Dimethylformamide → HCID 59853066, compound

HRID 1670335Notes

Reaction equation

HRID 1670335 reaction equation
[NH2:1][C:2]1[CH:3]=[N:4][C:5](Br)=[CH:6][CH:7]=1.[C:9]([Si:11]([CH3:14])([CH3:13])[CH3:12])#[CH:10].CC#N.CN(C=O)C>[Cu]I.C1C=CC([P]([Pd]([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)[P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1.CCN(CC)CC>[CH3:12][Si:11]([CH3:14])([CH3:13])[C:9]#[C:10][C:5]1[N:4]=[CH:3][C:2]([NH2:1])=[CH:7][CH:6]=1

Participants

8

Reactant 4

HCID 6228DimethylformamideHCID 6342AcetonitrileHCID 66111Trimethylsilylacetylene2×HCID 6428116-Bromopyridin-3-amine

Product 1

HCID 59853066HCID 59853066, compoundYield 68%

Reagents, catalysts & solvents 3

HCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)CatalystHCID 178418397HCID 178418397, compoundCatalystHCID 8471TriethylamineSolvent

Conditions

Temperature
45 °C

Procedure

A mixture of 3-amino-6-bromopyridine (Alfa Aesar, 1.0 g, 5.8 mmol), ethynyl trimethylsilane (1.7 mL, 17.3 mmol), CH3CN (3 mL), DMF (2 mL) and Et3N (2 mL) was treated with CuI (60 mg, 0.32 mmol) and (Ph3P)4Pd (114 mg, 0.10 mmol) and the mixture stirred at 45° C. for 1.5 h. More ethynyltrimethylsilane (1.7 mL, 17.3 mmol) was added to the reaction and the mixture was stirred for 2 h. The mixture was concentrated in vacuo and the residue partitioned between EtOAc and saturated aqueous NaHCO3 solution. The EtOAc phase was washed with brine, dried (MgSO4) and concentrated in vacuo. The crude product was purified by flash chromatography on SiO2 using 0-6% EtOAc/hexanes to give the title compound (0.75 g, 68%) as a brown solid. 1H NMR (DMSO-d6) δ 7.85 (s, 1H), 7.15 (d, 1H, J=8.1 Hz), 6.81 (d, 1H, J=8.1 Hz), 5.76 (s, 2H), 0.19 (s, 9H); MS (ESI+): m/z 191.20 (M+H)+.

Workup

  1. stirringthe mixture was stirred for 2 h
  2. concentrationThe mixture was concentrated in vacuo
  3. customthe residue partitioned between EtOAc and saturated aqueous NaHCO3 solution
  4. washThe EtOAc phase was washed with brine
  5. dry with materialdried (MgSO4)
  6. concentrationconcentrated in vacuo
  7. customThe crude product was purified by flash chromatography on SiO2 using 0-6% EtOAc/hexanes

Sources & evidence

ORD record
ord-5798107cf01e4c5c82dee17758cc8a9f
Source dataset
uspto-grants-2011_08
Patent number
US07989477B2

Reaction notes

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