1268
N. Saygılı, M. Özalp, and L. T. Yıldırım
Vol 51
(2H, m, 5-Hb and 4-H), 2.93 (2H, m, CH2Ph); 13C NMR (CDCl3,
100 MHz) dC 189.5 (C═S), 135.3, 129.1, 129.1, 127.4, 74.7 (5-C),
57.8 (4-C), 40.4 (CH2Ph); IR (KBr) nmax (neat/cmꢂ1) 3028, 1812,
1642, 1515, 1328; MS (EI) m/z 193 (M+, 83%), 117 (M + H+ – Ph,
11%), 102 (boc + H+, 98%), 91 (PhCH2, 100%). Anal. Calcd for
C10H11NOS: C, 62.15; H, 5.74; N, 7.25. Found: C, 62.36; H, 5.97;
N, 7.11%.
100 MHz) dC 184.3 (C═O), 149.2 (C═S), 135.1, 129.5, 129.3,
129.1, 128.6, 127.4 (Ph), 84.9 (CMe3), 70.2 (5-C), 60.2 (4-C),
38.4 (CH2Ph), 28.0 (3ꢁ CH3); IR (KBr) nmax (neat/cmꢂ1) 2980,
1759, 1722, 1370; MS (EI) m/z 193 (M + H+ – boc, 75%), 117
(M+ H+ – Ph, 8%), 102 (boc+ H+, 96%), 91 (PhCH2, 100%).
Anal. Calcd for C15H19NO3S: C, 61.41; H, 6.53; N, 4.77. Found:
C, 61.28; H, 6.35; N, 4.45%.
(4S)-4-Isopropyl-2-thioxo-oxazolidine-3-carboxylic acid tert-butyl
ester (6b): 5b. (0.50 g, 3.44 mmol) was used according to the
general method to afford the product as yellow solid (0.457 g,
23
(4S)-4-isopropyl-1,3-oxazolidine-2-thione (5b): 4b. (1.9 g,
18.0 mmol) was used according to the general method to afford
the product as yellow oil (2.2 g, 77%); Rf 0.56 (1:2 EtOAc-
1
hexane); H-NMR (CDCl3, 400 MHz) dH 9.04 (1H, br-s, NH),
54%); Rf 0.67 (1:2 EtOAc-hexane); ½aꢄ
= +34.24ꢀ (c 0.184,
589
4.71 (1H, t, J=9.1Hz, 5-Ha), 4.40 (1H, dd, J= 6.7 and 9.1 Hz, 5-
Hb), 3.93 (1H, m, 4-H), 1.85 (1H, m, CH), 1.00 (3H, d, J=6.8Hz,
CH3), 0.95 (3H, d, J=6.8Hz, CH3); 13C NMR (CDCl3, 100 MHz)
dC 189.4 (C═S), 73.5 (5-C), 62.4 (4-C), 31.8 (CH), 17.9
(2 ꢁ CH3); IR (KBr) nmax (neat/cmꢂ1) 2963, 1743, 1526, 1272,
1171; MS (EI) m/z 145 (M+, 100%), 102 (M+ – CH(CH3)2, 54%),
42 (CH(CH3)2 – H, 50%). Anal. Calcd for C6H11NOS: C, 49.62;
H, 7.63; N, 9.64. Found: C, 49.41; H, 7.34; N, 9.28%.
1
MeOH); H-NMR (CDCl3, 400 MHz) dH 4.33 (3H, m, 4-H and
5-H2), 2.23 (1H, m, CH), 1.50 (9H, s, 3 ꢁ CH3), 0.88 (3H, d,
J = 7.3Hz, CH3), 0.86 (3H, d, J = 7.0 Hz, CH3); 13C NMR (CDCl3,
100 MHz) dC 183.9 (C═O), 148.5 (C═S), 83.7 (CMe3), 66.6
(5-C), 62.6 (4-C), 29.6 (CHMe2), 26.9 (3 ꢁ CH3), 17.2 (CH3),
14.1 (CH3); IR (KBr) nmax (neat/cmꢂ1) 3109, 1812, 1722, 1368;
MS (EI) m/z 245 (M+, 5%), 189 (M+ H+ – CMe3, 100%), 145
(M+ H+ – boc, 33%), 102 (M + H+ – boc – CHMe2, 91%), (CMe3,
96%). Anal. Calcd for C11H19NO3S: C, 53.85; H, 7.81; N, 5.71.
Found: C, 53.66; H, 7.53; N, 5.41%.
(4S)-4-sec-Butyl-1,3-oxazolidine-2-thione (5c): 4c. (1.00 g,
8.53 mmol) was used according to the general method to afford the
product as white solid (0.96g, 71%); mp 145–153ꢀC, Rf 0.57 (1:2
30
(4S)-4-sec-Butyl-2-thioxo-oxazolidine-3-carboxylic
acid
EtOAc-hexane); ½aꢄ
= ꢂ44.18ꢀ (c 0.91, MeOH); 1H NMR
tert-butyl ester (6c): 5c. (0.50 g, 3.14 mmol) was used
589
according to the general method to afford the product as yellow
27
(CDCl3, 400 MHz) dH 8.99 (1H, br-s, NH), 4.73 (1H, t, J = 8.4 Hz,
5-Ha), 4.18 (2H, m, 5-Hb and 4-H), 1.64 (1H, m, CH), 1.38
(2H, m, CH2), 0.88 (3H, d, J=4.2Hz, CH3), 0.86 (3H, d, J=4.2Hz,
CH3); 13C NMR (CDCl3, 100 MHz) 189.0 (C═S), 75.8 (5-C), 55.1
(4-C), 43.5 (CH), 25.1 (CH2), 22.8 (CH3), 21.8 (CH3); IR (KBr)
oil (0.63 g, 39%); Rf 0.52 (1:2 EtOAc-hexane); ½aꢄ
= +80.88ꢀ
589
(c 1.36, MeOH); 1H NMR (CDCl3, 400MHz) dH 4.37 (2H, m, 5-H2),
4.09 (1H, m, 4-H), 1.46 (1H, m, CH), 1.40 (9H, s, 3 ꢁ CH3), 1.29
(2H, m, CH2), 0.8 (6H, m, 2ꢁ CH3); 13C NMR (CDCl3, 100MHz)
dC 184.5 (C═O), 149.0 (C═S), 84.3 (CMe3), 71.5 (5-C), 58.0
(4-C), 41.4 (CH), 27.7 (3 ꢁ CH3), 24.6 (CH2), 23.5 (CHCH3), 21.4
(CH2CH3); IR (KBr) nmax (neat/cmꢂ1) 3337, 2979, 1770, 1689,
1524. Anal. Calcd for C12H21NO3S: C, 55.57; H, 8.16; N, 5.40.
Found: C, 55.23; H, 7.84; N, 5.12%.
n
max (neat/cmꢂ1) 3500, 1792, 1560; MS (EI) m/z 159.0 (M+, 100%),
117, 102, 57. Anal. Calcd for C7H13NOS: C, 52.79; H, 8.23; N,
8.80. Found: C, 52.44; H, 8.01; N, 8.53%.
4-Methyl-1,3-oxazolidine-2-thione (5d): 4d. (0.75 g, 10.0 mmol)
was used according to the general method to afford the product as
yellow solid (0.32 g, 27%); mp 77ꢀC, Rf 0.34 (1:2 EtOAc-hexane);
1H NMR (CDCl3, 400MHz) dH 8.63 (1H, br-s, NH), 4.79 (2H, m,
5-H2), 4.25 (1H, m, 4-H), 1.37 (3H, d, J = 5.9 Hz, CH3); 13C NMR
(CDCl3, 100 MHz) dC 189.3 (C═S), 76.9 (5-C), 52.5 (4-C), 20.0
(CH3); IR (KBr) nmax (neat/cmꢂ1) 3167, 1532, 1285, 1181; MS
(EI) m/z 117 (M+, 100%), 102, 86, 42. Anal. Calcd for C4H7NOS:
C, 41.00; H, 6.02; N, 11.95. Found: C, 41.28; H, 5.81; N, 11.74%.
4-Methyl-2-thioxo-oxazolidine-3-carboxylic acid tert-butyl
ester (6d): 5d. (1.11 g, 9.47 mmol) was used according to the
general method to afford the product as yellow solid (1.98 g,
96%) and recrystallized from EtOAc; mp 98ꢀC, Rf 0.58 (1:2
1
EtOAc-hexane); H NMR (CDCl3, 400 MHz) dH 4.60 (1H, m,
4-H), 4.53 (1H, t, J = 8.5 Hz, 5-Ha), 4.15 (1H, dd, J = 3.0 and
8.5 Hz, 5-Hb), 1.58 (9H, s, C(CH3)3), 1.46 (3H, d, J = 6.2 Hz,
CH3); 13C NMR (CDCl3, 100 MHz) dC 184.4 (C═O), 149.3
(C═S), 84.7 (CMe3), 72.9 (5-C), 55.4 (4-C), 28.0 (3 ꢁ CH3),
19.3 (CH3); IR (KBr) nmax (neat/cmꢂ1) 2986, 1759, 1356,
1252, 1157; MS (EI) m/z 217 (M+), 162, 144, 118, 102, 84, 57,
41. Anal. calcd for C9H15NO3S: C, 49.75; H, 6.96; N, 6.45.
Found: C, 49.49; H, 6.66; N, 6.29%.
(4S)-4-Methyl-1,3-oxazolidine-2-thione (5e): 4e.
(1.93 g,
25.6mmol) was used according to the general method to afford the
product as yellow solid (1.09g, 36%); mp 77ꢀC, Rf 0.34 (1:2
23
EtOAc-hexane); ½aꢄ
= +35.28ꢀ (c 0.36, MeOH); 1H NMR
589
(CDCl3, 400MHz) dH 8.63 (1H, br-s, NH), 4.79 (2H, m, 5-H2),
4.25 (1H, m, 4-H), 1.37 (3H, d, J = 5.9 Hz, CH3); 13C NMR
(CDCl3, 100 MHz) dC 189.3 (C═S), 76.9 (5-C), 52.5 (4-C), 20.0
(CH3); IR (KBr) nmax (neat/cmꢂ1) 3167, 1532, 1285, 1181; MS
(EI) m/z 117 (M+, 100%), 102, 86, 42. Anal. Calcd for C4H7NOS:
C, 41.00; H, 6.02; N, 11.95. Found: C, 41.17; H, 5.76; N, 11.81%.
(4S)-4-Benzyl-2-thioxo-oxazolidine-3-carboxylic acid tert-butyl
(4S)-4-Methyl-2-thioxo-oxazolidine-3-carboxylic acid tert-butyl
ester (6e): 5e.
(0.50 g, 4.30 mmol) was used according to
the general method to afford the product as yellow solid (0.40 g,
23
44%); mp 98ꢀC, Rf 0.60 (1:2 EtOAc-hexane); ½aꢄ
= +73.42ꢀ
589
1
(c 1.2, MeOH); H NMR (CDCl3, 400 MHz) dH 4.54 (1H, m,
4-H), 3.51 (1H, dd, J= 7.4 and 11.0, 5-Ha), 2.73 (1H, d
J= 11.0 Hz, 5-Hb), 1.46 (9H, s, C(CH3)3), 1.40 (3H, d, J=6.3Hz,
CH3); 13C NMR (CDCl3, 100 MHz) dC 170.2 (C═O), 149.1
(C═S), 83.8 (CMe3), 55.3 (5-C), 32.2 (4-C), 28.3 (3 ꢁ CH3), 19.4
(CH3); IR (KBr) nmax (neat/cmꢂ1) 2986, 1759, 1356, 1252, 1157;
MS (EI) m/z 217 (M+), 162, 144, 118, 102, 84, 57, 41; Anal. calcd
for C9H15NO3S: C, 49.75; H, 6.96; N, 6.45; S, 14.76. Found: C,
50.01; H, 6.71; N, 6.36; S, 14.35%.
ester (6a): 5a.
(0.50 g, 2.59 mmol) was used according to the
general method to afford the product as white solid (0.76 g, 100%)
and recrystallized from hexane–dichloromethane (1:1); Rf 0.69
23
589
(1:2 EtOAc-hexane); ½aꢄ
= +25.34ꢀ (c 0.146, MeOH); 1H NMR
(CDCl3, 400 MHz) dH 7.19 (2H, d, J=7.2Hz, C6H5), 7.31 (3H,
2ꢁ t, J=7.3Hz, C6H5), 4.69 (1H, m, 4-H), 4.28 (2H, m, 5-H2),
3.29 (1H, dd, J= 3.5 and 13.3 Hz, CHaPh), 2.83 (1H, dd, J= 10.0
and 13.3 Hz, CHbPh), 1.61 (9H, s, C(CH3)3). 13C NMR (CDCl3,
Journal of Heterocyclic Chemistry
DOI 10.1002/jhet