75875-77-3Relevant academic research and scientific papers
A combined experimental and density functional study of 1-(arylsulfonyl)-2-R-4-chloro-2-butenes reactivity towards the allylic chlorine
Bondarchuk, Sergey V.,Smalius, Victor V.,Minaev, Boris F.
, p. 403 - 413 (2015/06/02)
Nucleophilic substitution and dehydrochlorination reactions of a number of the ring-substituted 1-(arylsulfonyl)-2-R-4-chloro-2-butenes are studied both experimentally and theoretically. The developed synthetic procedures are characterized by a general ra
Reactions of propargylic bromides with sodium sulfinates
Chang, Meng-Yang,Wu, Ming-Hao
supporting information, p. 411 - 416 (2014/03/21)
A one-pot, palladium-catalyzed synthesis of substituted 2,3-bissulfonylpropenes starting with propargylic bromides and sodium sulfinates (RSO2Na) in the presence of n-Bu4NF under refluxing aqueous 1,4-dioxane conditions for eight hours in moderate yields is described. Georg Thieme Verlag Stuttgart. New York.
Hydride affinities of cumulated, isolated, and conjugated dienes in acetonitrile
Zhu, Xiao-Qing,Liang, Hao,Zhu, Yan,Cheng, Jin-Pei
scheme or table, p. 8403 - 8410 (2009/04/11)
(Chemical Equation Presented) The hydride affinities (defined as the enthalpy changes in this work) of 15 polarized dienes [five phenyl sulfone substituted allenes (1a), the corresponding five isolated dienes (1b), and the corresponding five conjugated dienes (1c)] in acetonitrile solution were determined by titration calorimetry for the first time. The results display that the hydride affinity scales of the 15 dienes in acetonitrile range from -71.6 to -73.9 kcal/mol for 1a, from -46.2 to -49.7 kcal/mol for 1b, and from -45.0 to -46.5 kcal/mol for 1c, which indicates that the hydride-obtaining abilities of the cumulated dienes (1a) are not only much larger than those of the corresponding conjugated dienes (1c) but also much larger than those of the corresponding isolated dienes (1b). The hydrogen affinities of the 15 dienes as well as the hydrogen affinities and the proton affinities of the radical anions of the dienes (1-.) in acetonitrile were also evaluated by using relative thermodynamic cycles according to Hess's law. The results show that (i) the hydrogen affinities of the neutral dienes 1 cover a range from -44.5 to -45.6 kcal/mol for 1a, from -20.4 to -21.4 kcal/ mol for 1b, and from -17.3 to -18.5 kcal/mol for 1c; (ii) the hydrogen affinities of the radical anions of the dienes (1-.) in acetonitrile cover a range from -40.6 to -47.2 kcal/mol for 1a-., from -21.6 to -29.6 kcal/mol for 1b-., and from -10.0 to -15.4 kcal/mol for 1c-.; (iii) the proton affinities of the 15 1a-. in acetonitrile cover a range from -97.0 to -100.6 kcal/mol for 1a-., from -77.8 to -83.4 kcal/ mol for 1b -., and from -66.2 to -68.9 kcal/mol for 1c-.. The main reasons for the great difference between the cumulated dienes and the corresponding isolated and conjugated dienes in the hydride affinity, hydrogen affinity, and proton affinity have been examined. It is evident that these experimental results should be quite valuable to facilitate the elucidation of the origins of the especially high chemical potencies of the allenes, the choice of suitable hydride reducing agents to reduce the dienes, and the analyses on the reduction mechanisms.
Elimination and Addition Reactions. Part 41. Nucleophilic Eliminative Fission of Cyclopropanes: the Coiled Spring Effect of Ring Strain on Nucleofugality and its Evaluation
Hughes, Simon,Griffiths, Gwerydd,Stirling, Charles J. M.
, p. 1253 - 1264 (2007/10/02)
Rates have been measured of sulphonyl-activated eliminative ring fissions of a series of six cyclopropanes in which the leaving group is stabilised by alkoxycarbonyl, cyano, or sulphonyl groups.The measurements allow assignment of ranks (nucleofugalities) to carbon leaving groups in systems in which the connection to the leaving group is strained by incorporation in a cyclopropane ring.The values obtained are compered with those obtained for a unstrained (acyclic) analogues.Rank enhancements of about 9(log) units are obtained; these enhancements suggests that free energies of activation for leaving-group expulsion are reduced by about 53 kJmol-1, or about 46 percent of these excess of enthalpy of the strained ring, notwithstanding the small degree of ring fission in the transition structure.The effect of phenyl substitution at the leaving group suggests that cleavage of the ring is very little advanced in the transition structure, although this is variable with the nature of the leaving-group stabilisation.This is the first direct determination of the effect of strain on nucleofugality.
Cycloadditions of Ynamines with α,β-Unsaturated Sulfones: Approach to Versatile Four-Membered Carbocyclic Intermediates
Eisch, John J.,Galle, James E.,Hallenbeck, Lawrence E.
, p. 1608 - 1610 (2007/10/02)
The interaction of ynamines with various α,β-unsaturated sulfones, such as 1-alkenyl, 1-alkynyl, or 1,3-alkadienyl sulfones, leads to the ready formation of the vicinally amino- and sulfonyl-substituted cyclobuta ring in a regiospecific manner.The resulti
REACTION OF 1,3-DIENES WITH ARYLSULFONYL THIOCYANATES
Tanaskov, M. M.,Starodub, P. E.,Stadnichuk, M. L.,Tanaskova, E. A.
, p. 1609 - 1615 (2007/10/02)
At room temperature arylsulfonyl thiocyanates add to conjugated dienes with the formation of 1,4-addition products.In all cases the organic sulfonyl radical is fixed at the least substituted carbon atom of the 1,3-diene system.In reaction with triethylamine or sodium ethoxide the adducts which form eliminate thiocyanic acid with the formation of conjugated dienyl sulfones.
