TRYPTAMINES, CARBOLINES, AND RELATED COMPOUNDS: PART X. AN ALTERNATIVE SYNTHESIS, AND THE NITRATION, OF δ-CARBOLINE

1962 ◽  
Vol 40 (5) ◽  
pp. 864-869 ◽  
Author(s):  
R. A. Abramovitch ◽  
K. A. H. Adams
Keyword(s):  
Dipole Moment ◽  
Molecular Orbital ◽  
Good Yield ◽  
Molecular Orbital Calculations ◽  
Alternative Synthesis ◽  
Fischer Cyclization ◽  
Nitro Derivatives ◽  
Related Compounds ◽  
Predominant Product

δ-Carboline, together with β-carboline, has been synthesized in reasonably good yield by the Fischer cyclization of cyclohexanone 3-pyridylhydrazone followed by dehydrogenation of the separated tetrahydro derivatives. The isomer ratios of products formed in this and similar reactions are discussed. Nitration of δ-carboline gives a mixture of the 6- and 8-nitro derivatives, the latter being the predominant product. The magnitude of the dipole moment of δ-carboline is appreciably higher than that predicted from molecular orbital calculations (15).

Synthesis, Optical Properties, Structures and Molecular Orbital Calculations of Subazaporphyrins, Subphthalocyanines, Subnaphthalocyanines and Related Compounds

1999 ◽  
Vol 03 (06) ◽  
pp. 453-467 ◽  
Author(s):  
NAGAO KOBAYASHI
Keyword(s):  
Molecular Orbital ◽  
Magnetic Circular Dichroism ◽  
Soret Band ◽  
Ring Expansion ◽  
Molecular Orbital Calculations ◽  
Mo Calculations ◽  
Key Points ◽  
Adsorption Data ◽  
Ring Expansion Reaction ◽  
Related Compounds

The synthesis of and spectroscopic data on subazaporphyrins, subphthalocyanines, subnaphthalocyanines and their related compounds reported to date are summarized, together with the results of molecular orbital (MO) calculations from our laboratory. Thus the problems and key points in the synthesis of these subazamacrocycles and their electronic absorption and magnetic circular dichroism (MCD) spectra are discussed, together with those of the monosubstituted-type low-symmetrical phthalocyanines obtained by their ring expansion reaction. The Q bands of these subazamacrocycles are orbitally doubly degenerate, and in the Soret band region, three transitions to the orbitally degenerate state are found. The MO calculations suggest that the HOMO levels destabilize considerably while the LUMO levels change slightly with increasing size of the π system. In addition, the electronic adsorption data are reproduced by the calculation only when the two pyrrole hydrogens in the monosubstituted-type phthalocyanines are assumed to be linked to the two pyrrole nitrogens along the short axis.

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