Trimethylsilylacetylene → HCID 66730565, compound

HRID 1027993Notes

Reaction equation

HRID 1027993 reaction equation
[F:1][C:2]1[C:8]([CH3:9])=[CH:7][C:5]([NH2:6])=[C:4](I)[CH:3]=1.[CH3:11][Si:12]([C:15]#[CH:16])([CH3:14])[CH3:13]>C(N(CC)CC)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>[F:1][C:2]1[C:8]([CH3:9])=[CH:7][C:5]([NH2:6])=[C:4]([C:16]#[C:15][Si:12]([CH3:14])([CH3:13])[CH3:11])[CH:3]=1

Participants

6

Reactant 2

HCID 66111TrimethylsilylacetyleneHCID 250673514-Fluoro-2-iodo-5-methylaniline

Product 1

HCID 66730565HCID 66730565, compoundYield 97%

Reagents, catalysts & solvents 3

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

Procedure

Into a mixture of 4-fluoro-2-iodo-5-methylaniline (12.0 g, 47.8 mmol, plus ca. 10% of the undesired isomer), PdCl2(PPh3)2 (1.68 g, 2.39 mmol) and copper(I) iodide (0.455 g, 2.39 mmol) in triethylamine (125 mL) at 0° C. was added trimethylsilylacetylene (5.15 g, 52.6 mmol) dropwise. The mixture was warmed to room temperature and stirred overnight. The solvent was evaporated and the residue was dissolved in ethyl ether and filtered. The filtrate was evaporated and purified via flash chromatography with 5-35% ethyl acetate in hexane to give 4-fluoro-5-methyl-2-((trimethylsilyl)ethynyl)aniline (10.3 g, 97%), which contained ˜10% of the undesired isomer (4-fluoro-3-methyl-2-((trimethylsilyl)ethynyl)aniline).

Workup

  1. customThe solvent was evaporated
  2. dissolutionthe residue was dissolved in ethyl ether
  3. filtrationfiltered
  4. customThe filtrate was evaporated
  5. custompurified via flash chromatography with 5-35% ethyl acetate in hexane

Sources & evidence

ORD record
ord-fe380d07d33a4daeada819af80e6c618
Source dataset
uspto-grants-2014_05
Patent number
US08735414B2

Reaction notes

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