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A. Khan et al. / Journal of Organometallic Chemistry 776 (2015) 180e191
sequentially with (15 mL) 1.0 M NaOH, water and brine solution.
The organic layer was dried over anhydrous MgSO4 and removal of
solvent under reduced pressure afforded a white coloured solid.
NMR data (1H, 13C) obtained is essentially the same as reported in
literature [29]. Yield ¼ 4.7 g (89%).
distannane (Ph3SnSnPh3) produced as a side-product and unreac-
ted 2 were separated from 6 by sublimation (130 ꢂC for 4 h). The
product (a sticky semi-solid) was further purified to remove the
trace distannane (Ph3SnSnPh3) by dissolving in Et2O followed by
filtration. The removal of residual solvent under reduced pressure
afforded a white coloured powder. NMR data (1H, 13C, 119Sn) ob-
tained is essentially the same as previously reported by Molloy et al.
[3]. Yield: 5.1 g (70%).
1H NMR (400 MHz, CDCl3, d): 6.82e6.88 (m, 4H, C6H4), 6.06 (m,
1H, ¼CH), 5.41 (dq, 1H, cis-CH, 1J ¼ 17 Hz), 5.28 (dq, 1H, trans-CH,
1J ¼ 10.5 Hz, 2J ¼ 3J ¼ 1.5 Hz), 4.49 (dd, 2H, eOCH2, 1J ¼ 5.3 Hz,
2J ¼ 3J ¼ 1.5 Hz), 3.77 (s, 3H, eOCH3) ppm; 13C NMR (100 MHz,
1H NMR (400 MHz, CDCl3,
d): 7.55 (m, 6H, o-C6H5Sn), 7.46 (m,
CDCl3,
d
): 153.9 (p-C6H4O), 152.8 (i-C6H4O), 133.6 (¼CH), 117.5
2H, o-C6H5), 7.40 (m, 3H, m, p-C6H5), 7.37 (m, 9H, m, p-C6H5Sn), 7.30
(d, 2H, m-C6H4O), 6.85 (dd, 2H, o-C6H4O), 4.02 (t, 2H, eCH2O), 2.26
(m, 2H, eCH2CH2CH2), 1.67 (t, 2H, eCH2Sn) ppm; 13C NMR
(¼CH2), 115.8 (o-C6H4), 114.6 (m-C6H4), 69.6 (eOCH2), 55.7 (eOCH3)
ppm.
(100 MHz, CDCl3, d): 158.6 (i-C6H4), 141.0 (i-C6H4), 138.8 (i-C6H5Sn),
Synthesis of 1-allyloxy-3-trifluoromethylbenzene (4)
137.4 (p-C6H5), 137.2 (o-C6H5Sn, 2J117Sn-13C ¼ 35 Hz), 133.2 (i-C6H5),
4
129.0 (p-C6H5Sn, J117Sn-13C ¼ 11 Hz), 128.8 (m-C6H5), 128.7 (m-
Allyl bromide (1.49 g,12.3 mmol), K2CO3 (3.41 g, 24.7 mmol) was
C6H5Sn, 3J117Sn-13C ¼ 49 Hz), 128.2 (o-C6H5), 126.9 (m-C6H4O), 114.9
(o-C6H4O), 70.8 (eCH2O), 26.2 (-CH2CH2Sn), 7.06 (-CH2Sn) ppm;
added to
a solution of 3-(trifluoromethyl)phenol (2.00 g,
12.3 mmol) in 50 mL of acetone in a 250 mL round bottom flask and
refluxed for 16 h. The reaction mixture was then filtered and the
solvent removed under reduced pressure. The residue was dis-
solved in 50 mL of DCM and washed sequentially with (15 mL)
1.0 M NaOH, water and brine solution. The organic layer was dried
over anhydrous MgSO4, and solvent removed under reduced pres-
sure. The product was recovered as a yellow oil. NMR data (1H, 13C,
19F) is essentially the same as reported in the literature [30,31].
Yield ¼ 2.34 g (94%).
119Sn{1H}NMR (149.21 MHz, CDCl3,
d): -99.3 ppm.
Synthesis of triphenyl [3-(4-methoxyphenyloxy) propyl] tin (7)
Compound 3 (0.50 g, 3.05 mmol), Ph3SnH (1.03 g, 2.93 mmol)
and AIBN (0.02 g, 0.36 mmol) were heated at 120 ꢂC in a sealed
Schlenk flask for 1 h under dynamic N2. The crude product was
sublimed to remove the Ph3SnSnPh3 side-product and further pu-
rified by silica gel column chromatograph using hexane:EtOAc
(6:1). Yield 0.98 g (65%).
1H NMR (400 MHz, CDCl3, d): 7.40 (t, 1H, m-C6H4O), 7.22 (d, 1H,
p-C6H4O), 7.15 (br s, 1H, o-C6H4CF3), 7.10 (dd, 1H, o-C6H4O), 6.06 (m,
1H, ¼CH), 5.44 (qd, 1H, cis-CH), 5.32 (qd, 1H, trans-CH), 4.59 (m, 2H,
1H NMR (400 MHz, CDCl3,
d): 7.49e7.61 (m, 6H, o-C6H5Sn), 7.36-
eOCH2) ppm; 13C NMR (100 MHz, CDCl3,
d
): 158.8 (s, i-C6H4O),
7.38 (m, 9H, m, p-C6H5Sn), 6.71-80 (m, 4H, eC6H4), 3.90 (t, 2H,
132.7 (s, ¼CH), 131.9 (q, i-C6H4CF3, 2J13Ce19F ¼ 30 Hz), 130.0 (s, m-
eOCH2, 1J ¼ 6.2 Hz), 3.76 (s, 3H, eOCH3), 2.18 (tt, 2H, eCH2CH2CH2),
C6H4O), 124.1 (q, CF3, 1J13Ce19F ¼ 272 Hz), 118.4 (q, o-C6H4O,
1.64 (t, 2H, eCH2Sn, J ¼ 8.0 Hz) ppm; 13C NMR (100 MHz, CDCl3,
d):
4J13Ce19F
¼
1.5 Hz), 118.3 (s, ¼CH2), 117.6 (q, p-C6H4CF3,
153.9 (p-C6H4O), 153.2 (i-C6H4O), 138.9 (i-C6H5, 1J119Sn-13C ¼ 490 Hz,
2J13Ce19F ¼ 4.0 Hz), 111.7 (q, o-C6H4CF3, 2J13Ce19F ¼ 4.0 Hz), 69.2 (s,
1J117Sn-13C ¼ 468 Hz), 137.2 (m-C6H5, J119Sn-13C ¼ 35 Hz), 129.0 (p-
3
eCH2O), ppm; 19F NMR (376 MHz, CDCl3,
d
): -62.7 ppm.
C6H5, J119Sn-13C ¼ 11 Hz), 128.7 (o-C6H5, J119Sn-13C ¼ 48 Hz) 115.6
(o-C6H4O), 114.7 (m-C6H4O), 71.4 (eOCH2, 3J119Sn-13C ¼ 68 Hz), 55.9
4
2
2
Synthesis of triphenyl (3-phenyloxy)propyl tin (5)
(eOCH3), 26.5 (eCH2CH2Sn, J119Sn-13C ¼ 20 Hz), 7.09 (eCH2Sn,
1J119Sn-13C ¼ 392 Hz, J117Sn-13C ¼ 375 Hz) ppm; 119Sn{1H}NMR
1
Compound 1 (2.0 g, 14.3 mmol) and Ph3SnH (4.24 g, 7.45 mmol)
were heated with AIBN (0.05 g, 0.913 mmol) in a dried 100 mL
Schlenk flask at 140 ꢂC for 1 h. The reaction mixture was allowed to
cool to room temperature, which resulted in formation of a white
coloured gum. The distannane (Ph3SnSnPh3) byproduct was
precipitated from the mixture by adding hexane to the crude
product and subsequently removed by filtration. Unreacted 1 was
removed by heating under reduced pressure at 75 ꢂC which affor-
ded a colourless, highly viscous oil of 5. Yield: 5.68 g (79%).
(149.21 MHz, CDCl3,
d
): ꢁ99.3 ppm. Found: C, 64.39; H, 4.62. Calc.
for C28H28O2Sn: C, 65.27, H, 4.48%.
Synthesis of triphenyl [3-(3-trifluromethylphenyloxy) propyl] tin (8)
Compound 4 (1.0 g, 4.95 mmol), Ph3SnH (1.69 g, 4.83 mmol) and
AIBN (0.055 g, 0.99 mmol) were heated at 120 ꢂC for 1 h in a 50 mL
Schlenk flask. The crude product was washed with 2 ꢀ 5 mL of
MeOH to remove unreacted 4. The residue was then dissolved in
MeOH and after decanting the solvent removed under reduced
pressure. The product 8 was recovered as a white coloured powder
and recrystallized in MeOH:DCM. Yield: 2.13 g (79%) m.p. 60e65 ꢂC.
1H NMR (400 MHz, CDCl3,
d): 7.64 (m, 6H, o-C6H5Sn), 7.43 (m,
9H, m, p-C6H5Sn), 7.31 (m, 2H, m-C6H5O), 6.99 (t, 1H, p-C6H5O), 6.88
(d, 2H, o-C6H5O), 4.03 (t, 2H, eCH2O), 2.29 (m, 2H, eCH2CH2CH2),
1.71 (t, 2H, eCH2Sn) ppm; 13C NMR (100 MHz, CDCl3,
d): 159.0 (i-
C6H5O), 138.7 (i-C6H5Sn, 1J119Sn-13C ¼ 488 Hz, 1J117Sn-13C ¼ 468 Hz),
1H NMR (400 MHz, CDCl3,
d): 7.52-7.56 (m, 6H, o-C6H5Sn),
2
137.0 (o-C6H5Sn, J119Sn-13C ¼ 36 Hz), 129.4 (m-C6H5O), 128.9 (p-
7.33e7.37 (m, 9H, m,p-C6H5Sn), 7.30 (t, 1H, m-C6H4O, J ¼ 8.0 Hz),
7.15 (m, 1H, p-C6H4O), 6.98 (s, 1H, o-C6H4CF3); 6.90 (dd, 1H, o-
C6H4O, J ¼ 7.6 Hz, J ¼ 2.4 Hz), 3.96 (t, 2H, eOCH2, J ¼ 6.4 Hz), 2.22 (tt,
4
3
C6H5Sn, J119Sn-13C ¼ 11 Hz), 128.5 (m-C6H5Sn, J119Sn-13C ¼ 49 Hz),
120.6 (p-C6H5O), 114.6 (o-C6H5O), 70.5 (-CH2O), 26.4 (eCH2CH2Sn,
2J119Sn-13C ¼ 19 Hz), 6.93 (eCH2Sn, J119Sn-13C ¼ 388 Hz, J117Sn-
2H, eCH2CH2CH2), 1.63 (t, 2H, eCH2Sn,
J
J
¼
8.0 Hz,
d): 159.1 (i-
1
1
¼ 372 Hz) ppm; 119Sn{1H}NMR (149 MHz, CDCl3,
d
): -99.9 ppm.
119Sne1H ¼ 57 Hz) ppm; 13C NMR (100 MHz, CDCl3,
13C
Found: C, 66.64; H, 5.47. Calc. for C27H26OSn: C, 66.84, H, 5.40%.
C6H4O), 138.7 (i-C6H5Sn), 137.7 (o-C6H4CF3), 137.4 (i-C6H4CF3), 137.1
3
(m-C6H5Sn, J119Sn-13C ¼ 36.2), 129.9 (m-C6H4O), 129.1 (p-C6H5Sn,
2
Synthesis of triphenyl[3-(4-biphenyloxy)propyl]tin (6)
4J119Sn-13C ¼ 11 Hz), 128.7 (o-C6H5Sn, J119Sn-13C ¼ 50 Hz), 118.1 (q,
eCF3, J13Ce19F ¼ 1.5 Hz), 117.3 (d, p-C6H4O, J13Ce19F ¼ 4.0 Hz), 111.4
(d, o-C6H4O, J13Ce19F ¼ 4.0 Hz), 70.8 (eOCH2), 26.3 (eCH2CH2Sn),
Compound 2 (2.78 g, 13.22 mmol) and Ph3SnH (4.64 g,
13.18 mmol) were heated with AIBN (0.16 g, 0.973 mmol) in a dried
100 mL Schlenk flask at 140 ꢂC under inert atmosphere. The reac-
tion mixture was allowed to cool to room temperature. The
7.06 (eCH2Sn) ppm; 19F NMR (376 MHz, CDCl3,
d): -62.7 (s, CF3)
ppm; 119Sn{1H}NMR (149.21 MHz, CDCl3, d): ꢁ100.0 ppm. Found: C,
60.38, H, 4.55. Calc. for C27H26OSn: C, 60.79, H, 4.56%.