1
112 J. Chin. Chem. Soc., Vol. 49, No. 6, 2002
Li et al.
7
-1
(
see Table 1, TLC as monitored). When the reaction was fin-
2 2
4 PhSeCH CH CN, Oil; IR max (cm ) 3100, 3080,
ished, dilute HCl (0.1 M, 10 mL) was added to quench the re-
action and the mixture was extracted with ether (15 mL 2);
after the extracts were washed with brine, dried over anh y -
2990-2940, 2875, 2260, 1590, 1485, 1445, 1420, 1310, 1270,
1
1200, 1070, 1020, 1000, 935, 890, 740, 690, 660; H NMR
7.06-7.60 (5H, m), 2.93 (2H, t), 2.53 (2H, t).
7
-1
drous Na
2
SO
4
and the solvent was removed und e r reduced
2 3 2
5 PhSeCH CH(CH )CO Me, Oil; IR max (cm ) 3090,
pressure, the residue was then purified by preparative TLC on
Silica gel with light petroleum and ethyl ether (5:1) as eluent.
3080, 2990, 2960, 2940, 1740, 1590, 1485, 1460, 1440, 1380,
1
1350, 1200, 1160, 1020, 1000, 900, 820, 740, 690, 670; H
NMR 7.03-7.60 (5H, m), 3.50 (3H, s), 3.00 (2H, d), 2.50-2.80
(
1H, m), 1.15 (3H, d).
Scheme I
1
9
-1
6
o-MeC
6 4 2 2 2
H SeCH CH CO Me, Oil; IR max (cm )
3
100, 3080, 3020, 2980, 2960, 2940, 2885, 2800, 1739, 1600,
CeCl /Sm
CH =C(R)X
3
2
[ ArSe-]
ArSeSeAr
ArSeCH CH(R)X
2
1580, 1480, 1440, 1380, 1350, 1280, 1225, 1200, 1170, 1130,
4
0 C 4 h
R. T. 4 h
1
1040, 1010, 980, 890, 840, 740, 650; H NMR 7.10-7.60 (4H,
m), 3.53 (3H, s), 2.93 (2H, t), 2.57 (2H, t), 2.33 (3H, s).
In summary, a novel method for the preparation of
selenoesters has been provided, the advantages of which
19
-1
7
6 4 2 2 2
o-MeC H SeCH CH CO Et, Oil; IR max (cm )
-
3
1
6
100, 3080, 3020, 2990, 2980, 2950, 2885, 1736, 1600, 1580,
475, 1460, 1380, 1350, 1220, 1200, 1035, 860, 830, 740,
are easily available and cheap materials, single product, sim-
ple manipulation, and mild and neutral conditions.
1
50, 610; H NMR 6.93-7.43 (4H, m), 4.00 (2H, q), 2.93 (2H,
t), 2.56 (2H, t), 2.33 (3H, s), 1.16 (3H, t).
1
9
-1
8
6 4 2 2 2
o-MeC H SeCH CH CO Bu-n, Oil; IR max (cm )
DATA OF THE PRODUCTS
3
1
9
100, 3080, 3020, 2980, 2960, 2940, 2880, 1734, 1600, 1475,
460, 1420, 1380, 1350, 1275, 1220, 1200, 1170, 1060, 1035,
7
-1
1
PhSeCH
2
CH
2
CO
2
Me, Oil; IR max (cm ) 3090, 3080,
1
80, 960, 940, 740, 650; H NMR 6.96-7.50 (4H, m), 3.93
3
1
7
020, 2960, 2940, 2860, 1750, 1590, 1480, 1445, 1350, 1290,
(2H, t), 2.93 (2H, t), 2.56 (2H, t), 2.33 (3H, s), 1.30-1.60 (4H,
m), 1.00 (3H, t).
1
220, 1170, 1070, 1020, 1000, 957, 740, 685, 660; H NMR
1
9
-1
.10-7.60 (5H, m), 3.53 (3H, s), 2.90 (2H, t), 2.66 (2H, t).
9
6 4 2 2
o-MeC H SeCH CH CN, Oil; IR max (cm ) 3100,
7
-1
2
2 2 2
PhSeCH CH CO Et, Oil; IR max (cm ) 3095, 3080,
3
1
1
080, 3020, 2990, 2960-2940, 2890, 2880, 2249, 1600, 1580,
470, 1460, 1420, 1380, 1350, 1275, 1220, 1200, 1170, 1060,
2
1
990, 2940, 2920, 2890, 2880, 1750, 1590, 1485, 1440, 1380,
1
1
350, 1220, 1170, 1020, 740, 685, 660; H NMR 7.07-7.70
035, 980, 960, 940, 740; H NMR 6.93-7.40 (4H, m), 2.87
(
5H, m), 4.00 (2H, q), 2.97 (2H, t), 2.63 (2H, t), 1.67 (3H, t).
(2H, t), 2.47 (2H, t), 2.33 (3H, s).
7
-1
19
3
PhSeCH
2
CH
2
CO
2
Bu-n, Oil; IR max (cm ) 3100,
10 o-MeC H SeCH CH(CH )CO Me, Oil; IR
6
4
2
3
2
max
-
1
3
1
080, 2990, 2940, 2920, 2880, 1750, 1600, 1485, 1440, 1380,
(cm ) 3090, 3080, 3020, 2990, 2960, 2890, 1734, 1590,
1580, 1485, 1440, 1380, 1350, 1270, 1200, 1020, 1000, 900,
1
350, 1220, 1170, 1020, 740, 680, 660; H NMR 7.03-7.60
1
(
(
5H, m), 3.97 (2H, t), 2.97 (2H, t), 2.60 (2H, t), 1.20-1.60
4H, m), 0.90 (3H, t).
820, 740, 690, 660; H NMR 6.93-7.40 (4H, m), 3.50 (3H, s),
2.97 (2H, d), 2.50-2.80 (1H, m), 2.33 (3H, s), 1.15 (3H, d).
Table 1. Synthesis of the -Selenoesters and -Selenonitriles
a
Entry
Ar
R
X
Reaction Time/h
Yield ( )
1
2
3
4
5
6
7
8
9
Ph
Ph
Ph
Ph
Ph
H
H
H
H
CH3
H
H
H
H
CH3
CO Me
4
4
4
4
4
4
4
4
4
4
73
78
84
72
51
78
81
76
70
53
2
CO Et
2
CO Bu-n
2
CN
CO Me
2
o-CH C H
CO Me
3
6
4
4
4
4
4
2
o-CH C H
CO Et
3
6
2
o-CH C H
CO Bu-n
3
6
2
o-CH C H
CN
3
6
1
0
o-CH C H
CO Me
3
6
2
a
Isolated yields based on diselenides.