1-Butyne → HCID 9835915, compound

HRID 363350Notes

Reaction equation

C#CCC.[Li][CH2:6][CH2:7][CH2:8][CH3:9].Cl[C:11]1([C:24]([F:27])([F:26])[F:25])[C:16]2[CH:17]=[C:18]([O:21][CH3:22])[CH:19]=[CH:20][C:15]=2[NH:14][C:13](=[O:23])[O:12]1>C1COCC1>[C:6]([C:11]1([C:24]([F:26])([F:27])[F:25])[C:16]2[CH:17]=[C:18]([O:21][CH3:22])[CH:19]=[CH:20][C:15]=2[NH:14][C:13](=[O:23])[O:12]1)#[C:7][CH2:8][CH3:9]

Participants

Conditions

Temperature: -10 °C

Procedure

To a stirred, cooled(-78° C.) solution of 0.5 g(excess) of 1-butyne in 3 mL of anhydrous THF was added 1.6 mL(4.0 mmol) of a 2.5M solution of n-BuLi in hexanes over 3 min. The solution was stirred 5 min. and charged with 266 mg(1.00 mmol) of 4-chloro-6-methoxy-4-trifluoromethyl-1,4-dihydro-2H-3,1-benzoxazin-2-one as a single portion. The solution was warmed to -10° C. over 20 min., whereupon it was quenched with 20% aqueous citric acid. The mixture was extracted with ether, and the organic extract was washed with saturated aq. NaHCO3 then brine. The solution was concentrated under reduced pressure, and the crude product was recrystallized from ethyl acetate-hexanes to afford 144 mg(48%) of 4-(1-butynyl)-6-methoxy-4-trifluoromethyl-1,4-dihydro-2H-3,1-benzoxazin-2-one as a white solid, mp 161°-162° C. 1H NMR(300 MHz, CDCl3) δ8.81(br. s, 1H); 7.07(d, 1H, J=2 Hz); 6.94(dd, 1H, J=9, 2 Hz); 6.81(d, 1H, J=8 Hz); 3.82(s, 3H); 2.34(q, 2H, J=7 Hz); 1.22(t, 3H, J=7 Hz).

Workup

customwas quenched with 20% aqueous citric acid
extractionThe mixture was extracted with ether
extractionthe organic extract
washwas washed with saturated aq. NaHCO3
concentrationThe solution was concentrated under reduced pressure
customthe crude product was recrystallized from ethyl acetate-hexanes

Sources & evidence

ORD record: ord-56c74d98da0144ffb1dfd77ae846bd44
Source dataset: uspto-grants-1999_02
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US05874430

Reaction notes

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