Cyclopolymerization: Cyclization of diallylcyanamide to pyrrolidine derivatives

Abstract

SynopsisFree-radical addition of perfluoroalkyl iodides (RFI) to diallylcyanamide gave cis-and trans-l-cyan~3-iodomethyl~(pe~uoroalkyl)methylpyrrolidine (Ia,b). Five-membered ring products were preferentially formed in this reaction by other 1,g-dienes having terminal vinyl groups. This strongly suggests that cyclopolymerization of such monomers occurs in analogous fashion, instead of leading to &membered rings as has been previously understood. Dehydrohalogenation of Ia,b gave 3-methylenepyrrolidine derivatives as expected. Infrared and NMR spectra clearly show the exocyclic CHF group. The influence of reaction conditions on the yield of cyclization product Ia,b and certain side products was investigated.

SYNTHESIS AND STUDY OF THE POLYMERIZATION OF N-Alkyl-N-Allyl-(Β-Chloro)allylammonium DIHYDROPHOSPHATES

“…Analysis of 13 C NMR spectrum of the polymer suggests that the polymerization proceeds through the double bonds of the formation of a diallyl groups via a сyclo linear mechanism with the formation of a polymer with a pyrrolidine structure [10][11][12].…”

Cyclization of N-substituted diallylamines to pyrrolidine derivatives during the radical addition of perfluoroalkyl iodides

“…A, A-Diallylb enzamide (8),13'14 bp 101°( 0.25 mm), w25d 1.5380, was obtained in 92% yield from reaction of 5, benzoyl chloride, and sodium hydroxide solution at 15-25°:17 ir (KBr plates) rca: 3080, 3050, 3020, 3000, 2980, 2920, pC-o 1640, A,A-Diallyltrifluoroacetamide (7).18-To a well-stirred solution of 5 (97.0 g, 1.00 mol) in 200 ml of dichloromethane, protected from the atmosphere by a slow stream of nitrogen, redistilled trifluoroacetic anhydride (105 g, 0.500 mol) was added dropwise at 0-5°over a 4-hr period. After 0.5 hr of additional stirring the mixture was poured into 100 ml of water, rinsed with 25 ml of water, and dried (MgS04).…”

“…The spectrum of 16 bore a striking resemblance to that of 20 (Y = CN) previously isolated. 7 The formation of 16 from a piperidine-ring cyclic adduct 24 could not have occurred without unusual rearrange-I (Y = CH3CO) 24 ment. The nmr spectra of 17-19 showed the methyl group on C-3 at about 1.0 in each case (J = 7 Hz, with additional 2 Hz splitting).…”

“…7 The formation of 16 from a piperidine-ring cyclic adduct 24 could not have occurred without unusual rearrange-I (Y = CH3CO) 24 ment. The nmr spectra of 17-19 showed the methyl group on C-3 at about 1.0 in each case (J = 7 Hz, with additional 2 Hz splitting). Since cis and trans isomers were formed in unequal amount having different chemical shifts for the methyl group, the expected doublets overlapped, giving the appearance of a triplet.…”

“…Conversion to methyleneand methyl-substituted pyrrolidines (Chart I) was very helpful in deducing structures from nmr spectra. The exocyclic methylene in 16 gave a doublet at 5.1, J - 7 Hz, with additional splitting of 2 Hz by a ring proton; another doublet appeared at 4.1, 2 protons, J = 9 Hz, ascribed to the C-2 methylene because of the inductive effect of the double bond and because the C-2 protons are isolated. The CH3CO group gave a singlet at 1.95 and -CH2CF2 a triplet at 2.4, JHf = 20 Hz, with additional 7 Hz splitting by the methinyl proton.…”