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1、摘要摘要本論文主要研究四芳基卟啉的p位和芳基修飾,具體分為兩部分:四芳基卟啉的B位修飾和四芳基卟啉的芳基修飾。共合成了43個化合物,其中30個化合物是未見文獻(xiàn)報道的新化合物,其結(jié)構(gòu)通過1HNMR,MS,IR,UV等方法表征。一.四芳基卟啉的B位修飾使用改進(jìn)的Adler-Longo法合成了四苯基卟啉,經(jīng)過金屬化、甲?;?、還原、與二肽縮合并對官能化的卟啉進(jìn)行金屬化,合成了一系列p位修飾的四芳基卟啉。6R=H.M=H27R=H,M=Cu8R=CHO9R=CH,oH10R號X11R=Y12R=X,M=Mn13RiX.M=Zn14R亍Y.M
2、=Mn15R尋Y.M=ZnX=Y蘭由+①N7m-nitrobenzoicacid6—Cu(A—cO)2712.一POCl3/DIVIF.8N-Pht-L··Alanyl··L·-prolineN-Boc··L-Alanyl·-L-prolineDCC/DMAP二.四芳基卟啉的芳基修飾10Mn(Aco)2Zn(AcO)212141315以四苯基卟啉為原料,對其進(jìn)行硝化、還原、與二肽縮合并對官能化的卟啉進(jìn)行金屬化;以5.鄰羥基苯基.10,15,20.三對氯苯基卟啉為底物與二肽縮合并對官能化的卟啉進(jìn)行金屬化。R3A=臚蚶6Ri--R,=
3、R3=R4=I-I,M=H,16Rj=R1=R4=H.M=H,,R,=N0217Rt=R3=H,M=H,,R2=R4=N0218Ri=R3=R4=H,M=H2,R2=NH219Rl=R3=H,M=H2,R2=R4=NH220R2=如=Ik《l,M=H2.RI=OH29Rl-RfR4=H,M=MII'R2=A30Rl=R3=H,M=M11,R2=A,R4=NH231Rl=R{=H,M=Mn,R2=R4=A32R,=RfR4=C1,M=Mn,Rl--C33Rl=Rt=Rd=H,M=Mn,R,=B34Ri=R3=H,M2Mn,R2=B,
4、R4=NH235Rl-RfH,M=Mn,R,=&=B36R2=R3=Rd=CI,M=Mn.RI-D2lRl-R3=R4=H,M=H2,R2=A3722R12R32H,M2H2,R2=A,R4=NH2—38。23Ri=R3=H,M=H2,R2=R4=Aj924R22R32R42Cl’M=H2.Ri=C一4025Ri?R3R4H,M=H2,R2=B4126R12R32H,M2H2,R22B,R4。NH24i27Rl=R3=H,M=H2.R2=R4=B4—328R2=R3=R4=CI,M=H2,Rt=D44—6一HN03/C13CCOO
5、H“竺。墻■N面A孟lanyl■Lpr—oline-Pht-Lr..1719+占CHO0H+爺詈∞詈關(guān)鍵字:四芳基卟啉修飾合成金屬化HRl=Rl=lk=H,M=Zn.R2=AR廣R32H,M2Zn,R2=A.R4=NH2RI=R3=H,M=Zn,R2=R4=AR2=R3=R4=Cl,M=Zn,Rl_CRi=R3=R4=H.M=Zn.R2=BRr=R32H,M2zn,R2=B’R4=NH2Rl=R3=H,M=Zn,R,=R4=BR22R32R4。Cl,M=Zn,Ri=D2l2223242S2627勰O瞬≯◇。30383l393240
6、334l344235433644a申咖Abstract—————————————————————————————————————————————————一Inthisthesis,itmainlyexploresthefieldofthemodificationoftetraaryl·porphyrinsat13andarylposition.Thisthesisconsistsoftowparts:modificationoftetraarylporphyrinsatppositionandfunctionalgroupsubs
7、titutionatarylring·43c0珈【poundsweresynthesizedinthethesisand30ofthemarencw.Allthecompoundswerecharacterizedby1HNMR,MS,IRandUV-visspectra.Part1:IB-modificationoftetraarylporphyrinsTetraphenylporphyrinwassynthetizedbyusingimprovedAdler-Longomethod·Inthispart,wefocusedon
8、the13-modificationoftetraarylporphyrins,includingmetallization,formylation,reductionreaction,condensationreactionwithdipepfi