Mendeleev Communications Electronic Version, Issue 1, 2002 1 Synthesis of 3-aryl-5,7-dinitrothiochromane 1,1-dioxides based on 2,4,6-trinitrotoluene Mikhail D. Dutov, Ol’ga V. Serushkina and Svyatoslav A. Shevelev* N. D. Zelinsky Institute of Organic Chemistry, Russian Academy of Sciences, 119991 Moscow, Russian Federation. Fax: +7 095 135 5328; e-mail: shevelev@mail.ioc.ac.ru 10.1070/MC2002v012n01ABEH001551 3-Aryl-5,7-dinitrothiochromane 1,1-dioxides are formed by the condensation of methyl (2-methyl-3,5-dinitrobenzenesulfonyl)acetate and ethyl (2-methyl-3,5-dinitrobenzenesulfonyl)propionate, which are the products of 2,4,6-trinitrotoluene transformations, with aromatic aldehydes under conditions of the Knoevenagel reaction.This study was performed in the context of the chemical utilization of 2,4,6-trinitrotoluene (TNT)1 to prepare multipurpose intermediates for the synthesis of polyfunctional heterocyclic compounds.We examined the reactions of sulfone 1, which was synthesised previously2 from TNT, with aromatic aldehydes under conditions of the Knoevenagel reaction. The equimolar amounts of the sulfone and ArCHO in benzene in the presence of secondary aliphatic amine acetates were heated with the continuous removal of water formed in the reaction (Scheme 1).Under these conditions, 3-aryl-5,7-dinitrothiochromane 1,1- dioxide 6 was the reaction product. It can be formed either by the initial formation of stilbene 4 in the condensation of ArCHO 3 with the methyl group of sulfone 1 followed by the addition of an active methylene unit at the double bond of stilbene 4 (pathway a) or by the condensation of aldehydes 3 with the active methylene unit of sulfone 1 to form arylidene 5 followed by the intramolecular addition of an active methyl group at the double bond of arylidene 5 (pathway b).It is likely that the reaction can simultaneously proceed via pathways a and b. At least, the feasibility of pathway a was demonstrated by the formation of 3-aryl-2-methyl-5,7-dinitrothiochromane 1,1-dioxides 7 with the use of sulfone 22 in this reaction (Scheme 2).Thus, we developed a general procedure† for preparing previously unknown 3-aryl-5,7-dinitrothiochromane 1,1-dioxides 6 and 7. Compounds 6 and 7 were identified by 1H NMR spectroscopy and elemental analysis.‡ The stereochemistry of these compounds will be published elsewhere.This study was supported by the Russian Foundation for Basic Research (grant no. 01-03-32261) and the International Science and Technology Centre (project no. 419). Me O2N NO2 SO2CH2CO2Me + ArCHO 1 3 HC O2N NO2 SO2CH2CO2Me 4 CHAr CH3 O2N NO2 SO2CCO2Me 5 HC Ar R2NH·AcOH, C6H6, reflux a b – H2O S NO2 O2N O O Ar CO2Me 6 a Ar = Ph b Ar = 4-MeOC6H4 c Ar = 4-Me2NC6H4 d Ar = 4-ClC6H4 e Ar = 4-FC6H4 f Ar = 4-NO2C6H4 g Ar = 3-pyridyl Scheme 1 † General procedure.Piperidine (0.1 ml) and glacial acetic acid (0.11 ml) were added to a mixture of 0.01 mol of sulfone 1 or 2 and 0.011 mol of ArCHO in 30 ml of benzene. The mixture was refluxed for 2–5 h (with TLC monitoring) with the use of a Dean–Stark trap to remove water and then cooled.The precipitated product was filtered off, washed with a dilute aqueous NaCl solution, dried in air, and recrystallised from an acetone–methanol mixture. ‡ The 1H NMR spectra (in [2H6]acetone) were measured on a Bruker AC-200 instrument. 6a: 53% yield, mp 217–219 °C. 1H NMR, d: 9.02 (d, 1H, 4J 2.0 Hz), 8.90 (d, 1H, 4J 2.0 Hz), 7.31–7.48 (m, 5H), 5.17 (d, 1H, 3J 11.0 Hz), 4.07–4.20 (m, 1H), 3.56–3.75 (m, 5H). Found (%): C, 50.44; H, 3.29; S, 8.11; N, 7.02.Calc. for C17H14N2O8S (%): C, 50.25; H, 3.47; S, 7.89; N, 6.89. 6b: 82% yield, mp 197–199 °C. 1H NMR, d: 9.03 (d, 1H, 4J 2.2 Hz), 8.89 (d, 1H, 4J 2.2 Hz), 7.38 (d, 2H, 3J 8.6 Hz), 6.95 (d, 2H, 3J 8.6 Hz), 5.16 (d, 1H, 3J 11.1 Hz), 4.00–4.15 (m, 1H), 3.75–3.85 (m, 8H). Found (%): C, 49.83; H, 4.00; S, 7.47; N, 6.15.Calc. for C18H16N2O9S (%): C, 49.54; H, 3.70; S, 7.35; N, 6.42. 6c: 35% yield, mp 185–187 °C. 1HNMR, d: 9.03 (d, 1H, 4J 2.0 Hz), 8.89 (d, 1H, 4J 2.0 Hz), 7.28 (d, 2H, 3J 8.5 Hz), 6.72 (d, 2H, 3J 8.5 Hz), 5.02 (d, 1H, 3J 11.0 Hz), 3.90–4.05 (m, 1H), 3.60–3.72 (m, 5H), 2.94 (s, 6H). Found (%): C, 51.03; H, 4.37; S, 7.23; N, 9.07. Calc. for C19H19N3O8S (%): C, 50.78; H, 4.26; S, 7.13; N, 9.35. 6d: 24% yield, mp 234–236 °C. 1H NMR, d: 9.05 (d, 1H, 4J 2.1 Hz), 8.91 (d, 1H, 4J 2.1 Hz), 7.52 (d, 2H, 3J 8.9 Hz), 7.44 (d, 2H, 3J 8.9 Hz), 5.29 (d, 1H, 3J 11.3 Hz), 4.10–4.25 (m, 1H), 3.62–3.78 (m, 5H). Found (%): C, 46.14; H, 3.11; S, 7.05; Cl, 8.42; N, 6.03. Calc. for C17H13ClN2O8S (%): C, 46.32; H, 2.97; S, 7.27; Cl, 8.04; N, 6.35.Me O2N NO2 SO2CH(Me)CO 2Et + ArCHO 2 3 R2NH·AcOH, C6H6, reflux S NO2 O2N O O Ar CO2Et 7 Me b Ar = 4-MeOC6H4 e Ar = 4-FC6H4 g Ar = 3-pyridyl Scheme 2Mendeleev Communications Electronic Version, Issue 1, 2002 2 References 1 V. A. Tartakovsky, S. A. Shevelev, M. D. Dutov, A. Kh. Shakhnes, A. L. Rusanov, L. G. Komarova and A. M. Andrievsky, in Conversion Concepts for Commercial Applications and Disposal Technologies of Energetic Systems, ed.H. Krause, Kluwer Academic Publishers, Dordrecht, 1997, p. 137. 2 O. V. Serushkina, M. D. Dutov and S. A. Shevelev, Izv. Akad. Nauk, Ser. Khim., 2001, 252 (Russ. Chem. Bull., Int. Ed., 2001, 50, 261). 6e: 68% yield, mp 220–222 °C. 1H NMR, d: 9.04 (d, 1H, 4J 2.0 Hz), 8.90 (d, 1H, 4J 2.0 Hz), 7.45–7.58 (m, 2H), 7.19–7.21 (m, 2H), 5.18 (d, 1H, 3J 10.3 Hz), 4.10–4.25 (m, 1H), 3.61–3.75 (m, 5H).Found (%): C, 48.36; H, 3.01; S, 7.84; N, 6.73. Calc. for C17H13FN2O8S (%): C, 48.12; H, 3.09; S, 7.56; N, 6.60. 6f: 52% yield, mp 264–266 °C. 1HNMR, d: 9.05 (d, 1H, 4J 2.2 Hz), 8.92 (d, 1H, 4J 2.2 Hz), 8.29 (d, 2H, 3J 8.8 Hz), 7.80 (d, 2H, 3J 8.8 Hz), 5.44 (d, 1H, 3J 11.0 Hz), 4.26–4.45 (m, 1H), 3.70–3.81 (m, 2H), 3.64 (s, 3H).Found (%): C, 45.42; H, 3.10; S, 7.15; N, 9.03. Calc. for C17H13N3O10S (%): C, 45.24; H, 2.90; S, 7.10; N, 9.31. 6g: 55% yield, mp 183–185 °C. 1H NMR, d: 9.04 (d, 1H, 4J 2.1 Hz), 8.91 (d, 1H, 4J 2.1 Hz), 8.67 (m, 1H), 8.55 (m, 1H), 7.93 (m, 1H), 7.41 (m, 1H), 5.36 (d, 1H, 3J 11.0 Hz), 4.12–4.30 (m, 1H), 3.70–3.80 (m, 2H), 3.63 (s, 3H). Found (%): C, 47.48; H, 3.14; S, 8.13; N, 10.04.Calc. for C16H13N3O8S (%): C, 47.18; H, 3.22; S, 7.87; N, 10.32. 7b: 53% yield, mp 145.5–147.5 °C. 1HNMR, d: 9.05 (d, 1H, 4J 2.3 Hz), 8.90 (d, 1H, 4J 2.3 Hz), 7.32 (d, 2H, 3J 8.8 Hz), 6.95 (d, 2H, 3J 8.8 Hz), 4.41–4.49 (m, 1H), 4.08–4.22 (m, 2H), 3.74–3.83 (m, 5H), 1.58 (s, 3H), 1.16 (t, 3H, 3J 7.1 Hz). Found (%): C, 52.01; H, 4.32; S, 7.24; N, 5.88. Calc.for C20H20N2O9S (%): C, 51.72; H, 4.34; S, 6.90; N, 6.03. 7e: 40% yield, mp 149–151 °C. 1H NMR, d: 9.06 (d, 1H, 4J 2.3 Hz), 8.90 (d, 1H, 4J 2.3 Hz), 7.40–7.53 (m, 2H), 7.12–7.22 (m, 2H), 4.47–4.57 (m, 1H), 4.10–4.22 (m, 2H), 3.77–3.87 (m, 2H), 1.60 (s, 3H), 1.15 (t, 3H, 3J 7.2 Hz). Found (%): C, 50.22; H, 3.94; S, 6.93; N, 5.98. Calc. for C19H17FN2O8S (%): C, 50.44; H, 3.79; S, 7.09; N, 6.19. 7g: 74% yield, mp 177.5–179.5 °C. 1HNMR, d: 9.08 (d, 1H, 4J 2.3 Hz), 8.55–8.62 (m, 2H), 7.94–7.89 (m, 1H), 7.45–7.39 (m, 1H), 4.62–4.57 (m, 1H), 4.19–4.12 (m, 2H), 3.93–3.87 (m, 2H), 1.70 (s, 3H), 1.15 (t, 3H, 3J 7.2 Hz). Found (%): C, 49.91; H, 4.06; S, 7.52; N, 9.47. Calc. for C18H17N3O8S (%): C, 49.65; H, 3.94; S, 7.36; N, 9.65. Received: 9th January 2002; Com. 02/1877