3-Chloro-4-methylphenol

White powder

General procedure: A 8 mL screw cap test tube was charged with Cu(OAc)2*H2O (12 mg, 0.06 mmol, 2 mol percent), L (25 mg, 0.12 mmol, 4 mol percent), hexane-2, 5-dione (18 mg, 0.12 mmol, 4 mol percent), KOH (85 percent) (225 mg, 3.3 mmol, 110 mol percent), adipic acid (70 mg, 0.45 mmol, 15 mol percent), NaOAc (78 mg, 0.9 mmol, 30 mol percent), CTAB (60 mg, 0.15 mmol, 5 molpercent), H2O (0.3 mL), corresponding aryl chloride (3 mmol) and morpholine (350 mg, 3.9 mmol, 130 mol percent). Argon (flow rate 5-7 mL/min) was bubbled through the resulting mixture for 5 min. The reaction mixture was stirred in a closed test tube at 110 °C for 3 h, then cooled to room temperature and diluted with EtOAc (30 mL). The EtOAc solution was washed with water (230 mL), dried with anhydrous Na2SO4, filtered and analyzed by GC and GC-MS. Then EtOAc was evaporated under reduced pressure and the residue was chromatographed using a SiO2 column (EtOAc/hexane 1:5 or petroleum ether (40-70 °C)/EtOAc 9:1).2-(4-Chloro-2, 3-dihydro-2, 5-dimethylbenzofuran-7-yl)-N-methoxy-N-methyldiazenecarboxamide (2) 283 g of 3-chloro-4-methylaniline was added to a solution of 1000 ml of water and 500 ml of concentrated sulfuric acid, causing the temperature of the mixture to rise from ambient to 95° C. The mixture was cooled and stirred at room temperature for 30 minutes, then cooled to 5° C. and a solution of 145 g of sodium nitrite in 500 ml of water was slowly added (1.5 hours) to the stirred mixture at 5°-10° C. The mixture was stirred at about 5° C. for one hour, then added over two hours to a stirred solution of 1.2 liters of concentrated sulfuric acid in 2 liters of water, at 105°-110° C. The resulting mixture was stirred at 110° C. for one hour, then held at room temperature for 18 hours. Then 3.5 liters of hexane was added, the mixture was stirred for 30 minutes, allowed to stand, and the two liquid phases were separated. The hexane phase was filtered, washed with water, dried (MgSO4) and concentrated to dryness to give crude EXAMPLE 4 (5-chloro-3, 4-dihydro-2, 6-dimethyl-2H-1-benzopyran-8-yl)diazenecarboxylic acid methyl ester (4) 1.3 liters of concentrated sulfuric acid was added to a stirred mixture of 566 g of 3-chloro-4-methylaniline and 3 liters of water. The mixture warmed to 104° C. The mixture was cooled to 10°-15° C. and stirred while a solution of 290 g sodium nitrite in 1 liter of water was added drop-by-drop (over 2 hours). The mixture was stirred for 1 hour at about 10° C., then was added drop-by-drop (over 2 hours) to a stirred solution of 1 liter of concentrated sulfuric acid in 1.5 liters of water, at 110°-115° C. The resulting mixture was stirred at reflux temperature for one hour, cooled to room temperature and extracted with ether. The extract (4 liters) was mixed with 4 liters of water. The resulting mixture was stirred at 15° C. while 700 ml of a 50percent aqueous solution of sodium hydroxide was slowly added (over 1 hour). The aqueous phase was separated, cooled to 15°-20° C. and stirred while 1.3 liters of concentrated hydrochloric acid was added. The resulting mixture was extracted with ether, the extract was dried (MgSO4) and the solvent was evaporated to give

Molecular Weight:142.58
XLogP3:3.3
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