29431-37-6Relevant articles and documents
Multigram scale synthesis of 3,4- and 3,6-dihydro-2H-thiopyran 1,1-dioxides and features of their NMR spectral behavior
Chabanenko, Roman M.,Yu. Mykolenko, Svitlana,Kozirev, Eugene K.,Palchykov, Vitalii A.
supporting information, p. 2198 - 2205 (2018/07/15)
A new four-step synthesis of 3,4- and 3,6-dihydro-2H-thiopran-1,1-dioxides from dihydro-2H-thiopyran-3(4H)-one is reported. The title compounds are synthesized starting with oxidation of the ketone with a 30% aqueous solution of hydrogen peroxide in a mixture of AcOH-Ac2O. The keto group is then reduced by sodium borohydride followed by mesylation and elimination of methanesulfonic acid under basic conditions (pyridine for 3,4-isomer and aqueous NaOH for 3,6-isomer). This sequence is simpler, than previously known methods, uses cheaper and more readily available reagents, and leads to 2H-thiopran-1,1-dioxides on multigram scale with 64% and 74% total yields, respectively. The structure and purity of the compounds were confirmed by 2D NMR and GCMS methods. The proposed method expands the means to access functionalized cyclic sulfones as building blocks in the synthesis of combinatorial libraries of new biologically active compounds.
Role of different molecular fragments in formation of the supramolecular architecture of the crystal of 1,1-dioxo-tetrahydro-1λ6- thiopyran-3-one
Shishkin, Oleg V.,Medvediev, Volodymyr V.,Zubatyuk, Roman I.,Shyshkina, Olena O.,Kovalenko, Nataliya V.,Volovenko, Julian M.
, p. 8698 - 8707 (2013/02/23)
The crystal structure of 1,1-dioxo-tetrahydro-1λ6- thiopyran-3-one has been determined and analyzed in terms of the topology of intermolecular interactions between the basic molecule located in the asymmetric part of the unit cell and its first coordination sphere. Supramolecular architecture of the crystal represents packing of strongly bonded flat layers formed mainly due to the SO...H-C hydrogen bonds. Comparison of the crystal structure of the title compound and its analogues demonstrates the major role of the sulfonic group in the crystal organization. A layered structure is observed also for cyclic sulfone without the carbonyl group and in the case of replacement of the CO bond by a cyclic oxygen atom. Presence of a saturated six-membered ring is a second factor influencing the crystal structure of the title compound. Absence of a ring in the dimethylsulfone results in formation of a highly corrugated columnar structure. Similar architecture of the crystal is found also for the cyclohexanone. A highly corrugated columnar structure is observed also in the case of replacement of the carbonyl group of the title compound by a considerably more polar sulfoxide S-O bond which is more active in the formation of intermolecular hydrogen bonds than a sulfone SO2 group. The Royal Society of Chemistry.
Synthesis of Novel Cyclic Sulfone Dihydropyridines Facilitated by a Selective Ethyl Diazoacetate Ring Expansion
Dodd, John H.,Schwender, Charles F.,Gray-Nunez, Yolanda
, p. 1453 - 1456 (2007/10/02)
A series of novel cyclic sulfone dihydropyridines with five to nine membered rings have been synthesized.Anomalous intermediates isolated from the Hantzch condensation were found to vary depending on the sulfone ring size and aromatic substitution.Tin tetrachloride has been shown to be a superior Lewis acid catalyst for ethyl diazoacetate ring expansion of the requisite β-keto cyclic sulfone precursors.
