Facile Conversion of Ni(II) Cyclopropylchlorins into Novel ß-Substituted Porphyrins through Acid-Catalyzed Ring-Opening Reaction

被引:10
|
作者
Grover, Nitika [1 ]
Chaudhri, Nivedita [1 ]
Sankar, Muniappan [1 ]
机构
[1] Indian Inst Technol Roorkee, Dept Chem, Roorkee 247667, Uttar Pradesh, India
关键词
CONVENIENT SYNTHESIS; ELECTRONIC-STRUCTURE; DIIMIDE REDUCTION; NONINNOCENT; DERIVATIVES; COMPLEXES; NONPLANAR; CHEMISTRY; METALLO-2-NITRO-5,10,15,20-TETRAPHENYLPORPHYRINS; METALLOPORPHYRINS;
D O I
10.1021/acs.inorgchem.6b02333
中图分类号
O61 [无机化学];
学科分类号
070301 ; 081704 ;
摘要
The conversion of cydopropylchlorins into porphyrins represents a key step in the synthetic manipulation of macrocycles with tunable physical and chemical properties. Herein, we report a facile method for the synthesis of novel ss-substituted porphyrins from cyclopropylchlorins. A series of Ni(II) cyclopropylchlorins was converted into the corresponding Ni(II) and free base porphyrins using TFA and H2SO4 under mild reaction conditions in good yields (75-86%). The new chlorins and porphyrins were characterized by various spectroscopic techniques and the single-crystal X-ray diffraction method. The reaction proceeds very fast (<5 min.) with complete conversion of chlorin into porphyrin with distinct color change. Facile conversion, shorter reaction time scale, and good yield (75-86%) without any side products are the significant features of this new protocol. These porphyrinoids exhibited red-shifted electronic spectral features with varying degrees nonplanar conformation, tunable redox properties, and porphyrin core basicity.
引用
收藏
页码:424 / 437
页数:14
相关论文
共 50 条
  • [1] REINVESTIGATION OF DIRECTION OF ACID-CATALYZED RING-OPENING OF SUBSTITUTED SPIROCYCLOPROPYLCYCLOHEXADIENONES
    SCHWARTZ, LH
    FLOR, RV
    GULLO, VP
    JOURNAL OF ORGANIC CHEMISTRY, 1974, 39 (02): : 219 - 222
  • [2] ACID-CATALYZED RING-OPENING OF 2-SUBSTITUTED AZIRIDINES WITH ALCOHOLS
    BODENAN, J
    CHANETRAY, J
    VESSIERE, R
    SYNTHESIS-STUTTGART, 1992, (03): : 288 - 292
  • [3] ACID-CATALYZED RING-OPENING REACTIONS OF EPISULFOXIDES
    KONDO, K
    NEGISHI, A
    OJIMA, I
    JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1972, 94 (16) : 5786 - &
  • [4] Acid-Catalyzed Ring-Opening Isomerizations of Cyclopropenes
    Phun, Lien H.
    Aponte-Guzman, Joel
    France, Stefan
    SYNLETT, 2012, (19) : 2723 - 2728
  • [5] ACID-CATALYZED RING-OPENING OF THIOGLYCOLATOTETRAAQUOCHROMIUM (III)
    BERTHA, E
    DIAZ, H
    MIRALLES, A
    ACTA CIENTIFICA VENEZOLANA, 1971, 22 : 51 - +
  • [6] ACID-CATALYZED RING-OPENING OF CYCLOOCTENIMINE DERIVATIVES
    FUJITA, S
    HIYAMA, T
    NOZAKI, H
    BULLETIN OF THE CHEMICAL SOCIETY OF JAPAN, 1970, 43 (10) : 3239 - +
  • [7] ACID-CATALYZED RING-OPENING OF HALO-NORTRICYCLANES
    CAPPELLI, FP
    TIMMINS, G
    WERSTIUK, NH
    CANADIAN JOURNAL OF CHEMISTRY, 1972, 50 (13): : 2163 - &
  • [8] KINETICS OF ACID-CATALYZED CHELATE RING-OPENING IN NICKEL(II) POLYAMINE COMPLEXES
    READ, RA
    MARGERUM, DW
    INORGANIC CHEMISTRY, 1981, 20 (10) : 3143 - 3149
  • [9] CYCLOPROPANOLS .11. ACID-CATALYZED RING-OPENING OF ARYLCYCLOPROPANOLS
    DEPUY, CH
    KLEIN, RA
    CLARK, JP
    JOURNAL OF ORGANIC CHEMISTRY, 1974, 39 (04): : 483 - 486
  • [10] MECHANISM AND KINETICS OF ACID-CATALYZED RING-OPENING OF THIIRANS AND OXIRANS
    WYLDE, J
    MALEQ, R
    SELVE, C
    BULLETIN DE LA SOCIETE CHIMIQUE DE FRANCE, 1970, (11B): : 72 - &