6298
Y. Liu et al. / Tetrahedron 67 (2011) 6294e6299
Calcd. For C13H17N3O2S: C, 55.89; H, 6.13; N, 15.04. Found: C, 56.11;
H, 6.02; N, 15.18.
299 (Mþ, 6), 91 (100). Anal. Calcd. For C13H17NO5S: C, 52.16; H, 5.72;
N, 4.68. Found: C, 52.43; H, 5.57; N, 4.71.
4.2.6. 1-(Toluene-4-sulfonyl)-1H-[1,2,3]triazole-4-carboxylic
acid
4.3.4. 3-Propoxy-3-(toluene-4-sulfonylimino)-propionic acid ethyl
ester (6f). It is a yellow oil. IR
methyl ester (3g). It is a white solid, mp 110e112 ꢀC (lit.15
n ;
3469, 3196, 1743, 1613, 1320 cmꢁ1
115e117 ꢀC). 1H NMR
d
8.63 (s, 1H), 8.02 (d, J¼8.6 Hz, 2H), 3.95 (s,
1H NMR
d
7.81 (d, J¼8.3 Hz, 2H), 7.29 (d, J¼8.3 Hz, 2H), 4.20e4.13
3H), 2.47 (s, 3H); 13C NMR
128.8 (2C), 127.4, 52.5, 21.8.
d
159.9, 148.1, 139.0, 132.1, 130.6 (2C),
(m, 4H), 3.95 (s, 2H), 2.40 (s, 3H), 1.70e1.63 (m, 2H), 1.26 (t,
J¼7.2 Hz, 3H), 0.91 (t, J¼7.2 Hz, 3H); 13C NMR
d 167.6, 165.8, 143.2,
138.2, 129.1 (2C), 126.5 (2C), 70.5, 61.4, 39.7, 21.2, 21.1, 13.7, 9.9. MS
m/z (%) 286 (22), 172 (18), 155 (100). Anal. Calcd. For C15H21NO5S: C,
55.03; H, 6.47; N, 4.28. Found: C, 55.28; H, 6.36; N, 4.32.
4.2.7. 1-Benzenesulfonyl-4-phenyl-1H-[1,2,3]triazole
a white solid, mp 105e107 ꢀC (EtOAc/PE) (lit.7n 105e107 ꢀC).1H NMR
8.33 (s, 1H), 8.17e8.15 (m, 2H), 7.84e7.82 (m, 2H), 7.74e7.73 (m,
1H), 7.64e7.61 (m, 2H), 7.44e7.41 (m, 3H); 13C NMR
147.4, 136.2,
135.7,129.8 (2C),129.1,129.0 (2C),128.7,128.6 (3C),126.1 (2C),119.0.
(3h). It
is
d
d
4.3.5. 3-Isopropoxy-3-(toluene-4-sulfonylimino)-propionic acid ethyl
ester (6g). It is a yellowish oil. IR
1318 cmꢁ1; 1H NMR
7.81 (d, J¼8.3 Hz, 2H), 7.30 (d, J¼8.3 Hz, 2H),
5.14e5.10 (m, 1H), 4.22e4.15 (m, 2H), 3.91 (s, 2H), 2.42 (s, 3H),
1.28e1.23 (m, 9H); 13C NMR
166.8, 165.8, 143.1, 138.3, 129.0 (2C),
n 3469, 3196, 1743, 1612,
d
4.2.8. 1-Methanesulfonyl-4-phenyl-1H-[1,2,3]triazole
a white solid, mp 87e89 ꢀC (EtOAc/PE) (lit.11c 86e87 ꢀC). 1H NMR
8.31 (s, 1H), 7.88e7.85 (m, 2H), 7.47e7.41 (m, 3H), 3.57 (s, 3H); 13
NMR 147.4, 129.3, 129.1 (2C), 128.6, 126.1 (2C), 118.9, 42.6.
(3i). It
is
d
d
C
126.3 (2C), 72.7, 61.2, 39.9, 21.1, 20.7 (2C), 13.6; MS m/z (%) 286 (9),
172 (11),155 (84), 91 (100). Anal. Calcd. For C15H21NO5S: C, 55.03; H,
6.47; N, 4.28. Found: C, 55.31; H, 6.40; N, 4.34.
d
4.3. A Typical procedure for the preparation of chain-product
3-ethoxy-3-(toluene-4-sulfonylimino)-propionic acid methyl
ester (6b)
4.3.6. 3-Butoxy-3-(toluene-4-sulfonylimino)-propionic acid ethyl ester
(6h). It is a yellowish oil. IR
NMR
7.81 (d, J¼8.3 Hz, 2H), 7.29 (d, J¼8.3 Hz, 2H), 4.20e4.15 (m,
n
3196, 2962, 1744, 1618, 1323 cmꢁ1; 1H
d
4H), 3.94 (s, 2H), 2.40 (s, 3H), 1.64e1.60 (m, 2H), 1.36e1.33 (m, 2H),
To a stirred solution of methyl propynoate (1g, 93 mg, 1.1 mmol),
4-methylbenzenesulfonyl azide (2a, 197 mg, 1 mmol), and 2-
aminophenol (8a, 5.5 mg, 0.05 mmol) in EtOH (1 mL) was added
Cu(OAc)2$H2O (20 mg, 0.1 mmol) at room temperature. After 2a
was exhausted (ca. 15 min, monitored by TLC), the solvent was
removed off in vacuum. The residue was purified by chromatog-
raphy (silica gel, 10% EtOAc in PE) to give desired product 6b as
1.25 (t, J¼7.2 Hz, 3H), 0.88 (t, J¼7.2 Hz, 3H); 13C NMR
d 167.5, 165.7,
143.1, 138.1, 129.0 (2C), 126.4 (2C), 68.7, 61.3, 39.6, 29.6, 21.1, 18.5,
13.6, 13.2; MS m/z (%) 286 (22), 172 (19), 155 (100). Anal. Calcd.
For C16H23NO5S: C, 56.29; H, 6.79; N, 4.10. Found: C, 56.48; H,
6.62; N, 4.35.
4.3.7. 3-tert-Butoxy-3-(toluene-4-sulfonylimino)-propionic
ethyl ester (6i). It is a yellow oil. IR 3529, 3068, 1724, 1597,
1349 cmꢁ1; 1H NMR
7.80 (d, J¼8.3 Hz, 2H), 7.29 (d, J¼8.3 Hz, 2H),
acid
a white solid (284 mg, 95%). It is a colorless oil. IR
n
2982,1737,1595,
n
1462 cmꢁ1; 1H NMR
d
8.02 (d, J¼8.6 Hz, 2H), 7.32e7.27 (m, 2H), 4.24
d
(q, J¼6.9 Hz, 2H), 3.95 (s, 2H), 3.75 (s, 3H), 2.43 (s, 3H), 1.28 (t,
4.18 (q, J¼7.2 Hz, 2H), 3.86 (s, 2H), 2.41 (s, 3H), 1.46 (s, 9H), 1.26 (t,
J¼6.9 Hz, 2H); 13C NMR
d
167.5, 166.7, 143.5, 138.3, 129.3 (2C), 126.8
J¼7.2 Hz, 3H); 13C NMR
d 166.3, 166.0, 143.0, 138.6, 129.2 (2C), 126.3
(2C), 65.3, 52.6, 39.7, 21.5, 13.4; MS m/z (%) 299 (Mþ, 3.9), 155 (100).
Anal. Calcd. For C13H17NO5S: C, 52.16; H, 5.72; N, 4.68. Found: C,
52.41; H, 5.57; N, 4.71.
(2C), 86.1, 61.3, 40.8, 27.4 (3C), 21.3, 13.8; MS m/z (%) 171 (27), 155
(55), 108 (80), 91 (100). Anal. Calcd. For C16H23NO5S: C, 56.29; H,
6.79; N, 4.10. Found: C, 56.47; H, 6.86; N, 4.01.
By the similar procedure for the preparation of 6b, products
6cek were prepared. When H2O was used as a solvent, 6lem were
prepared.
4.3.8. 3-Benzenesulfonylimino-3-ethoxy-propionic acid ethyl ester
(6j). It is a yellowish oil. IR
NMR 7.96e7.93 (m, 2H), 7.56e7.50 (m, 3H), 4.26e4.20 (m, 4H),
3.95 (s, 2H), 1.30e1.28 (m, 6H); 13C NMR
167.7, 165.8, 141.0, 132.5,
n
3467, 3065, 1742, 1614, 1324 cmꢁ1; 1H
d
4.3.1. 3-Ethoxy-3-(toluene-4-sulfonylimino)-propionic acid ethyl ester
d
(6c). It is a colorless oil. IR
7.82 (d, J¼8.3 Hz, 2H), 7.30 (d, J¼8.3 Hz, 2H), 4.24e4.19 (m, 4H),
3.93 (s, 2H), 2.42 (s, 3H), 1.29e1.24 (m, 6H); 13C NMR
167.8, 166.3,
n
2989, 1742, 1599, 1450 cmꢁ1; 1H NMR
128.5 (2C), 126.4 (2C), 65.1, 61.4, 39.8, 13.7, 13.2; MS m/z (%) 299
(Mþ, 0.9), 254 (24), 77 (100). Anal. Calcd. For C13H17NO5S: C, 52.16;
H, 5.72; N, 4.68. Found: C, 52.28; H, 5.92; N, 4.47.
d
d
143.6,138.5,129.5 (2C),126.9 (2C), 65.4, 61.8, 40.1, 21.6, 14.1, 13.6. MS
m/z (%) 313 (Mþ, 2.3), 155 (100). Anal. Calcd. For C14H19NO5S: C,
53.66; H, 6.11; N, 4.47. Found: C, 53.43; H, 6.02; N, 4.69.
4.3.9. 3-Ethoxy-3-methanesulfonylimino-propionic acid ethyl ester
(6k). It is a yellowish oil. IR
NMR 4.41e4.18 (m, 4H), 3.86 (s, 2H), 3.07 (s, 3H), 1.50e1.22 (m,
6H); 13C NMR
d 168.2, 166.2, 65.2, 61.6, 42.3, 39.9, 13.9, 13.4; MS m/z
n
3468, 2987, 1743, 1622, 1308 cmꢁ1; 1H
d
4.3.2. 3-Ethoxy-3-(toluene-4-sulfonylimino)-propionic acid butyl
ester (6d). It is a colorless oil. IR
n
2980, 1740, 1604, 1439 cmꢁ1; 1H
(%) 237 (Mþ, 0.7), 86 (100). Anal. Calcd. For C8H15NO5S: C, 40.50; H,
6.37; N, 5.90. Found: C, 40.78; H, 6.42; N, 5.76.
NMR
d
7.82 (d, J¼8.3 Hz, 2H), 7.31e7.27 (m, 2H), 4.22 (q, J¼6.9 Hz,
2H), 3.85 (s, 2H), 2.42 (s, 3H), 1.47 (s, 9H), 1.28 (t, J¼7.2 Hz, 2H); 13C
NMR
d
168.0, 165.1, 143.2, 138.4, 129.2 (2C), 126.6 (2C), 82.3, 65.0,
4.3.10. 3-Oxo-3-(toluene-4-sulfonylamino)-propionic acid ethyl ester
41.1, 27.7 (3C), 21.3, 13.4; MS m/z (%) 312 (12), 171 (23), 155 (100).
Anal. Calcd. For C16H23NO5S: C, 56.29; H, 6.79; N, 4.10. Found: C,
56.46; H, 6.61; N, 4.23.
(6l). Mp 97e99 ꢀC (lit.15 97e98 ꢀC). 1H NMR
d 10.07 (s, 1H), 7.96 (d,
J¼8.3 Hz, 2H), 7.33 (d, J¼8.3 Hz, 2H), 4.20 (q, J¼7.2 Hz, 2H), 3.35 (s,
2H), 2.43 (s, 3H), 1.27 (t, J¼7.2 Hz, 3H); 13C NMR
d 167.4, 163.7, 144.9,
135.1, 129.3 (2C), 128.1 (2C), 61.9, 41.8, 21.3, 13.6.
4.3.3. 3-Methoxy-3-(toluene-4-sulfonylimino)-propionic acid ethyl
ester (6e). It is a white solid, mp 40e42 ꢀC (EtOAc/PE). IR
n
3449,
4.3.11. 3-Methanesulfonylamino-3-oxo-propionic acid ethyl ester
(6m). It is a yellowish solid, mp 57e59 ꢀC (EtOAc/PE). IR
3196,
3091, 1740, 1620, 1156 cmꢁ1; 1H NMR
d
7.83 (d, J¼8.3 Hz, 2H), 7.30
n
(d, J¼8.3 Hz, 2H), 4.20 (q, J¼7.2 Hz, 2H), 3.95 (s, 2H), 3.80 (s, 3H),
3030, 1738, 1691, 1348 cmꢁ1 1H NMR
; d 9.97 (s, 1H), 4.26 (q,
2.42 (s, 3H), 1.27 (t, J¼7.2 Hz, 3H); 13C NMR
d
168.0, 165.8, 143.3,
J¼7.2 Hz, 2H), 3.47 (s, 2H), 3.32 (s, 3H), 1.32 (t, J¼7.2 Hz, 3H); 13C
138.0, 129.1 (2C), 126.5 (2C), 61.4, 55.7, 39.5, 21.2, 13.7; MS m/z (%)
NMR d
167.7, 164.9, 62.2, 41.7, 41.2, 13.8; MS m/z (%) 209 (Mþ, 1), 80