6092 J . Org. Chem., Vol. 64, No. 16, 1999
Notes
(Z)-2-(P h en ylth io)-1-p-tolu en esu lfon yleth ylen e (3b): mp
107-108 °C; 1H NMR (CDCl3, 200 MHz) δ 2.45 (s, 3 H), 6.26 (d,
1 H, J ) 10.3 Hz), 7.22 (d, 1 H, J ) 10.3 Hz), 7.40-7.34 (m, 5
H), 7.42-7.47 (m, 2 H), 7.92 (d, 2 H, J ) 8.3 Hz); 13C NMR
(CDCl3, 50 MHz) δ 21.6, 122.9, 127.2, 128.7, 129.5, 129.8, 131.2,
H, J ) 10.2 Hz), 6.76 (d, 2 H, J ) 8.8 Hz), 7.03 (d, 1 H, J ) 10.2
Hz), 7.16 (d, 2 H, J ) 8.8 Hz), 7.25 (d, 2 H, J ) 8.1 Hz), 7.79 (d,
2 H, J ) 8.3 Hz); 13C NMR (CDCl3, 50 MHz) δ 21.6, 116.7, 121.3,
124.1, 127.0, 129.8, 133.8, 137.9, 144.7, 149.0, 157.3; IR (CHCl3)
ν 3400, 1599, 1288 cm-1. Anal. Calcd for C15H14O3S2: C, 58.82;
H, 4.57. Found: C, 58.90; H, 4.48.
134.6, 138.3, 144.5, 146.1; IR (KBr) ν 3045, 1319, 1290 cm-1
.
Anal. Calcd for C15H14O2S2: C, 62.07; H, 4.83. Found: C, 62.12;
H, 4.66.
(Z)-2-((2-Ca r b oxyet h yl)t h io)-1-p -t olu en esu lfon ylet h yl-
1
en e (3h ): H NMR (CDCl3, 300 MHz) δ 2.43 (s, 3 H), 2.72 (t, 2
(E)-2-(P h en ylth io)-1-p-tolu en esu lfon yleth ylen e (4b): mp
91-92 °C; 1H NMR (CDCl3, 200 MHz) δ 2.43 (s, 3 H), 5.99 (d, 1
H, J ) 14.4 Hz), 7.31 (d, 2 H, J ) 8.5 Hz), 7.41-7.46 (m, 5 H),
7.71 (d, 2 H, J ) 8.3 Hz), 7.80 (d, 1 H, J ) 14.4 Hz); 13C NMR
(CDCl3, 75 MHz) δ 21.6, 123.5, 127.4, 127.5, 129.8, 129.9, 133.3,
H, J ) 6.8 Hz), 3.03 (t, 2 H, J ) 6.8 Hz), 6.22 (d, 1 H, J ) 10.3
Hz), 6.45 (bs, 1 H), 7.13 (d, 1 H, J ) 10.3 Hz), 7.32 (d, 2 H, J )
8.1 Hz), 7.83 (d, 2 H, J ) 8.3 Hz); 13C NMR (CDCl3, 50 MHz) δ
21.6, 31.0, 35.4, 122.9, 127.1, 129.7, 138.2, 144.5, 146.1, 176.8;
IR (CH2Cl2)
ν . Anal. Calcd for
3055, 1715, 1421 cm-1
133.4, 135.4, 144.1, 145.6; IR (KBr) ν 3069, 1493, 1277 cm-1
.
C12H14O4S2: C, 50.35; H, 4.89. Found: C, 50.20; H, 4.95.
Anal. Calcd for C15H14O2S2: C, 62.07; H, 4.83. Found: C, 62.15;
H, 4.70.
(E)-2-((2-Ca r b oxyet h yl)t h io)-1-p -t olu en esu lfon ylet h yl-
en e (4h ). Compound 4h has not been isolated. Spectroscopic
data of this compound are deduced from an inseparable mixture
(1:1.2) of 3h and 4h : 1H NMR (CDCl3, 300 MHz) δ 2.44 (s, 6 H),
2.74 (t, 4 H, J ) 6.8 Hz), 3.03 (t, 2 H, J ) 6.8 Hz), 3.05 (t, 2 H,
J ) 6.8 Hz), 6.20 (d, 1 H, J ) 14.6 Hz), 6.24 (d, 1 H, J ) 10.2
Hz), 7.06 (d, 1 H, J ) 10.2 Hz), 7.33 (d, 4 H, J ) 8.3 Hz), 7.69
(d, 1 H, J ) 14.6 Hz), 7.75 (d, 2 H, J ) 8.3 Hz), 7.84 (d, 2 H, J
) 8.3 Hz).
Gen er a l P r oced u r e for Dep r otection of Th iols. A solution
of the protected thiol (Z isomer or mixture of E-Z isomers) in
CH3CN was added dropwise to a stirred solution of pyrrolidine
in CH3CN. The mixture was stirred at rt for the time indicated
in Table 2. Solvent was removed under reduced pressure, and
the residue was purified by chromatography on silica gel, using
mixtures of hexane-EtOAc (5:1 or 10:1) as eluant. Compounds
12 were isolated in the deprotection of compounds 3a ,b, 4b, and
3g. Compound 13 was isolated in the deprotection of 3f.
Compound 2e was isolated by distillation of the reaction crude
without previous elimination of the solvent.
(Z)-2-(p -Nit r op h en ylt h io)-1-p -t olu en esu lfon ylet h ylen e
(3c): mp 152-153 °C; 1H NMR (CDCl3, 200 MHz) δ 2.46 (s, 3
H), 6.43 (d, 1 H, J ) 10.0 Hz), 7.26 (d, 1 H, J ) 10.0 Hz), 7.37
(d, 2 H, J ) 8.1 Hz), 7.58 (d, 2 H, J ) 8.8 Hz), 7.88 (d, 2 H, J )
8.6 Hz), 8.22 (d, 2 H, J ) 9.0 Hz); 13C NMR (CDCl3, 50 MHz) δ
21.6, 124.4, 125.7, 127.3, 130.0, 130.2, 137.7, 141.2, 143.2, 145.0;
IR (KBr) ν 3651, 1545, 1342 cm-1. Anal. Calcd for C15H13
NO4S2: C, 53.73; H, 3.88. Found: C, 53.81; H, 3.65.
-
(E)-2-(p -Nit r op h en ylt h io)-1-p -t olu en esu lfon ylet h ylen e
(4c): 1H NMR (CDCl3, 200 MHz) δ 2.48 (s, 3 H), 7.24 (d, 1 H, J
) 14.2 Hz), 7.39 (d, 2 H, J ) 8.1 Hz), 7.57 (d, 1 H, J ) 14.2 Hz),
7.76 (d, 2 H, J ) 9.0 Hz), 7.81 (d, 2 H, J ) 9.0 Hz), 8.43 (d, 2 H,
J ) 9.0 Hz); 13C NMR (CDCl3, 75 MHz) δ 21.7, 124.6, 125.1,
125.4, 128.2, 130.4, 135.4, 135.4, 145.9, 146.8, 147.7; IR (CHCl3)
ν 2926, 1599, 1306 cm-1. Anal. Calcd for C15H13NO4S2: C, 53.73;
H, 3.88. Found: C, 53.68; H, 3.70.
(Z)-2-(p-Meth oxyp h en ylth io)-1-p-tolu en esu lfon yleth yl-
en e (3d ): mp 138-139 °C; 1H NMR (CDCl3, 200 MHz) δ 2.45
(s, 3 H), 3.80 (s, 3 H), 6.18 (d, 1 H, J ) 10.2 Hz), 6.88 (d, 2 H, J
) 9.0 Hz), 7.11 (d, 1 H, J ) 10.2 Hz), 7.35 (d, 2 H, J ) 8.1 Hz),
7.37 (d, 2 H, J ) 9.0 Hz), 7.91 (d, 2 H, J ) 8.3 Hz); 13C NMR
(CDCl3, 50 MHz) δ 21.6, 55.4, 115.0, 122.0, 125.1, 127.1, 129.7,
133.7, 138.4, 144.4, 148.0, 160.3; IR (KBr) ν 3385, 1493, 1249
cm-1. Anal. Calcd for C16H16O3S2: C, 60.00; H, 5.00. Found: C,
60.14; H, 4.92.
(E)-2-(1-P yr r olidyl)-1-p-tolu en esu lfon yleth ylen e (11): mp
1
126-127 °C; H NMR (CDCl3, 300 MHz) δ 1.93 (bs, 4 H), 2.40
(s, 3 H), 3.03 (bs, 2 H), 3.46 (bs, 2 H), 4.83 (d, 1 H, J ) 12.4 Hz),
7.26 (d, 2 H, J ) 7.8 Hz), 7.52 (d, 1 H, J ) 12.4 Hz), 7.75 (d, 2
H, J ) 8.3 Hz); 13C NMR (CDCl3, 75 MHz) δ 21.4, 25.2, 92.8,
(E)-2-(p-Meth oxyp h en ylth io)-1-p-tolu en esu lfon yleth yl-
126.2, 129.4, 142.0, 142.5, 146.5; IR (KBr) ν 2870, 1281 cm-1
.
1
en e (4d ): mp 87-88 °C; H NMR (CDCl3, 200 MHz) δ 2.42 (s,
Anal. Calcd for C13H17NO2S: C, 62.15; H, 6.77. Found: C, 61.99;
H, 6.60.
3 H), 3.82 (s, 3 H), 5.83 (d, 1 H, J ) 14.4 Hz), 6.92 (d, 2 H, J )
8.8 Hz), 7.30 (d, 2 H, J ) 8.5 Hz), 7.36 (d, 2 H, J ) 9.0 Hz), 7.69
(d, 2 H, J ) 9.3 Hz), 7.75 (d, 1 H, J ) 14.4 Hz); 13C NMR (CDCl3,
50 MHz) δ 21.5, 55.4, 115.5, 118.9, 122.8, 127.3, 129.8, 135.7,
2,2-B i s [(2′-fu r y l)m e t h y lt h i o ]-1-p -t o lu e n e s u lfo n y l-
eth a n e (12a ): 1H NMR (CDCl3, 200 MHz) δ 2.45 (s, 3 H), 3.49
(d, 2 H, J ) 6.6 Hz), 3.77 (d, 2 H, J ) 14.9 Hz), 3.88 (d, 2 H, J
) 14.9 Hz), 4.17 (t, 1 H, J ) 6.6 Hz), 6.14 (d, 2 H, J ) 3.2 Hz),
6.32 (dd, 2 H, J ) 1.9, 3.2 Hz), 7.29 (d, 2 H, J ) 8.5 Hz), 7.37
(dd, 2 H, J ) 0.7, 1.9 Hz), 7.65 (d, 2 H, J ) 8.3 Hz); 13C NMR
(CDCl3, 50 MHz) δ 21.7, 27.6, 43.9, 61.9, 108.3, 110.6, 127.4,
128.4, 129.7, 142.3, 144.8, 150.2; IR (CHCl3) ν 3050, 1323, 1288
cm-1. Anal. Calcd for C19H19O4S3: C, 56.02; H, 4.67. Found: C,
56.22; H, 4.79.
2,2-Bis(p h en ylth io)-1-p-tolu en esu lfon yleth a n e (12b): 1H
NMR (CDCl3, 200 MHz) δ 2.38 (s, 3 H), 3.45 (d, 2 H, J ) 6.6
Hz), 4.68 (t, 1 H, J ) 6.6 Hz), 7.19-7.28 (m, 8 H), 7.31-7.36 (m,
4 H), 7.65 (d, 2 H, J ) 8.3 Hz); 13C NMR (CDCl3, 50 MHz) δ
21.7, 50.6, 60.3, 128.4, 128.6, 129.2, 129.8, 132.3, 133.3, 133.4,
145.0; IR (CHC13) ν 3042, 2399, 1323 cm-1. Anal. Calcd for
C21H20O2S3: C, 63.00; H, 5.00. Found: C, 62.89; H, 5.13.
138.1, 143.9, 146.8, 161.0; IR (KBr) ν 3853, 1496, 1302 cm-1
.
Anal. Calcd for C16H16O3S2: C, 60.00; H, 5.00. Found: C, 59.87;
H, 4.79.
(Z)-2-(Eth ylth io)-1-p-tolu en esu lfon yleth ylen e (3e): mp
96-97 °C; 1H NMR (CDCl3, 200 MHz) δ 1.31 (t, 3 H, J ) 7.6
Hz), 2.42 (s, 3 H), 2.77 (q, 2 H, J ) 7.6 Hz), 6.21 (dd, 1 H, J )
0.7, 10.2 Hz), 7.05 (d, 1 H, J ) 10.5 Hz), 7.32 (d, 2 H, J ) 8.5
Hz), 7.84 (d, 2 H, J ) 8.5 Hz); 13C NMR (CDCl3, 50 MHz) δ 15.1,
21.5, 29.9, 122.7, 127.1, 129.6, 138.5, 144.2, 146.2; IR (KBr) ν
3651, 2926, 1541 cm-1. Anal. Calcd for C11H14O2S2: C, 54.54;
H, 5.78. Found: C, 54.62; H, 5.85.
(Z)-2-((2-H yd r oxyet h yl)t h io)-1-p -t olu en esu lfon ylet h yl-
en e (3f): mp 90-91 °C; 1H NMR (CDCl3, 200 MHz) δ 2.26 (t, 1
H, J ) 5.9 Hz), 2.44 (s, 3 H), 2.94 (t, 2 H, J ) 5.9 Hz), 3.85 (q,
2 H, J ) 5.9 Hz), 6.24 (d, 1 H, J ) 10.3 Hz), 7.13 (d, 1 H, J )
10.3 Hz), 7.34 (d, 2 H, J ) 8.5 Hz), 7.86 (d, 2 H, J ) 8.3 Hz); 13
C
NMR (CDCl3, 50 MHz) δ 21.5, 38.4, 61.8, 122.8, 127.0, 129.7,
138.1, 144.4, 146.8; IR (KBr) ν 3853, 3036, 1537 cm-1. Anal.
Calcd for C11H14O3S2: C, 51.16; H, 5.43. Found: C, 50.94; H,
5.55.
(E)-2-((2-H yd r oxyet h yl)t h io)-1-p -t olu en esu lfon ylet h yl-
en e (4f): 1H NMR (CDCl3, 200 MHz) δ 2.44 (s, 3 H), 3.00 (t, 2
H, J ) 5.9 Hz), 3.87 (t, 2 H, J ) 5.9 Hz), 6.25 (d, 1 H, J ) 14.6
Hz), 7.33 (d, 2 H, J ) 8.1 Hz), 7.70 (d, 1 H, J ) 14.6 Hz), 7.75
(d, 2 H, J ) 8.3 Hz); 13C NMR (CDCl3, 50 MHz) δ 21.6, 35.4,
60.7, 123.1, 127.4, 129.9, 138.1, 144.5; IR (CHCl3) ν 3489, 2926,
1269 cm-1. Anal. Calcd for C11H14O3S2: C, 51.16; H, 5.43.
Found: C, 51.23; H, 5.39.
2,2-Bis(p -h yd r oxyp h e n yl)t h io)-1-p -t olu e n e su lfon yl-
eth a n e (12g): mp 147-148 °C; H NMR (CDCl3, 200 MHz) δ
1
2.45 (s, 3 H), 3.45 (d, 2 H, J ) 6.3 Hz), 4.41 (t, 1 H, J ) 6.3 Hz),
5.87 (bs, 1 H), 6.78 (d, 4 H, J ) 8.5 Hz), 7.28-7.34 (m, 6 H),
7.70 (d, 2 H, J ) 8.3 Hz); 13C NMR (CDCl3, 50 MHz) δ 21.0,
30.9, 59.9, 77.2, 116.2, 128.3, 129.8, 136.7, 136.8, 156.9; IR (KBr)
ν 3421, 2924, 2852, 1138 cm-1. Anal. Calcd for C21H20O4S3: C,
58.33; H, 4.63. Found: C, 58.27; H, 4.54.
2-(p-Tolu en esu lfon ylm eth yl)-1,3-oxa th iola n e (13): 1H
NMR (CDCl3, 300 MHz) δ 2.47 (s, 3 H), 3.01 (dd, 2 H, J ) 4.9,
7.1 Hz), 3.46 (dd, 1 H, J ) 4.1, 14.4 Hz), 3.67 (dd, 1 H, J ) 7.6,
14.4 Hz), 3.81 (dt, 1 H, J ) 7.3, 9.0 Hz), 4.22 (quint, 1 H, J )
4.9 Hz), 5.47 (dd, 1 H, J ) 4.1, 7.8 Hz), 7.37 (d, 2 H, J ) 8.3 Hz),
(Z)-2-((p-Hyd r oxyp h en yl)th io)-1-p-tolu en esu lfon yleth yl-
1
en e (3g): H NMR (CDCl3, 200 MHz) δ 2.34 (s, 3 H), 6.08 (d, 1