3-CHLORO-5-METHYLPHENOL

General procedure: A suspension of bismacycle tosylate 1-OTs (1.0 equiv.; initial concentration = 0.05 M), K2CO3 (1.2 equiv.) and arylboronic acid (1.1 equiv.) in toluene/water (99:1, v/v) was stirred at 60 C for 2 h. After cooling to room temperature, substrates(naphthols, 0.90 equiv.; phenols, 3.0 equiv.) and mCPBA (titrated; 1.5 equiv.) were added. The reaction was stirred for 10 min at room temperature and then methanol (2 ml) was added. The mixture was diluted with diethyl ether and washed witha saturated aqueous solution of KHCO3. The organic phase was separated, dried (MgSO4), filtered and concentrated in vacuo before purification by flash column chromatography on silica gel. Following isolation of the desired arylation product, bismacycle acetate 1-OAc can be recovered by flushing the column with diethyl ether to remove organic impurities before elution with 2% acetic acid in methanol.To a solution of 3, 5-dibromo-1-(propan-2-yl)-1H- 1, 2, 4-triazole (Int-2, 500 mg, 1.9 mmol) and 3- chloro-5-methyl-phenol (290.5 mg, 2.0 mmol) in DMSO (5.0 mL) was added Cs2C03(1211.3 mg, 3.7 mmol). The stirring was continued in microwave at 120C for 1 h. After complete consumption of starting material (as monitored by TLC) reaction mixture was poured into water and extracted with MTBE. The organic layer was separated and dried over sodium sulphate. Solvent was evaporated under reduced pressure and purified by combi-flash columnchromatography (silica gel, eluting with ethyl acetate / n-hexane 2:98 v/v) to afford the title compound as white solid (280 mg, 46%). 1H NMR (DMSO-d6, 400 MHz): 1.41 (d, J = 6.6 Hz, 6H), 2.34 (s, 3H), 4.60 (hept, J = 6.6 Hz, 1H), 7.19 (s, 1H), 7.24 (s, 1H), 7.36 (s, 1H). MS (ES+) m/z 332.2 [M+H] .Int-79:In a 50 mL pressure vial, 3, 5-dibromo-1-methyl-1H-1, 2, 4-triazole (Int-41, 1.42 g, 5.89 mmol) was dissolved in DMF (12 mL) and potassium carbonate (1.36 mg, 9.82 mmol), followed by 3- chloro-5-methylphenol (700 mg, 4.91 mmol) were added. The vial was sealed, the reaction mixture was stirred for 15 h at 100 C. After cooling, it was concentrated in vacuo, the residue was purified by column chromatography (silica gel, 70 g, eluting with ethyl acetate / n-heptane, gradient 0: 100 to 25:75 v/v) to yield the title compound as white solid (1.37 g, 92%). 1H NMR (CDC13, 300 MHz): delta 2.37 (s, 3 H), 3.77 (s, 3 H), 6.99-7.02 (m, 1 H), 7.06-7.08 (m, 1 H), 7.11- 7.14 (m, 1 H). MS (ES+) m/z 302.0, 304.0, 306.0 [M+H, Br & CI isotopes] .To a mixture of phenol (0.032 mmol) and catalyst(0.0016 mmol) in deionized water (1 mL), UHP (0.08 mmol)was added gradually. The mixture was stirred at 45 C for90 min, and the products were characterized by GC or highperformanceliquid chromatography (HPLC).

Molecular Weight:142.58
XLogP3:2.6
Hydrogen Bond Donor Count:1
Hydrogen Bond Acceptor Count:1
Exact Mass:142.0185425
Monoisotopic Mass:142.0185425
Topological Polar Surface Area:20.2
Heavy Atom Count:9
Complexity:94.9
Covalently-Bonded Unit Count:1
Compound Is Canonicalized:Yes