5,12-Dimethyl-3,10-diphenyl-1,3,4,8,10,11-hexaazatetracyclo[6.6.1.0^2,6.0^9,13]pentadeca-2(6),4,9(13),11-tetraene, a new Tröger's base analogue

Abstract

The synthesis of the title Tröger's base analogue, C(23)H(22)N(6), was undertaken in order to study the influence of a methyl substituent on the structure. Minor differences were found in the bond lengths of the title structure in comparison with the values for free pyrazole and for the first pyrazolic Tröger's base reported in the literature. There are two molecules of opposite chirality in the asymmetric unit and the packing in the lattice is characterized by a non-crystallographic n-glide plane relating these molecules.

Mechanism of Synthesis of Tröger and Spiro‐Tröger Base Derivatives Starting from Naphthyl‐ and Anthracenylamines: A Computational Study

“…For this, different solvents were tested, [17] the sources of methylene and the nature of the acids used also were varied [18][19][20][21] and different amino-aromatic compounds (anilines, naphthylamine, aminopirazoles, among others) were used to obtain different families of TBs. [22,23] In one of the efforts to obtain TBs analogs with different functionalities, by reacting methyl-6-amino-naphthalene-2-carboxylate in an acid medium with a methylene source, it was possible to obtain a mixture of the corresponding TB and a new isomeric compound of the first, which was called Spiro Tröger's base (SpiroTB) due to to the formation of a bicycle similar to that of the TB and by the presence of a spiro carbon (Scheme 1). [23] As shown in Scheme 1, SpiroTB has a rigid chiral structure similar to TB, but in this case containing chirality on a nitrogen and a carbon, which allows both compounds to behave differently when passing through a column of chiral HPLC.…”

“…Due to the large number and variability of applications found for these compounds and analogues, many efforts have been made to improve and optimize their synthesis. For this, different solvents were tested, [17] the sources of methylene and the nature of the acids used also were varied [18–21] and different amino‐aromatic compounds (anilines, naphthylamine, aminopirazoles, among others) were used to obtain different families of TBs [22,23] …”

A New Class of Tröger’s Base Analogues Bearing Spiro[4.5] Lactone Straps

“…6,7 Whilst many analogues of 1 have been prepared, much of the chemistry has focused on generating compounds with different functionalities on the aryl rings [8][9][10][11][12] and on the incorporation of heteroaromatic rings. [13][14][15][16][17] In contrast, variations to the bridge region have received less attention. However, it is known that one of the nitrogen atoms in the bridge can be alkylated, [18][19][20] as can one 7,21 or both of the benzylic carbons.…”