3036 J . Org. Chem., Vol. 63, No. 9, 1998
Lucas and Schiesser
(850 mg, 20 mmol) and tert-butylthiol (480 mg, 5.3 mmol) in
DMF (40 mL) was added over a 10 min period to a stirred
cooled (0°) solution of 5 (1.5 g, 4.38 mmol) in DMF (20 mL) at
which time the solution was stirred at 0° for 5 h and room-
temperature overnight. Water (10 mL), 10% HCl (2 mL) and
hexane (80 mL) were added, the phases were separated, the
organic layer was dried (MgSO4), and the solvent was removed
in vacuo. Flash chromatography (hexane/ethyl acetate 80:20)
afforded the title compound as a pale oil (230 mg, 20%): 1H
NMR (CDCl3) δ 0.88 (3H, t, J ) 6.9 Hz), 1.27-1.45 (14H, m),
1.33 (9H, s), 1.70 (2H, m), 2.09 (1H, d, J ) 5.1 Hz), 2.66 (2H,
t, J ) 7.2 Hz), 3.71 (1H, m); 13C (CDCl3) NMR δ 14.01, 22.57,
24.81, 25.54, 29.18, 29.49, 29.57, 30.85, 31.79, 36.82, 37.49,
41.99, 71.17; IR ν (neat) 3365 cm-1; MS m/z (relative intensity)
260 (M+, 18), 243 (12), 185 (45), 87 (27), 57 (100). HRMS calcd
for C15H32OS 260.4772, found 260.4770.
1-(ter t-Bu tylth io)-3-u n decyl (ph en yltellu r o)for m ate (19)
was prepared according to standard protocol (B) in our
previously published paper17 using 1-(tert-butylthio)-3-unde-
canol. Flash chromatography (hexane/ethyl acetate 98:2)
aforded 19 as a yellow oil (61%): 1H NMR δ 0.91 (3H, t, J )
6.6 Hz), 1.22 (9H, s), 1.15-1.32 (13H, m), 1.44 (1H, m), 1.65
(1H, m), 1.79 (1H, m), 2.49 (2H, m), 5.29 (1H, m), 6.92-7.03
(3H, m), 7.79 (2H, d, J ) 6.9 Hz); 13C NMR δ 14.29, 23.01,
24.69, 25.64, 29.56, 29.65, 29.72, 31.05, 32.18, 34.67, 35.24,
41.86, 78.46, 114.19, 128.86, 129.52, 139.94, 156.18; 125Te NMR
δ 760.8; IR ν (neat) 1707 cm-1; MS m/z (relative intensity) 243
(11), 187 (39), 154 (22), 87 (19), 57 (100). Anal. Calcd for
J ) 6.9 Hz), 1.17-1.47 (18H, m), 2.20 (2H, t, J ) 6.9 Hz), 3.51
(2H, s), 5.01 (1H, m), 6.98-7.18 (8H, m), 7.57-7.62 (2H, m);
13C NMR δ 14.35, 23.04, 23.51, 25.60, 26.15, 26.97, 29.78,
32.21, 34.52, 79.17, 126.79, 126.95, 128.63, 128.94, 129.20,
129.32, 135.99, 139.97, 166.03; 77Se NMR δ 257.0, 504.5; IR ν
(neat) 1721 cm-1; MS m/z (relative intensity) 540 (M+, 0.92),
405 (1), 339 (40), 247 (19), 91 (100). Anal. Calcd for C26H36O2-
Se2: C, 57.99; H, 6.74. Found: C, 58.03; H, 6.70.
1-(Ben zylselen o)-4-d od ecyl Ch lor ofor m a te (25). A solu-
tion of phosgene in toluene (5.7 M, 1.02 mL, 5.84 mmol) was
added to a cooled (0 °C) solution of 1-(benzylseleno)-4-dodecanol
(15) in THF (10 mL), and the solution was stirred under
nitrogen for 90 min. The solvent was removed in vacuo to
afford 25 as a yellow oil (218 mg, 89%). 1H NMR δ 0.92 (3H,
t, J ) 6.9 Hz), 1.09-1.32 (18H, m), 2.15 (2H, m), 3.48 (2H, s),
4.68 (1H, m), 6.98-7.14 (5H, m); 13C NMR δ 14.33, 23.03,
23.26, 25.26, 25.75, 27.05, 29.57, 29.68, 32.18, 33.84, 84.26,
126.87, 128.66, 129.17, 139, 86, 150.19; IR ν (neat) 1760 cm-1
;
MS m/z (relative intensity) 418 (M+, 1.9), 374 (2), 247 (28), 91
(100). HRMS calcd for C20H31O235Cl80Se 418.1305, found
418.1301.
1-(ter t-Bu tylth io)-4-dodecyl (ph en yltellu r o)for m ate (26)
was prepared according to standard protocol (B) in our
previously published paper17 using 1-(tert-butylthio)-4-dode-
canol. Flash chromatography (hexane/ethyl acetate 98:2)
aforded 26 as a yellow oil (68%): 1H NMR δ 0.91 (3H, t, J )
6.9 Hz), 1.16-1.56 (18H, m), 1.22 (9H, s), 2.35 (2H, t, J ) 7.2
Hz), 5.17 (1H, m), 6.69-7.02 (3H, m), 7.80 (2H, dd, J ) 1.5,
7.5 Hz); 13C NMR δ 14.35, 23.03, 25.74, 26.14, 28.18, 29.60,
29.69, 29.77, 31.13, 32.20, 33.94, 34.71, 41.64, 78.75, 114.21,
128.84, 129.51, 139.95, 156.39; 125Te NMR δ 761.5; IR ν (neat)
1706 cm-1; MS m/z (relative intensity) 275 (57), 257 (24), 199
(49), 115 (4), 57 (100). Anal. Calcd for C23H38O2STe: C, 54.57;
H, 7.57. Found: C, 54.63, H, 7.51.
Th er m olysis of 1-(ter t-bu tylth io)-4-d od ecyl (p h en yl-
tellu r o)for m a te (26) (0.46M) was carried out according to
standard protocol (D) in our previously published paper17 at
160 °C for 32 h. Flash chromatography (hexane/ethyl acetate
98:2) afforded 2-octyltetrahydrothiophene (27) as a pale oil
(43%) contaminated with small amounts of impurities. 1H
NMR δ 0.91 (3H, t, J ) 7.2 Hz), 1.24-1.35 (14H, m), 1.49-
1.77 (4H, m), 2.45 (1H, t, J ) 7.5 Hz), 2.65 (1H, m), 3.22 (1H,
quin(apparent), J ) 7.2 Hz); 13C NMR δ 14.33, 23.05, 29.56,
29.68, 29.93, 30.53, 31.13, 32.07, 32.35, 37.68, 38.26, 49.48;
MS m/z (relative intensity) 201 (73), 154 (19), 87 (26), 77 (86),
28 (100). HRMS calcd for C12H24S: 201.1668, found 201.1665.
Further elution afforded 1-(tert-butylthio)-4-(phenyltelluro)-
dodecane (28) as a red oil (14%). 1H NMR δ 0.91 (3H, t, J )
6.9 Hz), 1.20-1.30 (10H, m), 1.23 (9H, s), 1.41-1.63 (6H, m),
1.91 (2H, m), 2.45 (1H, m), 2.71 (2H, t, J ) 7.5 Hz), 6.94-6.98
(3H, m), 7.72 (2H, dd, J ) 1.2, 7.8 Hz); 13C NMR δ 8.57, 14.27,
23.03, 27.13, 29.33, 29.72, 29.98, 30.18, 31.85, 32.27, 37.51,
39.37, 42.72, 42.91, 112.35, 127.28, 129.32, 138.87; 125Te NMR
δ 480.5; MS m/z (relative intensity) 464 (M+, 10), 407 (24), 373
(11), 257 (41), 57 (100). Anal. Calcd for C22H38STe: C, 57.17;
H, 8.29. Found: C, 57.37, H, 8.41.
C
22H36O2STe: C, 53.69; H, 7.37. Found: C, 53.89, H, 7.43.
2-Octyltetr a h yd r oselen op h en e (21) was prepared ac-
cording to standard protocol (F) in our previously published
paper17 using 1-(benzylseleno)-4-dodecyl (phenyltelluro)for-
mate (14) in benzene (0.46 M) with heating at 160 °C for 2 d.
Preparative TLC (hexane/ethyl acetate 98:2) afforded 21 as a
pale oil (87%). 1H NMR δ 0.91 (3H, t, J ) 6.9 Hz), 1.24-1.38
(13H, m), 1.63 (3H, m), 1.84 (2H, m), 2.69 (2H, dd, J ) 5.4,
7.5 Hz), 3.42 (1H, m); 13C NMR δ 14.33, 23.05, 24.62, 29.67,
29.92, 30.84, 32.25, 32.40, 38.71, 39.93, 45.67; 77Se NMR δ
263.8; MS m/z (relative intensity) 248 (M+, 25), 191 (8), 177
(14), 135 (25), 83 (100). HRMS calcd for C12H2480Se 248.1042,
found 248.1039.
2-Octylselen a n e (22) was prepared according to standard
protocol (F) in our previously published paper17 using 1-(ben-
zylseleno)-5-tridecyl (phenyltelluro)formate (15) in benzene
(1.05 M) with heating at 160 °C for 12 d. Preparative TLC
(hexane/ethyl acetate 98:2) afforded 22 as a pale oil (94%). 1H
NMR δ 0.90 (3H, t, J ) 6.6 Hz), 1.05-1.66 (18H, m), 1.78-
1.92 (2H, m), 2.35 (1H, dt, J ) 3.6, 12.3 Hz), 2.56 (1H, dt, J )
2.7, 12.3 Hz), 2.83 (1H, m); 13C NMR δ 14.32, 20.02, 23.05,
27.66, 27.95, 28.32, 29.69, 29.92, 32.25, 36.01, 36.91, 37.63;
77Se NMR δ 237.5; MS m/z (relative intensity) 262 (M+, 34),
205 (14), 163 (10), 149 (100). HRMS calcd for C13H2680Se
262.1199, found 262.1192.
2-Octylselen op a n e (23) was prepared according to stan-
dard protocol (F) in our previously published paper17 using
1-(benzylseleno)-6-tetradecyl (phenyltelluro)formate (16) in
benzene (0.79 M) with heating at 160 °C for 20 d. Preparative
TLC (hexane/ethyl acetate 98:2) afforded 23 as a pale oil (43%).
1H NMR δ 0.91 (3H, t, J ) 6.9 Hz), 1.26-2.00 (22H, m), 2.43
(1H, m), 2.61 (1H, m), 2.85 (1H, m); 13C NMR δ 14.33, 22.95,
23.06, 26.49, 28.17, 28.69, 29.70, 29.94, 29.98, 32.19, 32.25,
38.23, 38.67, 43.04; 77Se NMR δ 230.9; MS m/z (relative
intensity) 275 (M+, 100), 149 (12), 135 (11), 69 (31). Anal.
Calcd for C14H28Se: C, 61.07; H, 10.26. Found: C, 60.76 H,
9.91.
1-(Ben zylselen o)-4-d od ecyl (p h en ylselen o)for m a te (24)
was prepared according to standard protocol (D) in our
previously published paper17 using 1-(benzylseleno)-4-dode-
canol (10). Flash chromatography (hexane/ethyl acetate 98:
2) afforded 24 as a yellow oil (84%). 1H NMR δ 0.91 (3H, t,
Ack n ow led gm en t. We thank the Australian Re-
search Council for financial support.
Su p p or tin g In for m a tion Ava ila ble: Experimental pro-
cedures for the preparation of alcohols 5-12 and 1-(tert-
butylthio)-3-undecanol (3 pages). This material is contained
in libraries on microfiche, immediately follows this article in
the microfilm version of the journal, and can be ordered from
the ACS; see any current masthead page for ordering
information.
J O9722111