Synthesis and spectroscopic properties of novel benzochlorins derived from chlorophyll a

Sashikumar Mettath, Masayuki Shibata, James L. Alderfer, Mathias O. Senge, Kevin M. Smith, Robert Rein, Thomas J. Dougherty, Ravindra K. Pandey

Research output: Contribution to journalArticlepeer-review

26 Scopus citations


Methylpheophorbide-α (a chlorophyll α analog) was converted into methyl 131-deoxypyropheophorbide-α 2 in excellent yield. The Ni(II) complex of 2 on hydrogenation and subsequent Vilsmeier reaction with phosphorus oxychloride and 3-(N,N-dimethylamino)acrolein produced Ni(II) methyl 20-(2- formylvinyl)-131-deoxypyropheophorbide-α 4. In contrast to other synthetic and naturally occurring isobacteriochlorins, the isobacteriochlorin obtained by acid-catalyzed cyclization of 4 was found to be unstable and oxidized to the corresponding benzochlorin. The free base benzochlorin 7, obtained by demetalation, up on DDQ/methanol treatment produced a mixture of 132-oxo- and 131-methoxy-132-oxobenzochlorins 8,9. Surprisingly, under similar reaction conditions, an ethanolic solution of DDQ afforded 131,182 dioxobenzochlorin 13 as a major product. Vilsmeier reaction (POCl3/DMF) of Ni(II) benzochlorin 6 gave unexpected 5-formyl-132-oxobenzochlorin 15. Zn(II) complexes of the newly synthesized benzochlorins showed long wavelength absorptions in the range of 750-753 nm: Thus, compared to the respective free base analogues bathochromic shift of 4042 nm were observed. Despite extensive studies in benzochlorins, these are the first examples which exhibit such remarkable long wavelength absorptions in their electronic absorption spectra. The structures of novel benzochlorins were confirmed by extensive NMR [2D NMR (ROESY), 13C NMR] and X-ray crystallographic studies. On the basis of the crystal structure of oxobenzochlorin 8, the chemical reactivity of other benzochlorin analogues were examined by semiempirical molecular orbital theory. Our results are in agreement with the previous qualitative electron sextet hypothesis proposed for chlorin systems by Woodward. The fluorescence quantum yields and the singlet oxygen yields of the free base and Zn(II) benzochlorins were measured relative to tetraphenylporphyrin (TPP) in benzene.

Original languageEnglish (US)
Pages (from-to)1646-1656
Number of pages11
JournalJournal of Organic Chemistry
Issue number5
StatePublished - Mar 6 1998
Externally publishedYes

All Science Journal Classification (ASJC) codes

  • Organic Chemistry


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