Mesoporous Sn(IV) Doping DFNS Supported BaMnO3 Nanoparticles for Formylation of Amines…
radiation, the composition irradiated for 30 min. Then we
released a constant quantity of DI water in upper mentioned
solution and after that it was irradiated for 30 min. In order
to stop the reaction and decrease the pH to 7, a large amount
of deionized water was added to the solution. By using
Büchner funnel, the precipitate purifed and then washed by
ethyl alcohol and deionized water. The compositions dried
at the temperature of 75 °C for 2 h. Finally, we calcined the
precipitate at the temperature of 400 °C for 4 h.
Compound 7 1H NMR (500 MHz, CDCl3): δ (ppm) 8.02
(s, 1H), 3.69 (dt, J=14.20, 4.85 Hz, 4H), 3.60–3.56 (m, 2H),
3.39–3.36 (m, 2H). 13C NMR (125 MHz, CDCl3): δ (ppm)
160.6, 67.5, 66.2, 45.9, 40.3.
Compound 8 1H NMR (500 MHz, CDCl3): δ (ppm) 8.04
(s, 1H), 7.19 (t, J=7.80 Hz, 2H), 6.89–6.84 (m, 3H), 3.65
(t, J = 5.05 Hz, 2H), 3.42 (t, J = 5.05 Hz, 2H), 3.11 (dt,
J = 15.10, 5.05 Hz, 4H). 13C NMR (125 MHz, CDCl3): δ
(ppm) 160.9, 151.0, 129.4, 120.7, 116.9, 50.5, 49.1, 45.2,
40.0.
2.3 General Approach to the Catalytic
Compound 9 1H NMR (500 MHz, CDCl3): δ (ppm) 8.90
(s, 1H), 8.48 (dd, J=146.3, 6.5 Hz, 2H), 7.98 (s, 1H), 7.57
(d, J=7.8 Hz, 2H), 7.35 (dt, J=13.8, 8.0 Hz, 4H), 7.23–7.11
(m, 2H). 13C NMR (125 MHz, CDCl3): δ (ppm) 163.8,
159.2, 137.0, 129.6, 128.7, 125.6, 125.0, 119.8, 118.6.
Compound 10 1H NMR (500 MHz, CDCl3): δ (ppm) 8.49
(d, J=11.8 Hz, 1H), 8.33 (m, 2H), 7.51 (br, 1H), 7.47 (d,
J=8.9 Hz, 2H), 7.07 (d, J=8.7 Hz, 2H), 6.89–6.82 (m, 4H),
3.79 (s, 6H). 13C NMR (125 MHz, CDCl3): δ (ppm) 161.1,
159.2, 157.5, 157.0, 130.2, 129.9, 122.0, 121.8, 114.9,
114.5, 55.8, 55.7.
N‑Formylation of Amines
At the frst step, a glass reactor liner (50 mL) is charged with
the amines (15 mmol) and 1,4-dioxane (5 mL) in a glove
box. Then, 0.4 mol% of BaMnO3/SnD is added to the com-
pound. The Parr reactor was sealed and deleted from it. The
reactor is pressurized by CO2 under the pressure of 2.5 MPa
followed by H2 (with pressure of 2.5 Mpa) and the tem-
perature is increased to 100 °C. The reactor is cooled using
submersion in a bath of ice after 30 min and the remaining
gas is vented, slowly. After the reaction completion, for later
recycling experiments, the catalyst is separated utilizing a
magnet to be more utilized. After drying the resultant crude
product onto anhydrous sodium sulphate, the compound is
considered to Column Chromatography (CC) via a petro-
leum ether/EtOAc system that is an eluent (6:1) on silica
gel. For recycling procedure, catalyst was obsoleted using
fltration and also it’s washed with alcohol and dried with
the pump. It’s added to the main text.
Compound 11 1H NMR (500 MHz, CDCl3): δ (ppm) 8.41
(s, 1H), 7.30 (t, J = 7.8 Hz, 2H), 7.18 (t, J= 7.2 Hz, 1H),
7.07 (d, J=7.8 Hz, 2H), 3.25 (s, 3H). 13C NMR (125 MHz,
CDCl3): δ (ppm) 162.6, 142.4, 129.8, 126.5, 122.3, 32.4.
3 Results and Discussion
In the Scheme 1, it can be seen that, for production of
BaMnO3/SnD nanocatalysts, many stages have to be con-
ducted. The fbers of DFNS involve Si–OH bond groups
on the sites. Hence, it is expected that the DFNS is func-
tionalized using Sn(IV) for forming SnD. The quantity of
extracted Ananas comosus was varied to discover its efect
on BaMnO3 dimension, catalytic yield, and shape.
Compound 1 1H NMR (500 MHz, CDCl3): δ (ppm) 8.04
(s, 1H), 3.01 (s, 3H), 2.92 (s, 3H).
Compound 2 1H NMR (500 MHz, CDCl3): δ (ppm) 8.01
(s, 1H), 3.32 (q, J=8.0 Hz, 2H), 3.30 (q, J=8.0 Hz, 2H),
1.21 (t, J=8.0 Hz, 3H), 1.15 (t, J=8.0 Hz, 3H). 13C NMR
(125 MHz, CDCl3): δ (ppm) 162.5, 41.9, 36.9, 14.9, 13.1.
Compound 3 1H NMR (500 MHz, CDCl3): δ (ppm) 8.01
(s, 1H), 3.22–3.10 (m, 4H), 1.57–1.43 (m, 4H), 0.88–0.81
(m, 6H). 13C NMR (125 MHz, CDCl3): δ (ppm) 162.9, 49.6,
44.1, 21.8, 20.5, 11.1, 10.6.
The fbers of DFNS involve many bonds of Si–OH on
the sites. Therefore, it is expected that the fbers of DFNS
is easily functionalized utilizing Sn(IV) to construct SnD.
Compound 4 1H NMR (500 MHz, CDCl3): δ (ppm) 8.47
(s, 1H), 7.51–7.40 (m, 6H), 7.32–7.28 (m, 4H), 4.48 (s, 2H),
4.31 (s, 2H). 13C NMR (125 MHz, CDCl3): δ (ppm) 162.4,
136.3, 135.5, 129.1, 128.5, 128.4, 128.0, 127.4, 127.2, 50.2,
45.0.
Si
Si
Si
Si
O
O
Si
Si
O
O
Sn
Sn
OH
OH
Si
Si
BaMnO3
O
O
HO
HO
O
O
Sn
Sn
OH
OH
Ba(NO3)2
MnCl2
HO
HO
Sn
HO
HO
Sn
O
BaMnO3
Compound 5 1H NMR (500 MHz, CDCl3): δ (ppm) 8.29
(s, 1H), 3.47 (t, J=6.43 Hz, 2H), 3.45 (t, J=6.43 Hz, 2H),
1.98–1.92 (m, 4H) ppm; 13C NMR (100 MHz, CDCl3) δ
160.9, 46.0, 43.1, 24.9, 24.2
O
O
OH
HO
OH
Si
Si
O
BaMnO
3HO
Si
Si
OH
O
OH
O
Sn
Sn
Si
SnD
Si
BaMnO3/SnD
O
O
Si
Compound 6 1H NMR (500 MHz, CDCl3): δ (ppm) 7.98
(s, 1H), 3.42 (t, J=5.54 Hz, 2H), 3.28 (t, J=5.51 Hz, 2H),
1.72–1.49 (m, 6H). 13C NMR (125 MHz, CDCl3): δ (ppm)
161.0, 46.7, 40.9, 26.3, 24.8, 24.3.
Si
Scheme 1 Schematic illustration of the BaMnO3/SnD NPs prepara-
tion
1 3