SYNTHESIS OF NOVEL THIOETHERS AND SULFOXIDE COMPOUNDS
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1 Chloro-1,4,4-tris(benzylthio)-1,2,3-butatriene (7a): Compound (7a) was synthe-
sized from the reaction of 1,2-Dichloro-1,4,4-tris(benzylthio)-1,3-butadiene (6a) (1.0 g,
2.0 mmol) and potassium tert-butoxide (0.45 g, 4.0 mmol) by the general procedure 2.
(7a): 1.29 69%; Oil, Rf (Petroleum ether) : 0.42; IR (film): 3028, 3064, 3084
( C Harom), 2043 (C C C C); 1H NMR (CDCl3): 3.91 (s, 6H, CH2), 7.26 (m, 15H,
Harom); 13C NMR (CDCl3): 42.5, 39.9, 39.7 ( CH2), 127.2, 127.8, 128.8, 129.3, 129.5,
132.6, 136.7 (Carom, Cbutad); MS (ESI+): m/z 454 [M+H]+; C25H21ClS3 (453.08) Calc: C,
66.27; H, 4.67; S, 21.23 Found: C, 66.10; H, 4.55; S, 20.19.
3-Chloro-1,4,4-(2-(butyloxycarbonyl)ethyl)thio)-1-buten-3-yne (8e) and 3,4,4-
trichloro-1-(2-(butyloxycarbonyl)ethyl)thio)-1-buten-3-yne (9e): Compound (8e) and
(9e) were synthesized from the reaction of 1,3,3,4,4-hexachloro-1-butene (1) (1.0 g,
3.8 mmol) and butyl 3-mercaptopropionate (2e) (0.62 g, 3.8 mmol) by the general
procedure 1.
(8e): 0.35 g 22(%); Rf (Petroleum ether + Ethyl acetate 1:1): 0.40; IR (film): 2961,
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2923 (C H), 2157 (C≡C), 1729 (C O), 1564 (C C); H NMR (CDCl3): 0.80 (m, 9H,
CH3), 1.28 (m, 12H, C CH2), 2.25 (m, 6H, CH2 C O), 2.98 (m, 6H, S CH2), 4.01 (m,
6H, O CH2); 13C NMR (CDCl3): δ 13.1, 21.7 ( CH3, CH2), 28.7, 30.9 ( S CH2),
60.7 ( O CH2), 67.4, 102.5 (C≡C), 124.0, 146.8 (C C), 166.2 (C O); MS (ESI+): m/z
567 [M]+; C25H39ClO6S3 (M, 567,22). Calc: C, 52.94; H, 6.93; S, 16.96. Found: C, 53.26;
H, 6.78; S, 16.57.
(9e): 0.31 g 19(%); Rf (Petroleum ether + Ethyl acetate 1:1): 0.70; IR (film): 2957,
2923 (C H), 2158 (C≡C), 1724 (C O), 1546 (C C); 1H NMR (CDCl3): δ 0.80 (m, 3H,
CH3); 1.58 (m, 4H, C CH2), 2.63 (m, 2H, CH2 C O), 2.86 (m, 2H, S CH2), 4.11
(m, 2H, O CH2); 13C NMR (CDCl3): δ 13.1, 21.7 ( CH3, CH2), 29.5 ( S CH2), 60.7
(O CH2), 67.1, 91.1 (C≡C), 116.3, 129.1 (C C), 166.2 (C O); MS (ESI+): m/z 339.6
[M+Na+H]+; C11H13Cl3O2S (M, 315.64). Calc: C, 41.86; H, 4.15; S, 10.16. Found: C,
42.23; H, 4.33; S, 9.92.
1,3,4,4-Tetrakis(2-(butyloxycarbonyl)ethyl)thio)-1-buten-3-yne (10e): Compound
(10e) was synthesized from the reaction of 1,1,3,3,4,4-hexachloro-1-butene (1) (1.0 g,
3.8 mmol) and Butyl 3-mercaptopropionate (2e) (1.85 g, 11.4 mmol) by the general proce-
dure 1.
(10e): 1.02 g 36(%); Rf (Petroleum ether + Ethyl acetate 1:1): 0.45; IR (film):
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2958, 2925 (C H), 2157 (C≡C), 1714 (C O), 1588, 1569 (C C); H NMR (CDCl3):
0.81 (m, 12H, CH3), 1.27 (m, 16H, C CH2), 2.63 (m, 8H, CH2 C O), 3.01 (m, 8H,
S CH2), 4.06 (m, 8H, O CH2);13C NMR (CDCl3): δ 13.9, 22.9 (CH3, CH2), 29.2, 29.6,
29.9 (S CH2), 64.4 (O CH2), 68.4, 91.3 (C≡C), 114.8, 129.0 (C C), 166.4 (C O); MS
(ESI+): m/z 693 [M]+; C32H52O8S4 (M, 693.01). Calc: C, 55.46; H, 7.56; N, 4.06; S, 18.51.
Found: C, 55.23; H, 7.70; S, 18.04.
1,2-Dibromo-3,4,4-trichloro-1-(octadecylsulfinyl)-1,3-butadiene (12a): Com-
pound (12a) was synthesized from the reaction of 1,2-Dibromo-3,4,4-trichloro-1-(1-
octadecylthio)-1,3-butadiene (11a)12 (0.7 g, 1.16 mmol) and m-Chloroperbenzoic acid
(0.2 g, 1.16 mmol) at 0◦C by the general procedure 3.
(12a): 0.44g (62% ); m.p.:55-57◦C, Rf (Pethroleum ether + CHCl3 1:2): 0.54; IR
(KBr): 1560, 1610 (C C), 2849, 2916, 2955 (C H), 1064, 1095 (S O). 1H NMR (CDCl3):
δ 0.82 (t, J= 7.32Hz, 3H, CH3), 1.46 (m, 32H, (CH2)16-), 2.84 (m, J = 7.32, 2H, S CH2);
13C NMR (CDCl3): δ 14.3 ( CH3); 22.4, 22.5, 22.9, 22.9, 28.8, 29.3, 29.4, 29.5, 29.6, 29.7,
29.8, 29.9, 29.8, 29.9, 29.9, 32.14 ( CH2); 53.9 ( S CH2); 109.9, 115.4, 126.2, 137.9