Supplementary data Nano Fe3O4 supported hydrogensulfate ionic ...
Supplementary data Nano Fe3O4 supported hydrogensulfate ionic liquid catalyzed one pot synthesis of polysubstituted pyridines Heshmatollah Alinezhad*, Mahmood Tajbakhsh, Neda Ghobadi Faculty of Chemistry, University of Mazandaran, P. O. Box 47415, Babolsar, Iran *
Corresponding author: Email: [email protected]
General procedure for the synthesis of catalyst Preparation of Fe3O4@SiO2: Fe3O4 nanoparticles were synthesized by chemical co-precipitation of ferric and ferrous ions in alkali solution. In this procedure a mixture of FeCl3.6H2O (2.35 g, 8.7 mmol) and FeCl2.4H2O (0.86 g, 4.3 mmol) was dissolved in 40 mL deionized water. The resultant solution under nitrogen atmosphere was left to be stirred for 30 min at 80°C. Then 5 mL of NH4OH solution was added with vigorous stirring to produce a black solid and the reaction was continued for another 30 min. The black magnetite nanoparticles were isolated by magnetic decantation, washed several times with deionized water and then dried at 80 °C for 10 h. Fe3O4 nanoparticles (1 g) were suspended in a mixture of 100 mL ethanol and NH3.H2O (10 mL, 25%) with the help of ultrasonication. Subsequently, 0.4 mL of tetraethoxysilane (TEOS) was added to solution and the mixture was ultrasonicated for 2 h. Afterward silica coated MNPs (MNP@SiO2) was magnetically separated, washed three times with ethanol and dried at 80 °C for 10 h. Synthesis of 1-methy-3-(trimethoxysilylpropyl) imidazolium chloride ([pmim]Cl): A mixture of 0.12 mol (3chloropropyl)triethoxysilane and 0.12 mol of 1-methylimidazole was refluxed at 78 °C for 24 h under nitrogen atmosphere. The reaction mixture was cooled down and any remaining volatile substances were removed by rotary evaporation. The crude product was additionally washed with Et2O (5× 5 ml) and dried under vacuum to afford pure product (slightly yellow viscous oil). 1H NMR (400 MHz, CDCl3, TMS): δ = 10.04 (s, 1H), 7.57 (t, J= 2 Hz, 1H), 7.34 (t, J= 1.6 Hz 1H), 4.14 (t, 2H, J = 7.2 Hz), 3. 93 (s, 3H), 3.37 (s,6H) 1.84-1.76 (m, 2H), 0.464-0.423 (m, 2H), 13 C NMR (100 MHz, CDCl3 , TMS): δ = 137.3, 123.7, 121.9, 51.5, 50.5, 36.3, 23.9, 5.7 Synthesis of 1-methyl-3-(trimethoxysilylpropyl)imidazolium chloride anchored on Fe3O4@SiO2 ()-MNP[pmim]Cl: [pmim]Cl ( 0.5 gr, 1.3 mmol) was dissolved in 25 ml of dry toluene and treated with 1 g of previously prepared Fe3O4@SiO2. After heating the slurry at 90 °C for 16 h the resulting solid was then separated by an external magnet and washed with 100 ml of dichloromethane. In the following step, the unreacted ionic liquid was removed by 24 h extraction with boiling dichloromethane (soxhlet extraction). In the next step, the material was dried under high vacuum. Synthesis of 1-methyl-3-(trimethoxysilylpropyl)imidazolium hydrogensulfate anchored on Fe3O4@SiO2 (MNP-[pmim]HSO4) : In the round bottom flask equipped with stirrer, MNP[pmim]Cl (1gr) was suspended in 20 ml of dry CH2Cl2. During vigorous stirring, concentrated H2SO4 (1.3 mmol 98%) was introduced drop by drop at 0 °C. Then the mixture was warmed up to the room temperature, and was refluxed for 48 h. Then, the mixture was cooled, filtered and dried.
N
O O Si O
N
SiO2 Fe3O 4
O O Si O
Cl
O O Si O
HN
H2SO 4
N Cl
N
N
SiO2
Cl
Fe3O 4
OH OH OH
SiO2 Fe3O 4
O O Si O
N
N HSO4
Scheme S1: Immobilization of ionic liquid on the surface of nanoparticle Analyses were used to characterize the supported ionic liquid.
Fig S1. FTIR spectra of MNPs(a), MNP@SiO2 (b), [pim]Cl (c), MNP-[pim]Cl (d), MNP-[pmim]HSO4 (d)
Fig S2. XRD pattern of MNP (a), ), MNP [pmim]HSO4 (b)
Fig S3. The TGA thermogram of (a) MNP@SiO2 (b) MNP-[pmim]HSO4
Fig. S4 SEM images of MNP@SiO2 (left), MNP-[pmim]HSO4 (right) Elemental analysis (C:8.36%, H:1.32%, N:2.67% and S:3.19%). The content ratio of C/N (3.13) is very near to the theorical calculation (3.00). General procedure for the synthesis of triarylpyridines To a mixture of aldehyde (1.0 mmol), ketone (2.0 mmol), ammonium acetate (1.3 mmol) was added MNP([pmim]HSO4) (0.012 gr, 1.2 mol%) and the resulting mixture was stirred at 100oC for the specific period of time. The progress of the reaction was monitored by TLC. After completion of the reaction, EtOAc (10 ml) was added and cooled reaction mixture. The catalyst was separated by an external magnet, washed with EtOAC, dried and reused for a consecutive run under the same reaction conditions. Evaporation of the organic solvent under reduced pressure gave the crude products. Pure products were obtained by recrystallization by aqueous EtOH. The products were characterized with IR, 1HNMR and 13CNMR spectra.
Ar 1 Ar 1CHO + 2 Ar2COCH3 + NH4OAc
MNP-[pmim]HSO4 Solvent-free
Ar2
N
Scheme S2: Synthesis of triarylpyridines catalyzed by MNP-([pmim]HSO4
Ar2
Table S2: Synthesis of 2,4,6-triphenylpyridinea
Ar1
1
C6H5-
C6H5-
Time (min) 50
2
4-FC6H4-
C6H5-
55
87
204-206 [41]
3
4-ClC6H4-
C6H5-
45
95
124-125 [41]
4
4-BrC6H4-
C6H5-
40
90
102-104 [41]
5
4-NO2C6H4-
C6H5-
40
85
196-198 [41]
6
4-MeC6H4-
C6H5-
60
90
122-124 [41]
7
4-MeOC6H4-
C6H5-
70
87
99-100 [43]
8
4-OHC6H4-
C6H5-
75
87
195-197 [43]
9
4-N(Me)2C6H4-
C6H5-
80
90
138-140 [31]
10
Pyridine-4yl
C6H5-
65
83
187-190 [31]
11
Thiophen-2-yl
C6H5-
85
78
161-163 [41]
12
Furan-2-yl
C6H5-
80
75
179-181 [41]
13
C6H5-
4-ClC6H4-
45
85
126-128 [40]
14
4-ClC6H4-
4-ClC6H4-
35
90
269-270 [41]
15
4-MeC6H4-
4-ClC6H4-
50
89
118-119 [40]
16
4-MeOC6H4
4-ClC6H4-
45
88
190-191 [40]
Entry
a b
Ar2
Yieldb
M. p (oC) Ref
90
133-134 [41]
Conditions: aldehyde/acetophenone/NH4OAc/MNP-[pmim]HSO4: 1/2/1.3/0.012, 120 °C, solvent-free. Yields refer to pure isolated products
2,4,6-Tri phenyl pyridine (Table S2, entry 1): 1HNMR (400 MHz, DMSO-d6, δ/ppm): 7.01 (d, 2H, J= 8 Hz), 7.24-7.27 (m, 2H), 7.46-7.49 (m, 3H), 7.51-7.58 (m, 3H), 7.78 (d, 2H, J= 7.6 Hz),7.92 (s, 1H), 8.20 (s, 2H), 8.24 (d, 2H, J= 9.6 Hz).13C NMR (100 MHz, DMSO-d6, δ/ppm): 116.7, 117.2, 120.5, 125.9, 127.1, 127.2, 128.3, 128.7, 128.9, 129.0, 129.1, 130.8, 139.1, 139.6, 150.2, 157.5.
4-(4-Fluorophenyl)-2,6-di phenyl pyridine (Table S2, entry 2): 1HNMR (400 MHz, DMSO-d6, δ/ppm): 7.49-7.51 (m, 2H), 7.55-7.57 (m, 4H), 7.86 (b, 3H), 7.88 (b, 2H), 8.21-8.23 (m, 5H).13C NMR (100 MHz, DMSO-d6, δ/ppm):112.7, 116.8, 118.5, 127.6, 127.9, 128.8, 129.2, 129.4, 132.9, 139.0, 143.6, 143.2, 157.9. IR (KBr disc): (cm -1): 1600, 1542, 1514, 1246, 1179, 1026, 826, 753. m/z (ESI) 325.1 (M +•, 100%), 320.1 (50%), 172.1 (16.4%), 171.2 (14.6%), 154.1 (6.7%). 153.2 (4.2%).
4-(4-Choloro)-2,6-di phenyl pyridine (Table S2, entry 3): 1HNMR (400 MHz, DMSO-d6, δ/ppm): 7.137.19 (m, 2H), 7.28-7.35 (m, 3H), 7.58-7.62 (m, 2H), 7.63-7.72 (m, 3H), 7.74-7.76 (m, 2H), 7.95 (s, 2H), 8.10 (d, 2H, J= 7.2 Hz). 13C NMR (100 MHz, DMSO-d6, δ/ppm): 114.3, 115.0, 115.1, 115.6, 117.8, 120.0, 127.0, 128.3, 128.4, 128.8, 128.9, 133.9, 134.1, 141.2, 147.1, 157.7.
4-(4-Bromophenyl)-2,6-di phenyl pyridine (Table S2, entry 4): 1HNMR (400 MHz, DMSO-d6, δ/ppm): 6.84-6.89 (m, 2H), 6.99 (d, 2H, J= 8.8 Hz), 7.26 (d, 2H, J= 8.8 Hz), 7.41 (t, 2H, J= 7.6 Hz), 7.51 (s, 4H), 7.95 (d, 2H, J= 2.4 Hz), 8.02 (d, 2H, J= 7.2 Hz). 13C NMR (100 MHz, DMSO-d6, δ/ppm): 114.7, 115.1, 115.6, 118.1, 128.3, 128.8, 129.0, 133.4, 133.6, 134.2, 140.1, 140.2, 146.8, 146.9, 157.0.
4-(4-Nitrophenyl)-2,6-di phenyl pyridine (Table S2, entry 5): 1HNMR (400 MHz, DMSO-d6, δ/ppm): 8.11 (d, 2H, J= 7.6 Hz), 7.83 (s, 2H), 7.59 (d, 2H, J= 7.2 Hz), 7.54-7.48 (m, 4H), 7.43 (t, 2H, J= 7.2 Hz),7.26 (d, 2H, J= 8 Hz), 7.15 (t, 2H, J= 7.2 Hz).13C NMR (100 MHz, DMSO-d6, δ/ppm): 112.2, 120.7, 121.2, 125.1, 125.9, 127.6, 127.8, 130.4, 130.6, 135.0, 140.9, 141.2, 144.4, 156.4, 159.2.
4-(4-Methylphenyl)-2,6-di phenyl pyridine (Table S2, entry 6): 1HNMR (400 MHz, DMSO-d6, δ/ppm): 2.30 (s, 3H), 6.65 (d, 2H, J= 8 Hz), 6.90 (d, 2H, J= 7.2 Hz), 6.95 (t, 3H, J= 8 Hz), 7.04 (d, 2H, J= 8.4 Hz), 7.09 (d, 2H, J= 8.4 Hz), 7.31-7.7.36 (m, 3H), 8.02 (d, 2H, J= 4 Hz).13C NMR (100 MHz, DMSO-d6, δ/ppm): 21.0, 114.8, 115.5, 115.7, 116.8, 119.7, 126.9, 128.7, 128.8, 129.1, 129.7, 133.8, 135.8, 136.8, 137.7, 145.2, 157.1.
4-(4-Methoxyphenyl)-2,6-di phenyl pyridine (Table S2, entry 7): 1HNMR (400 MHz, DMSO-d6, δ/ppm): 2.42 (s, 3H), 6.67 (t, 2H, J= 7.6 Hz), 6.74 (d, 2H, J= 8 Hz), 7.11 (s, 2), 7.24 (t, 2H, J= 7.6 Hz), 7.34-7.41 (m, 3H), 7.49 (d, 2H, J= 8 Hz), 7.61 (d, 2H, J= 7.2 Hz), 8.20 (s, 2H).13C NMR (100 MHz, DMSO-d6, δ/ppm): 55.6, 114.8, 115.4, 117.6, 127.3, 127.8, 128.7, 128.9, 133.7, 142.1, 148.3.
4-(4-Hydroxy)-2,6-di phenyl pyridine (Table S2, entry 8): 1HNMR (400 MHz, DMSO-d6, δ/ppm): 6.826.83 (m, 2H), 6.86-6.92 (m, 4H), 7.16 (d, 2H, J= 9.6 Hz), 7.28 (t, 2H, J= 8 Hz), 7.95 (s, 2H), 8.06-8.11 (m, 2H), 8.18 (d, 2H, J= 8.4 Hz), 8.48 (s, 1H). 13C NMR (100 MHz, DMSO-d6, δ/ppm): 114.4, 115.1, 115.2, 115.6, 118.3, 118.9, 120.1, 128.0, 128.3, 128.4, 132.9, 133.6, 134.3, 146.5, 146.6, 146.7, 157.8.
4-(4-N,N-dimethylphenyl)-2,6-di phenyl pyridine (Table S2, entry 9): 1HNMR (400 MHz, DMSO-d6, δ/ppm): 2.29 (s, 3H), 2.49 (s, 3H), 6.65 (d, 2H, J= 8.4 Hz), 7.19 (d, 3H, J= 8.8 Hz), 7.31 (d, 3H, J= 7.6 Hz), 7.54 (d, 3H, J= 8.8 Hz), 7.85 (s, 2H), 8.05 (d, 3H, J= 8.0 Hz).13C NMR (100 MHz, DMSO-d6, δ/ppm): 23.7, 23.9, 128.2, 128.4, 128.9, 129.3, 130.9, 133.1, 134.9, 137.9, 141.4, 155.6.
4-(Pyridine-4yl)-2,6-di phenyl pyridine (Table S2, entry 10): 1HNMR (400 MHz, DMSO-d6, δ/ppm): 6.90 (d, 2H, J= 7.2 Hz), 7.16 (t, 2H, J= 7.2 Hz), 7.43-7.50 (m, 2H), 7.52-7.55 (m, 2H), 7.56-7.58 (m, 1H), 8.15 (d, 2H, J= 7.6 Hz), 8.28 (d, 2H, J= 6 Hz), 8.81 (s, 2H). 13C NMR (100 MHz, DMSO-d6, δ/ppm): 115.0, 1169.9, 119.8, 126.8, 126.9, 128.2, 128.9, 129.0, 134.0, 124.8, 138.4, 140.4, 145.0, 157.9.
4-(Thiophen-2-yl)-2,6-di phenyl pyridine (Table S2, entry 11): 1HNMR (400 MHz, DMSO-d6, δ/ppm): 7.06 (d, 2H, J= 8 Hz), 7.12 (s, 1H), 7.13 (d, 1H, J= 3.2 Hz), 7.17(d, 2H, J= 8.8 Hz), 7.26 (s, 2H), 7.357.40 (m, 2H), 7.42-7.46 (m, 1H), 7.51 (d, 1H, J= 6.8 Hz), 7.84 (d, 2H, J= 8 Hz), 7.91 (d, 2H, J= 2 Hz).13C NMR (100 MHz, DMSO-d6, δ/ppm): 122.8, 125.7, 126.2, 126.3, 127.5, 128.4, 129.0, 129.3, 130.2, 131.9, 132.6, 136.0, 139.4, 156.3.
4-(Furan-2-yl)-2,6-di phenyl pyridine (Table S2, entry 12): 1HNMR (400 MHz, DMSO-d6, δ/ppm): 6.62 (d, 1H, J= 7.6 Hz), 7.80 (d, 2H, J= 7.2 Hz), 6.89 (t, 1H, J= 7.2 Hz), 7.08 (d, 2H, J= 9.2 Hz), 7.26-7.32 (m, 4H), 7.33-7.37 (m, 2H), 8.02 (s, 1H), 8.03 (d, 2H, J= 8 Hz). 13C NMR (100 MHz, DMSO-d6, δ/ppm): 108.4, 114.2, 114.6, 116.6, 119.5, 126.8, 128.5, 128.7, 129.0, 133.3, 133.8, 139.9, 145.4, 158.1.
4-(Phenyl)-2,6-di-4-cholorophenyl pyridine (Table S2, entry 13): 1HNMR (400 MHz, DMSO-d6, δ/ppm): 7.35 (s, 2H), 7.46-7.49(m, 2H), 7.51-7.56 (m 2H), 7.57-7.59 (m, 4H), 7.78-7.79 (m, 2H),7.79 (s, 1H), 7.79-7.90 (s, 2H), 8.20-8.22 (d, 2H, J= 7.2 Hz).13C NMR (100 MHz, DMSO-d6, δ/ppm): 116.3, 122.9, 126.0, 127.0, 127.1, 127.5, 128.7, 129.1, 129.9, 134.3, 157.6.
2,4,6-Tri-4-choloro phenyl pyridine (Table S2, entry 14): 1HNMR (400 MHz, DMSO-d6, δ/ppm): 6.92 (d, 2H, J= 8.4 Hz), 7.25-7.29 (m, 3H), 7.47-7.48 (m, 4H), 7.77-7.79 (m, 3H), 7.92 (s, 2H), 8.20 (d, 2H, J= 4.8 Hz). 13C NMR (100 MHz, DMSO-d6, δ/ppm): 112.0, 121.6, 126,5, 126.7, 129.3, 130.5, 131.5, 132.0, 132.1, 136.2, 138.9, 142.1, 143.8, 151.3, 157.4.
4-(4-Methyl)-2,6-di-4-choloro phenyl pyridine (Table S2, entry 15): 1HNMR (400 MHz, DMSO-d6, δ/ppm): 2.30 (s, 3H), 7.17 (t, 2H, J= 7.6 Hz), 6.18-7.21 (m, 2H), 7.62 (s, 2H), 7.70-7.74 (m, 2H), 7.917.93 (m, 2H), 7.96-7.97 (m, 1H), 8.05 (d, 1H, J= 4.8 Hz), 8.34 (s, 2H). 13C NMR (100 MHz, DMSO-d6, δ/ppm):26.2, 114.9, 115.4, 117.7, 127.8, 128.7, 129.2, 133.4, 133.8, 141.1, 148.1, 157.6.
4-(4-Methoxy phenyl)-2,6-di-4-choloro phenyl pyridine (Table S2, entry 16): 1HNMR (400 MHz, DMSO-d6, δ/ppm): 3.88 (s, 3H), 6.97 (d, 2H, J= 8.4 Hz), 7.41 (t, 2H, J= 6.4 Hz), 7.46-7.49 (m, 3H), 7.577.58 (m, 3H), 7.62 (d, 2H, J= 8.8 Hz), 8.08 (d, 2H, J= 7.2 Hz), 8.28 (s, 2H). 13C NMR (100 MHz, DMSOd6, δ/ppm): 55.3, 115.9, 120.7, 125.8, 127.3, 127.5, 128.6, 130.4, 133.7, 141.2, 143.5, 144.7, 158.2.
Corresponding author: Email: [email protected]
General procedure for the synthesis of catalyst Preparation of Fe3O4@SiO2: Fe3O4 nanoparticles were synthesized by chemical co-precipitation of ferric and ferrous ions in alkali solution. In this procedure a mixture of FeCl3.6H2O (2.35 g, 8.7 mmol) and FeCl2.4H2O (0.86 g, 4.3 mmol) was dissolved in 40 mL deionized water. The resultant solution under nitrogen atmosphere was left to be stirred for 30 min at 80°C. Then 5 mL of NH4OH solution was added with vigorous stirring to produce a black solid and the reaction was continued for another 30 min. The black magnetite nanoparticles were isolated by magnetic decantation, washed several times with deionized water and then dried at 80 °C for 10 h. Fe3O4 nanoparticles (1 g) were suspended in a mixture of 100 mL ethanol and NH3.H2O (10 mL, 25%) with the help of ultrasonication. Subsequently, 0.4 mL of tetraethoxysilane (TEOS) was added to solution and the mixture was ultrasonicated for 2 h. Afterward silica coated MNPs (MNP@SiO2) was magnetically separated, washed three times with ethanol and dried at 80 °C for 10 h. Synthesis of 1-methy-3-(trimethoxysilylpropyl) imidazolium chloride ([pmim]Cl): A mixture of 0.12 mol (3chloropropyl)triethoxysilane and 0.12 mol of 1-methylimidazole was refluxed at 78 °C for 24 h under nitrogen atmosphere. The reaction mixture was cooled down and any remaining volatile substances were removed by rotary evaporation. The crude product was additionally washed with Et2O (5× 5 ml) and dried under vacuum to afford pure product (slightly yellow viscous oil). 1H NMR (400 MHz, CDCl3, TMS): δ = 10.04 (s, 1H), 7.57 (t, J= 2 Hz, 1H), 7.34 (t, J= 1.6 Hz 1H), 4.14 (t, 2H, J = 7.2 Hz), 3. 93 (s, 3H), 3.37 (s,6H) 1.84-1.76 (m, 2H), 0.464-0.423 (m, 2H), 13 C NMR (100 MHz, CDCl3 , TMS): δ = 137.3, 123.7, 121.9, 51.5, 50.5, 36.3, 23.9, 5.7 Synthesis of 1-methyl-3-(trimethoxysilylpropyl)imidazolium chloride anchored on Fe3O4@SiO2 ()-MNP[pmim]Cl: [pmim]Cl ( 0.5 gr, 1.3 mmol) was dissolved in 25 ml of dry toluene and treated with 1 g of previously prepared Fe3O4@SiO2. After heating the slurry at 90 °C for 16 h the resulting solid was then separated by an external magnet and washed with 100 ml of dichloromethane. In the following step, the unreacted ionic liquid was removed by 24 h extraction with boiling dichloromethane (soxhlet extraction). In the next step, the material was dried under high vacuum. Synthesis of 1-methyl-3-(trimethoxysilylpropyl)imidazolium hydrogensulfate anchored on Fe3O4@SiO2 (MNP-[pmim]HSO4) : In the round bottom flask equipped with stirrer, MNP[pmim]Cl (1gr) was suspended in 20 ml of dry CH2Cl2. During vigorous stirring, concentrated H2SO4 (1.3 mmol 98%) was introduced drop by drop at 0 °C. Then the mixture was warmed up to the room temperature, and was refluxed for 48 h. Then, the mixture was cooled, filtered and dried.
N
O O Si O
N
SiO2 Fe3O 4
O O Si O
Cl
O O Si O
HN
H2SO 4
N Cl
N
N
SiO2
Cl
Fe3O 4
OH OH OH
SiO2 Fe3O 4
O O Si O
N
N HSO4
Scheme S1: Immobilization of ionic liquid on the surface of nanoparticle Analyses were used to characterize the supported ionic liquid.
Fig S1. FTIR spectra of MNPs(a), MNP@SiO2 (b), [pim]Cl (c), MNP-[pim]Cl (d), MNP-[pmim]HSO4 (d)
Fig S2. XRD pattern of MNP (a), ), MNP [pmim]HSO4 (b)
Fig S3. The TGA thermogram of (a) MNP@SiO2 (b) MNP-[pmim]HSO4
Fig. S4 SEM images of MNP@SiO2 (left), MNP-[pmim]HSO4 (right) Elemental analysis (C:8.36%, H:1.32%, N:2.67% and S:3.19%). The content ratio of C/N (3.13) is very near to the theorical calculation (3.00). General procedure for the synthesis of triarylpyridines To a mixture of aldehyde (1.0 mmol), ketone (2.0 mmol), ammonium acetate (1.3 mmol) was added MNP([pmim]HSO4) (0.012 gr, 1.2 mol%) and the resulting mixture was stirred at 100oC for the specific period of time. The progress of the reaction was monitored by TLC. After completion of the reaction, EtOAc (10 ml) was added and cooled reaction mixture. The catalyst was separated by an external magnet, washed with EtOAC, dried and reused for a consecutive run under the same reaction conditions. Evaporation of the organic solvent under reduced pressure gave the crude products. Pure products were obtained by recrystallization by aqueous EtOH. The products were characterized with IR, 1HNMR and 13CNMR spectra.
Ar 1 Ar 1CHO + 2 Ar2COCH3 + NH4OAc
MNP-[pmim]HSO4 Solvent-free
Ar2
N
Scheme S2: Synthesis of triarylpyridines catalyzed by MNP-([pmim]HSO4
Ar2
Table S2: Synthesis of 2,4,6-triphenylpyridinea
Ar1
1
C6H5-
C6H5-
Time (min) 50
2
4-FC6H4-
C6H5-
55
87
204-206 [41]
3
4-ClC6H4-
C6H5-
45
95
124-125 [41]
4
4-BrC6H4-
C6H5-
40
90
102-104 [41]
5
4-NO2C6H4-
C6H5-
40
85
196-198 [41]
6
4-MeC6H4-
C6H5-
60
90
122-124 [41]
7
4-MeOC6H4-
C6H5-
70
87
99-100 [43]
8
4-OHC6H4-
C6H5-
75
87
195-197 [43]
9
4-N(Me)2C6H4-
C6H5-
80
90
138-140 [31]
10
Pyridine-4yl
C6H5-
65
83
187-190 [31]
11
Thiophen-2-yl
C6H5-
85
78
161-163 [41]
12
Furan-2-yl
C6H5-
80
75
179-181 [41]
13
C6H5-
4-ClC6H4-
45
85
126-128 [40]
14
4-ClC6H4-
4-ClC6H4-
35
90
269-270 [41]
15
4-MeC6H4-
4-ClC6H4-
50
89
118-119 [40]
16
4-MeOC6H4
4-ClC6H4-
45
88
190-191 [40]
Entry
a b
Ar2
Yieldb
M. p (oC) Ref
90
133-134 [41]
Conditions: aldehyde/acetophenone/NH4OAc/MNP-[pmim]HSO4: 1/2/1.3/0.012, 120 °C, solvent-free. Yields refer to pure isolated products
2,4,6-Tri phenyl pyridine (Table S2, entry 1): 1HNMR (400 MHz, DMSO-d6, δ/ppm): 7.01 (d, 2H, J= 8 Hz), 7.24-7.27 (m, 2H), 7.46-7.49 (m, 3H), 7.51-7.58 (m, 3H), 7.78 (d, 2H, J= 7.6 Hz),7.92 (s, 1H), 8.20 (s, 2H), 8.24 (d, 2H, J= 9.6 Hz).13C NMR (100 MHz, DMSO-d6, δ/ppm): 116.7, 117.2, 120.5, 125.9, 127.1, 127.2, 128.3, 128.7, 128.9, 129.0, 129.1, 130.8, 139.1, 139.6, 150.2, 157.5.
4-(4-Fluorophenyl)-2,6-di phenyl pyridine (Table S2, entry 2): 1HNMR (400 MHz, DMSO-d6, δ/ppm): 7.49-7.51 (m, 2H), 7.55-7.57 (m, 4H), 7.86 (b, 3H), 7.88 (b, 2H), 8.21-8.23 (m, 5H).13C NMR (100 MHz, DMSO-d6, δ/ppm):112.7, 116.8, 118.5, 127.6, 127.9, 128.8, 129.2, 129.4, 132.9, 139.0, 143.6, 143.2, 157.9. IR (KBr disc): (cm -1): 1600, 1542, 1514, 1246, 1179, 1026, 826, 753. m/z (ESI) 325.1 (M +•, 100%), 320.1 (50%), 172.1 (16.4%), 171.2 (14.6%), 154.1 (6.7%). 153.2 (4.2%).
4-(4-Choloro)-2,6-di phenyl pyridine (Table S2, entry 3): 1HNMR (400 MHz, DMSO-d6, δ/ppm): 7.137.19 (m, 2H), 7.28-7.35 (m, 3H), 7.58-7.62 (m, 2H), 7.63-7.72 (m, 3H), 7.74-7.76 (m, 2H), 7.95 (s, 2H), 8.10 (d, 2H, J= 7.2 Hz). 13C NMR (100 MHz, DMSO-d6, δ/ppm): 114.3, 115.0, 115.1, 115.6, 117.8, 120.0, 127.0, 128.3, 128.4, 128.8, 128.9, 133.9, 134.1, 141.2, 147.1, 157.7.
4-(4-Bromophenyl)-2,6-di phenyl pyridine (Table S2, entry 4): 1HNMR (400 MHz, DMSO-d6, δ/ppm): 6.84-6.89 (m, 2H), 6.99 (d, 2H, J= 8.8 Hz), 7.26 (d, 2H, J= 8.8 Hz), 7.41 (t, 2H, J= 7.6 Hz), 7.51 (s, 4H), 7.95 (d, 2H, J= 2.4 Hz), 8.02 (d, 2H, J= 7.2 Hz). 13C NMR (100 MHz, DMSO-d6, δ/ppm): 114.7, 115.1, 115.6, 118.1, 128.3, 128.8, 129.0, 133.4, 133.6, 134.2, 140.1, 140.2, 146.8, 146.9, 157.0.
4-(4-Nitrophenyl)-2,6-di phenyl pyridine (Table S2, entry 5): 1HNMR (400 MHz, DMSO-d6, δ/ppm): 8.11 (d, 2H, J= 7.6 Hz), 7.83 (s, 2H), 7.59 (d, 2H, J= 7.2 Hz), 7.54-7.48 (m, 4H), 7.43 (t, 2H, J= 7.2 Hz),7.26 (d, 2H, J= 8 Hz), 7.15 (t, 2H, J= 7.2 Hz).13C NMR (100 MHz, DMSO-d6, δ/ppm): 112.2, 120.7, 121.2, 125.1, 125.9, 127.6, 127.8, 130.4, 130.6, 135.0, 140.9, 141.2, 144.4, 156.4, 159.2.
4-(4-Methylphenyl)-2,6-di phenyl pyridine (Table S2, entry 6): 1HNMR (400 MHz, DMSO-d6, δ/ppm): 2.30 (s, 3H), 6.65 (d, 2H, J= 8 Hz), 6.90 (d, 2H, J= 7.2 Hz), 6.95 (t, 3H, J= 8 Hz), 7.04 (d, 2H, J= 8.4 Hz), 7.09 (d, 2H, J= 8.4 Hz), 7.31-7.7.36 (m, 3H), 8.02 (d, 2H, J= 4 Hz).13C NMR (100 MHz, DMSO-d6, δ/ppm): 21.0, 114.8, 115.5, 115.7, 116.8, 119.7, 126.9, 128.7, 128.8, 129.1, 129.7, 133.8, 135.8, 136.8, 137.7, 145.2, 157.1.
4-(4-Methoxyphenyl)-2,6-di phenyl pyridine (Table S2, entry 7): 1HNMR (400 MHz, DMSO-d6, δ/ppm): 2.42 (s, 3H), 6.67 (t, 2H, J= 7.6 Hz), 6.74 (d, 2H, J= 8 Hz), 7.11 (s, 2), 7.24 (t, 2H, J= 7.6 Hz), 7.34-7.41 (m, 3H), 7.49 (d, 2H, J= 8 Hz), 7.61 (d, 2H, J= 7.2 Hz), 8.20 (s, 2H).13C NMR (100 MHz, DMSO-d6, δ/ppm): 55.6, 114.8, 115.4, 117.6, 127.3, 127.8, 128.7, 128.9, 133.7, 142.1, 148.3.
4-(4-Hydroxy)-2,6-di phenyl pyridine (Table S2, entry 8): 1HNMR (400 MHz, DMSO-d6, δ/ppm): 6.826.83 (m, 2H), 6.86-6.92 (m, 4H), 7.16 (d, 2H, J= 9.6 Hz), 7.28 (t, 2H, J= 8 Hz), 7.95 (s, 2H), 8.06-8.11 (m, 2H), 8.18 (d, 2H, J= 8.4 Hz), 8.48 (s, 1H). 13C NMR (100 MHz, DMSO-d6, δ/ppm): 114.4, 115.1, 115.2, 115.6, 118.3, 118.9, 120.1, 128.0, 128.3, 128.4, 132.9, 133.6, 134.3, 146.5, 146.6, 146.7, 157.8.
4-(4-N,N-dimethylphenyl)-2,6-di phenyl pyridine (Table S2, entry 9): 1HNMR (400 MHz, DMSO-d6, δ/ppm): 2.29 (s, 3H), 2.49 (s, 3H), 6.65 (d, 2H, J= 8.4 Hz), 7.19 (d, 3H, J= 8.8 Hz), 7.31 (d, 3H, J= 7.6 Hz), 7.54 (d, 3H, J= 8.8 Hz), 7.85 (s, 2H), 8.05 (d, 3H, J= 8.0 Hz).13C NMR (100 MHz, DMSO-d6, δ/ppm): 23.7, 23.9, 128.2, 128.4, 128.9, 129.3, 130.9, 133.1, 134.9, 137.9, 141.4, 155.6.
4-(Pyridine-4yl)-2,6-di phenyl pyridine (Table S2, entry 10): 1HNMR (400 MHz, DMSO-d6, δ/ppm): 6.90 (d, 2H, J= 7.2 Hz), 7.16 (t, 2H, J= 7.2 Hz), 7.43-7.50 (m, 2H), 7.52-7.55 (m, 2H), 7.56-7.58 (m, 1H), 8.15 (d, 2H, J= 7.6 Hz), 8.28 (d, 2H, J= 6 Hz), 8.81 (s, 2H). 13C NMR (100 MHz, DMSO-d6, δ/ppm): 115.0, 1169.9, 119.8, 126.8, 126.9, 128.2, 128.9, 129.0, 134.0, 124.8, 138.4, 140.4, 145.0, 157.9.
4-(Thiophen-2-yl)-2,6-di phenyl pyridine (Table S2, entry 11): 1HNMR (400 MHz, DMSO-d6, δ/ppm): 7.06 (d, 2H, J= 8 Hz), 7.12 (s, 1H), 7.13 (d, 1H, J= 3.2 Hz), 7.17(d, 2H, J= 8.8 Hz), 7.26 (s, 2H), 7.357.40 (m, 2H), 7.42-7.46 (m, 1H), 7.51 (d, 1H, J= 6.8 Hz), 7.84 (d, 2H, J= 8 Hz), 7.91 (d, 2H, J= 2 Hz).13C NMR (100 MHz, DMSO-d6, δ/ppm): 122.8, 125.7, 126.2, 126.3, 127.5, 128.4, 129.0, 129.3, 130.2, 131.9, 132.6, 136.0, 139.4, 156.3.
4-(Furan-2-yl)-2,6-di phenyl pyridine (Table S2, entry 12): 1HNMR (400 MHz, DMSO-d6, δ/ppm): 6.62 (d, 1H, J= 7.6 Hz), 7.80 (d, 2H, J= 7.2 Hz), 6.89 (t, 1H, J= 7.2 Hz), 7.08 (d, 2H, J= 9.2 Hz), 7.26-7.32 (m, 4H), 7.33-7.37 (m, 2H), 8.02 (s, 1H), 8.03 (d, 2H, J= 8 Hz). 13C NMR (100 MHz, DMSO-d6, δ/ppm): 108.4, 114.2, 114.6, 116.6, 119.5, 126.8, 128.5, 128.7, 129.0, 133.3, 133.8, 139.9, 145.4, 158.1.
4-(Phenyl)-2,6-di-4-cholorophenyl pyridine (Table S2, entry 13): 1HNMR (400 MHz, DMSO-d6, δ/ppm): 7.35 (s, 2H), 7.46-7.49(m, 2H), 7.51-7.56 (m 2H), 7.57-7.59 (m, 4H), 7.78-7.79 (m, 2H),7.79 (s, 1H), 7.79-7.90 (s, 2H), 8.20-8.22 (d, 2H, J= 7.2 Hz).13C NMR (100 MHz, DMSO-d6, δ/ppm): 116.3, 122.9, 126.0, 127.0, 127.1, 127.5, 128.7, 129.1, 129.9, 134.3, 157.6.
2,4,6-Tri-4-choloro phenyl pyridine (Table S2, entry 14): 1HNMR (400 MHz, DMSO-d6, δ/ppm): 6.92 (d, 2H, J= 8.4 Hz), 7.25-7.29 (m, 3H), 7.47-7.48 (m, 4H), 7.77-7.79 (m, 3H), 7.92 (s, 2H), 8.20 (d, 2H, J= 4.8 Hz). 13C NMR (100 MHz, DMSO-d6, δ/ppm): 112.0, 121.6, 126,5, 126.7, 129.3, 130.5, 131.5, 132.0, 132.1, 136.2, 138.9, 142.1, 143.8, 151.3, 157.4.
4-(4-Methyl)-2,6-di-4-choloro phenyl pyridine (Table S2, entry 15): 1HNMR (400 MHz, DMSO-d6, δ/ppm): 2.30 (s, 3H), 7.17 (t, 2H, J= 7.6 Hz), 6.18-7.21 (m, 2H), 7.62 (s, 2H), 7.70-7.74 (m, 2H), 7.917.93 (m, 2H), 7.96-7.97 (m, 1H), 8.05 (d, 1H, J= 4.8 Hz), 8.34 (s, 2H). 13C NMR (100 MHz, DMSO-d6, δ/ppm):26.2, 114.9, 115.4, 117.7, 127.8, 128.7, 129.2, 133.4, 133.8, 141.1, 148.1, 157.6.
4-(4-Methoxy phenyl)-2,6-di-4-choloro phenyl pyridine (Table S2, entry 16): 1HNMR (400 MHz, DMSO-d6, δ/ppm): 3.88 (s, 3H), 6.97 (d, 2H, J= 8.4 Hz), 7.41 (t, 2H, J= 6.4 Hz), 7.46-7.49 (m, 3H), 7.577.58 (m, 3H), 7.62 (d, 2H, J= 8.8 Hz), 8.08 (d, 2H, J= 7.2 Hz), 8.28 (s, 2H). 13C NMR (100 MHz, DMSOd6, δ/ppm): 55.3, 115.9, 120.7, 125.8, 127.3, 127.5, 128.6, 130.4, 133.7, 141.2, 143.5, 144.7, 158.2.
