Abstract: This paper summarizes the progresses in using amine-SO2 electron transfer products (mainly DABSO) gained in desulfurization as a gaseous sulfur dioxide substitute to carry out organic reaction.The synthesis of various sulfones,sulfonamides,sulfonyl chloride and other high value products by using amine-SO2 electron transfer products as sulfur resources is reviewed,and part of the reaction mechanism are summarized.It is noted that although this reaction route has advantages such as mild reaction conditions and easy availability of reaction raw materials and provides a new idea for the synthesis of a plurality of sulfonyl-containing compounds,but there exist problems including few alternative systems available,some harsh reaction conditions,high cost or others.It is suggested that in the future study,the amine-way flue gas desulfurization technology and the re-utilization of amine-sulfur dioxide electron transfer products shall be developed in an integrating way,while the research on new organic amine absorption system with excellent adsorption capacity and high reactivity shall be strengthened.
[1] Sato K,Hyodo M,Aoki M,et al.Oxidation of sulfides to sulfoxides and sulfones with 30% hydrogen peroxide under organic solvent-and halogen-free conditions[J].Tetrahedron,2001,57(13):2469-2476. [2] Wojcinski L M,Boyer M T,Sen A.Palladium (Ⅱ)-catalyzed alternating copolymerization of alkenes with sulfur dioxide[J].Inorganica Chimica Acta,1998,270(1/2):8-11. [3] Yang Z Z,He L N,Zhao Y N,et al.Highly efficient SO2 absorption and its subsequent utilization by weak base/polyethylene glycol binary system[J].Environmental Science & Technology,2013,47(3):1598-1605. [4] Vogel P,Sordo J A.Hetero-Diels-Alder and cheletropic additions of sulfur dioxide to conjugated dienes.Experimental facts and theoretical analysis[J].Current Organic Chemistry,2006,10(16):2007-2036. [5] Malet-Sanz L,Madrzak J,Ley S V,et al.Preparation of arylsulfonyl chlorides by chlorosulfonylation of in situ generated diazonium salts using a continuous flow reactor[J].Organic & Biomolecular Chemistry,2010,8(23):5324-5332. [6] Rogic M M,Masilamani D.Organic reactions of sulfur dioxide.3.Ene reaction:A facile regiospecific isomerization of olefins[J].Journal of the American Chemical Society,1977,99(15):5219-5220. [7] Wu J P,Emeigh J,Su X P.Alkylation of magnesium sulfinates:A direct transformation of functionalized aromatic/heteroaromatic halides into sulfones[J].Organic Letters,2005,7(7):1223-1225. [8] Schareina T,Zapf A,Beller M.Potassium hexacyanoferrate (Ⅱ)-a new cyanating agent for the palladium-catalyzed cyanation of aryl halides[J].Chemical Communications,2004,(12):1388-1389. [9] Hogan P J,Cox B G.Aqueous process chemistry:The preparation of aryl sulfonyl chlorides[J].Organic Process Research & Development,2009,13(5):875-879. [10] Woolven H,González-Rodríguez C,Marco I,et al.DABCO-bis (sulfur dioxide),DABSO,as a convenient source of sulfur dioxide for organic synthesis:Utility in sulfonamide and sulfamide preparation[J].Organic Letters,2011,13(18):4876-4878. [11] Nguyen B,Emmett E J,Willis M C.Palladium-catalyzed aminosulfonylation of aryl halides[J].Journal of the American Chemical Society,2010,132(46):16372-16373. [12] Ye S,Wu J.A palladium-catalyzed three-component coupling of arylboronic acids,sulfur dioxide and hydrazines[J].Chemical Communications,2012,48(62):7753-7755. [13] Wang X,Xue L,Wang Z.A copper-catalyzed three-component reaction of triethoxysilanes,sulfur dioxide,and hydrazines[J].Organic Letters,2014,16(15):4056-4058. [14] Du B,Wang Y,Sha W,et al.Copper-catalyzed selective aerobic oxidative cascade reaction of hydrazines,DABSO,and amines for the direct synthesis of sulfonamides[J].Asian Journal of Organic Chemistry,2017,6(2):153-156. [15] Deeming A S,Russell C J,Hennessy A J,et al.DABSO-based,three-component,one-pot sulfone synthesis[J].Organic Letters,2013,16(1):150-153. [16] Richards-Taylor C S,Blakemore D C,Willis M C.One-pot three-component sulfone synthesis exploiting palladium-catalysed aryl halide aminosulfonylation[J].Chemical Science,2014,5(1):222-228. [17] Pandya R,Murashima T,Tedeschi L,et al.Facile one-pot synthesis of aromatic and heteroaromatic sulfonamides[J].The Journal of Organic Chemistry,2003,68(21):8274-8276. [18] Mao R,Zheng D,Xia H,et al.Copper (Ⅰ)-catalyzed sulfonylation of (2-alkynylaryl) boronic acids with DABSO[J].Organic Chemistry Frontiers,2016,3(6):693-696. [19] Zheng D,An Y,Li Z,et al.Metal-free aminosulfonylation of aryldiazonium tetrafluoroborates with DABCO (SO2)2 and hydrazines[J].Angewandte Chemie International Edition,2014,53(9):2451-2454. [20] Zhao W,Zhao Q,Zhang Z,et al.Liquid-solid phase-change absorption of acidic gas by polyamine in nonaqueous organic solvent[J].Fuel,2017,209:69-75.