Pyrrolidinium

Alkylation of enamino ketones occurs on oxygen, as would be expected from the site of protonation. Thus 4-N-pyrrolidino-3-penten-2-one (47) gave N-(2-ethoxy-2-penten-4-ylidene)-pyrrolidinium iodide (48) on alkylation with ethyl iodide (22), and the enamino ketones derived from 5,5-... 

The enamino ketone (49) was reported to give no identifiable products on reaction with N,N-dimethyl carbamoyl chloride 63). However, reaction of (49) with N,N-diethyl carbamoyl chloride in refluxing chlorobenzene gave the N-(3-diethyl-amino-5,5-dimethylcyclohex-2-en-1 -ylidene)pyrrolidinium salt, isolated as the perchlorate. The latter must have been formed as outlined in Scheme I, involving initial O carbamoylation followed by an addition-elimination reaction to give 138 cation which can react with diethylamino anion by a further addition-elimination displacement to give the product 46). 

Radical polymerization of diallylamine derivatives produce water-soluble polymers of low molecular weight [22,55-57]. In order to increase the molecular weight, acrylamide has been copolymerized with these diallylamine derivatives to produce cationic polymers with variable charge density depending on the content of the structural units of pyrrolidinium rings and acrylamide in polymeric chains [22,55,58-61]. 

Polymetric matrix Polydiallyldimethylammonium bromide [9] Polypyrrole [10[ Poly (MA -dimethyb-S -pyrrolidinium bromide [11J Styrene-divinyl benzene copolymers [4] Polyacrylamide [12]... 

IV-chloromethyl-iV-methyl pyrrolidinium bromide (C-MEP) [48, 49, 75] /V-chloromethyl-/V-methyl morpholidinium bromide (C-MEM) [49] 2-Bromo-cyclohexylpyridinium bromide [50, 56, 63, 76]... 

CN 1 -methyl-1 -[ 1 -methyl-2-oxo-2-( 10//-phenothiazin-10-yl)cthyl]pyrrolidinium bromide... 

CN (la,3p,5a)-3-[(hydroxydiphcnylacetyl)oxy]spiro[8-azoniabicyclo[3.2. l]octane-8,r-pyrrolidinium] chloride... 

New electrophilic substitution reaction methods for the preparation of dipyrromethanes have been reported. The condensation of IV-methylpyrrole with benzaldehyde leading to the corresponding dipyrromethane was promoted by the addition of the organic catalyst, pyrrolidinium tetrafluoroborate <06T12375>. The reaction between pyrrole and N-tosyl imines promoted by metal triflates gave dipyrromethanes whereas tripyrromethane byproducts were not observed <06T10130>. 

A variety of imidazolidinium and pyrrolidinium salts (Fig. 2.38) have been found to catalyze the reaction between nitrones and cyclic a, p-unsaturated aldehydes, affording bicyclic adducts with high diastereoselectivity and enantioselec-tivity (Scheme 2.256) (759). 

Scheme 12 Syntheses of the piperdinium and pyrrolidinium cobaltacarboranes. Reproduced by permission from J. Mol. Struct. 2003, 656, 239.

Phenyl 2,6-dinitro-4-trifluoromethylphenyl sulphide. Chamberlain and Crampton130 studied also the reaction of phenyl 2,6-dinitro-4-trifluoromethylphenyl sulphide with amines in DMSO. They observed a single rate process with butylamine giving the expected substituted product again, the observed rate constant increased with [butylamine]. In the reaction with pyrrolidine a rapid reaction giving the 3-pyrrolidino adduct was observed, which could be suppressed by addition of pyrrolidinium perchlorate. Under these conditions the expected 1-substituted product was formed. 

In two recent reports (Mroz et al., 2007b Tegos et al., 2005) we studied the photosensitizer properties of two series of three functionalized fullerene compounds, one series with polar diserinol groups (BF1-BF3), and a second series of three compounds with quaternary pyrrolidinium groups (BF4-BF6) (Fig. 4.5). The bis-substituted and tris-substituted fullerenes are actually mixtures of regioisomers of the same molecular formula due to reaction with different double bonds. We asked the question whether the photodynamic effects displayed by these compounds operated... 

The X-ray crystal structure of the hexafluoroantimonate salt of 1,4-diithin radical cation stabilized by bicyclo[2.2.2]octane annelation revealed a planar ring and was in agreement with theoretical calculations. Tertiary aminium radical cations underwent facile 5-exo-cyclization to give distonic 2-substituted pyrrolidinium radical cations. 

The cyclization process can be promoted by using a single electron transfer mediator. Electron transfer from the mediator generates the carbonyl radical-ion away from the electrode surface so that cyclization can occur before there is opportunity for a second electron transfer. Thus reduction of 16, R = Me, in dimethyl-forraaraide at mercury in the presence of tetraethylammonium fluoroborate leads only to conversion of the ketone function to the secondaiy alcohol. However addition of a low concentration of N,N-dimethyl pyrrolidinium fluoroborate alters the course of reaction and the cyclized tertiary alcohol is now formed. This pyrrolidinium salt is reduced at -2.7 V vs. see at mercuiy to yield a complex DMP(Hg5) which is thought to act as a single electron transfer mediator [94]. Cyclization can... 

---