Phenanthroline rings

In this study, we report synthesis of a new thiourea derivative (2) which contain crown ether and phenanthroline ring by the reaction of 5-amino-1,10-phenanthro-line with 15-isothiocyanatobenzo[15-crown-5] (1) (Fig. 43.1) and its complex with Cu(I) is obtained. The structures of the ligand and the complex were determined by their elemental analysis, UV-vis, FTIR, H NMR (DMSO-d ), C NMR (DMSO-dg) and Mass spectra (LC-MS). 

The synthesis of thieno[2, 3 4,5]thieno[2,3-f][l,10]phenanthroline 361 has been described <1996JHC119>. The compound was obtained in four steps from known starting materials. The basic skeleton of the molecule of the phenanthroline ring was formed via photocyclization. 

A related entry to the 1,7-phenanthroline ring system involves reaction of m-phenylenediamine with dimethyl acetylenedicarboxylate in methanol at ambient temperature.177 This affords the intermediate bis-fumarate which cyclizes in diphenyl ether at 250° giving, in 95% yield, 2,8-dicarbomethoxy-4,10-dihydroxy-1,7-phenanthroline. The angular... 

A novel route to the 4,7-phenanthroline ring system involves cyclization of N,N,N N -tetrakis-2 -cyanoethyl-p-phenylenediamine... 

Reductive dehalogenation by catalytic hydrogenation of 3-chloro-,233 l,3-dichloro-2-phenyl-, and 2-benzyl-l,3-dichloro-4,7-phenanthrolines can be accomplished without accompanying reduction of the 4,7-phenanthroline ring skeleton101 but with l,3-dichloro-2-methyl- and 1,3-dichloro-2-ethyl-4,7-phenanthrolines mixtures of products were obtained due to concomitant reduction of the ring system. 

Figure 6.1 Synthesis of the [2]-catenane, 4, incorporating 2,9-substituted, Q-phenanthroline ring derivatives co-ordinated to copper(If...

The photophysical properties of the complexes thus obtained (Cu.l4+, CuCu.M " ", CuAg.l4 , CuZn.14 ) are reported in Ref. [52bj. The absorption spectra exhibit the usual LC nn bands in the UV, and the weaker MLCT bands in the visible spectral region. The spectra are rather different from those of the above homodinuclear series, and this is a consequence of the fact that two phenyl substituents are placed on the phenanthroline rings, whereas in the previous case there is one phenyl and one alkyl residue. This is expected to strongly affect the electronic MLCT transitions, also as a consequence of a slightly different coordination geometry. 

Among phenanthroline complexes, one feature present in many solid-state structures is tt—tt stacking between the planar phenanthroline rings. The first complex with a noncoordinating anion to be characterized fully was [Ce(phen)4(MeCN)2](C104)3 3MeCN, which has 10-coordinate cerium in a bicapped square antiprismatic geometry. 

UNSATURATED PI-ELECTRON CLOUD SYSTEM OF THE 0-PHENANTHROLINE RINGS... 

Buu-Hoi [67JCS(C)213] used a quite different method for the construction of the benzo[b][l,7]phenanthroline ring system. Condensation of 2-naphthol with 5-aminoquinolines 75 and paraformaldehyde generated naphthaleno[6][l,7]-phenanthrolines 76 (Scheme 15). 

A quite different approach to the construction of the benzo[h][l,10]-phenanthroline ring system, for example, 90, was used by Koft and Case... 

Condensation of 5,6-dihydroquinolin-8(7//)-ones, such as 93, with 2-aminoaromatic aldehydes, such as 94, afforded dihydrobenzo[h][l,10]phe-nanthrolines, such as 95 (Scheme 17), as precursors of a number of interesting compounds (88JA3673 90AGE923 93JOC1666). Condensation of 5,6-dihydroquinolin-8(7//)-one 93 with ternary iminium perchlorates, for example, 96, in the presence of ammonium acetate has been reported to give compounds such as 97 that contain the benzo[h][l,10]phenanthroline ring system (Scheme 18) (93TL1775). 

Oxidation of l,3-diphenyl[4,7]phenanthroline with potassium permanganate in alkaline medium resulted in transformation of the 4,7-phenanthroline ring system into 1,8-diazafluorenone. Oxidation of 12-aryl-9,9-dimethyl-8,9,10,12-tetrahydro-7H-benzo[i ][4,7]phenanthrolin-11-ones, resulting from the condensation of 6-arylmethyleneaminoquino-lines and 1 with sodium nitrite in acetic acid led to 12-aryl-9,10-dihydro-8H-benzo[frJ[4,7Jphenanthrolin-ll-ones (04RJOC1322) (Scheme 83). 

Monoprotonation of the free ligand (1) leads to a relative arrangement of the rings similar to that observed in Cu(l)" or in Here too, the two phenanthroline rings are facing each... 

Hydrogen chloride acetic acid Benzo[a][3,6]phenanthroline ring by double ring closure... 

---