The possible generation of cyclopropenyl radicals by ultraviolet irradiation of different cyclopropenyl derivatives in fluid solution and in the presence of 5,5-dimethyl-1-pyrroline--oxide (DMPO) as spin trap has been detected by electron paramagnetic resonance. The spectra consist of doublets of triplets in which the β-hydrogen splitting is larger than that of the nitrogen, in good agreement with data reported in the literature for other DMPO adducts.This methodology is unprecedented in the study of these transient radical species, and these results suggest the participation of cyclopropenyl radicals in the photosensitized decarboxylation of -(2-cyclopropenylcarbonyloxy)phthalimides.
Download full-text PDF |
Source |
|---|---|
| http://dx.doi.org/10.1021/jo9900026 | DOI Listing |
Publication Analysis
Top Keywords
Similar Publications
Silicon Analogues of Cyclopropyl Radical Derived from a Highly Stable Cyclic Disilene Compound Featuring a Si-Br Bond.
J Am Chem Soc
September 2024
Department of Applied Chemistry, Faculty of Science and Engineering, Kindai University, 3-4-1 Kowakae, Osaka 577-8502, Japan.
Article Synopsis
- A new compound called bromocyclotrisilene has been synthesized, known for its strong air stability and unique structure, through reactions involving 1,2-dibromodisilene.
- The compound features a slightly bent planar structure and retains a reactive Si-Br bond, particularly under reducing conditions.
- Further reactions with lithium metal result in the creation of stable silicon homologues of cyclopropyl radicals, demonstrating intriguing properties of three-membered silicon rings in organic chemistry.
Spectroscopic characterization of C7H3(+) and C7H3˙: electronic absorption and fluorescence in 6 K neon matrices.
Phys Chem Chem Phys
April 2014
Department of Chemistry, University of Basel, Klingelbergstarasse 80, CH-4056, Basel, Switzerland.
Mass selective deposition of C7H3(+) (m/z = 87) into solid neon reveals the 1(1)A1←X(1)A1 electronic absorption system of hepta-1,2,3,4,5,6-heptahexaenylium cation B(+) [H2CCCCCCCH](+) with an origin band at 441.3 nm, 1(1)A'←X(1)A' transition of 2,4-pentadiynylium,1-ethynyl cation C(+) [HCCCHCCCCH](+) starting at 414.6 nm and the 1(1)A1←X(1)A1 one of cyclopropenylium,1,3-butadiynyl cation A(+) [HCCCCC<(CH=CH)](+) with an onset at 322.
View Article and Find Full Text PDFCarbon-hydrogen bond dissociation energies: the curious case of cyclopropene.
J Org Chem
December 2013
Department of Chemistry, Tongji University, Shanghai 200092, China.
The ionization energy (IE) of the 3-cyclopropenyl radical (6.00 ± 0.17 eV) was measured in the gas phase by reacting 3-cyclopropenium cation (c-C3H3(+)) with a series of reference reagents of known IEs.
View Article and Find Full Text PDFA crossed molecular beam study on the reaction of methylidyne radicals [CH(X(2)Π)] with acetylene [C(2)H(2)(X(1)Σ(g)(+))]-competing C(3)H(2) + H and C(3)H + H(2) channels.
Phys Chem Chem Phys
January 2011
Department of Chemistry, University of Hawaii at Manoa, Honolulu, HI 96822, USA.
We carried out the crossed molecular beam reaction of ground state methylidyne radicals, CH(X(2)Π), with acetylene, C(2)H(2)(X(1)Σ(g)(+)), at a nominal collision energy of 16.8 kJ mol(-1). Under single collision conditions, we identified both the atomic and molecular hydrogen loss pathways forming C(3)H(2) and C(3)H isomers, respectively.
View Article and Find Full Text PDFCatalyst-controlled ring-opening cycloisomerization reactions of cyclopropenyl carboxylates for highly regioselective synthesis of different 2-alkoxyfurans.
Chem Asian J
November 2010
State Key Laboratory of Organometallic Chemistry, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, 354 Fenglin Road, Shanghai 200032, P.R. China.
Differently substituted 2-alkoxyfurans (2,3,4- or 2,3,5-trisubstituted furans) were highly regioselectively synthesized by means of the ring-opening cycloisomerization of the same cyclopropenyl carboxylates with good yields in different solvents and excellent regioselectivity by using [Cu(acac)(2)] (acac=acetylacetonate) or [RuCl(2)(PPh(3))(3)] as the catalyst, respectively. The structures of these two different types of furans were established by X-ray diffraction studies. A rationale has been proposed.
View Article and Find Full Text PDFWant AI Summaries of new PubMed Abstracts delivered to your In-box?
Enter search terms and have AI summaries delivered each week - change queries or unsubscribe any time!