3
NMR (100 MHz, CDCl3): δ = 163.8 (d, 1JC-F = 250 Hz),
161.8, 142.1 (d, 4JC-F = 2.9 Hz), 128.0 (d, 3JC-F = 9.5 Hz),
115.3 (d, 2JC-F = 22.0 Hz), 40.5 ppm; 19F NMR (376 MHz,
Henichart, J. Tetrahedron Lett. 2006, 47, 6087-6090. (e) Lange, J.
H. M.; Verhoog, S.; Sanders, H. J.; Leovezijn, A.; Kruse, C. G.
Tetrahedron Lett. 2011, 52, 3198-3200. (f) Tan, D.; Mottillo, C.;
Katsenis, A. D.; Strukil, V.; Friscic, T. Angew. Chem. Int. Ed.,
2014, 53, 9321-9324. (g) Yang, W.; Huang, D.; Zeng, X.; Luo, D.;
Wang, X.; Hu, Y. Chem. Commun. 2018, 54, 8222-8225.
CDCl3): δ = –109.7 ppm; ESI-HRMS: calcd for C11H16FN3O2S
(MH+): 274.1027; found: 274.1022.
9. N-(Bis(dimethylamino)methylene)-4-
6. General: All starting materials were obtained from commercially
(trifluoromethyl)benzenesulfonamide (3f). An EtOH mixture
of tetramethylthiourea 2b (34.4 mg, 0.25 mmol) and 4-
trifluoromethylbenzenesulfonyl azide 1f (66.8 mg, 0.25 mmol)
was refluxed for 20 h. After the solvent was removed in
vacuo, the residue was purified by column chromatography
(SiO2; eluent, hexane:EtOAc = 1:1 followed by EtOAc only)
to afford 3f as a white solid (41.6 mg, 0.18 mmol, 69%). MP
90–91°C; IR (KBr): 2969, 1559, 1523, 1478, 1400, 1327,
1281, 1136, 1098, 1062 cm–1; 1H NMR (400 MHz, CDCl3): δ
= 8.07 (d, J = 8.4 Hz, 2 H), 7.71 (d, J = 8.0 Hz, 2 H), 2.95 (s,
12 H) ppm; 13C NMR (100 MHz, CDCl3): δ = 162.0, 149.2,
132.5 (q, 2JC-F = 32.3 Hz), 126.2, 125.6 (q, 3JC-F = 3.8 Hz),
123.6 (q, 1JC-F = 271 Hz), 40.5 ppm; 19F NMR (376 MHz,
CDCl3): δ = –63.3 ppm; ESI-HRMS: calcd for C12H16F3N3O2S
(MH+): 324.0995; found: 324.0985.
available products without further purification. 1H, 13C, and 19
NMR spectra were recorded at 400, 100, and 376 MHz,
F
respectively, on a JEOL ECX-400P spectrometer. ESI-HRMS
analyses were carried out on a Thermo LTQ Orbitrap XL ETD. IR
spectra were recorded on a JASCO FT/IR 460 plus spectrometer.
Melting points recorded on a Yanako MP-S3 micro-melting point
apparatus were not corrected. Products 3a,5c,5d 3b,5c,5d,5g and 3d5d
are known compounds.
7. N-(Bis(dimethylamino)methylene)-4-
methoxybenzenesulfonamide (3c). An EtOH mixture of
tetramethylthiourea 2b (36.9 mg, 0.25 mmol) and 4-
methoxybenzenesulfonyl azide 1c (54.4 mg, 0.25 mmol) was
stirred under reflux for 20 h. After the solvent was removed in
vacuo, the residue was purified by column chromatography
(SiO2; eluent, hexane:EtOAc = 1:1 followed by EtOAc only)
to afford 3c as a white solid (24.0 mg, 0.08 mmol, 28%). MP
115–116°C; IR (KBr): 2915, 1643 1523, 1065 cm–1; 1H NMR
(400 MHz, CDCl3): δ = 7.87 (d, J = 8.8 Hz, 2 H), 6.92 (d, J =
8.8 Hz, 2 H), 3.84 (s, 3 H), 2.93 (s, 12 H) ppm; 13C NMR (100
MHz, CDCl3): δ = 161.7, 161.2, 138.3, 127.4, 113.4, 55.4,
40.4 ppm; ESI-HRMS: calcd for C12H19N3O3S (MH+):
286.1226; found: 286.1217.
10. N-(Bis(dimethylamino)methylene-3,5-
bis(trifluoromethyl)benzenesulfonamide (3g). 3,5-
Bis(trifluoromethyl)phenylsulfonyl azide 1g (0.25 mmol) was
added to a 1,4-dioxane solution of tetramethylthiourea 2b
(0.25 mmol). The reaction mixture was stirred at 80–85°C for
20 h. Third, after the solvent was removed in vacuo, the
residue was purified by column chromatography (SiO2; eluent,
hexane:EtOAc = 1:1) to afford 3g as a white solid (88.5 mg,
0.23 mmol, 92%). MP 103–104°C; IR (KBr): 3087, 2952,
1568, 1530, 1478, 1412, 1361, 1331, 1281, 1181, 1126, 1065
cm–1; 1H NMR (400 MHz, CDCl3): δ = 8.41 (s, 2 H), 7.95 (s, 1
H), 2.97 (s, 12 H) ppm; 13C NMR (100 MHz, CDCl3): δ =
162.0, 148.2, 132.0 (q, 2JC-F = 33.8 Hz), 126.1 (q, 3JC-F = 3.8
Hz), 124.2 (sep, 3JC-F = 3.8 Hz), 122.8 (q, 1JC-F = 272 Hz), 40.6
ppm; 19F NMR (376 MHz, CDCl3): δ = –63.4 ppm; ESI-
HRMS: calcd for C13H15F6N3O2S (MH+): 392.0869; found:
392.0856.
8. N-(Bis(dimethylamino)methylene)-4-
fluorobenzenesulfonamide (3e). An EtOH mixture of
tetramethylthiourea 2b (35.6 mg, 0.25 mmol) and 4-
fluorobenzenesulfonyl azide 1e (53.2 mg, 0.25 mmol) was
refluxed for 20 h. After the solvent was removed in vacuo, the
residue was purified by column chromatography (SiO2; eluent,
hexane:EtOAc = 1:1) to afford 3e as a white solid (35.5 mg,
0.13 mmol, 48%). MP 98–99°C; IR (KBr): 1648, 1523, 1136
cm–1; 1H NMR (400 MHz, CDCl3): δ = 7.95 (dd, J = 8.8, 4.8
Hz, 2 H), 7.12 (t, J = 8.8 Hz, 2 H), 2.94 (s, 12 H) ppm; 13
C
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• An alternative route for generating
sulfonylguanidines is developed.
• The synthesis from sulfonyl azides and N-
substituted thiourea is described.
• The synthetic method might be a new class of the
sulfo-click-type reaction.