25337-75-1Relevant academic research and scientific papers
The out,out to out,in transition for 1,(n+2)-diazabicyclo[n.3.1]alkanes
Alder, Roger W.,Heilbronner, Edgar,Honegger, Evi,McEwen, Alan B.,Moss, Richard E.,Olefirowicz, Edward,Petillo, Peter A.,Sessions, Richard B.,Weisman, Gary R.,White, Jonathan M.,Yang, Zhong-Zhi
, p. 6580 - 6591 (2007/10/02)
Hexahydropyrimidines N,N-bridged by a chain of n methylene groups (1,(n+2)-diazabicyclo[n.3.1]alkanes) adopt out,out (axial,axial) structures for n=2,3 , and 4. When n=5, the photoelectron spectrum shows evidence of the presence of some of the out,in (axial,equatorial) isomer in the gas phase, although none can be found in solution. When n=6, the compound is apparently entirely out,in in the gas phase but exists as a mixture of out,out and out,in confonners in solution. For n=7, only the diamond lattice out,in isomer can be detected in solution. These experimental data are correlated with force field (MM2) calculations; multiple minimum search methods have been used to locate all low-energy conformations. Semiempirical calculations (MNDO, AM1, and PM3) have been carried out on model systems. Related tricyclic bis-aminals having 10- and 12-membered rings have also been studied. They adopt [2323] and [3333] conformations, respectively, each having out,in (equatorial,axial) bridged hexahydropyrimidine rings. For several of the compounds, dynamic NMR processes are observed, and possible mechanisms for these are discussed.
DEPROTONATION OF HYDRAZINIUM DICATIONS IN THE DIAZONIAPROPELLANE SERIES TO FORM BRIDGEHEAD IMINIUM IONS; EXTERNAL AND INTRAMOLECULAR TRAPPING
Alder, Roger W.,Sessions, Richard B.,Gmuender, John O.,Grob, Cyril A.
, p. 411 - 418 (2007/10/02)
The reactions of hexa-alkylhydrazinium dications with bases and nucleophiles are described. 1,5-Diazonia-tricyclodecane (1) is hydrolysed rapidly by SN2 attack on the four-membered ring with ring opening (C-N+ cleavage).In all other cases deprotonation at α-C with concomitant N+-N+ cleavage (E2 reaction) is the only primary process.The cis-1,6-dimethyl-1,6-diazoniabicyclodecane ion (6), is exclusively deprotonated at a methyl group (Hofmann orientation). 1,5-Diazoniatricycloundecane (2), 1,6-diazoniatricyclododecane (3), 1,6-diazoniatricyclotridecane (4), and 1,6-diazoniatricyclotetradecane (5) ions generate bridgehead iminium ions, which may be trapped intramolecularly by the transannular amino group or externally by added nucleophiles.Reaction with cyanide ion gives detailed information on the regio- and stereo-chemistry of the trapping sequence.Although intramolecular/external trapping is truly competitive, the products of these reactions (α-amino-ammonium ions and α-aminonitriles) may be interconverted under different reaction conditions.The solvolysis of 1-(3-phenoxypropyl)-1,5-diazabicyclooctanium bromide in aqueous 48percent HBr is 103 faster than that of 3-phenoxypropyltrimethylammonium bromide, and the products are consistent with the intermediacy of the dication (2).These observations provide an explanation for the formation of 1,5-diazacyclo-octane in the reaction of 1,3-dibromopropane with hydrazine.
