2,7‐Diazapyren und sein Bis(<i>N</i>‐methyl)quartärsalz

Lier, Edouard Frederic; Hünig, Siegfried; Quast, Helmut

doi:10.1002/ange.19680801912

Cited by 8 publications

(2 citation statements)

References 4 publications

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“…It should be noted in particular that, in contrast to 4,9-[6] and 2,7-diazapyrenes [7,8], the products of a double quaternization of the 1,3,7-triazapyrenes 1a-e were not observed.…”

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confidence: 75%

Synthesis and hydroxylation of 1-alkyl- and 7-alkyl- 1,3,7-triazapyrenium salts

Писаренко

Демидов

Аксенов

et al. 2009

Chem Heterocycl Comp

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Virtually nothing was known up to this time regarding the preparation and properties of 1,3,7-triazapyrenes. We have recently developed a series of synthetic methods for these compounds from perimidines, including the parent of the series [1-4]. The aim of our work was to study the regioselectivity of the quaternization process for 1,3,7-triazapyrenes and to investigate hydroxylation reactions for the 1,3,7-triazapyrenium salts obtained. N N N R R N N N R R R 1 X 1a,b 2a-d 1 2 3 4 5 6 7 8 9 10 R 1 X + -1 а R = H, b R=Ph; 2 a R = H, R 1 = Me, X = I; b R = H, R 1 = Et, X = I; c R = H, R 1 = PhCOCH 2 , X = Br; d R = Ph, R 1 = Me, X = I

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“…It should be noted in particular that, in contrast to 4,9-[6] and 2,7-diazapyrenes [7,8], the products of a double quaternization of the 1,3,7-triazapyrenes 1a-e were not observed.…”

mentioning

confidence: 75%

Synthesis and hydroxylation of 1-alkyl- and 7-alkyl- 1,3,7-triazapyrenium salts

Писаренко

Демидов

Аксенов

et al. 2009

Chem Heterocycl Comp

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“…Templates 6 and 7 were prepared by following literature procedures. [15,16] Cages were formed as NMR samples in CDCl 3 by combining the components, either by heating to 65 8C and appling a cooling cycle, or by leaving the solutions to equilibrate for 24 h. [5] In all experiments, Zn2 (2.00 mg, 1.50 mmol) was dissolved in CDCl 3 (200 mL) in a degassed NMR tube, fitted with a rubber septum; the acceptor-porphyrins (1.50 mmol in 200 mL CDCl 3 ) and the templates (0.75 mmol in 20 mL CDCl 3 ) were added by using a syringe, and the solvent was adjusted to 600 mL. NMR spectra were then recorded.…”

Section: Methodsmentioning

confidence: 97%

Selection and Amplification of Mixed‐Metal Porphyrin Cages from Dynamic Combinatorial Libraries

Stulz

Scott

Bond

et al. 2003

Chemistry A European J

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Mixed metallo-porphyrin cages were selected and amplified from dynamic combinatorial libraries (DCLs) by using appropriate templates. The cages are composed of two bisphosphine substituted zinc(II) porphyrins as ligand donors and two rhodium(III) or ruthenium(II) porphyrins as ligand acceptors, and are connected through metal-phosphorus coordination. Ru and Rh porphyrins that display a large structural diversity were employed. The templating was achieved by using 4,4'-bpy, 3,3'-dimethyl-4,4'-bipyridine and benzo[lmn]-3,8-phenanthroline, and acts through zinc-nitrogen coordination. The absolute amount of amplification from the DCLs is strongly dependent on the combination of the Ru/Rh porphyrin and the template; cages with sterically demanding porphyrins can only form with smaller templates. In the case of tert-butyl-substituted TPP (TPP=tetraphenylporphyrin), cages are not formed at all. The formation of the cages is usually complete within 24 h at an ambient temperature; in the case of the cage containing Rh(III)OEP (OEP=octaethylporphyrin) and bpy, the pseudo-first-order rate constant of cage formation was determined to be 2.1+/-0.1x10(-4) s(-1) (CDCl(3), 25 degrees C). Alternatively, heating the mixtures to 65 degrees C and cooling to room temperature yields the cages within minutes. The (1)H NMR chemical shifts of several characteristic protons show large differences upon changing the identity of the Ru/Rh porphyrin and the central metal; this is most likely to arise from variations in the geometry of the cages. The X-ray crystal structure of a cage, which contains Rh(III)OEP as a porphyrin acceptor and bpy as template, demonstrates that the cages can adopt severely distorted conformations to accommodate the relatively short templates. An extension to mixed DCLs showed that only limited selectivity is displayed by the various templates. Formation of mixed cages that contain two different rhodium porphyrins prevents effective selection, although the kinetic lability of the systems allows for some amplification. This lability, however, also prevents isolation of the individual cages. Removal of the template leads to re-equilibration, thus the templates act as scaffolds to keep the structures intact.

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