Eco-friendly Oxidative Iodination of Various Arenes with Sodium Percarbonate as the Oxidant†
Abstract
:Introduction
Results and discussion
Conclusions
Experimental
General
Optimized iodinating procedures, with using sodium percarbonate (SPC) as the oxidant
- (a)
- 4.26 mL H2SO4 (7.84 g; 80 mmol) for the iodination of C6H5NHAc or uracil;
- (b)
- 4.80 mL H2SO4 (8.83 g; 90 mmol) for the iodination of C6H6, C6H5Br or C6H5Cl;
- (c)
- 5.33 mL H2SO4 (9.80 g; 100 mmol) for the iodination of 4-MeC6H4COOH, 4-MeC6H4COOMe, 4-O2NC6H4Me or 4-O2NC6H4OMe;
- (d)
- 7.50 mL H2SO4 (13.8 g; 140 mmol) for the diiodination of PhH.
- (a)
- 3.60 mL H2SO4 (6.60 g; 67.5 mmol) for the iodination of PhCOOH;
- (b)
- 4.80 mL H2SO4 (8.83 g; 90.0 mmol) for the iodination of PhI, PhCOOMe, 4-MeC6H4COOH, 4-O2NC6H4Me, and for the diiodination of PhH;
- (c)
- 6.80 mL H2SO4 (12.5 g; 127 mmol) for the diiodination of PhCOPh.
- (a)
- for 2 h at 40 °C for the iodination of PhOMe;
- (b)
- for 2 h at 50−60 °C for the iodination of 1- or 2-MeOC10H7;
- (c)
- for 3 h at 40 °C for the iodination of PhNH2.
Substrate | Procedure | Product | Yield (%)a | Mp (°C) (S),b or bp (°C/mmHg); |
---|---|---|---|---|
Lit. [12] mp (°C), or bp (°C/mmHg) | ||||
PhNH2 | 1 | 4-IC6H4NH2 | 68 | 63−65 (H); 63−65 |
PhNH2 | 1 | 2,4-I2C6H3NH2 | 85 | 93−94 (H); 95−96 |
4-IC6H4NH2 | 1 | 2,4-I2C6H3NH2 | 78 | 96−97 (H); 95−96 |
2-BrC6H4NH2 | 1 | 2-Br-4-IC6H3NH2 | 67 | 71−74 (Hp); 71−72 |
2-MeC6H4NH2 | 1 | 4-I-2-MeC6H3NH2 | 86 | 86−87 (H); 88 |
PhNMe2 | 2 | 4-IC6H4NMe2 | 60 | 81−83 (E); 82 |
2-ClC6H4NH2 | 2 | 2-Cl-4-IC6H3NH2 | 73 | 60−61 (H); 62−63 |
2-BrC6H4NH2 | 2 | 2-Br-4-IC6H3NH2 | 62 | 70−73 (Hp); 71−72 |
2-MeC6H4NH2 | 2 | 4-I-2-MeC6H3NH2 | 48 | 87−88 (H); 86−88 |
PhH | 3 | PhI | 40 | bp 76−78/20; bp 78-80/25 [5] |
PhH | 3 | 1,4-I2C6H4 | 83 | 128−130 (L); 129 |
4-O2NC6H4Me | 3 | 2-I-4-O2NC6H3Me | 75 | 51−52 (N); 53−54 |
4-O2NC6H4OMe | 3 | 2-I-4-O2NC6H3OMe | 92 | 95−96 (L); 97 |
4-MeOC6H4CO2Me | 3 | 3-I-4-MeOC6H4CO2Me | 85 | 93−95 (N); 95−97 |
PhNHCOMe | 3 | 4-IC6H4NHCOMe | 62 | 183−185 (E); 184 |
PhCl | 3 | 4-ClC6H4I | 80 | 55−56 (E); 57 |
PhBr | 3 | 4-BrC6H4I | 68 | 91−92 (L); 91−92 |
uracil | 3 | 5-iodouracil | 84 | 276−276.5 (E); 276−278 |
4-RC6H4CO2Hc | 3 | 3-I-4-RC6H3CO2Hc | 92 | 238−239 (W); 230 |
PhH | 4 | 1,4-I2C6H4 | 83 | 128−130 (L); 129 |
PhI | 4 | 1,4-I2C6H4 | 94 | 128−129 (L); 129 |
PhCO2H | 4 | 3-IC6H4CO2H | 93 | 185−187 (C); 187−188 |
4-MeC6H4CO2H | 4 | 3-I-4-MeC6H3CO2H | 79 | 208−209 (C); 210−212 |
PhCO2Me | 4 | 3-IC6H4CO2Me | 60 | 52−53 (L); 54−55 |
4-O2NC6H4Me | 4 | 2-I-4-O2NC6H3Me | 87 | 51−53 (N); 53−54 |
PhCOPh | 4 | 3-IC6H4COC6H4I-3’ | 51 | 140−142 (A); 141−143 [5] |
C6H5OMe | 5 | 4-IC6H4OMe | 64 | 50−51 (H); 51−52 |
1-MeOC10H7 | 5 | 4-I-1-MeOC10H6 | 68 | 50−51 (E); 52−53 [11] |
2-MeOC10H7 | 5 | 1-I-2-MeOC10H6 | 62 | 82−84 (E); 82−84 [11] |
PhNH2 | 5 | 4-IC6H4NH2 | 53 | 60−62 (H); 63−65 |
2-O2NC6H4OH | 6 | 2,4-I2-6-O2NC6H2OH | 80 | 93−94 (E); 94 [13] |
4-O2NC6H4OH | 6 | 2,6-I2-4-O2NC6H2OH | 72 | 149−150 (E); 150−151 [11] |
4-CH3C6H4OH | 6 | 2,6-I2-4-CH3C6H2OH | 83 | 58−59 (E); 55−58 [14] |
8-hydroxyquinoline | 6 | 5,7-diiodo-8-hydroxyquinoline | 85 | 216−217 dec. (E); ca. 214 dec. |
PhNH2 | 6 | 4-IC6H4NH2 | 77 | 60−62 (H); 63−65 |
4-IC6H4NH2 | 6 | 2,4-I2C6H3NH2 | 59 | 95−96 (H); 95−96 |
- a
- Optimized yield of pure isolated product. Satisfactory microanalyses obtained for the purified products: I% ± 0.4; their purities and homogeneities were checked by TLC and 1H and 13C NMR solution spectra (not shown here).
- b
- S = Solvent used for recrystallization. A: acetone; C: CCl4; E: EtOH; H: hexane; Hp: heptane; L: EtOH−H2O (4:1); N: EtOH−H2O (3:2); W: H2O−EtOH (5:1).
- c
- R = 4-MeCONH.
References and Notes
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- Sample Availability: Contact the authors.
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Zielinska, A.; Skulski, L. Eco-friendly Oxidative Iodination of Various Arenes with Sodium Percarbonate as the Oxidant†. Molecules 2005, 10, 1307-1317. https://doi.org/10.3390/10101307
Zielinska A, Skulski L. Eco-friendly Oxidative Iodination of Various Arenes with Sodium Percarbonate as the Oxidant†. Molecules. 2005; 10(10):1307-1317. https://doi.org/10.3390/10101307
Chicago/Turabian StyleZielinska, Agnieszka, and Lech Skulski. 2005. "Eco-friendly Oxidative Iodination of Various Arenes with Sodium Percarbonate as the Oxidant†" Molecules 10, no. 10: 1307-1317. https://doi.org/10.3390/10101307
APA StyleZielinska, A., & Skulski, L. (2005). Eco-friendly Oxidative Iodination of Various Arenes with Sodium Percarbonate as the Oxidant†. Molecules, 10(10), 1307-1317. https://doi.org/10.3390/10101307