One-pot synthesis of arylfluoroalkylsulfoxides and study of their anomalous 19F NMR behavior

Metal‐Free Difluoromethylthiolation, Trifluoromethylthiolation, and Perfluoroalkylthiolation with Sodium Difluoromethane‐ sulfinate, Sodium Trifluoromethanesulfinate or Sodium Perfluoro‐ alkanesulfinate

“…Other than starting material 1d ( δ =−124.57 ppm) and product 3a ( δ =−89.25 ppm), a new peak ( δ =−116.05 ppm) for compound 7a with an MS peak matching with HCF 2 S(O) was observed during the reaction, but it had disappeared when the reaction was completed after 3 h. The peak of HCF 2 SSCF 2 H 8 ( δ =−87.0 ppm) was also observed and it increased with the reaction progress without being consumed. The 19 F NMR peaks for SCF 2 H and SCF 3 related compounds are listed in Table ,. For the mechanism of the difluoromethylthiolation reaction (Scheme ), we believe that HCF 2 SO 2 Na 1d is reduced with (EtO) 2 P(O)H to form HCF 2 S(O) 7a followed by an intramolecular nucleophilic collapse to form 7b HCF 2 SOH which is unstable and thus difficult to detect by the 19 F NMR.…”

Efficient synthesis of unsymmetrical S-(bromodifluoromethyl)diarylsulfonium salts for electrophilic bromodifluoromethylating reagents

“…The characterization data was consistent with the previous report. 13 (Bromodifluoromethyl)(o-bromophenyl)sulfoxide 2c. White solid, 96% yield, eluent: hexane/dichloromethane = 4 : 1.…”

“…White solid, 62% yield. 1 H NMR (CDCl 3 , 300 MHz) d 8.23 (d, J = 8.1 Hz, 2H), 7.83-7.91 (m, 3H), 7.45 (s, 1H), 2.75 (s, 3H), 2.40 (s, 3H), 2.34 (s, 3H), 2.33 (s, 3H); 19 F NMR (CDCl 3 , 282.3 MHz) d À35.0 (dd, J = 366.7 Hz, 125.9 Hz, 2F), À152.6 (s 1F), À152.7 (s, 3F); 13 C NMR (CDCl 3 , 150.9 MHz) d 17. 5, 17.7, 19.0, 21.7, 114.9, 117.2 (t, J = 356.1 Hz), 120.0, 128.9, 132.6, 133.3, 137.0, 139.3, 140.8, 141.3, 147.0;IR (KBr) 3430, 3082, 2930, 1451, 1272, 1255, 1217, 1063 S-Bromodifluoromethyl-S-p-nitrophenyl-2,4,6-trimethoxyphenylsulfonium tetrafluoroborate (1h).…”

“…Brown solids, 49% yield. 1 H NMR (CDCl 3 , 300 MHz) d 8.53 (d, J = 9.0 Hz, 2H), 8.12 (d, J = 9.0 Hz, 2H), 6.44 (s, 1H), 4.05 (s, 3H), 4.00 (s, 6H),; 19 F NMR (CDCl 3 , 282.3 MHz) d À26.4 (dd, J = 429.9 Hz, 107.8 Hz, 2F), À153.0 (s 1F), À153.1 (s, 3F); 13 C NMR (CDCl 3 , 150.9 MHz) d 58. 1, 58.4, 81.7, 94.5, 118.4, 117.2 (dd, J = 366.7 Hz, 356.1 Hz), 126.7, 128.5, 132.9, 152.4, 165.2, 173.2;IR (KBr) 3110, 1600, 1532, 1422, 1345, 1240, 1086, 1059, 1029 S-Bromodifluoromethyl-S-o-bromophenyl-2,3,4,5-tetramethylphenylsulfonium triflate (1i 0 ).…”

“…White solids, 71% yield. 1 H NMR (CDCl 3 , 300 MHz) d 8.41 (d, J = 8.1 Hz, 1H), 8.07 (t, J = 8.1 Hz, 1H), 7.95 (d, J = 7.8 Hz, 1H), 7.85 (t, J = 7.8 Hz, 1H), 7.40 (s, 1H), 2.78 (s, 3H), 2.38 (s, 6H),2.33 (s, 3H); 19 F NMR (CDCl 3 , 282.3 MHz) d À33.9 (dd, J = 140.6 Hz, 124.8 Hz, 2F), -78.6 (t, J = 20.9 Hz, 3F); 13 C NMR (CDCl 3 , 150.9 MHz) d 17. 2, 17.4, 18.4, 21.1, 114.1, 115.9 (t, J = 357.6 Hz), 121.7, 122.0 (t, J = 319.9 Hz), 126.0, 129.1, 133.3, 136.0, 138.0, 140.1, 140.3, 140.4,147.6;IR (KBr) 3067, 2978, 1450, 1248, 1168, 1097, 1026 Bromodifluoromethylation of alkynes using Sbromodifluoromethyl-S-o-bromophenyl-2,3,4,5tetramethylphenylsulfonium triflate 1i 0 n-BuLi (2.6M in THF, 1.3 equiv.)…”