Trimethylsilylacetylene → 5-[(Trimethylsilyl)ethynyl]pyrimidine

HRID 349258Notes

Reaction equation

HRID 349258 reaction equation
Br[C:2]1[CH:3]=[N:4][CH:5]=[N:6][CH:7]=1.[CH3:8][Si:9]([C:12]#[CH:13])([CH3:11])[CH3:10]>C(N(CC)CC)C.[Cu]I>[CH3:8][Si:9]([C:12]#[C:13][C:2]1[CH:3]=[N:4][CH:5]=[N:6][CH:7]=1)([CH3:11])[CH3:10]

Participants

5

Reactant 2

HCID 66111TrimethylsilylacetyleneHCID 783445-Bromopyrimidine

Product 1

HCID 153496695-[(Trimethylsilyl)ethynyl]pyrimidine

Reagents, catalysts & solvents 2

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

Procedure

Dissolve 5-bromopyrimidine (50.0 g, 314.4 mmol) in triethylamine (400 mL), add copper (1) iodide (1.20 g, 6.2 mmol) and stir mixture under nitrogen. After 15 min., add trimethylsilyl acetylene (53.3 mL, 377.3 mmol), followed by dichlorobis(triphenyl-phosphine) palladium (11) (8.82 g, 12.5 mmol) and stir at RT. After 3 h, filter the solution through Celite®, rinsing with ether. Concentrate the filtrate under reduced pressure. Purification by flash chromatography on silica gel eluting first with hexanes (100%), then with hexanes:EtOAc (3:1) gives the title compound: 1H NMR (300 MHz, CDCl3) δ 9.10 (s, 1H), 8.77 (s, 2H), 0.27 (s, 9H).

Workup

  1. stirringstir at RT
  2. waitAfter 3 h
  3. filtrationfilter the solution through Celite®
  4. washrinsing with ether
  5. concentrationConcentrate the filtrate under reduced pressure
  6. customPurification by flash chromatography on silica gel eluting first with hexanes (100%)

Sources & evidence

ORD record
ord-d041ee9e08b54df8a6d0733841ee098a
Source dataset
uspto-grants-2007_02
Patent number
US07179804B2

Reaction notes

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