First example of a diazepinoporphyrazine with dendrimeric substituents

A Sterically Driven Approach to the Efficient Synthesis of Low-Symmetry 1,4-Diazepinoporphyrazines

“…Recently, it has been demonstrated that the physicochemical properties of diazepinoporphyrazine macrocycles can be easily controlled by the specific choice of peripheral diazepine substituents with a special accent on their steric effect. [2][3][4]27] However, classical procedure of the condensation between diaminomaleonitrile (DAMN) and sterically hindered 2-substituted-1,3-diketone [26] (in our case, 3-n-propyl-2,4-pentanedione 1b) proved to be ineffective, resulting in low yield of 1,4-diazepine-2,3-dicarbonitrile 2b. Therefore, we have attempted to increase the yield of 2b [ †] by applying the method [28][29][30] commonly used for synthesis of imines from sterically hindered ketones.…”

Electronic and steric effects controlling monomer–dimer self-assembly in 6H-1,4-diazepinoporphyrazines: an experimental and theoretical study

“…Thus, the characteristics of the resonance signals of diastereotopic CH 2 protons can be used as an instrument for the identification of the dimeric/monomeric form of 6H-1,4-diazepinefused porphyrazines in solution (Table S1 †). 6,14,[17][18][19][20][31][32][33][34][35][36][37]…”

Magnesium porphyrazine with peripheral methyl (3,5-dibromophenylmethyl)amino groups – synthesis and optical properties

“…Detailed analysis of NMR spectra is presented in Figure 1 and in Table 1. COSY and 1 H- 13 C HMBC experiments turned out particularly useful to elucidate the structure of porphyrazine 7. The signals at 5.57 ppm were assigned to NCH 2 hydrogen atoms of methyl(3,5-dibromophenylmethyl)amino substituent due to the long-range correlations to protons at C2' (7.85 ppm) and C4' (7.74 ppm) of the 3,5-dibromophenyl fragment via 4 J and 6 J couplings, respectively, and correlations to the macrocyclic core C2, C3 carbons at 139.2 ppm.…”

“…In recent years, diaminomaleonitrile (DAMN) and its derivatives have been applied in the synthesis of many heterocyclic compounds, including imidazoles, pyrazines, pyrimidines, purines, azepines, pyrroles, oxazoles, nucleosides as well as porphyrazine macrocycles [1][2][3][4][5][6][7][8][9][10]. At present, after many years of research, porphyrazines (Pzs) substituted with nitrogen atoms in the β positions or having rings bound to both β,β positions form a distinct class of novel macrocycles (aminoporphyrazines), along with other porphyrazines substituted with sulphur, oxygen, alkyl or aryl residues [11][12][13][14]. Aminoporphyrazines reveal coordination properties due to the presence of metal ion binding sites in the macrocyclic core and the periphery.…”