Month 2017
Synthesis of ω-(oxathiolan-2-thion-5-yl)-α-oxazolidin-2-ones
obtain the ω-(oxathilan-2-thione-5-yl)-α-oxazolidin-2-ones 3a–h as
viscous oils.
4.06 (m, 1H), 4.08–4.13(m, 2H), 4.74–4.81 (m, 1H), 5.22–5.29
(m, 1H), 7.09–7.14 (m, 1H, Harom), 7.33–7.38 (m, 2H, Harom),
13
General procedure one-pot three-component preparation
of ω-(oxathilan-2-thione-5-yl)-α-oxazolidin-2-ones 3a–h. The
reaction was carried out under a nitrogen atmosphere. The
solution of oligoethylene glycols diglycidyl ether 1a–d (3 mmol)
in 10 mL of anhydrous THF was added to lithium bromide
7.53–7.55 (m, 2H, Harom). C NMR (75 MHz, CDCl
3
) δ 35.9,
46.9, 69.8, 70.6 (m, 8C, CH O), 71.08, 71.3, 89.4, 118.0 (s, 2C),
2
123.8 (s, 1C), 128.9 (s, 2C), 138.2, 154.6, 212.2. HRMS (ESI)
+
calc for C H O NS Na [M + Na] 524.1389, found: 524.1386.
22
31
8
2
5-(6-oxathiolan-2-thione-2,5,8-trioxanonan-5-yl)-3-
cyclohexyloxazolidin-2-one (3e). Colorless viscous oil,
282 mg, 64% yield. IR (CHCl ) 1719 (C = O), 1121 (C = S)
H NMR (300 MHz, CDCl ) δ 1.03–1.11 (m, 1H),
(
0.3 mmol, 0.026 g). After stirring the mixture at reflux for 0.5 h,
a solution of isocyanate (3.3 mmol) in dry THF (5 mL) was added
dropwise. After the consummation of totally amount of isocyanate
monitored by TLC (Acetone/Ether: 80/20), the mixture was
cooled at room temperature, and 3.3 mmol of carbon disulfide
was also added, and then, the reaction was left to stand at room
temperature. After completion of the reaction, as indicated by
TLC (Acetone/Ether: 60/40), the mixture was diluted with water
3
À1
1
cm
.
3
1.21–1.36(m, 5H), 1.50–1.68 (m, 5H), 3.34–3.40 (m, 1H),
3.50–3.56( m, 2H), 3.64–3.66 (m, 8H), 3.68–3.72 (m, 2H),
3.75–3.83 (m, 2H), 4.06–4.14 (m, 2H), 4.67–4.78 (m, 1H),
13
3
5.15–5.23 (m, 1H). C NMR (75 MHz, CDCl ) δ 24.7, 25.4
(s, 2C), 29.6 (s, 2C), 33.3, 36.0, 49.8, 63.5; 69.8 (m, 6C), 70.5,
(
40 mL), and then extracted with dichloromethane (4 × 40 mL).
71.2, 89.3, 155.5, 212.1. HRMS (ESI) calc for C H NO S Na
18
29
6 2
+
It was washed with water (2 × 30 mL) and dried on MgSO
4
.
[M + Na] 442.1334, found: 442.1337.
5-(12-oxathiolan-2-thione-2,5,8,11-tetraoxa dodecan-5-yl)-3-
cyclohexyloxazolidin-2-one (3f). Colorless viscous oil,
345 mg, 71% yield. IR (CHCl ) 1720 (C = O), 1120 (C = S)
The solvent was removed, and the residue was purified on
column chromatography (eluent: Acetone /Ether: 60/40) to
obtain the ω-(oxathilan-2-thione-5-yl)-α-oxazolidin-2-ones 3a–h
as viscous oils.
3
À1
1
cm
. H NMR (300 MHz, CDCl ) δ 1.06–1.11( m, 1H),
3
5
-(6-oxathiolan-2-thione-2,5-dioxahexan-5-yl)-3-
phenyloxazolidin-2-one (3a). Colorless viscous oil, 235 mg,
) 1758 (C = O), 1420–1607 (C = C),
1.25–1.42 (m, 5H), 1.64–1.79 (m, 5H), 3.36–3.39(m, 1H),
3.53–3.59( m, 2H), 3.64–3.65 (m, 12H), 3.66–3.70 (m, 2H),
6
0% yield. IR (CHCl
140 (C = S) cm . H NMR (300 MHz, CDCl ) δ 3.37–3.58
3
3.72–3.76 (m, 2H), 3.81–3.93 (m, 2H), 4.59–4.67 (m, 1H),
À1
1
13
1
5.25–5.33 (m, 1H). C NMR (75 MHz, CDCl ) δ 25.3, 30.0
3
3
(
m, 2H), 3.61–3.70 (m, 4H), 3.72–3.80 (m, 2H), 3.89–3.94(m,
(s, 2C), 30.3 ( s, 2C), 36,0, 42,5, 52,3, 69.8, 70.5 (m, 6C), 71.1,
2
7
7
4
1
H), 4.03–4.09 (m, 2H), 4.72–4.80 (m, 1H), 5.05–5.19 (m, 1H),
71,7, 89.4, 157.0, 212.2. HRMS (ESI) calc for C20
[M + Na] 486,1596, found: 486.1593.
H
33NO
7
S
2
Na
+
.09–7.14 (m, 1H, Harom), 7.33–7.38 (m, 2H, Harom),
1
3
.52–7.55 (m, 2H, Harom). C NMR (75 MHz, CDCl ) δ 35.9,
5-(6-oxathiolan-2-thione-2,5,8-trioxanonan-5-yl)-3-
propyloxazolidin-2-one (3g). Colorless viscous oil, 229 mg,
57% yield. IR (CHCl ) 1748 (C = O), 1116 (C = S) cm . H
NMR (300 MHz, CDCl ) δ 0.82–0.87 (t, 3H), 1.41–1.49(m,
3
6.8, 69.7, 69.9, 70.61 (m, 2C), 71.4, 89.5, 118.1 (s, 2C),
À1
1
23.9, 129.0 (s, 2C), 138.1, 154.6, 212.2. HRMS (ESI) calcd
3
+
for C16
H
19
O
5
S
2
NNa [M + Na] 392.0602, found: 392.0605.
3
5
-(9-oxathiolan-2-thione-2,5,8-trioxano nan-5-yl)-3-phenyl
oxazolidin-2-one (3b). Colorless viscous oil, 296 mg, 68%
yield. IR (CHCl ) 1738 (C = O), 1452, 1609 (C = C), 1132
2H), 3.04–3.09 (t, 2H), 3.52–3.61(m, 2H), 3.63–3.64 (m, 8H),
3.65–3.68 (m, 2H), 3.78–3.82 (m, 2H), 4.14–4.17 (m, 2H),
13
4.76–4.80 (m, 1H), 5.15–5.23 (m, 1H). C NMR (75 MHz,
CDCl ) δ 11.2, 23.1, 36.1, 42.8, 63.7, 69.7; 69.8, 70.6 (m, 4C),
3
À1
1
(
C = S) cm . H NMR (300 MHz, CDCl
3
) δ 3.32–3.53 (m,
H), 3.63–3.70 (m, 8H), 3.73–3.84 (m, 2H), 3.91–4.07(m, 2H),
.10–4.23(m, 2H), 4.65–4.73 (m, 1H), 5.08–5.22 (m, 1H),
3
2
4
6
71.3, 89.2, 156.4, 212.0. HRMS (ESI) calc for C15
[M + Na] 402.1021, found: 402,1023.
H
25NO
6
S
2
Na
+
13
.96–7.05 (m, 1H), 7.18–7.32 (m, 2H), 7.45–7.53 (m, 2H).
NMR (75 MHz, CDCl ) δ 35.9, 47.0, 69.4, 69.8, 70.6 (m, 4C),
1.3, 89.5, 118.3 (s, 2C), 124.1, 129.0 (s, 2C), 138.1, 154.8,
12.2. HRMS (ESI) calc for C18
36.0864, found: 436.0866.
C
5-(12-oxathiolan-2-thion-2,5,8,11-tetraoxa dodecan-5-yl)-3-
propyloxazolidin-2-one (3h). Colorless viscous oil, 276 mg,
62% yield. IR (CHCl ) 1723 (C = O), 1115 (C = S), cm . H
NMR (300 MHz, CDCl ) δ 0.90–0.95 (t, 3H), 1.52–1.64 (m,
3
À1
1
7
2
4
3
+
H
23
O
6
NS
2
Na [M + Na]
3
2H), 3.19–3.24 (t, 2H), 3.58–3.63(m, 2H), 3.64–3.66 (m, 12H),
5
-(12-oxathiolan-2-thione-2,5,8,11-tetra oxadodecan-5-yl)-3-
3.67–3.69 (m, 2H), 3.71–3.74 (m, 2H), 3.83–3.94 (m, 2H),
13
phenyloxazolidin-2-one (3c). Colorless viscous oil, 364 mg,
6% yield. IR (CHCl
117 (C = S) cm
.42–3.53 (m, 2H), 3.60–3.64(m, 8H), 3.68–3.75 (m, 2H),
.81–3.87(m, 2H), 3.92–4.03(m, 2H), 4.68–4.75 (m, 1H),
,13–5,24 (m, 1H), 7.01–7.09 (m, 1H, Harom), 7.29–7.38 (m,
4.63–4.67 (m, 1H), 5.28–5.33 (m, 1H). C NMR (75 MHz,
CDCl ) δ 11.0, 22.17, 35.89, 42.11, 62.8, 69.7, 69.8; 70.5 (m,
7
1
3
3
5
2
3
) 1757 (C = O), 1453, 1609 (C = C),
3
À1
1
.
H NMR (300 MHz, CDCl
3
) δ
6C), 71.6, 89.6, 157.8, 212.4. HRMS (ESI) calc for
+
C H NO S Na [M + Na] 446.5344, found: 446.5346.
17
29
7 2
1
3
H, Harom), 7.46–7.52 (m, 2H, Harom). C NMR (75 MHz,
) δ 35.7, 46.7, 69.6, 70.2, 70.5 (m, 4C), 71.4, 89.6,
18.2 (s, 2C), 124.0, 128.8 (s, 2C), 138.2, 154.5, 212.4.
Acknowledgments. The authors are grateful to the Tunisian
Ministry of Higher Education and Scientific Research for
financial support (LR99ES14) of this research and to Dr. M. A.
Sanhoury, MRSC of the Department of Chemistry, Faculty of
Sciences of Tunis for helpful discussions and technical assistance.
CDCl
3
1
+
HRMS (ESI) calc for C H O NS Na [M + Na] 480.1127,
2
0
27
7
2
found: 480.1126.
-(15-oxathiolan-2-thione-2,5,8,11,14-penta oxapentadecan-
-yl)-3-phenyloxazolidin-2-one (3d). Colorless viscous oil,
50 mg, 86% yield. IR (CHCl ) 1737 (C = O) 1453–1609
5
5
4
(
3
REFERENCES AND NOTES
À1
1
C = C), 1115 (C = S) cm . H NMR (300 MHz, CDCl ) δ
3
3
3
.41–3.51 (m, 2H), 3.60–3.66 (m, 16H), 3.68–3.71 (m, 1H),
.73–3.76 (m, 1H), 3.81–3.87 (m, 1H), 3.90–3.96(m, 1H), 4.02–
[
1] (a) Zhu, J.; Bienayme, H., Eds. Domino Reactions in Organic
Synthesis; Wiley-VCH: Weinheim, 2005; (b) Tietze, L. F.; Brasche, G.;
Journal of Heterocyclic Chemistry
DOI 10.1002/jhet