ꢀꢀꢀꢁ
4ꢀ ꢀL. Wechteti et al.: Synthesis of 1,4-oxathian-2-ones by Triton B-catalyzed one-pot reaction of epoxides
Hexahydrobenzo[b][1,4]-oxathiin-2(3H)-one (4a)ꢁWhite solid;
mp 88–89°C (lit. [26] mp 87–88°C); yield 97%;ꢀ1H NMR: δ 1.22–2.24
[m, 8H, (CH2)4], 3.00 (ddd, Jꢀ=ꢀ12.2, 12.0, 4.2 Hz, 1H, CHS), 3.22 (d,
Jꢀ=ꢀ15.0 Hz, 1H, CH2CO), 3.68 (d, Jꢀ=ꢀ15.0 Hz, 1H, CH2CO), 4.17 (ddd,
Jꢀ=ꢀ12.2, 12.0, 4.2 Hz, 1H, CHO), 13C NMR: δ 23.8, 25.1, 26.8, 32.2, 32.6,
References
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+
43.1, 81.7, 168.1; MS: m/z 172.245 (M ). Anal. Calcd for C8H12O2S: C,
55.78; H, 7.02. Found: C, 55.65; H, 7.22.
[3] Romdhani-Younes, M.; Chaabouni, M. M. Efficient synthesis of
β,β′-dihydroxysulfides by ring opening of epoxides with mer-
captoethanol catalyzed under solvent-free conditions. J. Sulfur
Chem. 2012, 33, 223–228.
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athian-2-one S-oxide in argon matrices. Eur. J. Org. Chem.
2006, 13, 2918–2924.
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a 1,4-dioxane, 1,4-oxathiane or 1,4-oxazine ring structure as the
carbohydrate fragment. Tetrahedron Lett. 2011, 52, 3614–3617.
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cansaure-methylester und Styroloxyd mit Mercaptanen. Fette
Seifen Anstrichm. 1963, 65, 851–856.
6-Ethyl-1,4-oxathian-2-one (4b)ꢁColorless viscous oil; yield 90%;
1H NMR: δ 1.04 (t, Jꢀ=ꢀ7.5 Hz, 3H, CH3), 1.70–1.90 (m, 2H, MeCH2), 2.74–
2.97 (m, 2H, SCH2), 3.17 (d, Jꢀ=ꢀ15.0 Hz, 1H, CH2CO), 3.58 (d, Jꢀ=ꢀ15.0 Hz,
1H, CH2CO), 4.35–4.43 (m, 1H, CH-O); 13C NMR: δ 9.5, 25.8, 28.0, 29.0,
80.3, 168.3. HRMS. Calcd for C6H10O2S: m/z 146.04015. Found: m/z
146.03957.
6-Butyl-1,4-oxathian-2-one (4c)ꢁColorless viscous oil; yield 92%;
1H NMR: δ 0.89 (t, Jꢀ=ꢀ7.0 Hz, 3H, CH3), 1.23–1.88 (m, 6H, (CH2)3), 2.75–
2.94 (m, 2H, SCH2); 2.90 (d, Jꢀ=ꢀ15.0 Hz, 1H, CH2CO), 3.72 (d, Jꢀ=ꢀ15.0 Hz,
1H, CH2CO), 4.35–4.48 (m, 1H, CH); 13C NMR: δ 13.8, 22.3, 25.8, 27.1,
29.3, 34.7, 79.2, 168.4. HRMS. Calcd for C8H14O2S: m/z 174.262. Found:
m/z 174.261. Anal. Calcd for C8H14O2S: C, 55.14; H, 8.10. Found: C,
55.01; H, 8.18.
6-Methyl-1,4-oxathian-2-one (4d) [27]ꢁColorless viscous oil; yield
88%; 1H NMR: δ 1.48 (d, Jꢀ=ꢀ6.0 Hz, 3H, CH3), 2.78–2.97 (m, 2H, SCH2),
3.18 (d, Jꢀ=ꢀ15.0 Hz, 1H, CH2CO), 3.58 (d, Jꢀ=ꢀ15.0 Hz, 1H, CH2CO), 4.61–
4.68 (m, 1H, CH); 13C NMR: δ 20.9, 25.7, 30.7, 75.5, 168.3. HRMS. Calcd
for C5H8O2S: m/z 132.02450. Found: m/z 132.02465.
6-(Chloromethyl)-1,4-oxathian-2-one (4e)ꢁOil; yield 70%; 1H
NMR: δ 2.04–2.29 (m, 2H, SCH2), 3.37–3.51 (m, 2H, CH2CO), 3.74–3.78
(m, 2H, CH2Cl), 5.21 (m, 1H, CH); 13C NMR: δ 33.3, 33.9, 44.1, 72.5, 170.0.
HRMS. Calcd for C5H7O2SCl: m/z 165.98553. Found: m/z 165.98635.
6-(Phenoxymethyl)-1,4-oxathian-2-one (4f)ꢁOil; yield 85%; 1H
NMR: δ 2.51–2.69 (m, 2H, CH2S), 3.30 (d, Jꢀ=ꢀ15.0 Hz, 1H, CH2CO), 3.62
(d, Jꢀ=ꢀ15.0 Hz, 1H, CH2CO), 4.00–4.03 (m, 2H, CH2O); 5.13–5.23 (m, 1H,
CH), 6.89–7.30 (m, 5Har); 13C NMR: δ 27.7, 28.9, 69.7, 79.1, 114.9, 121.5,
129.6, 159.7, 167.7. HRMS. Calcd for C11H12O2S: m/z 208.55800. Found:
m/z 208.55812.
[12] Black, D. K. 1,4-Thiazepines and 1,4-thioxans from thiols. J.
Chem. Soc. (C) 1966, 1708–1710.
[13] Orszulik, S. T. The action of mercaptoacetic acid on trialkyl
epoxide. Tetrahedron Lett. 1986, 27, 3781–3782.
6-Phenyl-1,4-oxathian-2-one (4g)ꢁWhite solid; mp 116–117°C (lit.
[27] mp 117°C); yield 55%; 1H NMR: δ 3.08–3.10 (m, 2H, CH2S), 3.25 (d,
Jꢀ=ꢀ15.0 Hz, 1H, CH2CO), 3.68 (d, Jꢀ=ꢀ15.0 Hz, 1H, CH2CO), 5.47–5.51 (m,
1H, CH); 7.26–7.41 (5H, CHar); 13C NMR: δ 25.9, 31.2, 80.3, 125.7, 128.5,
128.9, 137.1, 167.5. HRMS. Calcd for C10H10O2S: m/z 194.04015. Found:
m/z 194.03963.
[14] Madje, B. R.; Patil, P. T.; Shindalkar, S. S.; Benjamin, S. B.;
Shingare, M. S.; Dongare, M. K. Facile transesterification of
β-ketoesters under solvent-free condition using borate zirconia
solid acid catalyst. Catal. Commun. 2004, 5, 353–357.
[15] Percias, A.; Shafir, A.; Vallribera, A. Zinc(II) oxide: an effect
catalyst for selective transesterification of β-ketoesters. Tetra-
hedron 2008, 64, 9258–9263.
[16] Koval, L. I.; Dzyuba, V. I.; Ilnitska, O. L.; Pekhnyo, V. I. Efficient
transesterification of ethyl acetate with higher alcohols with-
out catalysts. Tetrahedron Lett. 2008, 49, 1645–1647.
[17] Romdhani-Younes, M.; Chaabouni, M. M.; Baklouti, A. Dimercap-
toethaneoxirane ring opening reaction: β,β′-dihydroxydithioether
synthesis. Tetrahedron Lett. 2001, 42, 3167–3169.
5-Phenyl-1,4-oxathian-2-one (4g′)ꢁWhite solid; mp 90°C (lit. [27]
1
mp 90–91°C); yield 45%; H NMR: δ 3.32 (d, Jꢀ=ꢀ15.0 Hz, 1H, CH2S);
3.43 (d, Jꢀ=ꢀ15.0 Hz, 1H, CH2S); 4.49–4.59 (m, 3H, SCH, CH2O); 7.32–7.38
(m, 5H, CHar); 13C NMR: δ 26.7, 43.9, 72.5, 125.9, 127.9, 128.4, 137.7, 167.4.
HRMS. Calcd for C10H10O2S: m/z 194.04015. Found: m/z 194.03963.
Acknowledgment: The authors would like to thank the
Tunisian Ministry of Higher Education and Scientific
Research for the financial support (LR99ES14) and Dr San-
houry, Department of Chemistry, Faculty of Sciences of
Tunis, for correcting the text.
[18] Zhu, C.; Chen, P.; Wu, W.; Qi, C.; Ren, Y.; Jiang, H. Transition-
metal-free diastereoselective epoxidation of trifluoromethyl-
ketones with N-tosylhydrazones: access to tetrasubstituted
trifluoromethylated oxiranes. Org. Lett. 2016, 18, 4008–4011.
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