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General Procedure
for the Synthesis of 3
A solution of sulfonyl azide
(1.2 mmol), amine (1.2 mmol), propiolic acid (1.0 mmol), DBU (1.5
mmol), and CuI (0.1 mmol) in THF (2 mL) was stirred at r.t. under
N2 for 10 h. After the reaction was completed, which
was monitored with TLC, the reaction solution was diluted with CH2Cl2 (2
mL) and then with aq NH4Cl solution (3 mL). The mixture
was stirred for an additional 30 min at r.t., and the two layers were
separated. The aqueous layer was extracted with CH2Cl2 (3 × 3
mL), and the combined organic layers were dried over Na2SO4 and
concentrated in vacuo. The crude residue was purified by flash column
chromatography with EtOAc-PE to give N-sulfonylacetamidines 3a-l.
Selected Data
N
-Ethyl-
N
-phenyl-
N
′-tosylacetamidine
(3a)
Light yellow solid, mp 130.0-131.0 ˚C.
IR (KBr): 3458, 2929, 1547, 1495, 1267, 1139, 1089, 685 cm-¹. ¹H
NMR (500 MHz, CDCl3): d = 7.88
(2 H, d, J = 8.2
Hz), 7.45 (2 H, t, J = 7.8
Hz), 7.39 (1 H, t, J = 7.5
Hz), 7.29 (2 H, d, J = 8.0 Hz),
7.12 (2 H, d, J = 7.5
Hz), 3.83 (2 H, q, J = 14.2
Hz,), 2.42 (3 H, s), 2.24 (3 H, s), 1.12 (3 H, t, J = 7.1
Hz). ¹³C NMR (125 MHz, CDCl3):
d = 165.4, 141.9, 141.6, 140.3, 130.0,
129.1, 128.6, 127.7, 126.3, 47.2, 21.4, 19.8, 11.9. ESI-MS: m/z (%) = 316 [M+].
HRMS: m/z calcd for C17H21N2O2S:
317.1324 [M + H]+;
found: 317.1321.
N
-
p
-Tolyl-
N
′-tosylacetamidine (3k)
Light
yellow solid (a mixture of two isomers with a ratio 1:3, which is
tentatively assigned as Z/E of the generated imino C=N
double bond), mp 109.6-127.9 ˚C. IR (KBr): 3750, 3308,
1535, 1457, 1275, 1143, 1089, 730 cm-¹. ¹H
NMR (500 MHz, CDCl3): δ = 9.7
(0.7 H, br, Z/E),
7.87 (1.9 H, d, J = 8.2
Hz, E), 7.82 (0.6 H, d, J = 8.0
Hz, Z), 7.36 (0.6 H, d, J = 8.5
Hz, Z), 7.31 (2 H, d, J = 8.1
Hz, E), 7.26 (0.6 H, d, J = 8.0
Hz, Z), 7.20 (2 H,d, J = 8.0
Hz, E), 7.08 (0.6 H, d, J = 8.5
Hz, Z), 7.02 (2 H, d, J = 8.2
Hz, E), 2.61 (0.9 H, s, Z), 2.43
(3 H, s, E), 2.41 (1.0 H, s, Z), 2.37 (3 H, s, E),
2.30 (1.0 H, s, Z), 2.01 (2.9 H, s, E). ¹³C
NMR (125 MHz, CDCl3): δ = 165.6,
162.9, 143.0, 142.2, 140.4, 139.3, 138.2, 135.2, 134.8, 134.0, 130.2,
129.4, 129.3, 129.2, 126.4, 126.3, 126.1, 121.7, 22.0, 21.7, 21.5,
21.4, 20.9, 20.8. ESI-MS:
m/z (%) = 302 [M+].
HRMS: m/z calcd for C16H19N2O2S: 303.1167 [M + H]+;
found: 303.1170.
17
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Ahlquist M.
Bae I.
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Chang S.
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