ethyl 6-chloro-8-iodo-2-(trifluoromethyl)-2H-chromene-3-carboxylate → HCID 69516741, compound

HRID 854997Notes

Reaction equation

[CH2:1]([O:3][C:4]([C:6]1[CH:7]([C:18]([F:21])([F:20])[F:19])[O:8][C:9]2[C:14]([CH:15]=1)=[CH:13][C:12]([Cl:16])=[CH:11][C:10]=2I)=[O:5])[CH3:2]>C1C=CC(P(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1.C1C=CC(P(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1.C1C=CC(P(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1.C1C=CC(P(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1.[Pd].[Cu]I>[CH2:1]([O:3][C:4]([C:6]1[CH:7]([C:18]([F:21])([F:20])[F:19])[O:8][C:9]2[C:14]([CH:15]=1)=[CH:13][C:12]([Cl:16])=[CH:11][C:10]=2[C:4]#[C:6][CH2:15][CH3:14])=[O:5])[CH3:2]

Participants

Conditions

Temperature: -78 °C

Procedure

A mixture of 1.00 g (2.31 mmole) of ethyl-6-chloro-8-iodo-2-(trifluoromethyl)-2H-chromene-3-carboxylate, 134 mg (0.116 mmole) tetrakis(triphenylphosphine)palladium(O), 44 mg (0.231 mmole) copper (I) iodide, 20 mL degassed toluene and 0.965 mL (6.94 mmole) degassed TEA was cooled to −78° C. and treated with an excess of condensed gaseous 1-butyne. The mixture was stirred for thirty minutes at −78° C. and allowed to warm to room temperature and stirred overnight. The reaction mixture was concd and the resulting oil was purified using reverse phase chromatography to afford 0.768 g (93%) of a crystalline solid: 1H NMR (CDCl3/400 MHz) 1.24 (t, 3H, J=7.2 Hz), 1.34 (t, 3H, J=7.2 Hz), 2.45 (q, 2H, J=7.6 Hz), 4.27-4.35 (m, 2H), 5.78 (q, 1H, J=6.8 Hz), 7.10 (d, 1H, J=2.4 Hz), 7.32 (d, 1H, J=2.4 Hz), 7.59 (s, 1H); MS (ES+) 359 (M+1, 100).

Workup

customdegassed toluene and 0.965 mL (6.94 mmole)
customdegassed TEA
additiontreated with an
customexcess of condensed gaseous 1-butyne
temperatureto warm to room temperature
stirringstirred overnight
customthe resulting oil was purified

Sources & evidence

ORD record: ord-a00a2a4d33cc4925a14a18e0757923c9
Source dataset: uspto-grants-2007_08
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US07259266B2

Reaction notes

Loading…