TY - JOUR A1 - Umemoto, Teruo A1 - Garrick, Lloyd M. A1 - Saito, Norimichi T1 - Discovery of practical production processes for arylsulfur pentafluorides and their higher homologues, bis- and tris(sulfur pentafluorides): Beginning of a new era of “super-trifluoromethyl” arene chemistry and its industry JF - Beilstein Journal of Organic Chemistry PY - 2012/// VL - 8 SP - 461 EP - 471 SN - 1860-5397 DO - 10.3762/bjoc.8.53 PB - Beilstein-Institut JA - Beilstein J. Org. Chem. UR - https://doi.org/10.3762/bjoc.8.53 KW - arylsulfur chlorotetrafluoride KW - arylsulfur pentafluoride KW - pentafluorosulfanyl KW - sulfur pentafluoride KW - super-trifluoromethyl N2 - Various arylsulfur pentafluorides, ArSF5, have long been desired in both academic and industrial areas, and ArSF5 compounds have attracted considerable interest in many areas such as medicines, agrochemicals, and other new materials, since the highly stable SF5 group is considered a “super-trifluoromethyl group” due to its significantly higher electronegativity and lipophilicity. This article describes the first practical method for the production of various arylsulfur pentafluorides and their higher homologues, bis- and tris(sulfur pentafluorides), from the corresponding diaryl disulfides or aryl thiols. The method consists of two steps: (Step 1) treatment of a diaryl disulfide or an aryl thiol with chlorine in the presence of an alkali metal fluoride, and (step 2) treatment of the resulting arylsulfur chlorotetrafluoride with a fluoride source, such as ZnF2, HF, and Sb(III/V) fluorides. The intermediate arylsulfur chlorotetrafluorides were isolated by distillation or recrystallization and characterized. The aspects of these new reactions are revealed and reaction mechanisms are discussed. As the method offers considerable improvement over previous methods in cost, yield, practicality, applicability, and large-scale production, the new processes described here can be employed as the first practical methods for the economical production of various arylsulfur pentafluorides and their higher homologues, which could then open up a new era of “super-trifluoromethyl” arene chemistry and its applications in many areas. ER - TY - BOOK AU - Kirsch, P. T1 - Modern Fluoroorganic Chemistry PY - 2004/// SP - 151 DO - 10.1002/352760393X PB - Wiley-VCH CY - Weinheim, Germany ER - TY - JOUR AU - Sheppard, W. A. JF - J. Am. Chem. Soc. PY - 1962/// VL - 84 SP - 3072 EP - 3076 DO - 10.1021/ja00875a007 ER - TY - JOUR AU - Sheppard, W. A. JF - J. Am. Chem. Soc. PY - 1962/// VL - 84 SP - 3064 EP - 3072 DO - 10.1021/ja00875a006 ER - TY - JOUR AU - Hansch, C. AU - Muir, R. M. AU - Fujita, T. AU - Maloney, P. P. AU - Geiger, F. AU - Streich, M. JF - J. Am. Chem. Soc. PY - 1963/// VL - 85 SP - 2817 EP - 2824 DO - 10.1021/ja00901a033 ER - TY - JOUR AU - Stump, B. AU - Eberle, C. AU - Schweizer, W. B. AU - Kaiser, M. AU - Brun, R. AU - Krauth-Siegel, R. L. AU - Lentz, D. AU - Diederich, F. JF - ChemBioChem PY - 2009/// VL - 10 SP - 79 EP - 83 DO - 10.1002/cbic.200800565 ER - TY - JOUR AU - Mo, T. AU - Mi, X. AU - Milner, E. E. AU - Dow, G. S. AU - Wipf, P. JF - Tetrahedron Lett. PY - 2010/// VL - 51 SP - 5137 EP - 5140 DO - 10.1016/j.tetlet.2010.07.113 ER - TY - JOUR AU - Gujjar, R. AU - El Mazouni, F. AU - White, K. L. AU - White, J. AU - Creason, S. AU - Shackleford, D. M. AU - Deng, X. AU - Charman, W. N. AU - Bathurst, I. AU - Burrows, J. AU - Floyd, D. M. AU - Matthews, D. AU - Buckner, F. S. AU - Charman, S. A. AU - Phillips, M. A. AU - Rathod, P. K. JF - J. Med. Chem. PY - 2011/// VL - 54 SP - 3935 EP - 3949 DO - 10.1021/jm200265b ER - TY - JOUR AU - Coteron, J. M. AU - Marco, M. AU - Esquivias, J. AU - Deng, X. AU - White, K. L. AU - White, J. AU - Koltun, M. AU - El Mazouni, F. AU - Kokkonda, S. AU - Katneni, K. AU - Bhamidipati, R. AU - Shackleford, D. M. AU - Angulo-Barturen, I. AU - Ferrer, S. B. AU - Jiménez-Díaz, M. B. AU - Gamo, F.-J. AU - Goldsmith, E. J. AU - Charman, W. N. AU - Bathurst, I. AU - Floyd, D. AU - Matthews, D. AU - Burrows, J. N. AU - Rathod, P. K. AU - Charman, S. A. AU - Phillips, M. A. JF - J. Med. Chem. PY - 2011/// VL - 54 SP - 5540 EP - 5561 DO - 10.1021/jm200592f ER - TY - PAT AU - Bossemaier, B. AU - Friebe, W.-G. AU - Georges, G. AU - Rueth, M. AU - Voss, E. T2 - Novel pentafluorosulfanyl compounds T1 - U.S. Patent Appl. PY - 2005/9/8/ IS - 0,197,370 ER - TY - PAT AU - Andeotti, D. AU - Checchia, A. AU - Hamprecht, D. AU - Micheli, F. T2 - 3-triazolylthioalkyl-3-azabicyclo(3.1.0)hexanes and their use as dopamine D3 receptor ligands T1 - WO Patent PY - 2006/10/19/ IS - WO/2006/108700 ER - TY - PAT AU - Frank, R. AU - Sundermann, B. AU - Schick, H. T2 - Pentafluorosulphanyl-substituted compound and its use for producing medicaments T1 - WO Patent PY - 2006/11/23/ IS - WO/2006/122773 ER - TY - PAT AU - Billen, D. AU - Boyle, J. AU - Critcher, D. J. AU - Gethin, D. M. AU - Hall, K. T. AU - Kyne, G. M. T2 - Substituted arylpyrazoles T1 - US Patent Appl. PY - 2008/7/24/ IS - 176,865 ER - TY - PAT AU - Kleeman, H.-W. T2 - Pentafluorosulfanylphenyl-substituted benzoylguanidines, method for the production thereof, their use as a medicament or diagnostic agent, and a medicament containing these compounds T1 - U.S. Patent PY - 2008/11/4/ IS - 7,446,225 ER - TY - PAT AU - Stamford, A. W. AU - Cumming, J. N. T2 - Pentafluorosulfurimino heterocyclic compounds as BACE-1 inhibitors, compositions and their use T1 - WO Patent PY - 2011/4/11/ IS - WO/2011/044184 ER - TY - JOUR AU - Crowley, P. J. AU - Mitchell, G. AU - Salmon, R. AU - Worthington, P. A. JF - Chimia PY - 2004/// VL - 58 SP - 138 EP - 142 ER - TY - JOUR AU - Lim, D. S. AU - Choi, J. S. AU - Pak, C. S. AU - Welch, J. T. JF - J. Pestic. Sci. PY - 2007/// VL - 32 SP - 255 EP - 259 DO - 10.1584/jpestics.G06-50 ER - TY - PAT AU - Chern, R. T. AU - Zingerman, J. R. AU - Clark, J. N. AU - Drag, M. D. T2 - Sulfurpentafluorophenyl pyrazoles for controlling ectoparasitic infestations T1 - WO Patent PY - 1999/9/23/ IS - WO/1999/047139 ER - TY - PAT AU - Matsuzaki, Y. AU - Morimoto, M. AU - Fujioka, S. AU - Tohnishi, M. T2 - Phtalimide derivative, agricultural or horticultural insecticide, and method of use thereof T1 - WO Patent PY - 2003/11/13/ IS - WO/2003/093228 ER - TY - JOUR AU - Nixon, P. G. AU - Winter, R. AU - Castner, D. G. AU - Holcomb, N. R. AU - Grainger, D. W. AU - Gard, G. L. JF - Chem. Mater. PY - 2000/// VL - 12 SP - 3108 EP - 3112 DO - 10.1021/cm000339k ER - TY - JOUR AU - Kirsch, P. AU - Hahn, A. JF - Eur. J. Org. Chem. PY - 2005/// SP - 3095 EP - 3100 DO - 10.1002/ejoc.200500125 ER - TY - JOUR AU - Gao, H. AU - Ye, C. AU - Winter, R. W. AU - Gard, G. L. AU - Sitzmann, M. E. AU - Shreeve, J. M. JF - Eur. J. Inorg. Chem. PY - 2006/// SP - 3221 EP - 3226 DO - 10.1002/ejic.200600098 ER - TY - JOUR AU - Ye, C. AU - Gard, G. L. AU - Winter, R. W. AU - Syvret, R. G. AU - Twamley, B. AU - Shreeve, J. M. JF - Org. Lett. PY - 2007/// VL - 9 SP - 3841 EP - 3844 DO - 10.1021/ol701602a ER - TY - PAT AU - Zahn, S. AU - Nordquist, A. F. AU - Minnich, K. E. AU - Lal, G. S. AU - Burgoyne, W. F., Jr AU - Klauck-Jacobs, A. T2 - Pentafluorosulfanyl-substituted thienothiophene monomers and conducting polymers T1 - U.S. Patent PY - 2006/6/13/ IS - 7,060,846 ER - TY - JOUR AU - Simons, J. H. AU - Lewis, C. J. JF - J. Am. Chem. Soc. PY - 1938/// VL - 60 SP - 492 DO - 10.1021/ja01269a507 ER - TY - JOUR AU - Pouterman, E. AU - Girardet, A. JF - Helv. Chim. Acta PY - 1947/// VL - 30 SP - 107 EP - 112 DO - 10.1002/hlca.19470300114 ER - TY - JOUR AU - McBee, E. T. AU - Hass, H. B. AU - Weiner, P. E. AU - Rothrock, G. M. AU - Burt, W. E. AU - Robb, R. M. AU - Van Dyken, A. R. JF - Ind. Eng. Chem. PY - 1947/// VL - 39 SP - 298 EP - 301 DO - 10.1021/ie50447a613 ER - TY - BOOK T1 - Organofluorine Chemicals and Their Industrial Applications PY - 1979/// PB - Ellis Horwood Ltd. CY - Chichester A2 - Banks, R. E. ER - TY - BOOK T1 - Organofluorine Chemistry, Principles and Commercial Applications PY - 1994/// PB - Plenum Press CY - New York A2 - Banks, R. E. A2 - Smart, B. E. A2 - Tatlow, J. C. ER - TY - CHAP AU - Hiyama, T. T1 - Organofluorine Compounds, Chemsitry and Applications PY - 2000/// PB - Springer CY - Heidelberg, Germany A2 - Yamamoto, H. ER - TY - BOOK AU - Kirsch, P. T1 - Modern Fluoroorganic Chemistry PY - 2004/// DO - 10.1002/352760393X PB - Wiley-VCH CY - Weinheim, Germany ER - TY - JOUR AU - Sipyagin, A. M. AU - Bateman, C. P. AU - Tan, Y.-T. AU - Thrasher, J. S. JF - J. Fluorine Chem. PY - 2001/// VL - 112 SP - 287 EP - 295 DO - 10.1016/S0022-1139(01)00514-0 ER - TY - JOUR AU - Sipyagin, A. M. AU - Enshov, V. S. AU - Kashtanov, S. A. AU - Bateman, C. P. AU - Mullen, B. D. AU - Tan, Y.-T. AU - Thrasher, J. S. JF - J. Fluorine Chem. PY - 2004/// VL - 125 SP - 1305 EP - 1316 DO - 10.1016/j.jfluchem.2004.03.008 ER - TY - JOUR AU - Bowden, R. D. AU - Comina, P. J. AU - Greenhall, M. P. AU - Kariuki, B. M. AU - Loveday, A. AU - Philp, D. JF - Tetrahedron PY - 2000/// VL - 56 SP - 3399 EP - 3408 DO - 10.1016/S0040-4020(00)00184-8 ER - TY - JOUR AU - Ou, X. AU - Janzen, A. F. JF - J. Fluorine Chem. PY - 2000/// VL - 101 SP - 279 EP - 283 DO - 10.1016/S0022-1139(99)00171-2 ER - TY - JOUR AU - Hoover, F. W. AU - Coffman, D. D. JF - J. Org. Chem. PY - 1964/// VL - 29 SP - 3567 EP - 3570 DO - 10.1021/jo01035a030 ER - TY - JOUR AU - Winter, R. W. AU - Gard, G. L. JF - J. Fluorine Chem. PY - 2004/// VL - 125 SP - 549 EP - 552 DO - 10.1016/j.jfluchem.2003.11.028 ER - TY - JOUR AU - Sergeeva, T. A. AU - Dolbier, W. R., Jr JF - Org. Lett. PY - 2004/// VL - 6 SP - 2417 EP - 2419 DO - 10.1021/ol0491991 ER - TY - JOUR AU - Dolbier, W. R., Jr AU - Mitani, A. AU - Warren, R. D. JF - Tetrahedron Lett. PY - 2007/// VL - 48 SP - 1325 EP - 1326 DO - 10.1016/j.tetlet.2006.12.123 ER - TY - JOUR AU - Dolbier, W. R., Jr AU - Mitani, A. AU - Xu, W. AU - Ghiviriga, I. JF - Org. Lett. PY - 2006/// VL - 8 SP - 5573 EP - 5575 DO - 10.1021/ol0622662 ER - TY - JOUR AU - Dolbier, W. R., Jr AU - Zheng, Z. JF - J. Fluorine Chem. PY - 2011/// VL - 132 SP - 389 EP - 393 DO - 10.1016/j.jfluchem.2011.03.017 ER - TY - JOUR AU - Dolbier, W. R., Jr AU - Zheng, Z. JF - J. Org. Chem. PY - 2009/// VL - 74 SP - 5626 EP - 5628 DO - 10.1021/jo9007699 ER - TY - JOUR AU - Wessel, J. AU - Hartl, H. AU - Seppelt, K. JF - Chem. Ber. PY - 1986/// VL - 119 SP - 453 EP - 463 DO - 10.1002/cber.19861190208 ER - TY - PAT AU - Umemoto, T. T2 - Process for producing arylsulfur pentafluorides T1 - WO Patent PY - 2008/10/2/ IS - WO/2008/118787 ER - TY - PAT AU - Umemoto, T. T2 - Process for producing arylsulfur pentafluorides T1 - U.S. Patent PY - 2009/9/22/ IS - 7,592,491 ER - TY - PAT AU - Umemoto, T. T2 - Process for producing arylsulfur pentafluorides T1 - U.S. Patent PY - 2010/10/26/ IS - 7,820,864 ER - TY - PAT AU - Umemoto, T. T2 - Process for producing arylsulfur pentafluorides T1 - U.S. Patent PY - 2010/12/14/ IS - 7,851,646 ER - TY - PAT AU - Umemoto, T. T2 - Method for producing fluorinated phenylsulfur pentafluorides T1 - U.S. Patent Appl. PY - 2010/5/27/ IS - 2010/0,130,790 ER - TY - PAT AU - Umemoto, T. T2 - Processes for preparing poly(pentafluorosulfanyl)aromatic compounds T1 - WO Patent PY - 2010/3/25/ IS - WO/2010/033930 ER - TY - JOUR AU - Pashinnik, V. E. AU - Martyniuk, E. G. AU - Tabachuk, M. R. AU - Shermolovich, Yu. G. AU - Yagupolskii, L. M. JF - Synth. Commun. PY - 2003/// VL - 33 SP - 2505 EP - 2509 DO - 10.1081/SCC-120021841 ER - TY - JOUR AU - Umemoto, T. AU - Singh, R. P. AU - Xu, Y. AU - Saito, N. JF - J. Am. Chem. Soc. PY - 2010/// VL - 132 SP - 18199 EP - 18205 DO - 10.1021/ja106343h ER - TY - JOUR AU - Xu, W. AU - Martinez, H. AU - Dolbier, W. R., Jr JF - J. Fluorine Chem. PY - 2011/// VL - 132 SP - 482 EP - 488 DO - 10.1016/j.jfluchem.2011.05.001 N1 - (Discussing the use of bromine (Br2) instead of chlorine (Cl2) for the preparation of arylsulfur trifluorides.) ER - TY - JOUR AU - Ou, X. AU - Bernard, G. M. AU - Janzen, A. F. JF - Can. J. Chem. PY - 1997/// VL - 75 SP - 1878 EP - 1884 DO - 10.1139/v97-621 ER - TY - JOUR AU - Sheppard, W. A. JF - J. Am. Chem. Soc. PY - 1962/// VL - 84 SP - 3058 EP - 3063 DO - 10.1021/ja00875a005 N1 - It was described that the hydrolysis of PhSF3 to benzenesulfinic acid occurs with almost explosive violence. ER - TY - JOUR AU - Taft, R. W. AU - Price, E. AU - Fox, I. R. AU - Lewis, I. C. AU - Anderson, K. K. AU - Davis, G. T. JF - J. Am. Chem. Soc. PY - 1963/// VL - 85 SP - 3146 EP - 3155 DO - 10.1021/ja00903a022 ER - TY - JOUR AU - Kice, J. L. AU - Hampton, D. C. AU - Fitzgerald, A. JF - J. Org. Chem. PY - 1965/// VL - 30 SP - 882 EP - 885 DO - 10.1021/jo01014a053 ER -