Dimethylformamide → HCID 86712672, compound

HRID 1779021Notes

Reaction equation

HRID 1779021 reaction equation
Br[C:2]1[CH:7]=[C:6]([C:8]([F:11])([F:10])[F:9])[CH:5]=[CH:4][C:3]=1[CH2:12][C:13]([O:15][CH3:16])=[O:14].F[B-](F)(F)F.[Si:22]([C:26]#[CH:27])([CH3:25])([CH3:24])[CH3:23].CN(C=O)C>CCN(CC)CC.Cl[Pd](Cl)([P](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1)[P](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1.[Cu]I>[F:9][C:8]([F:11])([F:10])[C:6]1[CH:5]=[CH:4][C:3]([CH2:12][C:13]([O:15][CH3:16])=[O:14])=[C:2]([C:27]#[C:26][Si:22]([CH3:25])([CH3:24])[CH3:23])[CH:7]=1

Participants

8

Reactant 4

HCID 6228DimethylformamideHCID 26255TetrafluoroborateHCID 66111TrimethylsilylacetyleneHCID 75487957HCID 75487957, compound

Product 1

HCID 86712672HCID 86712672, compound

Reagents, catalysts & solvents 3

HCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)CatalystHCID 178418476HCID 178418476, compoundCatalystHCID 8471TriethylamineSolvent

Conditions

Temperature
80 °C

Procedure

A suspension of methyl 2-(2-bromo-4-(trifluoromethyl)phenyl)acetate (A57) (1.60 g, 5.38 mmol), PdCl2(PPh3)2 (189 mg, 269 μmmol), t-Bu3PH.BF4 (78.1 mg, 269 μmmol), CuI (51.3 mg, 269 μmol) and TMS-acetylene (1.52 mL, 10.8 mmol) in Et3N (10 mL) and anhydrous, degassed DMF (10 mL) was stirred at 80° C. for 16 hours. The resulting mixture was adsorbed onto silica gel and purified using column chromatography (Biotage Isolera, SiO2 cartridge, 0-10% EtOAc in petroleum benzine 40-60° C.) to give the title compound A58 as an orange liquid (1.56 g, 92%); 1H NMR (400 MHz, CDCl3) δ 7.73 (d, J=1.1 Hz, 1H), 7.53 (dd, J=8.1, 1.3 Hz, 1H), 7.39 (d, J=8.1 Hz, 1H), 3.87 (s, 2H), 3.71 (s, 3H), 0.26 (s, 9H). LCMS-A: rt 6.979 min; m/z 315 [M+H]+.

Workup

  1. custompurified
  2. customcolumn chromatography (Biotage Isolera, SiO2 cartridge, 0-10% EtOAc in petroleum benzine 40-60° C.)

Sources & evidence

ORD record
ord-a6828962605843558e62dbe3de2f3394
Source dataset
uspto-grants-2016_02
Patent number
US09266864B2

Reaction notes

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