Synthesis, cyclopolymerization, and cyclocopolymerization of 4‐(diallylamino)pyridine: A new monomer

Abstract

44Dialkylamino)pyridines have been used as supernucleophilic catalysts in a large number of reactions. In many systems, these catalysts provide a level of reactivity combined with selectivity that is unique. Several reviews of the synthesis and a p plications of these catalysts have appearedJ3 Facile commercial synthesis has made dimethylaminopyridine (1, DMAP) the most popular member of this class of supernucleophiles, although the pyrrolidine analog (2, PPY) is the most active. Both steric and electronic arguments have been put forth to explain its enhanced catalytic activity compared with DMAP.' 0 1 2Three main types of polymer-bound dialkylaminopyridines, have been reported. The first4s5 dealt with reaction of several carboxylic acid-containing dialkylaminopyridines with commercial polyethyleneimine (PEI) to give reagents of general structure 3. These compounds were examined for catalytic behavior in the hydrolysis of p-nitrophenyl esters and found to be highly active. 0 I 1 PE I N c R NR' 3 4The other two reports dealt with incorporation of the dialkylaminopyridine moiety into typical functionalized, crosslinked polystyrene (4) by both reaction on preformed polymel.6.' and synthesis of a monomer and subsequent copolymerization! Application of these catalysts to esterification reactions, under Michaelis-Menten conditions, yielded results comparable to those obtained with the corresponding small molecular analogs.The polymeric catalysts synthesized in these reports have several limitations arising from the nature of the substrate polymer. First, two of these p o l y m e w

Synthesis of polyamines with pendant cyanoimidazole units and their electrochemical properties

“…However, attempted cyclopolymerization of 2 under similar conditions was unsuccessful. Unlike other aromatic amines, 16 2 did not readily form a quaternary salt in a dilute HCl solution and dissolved only in 17% or higher HCl solution. In such a strong acidic condition, the attempted polymerization resulted in hydrolysis of the nitrile.…”

Synthesis and properties of PVC‐bound N,N‐dialkylaminopyridine

“…IR (cm Ϫ1 ): 3020, 3010 (ACH pyridine ring), 2950, 2846 (CH 2 or CH), 1640 -1530 (pyridine ring), 1201 (C-N). 1…”

“…In previous articles, dimethylaminopyridine moieties bound to insoluble polymer supports were reported. [1][2][3] Insoluble polymer-bound dimethylaminopyridine (DMAP) catalysts can be easily separated from a reaction mixture by simple filtration, and the catalysts are reusable. However, the catalytic activity of the DMAP unit bound to polymers is somewhat lower than is DMAP in a homogeneous system.…”

Synthesis of polymers with alkyaminopyridine functions as a supernucleophilic reagent

“…prepared homopolymers and copolymers that conture in the prepared resin: tain the PPY structure by involving the 4-(N,N-dialkylamino)pyridine ( 4, DAAP) in a cyclopolymerization with 2,2-azobis(2-amidinopropane)hydrochloride as an initiator. 4 DAAP polymers demonstrated a catalytic activity, which was even higher than that of PPY: Then, a crosslinked polymer was effected by involving 1,4-dibenzenedicarbonyl dichloride; this gave a netCrosslinked Polymer (7) work structure 7. This polymeric supernucleophilic reagent 7, which was prepared according to the above A solution of 1.4-benzenedicarbonyl dichloride (1 simple method, possessed remarkable approachability mmol) in 30 mL of CHCl 3 was added to the stirred and was capable of being repeatedly used.…”