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275
were reported in d units downfield from internal
reference Me Si. Mass spectra were obtained on a
Finnigan MAT-312 spectrometer at 70 eV by EI
methods and measurements were carried out on Se
isotope. Melting points were measured on a Gallenkamp
melting point apparatus and are uncorrected. Micro-
analyses for carbon, hydrogen and nitrogen were
performed at the Microanalytical Center of Kyoto
3260w, 3130s, 3010w, 2938w, 2970w, 1620s, 1460s,
1
1340s, 670s, 370w. H NMR (CDCl ): 3.92 (s, 3H);
4
3
7.02 (q, 2H); 7.50 (m, 1H); 8.70 (d, 1H); 9.20ꢀ10.30
/
8
0
(s,br, 2H). Mass spectrum: m/z (relative intensity):
91(28); 134(100); 213(91); 215(78).
2.2.4. 4-Methoxyphenylselenocarboxamide (4)
An orange solid was obtained in 98% yield (lit. [2]
University (Japan) and by a Perkinꢀ/Elmer 240B ele-
70%). M.p. 155ꢀ
/
156 8C (lit. [2] 157 8C). Anal. Found:
mental analyzer.
C, 44.61; H, 3.98; N, 6.34. Calc. for C H ONSe: C,
ꢂ1
8
9
44.87; H, 4.24; N, 6.54%. IR (KBr, cm ): 3350s, 3258s,
3130s, 3080sh, 2958s, 2920sh, 1610s, 1430s, 1395s, 640s,
2
.2. Synthesis
All arylselenocarboxamides were prepared by the
1
78m. H NMR (DMSO-d ): 3.80 (s, 3H); 6.96 (d, 2H);
3
7.98 (m, 1H); 9.95 (s, br, 1H); 10.47 (s,br, 1H).
6
1
3
C
NMR (DMSO-d ): 55.52, 110.54, 122.54, 134.01,
153.22, 202.52.
following general procedure according to a literature
method [1] with a slight modification.
6
Sodium borohydride (2.04 g, 54 mmol) was added
dropwise over 30 min to a suspension of selenium
3
powder (3.95 g, 50 mmol) in dry ethanol (50 cm ) under
2.2.5. 4-Methylthiophenylselenocarboxamide (5)
An orange solid was obtained in 97% yield. M.p. 145ꢀ
/
nitrogen atmosphere while hydrogen evolved vigor-
ously. The resulting solution stirred for additional 30
146 8C. Anal. Found: C, 41.61; H, 3.95; N, 6.11. Calc.
for C H ONSSe: C, 41.74; H, 3.94; N, 6.08%. IR (KBr,
cm ): 3260s, 3280sh, 3080s, 2960w, 2900w, 1618s,
8
9
3
min. Pyridine (8.1 cm , 100 mmol) and arylnitrile (25
ꢂ1
1
1475m, 1400s, 688s, 365m. H NMR (DMSO-d ): 2.50
(s, 3H); 7.25 (d, 2H); 7.94 (d, 2H); 10.10 (s,br, 1H); 10.60
mmol) were added to the resulting solution at room
temperature (r.t.). The solution was heated under reflux
3
while hydrochloric acid (30 cm , 2 M) was added
6
13
(s, br, 1H). C NMR (DMSO-d ): 15.43, 112.14, 122.65,
133.79, 153.53, 203.20.
6
dropwise over 2 h. The solution was refluxed for 30
min then filtered hot. The filtrate was cooled to r.t. Ice
water was added in small portions with continuous
stirring until the precipitation of arylselenocarboxamide
was completed. The precipitate was recrystallized from
benzene to give orange or yellow powder.
2.2.6. 4-Ethoxyphenylselenocarboxamide (6)
An orange solid was obtained in 95% yield. M.p
124 8C. Anal. Found: C, 47.53; H, 4.79; N, 6.01. Calc.
for C H ONSe : C, 47.38; H, 4.86; N, 6.14. IR (KBr,
9
11
ꢂ1
cm ): 3320s, 3250m, 3100s, 2978w, 2920w, 1615s,
1
1460m, 1395s, 620s, 385m. H NMR (DMSO-d ): 1.45
(t, 3H); 4.10 (q, 2H); 6.93 (d, 2H); 7.97 (d, 2H); 9.95
2
.2.1. Phenylselenocarboxamide (1)
A yellow solid was obtained in 90% yield (lit. [2] 88%).
6
1
(s,br, 1H); 10.45 (s,br, 1H). C NMR (DMSO-d ): 8.23,
3
M.p. 105 8C (lit. [2] 125 8C). Anal. Found: C, 46.03; H,
6
3
7
1
7
.81; N, 7.71. Calc. for C H NSe: C, 45.92; H, 3.85; N,
ꢂ1
50.32, 126.51, 127.35, 135.20, 138.23, 202.53. Mass
spectrum: m/z (relative intensity): 91(30). 148(100),
227(31), 229(75).
7
6
.65%. IR (KBr, cm ): 3325s, 3270s, 3140m, 3070sh,
1
615s, 630s, 370m. H NMR (DMSO-d ): 7.40 (m, 3H);
.88 (m, 2H); 10.27 (s,br,1H); 10.70 (s,br,1H). Mass
6
spectrum: m/z (relative intensity): 51(35); 77(51);
1
2.2.7. 2,3-Dimethoxyphenylselenocarboxamide (7)
04(100); 183(30); 185(58).
A yellow solids was obtained in 23% yield. M.p. 154ꢀ
55 8C. Anal. Found: C, 44.31; H, 4.50; N, 5.62. Calc.
for C H O NSe: C, 44.28; H, 4.54; N, 5.74%. IR (KBr,
/
1
2
.2.2. 4-Bromophenylselenocarboxamide (2)
An orange solid was obtained in 94% (lit. [3] 74%).
9
11
2
ꢂ1
cm ): 3380s, 3300w, 3160s, 3010w, 2980w, 2940w,
1
1635s, 1430s, 1390s, 675s, 385w. H NMR (DMSO-d ):
M.p. 136ꢀ
/
138 8C (lit. [3] 138 8C). Anal. Found: C,
6
3
H, 1.92; N, 5.34%. IR (KBr, cm ): 3340s, 3180s,
2.11; H, 1.85; N, 5.18. Calc. for C H BrNSe: C, 32.09;
3.18 (s, 3H); 3.94 (s, 3H); 7.00ꢀ7.26 (m, 3H); 10.10 (s,br,
1H); 10.75 (s,br,1H). Mass spectrum: m/z (relative
intensity): 164(100), 243(25), 145(56).
/
7
5
ꢂ1
1
060w, 1610s, 660s, 370m. H NMR (DMSO-d ): 7.58
3
6
(
Mass spectrum: m/z (relative intensity): 50(45); 76(44);
d, 2H); 7.83 (d, 2H); 10.30 (s,br, 1H); 10.85 (s,br,1H).
2.2.8. 3,4-Dimethoxyphenylselenocarboxamide (8)
Orange crystals were obtained in 99% yield (lit. [1]
1
03(40); 182(98); 184(95); 261(52); 263(85).
7
4%). M.p. 175ꢀ
/
176 8C (lit. [1] 177ꢀ179 8C). Anal.
/
2
.2.3. 2-Methoxyphenylselenocarboxamide (3)
Yellow solid, 53% yield. M.p. 186 8C. Anal. Found:
Found: C, 44.34; H, 3.90; N, 5.52. Calc. for
C H O NSe: C, 44.28; H, 4.54; N, 5.74%. IR (KBr,
cm ): 3300s, 3260sh, 3070m, 2950m, 2920w, 1630s,
9
11
ꢂ1
2
C, 44.73; H, 4.18; N, 6.74. Calc. for C H ONSe: C,
8
9
4.87; H, 4.24; N, 6.54%. IR (KBr, cmꢂ1): 3335s,
1
1450m, 1385w, 625m, 370w. H NMR (DMSO-d ): 3.81
4
6