3-Methylbut-1-yne → ethyl 6-chloro-8-(3-methylbut-1-ynyl)-2-(trifluoromethyl)-2H-chromene-3-carboxylate

HRID 855003Notes

Reaction equation

HRID 855003 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].[CH3:22][CH:23]([CH3:26])[C:24]#[CH:25]>[Cu]I>[Cl:16][C:12]1[CH:13]=[C:14]2[C:9](=[C:10]([C:25]#[C:24][CH:23]([CH3:26])[CH3:22])[CH:11]=1)[O:8][CH:7]([C:18]([F:21])([F:20])[F:19])[C:6]([C:4]([O:3][CH2:1][CH3:2])=[O:5])=[CH:15]2

Participants

4

Reactant 2

HCID 690193-Methylbut-1-yneHCID 21883552ethyl 6-chloro-8-iodo-2-(trifluoromethyl)-2H-chromene-3-carboxylate

Product 1

HCID 58934587ethyl 6-chloro-8-(3-methylbut-1-ynyl)-2-(trifluoromethyl)-2H-chromene-3-carboxylateYield 91.3%

Reagents, catalysts & solvents 1

HCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)Catalyst

Procedure

To 2.000 g (4.624 mmole) of ethyl-6-chloro-8-iodo-2-(trifluoromethyl)-2H-chromene-3-carboxylate was added 267 mg (0.231 mmole) tetrakis(triphenylphospine)palladium(0), 88 mg (0.462 mmole) copper (I) iodide, 40 mL degassed toluene, 1.930 mL (13.87 mmole) degassed TEA, and 0.473 g (6.94 mmole) 3-methyl-1-butyne. The mixtures was stirred overnight at room temperature. The mixture was concd and the resulting oil was purified using reverse phase chromatography to afford 1.573 g (91%) of a yellow crystalline solid: 1H NMR (CDCl3/400 MHz) 1.26 (d, 6H, J=6.8 Hz), 1.34 (t, 3H, J=7.2 Hz), 2.80 (septet, 1H, J=6.8 Hz), 4.27-4.35 (m, 2H), 5.78 (q, 1H, J=6.8 Hz), 7.09 (d, J=2.4 Hz), 7.31 (d, 1H, J=2.4 Hz), 7.59 (s, 1H); MS (ES+) 373 (M+1, 100): MS (EI) 372 (M+, 22), 303 (100), 275 (35).

Workup

  1. customdegassed toluene, 1.930 mL (13.87 mmole)
  2. customthe resulting oil was purified

Sources & evidence

ORD record
ord-68575bb71833495c8e17ad814447f922
Source dataset
uspto-grants-2007_08
Patent number
US07259266B2

Reaction notes

Loading…