The reactivity of azadiene system of non-aromatic 3H-pyrroles toward nitrogen-, oxygen-, and sulfur-nucleophiles has been evaluated both experimentally and theoretically. The obtained results demonstrate, for the first time, low reactivity of 3H-pyrrole system and allow future research directions in...
Pyrrole is a five-member nitrogen heterocyclic ring that contains two carbon-carbon double bond configurations which gives the solvent a pronounced aromatic character. Pyrrole is an intermediate in the synthesis of a variety of commercial chemical derivatives. Pyrrole has only limited solubility in water...
Nitrogen and carbon monoxide molecules are isoelectronic and have electric quadrupole moment, the later molecule has an additional dipole moment, which is found to be very small. The interaction sites in the aromatic ring for the nitrogen and carbon monoxide [2] have been intensively studied for ...
The molecule is not planar due to the twisted 3,4-disubstituted phenyl rings with respect to the pyrrole moiety; the dihedral angle between the latter and each of the two mentioned rings is 60.2(3)° and 66.9(3)°, respectively. The rest of the molecule could be considered nearly planar ...
Non‐Aromatic 3H‐Pyrroles in the Reaction with Nucleophiles: Is High Reactivity a Myth?doi:10.1002/ejoc.201900152Nitrogen heterocyclesNucleophilic additionReactive intermediatesAb initio calculationsSynthetic methodsThe reactivity of azadiene system of non‐aromatic 3H‐pyrroles toward nitrogen‐, oxygen‐,...
However, in pyrrole, the nonbonded electron pair on nitrogen is part of the aromatic 6p- electron sextet and is not available for NH salt formation, since this would generate an aliphatic (highly reactive) diene imminium cation, which would destroy pyrrole's aromaticity. However, electrophilic ...
unique 14π-aromatic macrocycles and excellent physicochemical properties (Fig. 1)[5,6]. In 1972, Meller and Ossko first accidentally discovered the SubPcs, which is the most famous member in the ring-contracted porphyrinoid[7]. Nowadays, SubPc is mainly obtained in moderate yield through the...
However, the LUMOs are quite different; for TePP and PPP, localization occurs on the pyrrole and phenyl rings at the 2,5-positions or 1,2,5-positions and localization of TPM and TPM-Cl is mainly on the aromatic carbonyl at the N-positions. Therefore, the LUMOs and HOMOs of TPM and ...
One might assume that, since the dimer is composed of identical units, the back transfer is fast and the CT complex has a negligible lifetime; however, we do not find any evidence for back transfer, which suggests that the CT complex is sufficiently long lived to potentially form a pyrrole...
type of pyrroles were prepared efficiently (compounds 4u-4y). It should be noted that in this case, ammonia was used in excess amount (1.5 mL for 1 mmol of BMTNE). Aromatic amines were also used and studies shown that only one equivalent of amine is presented in the final product even...