Abstract
A series of pyrazole-4-sulfonyl chlorides was obtained by a convenient 2-step method starting from synthetically available 2-(benzylthio)malonaldehyde. The method can be applied for the effective multi-gram synthesis of diverse pyrazole-containing sulfonyl chlorides which are mostly not available by other methods.
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References
Patai S, Rapport Z (1991) The chemistry of sulfonic acids, esters and their derivatives (The Chemistry of Functional Groups). New York, Wiley. doi:10.1002/0470034394
Shah SSA, Rivera G, Ashfaq M (2013) Recent advances in medicinal chemistry of sulfonamides. Rational design as anti-tumoral, anti-bacterial and anti-inflammatory agents. Mini-Rev Med Chem 13:70–86. doi:10.2174/1389557511307010070
Carta FScozzafava A, Supuran CT (2012) Sulfonamides: a patent review (2008–2012). Expert Opin Ther Pat 22:747–758. doi:10.1517/13543776.2012.698264
Turner SR, Stohbach JW, Tommasi RA, Aristoff PA, Johnson PD, Skulnick HI, Dolak LA, Seest EP, Tomich PK, Bohanon MJ, Horng M-M, Lynn JC, Chong K-T, Hinshaw RR, Watenpaugh KD, Janakiraman MN, Thaisrivongs S (1998) Tipranavir (PNU-140690): a potent, orally bioavailable nonpeptidic HIV protease inhibitor of the 5,6-dihydro-4-hydroxy-2-pyrone sulfonamide class. J Med Chem 41:3467–3476. doi:10.1021/jm9802158
Conrow RE, Dean WD, Zinke PW, Deason ME, Sproull SJ, Dantanarayana AP, DuPriest MT (1999) Enantioselective synthesis of brinzolamide (AL-4862), a new topical carbonic anhydrase inhibitor. The “DCAT Route” to thiophenesulfonamides. Org Process Res Dev 3:114–120. doi:10.1021/op9802125
Kondo Y, Fukuda K, Makabe T, Kondo Y, Fukuda K, Sakurai Y, Utsunomiya T, Tanaka (2007) Processes for production of indole compounds. Patent EP1829872
Bell BM, Fanwick PE, Graupner PR, Roth GA (2006) Application of the tisler triazolopyrimidine cyclization to the synthesis of a crop protection agent and an intermediate. Org Process Res Dev 10:1167–1171. doi:10.1021/op0601518
Porcs-Makkay M, Lukacs G, Pandur A, Simig G, Volk B (2014) Synthesis of 4-unsubstituted 2H–1,2,3-benzothiadiazine 1,1-dioxides via ortho lithiation of protected benzaldehyde derivatives. Tetrahedron 70:286–293. doi:10.1016/j.tet.2013.11.058
De Bergh JR, Niljianskul N, Buchwald SL (2013) Synthesis of aryl sulfonamides via palladium-catalyzed chlorosulfonylation of arylboronic acids. J Am Chem Soc 135:10638–10641. doi:10.1021/ja405949a
Pandya R, Murashima T, Tedeschi L, Barrett AGM (2003) Facile one-pot synthesis of aromatic and heteroaromatic sulfonamides. J Org Chem 68:8274–8276. doi:10.1021/jo034643j
Ichinose M, Suematsu H, Yasutomi Y, Nishioka Y, Uchida T, Katsuki T (2011) Enantioselective intramolecular benzylic C–H bond amination: efficient synthesis of optically active benzosultams. Angew Chem Int Ed Engl 50:9884–9887. doi:10.1002/anie.201101801
Velazquez C, Abdellatif K, Chowdhury M, Jain S, Reisz J, DuMond J, King SB, Knaus E (2010) Acyclic triaryl olefins possessing a sulfohydroxamic acid pharmacophore: synthesis, nitric oxide/nitroxyl release, cyclooxygenase inhibition, and anti-inflammatory studies. Org Biomol Chem 8:4124–4130. doi:10.1039/C005066K
Foschi F, Tagliabule A, Mihali V, Pilati T, Pecnikaj I, Penso M (2013) Memory of chirality approach to the enantiodivergent synthesis of chiral benzo[d]sultams. Org Lett 14:3686–3689. doi:10.1021/ol401557v
Malet-Sanz L, Madrzak J, Ley SV, Baxendale IR (2010) Preparation of arylsulfonyl chlorides by chlorosulfonylation of in situ generated diazonium salts using a continuous flow reactor. Org Biomol Chem 8:5324–5332. doi:10.1039/C0OB00450B
Hogan PJ, Cox BG (2009) Aqueous process chemistry: the preparation of aryl sulfonyl chlorides. Org Proc Res Dev 13:875–879. doi:10.1021/op9000862
Yang L, Xue X, Zhang Y (2010) Simple and efficient synthesis of belinostat. Synth Commun 40:2520–2524. doi:10.1080/00397911.2010.510386
Tang G, Lin X, Qiu Z, Li W, Zhu L, Wang L, Li S, Li H, Lin W, Yang M, Guo T, Chen L, Lee D, Wu JZ, Yang W (2011) Design and synthesis of benzenesulfonamide derivatives as potent anti-influenza hemagglutinin inhibitors. ACS Med Chem Lett 2:603–607. doi:10.1021/ml2000627
Bahrami K, Khodaei MM, Soheilizad M (2009) Direct conversion of thiols to sulfonyl chlorides and sulfonamides. J Org Chem 74:9287–9291. doi:10.1021/jo901924m
Bahrami K, Khodaei MM, Soheilizad M (2009) A novel, practical synthesis of sulfonyl chlorides from thiol and disulfide derivatives. Synlett 17:2773–2776. doi:10.1055/s-0029-1217989
Bahrami K, Khodaei MM, Khaledian D (2012) Synthesis of sulfonyl chlorides and thiosulfonates from \(\text{ H }_{2}\text{ O }_{2}-\text{ TiCl }_{4}\). Tetrahedron Lett 53:354–358. doi:10.1016/j.tetlet.2011.11.052
Veisi H, Ghorbani-Vaghei R, Hemmati S, Mahmoodi J (2011) Convenient one-pot synthesis of sulfonamides and sulfonyl azides from thiols using N-chlorosuccinimide. Synlett 16:2315–2320. doi:10.1055/s-0030-1261232
Prakash GKS, Mathew T, Panja C, Olah GA (2007) Chlorotrimethylsilane-nitrate salts as oxidants:? direct oxidative conversion of thiols and disulfides to sulfonyl chlorides. J Org Chem 72:5847–5850. doi:10.1021/jo070907g
Nishiguchi A, Maeda K, Miki S (2006) Sulfonyl chloride formation from thiol derivatives by N-chlorosuccinimide mediated oxidation. Synthesis 24:4131–4134. doi:10.1055/s-2006-950353
Muesmann TWT, Wickleder MS, Christoffers J (2011) Preparation of linear aromatic disulfonic acids: new linker molecules for metal-organic frameworks. Synthesis 17:2775–2780. doi:10.1055/s-0030-1260123
Percec V, Bera TK, De BB, Sanai Y, Smith J, Holerca MN, Barboiu B, Grubbs RB, Frechet JMJ (2001) Synthesis of Functional Aromatic Multisulfonyl Chlorides and Their Masked Precursors. J Org Chem 66:2104–2117. doi:10.1021/jo001694x
Wall M, Benkovic SJ (2002) Synthesis and biological evaluation of 9-thia-5,10-dideazafolic acid. J Heterocyclic Chem 39:1097–1099. doi:10.1002/jhet.5570390541
Demydchuk BA, Kondratyuk KM, Korniyenko AN, Brovarets VS, Vasylyshyn RY, Tolmachev A, Lukin O (2012) A facile synthesis of 1,3-thiazole-4-sulfonyl chlorides. Synth Commun 42:2866–2875. doi:10.1080/00397911.2011.571356
Zhersh S, Lukin O, Matvienko V, Tolmachev A (2010) Synthesis of isomeric fluoronitrobenzene-sulfonyl chlorides. Tetrahedron 66:5982–5986. doi:10.1016/j.tet.2010.06.036
Pu YM, Christesen A, Ku Y-Y (2010) A simple and highly effective oxidative chlorination protocol for the preparation of arenesulfonyl chlorides. Tetrahedron Lett 51:418–421. doi:10.1016/j.tetlet.2009.11.047
Acknowledgments
We express our appreciation to Dr. S. I. Vdovenko and O. A. Fedorenko (Institute of Bioorganic Chemistry and Petrochemistry, National Academy of Sciences, Ukraine) for measuring the IR-spectra.
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Sokolyuk, P.A., Kondratov, I.S., Gavrylenko, O.V. et al. Synthesis of diverse pyrazole-4-sulfonyl chlorides starting from 2-(benzylthio)malonaldehyde. Mol Divers 20, 1–7 (2016). https://doi.org/10.1007/s11030-015-9633-z
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DOI: https://doi.org/10.1007/s11030-015-9633-z