Trimethylsilylacetylene → 2-Fluoro-4-((trimethylsilyl)ethynyl)aniline

HRID 1792995Notes

Reaction equation

HRID 1792995 reaction equation
[F:1][C:2]1[CH:8]=[C:7](I)[CH:6]=[CH:5][C:3]=1[NH2:4].[Si:10]([C:14]#[CH:15])([CH3:13])([CH3:12])[CH3:11]>C(OCC)C.[Cu]I.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>[F:1][C:2]1[CH:8]=[C:7]([C:15]#[C:14][Si:10]([CH3:13])([CH3:12])[CH3:11])[CH:6]=[CH:5][C:3]=1[NH2:4]

Participants

6

Reactant 2

HCID 66111TrimethylsilylacetyleneHCID 1856942-Fluoro-4-iodoaniline

Product 1

HCID 220256802-Fluoro-4-((trimethylsilyl)ethynyl)aniline

Reagents, catalysts & solvents 3

HCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)CatalystHCID 178418476HCID 178418476, compoundCatalystHCID 3283Diethyl EtherSolvent

Procedure

2-Fluoro-4-iodoaniline (5.00 g, 21.1 mmol), CuI (90 mg, 0.42 mmol), and (Ph3P)2PdCl2 (300 mg, 0.42 mmol) were weighed into a flask which was sealed and flushed with N2. A solution of TMS-acetylene (2.28 g, 23.2 mmol) in TEA (20 mL) was added, then the entire mixture stirred 15 hours at room temperature. The reaction mixture was diluted with diethyl ether (200 mL), filtered through Celite®, then all solvents removed under reduced pressure. The resulting dark brown oil was purified by filtration through a plug of flash silica (5% EtOAc/hexanes as eluant) to afford the desired product as a pale brown oil which rapidly solidified to give a crystalline solid (3.85 g, 88%); m.p. (EtOAc/hexanes) 45–47° C. 1H NMR (400 MHz, CDCl3) δ 7.10 (dd, J=11.7, 1.8 Hz, 1 H), 7.06 (ddd, J=8.3, 1.8, 1.0 Hz, 1 H), 6.66 (dd, J=9.4, 8.3 Hz, 1 H), 3.86 (br s, 2 H), 0.22 (s, 9 H). Anal. Calcd for C11H14FNSi: C, 63.7; H, 6.8; N, 6.8. Found: C, 63.7; H, 6.9; N, 6.7.

Workup

  1. customwhich was sealed
  2. customflushed with N2
  3. filtrationfiltered through Celite®
  4. customall solvents removed under reduced pressure
  5. filtrationThe resulting dark brown oil was purified by filtration through a plug of flash silica (5% EtOAc/hexanes as eluant)

Sources & evidence

ORD record
ord-5e94547ceccb45d0af9b3876b217d010
Source dataset
uspto-grants-2006_07
Patent number
US07078438B2

Reaction notes

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