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Oxidation of metribuzin (1) with hydrogen peroxide cata-
lyzed by 5,10,15,20-tetraarylporphyrinatoiron(III) chlo-
rides (6a–d) in dichloromethane: Metribuzin (1)
(1 mmol) and a catalytic amount of 5,10,15,20-tetra-
kis(pentafluorophenyl)porphyrinatoiron(III) chloride (6d)
(0.01 mmol) in dichloromethane (15 mL) was stirred
under a nitrogen atmosphere. To this, hydrogen peroxide
solution (2 mmol, 30%) was added. The progress of
the reaction was monitored by TLC and HPLC ana-
lyses. After the reaction, the solvent was removed under
reduced pressure and the oxidative products were sepa-
rated by column chromatography over neutral alumina.
Elution of the column with chloroform/methanol (99:1,
v/v) gave triazines 2, 3 and 4. Intermediate 5 was iso-
lated by preparative TLC (solvent system: chloroform/
ethyl acetate 1:1, v/v) after 25 min of reaction.
Data for 2: mp 199–200 °C; UV–vis: kmax (CH2Cl2)/nm
236 (1.47); IR (KBR): mmax/cmÀ1 3450, 2970, 2929, 2766,
1615, 1583, 1517, 1449, 1384, 1357, 1193, 590; 1H NMR:
dH (300 MHz; CDCl3; Me4Si) 1.35 (s, 9H, –C(CH3)3),
2.55 (s, 3H, –SCH3); EI-MS: m/z 199 (M+), 198, 181,
171, 144, 116, 85, 71, 57, 43.
Data for 3: mp 167–168 °C; UV–vis: kmax (CH2Cl2)/nm
258 (0.95); IR (KBR): mmax/cmÀ1 3326, 3232, 2957, 2927,
1
1721, 1661, 1550, 1453, 1248, 1144, 909, 736, 669; H
NMR: dH (300 MHz; CDCl3; Me4Si) 1.33 (s, 9H,
–C(CH3)3), 5.25 (s, 3H, –SCH3); EI-MS: m/z 184
(M+), 183, 167, 152, 141, 114, 83, 69, 57, 41.
20. Cunningham, I. D.; Danks, T. N.; Hay, J. N.; Hamerton,
I.; Gunathilagan, S.; Janczak, C. Tetrahedron 2001, 57,
6847.
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22. Meunier, B.; de Visser, S. P.; Shaik, S. Chem. Rev. 2004,
104, 3947.
Data for 4: sublimed 260–264 °C; IR (KBR): mmax/cmÀ1
1
3325, 2922, 1721, 1664, 1551, 1452, 909; H NMR: dH
(300 MHz; CDCl3; Me4Si) 1.34 (s, 9H, –C(CH3)3); EI-
MS: m/z 169 (M+), 168, 153, 141, 85, 71, 57, 43.
Data for 5: UV–vis: kmax (CH2Cl2)/nm 231 (1.74), 274
(1.73); IR (film): mmax/cmÀ1 3301, 3242, 3182, 1672,
1558, 1541, 1461, 1363, 1247, 1187, 1050, 967, 720; H
23. Rebelo, S. L. H.; Pereira, M. M.; Simoes, M. M. Q.;
Neves, M. G. P. M. S.; Cavaleiro, J. A. S. J. Catal. 2005,
234, 76.
1
24. Fujii, H. Coord. Chem. Rev. 2002, 226, 51.
25. Nam, W.; Han, H. J.; Oh, S.-Y.; Lee, Y. J.; Cho, M.-H.;
Han, S.-Y.; Kim, C.; Woo, S. K.; Shin, W. J. Am. Chem.
Soc. 2000, 122, 8677.
NMR: dH (300 MHz; CDCl3; Me4Si) 1.49 (s, 9H,
–C(CH3)3), 3.25 (s, 3H, –S(O)CH3), 5.91 (s, 2H, NH2);
ESI-MS: m/z 231 [M+H]+, 253 [M+Na]+.
26. Stephenson, N. A.; Bell, A. T. J. Am. Chem. Soc. 2005,
127, 8635.
Acknowledgements
27. Crestoni, M. E.; Fornarini, S. Inorg. Chem. 2005, 44, 5379.
28. Chauhan, S. M. S.; Kalra, B.; Mohapatra, P. P. J. Mol.
Catal. A: Chem. 1999, 137, 85.
29. Chauhan, S. M. S.; Mahapatra, P. P.; Rao, K. V.;
Vijayaraghavan, B.; Shahi, S. P. Indian J. Heterocyl.
Chem. 1996, 5, 181.
The author (P.K.) thanks the Council of Scientific and
Industrial Research (CSIR), New Delhi, India, for pro-
viding a senior research fellowship (SRF). P.K. is also
thankful to Anil Kumar for discussion and reading the
manuscript.
30. Chauhan, S. M. S.; Vijayaraghavan, B.; Rao, K. V. Indian
J. Chem. B 1987, 26, 122.
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In Herbicides Chemistry, Degradation and Mode of Action;