J.S. Dhau et al. / Journal of Organometallic Chemistry 696 (2011) 2406e2413
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4.2.2. Bis[3-(4-methoxy-N,N-diisopropylpyridine-2-carboxamide)]
495. MS (ESI): 335 [Mþ$
,
80Se, 36Cl], Anal. Calcd (%) for
diselenide (3b)
C13H19ClN2OSe: C, 46.80, H, 5.74, N, 8.39. Found: C, 46.83, H, 5.88,
N, 8.23.
The selenolate anion of 1b was hydrolyzed and subjected to
aerial oxidation for 30 min. The reaction mixture was worked-up as
described above. Yield: 0.76 g (61%), 1H NMR: CDCl3, 400 MHz
4.3.4. 4-Methoxy-3-(selenenylmethyl)-N,N-diisopropylpyridine-2-
carboxamide (5b)
d
(ppm): 8.35e8.37 (d, J ¼ 5.7 Hz, 2H), 6.75e6.77 (d, J ¼ 5.7 Hz, 2H),
3.7 (s, 6H), 3.48e3.55 (m, J ¼ 6.6 Hz, 2H), 3.40e3.47 (m, J ¼ 6.8 Hz,
2H), 1.46e1.48 (d, J ¼ 6.8 Hz, 12H,), 1.01e1.03 (d, J ¼ 6.6 Hz, 12H). IR
(KBr, cmꢀ1): 2924, 1710, 1624, 1364, 1218, 1089, 927, 770, 668, 530.
MS (ESI): 631 [M þ H]þ 630 [Mþ$ 80Se], 629 [M ꢀ H]þ. Anal. Calcd
(%) for C26H38N4O4Se2: C, 49.69, H, 6.09, N, 8.91. Found: C, 49.76, H,
6.03, N, 8.49.
Electrophile: Iodomethane (1.14 g, 0.5 ml, 8 mmol). Yield: 0.84 g
(64%, n-BuLi), 1.02 g (78%, LDA), m.p. 140e142 ꢁC, 1H NMR: CDCl3,
400 MHz
d
(ppm): 8.47e8.48 (d, J ¼ 4.8 Hz, 1H), 6.91e6.92 (d,
J ¼ 4.8 Hz,1H), 4.0 (s, 3H), 3.55e3.58 (m,1H), 3.43e3.46 (m,1H), 2.3
(s, 3H),1.60e1.62 (d, J ¼ 6.8 Hz, 6H),1.22e1.24 (d, J ¼ 6.6 Hz, 6H). 13C
NMR: CDCl3, 400 MHz d (ppm): 167.0,166.7,160.5,150.6,117.1,106.1,
56.2, 50.8, 45.8, 20.6, 20.2, 18.1. 77Se NMR:
d (ppm): 93.79. IR (KBr,
4.3. General method for the preparation of unsymmetrical
3-sulfanyl- and 3-selenenylalkyl derivatives of 1a and 1b
cmꢀ1): 3018, 2922, 2848, 1628, 1565, 1432, 1364, 1218, 1163, 1034,
770, 668, 530. MS (ESI): 329 [(M ꢀ H)þ, 80Se], 330, [Mþ$
,
80Se], 331
[(M þ H)þ, 80Se]. Anal. Calcd (%) for C14H22N2O2Se: C, 51.07, H, 6.73,
The chalcogenolate anion of 1a/1b was cooled to ꢀ78 ꢁC and the
desired electrophile (8 mmol) was added drop-wise. The reaction
mixture was slowly brought to room temperature and stirred for
30 min. The nitrogen supply to the reaction mixture was stopped.
The reaction mixture was hydrolyzed and extracted with diethyl
ether (3 ꢂ 50 ml). The organic layer was dried over anhydrous
sodium sulfate. The solvent was removed on a rota-evaporator and
the crude residue was purified by column chromatography using
silica gel and hexane-ethyl acetate as eluent (10:3).
N, 8.51. Found: C, 50.96, H, 6.89, N, 8.47.
4.3.5. 4-Chloro-3-(selenenylbutyl)-N,N-diisopropylpyridine-2-
carboxamide (6a)
Electrophile: 1-Iodobutane (1.472 g, 0.91 ml, 8 mmol). Yield:
0.85 g (57%), m.p. low melting point solid. 1H NMR: CDCl3, 400 MHz
d
(ppm): 8.31e8.32 (d, J ¼ 5.3 Hz, 1H), 7.28.7.27 (d, J ¼ 5.3 Hz, 1H),
3.44e3.50 (m, J ¼ 6.8 Hz, 1H), 3.32e3.38 (m, J ¼ 6.7 Hz, 1H), 2.9 (s,
broad peak, 2H), 1.54e1.61 (m, J ¼ 7.2e7.6 Hz, 2H,), 1.51e1.53 (d,
J ¼ 6.8 Hz, 6H), 1.31e1.36 (m, 7.3e7.6 Hz, 2H), 1.10 (s, broad peak,
6H), 0.80e0.84 (t, J ¼ 7.4 Hz, 3H). 13C NMR: CDCl3, 400 MHz
4.3.1. 4-Chloro-3-(sulfanylpropyl)-N,N-diisopropylpyridine-2-
carboxamide (4a)
d
(ppm): 167.1, 162.8, 151.2, 149.6, 124.1, 122.6, 50.9, 45.9, 32.1, 30.1,
Electrophile: 1-Bromopropane (0.984 g, 0.73 ml, 8 mmol). Yield:
22.8, 20.5, 13.5. IR (KBr, cmꢀ1): 2970, 1643, 1537, 1469, 1368, 1258,
0.8 g (64%), m.p. 68e70 ꢁC, 1H NMR: CDCl3, 400 MHz
d
(ppm):
1211, 1136, 1040, 830, 728, 634, 604, 531. MS (ESI): 377, [Mþ$ 80Se,
,
8.32e8.33 (d, J ¼ 5.2 Hz, 1H), 7.28e7.29 (d, J ¼ 5.2 Hz, 1H),
3.44e3.51 (m, J ¼ 6.8 Hz, 1H), 3.28e3.34 (m, J ¼ 6.6 Hz, 1H),
2.86e2.90 (m, 2H), 1.52e1.53 (d, J ¼ 6.7 Hz, 6H,), 1.32e1.37 (m, 2H),
1.05e1.12 (broad doublet, 6H), 0.81e0.85 (t, J ¼ 7.3 Hz, 3H). 13C
36Cl]. Anal. Calcd (%) for C16H25ClN2OSe: C, 51.15, H, 6.71, N, 7.45.
Found: C, 51.47, H, 6.71, N, 7.29.
4.3.6. 4-Methoxy-3-(sulfanylmethyl)-N,N-diisopropylpyridine-2-
carboxamide (6b)
NMR: CDCl3, 400 MHz
d (ppm): 166.3, 162.0, 151.2, 149.3, 127.6,
124.4, 51.0, 45.9, 38.3, 36.1, 31.4, 22.9, 21.8, 20.5,13.6. IR (KBr, cmꢀ1):
2929, 2435, 2132, 1716, 1636, 1439, 1364, 1218, 1090, 771, 670, 530.
MS (ESI): 314 [Mþ$]. Anal. Calcd (%) for C15H23ClN2OS: C, 57.22, H,
7.36, N, 8.90, S, 10.18. Found: C, 57.52, H, 7.33, N, 8.11, S, 9.31.
Electrophile: Iodomethane (1.14 g, 0.5 ml, 8 mmol). Yield: 0.83 g,
(74%), m.p. 142e143 ꢁC, 1H NMR: CDCl3, 400 MHz
d (ppm):
8.32e8.33 (d, J ¼ 5.8 Hz, 1H), 6.71e6.73 (d, 5.8 Hz, 1H), 3.90 (s, 3H),
3.44e3.48 (m, 1H), 3.37e3.40 (m, 1H), 2.29 (s, 3H), 1.51e1.53 (d,
J ¼ 6.8 Hz, 6H), 1.08e1.09 (d, 6H). 13C NMR: CDCl3, 400 MHz
4.3.2. 4-Methoxy-3-(selenenylpropyl)-N,N-diisopropylpyridine-2-
carboxamide (4b)
d (ppm): 167.5, 166.5, 160.7, 150.6, 111.7, 105.9, 56.2, 50.9, 45.9, 29.7,
20.6, 20.2, 8.3. IR (KBr, cmꢀ1): 2922, 2435, 1629, 1560, 1458, 1364,
1338,1217, 1035, 756, 667, 530, 458. MS (ESI): 282 [M]þ$. Anal. Calcd
(%) for C14H22N2O2S: C, 59.54, H, 7.85, N, 9.91, S, 11.35. Found: C,
59.71, H, 7.81, N, 9.64, S, 11.01.
Electrophile: 1-Bromopropane (0.984 g, 0.73 ml, 8 mmol). Yield:
0.86 g (60%), m.p. 46e48 ꢁC, 1H NMR: CDCl3, 400 MHz
d (ppm):
8.39e8.40 (d, J ¼ 5.6 Hz, 1H), 6.73e6.75 (d, J ¼ 5.7 Hz, 1H), 3.95 (s,
3H), 3.44e3.56 (m, J ¼ 6.8, 6.2, 6.7 Hz, 2H), 2.86e2.91 (t, J ¼ 7.3,
7.4 Hz, 2H), 1.66.1.69 (m, 2H), 1.56e1.65 (d, J ¼ 8.0 Hz, 6H), 1.15e1.17
(d, J ¼ 6.6 Hz, 6H), 0.95e0.98 (t, J ¼ 7.3, 7.4 Hz, 3H). 13C NMR: CDCl3,
4.3.7. 4-Chloro-3-(selenenylbenzyl)-N,N-diisopropylpyridine-2-
carboxamide (7a)
Method A: Electrophile: Benzyl chloride (1.01 g, 0.92 ml,
8 mmol). Yield: 1.0 g, (59%).
Method B: To a vigorously stirred solution of 1a (0.962 g,
4 mmol) in dry THF at ꢀ78 ꢁC, n-BuLi (1.39 N in hexane, 6.0 ml,
8 mmol) was added drop-wise. The reaction mixture was stirred for
2 h at the same temperature. To the dark red solution of the carb-
anion, dibenzyl diselenide (2.74 g, 8 mmol) was added and the
reaction mixture was slowly brought to the room temperature and
worked-up as described above. Yield: 0.71 g, (41%) m.p.104e106 ꢁC,
400 MHz
d
(ppm): 167.1, 167.0, 161.0, 150.3, 111.2, 105.8, 99.9, 56.2,
50.9, 45.9, 32.2, 23.6, 20.6, 14.4, 1.02. IR (KBr, cmꢀ1): 2966, 1625,
1566, 1468, 1427, 1371, 1335, 1296, 1212, 1132, 1039, 817, 751, 616.
MS (ESI): 359 [M þ H]þ. Anal. Calcd (%) for C16H26N2O2Se: C, 53.78,
H, 7.33, N, 7.84. Found: C, 53.69, H, 7.22, N, 7.58.
4.3.3. 4-Chloro-3-(selenenylmethyl)-N,N-diisopropylpyridine-2-
carboxamide (5a)
Electrophile: Iodomethane (1.14 g, 0.5 ml, 8 mmol). Yield: 0.81 g
(61%, n-BuLi), 1.1 g (82%, LDA) m.p. 82e84 ꢁC, 1H NMR: CDCl3,
1H NMR: CDCl3, 400 MHz
d
(ppm): 8.32e8.33 (d, J ¼ 5.2 Hz, 1H),
400 MHz
d
(ppm): 8.39e8.41 (d, J ¼ 5.3 Hz, 1H), 7.36e7.37 (d,
7.23e7.24 (d, J ¼ 5.2 Hz, 1H), 7.17e7.22 (m, 2H), 7.09e7.16 (m, 3H),
4.19 (s, 2H), 3.45e3.52 (m, J ¼ 6.8 Hz, 1H), 3.33e3.39 (m, J ¼ 6.6 Hz,
1H), 1.53e1.55 (d, J ¼ 6.9 Hz, 6H), 1.08e1.09 (d, J ¼ 6.6 Hz, 6H). 13C
J ¼ 5.2 Hz, 1H), 3.52e3.59 (m, J ¼ 6.9 Hz, 1H), 3.3e3.42 (m,
J ¼ 6.7 Hz, 1H), 2.3 (s, 3H), 1.59e1.69 (d, J ¼ 6.9 Hz, 6H,), 1.18e1.20
(d, 6.6 Hz, 6H), 0.9 (t, 3H). 13C NMR: CDCl3, 400 MHz
d
(ppm):
NMR: CDCl3, 400 MHz d (ppm): 167.2, 163.1, 151.6, 149.9, 137.5,
166.9, 161.9, 151.1, 149.3, 124.3, 123.4, 51.0, 46.0, 20.5, 20.1, 9.6. 77Se
NMR:
(ppm): 162.04. IR (KBr, cmꢀ1): 2968, 2361, 1629, 1547, 1466,
1422, 1370, 1331, 1209, 1162, 1098, 916, 824, 733, 634, 605, 532,
129.2, 128.4, 127.1, 124.0, 122.6. 77Se NMR:
cmꢀ1): 2968, 2363, 1631, 1542, 1475, 1424, 1368, 1324, 1212, 1039,
866, 763, 724, 594. MS (ESI): 441 [Mþ$ 80Se, 36Cl]. Anal. Calcd (%) for
d (ppm): 302.38. IR (KBr,
d
,