80
V. Chandrasekhar et al. / Journal of Organometallic Chemistry 695 (2010) 74–81
yields was noticed. The following are the data pertaining to these
compounds. The yields pertain to the microwave method.
4.2.3. Synthesis of diorganotellurium dichlorides
4.2.3.1. Method-A: (1a, 1d, 1e, 2a–2c, 3a and 3b). A suspension of 1
(0.055 g, 0.100 mmol) and 4-MeO-C6H4TeCl3 (0.034 g, 0.100 mmol)
in chloroform (100 mL) were refluxed for 20 h with stirring under
N2. The hot reaction mixture was filtered to remove the precipi-
tated HgCl2. Concentration of the filtrate and addition of petroleum
ether (40–60 °C) gave a solid which was recrystallized twice from
CHCl3 to obtain an orange-red solid of 1a. Yield: 0.046 g (73%). M.p.
4.2.1.1.
4-Methyl-N-(pyrene-1-ylmethylene)aniline (SB-1). Yield:
masym (CH@N): 1616.7.
0.29 g (91%); M.p.: 132 °C. IR (KBr)/cmꢂ1
:
1H NMR (400 MHz, CDCl3): d 2.36 (s, Me), 7.18–8.97 (m, aryl),
9.44 (s, CH@N) ppm. 13C NMR (500 MHz, DMSO-d6): 21.5 (Me),
121.0, 122.4, 125.1, 125.9, 126.1, 126.2, 126.6, 127.1, 127.2,
127.5, 128.9, 129.7 (i-pyrene), 129.9 (p-tolyl), 130.9 (i-tolyl),
158.1 (CH@N) ppm. ESI-HRMS: m/z = 320.1437 (found), 320.1439
(calculated) for [M+H]+. Anal. Calc. for C24H17N (319.40): C,
90.25; H, 5.36; N, 4.39. Found: C, 90.12; H, 5.53; N, 4.51%.
187 °C. IR (KBr)/cmꢂ1 masym (CH@N): 1631.1. 1H NMR (400 MHz,
:
DMSO-d6): d 2.31 (s, Me), 3.84 (s, OMe), 6.81–8.80 (m, aryl), 9.40
(s, CH@N) ppm). 13C NMR (500 MHz, DMSO-d6): 21.0 (Me), 55.5
(OMe), 157.0 (CH@N) ppm. ESI-HRMS: m/z = 572.0864 (found),
572.0.869 (calculated) for [M(ꢂ2Cl)+OH]+; 662.1313 (found),
662.0508 (calculated) for [M+2H2O+H]+. Anal. Calc. for
C31H23Cl2NOTe (624.03): C, 59.67; H, 3.72; N, 2.24. Found: C,
59.43; H, 3.83; N, 2.35%.
4.2.1.2. 4-Methyl-N-(anthracene-9-ylmethylene)aniline (SB-2). Yield:
0.27 g (92%); M.p.: 103 °C (105 °C, lit. [23]). IR (KBr)/cmꢂ1
: masym
(CH@N): 1620.7. 1H NMR (500 MHz, DMSO-d6): d 2.21 (s, Me),
6.82–9.12 (m, aryl), 9.21 (s, CH@N) ppm. 13C NMR (500 MHz,
DMSO-d6): 22.4 (Me), 121.7, 121.9, 123.2, 128.3, 128.7, 129.6,
130.1, 130.4, 130.9, 132.2 (i-anthracene), 133.0 (p-tolyl), 134.5 (i-
tolyl), 161.7 (CH@N) ppm. ESI-HRMS: m/z = 296.1444 (found),
Compounds 1d, 1e, 2a–2c, 3a and 3b were prepared similarly.
1d: Yield: 0.037 g (63%). M.p. 171–173 °C. IR (KBr)/cmꢂ1
: masym
(CH@N): 1615.4. 1H NMR (400 MHz, DMSO-d6): d 2.42 (s, Me),
7.19–8.42 (m, aryl), 9.38 (s, CH@N) ppm. 13C NMR (500 MHz,
DMSO-d6): 22.1 (Me), 153.2 (CH@N) ppm. ESI-HRMS: m/
z = 592.0926 (found), 592.0687 (calculated) for [M(ꢂCl)+MeOH]+;
773.0131 (found), 773.1305 (calculated) for [M+3H2O+
3MeCN+H]+. Anal. Calc. for C30H21Cl2NTe (594.00): C, 60.66; H,
3.56; N, 2.36. Found: C, 60.78; H, 3.38; N, 2.47%.
296.1439 (calculated) for [M+H]+. Anal. Calc. for C22H17
N
(295.38): C, 89.46; H, 5.80; N, 4.74. Found: C, 90.01; H, 5.60; N,
4.78%.
1e: Yield: 0.0.043 g (71%). M.p. 153–157 °C. IR (KBr)/cmꢂ1
: masym
4.2.1.3.
4-Methyl-N-(phenanthrene-9-ylmethylene)aniline (SB-
(CH@N): 1615.0. 1H NMR (400 MHz, DMSO-d6): d 2.48 (s, Me-SB),
2.33 (s, Me-tolyl-Te), 7.12–8.45 (m, aryl), 9.42 (s, CH@N) ppm.
13C NMR (500 MHz, DMSO-d6): 22.1 (Me-SB), 28.7 (Me-tolyl-Te),
157 (CH@N) ppm. ESI-HRMS: m/z = 610.2531 (found), 610.0348
(calculated) for [M+H]+; 842.3364 (found), 842.1883 (calculated)
for [M+MeOH+4MeCN+2H2O+H]+. Anal. Calc. for C31H23Cl2NTe
(608.03): C, 61.24; H, 3.81; N, 2.30. Found: C, 61.33; H, 3.69; N,
2.17%.
3). Yield: 0.26 g (88%); M.p.: 142 °C. IR (KBr)/cmꢂ1
:
masym (CH@N):
1625.0. 1H NMR (500 MHz, DMSO-d6): d 2.32 (s, Me), 6.89–8.91 (m,
aryl), 9.31 (s, CH@N) ppm. 13C NMR (500 MHz, DMSO-d6): 21.9
(Me), 122.1, 122.8, 124.7, 125.2, 125.7, 126.5, 127.3, 127.8, 128.1,
128.3, 129.5, 130.0 (i-phenanthrene), 131.2 (p-tolyl), 131.7 (i-to-
lyl), 160.8 (CH@N) ppm. ESI-HRMS: m/z = 328.1712 (found),
328.1701 (calculated) for [M+MeOH+H]+. Anal. Calc. for C22H17
N
(295.38): C, 89.46; H, 5.80; N, 4.74. Found: C, 89.83; H, 5.67; N,
4.58%.
2a. Yield: 0.043 g (71.6%). M.p. 179 °C. IR (KBr)/cmꢂ1
: masym
(CH@N): 1625.3. 1H NMR (500 MHz, DMSO-d6): d 2.38 (s, Me),
3.90 (s, OMe), 7.13–9.02 (m, aryl), 10.15 (s, CH@N) ppm). 13C
NMR (500 MHz, DMSO-d6): 22.7 (Me), 55.6 (OMe), 158.6 (CH@N)
ppm. ESI-HRMS: m/z = 666.0837 (found), 666.0821 (calculated)
for [M+2MeOH+H]+; 630.1068 (found), 630.1055 (calculated) for
[M(ꢂCl)+2MeOH]+. 549.0857 (found), 548.0869 (calculated) for
[M(ꢂ2Cl+OH]+. Anal. Calc. for C29H23Cl2NOTe (600.01): C, 58.05;
H, 3.86; N, 2.33. Found: C, 58.22; H, 3.71; N, 2.35%.
4.2.2. Syntheses of the organomercury compounds 1–3
0.5 mmol of the Schiff base (SB-1: 0.16 g, SB-2: 0.15 g, SB-3:
0.15 g) and mercury(II) acetate (0.17 g, 0.51 mmol) were stirred
(24 h) together in refluxing methanol (ꢁ40 ml). The reaction mix-
ture was cooled and LiCl (0.05 g, 1.2 mmol) in hot methanol was
added under stirring. The resulting precipitate was filtered, washed
with diethyl ether and dried. The solid obtained was extracted by
hexane via a G-4 soxlet frit to avoid the impurity of salts. Recrys-
tallization from CHCl3–MeOH (1:1) solution gave the organomer-
cury compounds 1–3 as yellow needles.
2b: Yield: 0.053 g (85%). M.p. 207–209 °C. IR (KBr)/cmꢂ1
: masym
(CH@N): 1621.0. 1H NMR (500 MHz, DMSO-d6): d 2.48 (s, Me),
7.23–8.98 (m, aryl), 10.12 (s, CH@N) ppm. 13C NMR (500 MHz,
DMSO-d6): 23.4 (Me), 157.5 (CH@N) ppm. ESI-HRMS: m/
z = 622.0352 (found), 622.0348 (calculated) for [M+H]+; 727.1489
(found), 727.1483 (calculated) for [M(ꢂCl)+3MeCN+H2O]+. Anal.
Calc. for C32H23Cl2NTe (620.04): C, 61.99; H, 3.74; N, 2.26. Found:
C, 62.34; H, 3.67; N, 2.32%.
1, Yield: 0.19 g (68%); M.p.: 222–225 °C. IR (KBr)/cmꢂ1
: masym
(CH@N): 1609.1. 1H NMR (500 MHz, CDCl3): d 2.36 (s, Me), 7.12–
9.02 (m, aryl), 9.62 (s, CH@N). 13C NMR (500 MHz, CDCl3): 21.0
(Me), 158.2 (CH@N) ppm. ESI-HRMS: m/z @ 556.0759 (found),
556.0756 (calculated) for [M+H]+; 839.2335 (found), 839.2350
(calculated) for [M(ꢂCl)+SB]+.
2c: Yield: 0.039 g (63.7%). M.p. 169 °C. IR (KBr)/cmꢂ1
: masym
(CH@N): 1602.8. 1H NMR (500 MHz, DMSO-d6): d 2.32 (s, Me-SB),
2.67 (s, Me-o-Mes), 2.12 (s, Me-p-Mes), 6.92–8.59 (m, aryl), 10.23
(s, CH@N) ppm. 13C NMR (500 MHz, DMSO-d6): 23.5 (Me-SB),
28.8 (p-Me-mes), 30.3 (o-Me-mes), 162.7 (CH@N) ppm. ESI-HRMS:
m/z = 728.1454 (found), 728.1454 (calculated) for [M+2MeCN+-
MeOH+H]+. Anal. Calc. for C31H27Cl2NTe (612.06): C, 60.83; H,
4.45; N, 2.29. Found: C, 60.57; H, 4.35; N, 2.47%.
2, Yield: 0.21 g (82%); M.p.: 178–179 °C. IR (KBr)/cmꢂ1
: masym
(CH@N): 1612.4. 1H NMR (500 MHz, CDCl3): d 2.32 (s, Me), 6.93–
8.87 (m, aryl), 9.52 (s, CH@N). 13C NMR (500 MHz, CDCl3): 21.9
(Me), 160.4 (CH@N) ppm. ESI-HRMS: m/z = 550.0857 (found),
550.0861 (calculated) for [M+H2O+H]+; 646.1554 (found),
646.1549 (calculated) for [M+2MeCN+MeOH+H]+.
3, Yield: 0.17 g (66%); M.p.: 201–204 °C. IR (KBr)/cmꢂ1
:
masym
3a: Yield: 0.038 g (63%). M.p. 178 °C. IR (KBr)/cmꢂ1
: masym
(CH@N): 1608.9. 1H NMR (500 MHz, CDCl3): d 2.27 (s, Me), 7.30–
9.18 (m, aryl), 9.57 (s, CH@N). ESI-HRMS: m/z = 532.0743 (found),
532.0756 (calculated) for [M+H]+; 560.1510 (found), 560.1513 (cal-
culated) for [M(ꢂCl)+2MeOH]+. The 13C NMR of 3 could not be ob-
tained due to its insufficient solubility.
(CH@N): 1607.1. 1H NMR (500 MHz, DMSO-d6): d 2.49 (s, Me),
3.82 (s, OMe), 7.20–8.73 (m, aryl), 9.69 (s, CH@N) ppm). ESI-HRMS:
m/z = 757.1467 (found), 757.1455 (calculated) for [M+MeCN+3-
MeOH+H2O+H]+; 620.0798 (found), 620.0847 (calculated) for
[M(–Cl)+3H2O]+. Anal. Calc. for C29H23Cl2NOTe (600.01): C, 58.05;