Z. Kiani et al.
Inorganic Chemistry Communications 130 (2021) 108696
2.3. The global method for the creation of DFNS/3-Chloropropyl NPs
The DFNS (3.0 g) was added to the solution of NaOH (50 mL, 0.5 M),
and refluxed for 3 h to boost hydrophilicity. The generated nanoparticles
were washed with H2O to neutralize the pH of the deionized H2O and
then vacuum-dried at 70 ◦C for 6 h. Next, 3-Chloropropyltrimethoxysi-
lane was supported on the DFNS outer layer to synthesis amino-
modified DFNS/3-Chloropropyl. A mixture of activated DFNS (3.0 g)
and 3-Chloropropyltrimethoxysilane (6.0 mL) was mixed in 100 mL
ethanol at 100 ◦C for 17 h. Finally, DFNS/3-Chloropropyl was filtered,
cleansed twice with deionized water, and dried at 80 ◦C for 10 h.
Scheme 1. The reduction of nitro groups using tmtppa-Zn/DFNS catalysts.
under transfer hydrogenation situations. However, these common
techniques require stoichiometric reducing agents, high pressure and
temperature, as well as the employment of hazardous reagents (e.g.,
hydrazine). Notably, a variety of these techniques suffer from the
absence of chemo selectivity compared to other functional groups that
are usually exist in the substrates like alkene, halide, and nitrile.
Moreover, the reduction of nitro-compounds often stops at an interme-
diate phase and results in the production of hydroxylamine, hydrazines,
and azoreans. The excessive significance of the selective reduction of
nitro-compounds has made the search for alternative techniques an
important goal in organic synthesis.
2.4. Synthesis of tmtppa-Zn complex
For the synthesis of tmtppa-Zn, urea (8 g), 2,3-Pyridinedicarboxylic
acid (4 g), ammonium heptamolybdate ((NH4)6Mo7O24⋅4H2O; 25 mg),
and Zn(OAc)2 (2 g) were mixed and a homogenous blend was obtained.
The blend was located in a heating mantle and warmed up under a
solvent-free situation at 160 ◦C for 15 h. The achieved rough dark-blue
solid was mangled, filtered, and cleansed with EtOH (15 mL), aqueous
NaOH blend (0.1 %w/v, 2.5 mL), H2O (6 mL), warm diluted aqueous
HCl (0.2 %v/v, 7.5 mL), and H2O (15 mL). The final product was dried at
70 ◦C.
Here, a 2D closely packed amide polyphthalocyaninezinc (tmtppa-
Zn) was synthesized employing a one-step solid-state technique. Catalyst
achieved by tmtppa-Zn supported on DFNS (tmtppa-Zn/DFNS) was
predicted to be highly active, sustainable, and potentially catalytic for
transfer hydrogenation of nitro-compounds to primary amines. A cata-
lytic reaction is an approach for the reduction of nitro groups under mild
reaction situations (Scheme 1).
2.5. The global method for the creation of tmtppa-Zn/DFNS NPs
The 3.0 g of DFNS/3-Chloropropyl was suspended in tmtppa-Zn (3.0
g). Then, tetrahydrofuran (50.0 mL) was released and the blend was
mixed at 75 ◦C for 20 h. Then, tmtppa-Zn/DFNS was added into
deionized water. EtOH mixture (5:5 v/v, 80 mL) consisted of 2-chloro-
acetic acid (3.0 g), and the reaction was done at r.t. for 2.5 h. After
isolating the solvent, the resulting mixture was filtered and vacuum-
dried at 50 ◦C.
2. Experimental
2.1. Materials and methods
High purity chemicals were purchased from Fluka and Merck.
Melting points were specified in the open capillaries employing the
Electrothermal 9100 apparatus and were not modified. Particle size and
structure of nanoparticles were perceived using a Philips CM10 Trans-
mission Electron Microscope (TEM) operating at 100 kV. Field Emission
Scanning Electron Microscopy (FE-SEM) images were obtained from a
HITACHI S-4160. XPS studies were carried out employing an XR3E2 (VG
2.6. The global method for the reduction of Nitro-Compounds
In the first step, Nitro-Compounds (1 mmol) were released in water
(10.0 mL) and mixed with 1.0 mmol of K2CO3 to give a deep yellow
solution. Next, tmtppa-Zn/DFNS (10 mg) and NaBH4 (2 mmol) were
added to the yellow solution. While the solution was decolorizing, the
reaction became complete. Reaction progress was analyzed utilizing
UV–Vis absorption spectra for the reaction mixture.
Microtech) twin anode X-ray source with AlKα = 1486.6 eV. EDX
spectroscopy was done deploying a field emission scanning electron
microscope (FESEM, JEOL 7600F), equipped with energy dispersed X-
ray Spectroscopy (Oxford instruments). Powder X-ray Diffraction data
were obtained using Bruker D8 Advance model with Cu karadiation. ICP
experiments were done employing a VARIAN VISTA-PRO CCD Simul-
taneous ICP-OES instrument. NMR spectra of 1H and 13C were deter-
mined with BRUKER DRX-300 AVANCE and BRUKER DRX-400
AVANCE Spectrometers. The surface area, pore-volume, and pore
1
Compound 1a: colorless oil. H NMR (400 MHz, CDCl3) δ (ppm) =
3.56 (s, 2H), 6.58–6.77 (m, 3H), 7.09 (t, J = 8 Hz, 2H); 13C NMR (100
MHz, CDCl3) δ (ppm) = 115.1, 118.4, 128.9, 146.2.
1
◦
Compound 1b: whrite solid, m.p. = 65–67 C. H NMR (400 MHz,
CDCl3) δ (ppm) = 3.59 (s, 2H), 6.60 (d, J = 8.4 Hz, 2H), 7.11 (d, J = 8.4
Hz, 2H); 13C NMR (100 MHz, CDCl3): δ (ppm) = 116.4, 122.9, 128.9,
145.0.
◦
diameter of NPs were specified by N2 physisorption at ꢀ 196 C using
Micromeritics ASAP 2000 instrumentand BET method. Determination of
the purity of the products and monitoring the reaction were performed
by TLC on silica gel (Polygram®SILG/UV 254 pre-coated plates).
Compound 2a: yellow solid, m.p. = 207–209 ◦C. 1H NMR (400 MHz,
CDCl3) δ (ppm) = 9.04 (s, 1H), 7.53 (s, 1H), 6.90 (d, J = 8.0 Hz, 2H),
6.49 (d, J = 8.0 Hz, 2H), 4.99 (s, 2H), 4.96 (s, 1H), 4.00 (q, J = 6.8 Hz,
2H), 2.19 (s, 3H), 1.09 (t, J = 6.8 Hz, 3H); 13C NMR (100 MHz, CDCl3): δ
(ppm) = 170.5, 157.6, 152.9, 152.4, 137.2, 131.9, 118.9, 104.9, 64.3,
58.6, 23.0, 19.4.
2.2. The global approach for the creation of DFNS nanoparticles
Urea (1.8 g) and CTAB (3 g) were released in distilled water and
mixed for 5 h to dissolve. It was added to a blend of TEOS (7.5 g),
pentanol (3.5 mL), and cyclohexane (50 mL) and stirred for 45 min at
room temperature. Next, it was refluxed for 4 h at 140 ◦C while stirring
in an oil bath. The final product was placed in an oven at 80 ◦C for 20 h.
The silica was isolated by centrifugation (45 min, 4000 rpm), washed
with acetone as well as distilled water, and vacuum-dried for 20 h. The
synthesized DFNS was then calcined at 400 ◦C in the air for 6 h.
Compound 2c: yellow oil. 1H NMR (400 MHz, CDCl3) δ (ppm) = 9.10
(s, 1H), 7.05 (t, J = 5.2 Hz, 1H), 6.69 (d, J = 1.2 Hz, 1H), 6.59–6.62 (m,
2H), 5.23 (s, 1H), 4.20–4.24 (m, 2H), 3.96 (s, 2H), 3.79–3.83 (m, 1H),
3.49–3.54 (m, 1H), 2.81–2.86 (m, 1H), 2.64 (s, 3H), 2.44–2.49 (m, 1H),
1.20 (t, J = 4.4 Hz, 3H); 13C NMR (100 MHz, CDCl3): δ (ppm) = 165.1,
151.9, 147.9, 147.4, 145.1, 128.4, 115.4, 113.1, 112.4, 110.9, 99.3,
59.4, 54.1, 41.8, 19.4, 17.9, 13.9.
3. Results and discussion
The impact of tmtppa-Zn/DFNS NPs catalyst on the synthesis of
2