C-13 NUCLEAR MAGNETIC-RESONANCE STUDIES OF PORPHYRINS AND RELATED COMPOUNDS .2. ELECTROPHILIC REACTIONS OF CHLORIN DERIVATIVES AND A COMPREHENSIVE COLLECTION OF C-13 DATA OF THESE PRODUCTS AND CLOSELY RELATED COMPOUNDS

被引:33
作者
WRAY, V
JURGENS, U
BROCKMANN, H
机构
[1] Gesellschaft für Biotechnologische Forschung mbH, D-3300 Braunschweig
关键词
D O I
10.1016/0040-4020(79)80122-2
中图分类号
O62 [有机化学];
学科分类号
070303 ; 081704 ;
摘要
Vilsmeier-formylation of the copper(II) complex of chlorin-e6 trimethyl ester (2), under mild conditions, gives selective substitution in the 3-vinyl group. In contrast chlorination of 2 is shown to lead to selective substitution at position 20 of the macrocycle. A similar result is found for [3-ethyl]-isochlorin-e4 dimethyl ester (17) although further reaction leads to more highly chlorinated products which have been isolated and identified. 13C NMR data for some of these compounds and several related chlorin derivatives are reported. In particular, after correction of the literature, many of the quaternary carbon signals of the macrocycle are assigned and substituent effects assessed. Consideration of the shifts of the α-pyrrolic carbons confirms that chlorin and its derivatives exist in a tautomeric form with the two inner H atoms on diagonally opposite pyrrole rings A and C. Such a form allows a satisfactory explanation of the substituent chemical shifts of the formyl group at positions 15 and 20 to be made. © 1979.
引用
收藏
页码:2275 / 2283
页数:9
相关论文
共 27 条
[1]   EFFECT OF MAGNESIUM COORDINATION ON C-13 AND N-15 MAGNETIC-RESONANCE SPECTRA OF CHLOROPHYLL-A - RELATIVE ENERGIES OF NITROGEN N-PI-STAR STATES AS DEDUCED FROM A COMPLETE ASSIGNMENT OF CHEMICAL-SHIFTS [J].
BOXER, SG ;
CLOSS, GL ;
KATZ, JJ .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1974, 96 (22) :7058-7066
[2]  
BROCKMANN H, TETRAHEDRON LETT
[3]   NUCLEAR MAGNETIC RESONANCE SPECTRA AND MOLECULAR ASSOCIATION OF CHLOROPHYLLS A AND B, METHYL CHLOROPHYLLIDES, PHEOPHYTINS, AND METHYL PHEOPHORBIDES [J].
CLOSS, GL ;
STRAIN, HH ;
THOMAS, MR ;
KATZ, JJ ;
PENNINGTON, FC .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1963, 85 (23) :3809-+
[4]  
Fischer H, 1937, LIEBIGS ANN CHEM, V528, P265
[5]   CRYSTAL AND MOLECULAR STRUCTURE OF METHYL PHEOPHORBIDE WITH APPLICATIONS TO CHLOROPHYLL ARRANGEMENT IN PHOTOSYNTHETIC LAMELLAE [J].
FISCHER, MS ;
TEMPLETON, DH ;
ZALKIN, A ;
CALVIN, M .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1972, 94 (10) :3613-+
[6]   BACTERIOCHLOROPHYLL-CS, A NEW BACTERIOCHLOROPHYLL FROM CHLOROFLEXUS-AURANTIACUS [J].
GLOE, A ;
RISCH, N .
ARCHIVES OF MICROBIOLOGY, 1978, 118 (02) :153-156
[7]   REACTION OF DICYANOCOBYRINIC HEPTAMETHYL ESTER WITH ASCORBIC-ACID [J].
GOSSAUER, A ;
GRUNING, B ;
ERNST, L ;
BECKER, W ;
SHELDRICK, WS .
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION IN ENGLISH, 1977, 16 (07) :481-482
[8]  
JECKEL G, 1967, THESIS TU BRAUNSCHWE
[9]  
JURGENS U, 1978, THESIS TU BRAUNSCHWE
[10]  
JURGENS U, LIEBIGS ANN