REACTIONPRODUCTOF44OXYDIPHENOLWITH1CHLORO23EPOXYPROPANE synthesis

Yield:19389-73-2 64%

Reaction Conditions:

Stage #1: 4,4'-dihydroxydiphenyl etherwith sodium hydride in N,N-dimethyl-formamide; for 0.166667 h;Inert atmosphere;
Stage #2: epichlorohydrin in N,N-dimethyl-formamide at 20; for 21 h;Inert atmosphere;
Stage #3: with water in N,N-dimethyl-formamide at 20;Inert atmosphere;

Steps:

1

(JG-112). A round-bottomed flask was charged sequentially with NaH (148 mg, 3.71 mmol, 3 equiv), anhydrous dimethyl formamide (4 mL), and 4,4'-dihydroxydiphenyl ether (250 mg, 1.23 mmol, 1 equiv) and the contents were stirred under an atmosphere of argon for 10 min. Racemic epichlorohydrin (290 μ,, 3.71 mmol, 3 equiv) was added via syringe and the mixture was allowed to react at room temperature for 21 h. Then, the solution was quenched with deionized water (~ 2 mL) and the mixture was extracted with ethyl acetate (3 mL). The organic layer was washed with deionized water (2 mL), was dried over anhydrous magnesium sulfate, was filtered, and was concentrated under reduced pressure. The resulting residue was purified by flash column chromatography on silica gel (eluent: dichloromethane) to provide JG-112 (247 mg, 64%) as a white solid.H NMR (400 MHz, DMSO-i/₆): δ 6.94 (d, J= 8.8, 4H), 6.89 (d, J= 9.2, 4H), 4.27(dd, J= 11.2, 2.4, 2H), 3.79 (dd, J= 11.2, 6.4, 2H), 3.30 (s, 2H), 2.82 (dd, J= 4.8, 2H), 2.69 (m, 2H).13C NMR (100 MHz, DMSO-c?): δ 154.7, 151.8, 120.0, 116.3, 70.0, 50.3, 44.4.HRMS (ESI) (m/z): calc'd for d₈Hi₈0₅Na [M+Na]⁺: 337.1052, found: 337.1099.TLC (5% methanol in dichloromethane), R i 0.75 (UV, j3-anisaldehyde).

References:

WO2011/82488,2011,A1 Location in patent:Page/Page column 96