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R.S. Baligar et al. / Journal of Organometallic Chemistry 696 (2011) 3015e3022
4.2.2. Synthesis of compound 10
(0.20 g, 0.52 mmol). On heating the reaction mixture to 60 ꢀC,
a colorless solution was obtained. To it was added dropwise an
ethanolic solution (9 mL) of 3-amino-1-propanol (0.04 g, 0.52 mmol)
over a period of 10 min. The reaction mixture was refluxed for
a period of 52 h to obtain a pale yellowish solution. Then the volume
of the reaction mixture was reduced to 5 mL on a rotary evaporator
and kept at room temperature to obtain colorless crystals of 13. The
lumps of colorless crystals of 13 were collected by filtration, washed
with cold benzene, hexane and dried under vacuum (0.16 g, 70%
yield). M.p 112e114 ꢀC. Anal. Calcd for C10H12BrHgNO: C, 27.13; H,
2.73; N, 3.16. Found: C, 27.65; H, 2.32; N, 3.70; FT-IR (KBr) 3335, 3062,
2944, 2925, 2874, 2829, 1646, 1434, 1212, 1115, 1072, 756 cmꢂ1; 1H
In a 250-mL two-necked flask containing100 mL acetone, was
added compound 9 (4.08 g, 9.5 mmol), p-toluenesulfonic acid
monohydrate (0.20 g, 1.1 mmol) and refluxed for 5 h. The volume of
the reaction mixture was reduced to 20 mL on a rotary evaporator
and distilled water was added to it. The precipitate so obtained was
filtered, washed with distilled water and dried under vacuum to get
(2-formylphenyl)mercury(II) bromide as a off-white solid. It was
further purified by recrystallization with ethanol (3.45 g, 66% yield).
M.p 170e172 ꢀC. Anal. Calcd for C7H5BrHgO: C, 21.80; H, 1.30.
Found: C, 21.83; H, 0.95; FT-IR (KBr) 3436, 3061, 1671, 1662, 1575,
1561, 1202, 849, 756 cmꢂ1
1H), 7.88 (dd, J ¼ 7.6, 1.2 Hz, 1H.), 7.73 (td, J ¼ 7.4, 1.3 Hz, 1H,),
7.59e7.55 (m, 2H,); 13C NMR (400 MHz, CDCl3):
194.1, 151.3, 140.6,
; d 10.13 (s,
1H NMR (400 MHz, CDCl3)
NMR# (400 MHz, CDCl3)
d 8.50 (s, 1H), 7.52e7.37 (m, 4H), 3.83 (t,
d
J ¼ 6.5 Hz, 2H), 3.78 (t, J ¼ 5.8 Hz, 2H), 2.06e2.00 (m, 2H); 13C NMR
137.7, 136.1, 136.0, 129.8; ES-MS m/z (relative intensity, nature of
peak) 387.1 (100, [M þ 1]þ; UVeVis (dichloromethane, lmax nm
(400 MHz, CDCl3) d 163.7, 163.5, 149.7, 138.9, 137.3, 132.4, 128.8, 60.1,
56.3, 33.2; ES-MS m/z (relative intensity, nature of peak) 443.9 (100,
(cmꢂ1); , Mꢂ1 cmꢂ1)): 301 (32258); 2092; UV/Vis (solid): lmax
3 :
[M þ 1]þ), 363.9 (30, [M e Br]þ; UVeVis (dichloromethane, lmax nm
351 nm; Emission (solid): 420, 456, 483 nm (lex 351 nm).
(cmꢂ1); , Mꢂ1 cmꢂ1)): 296 (33783); 1479; UV/Vis (solid): lmax
3 :
317 nm; Emission (solid): 420, 442, 456, 483 nm (lex 317 nm).
4.2.3. Synthesis of compound 11
Although, the FT-IR spectrum showed peak for OH group, in 1H
NMR spectrum the peak due to OH proton could not be observed.
In a 50 mL two-necked round bottomed flask, (2-formylphenyl)
mercury(II) bromide 10 (0.200 g, 0.52 mmol) was taken and 12 mL of
absolute ethanol was added. The reaction mixture was refluxed to
give a clear solution. To this clear solution, an ethanolic solution
(6 mL) of aniline (0.048 g, 0.52 mmol) was added drop-wise over
a period of 8 min. After complete addition of the amine solution, the
resulting clear solution was refluxed with stirring, at w100 ꢀC for
48 h. Then the volume of the pale yellowish solution was reduced
and kept at room temperature. The off-white crystalline product
was collected by filtration, washed with small amount of ethanol,
dried under vacuum (0.16 g, 66% yield). M.p 140e142 ꢀC. Anal. Calcd
for C13H10BrHgN: C, 33.89; H, 2.19; N, 3.04. Found: C, 34.22; H, 1.70;
N, 3.37; FT-IR (KBr) 3047, 2923,1621,1583,1557,1526,1185, 765, 714,
4.2.6. Synthesis of compound 14
In a 50 mL, two-necked round bottomed flask, fitted with
condenser, hydroxylamine hydrochloride (0.049 g, 0.70 mmol) and
NaOH (0.028 g, 0.70 mmol) were taken and dissolved in 5 mL of
methanol by stirring at room temperature. This solution was added
to a vigorously stirred, methanolic (12 mL) suspension of (2-
formylphenyl)mercury(II) bromide (0.275 g, 0.71 mmol). The stir-
ring was continued for 4 h at room temperature. The resulting pale
yellowish solution was filtered and the solvent was removed
completely under reduced pressure. The off-white solid was thor-
oughly washed with distilled water and dried under vacuum
(0.26 g, 91% yield). M.p. 182e185 ꢀC. Anal. Calcd for C7H6BrHgNO: C,
20.98; H, 1.50; N, 3.49. Found: C, 21.63; H, 0.98; N, 2.92; FT-IR (KBr)
686 cmꢂ1
;
1H NMR (400 MHz, CDCl3)
160.8, 150.9, 148.6, 140.4, 137.8,
d 8.77 (s, 1H), 7.63e7.28 (m,
9H); 13C NMR (400 MHz, CDCl3)
d
133.9, 133.1, 129.6, 129.3, 127.4, 121.7; ES-MS m/z (relative intensity,
nature of peak) 461.8 (100, [M þ 1]þ); UVeVis (dichloromethane,
3397, 1651, 1464, 1440, 1300, 1206, 960, 883, 754 cmꢂ1
;
1H NMR
(400 MHz, CDCl3) 8.21 (s, 1H), 8.16 (br, 1H), 7.47e7.7.43 (m, 1H),
d
lmax nm (cmꢂ1);
3
, Mꢂ1 cmꢂ1): 299 (33444); 11473; UV/Vis (solid):
7.39e7.27 (m, 3H); ES-MS m/z (relative intensity, nature of peak)
400.9 (65, [M]þ, 383.9 (30, [M e OH]þ); UVeVis (dichloromethane,
lmax: 387 nm; Emission (solid): 442, 483, 765 nm (lex 387 nm).
lmax nm (cmꢂ1); , Mꢂ1 cmꢂ1)): 301 (33222); 2063; UV/Vis (solid):
3
4.2.4. Synthesis of compound 12
lmax: 309 nm; Emission (solid): 421, 445, 483, 520 nm (lex 309 nm).
A 50 mL two-necked flask was charged with (2-formylphenyl)
mercury(II) bromide (0.200 g, 0.52 mmol) in 12 mL of absolute
ethanol. To this solution, an ethanolic solution (5 mL) of N, N-
dimethylethylenediamine (0.046 g, 0.52 mmol) was added drop-
wise over a period of 8 min with vigorous stirring. After complete
addition of the amine solution, the resulting colorless solution was
refluxed at 100 ꢀC for 28 h. The pale yellow solution obtained was
reduced under vacuum and kept at room temperature for crystal-
lization. The resulting microcrystalline solid was collected by
filtration, washed with ethanol and dried under vacuum (0.14 g,
61% yield). M.p 144e146 ꢀC. Anal. Calcd for C11H15BrHgN2: C, 28.99;
H, 3.32; N, 6.15. Found: C, 29.27; H, 2.50; N, 6.85; FT-IR (KBr) 3051,
4.2.7. Synthesis of compound 15
To a 50 mL two-neckedflaskcontaining 14 mLof absolute ethanol
at 70 ꢀC, (2-formylphenyl)mercury(II) bromide (0.22 g, 0.57 mmol)
was added. To the colorless solution, an ethanolic solution (5 mL) of
ethylenediamine (0.017 g, 0.28 mmol) was added drop-wise for
a period of 5 min. After complete addition of the amine solution, the
reaction mixture was refluxed 5 h. Then the reaction mixture was
filtered hot, washed with hot ethanol and dried under vacuum to
obtain 15 as white solid (0.156 g, 69% yield). M.p. 263e264 ꢀC. Anal.
Calcd for C16H14Br2Hg2N2: C, 24.16; H, 1.77; N, 3.52. Found: C, 24.50;
H,1.36; N, 4.02; FT-IR (KBr) 2924, 2877, 2848,1644, 1213, 1031, 1019,
2971, 2940, 2857, 1642, 1459, 1212, 1039, 758 cmꢂ1
;
1H NMR
752, 715 cmꢂ1; 1H NMR (400 MHz, CDCl3)
d 8.64 (s, 2H), 7.55e7.38
(400 MHz, CDCl3)
d
8.49 (s, 1H), 7.49e7.37 (m, 4H), 3.82 (t,
(m, 8H), 4.21 (s, 4H); ES-MS m/z (relative intensity, nature of peak)
J ¼ 5.5 Hz, 2H), 2.80 (t, J ¼ 5.4 Hz, 2H), 2.30 (s, 6H); 13C NMR
(400 MHz, CDCl3, ppm) 163.9, 163.7, 150.1, 140.1, 137.4, 132.4, 128.8,
59.2, 57.9, 45.6; ES-MS m/z (relative intensity, nature of peak) 456.9
347.1 (44, [M þ 1H e C7H5Br2Hg]þ; UVeVis (dichloromethane, lmax
nm (cmꢂ1); , Mꢂ1 cmꢂ1)): 300 (33333); 2300; UV/Vis (solid): lmax
3 :
302 nm; Emission (solid): 396, 465, 489, 527 nm (lex 302 nm).
(100, [M þ 1]þ); UVeVis (dichloromethane, lmax nm (cmꢂ1);
3,
Mꢂ1 cmꢂ1): 298 (33557); 1909; UV/Vis (solid): lmax: 329 nm;
Emission (solid): 421, 446, 457, 483 nm (lex 329 nm).
4.2.8. Synthesis of compound 16
To a 50 mL two-necked flask charged with 12 mL of absolute
ethanol at 70 ꢀC, (2-formylphenyl)mercury(II) bromide (0.20 g,
0.52 mmol) was added and dissolved to obtain a clear solution. To
this colorless solution, an ethanolic solution (5 mL) of trans-1,2-
diaminocyclohexane (0.029 g, 0.26 mmol) was added drop-wise
4.2.5. Synthesis of compound 13
In a two-necked 50 mL round bottomed flask containing 12 mL of
absolute ethanol, was added (2-formylphenyl)mercury(II) bromide