Dimethylformamide → HCID 86712709, compound

HRID 1779068Notes

Reaction equation

HRID 1779068 reaction equation
Br[C:2]1[CH:7]=[CH:6][C:5]([C:8]([F:11])([F:10])[F:9])=[CH:4][C:3]=1[CH2:12][C:13]([O:15][CH3:16])=[O:14].F[B-](F)(F)F.[CH3:22][Si:23]([C:26]#[CH:27])([CH3:25])[CH3:24].CN(C=O)C>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.CCN(CC)CC>[F:9][C:8]([F:11])([F:10])[C:5]1[CH:6]=[CH:7][C:2]([C:27]#[C:26][Si:23]([CH3:25])([CH3:24])[CH3:22])=[C:3]([CH2:12][C:13]([O:15][CH3:16])=[O:14])[CH:4]=1

Participants

8

Reactant 4

HCID 6228DimethylformamideHCID 26255TetrafluoroborateHCID 66111TrimethylsilylacetyleneHCID 86712710HCID 86712710, compound

Product 1

HCID 86712709HCID 86712709, 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-5-(trifluoromethyl)phenyl)acetate (A103) (1.00 g, 3.36 mmol), PdCl2(PPh3)2 (0.118 g, 0.168 mmol), t-Bu3PH.BF4 (0.049 g, 0.17 mmol), CuI (0.032 g, 0.17 mmol) and trimethylsilylacetylene (0.951 mL, 6.73 mmol) in anhydrous degassed DMF (10 mL) and Et3N (10 mL) was stirred at 80° C. for 16 hours. The resulting mixture was adsorbed onto silica gel and purified by column chromatography (Biotage Isolera, SiO2 cartridge, 0-10% EtOAc in petroleum benzine 40-60° C.) to give the title compound A104 as an orange liquid (0.863 g, 82%); 1H NMR (400 MHz, CDCl3) δ 7.57 (d, J=8.0 Hz, 1H), 7.53 (d, J=0.5 Hz, 1H), 7.50-7.44 (m, 1H), 3.87 (s, 2H), 3.7s (s, 3H), 0.24 (s, 9H). LCMS: rt 6.931 min; m/z 315.1 [M+H]+.

Workup

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

Sources & evidence

ORD record
ord-a94afb17d139430db1f9fb6043d4a655
Source dataset
uspto-grants-2016_02
Patent number
US09266864B2

Reaction notes

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