RSC Advances: Paper
RSC Advances: Paper
RSC Advances: Paper
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1,3,5-triazine derivatives†
Shouchun Feng,*a Jinwang Tan,a Yufan Maa and Li-Yuan Chang *b
In recent years, magnetic nanocatalysts have been recommended as one of the best catalysts by chemists.
Among magnetic nanoparticles, Fe3O4 nanoparticles are highly suitable due to their magnetic properties,
chemical stability and low toxicity. These catalysts can be separated via magnetic separation after the
chemical process is over and reused after regeneration. Owing to the importance of 1,3,5-triazine
derivatives in pharmaceutical and medicinal chemistry, the synthesis of these compounds is always one
of the important goals of organic chemists. In this research work, we first successfully synthesized CuBr2
immobilized on magnetic Fe3O4 nanoparticles functionalized with Dop-OH (prepared via the reaction of
Received 5th April 2023
Accepted 12th May 2023
MNP-dopamine with 2-phenyloxirane) nanocomposites and then investigated their catalytic application
in the synthesis of 1,3,5-triazine derivatives via an oxidative coupling reaction of amidine hydrochlorides
DOI: 10.1039/d3ra02261g
and alcohols in air. Recycling experiments clearly revealed that MNP-[Dop-OH]-CuBr2 nanocatalysts
rsc.li/rsc-advances could be reused for at least 8 times without much loss of catalytic activity.
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FT-IR technique was used to detect the functional groups a scale of less than 25 nm. Moreover, this image shows that the
xed on nanoparticles. An obvious peak in the region of nano catalyst particles were synthesized in uniform and equal
574 cm−1 indicates the presence of Fe–O bonding, and the sizes and their shape was spherical.
broad absorption peak in the region of 3350 cm−1 is also Energy-dispersive X-ray analysis (EDX) was applied to study
attributed to the O–H stretching vibrations. In the spectrum of the elements existing in the structure of the as-fabricated MNP-
MNP-dopamine and MNP-[Dop-OH] ligand, C–H stretching [Dop-OH]-CuBr2 nanocatalyst. The presence of Fe, C, O, N and
vibrations appeared near 2700 cm−1; and the peak that Cu peaks conrmed the construction of MNP-[Dop-OH]-CuBr2
appeared in the region of 3400 cm−1 is related to the N–H group, nanocatalysts (Fig. 5).
which overlaps with the O–H stretching vibrations. Moreover, X-ray diffraction analysis was used to identify the crystal
the peaks in the regions of 1200–1500 cm−1 conrm the structure of Fe3O4 MNPs and MNP-[Dop-OH]-CuBr2 nano-
formation of C–N and C–O bonds in the non-catalyst structure. catalysts. As shown in Fig. 6, the target nanocatalyst was
In the infrared spectrum of MNP-[Dop-OH]-CuBr2 nano- synthesized without changing the crystal structure of the Fe3O4
catalysts, it shows a peak in the region of 1623 cm−1 assigned to core, and the peaks observed in the X-ray diffraction pattern
the C–N stretching vibration of the copper complex (Fig. 2).15 conrmed this issue. The diffraction pattern includes peaks
SEM and TEM techniques were used to identify MNP-[Dop- (220), (311), (400), (422), (511) and (440), which indicates that
OH]-CuBr2 nanocatalysts, which show the nanocatalyst surface the structure of the magnetic Fe3O4 nanoparticle was not
at a very high magnication (Fig. 3 and 4). The SEM images destroyed during functionalization .12
show that the nano-catalyst particles have been synthesized on
16080 | RSC Adv., 2023, 13, 16078–16090 © 2023 The Author(s). Published by the Royal Society of Chemistry
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Fig. 5 EDX analysis of MNP-[Dop-OH]-CuBr2 nanocatalysts. Fig. 7 VSM analysis of Fe3O4 MNPs and MNP-[Dop-OH]-CuBr2
nanocatalysts.
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Table 1 Optimization of reaction conditions for the reaction of benzamidine hydrochloride with benzyl alcohol (product 3a)
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Entry Catalyst (mg) Base Solvent (tem. oC) Time (h) Yielda (%) TON TOF (h−1)
KOAc as the base. To nd the medium reaction, the model methoxy, chloro, bromo, uoro and nitro were well tolerated. All
reaction was tested in different solvents. The maximum yield products are known and the physical properties of the corre-
and suitable time were observed in PEG at 120 °C aer 8 h. To sponding products are in good agreement with the reported
expand the scope of application of this synthetic method, the samples .20–24
oxidative coupling reaction of different amidine hydrochlorides Based on the literature search,24 we present a tentative
with a wide range of alcohols was studied under the standard- mechanism for the synthesis of 1,3,5-triazine derivatives via the
ized conditions (Table 2). Under this catalytic system, a wide oxidative coupling reaction of amidine hydrochlorides and
range of aromatic alcohols with both electron-donating and alcohols catalyzed by MNP-[Dop-OH]-CuBr2 nanocomposites
electron-withdrawing substituents were successfully reacted under air conditions in Scheme 2.
with amidine hydrochlorides and the target products were The ability to recycle and reuse the catalyst is one of the
synthesized in good to excellent yields. It is noteworthy that most important features of heterogeneous catalytic systems,
several functional groups, such as methyl, ethyl, isopropyl, which makes these catalysts suitable for industrial
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Table 2 Scope of the oxidative coupling reaction of amidine hydrochlorides and alcohols catalyzed by MNP-[Dop-OH]-CuBr2 nanocomposites
under air conditionsa
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Open Access Article. Published on 30 May 2023. Downloaded on 6/10/2023 8:18:39 AM.
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a
Table 2
Isolated yield.
(Contd. )
RSC Advances
Scheme 2 Suggested mechanism for the oxidative coupling reaction of amidine hydrochlorides and alcohols catalyzed by MNP-[Dop-OH]-
CuBr2 nanocomposites under air conditions.
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Table 3 Comparison of the catalytic activity of MNP-[Dop-OH]-CuBr2 nanocatalysts with existing catalysts
1 Potassium tert-butoxide 8 69 25
2 1,10-Phenanthroline, cupric acetate 24 89 26
3 N-Iodosuccinimide 16 88 27
4 Bis(dichloro(h6-p-cymene)ruthenium) 16 85 28
5 Nitrogen-doped carbon supported nanocobalt 16 51 29
6 [Cp*IrI2]2/xantphos 20 85 30
7 MNPs-[Dop-OH]-CuBr2 (20) 8 98 This work
a
Isolated yields.
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1H NMR (400.1 MHz, CDCl3): d = 8.22 (d, J = 7.1 Hz, 2H), 8.18
(d, J = 8.6 Hz, 2H), 7.92 (s, 1H), 7.87 (s, 1H), 7.78–7.74 (d, J =
6.9 Hz, 2H), 7.66–7.64 (d, J = 8.6 Hz, 2H), 7.56–7.26 (m, 4H). 13C
{1H} NMR (100.6 MHz, CDCl3): d = 169.7, 167.3, 150.4, 140.5,
138.9, 139.5, 132.9, 130.3, 130.2, 130.2, 128.8, 128.8, 127.3,
1H NMR (400.1 MHz, CDCl3): d = 8.14 (d, J = 7.5 Hz, 2H), 7.70
126.2, 123.6, 118.5, 117.8.
(d, J = 7.5 Hz, 1H), 7.67 (s, 1H), 7.54–7.29 (m, 10H), 13C{1H}
NMR (100.6 MHz, CDCl3): d = 169.7, 163.8, 161.4, 141.8, 141.5,
139.3, 134.5, 130.1, 129.7, 129.6, 129.6, 129.6, 129.4, 128.1,
127.7, 125.0, 121.7.
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1H NMR (400.1 MHz, CDCl3): d = 8.09 (d, J = 7.4 Hz, 2H), 8.03
1H NMR (400.1 MHz, CDCl3): d = 8.16 (d, J = 7.2 Hz, 2H), 7.92
(d, J = 7.4 Hz, 2H), 7.63–7.53 (m, 4H), 7.51–7.43 (m, 5H), 7.41–
(s, 1H), 7.83 (s, 2H), 7.78 (d, J = 7.0 Hz, 2H), 7.58–7.47 (m, 7H),
7.40 (m, 2H), 13C{1H} NMR (100.6 MHz, CDCl3): d = 166.2,
13C{1H} NMR (100.6 MHz, CDCl3): d = 166.8, 164.3, 160.1,
161.0, 153.9, 143.2, 139.2, 138.2, 134.2, 133.8, 129.5, 127.9,
159.9, 144.3, 139.5, 137.9, 128.2, 128.2, 127.8, 126.3, 126.2,
127.8, 127.7, 127.4, 127.4126.0, 124.8, 23.1.
118.0, 116.2, 33.2, 23.1.
2-(4-Ethylphenyl)-4,6-diphenyl-1,3,5-triazine (product 3h).
2,4-Diphenyl-6-(pyridin-3-yl)-1,3,5-triazine (product 3k).
1H NMR (400.1 MHz, CDCl3): d = 8.23 (d, J = 8.3 Hz, 2H), 7.63
1H NMR (400.1 MHz, CDCl3): d = 8.17 (d, J = 7.5 Hz, 2H), 7.72 (s, 1H), 7.54–7.43 (m, 9H), 7.36 (t, J = 7.4 Hz, 1H), 7.23 (d, J =
(d, J = 7.5 Hz, 1H), 7.63 (m, 3H), 7.55–7.41 (m, 8H), 13C{1H} 8.5 Hz, 1H), 13C{1H} NMR (100.6 MHz, CDCl3): d = 164.5,
NMR (100.6 MHz, CDCl3): d = 170.7, 164.8, 162.4, 141.8, 141.5, 162.3, 159.4, 139.7, 139.5, 137.3, 135.4, 128.2, 127.9, 127.8,
139.3, 134.5, 130.1, 129.7, 129.6, 129.6, 129.6, 129.4, 128.1, 127.8, 127.6, 127.1, 127.0, 126.6, 125.2, 125.9, 123.9, 120.0.
127.7, 124.0, 120.7, 22.4, 14.9. 2-(3-Chlorophenyl)-4,6-diphenyl-1,3,5-triazine (product 3l).
2-(4-Methoxyphenyl)-4,6-diphenyl-1,3,5-triazine (product 3i).
1H NMR (400.1 MHz, CDCl3): d = 8.15 (d, J = 8.6 Hz, 2H), 8.09
(d, J = 8.6 Hz, 2H), 7.88 (s, 2H), 7.76 (d, J = 6.9 Hz, 2H), 7.67 (d, J
1H NMR (400.1 MHz, CDCl3): d = 8.15 (d, J = 7.6 Hz, 2H), 7.75– = 8.6 Hz, 2H), 7.63–7.47 (m, 4H). 13C{1H} NMR (100.6 MHz,
7.70 (m, 2H), 7.67 (s, 1H), 7.56–7.41 (m, 9H), 13C{1H} NMR CDCl3): d = 156.6, 156.5, 150.8, 138.8, 138.4, 137.9, 135.5, 132.0,
(100.6 MHz, CDCl3): d = 169.6, 164.2, 161.7, 142.6, 141.4, 139.5, 129.4, 129.3, 129.1, 128.8, 128.5, 127.3, 123.8, 117.3, 117.2.
130.6, 129.9, 129.7, 129.7, 129.6, 128.2, 128.0, 128.0, 128.1, 12.0,
121.1, 58.1.
16088 | RSC Adv., 2023, 13, 16078–16090 © 2023 The Author(s). Published by the Royal Society of Chemistry
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1H NMR (400.1 MHz, CDCl3): d = 8.29 (d, J = 7.5 Hz, 2H), 7.93 1H NMR (400.1 MHz, CDCl3): d = 8.71 (d, J = 4.0 Hz, 1H), 8.61–
(s, 2H), 7.68 (d, J = 7.7 Hz, 2H), 7.58–7.53 (m, 4H), 7.48 (t, 2H), 8.58 (m, 2H), 7.97 (t, 1H), 7.87–7.82 (m, 3H), 7.58 (s, 1H), 7.53–
7.38 (d, J = 7.7 Hz, 2H), 13C{1H} NMR (100.6 MHz, CDCl3): d = 7.43 (m, 3H), 7.32 (dd, J = 5.0 Hz, J = 6.5 Hz, 1H), 7.26 (d, J =
167.5, 160.1, 140.8, 140.1, 137.2, 129.9, 128.1, 127.8, 126.2, 3.3 Hz, 1H), 13C{1H} NMR (100.6 MHz, CDCl3): d = 156.4,
126.1, 118.0, 22.3. 156.1, 154.3, 150.1, 149.4, 149.2, 143.3, 138.5, 136.8, 129.1,
2-(3-Nitrophenyl)-4,6-diphenyl-1,3,5-triazine (product 3n). 129.0, 127.1, 123.9, 121.5, 117.3, 116.4, 112.2, 108.9.
2-(2-Chlorophenyl)-4,6-diphenyl-1,3,5-triazine (product 3q).
1H NMR (400.1 MHz, CDCl3): d = 8.24 (d, J = 7.8 Hz, 2H), 8.21
(d, J = 8.8 Hz, 2H), 7.86 (s, 1H), 7.85 (s, 1H), 7.78 (d, J = 7.2 Hz,
2H), 7.55–7.43 (m, 6H), 13C{1H} NMR (100.6 MHz, CDCl3): d = 1H NMR (400.1 MHz, CDCl3): d = 8.22 (d, J = 7.4 Hz, 2H), 7.88
161.7, 158.5, 158.2, 151.2, 139.8, 138.3, 133.4, 129.2, 129.1, (s, 1H), 7.55–7.50 (m, 4H), 7.46–7.43 (m, 3H), 7.33 (d, J = 7.6 Hz,
129.0, 128.8, 128.5, 127.3, 127.2, 117.6, 117.4, 115.2, 56.5. 1H), 7.27–7.25 (m, 1H), 13C{1H} NMR (100.6 MHz, CDCl3): d =
161.3, 158.6, 151.1, 141.6, 139.7, 131.3, 129.1, 127.8, 126.2,
118.7, 116.2, 113.3, 112.1, 25.5.
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