiophene6b.Inathree-neckedflaskequippedwithaDeanandStarckseparato
6、r,amixtureof3-methoxythiophene(1g,8.76mmol),of3-hydroxypropionitrile(2mL,2eq.)andNaHSO4(50mg,0.05eq.)intoluene(10mL)washeatedonenightunderN2at80°C.AfterwardtoluenewasevaporatedandtheresiduewasdissolvedinCH2Cl2,thisorganicphasebeingwashedwithwater,driedoverNa2SO4andconcentrated.Theresultingsolid
7、waschromatographedonsilicagel(1:1CH2Cl2/PE)togive6basabeigesolid(460mg,34%yield).M.p.67–69°C.1HNMR(CDCl3)d=2.82(t,2H,3J=6.4Hz),4.18(t,2H,3J=6.4Hz),6.30(dd,1H,4J=3.0Hz,4J=1.6Hz),6.78(dd,1H,3J=5.2Hz,4J=1.6Hz),7.21(dd,1H,3J=5.2Hz,4J=
