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New Journal of Chemistry
Page 2 of 10
DOI: 10.1039/D0NJ00345J
ARTICLE
Journal Name
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plentiful three-dimensional (3D) porous construction, and ultra-low 2.3. General procedure for the cross-coupling of aniline with aryl
density 33,34
halides
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Due to the importance of the aerogel catalysts prepared by the SCD In a round-bottomed flask equipped with a magnetic stirrer, aryl
method and the resulted diphenylamines, we aim to prepare a halide (1 mmol), aniline (1.2 mmol), catalyst (3 mg, NiO-CuO-
nanoporous structure by the sol-gel method and CO2 supercritical CoO/SiO2 nanocomposite aerogels) and KOH (3 mmol) were stirred
drying (SCD) technique for the construction of NiO-CuO-CoO/SiO2 in 5 mL DMF under air atmosphere at 130 oC. The progress of the
nanocomposite aerogels. In addition, the catalysis performance of reaction was monitored by Thin-layer chromatography (TLC). After
this nanocomposite in the reaction of C–N bond formation has been completion of the reaction, ethyl acetate (15 ml) was added and the
studied. Therefore, NiO-CuO-CoO/SiO2 nanocomposite aerogel is catalyst was separated by filtration. The organic layer was washed
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an encouraging catalyst for the synthesis of diphenylamines.
2. Experimental
2.1. Materials and apparatus
All the commercially available reagents were purchased from Merck further use.
and Sigma-Aldrich Chemical Company in high purity. All the
reagents were used without any further purification. If needed, the 4-(Phenylamino)benzonitrile (3a);Yellow solid; m.p.: 97-98 C (Lit.
products were purified via a thin-layer chromatography process to m.p 97-98 oC) 35; IR (KBr) ʋ = 3375, 3086, 3035, 2221, 1590, 745, 1
obtain the corresponding products in 69-98% yields. Hydrogen-1 H NMR (400 MHz, CDCl3) δ 7.43 (d, J= 8.5 Hz, 2H), 7.31 (t, J=
nuclear magnetic resonance (1H NMR) spectra were recorded in 8.5 Hz, 2H), 7.11 (d, J= 8.5 Hz, 2H), 6.96 (t, J= 8.5 Hz, 1H), 6.82
CDCl3 on a Bruker DRX-400 spectrometer with tetramethylsilane (d, J= 8.5 Hz, 2H), 5.96 (br, 1H).
with water (3 × 10 ml) and dried over anhydrous Na2SO4. The
product was isolated by column chromatography. The recovered
catalyst was washed with ethanol and water and dried at 80 C for
o
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(TMS) as an internal reference. IR spectra were recorded as KBr
o
pellets on a Nicolet FT-IR spectrophotometer. A BANDELIN 4-Nitro-N-phenylaniline (3b); Orange solid; m.p.: 133-135 C (Lit.
ultrasonic HD 3200 with probe model KE76, with a diameter of 6 m.p 133-134 C) 36; IR (KBr) ʋ = 3380, 3099, 3029, 1954, 1594,
o
mm, was used for homogenizing the reaction mixture. Melting 1517, 1313, 741, 1 H NMR (400 MHz, CDCl3) δ 8.3 (d, J= 8.5 Hz,
points were measured by Yanagimoto micro melting point 2H), 7.40 (t, J= 8.5 Hz, 2H), 7.14-7.23 (m, 3H), 6.95 (d, J= 8.5 Hz,
equipment. XRD patterns were reported by an X'Pert Pro (Philips) 2H), 6.28 (br, 1H).
apparatus with 1.54 Ångström wavelengths of the X-ray beam and
Cu anode material. Nitrogen adsorption-desorption isotherms were 4-Bromo-N-phenylaniline (3c); White solid; m.p.: 85-86 oC (Lit. m.p
estimated using a BELSORP-mini II apparatus (Microtrac BEL, 84-86 oC) 37; IR (KBr) ʋ =3390, 3059, 3020, 1931, 1581, 1078, 688,
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Japan) at 77 K. The specific surface area of the nanocomposite
aerogels samples was measured by the Brunauer-Emmett-Teller 5H), 5.72 (br, 1H).
(BET) method. The field emission scanning electron microscope
(FE-SEM) of nanoparticles was performed on Zeiss that operated at 1-(4-(Phenylamino)phenyl)ethan-1-one (3d); Yellow solid; m.p.: 94-
a 15 kV accelerating voltage.
2.2. General procedure for the preparation of nanocomposite 1591, 1495, 1266, 747, 1 H NMR (400 MHz, CDCl3) δ 7.55 (d, J=
H NMR (400 MHz, CDCl3) δ 7.29-7.35 (m, 4H), 7.13-7.22 (m,
95oC (Lit. m.p 93-95oC) 38; IR (KBr) ʋ = 3385, 3041, 2922, 1682,
aerogels
8.0 Hz, 2H), 7.35 (t, J= 8.0 Hz, 2H), 7.20 (d, J= 4.0 Hz, 2H), 7.11 (t,
To prepare Ni+2 ionic solution, Co+2 and Cu+2 were added to 1 mmol J= 8.0 Hz, 1H), 6.99 (d, J= 8.0 Hz, 2H), 6.22 (br, 1H), 2.52 (s, 3H).
of copper (II) chloride, nickel (II) chloride and cobalt (II) chloride
and were dispersed in 30 mL distilled water through sonication for Methyl 4-(Phenylamino)benzoate (3e); Yellow solid; m.p.: 110-
10 minutes.Then, the silica-sol was prepared by mixing tetraethyl 111oC (Lit. m.p 109-111oC) 39; IR (KBr) ʋ = 3390, 3035, 2951,
orthosilicate (TEOS), distilled water and ethanol in the mole ratio of 1720, 1592, 1516, 1111, 1282, 1 H NMR (400 MHz, CDCl3) δ 7.20
1:4:8 at 50 °C for 30 min. The ionic solution and silica-sol were then (t, J= 8.5 Hz, 2H), 6.87-6.92 (m, 7H), 5.74 (br, 1H), 3.85 (s, 3H).
combined in the mole ratio of 1:1 and the pH was set to 3.0 by
adding hydrochloric acid (HCl, 1.2 M) to silica-sol. The pH value of N1,N4-Diphenylbenzene-1,4-diamine (3f); white solid; m.p.: 152-
the combined solution was set to 11 by adding liquid ammonia 153 oC (Lit. m.p 152-154 C) 40; IR (KBr) ʋ =3380, 3034, 1506,
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(NH3, 2.5 M), after about a minute, the reaction container was placed 1517, 1462, 1315, 742, 1 H NMR (400 MHz, CDCl3) δ 7.37 (t, J=
in a constant environment. The reaction mixture became a composite 8.0 Hz, 4H), 7.16-7.22 (m, 8H), 7.11 (t, J= 12.0 Hz, 2H), 5.44 (br,
wet gel after 45 minutes. The wet gel was exchanged with ethanol 2H).
and then aged in ethanol solvent for 3 days to enhance gel firmness.
3-Chloro-N-phenylaniline (3g); Yellow Oil; IR (KBr) ʋ = 3392,
2.2.3. General procedure for CO2 supercritical drying (SCD) of 3058, 1596, 1478, 693, 1 H NMR (400 MHz, CDCl3) δ 8.69 (t, J=
NiO-CuO-CoO/SiO2 nanocomposite wet gels
12.0 Hz, 2H), 8.39 (t, J= 16.0 Hz, 1H), 7.55 (d, J= 8.5 Hz, 2H), 7.45
The wet gel exchanged with liquid CO2 was dried via cold SCD at (s, 1H), 7.37 (t, J= 8.5 Hz, 1H), 7.13-7.22 (m. 2H), 6.13 (br, 1H).
35 °C and 7.3 MPa for 3 h, followed by venting of CO2 gas for 24 h
to obtain nanocomposite aerogels. Then, the dried gel was heated to Diphenylamine (3h); White solid; m.p.: 52-53oC (Lit. m.p 52-53oC)
500 oC for 3 hours to stabilize the nanoparticles.
41; IR (KBr) ʋ = 3382, 3037, 1941, 1596, 1490, 1315, 745, 1 H NMR
(400 MHz, CDCl3) δ 7.36 (t, J= 8.5 Hz, 4H), 7.16 (d, J= 8.5 Hz,
4H), 7.03 (t, J= 8.5 Hz, 2H), 5.72 (br, 1H).
2 | J. Name., 2012, 00, 1-3
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