Multicomponent reactions mediated by NbCl 5 for the synthesis of phthalonitrile-quinoline dyads: Methodology, scope, mechanistic insights and applications in phthalocyanine synthesis

Abstract

Herein, we demonstrate the efficiency of NbCl 5 to promote a multicomponent reaction (MCR) for the synthesis of a library of phthalonitrile-quinoline dyads, which are very useful and new functionalized building blocks for phthalocyanine (PC) synthesis. Experimental mechanistic insights on the key MCR process are described, using a deuterated reagent, clearly showing the pericyclic nature of a hetero-Diels-Alder reaction. Examples of phthalocyanine (PC) syntheses were performed in order to demonstrate the versatility of the phthalonitrile-quinoline dyads. Preliminary photophysical measurements show that our phthalonitrile library is very promising for the production of new molecular scaffolds of PC derivatives with potential applications.

CuI nanoparticle-immobilized on a hybrid material composed of IRMOF-3 and a sulfonamide-based porous organic polymer as an efficient nanocatalyst for one-pot synthesis of 2,4-diaryl-quinolines

“…Finally, the target products are formed via oxidation (Scheme 2). 64 As shown in Fig. 12, the stability of the catalysts was proved via the characterization by FT-IR and FESEM (90, 90, 88, 87, 85, and 82).…”

New Synthetic Quinolines as Cathepsin K Inhibitors

“…The product was chromatographed over silica gel (70-230 mesh) and eluted with hexane/EtOAc (8:2, v/v) to give the product in 25% yield (148 mg, 0.5 mmol). Data for 4i: mp 195-197 °C; 1 The procedure is the same as that we reported previously 35 for phthalonitrile-quinoline dyads 4b-4f. To a 15-mL glass pressure tube, it was sequentially added p-chloranil (135.2 mg, 0.55 mmol), NbCl 5 (67.5 mg, 0.25 mmol, 50 mol%), and anhydrous CH 3 CN (1 mL) under an argon atmosphere.…”

“…The synthesis of 2,4-diphenylquinolines (4a and 4g-4i) and phthalonitrile-quinoline dyads (4b-4f) was carried out by a multicomponent reaction involving benzaldehydes (2a and 2c-2e) (or 4-formylphthalonitrile, 2b), anilines (1a-1d) and phenylacetylenes (3a and 3b) in the presence of a Lewis acid (FeCl 3 or NbCl 5 ) and an oxidant agent (p-chloranil or O 2 from air) ( Table 1). 31,35 Due to the incompatibility of phenol group with this multicomponent reaction, the quinoline 4i was synthesized from the acetyl-protected 4-hydroxybenzaldehyde (2e). The deprotection of acetyl group occurred in situ and produced quinoline 4i in 25% yield (Table 1, entry 9).…”

“…Detailed information on the synthesis and characterization ( 1 H NMR, 13 C NMR, HRMS, IR, mp) of the phthalonitrile-quinoline dyads 4b-4f (Table 1, entries 2-6) is provided in literature. 35…”

Synthesis of a Naphthalocyanine-Like Dye: The First Report on Zn(II)-1,6-methano[10]annulenecyanine

“…Near-infrared (NIR) dyes have received increasing attention due to their versatile applications in materials science [1][2][3][4][5], medical applications [6][7][8][9][10][11][12][13][14], catalysis and other advanced technology devices [12,[15][16][17]. In this context, phthalocyanines and naphthalocyanines are very robust dyes with relevant photophysical properties and must be highlighted [18][19][20][21][22][23].…”