Additions to 1-Phenylseleno-2-(p-toluenesulfonyl)ethyne
J . Org. Chem., Vol. 63, No. 22, 1998 7917
acetate-hexanes) (lit.37 mp 83-86 °C), with spectra identical
to those of an authentic sample.
mmol) in THF (4 mL) was added via a syringe pump over a
period of 2 h. The mixture was stirred for 4 h, then quenched
with an NH4Cl solution, and poured into ether. The organic
phase was washed with water, dried (MgSO4), and evaporated.
Chromatography over alumina (elution with 30% ethyl acetate-
hexanes) afforded 20 (236 mg, 63%) as pale yellow crystals:
mp 103-105 °C (from hexanes); IR (CH2Cl2) 1596, 1317, 1151,
1-(p-Tolu en esu lfon yl)-1,2-h exa d ien e (15). Vinyl sulfone
5b (393 mg, 1.00 mmol) was treated with m-CPBA as in the
preceding procedure to afford 15 (187 mg, 79%) as a colorless
oil, with spectra identical to those of an authentic sample.37
(E)-2-P h en ylselen o-1-(N-p yr r olid in yl)-1-(p-tolu en esu l-
fon yl)eth en e (16) a n d (Z)-1-P h en ylselen o-1-(N-p yr r oli-
d in yl)-2-(p-tolu en esu lfon yl)eth en e (17) (En tr y 1, Ta ble
2). Pyrrolidine (84 µL, 1.0 mmol) was added dropwise to a
solution of 4 (335 mg, 1.00 mmol) in THF (1 mL) under argon.
The solution was stirred at room temperature for 2 h. Alumina
(400 mg) was added, and the solvent was evaporated. The
residue was loaded onto alumina in a chromatographic column
and eluted with 5% ethyl acetate-hexanes and then 15% ethyl
acetate-hexanes to give 268 mg (66%) of 16 as white crystals
and 130 mg (32%) of 17 as pale yellow crystals.
1
1049 cm-1; H NMR (200 MHz) δ 7.79 (d, J ) 8.2 Hz, 4 H),
7.58-7.53 (m, 4 H), 7.54 (s, 2 H), 7.37-7.30 (m, 10 H), 4.28 (t,
J ) 6.3 Hz, 4 H), 2.41 (s, 6 H), 2.11 (quintet, J ) 6.3 Hz, 2 H);
mass spectrum, m/z (relative intensity, %) 748 (1.4, M+), 395
(16), 200 (26), 170 (34), 124 (100). Anal. Calcd for C33H32O6S2-
Se2: C, 53.08; H, 4.32. Found: C, 53.02; H, 4.16.
(Z)-2-Eth ylth io-1-p h en ylselen o-1-(p-tolu en esu lfon yl)-
eth en e (21) a n d (Z)-1-Eth ylth io-1-p h en ylselen o-2-(p-tolu -
en esu lfon yl)eth en e (22) (En tr y 5, Ta ble 2). Ethanethiol
(741 µL, 10.0 mmol) was added dropwise to sodium hydride
(480 mg, 10.0 mmol, 50% suspension in oil) and THF (4 mL)
in a 10 mL volumetric flask. After hydrogen evolution had
ceased, the flask was filled to the mark with THF. One
milliliter of this solution (1.00 mmol) was added slowly to a
solution of 4 (335 mg, 1.00 mmol) in THF (1 mL) under argon
at 0 °C. After the solution had warmed to room temperature,
stirring was continued for 2 h. Alumina (400 mg) was added,
the solvent was evaporated, and the residue was chromato-
graphed over alumina (elution with 20% ether-hexanes) to
give 322 mg (81%) of 21 and 64.4 mg (16%) of 22, both as white
crystals.
Com p ou n d 21: mp 97-98 °C (from ethyl acetate-hex-
anes): IR (CH2Cl2) 1592, 1301, 1146 cm-1; 1H NMR (200 MHz)
δ 8.58 (s, 1 H), 7.78 (d, J ) 8.3 Hz, 2 H), 7.23-7.10 (m, 7 H),
2.93 (q, J ) 7.5 Hz, 2 H), 2.39 (s, 3 H), 1.39 (t, J ) 7.4 Hz, 3
H); 13C NMR (100 MHz) 157.2, 144.0, 136.2, 131.3, 129.4,
129.0, 128.8, 127.3, 123.6, 28.7, 21.5, 15.7; mass spectrum, m/z
(relative intensity, %) 398 (82, M+), 243 (85), 182 (100), 134
(86), 91 (63); exact mass calcd for C17H18O2S2Se 397.9915,
found 397.9890. The structure was confirmed by X-ray
crystallography (Supporting Information).
Com p ou n d 16: mp 72-75 °C (dec, from ethyl acetate-
hexanes): IR (KBr) 1573, 1349, 1144 cm-1; 1H NMR (200 MHz)
δ 7.76 (d, J ) 8.2 Hz, 2 H), 7.64 (s, 1 H), 7.60-7.57 (m, 2 H),
7.37-7.30 (m, 5 H), 3.06-3.02 (m, 4 H), 2.44 (s, 3 H), 1.72-
1.68 (m, 4 H); mass spectrum, m/z (relative intensity, %) 407
(5, M+), 252 (38), 157 (78), 77 (100). Anal. Calcd for C19H21
-
NO2SSe: C, 56.15; H, 5.21; N, 3.44. Found: C, 55.68; H, 5.23;
N, 3.41.
Com p ou n d 17: mp 152-155 °C (from methanol): IR (KBr)
1
1596, 1360, 1132 cm-1; H NMR (200 MHz) 7.92 (d, J ) 8.2
Hz, 2 H), 7.19-6.99 (m, 7 H), 5.66 (s, 1 H), 3.26-3.19 (m, 4
H), 2.34 (s, 3 H), 1.81-1.74 (m, 4 H); mass spectrum, m/z
(relative intensity, %) 407 (3, M+), 250 (61), 186 (21), 123 (100),
98 (77), 55 (51). Anal. Calcd for C19H21NO2SSe: C, 56.15; H,
5.21; N, 3.44. Found: C, 55.81; H, 5.01; N, 3.38.
(E)-3,6-Dia za -3-m et h yl-1-p h en ylselen o-2-(p -t olu en e-
su lfon yl)-1-h ep ten e (18) (En tr y 2, Ta ble 2). N,N′-Dimeth-
ylethylenediamine (106 µL, 1.00 mmol) was added dropwise
to a solution of 4 (335 mg, 1.00 mmol) in THF (1 mL) under
argon. The solution was stirred at room temperature for 2 h.
The solvent was evaporated in vacuo, and the resulting oil was
rapidly chromatographed over alumina (elution with 5% ethyl
acetate-hexanes) to afford 355 mg (84%) of 18 as a colorless
oil: IR (neat) 3213, 1549, 1370, 1138 cm-1; 1H NMR (200 MHz)
δ 7.90 (s, 1 H), 7.78 (d, J ) 8.3 Hz, 2 H), 7.61-7.56 (m, 2 H),
7.38-7.31 (m, 5 H), 3.05 (t, J ) 5.9 Hz, 2 H), 2.55 (t, J ) 5.9
Hz, 2 H), 2.54 (s, 3 H), 2.43 (s, 3 H), 2.36 (s, 3 H), 2.39-2.34
(br s, 1 H). Further characterization of 18 was precluded by
its instability (decomposition within a few hours even at -20
°C).
Com p ou n d 22: mp 94-97 °C (from ethyl acetate-hexanes);
IR (CH2Cl2) 1597, 1312, 1142 cm-1; 1H NMR (200 MHz) δ 7.79
(d, J ) 8.3 Hz, 2 H), 7.55-7.30 (m, 7 H), 6.15 (s, 1 H), 2.99 (q,
J ) 7.4 Hz, 2 H), 2.43 (s, 3 H), 1.21 (t, J ) 7.3 Hz, 3 H); NOE
observed between signals at δ 6.15 and 7.79, 6.15 and 2.99;
mass spectrum, m/z (relative intensity, %) 398 (6, M+), 242
(18), 155 (39), 139 (80), 91 (100). Anal. Calcd for C17H18O2S2-
Se: C, 51.38; H, 4.57. Found: C, 51.09; H, 4.50.
(E)-1,2-Di(eth ylth io)-1-(p-tolu en esu lfon yl)eth en e (23)
a n d 1,1-Di(eth ylth io)-2-(p-tolu en esu lfon yl)eth en e (24)
(En tr y 6, Ta ble 2). Two milliliters of the solution of sodium
ethanethiolate in THF (2.00 mmol) prepared in the preceding
procedure was added slowly to a solution of 4 (335 mg, 1.00
mmol) in THF (1 mL) under argon. After 5 h, the mixture
was quenched with an NH4Cl solution, poured into ether, and
washed with an NH4Cl solution. The organic phase was dried
(MgSO4), evaporated, and chromatographed over silica gel
(elution with 10% ethyl acetate-hexanes) to afford 23 (225
mg, 74%) and 24 (40 mg, 13%), both as white crystals.
Com p ou n d 23: mp 65-67 °C (from hexanes); IR (CH2Cl2)
(E)-2-P h en ylselen o-1-p r op oxy-1-(p -t olu en esu lfon yl)-
eth en e (19) (En tr y 3, Ta ble 2). 1-Propanol (748 µL, 10.0
mmol) was added dropwise to sodium hydride (480 mg, 10.0
mmol, 50% suspension in oil) and THF (4 mL) in a 10 mL
volumetric flask. After hydrogen evolution had ceased, the
flask was filled to the mark with THF. One milliliter of this
solution (1.00 mmol) was then added slowly to a solution of 4
(335 mg, 1.00 mmol) in THF (1 mL) under argon. The mixture
was stirred at room temperature for 2 h. Alumina (400 mg)
was added, the solvent was evaporated, and the residue was
chromatographed over alumina (elution with 20% ether-
hexanes) to give 364 mg (92%) of 19 as white crystals, mp 59-
1596, 1312, 1146 cm-1 1H NMR (200 MHz) δ 8.36 (s, 1 H),
;
7.80 (d, J ) 8.2 Hz, 2 H), 7.31 (d, J ) 8.1 Hz, 2 H), 2.93 (q, J
) 7.4 Hz, 2 H), 2.80 (q, J ) 7.4 Hz, 2 H), 2.42 (s, 3 H), 1.40 (t,
J ) 7.4 Hz, 3 H), 1.19 (t, J ) 7.4 Hz, 3 H); mass spectrum,
m/z (relative intensity, %) 302 (61, M+), 147 (100), 118 (38 ),
103 (36), 91 (40), 87 (65). Anal. Calcd for C13H18O2S3: C,
51.62; H, 6.00. Found: C, 51.54; H, 5.74.
63 °C (from hexanes): IR (KBr) 1597, 1318, 1152, 1092 cm-1
;
1H NMR (200 MHz) δ 7.79 (d, J ) 8.3 Hz, 2 H), 7.59-7.54 (m,
2 H), 7.53 (s, 1 H), 7.34-7.31 (m, 5 H), 4.11 (t, J ) 6.6 Hz, 2
H), 2.44 (s, 3 H), 1.72 (tq, J ) 7.4 Hz, 6.8 Hz, 2 H), 0.97 (t, J
) 7.4 Hz, 3 H); mass spectrum, m/z (relative intensity, %) 396
(26, M+), 198 (100), 170 (72), 91 (51), 43 (59 ). Anal. Calcd
for C18H20O3SSe: C, 54.68; H, 5.10. Found: C, 54.66; H, 5.03.
(E,E)-1,9-Di(p h en ylselen o)-2,8-d i(p -t olu en esu lfon yl)-
3,7-d ioxa -1,8-n on a d ien e (20) (En tr y 4, Ta ble 2). 1,3-
Propanediol (72 µL, 1.0 mmol) was added to sodium hydride
(96 mg, 2.0 mmol, 50% suspension in oil) in THF (2 mL) under
argon at room temperature. After 30 min, 4 (337 mg, 1.00
Com p ou n d 24: mp 68-70 °C (from hexanes): IR (CH2Cl2)
1597, 1312, 1142 cm-1; 1H NMR (200 MHz) δ 7.90 (d, J ) 8.3
Hz, 2 H), 7.31 (d, J ) 8.4 Hz, 2 H), 6.19 (s, 1 H), 2.94 (q, J )
7.4 Hz, 2 H), 2.84 (q, J ) 7.4 Hz, 2 H), 2.44 (s, 3 H), 1.32 (t, J
) 7.4 Hz, 3 H), 1.17 (t, J ) 7.4 Hz, 3 H); 13C NMR (50 MHz)
δ 156.4, 143.7, 139.5, 129.3, 127.8, 120.2, 28.1, 27.3, 21.6, 14.4,
12.7; mass spectrum, m/z (relative intensity, %) 302 (12, M+),
210 (70), 155 (21), 152 (36), 147 (55), 139 (36), 119 (39), 105
(32), 91 (100); exact mass calcd for C13H18O2S3 302.0469, found
302.0454.
(37) Back, T. G.; Krishna, M. V.; Muralidharan, K. R. J . Org. Chem.
1989, 54, 4146.