32
4 Experimental Data
1.2k N-Methylpyridine-2-sulfonamide
2-Mercaptopyridine (0.561 g, 5 mmol) was stirred in a mixture of 25 mL of DCM
and 25 mL of a 1 M solution of HCl for 10 min at -10 to -5 °C. Then, a cold (5 °C)
solution of sodium hypochlorite (11% (aq.), 9.3 mL, 16.5 mmol) was added dropwise under vigorous stirring. After the addition was completed, the mixture was
stirred for 15 min at -10 to -5 °C. It was transferred to a separatory funnel (precooled in the freezer) and the organic layer was rapidly separated and collected in
an Erlenmeyer flask cooled in a dry ice-acetone bath. Methylamine (2 M in THF,
6.25 mL, 12.5 mmol) was added while stirring, whereupon the organic layer became a white suspension. The suspension was stirred for 30 min at 0 °C. Then, the
mixture was washed with 1 M solution of HCl, water and a solution of saturated
NaCl, dried with MgSO4 and concentrated under reduced pressure. Purification by
column chromatography on silica gel (EtOAc:heptane = 1:1) yielded the product
as a white solid (400 mg, 47%).
[50]
1
H NMR (400 MHz, CDCl3): δ = 8.75–8.69 (m, 1H
8
), 8.02 (dt, J = 7.7, 0.9
Hz, 1H
11
), 7.93 (td, J = 7.7, 1.7 Hz, 1H
10
), 7.51 (ddd, J = 7.6, 4.7, 1.2 Hz, 1H
9
),
4.92 (s, 1H
NH
), 2.75 (d, J = 5.3 Hz, 3H
6
) ppm;
13
C NMR (175 MHz, CDCl3): δ =
156.7 (C
2
), 150.2 (CH
Ar
), 138.2 (CH
Ar
), 126.8 (CH
Ar
), 122.7 (CH
Ar
), 23.0 (CH
6
)
ppm; IR (neat):
= 3289, 1579, 1454, 1428, 1325, 1174, 1117, 1086, 992, 844,
777, 738, 590 cm
-1
; HRMS (ESI): m/z calculated for [M+Na]
+
(C6H8N2O2SNa)
195.0199, found 195.0198.
1.2l N-Methyl-5-nitropyridine-2-sulfonamide
5-Nitro-2-mercaptopyridine (312 mg, 2 mmol) was stirred in a mixture of 10 mL
of DCM and 10 mL of a 1 M solution of HCl for 10 min at 0 °C. Then, a cold (0
°C) solution of sodium hypochlorite (11% (aq.), 26 mL, 6.6 mmol) was added
dropwise under vigorous stirring. After the addition was completed, the mixture
was stirred for 60 min at 0 °C. It was transferred to a separatory funnel (pre-cooled