T. Kato et al. / Tetrahedron 62 (2006) 8458–8462
8461
reaction mixture. After 2.5 h, the reaction mixture was
poured into ice, and was extracted with CH2Cl2 (50 mL).
The organic layer was successively washed with 2 M HCl
(10 mL), brine (15 mL), and dried over Na2SO4. The solvent
was evaporated. The crude product was recrystallized from
CH2Cl2 and methanol to produce pure 1-(N-benzenesulfonyl-
amino)-2-(N-benzenesulfonyl-N-methylamino)benzene
(0.78 g, 96%). Mp 156 ꢀC. IR (KBr) n 1180, 1350,
2H), 7.65–7.73 (m, 3H), 7.93 (s, 1H). 13C NMR
(100 MHz, CDCl3): d 21.5, 21.6, 38.9, 124.5, 125.4, 126.2,
127.5, 128.3, 129.1, 129.5, 129.6, 132.0, 133.5, 135.5,
137.0, 143.6, 144.5. MS (FAB): m/z¼431.2 [M+H]+. Anal.
Calcd for C21H22N2O4S2: C, 58.58; H, 5.15; N, 6.51. Found:
C, 58.84; H, 4.97; N, 6.55.
4.4. X-ray crystallographic study
1
3280 cmꢁ1. H NMR (400 MHz, CDCl3): d 2.50 (s, 3H),
6.17 (dd, J¼8.0, 1.6 Hz, 1H), 6.89–6.95 (m, 1H), 7.24–
7.31 (m, 1H), 7.40–7.56 (m, 7H), 7.58–7.64 (m, 1H), 7.71
(dd, J¼8.0, 2.0 Hz, 1H), 7.79–7.84 (m, 2H), 7.98 (s, 1H).
13C NMR (100 MHz, CDCl3): d 38.9, 125.1, 125.8, 126.1,
127.4, 128.2, 128.9, 129.2, 132.8, 133.5, 133.6, 134.7,
135.2, 139.9. MS (FAB): m/z¼403 [M+H]+. HRMS Calcd
for C19H18N2O4S2Na [M+Na]+: 425.0605. Found
425.0616. Anal. Calcd for C19H18N2O4S2: C, 56.70; H,
4.51; N, 6.96. Found: C, 56.70; H, 4.52; N, 6.90.
X-ray data were collected on Bruker ApexII CCD detector
(for compounds 2 and 4) and Bruker Smart1000 CCD detec-
tor (for compound 3) with graphite monochromated Mo Ka
˚
(l¼0.71073 A) radiation at room temperature. The crystal
structures were solved by direct methods SHELXS-97 (Shel-
drick, 1997) and refined by full-matrix least-squares
SHELXL-97 (Sheldrick, 1997). All non-hydrogen atoms
were refined anisotropically. The sulfonamide hydrogen
atoms were located in a difference map and their coordinates
were refined. Other hydrogen atoms were included as their
calculated positions.
4.2. 1,2-Bis(N-4-toluenesulfonylamino)benzene (3)
4-Toluenesulfonyl chloride (0.95 g, 5.0 mmol) was added to
a solution of o-phenylenediamine (0.22 g, 2.0 mmol) in pyri-
dine (20 mL) at 0 ꢀC, with stirring under Ar atmosphere.
After stirring at room temperature for 3 h, 4-toluenesulfonyl
chloride (0.19 g, 1.0 mmol) was added once again to the re-
action mixture. After 5.5 h, the reaction mixture was poured
into ice, and was extracted with AcOEt (50 mL). The
organic layer was washed with 2 M HCl (10 mL), brine
(10 mL), saturated NaHCO3 aq (10 mL), brine (10 mLꢂ2),
and dried over Na2SO4. The solvent was evaporated. The
crude product was recrystallized from CH2Cl2 and n-hexane
to give pure 1,2-bis(N-4-toluenesulfonylamino)benzene
(0.67 g, 81%). Mp 206 ꢀC (lit.10 204–205 ꢀC). IR (KBr)
Acknowledgements
This work was supported by Grant-in-aid for Scientific
Research (C) (No. 16590011) from the Japan Society for
the Promotion of Science and the Sasakawa Scientific
Research Grant from The Japan Science Society.
References and notes
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1
n 1150, 1320, 3210 cmꢁ1. H NMR (400 MHz, DMSO):
d 2.33 (s, 6H), 6.87–6.93 (m, 2H), 6.93–6.99 (m, 2H), 7.30
(d, J¼8.0 Hz, 4H), 7.56 (d, J¼8.0 Hz, 4H), 9.23 (br s, 2H).
13C NMR (100 MHz, DMSO): d 21.0, 122.6, 125.1, 126.9,
129.6, 130.2, 136.5, 143.3. MS (FAB): m/z¼417 [M+H]+.
HRMS Calcd for C20H20N2O4S2Na [M+Na]+: 439.0762.
Found 439.0775. Anal. Calcd for C20H20N2O4S2: C, 57.67;
H, 4.84; N, 6.73. Found: C, 57.60; H, 4.90; N, 6.72.
4.3. 1-(N-Methyl-N-4-toluenesulfonylamino)-2-(N-4-
toluenesulfonylamino)benzene (4)
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4-Toluenesulfonyl chloride (0.95 g, 5.0 mmol) was added
dropwise to a solution of N-methyl-1,2-phenylenediamine
(0.23 mL, 2.0 mmol) in dry CH2Cl2 (20 mL) and pyridine
(0.81 mL) at 0 ꢀC, with stirring under Ar atmosphere. After
stirring at room temperature for 3.3 h, 4-toluenesulfonyl
chloride (0.38 g, 2.0 mmol) was added once again to the re-
action mixture. After 2 h, the reaction mixture was poured
into ice, and was extracted with CH2Cl2 (50 mL). The
organic layer was successively washed with 2 M HCl
(10 mL), brine (10 mL), and dried over Na2SO4. The solvent
was evaporated. The crude product was recrystallized from
CH2Cl2 and methanol to give pure 1-(N-methyl-N-4-tolu-
enesulfonylamino)-2-(N-4-toluenesulfonylamino)benzene
(0.66 g, 77%). Mp 138–140 ꢀC. IR (KBr) n 1173, 1347,
1
3247 cmꢁ1. H NMR (400 MHz, CDCl3): d 2.36 (s, 3H),
2.43 (s, 3H), 2.56 (s, 3H), 6.91 (ddd, J¼7.8, 7.8, 1.4 Hz,
1H), 7.21–7.29 (m, 5H), 7.39 (ddd, J¼8.3, 1.8, 1.8 Hz,