Y. Mutoh et al. / Journal of Organometallic Chemistry 692 (2007) 129–135
133
1
Chemical Industry Co., Ltd., and used without further
purification. Selenoiminium salts 1 were prepared as
described in the literature [7]. Florisil used in column chro-
matography was Florisil (150–250 lm) from Kanto Chem-
ical Co., Inc.
(Ar), 197.6 (C@Te, JC@Te = 553.8 Hz); 125Te NMR
(CDCl3, 50 ꢁC) d 915.9; MS (EI) m/z 293 (M+, 130Te);
HRMS (EI) calcd for C10H13NO130Te 293.0059, found:
293.0065.
All reactions were carried out under dry argon
atmosphere, and all handling should be carried out in a
well-ventilated hood. All glassware was wrapped with alu-
minum foil because of the characteristic photosensitivity of
tellurium compounds, and laboratory lights were extin-
guished to minimize any illumination. All solvents were
degassed by bubbling with argon or by the freeze-pump-
thaw method.
4.2.3. N,N-Dimethyl 4-
dimethylaminobenzenecarbotelluroamide (2c)
Telluroamide 2c was prepared by utilizing the procedure
described for 2b. The title compound was obtained in 41%
yield as a wine red solid: mp 64.5–69.0 ꢁC; IR (Nujol) 1607,
1511, 1284, 1230, 1186, 1121, 1084, 946, 903, 813,
765 cmꢀ1 1H NMR (CDCl3) d 2.89 (s, 6H, N(CH3)2),
;
3.07 (s, 3H, NCH3), 3.72 (s, 3H, NCH3), 6.49 (d,
J = 8.6 Hz, 2H, Ar), 7.23 (d, J = 8.6 Hz, 2H, Ar); 13C
NMR (CDCl3) d 40.0 (NCH3)2), 44.6, 55.5 (NCH3),
110.2, 126.3, 139.0, 150.2 (Ar), 196.9 (C@Te,
JC@Te = 545.5 Hz); 125Te (CDCl3, 50 ꢁC) d 849.2; MS
(EI) m/z 306 (M+, 130Te); HRMS (EI) calcd for
C11H16N2130Te (M+) 306.0376, found: 306.0357.
4.2. Synthesis of Telluroamides 2
4.2.1. N,N-Dimethyl benzenecarbotelluroamide (2a)
To a THF suspension (15 mL) of tellurium (0.459 g,
3.6 mmol) was added LiAlH4 (0.138 g, 3.6 mmol) at 0 ꢁC,
and this was stirred at the temperature for 1 h. Then, to
an Et2O suspension (15 mL) of selenoiminium salt 1a
(1.128 g, 3.0 mmol) was cannulated the gray THF suspen-
sion at 0 ꢁC, and the mixture was stirred at room tempera-
ture for 3 h. The mixture was passed through a sintered
glass filter (G4), and the solvent was removed under
reduced pressure. The residue was purified by column chro-
matography (Florisil, CH2Cl2) to give telluroamide 2a
4.2.4. N,N-Dimethyl 4-bromobenzenecarbotelluroamide
(2d)
Telluroamide 2d was prepared by utilizing the procedure
described for 2b. The title compound was obtained in 26%
yield as a wine red solid: mp 116.5–129.0 ꢁC; IR (Nujol)
1578, 1525, 1389, 1254, 1130, 1103, 1007, 906, 870,
1
817 cmꢀ1; H NMR (CDCl3) d 2.93 (s, 3H, NCH3), 3.73
1
(0.492 g, 63%) as a wine-red solid: H NMR (CDCl3) d
(s, 3H, NCH3), 7.11 (d, J = 8.8 Hz, 2H, Ar), 7.22 (d,
J = 8.8 Hz, 2H, Ar); 13C NMR (CDCl3) d 44.6, 55.0
(NCH3), 122.3, 124.5, 131.0, 150.8 (Ar), 196.4 (C@Te,
JC@Te = 559.7 Hz); 125Te (CDCl3, 50 ꢁC) d 978.7; MS
(EI) m/z 341 (M+, 130Te); HRMS (EI) calcd for
C9H10BrN130Te (M+) 340.9059, found: 340.9032.
2.96 (s, 3H, CH3), 3.78 (s, 3H, CH3), 7.23–7.36 (m, 5H,
Ar); 13C NMR (CDCl3) d 44.7, 55.2 (NCH3), 123.1,
128.0, 128.3, 152.6 (Ar), 197.5 (C@Te); 125Te NMR
(CDCl3, 50 ꢁC) d 913.4. 1H NMR spectroscopic data
matched the data reported previously [5a].
4.2.2. N,N-Dimethyl 4-methoxybenzenecarbotelluroamide
(2b)
4.2.5. N,N-Di-2-propenyl benzenecarbotelluroamide (2e)
Telluroamide 2e was prepared by utilizing the procedure
described for 2b. The title compound was obtained in 45%
yield as a wine red solid: IR (neat) 3079, 2985, 1701, 1638,
1494, 1477, 1410, 1257, 1202, 1156, 1028, 991, 756, 698,
To an Et2O solution (15 mL) of N,N-dimethyl 4-meth-
oxybenzamide (0.895 g, 5.0 mmol) was added oxalyl chlo-
ride (0.45 mL, 5.0 mmol) at 0 ꢁC, and the mixture was
stirred at this temperature for 0.5 h. The reaction mixture
was further stirred at room temperature overnight. On
the other hand, to a THF suspension (15 mL) of tellurium
(0.638 g, 5.0 mmol) was added LiAlH4 (0.19 g, 5.0 mmol)
at 0 ꢁC, and this was stirred at the same temperature for
1 h. To the white Et2O suspension was then cannulated
the gray THF suspension at 0 ꢁC, and the mixture was stir-
red at room temperature for 3 h. The mixture was passed
through a sintered glass filter (G4), and the solvent was
removed under reduced pressure. The residue was purified
by column chromatography (Florisil, CH2Cl2) to give tellu-
roamide 2b (0.623 g, 43%) as a wine-red solid: mp 67.0–
70.5 ꢁC; IR (Nujol) 1626, 1601, 1571, 1531, 1504, 1438,
1393, 1296, 1247, 1175, 1129, 1110, 1082, 1026, 831,
1
657 cmꢀ1; H NMR (CDCl3) d 3.89 (d, J = 5.6 Hz, 2H,
NCH2), 4.89 (d, J = 6.0 Hz, 2H, NCH2), 5.10 (d,
J = 17.2 Hz, 1H, CH2@CH), 5.21 (d, J = 10.0 Hz, 1H,
CH2@CH), 5.32 (d, J = 17.2 Hz, 1H, CH2@CH), 5.35 (s,
1H, 5.83 CH2@CH), 5.65 (ddt, J = 7.8, 10.1, 17.2 Hz,
1H, CH2@CH), 6.01 (ddt, J = 7.8, 10.1, 17.2 Hz, 1H,
CH2@CH), 7.16–7.26 (m, 5H, Ar); 13C NMR (CDCl3) d
55.6, 64.0 (NCH2), 120.0, 120.2 (CH2@CH), 122.1, 127.6,
128.1 (Ar), 129.8 (CH2@CH · 2), 152.0 (Ar), 200.2 (C@Te,
1JC@Te = 561.6 Hz); 125Te NMR (CDCl3, 50 ꢁC) d 957.3;
MS (EI) m/z 315 (M+, 130Te); HRMS (EI) calcd for
C13H15N130Te (M+) 315.0267, found: 315.0282.
4.2.6. N-(Phenylmethyl)benzenecarbotelluroamide (2g)
Telluroamide 2g was prepared by utilizing the procedure
described for 2a. The title compound was obtained in 80%
yield as a chocolate viscous oil: IR (neat) 3026, 2917, 2849,
1
593 cmꢀ1; H NMR (CDCl3) d 3.07 (s, 3H, CH3), 3.809
(s, 3H, CH3), 3.812 (s, 3H, CH3), 6.83 (d, J = 8.8 Hz, 2H,
Ar), 7.29 (d, J = 8.8 Hz, 2H, Ar); 13C NMR (CDCl3) d
44.6 (CH3), 55.4, 55.4 (CH3), 113.2, 125.3, 144.7, 159.6
1
1607, 1524, 1493, 1443, 1384, 1341, 1027, 693 cmꢀ1; H