JOURNAL OF CHEMICAL RESEARCH 2015 615
solid product, which was washed with petroleum ether (30–60 °C)
(2 × 5 mL), and dried in a vacuum to afford 3.14 g of 4-formyl-N-(3-
triethoxysilylpropyl)benzamide as a light yellow solid; 89% yield; m.p.
54–57 °C. IR (KBr): 2974, 2927, 2887, 1638, 1547, 1443, 1390, 1102,
1077, 958, 789 cm-1; 1H NMR (400 MHz, CDCl3): δ 10.5 (s, 1H), 7.82
(d, J = 8.0 Hz, 2H), 7.63 (d, J = 8.0 Hz, 2H), 6.65 (br, 1H), 3.81 (q, J =
6.4 Hz, 6H), 3.52–3.43 (m, 2H), 1.81–1.72 (m, 2H), 1.22 (t, J = 6.4 Hz,
9H), 0.71 (t, J = 7.6 Hz, 2H). Anal. calcd for C17H27NO5Si: C, 57.76; H,
7.70; N, 3.96; found: C, 57.39; H, 7.41; N, 3.58%.
4-Cyanophenyl phenyl sulfide (3e): Oil.47 IR (neat): 3065, 2219,
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1589, 1484, 692 cm-1; H NMR (400 MHz, CDCl3): δ 7.57–7.42 (m,
7H), 7.22–7.18 (m, 2H); 13C NMR (100 MHz, CDCl3): δ 145.7, 134.5,
132.4, 130.9, 129.9, 129.4, 127.4, 118.8, 108.8.
4-Nitrophenyl phenyl sulfide (3f): Yellow solid; m.p. 55–56 °C (lit.46
54–55 °C). IR (KBr): 3062, 1575, 1512, 1475, 1334, 857, 691 cm-1;
1H NMR (400 MHz, CDCl3): δ 8.05 (d, J = 8.8 Hz, 2H), 7.55–7.53 (m,
2H), 7.46–7.44 (m, 3H), 7.16 (t, J = 7.6 Hz, 2H); 13C NMR (100 MHz,
CDCl3): δ 148.5, 145.4, 135.1, 130.9, 130.5, 130.1, 127.1, 124.1.
4-Methoxyphenyl 4-methylphenyl sulfide (3g): White solid; m.p.
44–45 °C (lit.47 45–46 °C). IR (KBr): 3075, 3036, 2945, 2812, 1589,
1476, 1109, 691 cm-1;1H NMR (400 MHz, CDCl3): δ 7.36 (d, J = 8.4
Hz, 2H), 7.13 (d, J = 8.0 Hz, 2H), 7.06 (d, J = 8.4 Hz, 2H), 6.86 (d, J =
8.0 Hz, 2H), 3.81 (s, 3H), 2.30 (s, 3H); 13C NMR (100 MHz, CDCl3): δ
159.5, 136.1, 134.3, 129.8, 129.4, 126.3, 125.7, 114.9, 55.4, 21.0.
4-Acetylphenyl 4-methylphenyl sulfide (3h): White solid; m.p.
70–71 °C. IR (KBr): 3062, 2928, 2834, 1681, 1594, 1489, 692 cm-1;
1H NMR (400 MHz, CDCl3): δ 7.79 (d, J = 8.0 Hz, 2H), 7.41 (d,
J = 8.0 Hz, 2H), 7.22 (d, J = 8.0 Hz, 2H), 7.15 (d, J = 8.0 Hz, 2H), 2.54
(s, 3H), 2.39 (s, 3H); 13C NMR (100 MHz, CDCl3): δ 197.1, 145.9,
139.3, 134.5, 134.2, 130.5, 128.8, 128.0, 126.7, 26.4, 21.3. Anal. calcd
for C15H14OS: C, 74.34; H, 5.82; found: C, 74.19; H, 5.54%.
Synthesis of formyl-functionalised MCM-41(MCM-41-CHO)
A solution of 3.05 g of 4-formyl-N-(3-triethoxysilylpropyl)benzamide
in 16 mL of dry chloroform was added to a suspension of 2.6 g of the
MCM-41 in 160 mL of dry toluene. The mixture was stirred at 100 °C
under Ar for 24 h. Then the solid was filtered off and washed by CHCl3
(2 × 20 mL) and dried in a vacuum at 160 °C for 5 h to give 3.88 g of
white solid product (MCM-41-CHO). The nitrogen content was found
to be 1.28 mmol g-1 by elemental analysis.
Synthesis of tridentate hydroxy-functionalised MCM-41(MCM-41-3OH)
A mixture of MCM-41-CHO (2.16 g), 2-amino-2-(hydroxymethyl)
propane-1,3-diol (0.43 g, 3.5 mmol) in dry ethanol (12 mL) was stirred
at 30 °C under Ar for 48 h. The solid product was filtered, washed with
ethanol (3 × 20 mL) and diethyl ether (20 mL), and dried in a vacuum
at 120 °C for 5 h to obtain 2.31 g of hybrid material MCM-41-3OH. The
nitrogen content was found to be 1.97 mmol g-1 by elemental analysis.
4-Acetylphenyl 4-chlorophenyl sulfide (3i): White solid; m.p.
83–84 °C. IR (KBr): 3057, 3019, 2919, 2825, 1680, 1498 cm-1; 1H NMR
(400 MHz, CDCl3): δ 7.83 (d, J = 8.4 Hz, 2H), 7.42–7.35 (m, 4H), 7.22
(d, J = 8.4 Hz, 2H) 2.55 (s, 3H); 13C NMR (100 MHz, CDCl3): δ 197.0,
144.0, 135.1, 134.8, 131.0, 129.9, 129.0, 128.7, 127.8, 26.4. Anal. calcd
for C14H11OSCl: C, 63.98; H, 4.22; found: C, 63.72; H, 4.35%.
4-Cyanophenyl 4-methylphenyl sulfide (3j): White solid; m.p.
68–69 °C. IR (KBr): 3058, 2924, 2216, 1589, 1496, 695 cm-1; 1H NMR
(400 MHz, CDCl3): δ 7.46–7.40 (m, 4H), 7.24 (d, J = 8.0 Hz, 2H), 7.12
(d, J = 8.0 Hz, 2H), 2.40 (s, 3H); 13C NMR (100 MHz, CDCl3): δ 146.6,
139.9, 134.9, 132.3, 130.8, 126.9, 126.8, 118.9, 108.4, 21.3. Anal. calcd
for C14H11NS: C, 74.63; H, 4.92; N, 6.21; found: C, 74.36; H, 4.69; N,
6.38%.
4-Chlorophenyl 4-cyanophenyl sulfide (3k): White solid; m.p.
88–89 °C (lit.46 90–91 °C). IR (KBr): 3032, 2223, 1578, 1494, 691 cm-1;
1H NMR (400 MHz, CDCl3): δ 7.50 (d, J = 8.4 Hz, 2H), 7.45–7.39 (m,
4H), 7.17 (d, J = 8.4 Hz, 2H); 13C NMR (100 MHz, CDCl3): δ 144.9,
135.7, 132.5, 130.2, 129.6, 127.6, 118.6, 109.2.
4-Methylphenyl 4-nitrophenyl sulfide (3l): Yellow solid; m.p.
80–81 °C (lit.48 81–82 °C). IR (KBr): 3032, 2926, 1578, 1517, 1497,
1336, 691 cm-1; 1H NMR (400 MHz, CDCl3): δ 8.02 (d, J = 8.8 Hz, 2H),
7.42 (d, J = 8.8 Hz, 2H), 7.27 (d, J = 8.0 Hz, 2H), 7.13 (d, J = 8.0 Hz,
2H), 2.42 (s, 3H); 13C NMR (100 MHz, CDCl3): δ 148.8, 144.7, 139.7,
134.6, 130.4, 126.1, 125.7, 123.5, 20.8.
Synthesis of tridentate hydroxy-functionalised MCM-41-supported
copper catalyst (MCM-41-3OH-CuI)
In a small Schlenk tube, 1.50 g of the above-functionalised MCM-41
(MCM-41-3OH) was mixed with 0.18 g (0.94 mmol) of CuI in 15 mL
of dry DMF. The mixture was stirred at room temperature for 7 h
under an argon atmosphere. The solid product was filtered by suction,
washed with DMF and acetone and dried at 40 °C/26.7 Pa under Ar
for 5 h to give 1.51 g of a pale blue copper complex (MCM-41-3OH-
CuI). The nitrogen and copper contents were found to be 1.76 and
0.51 mmol g-1, respectively.
Heterogeneous copper-catalysed coupling reaction of aryl iodides
with thiols; typical procedure
A mixture of aryl iodide (0.5 mmol), aromatic thiol (0.6 mmol), MCM-
41-3OH-CuI (0.05 mmol), Cs2CO3 (1.0 mmol) in DMF (0.2 mL),
and dioxane (1.8 mL) was stirred at 110 °C under Ar for 24 h. After
completion of the reaction, the reaction mixture was cooled to room
temperature, diluted with ethyl acetate (5 mL) and filtered. The MCM-
41-3OH-CuI complex was washed with distilled water (2 × 5 mL),
ethanol (2 × 5 mL) and Et2O (2 × 5 mL), and reused in the next run.
The filtrate was concentrated at 50 °C under reduced pressure and the
residue was purified by flash column chromatography on silica gel
(petroleum ether (30–60 °C)/ethyl acetate = 30:1 to 60:1) to provide
the desired product.
4-Chlorophenyl 4-nitrophenyl sulfide (3m): Yellow solid; m.p.
86–87 °C (lit.48 87–88 °C). IR (KBr): 3064, 1593, 1514, 1487, 1335,
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690 cm-1; H NMR (400 MHz, CDCl3): δ 8.08 (d, J = 8.8 Hz, 2H),
7.48–7.41 (m, 4H), 7.19 (d, J = 8.4 Hz, 2H); 13C NMR (100 MHz,
CDCl3): δ 147.6, 145.7, 136.0, 135.8, 130.2, 129.2, 127.0, 124.2.
2-Methoxyphenyl phenyl sulfide (3n): Oil.21 IR (neat): 3064, 3035,
Diphenyl sulfide (3a): Oil.21 IR (neat): 1580, 1476, 1438, 738,
690 cm-1; 1H NMR (400 MHz, CDCl3): δ 7.35–7.20 (m, 10H); 13C NMR
(100 MHz, CDCl3): δ 136.2, 131.5, 129.6, 127.5.
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2943, 2813, 1557, 1478, 1106 cm-1; H NMR (400 MHz, CDCl3): δ
4-Methoxyphenyl phenyl sulfide (3b): Oil.21 IR (neat): 3085, 3042,
2942, 2802, 1587, 1474, 1108, 690 cm-1; 1H NMR (400 MHz, CDCl3):
δ 7.41 (d, J = 8.4 Hz, 2H), 7.25–7.11 (m, 5H), 6.89 (d, J = 8.8 Hz, 2H),
3.81 (s, 3H); 13C NMR (100 MHz, CDCl3): δ 159.9, 138.6, 135.4, 128.9,
128.3, 125.8, 124.4, 115.0, 55.4.
7.36–7.22 (m, 6H), 7.09 (d, J = 7.6 Hz, 1H), 6.92-6.85 (m, 2H), 3.86 (s,
3H); 13C NMR (100 MHz, CDCl3): δ 157.4, 134.6, 131.7, 131.5, 129.0,
128.4, 127.1, 124.1, 121.3, 110.9, 55.9.
2-Methoxyphenyl 4-methylphenyl sulfide (3o): Oil. IR (neat): 3056,
3023, 2956, 2826, 1587, 1494, 1109 cm-1; 1H NMR (400 MHz, CDCl3):
δ 7.31 (d, J = 8.0 Hz, 2H), 7.17–7.13 (m, 3H), 6.94 (d, J = 7.6 Hz, 1H),
6.89–6.83 (m, 2H), 3.89 (s, 3H), 2.35 (s, 3H); 13C NMR (100 MHz,
CDCl3): δ 159.5, 136.1, 134.3, 129.8, 129.4, 128.6, 127.3, 126.9, 125.7,
114.9, 55.4, 21.0. Anal. calcd for C14H14OS: C, 73.00 H, 6.13; found: C,
72.74; H, 5.87%.
2-Methylphenyl 4-methylphenyl sulfide (3p): Oil.49 IR (neat): 3065,
3027, 2937, 2856, 1579, 1487 cm-1; 1H NMR (400 MHz, CDCl3): δ 7.28
(d, J = 8.4 Hz, 2H), 7.15–7.11 (m, 4H), 7.07–6.98 (m, 2H), 2.32 (s, 3H),
2.29 (s, 3H); 13C NMR (100 MHz, CDCl3): δ 138.7, 137.3, 136.4, 132.2,
131.5, 130.4, 130.2, 128.7, 127.2, 127.1, 21.3, 21.1.
4-Methylphenyl phenyl sulfide (3c): Oil.46 IR (neat): 3050, 2930,
1590, 1490, 1440, 740, 690 cm-1; 1H NMR (400 MHz, CDCl3): δ
7.45–6.92 (m, 9H), 2.26 (s, 3H); 13C NMR (100 MHz, CDCl3): δ 137.5,
137.0, 132.1, 131.2, 130.1, 129.7, 128.9, 128.3, 21.1.
4-Acetylphenyl phenyl sulfide (3d): White solid; m.p. 65–66 °C (lit.10
66–67 °C). IR (KBr): 3060, 3012, 2942, 2910, 2821, 1680, 1594, 1487,
692 cm-1; 1H NMR (400 MHz, CDCl3): δ 7.80 (d, J = 8.4 Hz, 2H), 7.48
(d, J = 8.4 Hz, 2H), 7.40–7.36 (m, 3H), 7.20 (d, J = 8.4 Hz, 2H), 2.53 (s,
3H); 13C NMR (100 MHz, CDCl3): δ 197.1, 144.9, 134.5, 133.9, 132.2,
129.7, 128.8, 128.7, 127.5, 26.5.