Synthesis of Amino‐ and Bis(bromomethyl)‐Substitued Bi‐ and TetradentateN‐Heteroaromatic Ligands: Building Blocks for Pyrazino‐Functionalized Fullerene Dyads

Abstract

In this paper we describe the synthesis of amino-and bis(bromomethyl)-substituted derivatives of phenanthroline (phen),These substituted bi-and tetradentate N-heteroaromatic ligands are potential synthons for the preparation of the fullerene ligands 4-9. The diketones, 1,10-phenanthroline-5,6-dione 11a (phendione), 2,2-pyridyl 11b and 1,4-dibromo-2,3-butanedione 33 were used as starting materials. Phendione was converted into the phendiamine 13 by a two-step synthesis via the dioxime of the diketone 11a. Amino-substituted dppz and dpq derivatives were obtained by the reduction of the corresponding nitro compounds that were obtained by the Schiff base condensation of the diketones 11a and 11b and the appropriate o-phenylenediamine

Fe–N∕C Oxygen Reduction Catalysis Prepared by Covalent Attachment of 1,10-Phenanthroline to a Carbon Surface

“…23 In this strategy, the diamine is synthesized from 1,10-phenanthroline-5,6-dioxime by a palladium-catalyzed reduction using hydrazine hydrate as a hydrogen source. Isolation of the dioxime from 1,10-phenanthroline-5,6-dione required careful control of the reaction pH with barium carbonate to prevent the formation of unwanted byproducts.…”

Synthesis, spectroscopic and electrochemical studies of a series of transition metal complexes with amino- or bis(bromomethyl)-substituted dppz-ligands: Building blocks for fullerene-based donor–bridge–acceptor dyads

“…The dppz ligands were synthesized as described elsewhere [13]. [Ru-(bpy 2 ) 2 ]Cl 2 [16] and [Cu(CH 3 CN) 2 (PPh 3 ) 2 ]BF 4 [25] were prepared according to the literature procedures.…”

“…11-Nitrodipyrido[3,2-a:2 0 ,3 0 -c]phenazine (ndppz), 11-aminodipyrido-[3,2-a:2 0 ,3 0 -c]phenazine (adppz), 11,12-dinitrodipyrido[3,2-a:2 0 ,3 0 -c]phenazine (dndppz), 11,12-diaminodipyrido[3,2-a:2 0 ,3 0 -c]phenazine (dadppz) and 11,12-bis(bromomethyl)dipyrido[3,2-a:2 0 ,3 0 -c]phenazine (dbrdppz) were used as ligands. The preparation of the above-mentioned ligands was described elsewhere [13]. Synthesis of the ligands ndppz and dndppz was based on Schiff-base condensation of 1,10-phenanthroline-5,6-dione with the nitro-substituted o-phenylen-derivatives.…”

“…Recently, we reported on the synthesis of amino-and bis(bromomethyl)-substituted dppz derivatives as building blocks for pyrazino-functionalized fullerene dyads containing the bpy fragment [13]. For the preparation of molecular architectures that combine the fullerene as acceptor and a metal fragment as donor, we follow the synthetic strategies -condensation of diamines with fullerene substituted cyclohexane-1,2-dione or Diels-Alder reaction of C 60 with o-quinodimethanes generated in situ from the corresponding bis(bromomethyl) derivative -leading to these pyrazino-functionalized fullerene dyads as depicted in Scheme 1.…”

Synthesis of Substituted Coumarins and 2‐Quinolinones by Cycloisomerisation of (Hydroxy/aminophenyl)propargyl Alcohols

“…Synthesis of 5a from 8: [10] Tosylated derivative 8 (357 mg, 1 mmol) and concd. sulfuric acid (5 mL) were heated at 100°C for 4 h. The solution was then added dropwise to ice/water, and any precipitate formed was removed by filtration.…”