Trimethylsilylacetylene → HCID 66812844, compound

HRID 401600Notes

Reaction equation

HRID 401600 reaction equation
[Cl:1][C:2]1[CH:8]=[C:7]([S:9]([CH3:12])(=[O:11])=[O:10])[CH:6]=[C:5](I)[C:3]=1[NH2:4].[CH3:14][Si:15]([C:18]#[CH:19])([CH3:17])[CH3:16]>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.C(N(CC)CC)C>[Cl:1][C:2]1[CH:8]=[C:7]([S:9]([CH3:12])(=[O:11])=[O:10])[CH:6]=[C:5]([C:19]#[C:18][Si:15]([CH3:17])([CH3:16])[CH3:14])[C:3]=1[NH2:4]

Participants

6

Reactant 2

HCID 66111TrimethylsilylacetyleneHCID 66813138HCID 66813138, compound

Product 1

HCID 66812844HCID 66812844, compoundYield 1,308.5%

Reagents, catalysts & solvents 3

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

Procedure

To the suspension of 2-chloro-6-iodo-4-methanesulfonylaniline (886.9 mg, 2.7 mmol.), Pd(PPh3)2Cl2 (94.5 mg, 0.13 mmol), and CuI (24.3 mg, 0.13 mmol.) was added triethyl amine (2 mL), and the suspension was slowly treated with (trimethylsilyl)acetylene (0.22 mL, 0.16 mmol.) at 0° C. The reaction mixture was stirred at room temperature for ˜16 h. Solvent was removed under vacuum. The residue was diluted with ethyl acetate, and filtered through Celite. The filtrate was washed with saturated NaCl, water, dried over anhydrous sodium sulfate and concentrated. The residue was purified by column chromatography on silica gel using 20% ethyl acetate—hexane to give 2-chloro-4-methanesulfonyl-6-trimethylsilanylethynyl-phenylamine (632 mg, 78%). The 1H NMR (500 MHz, CDCl3) spectrum was: 0.27 (s, 9H), 3.01 (s, 3H), 5.17 (s, 2H), 7.77 (d, J=2.5 Hz, 1H), 7.78 (d, J=2.5 Hz, 1H).

Workup

  1. customSolvent was removed under vacuum
  2. additionThe residue was diluted with ethyl acetate
  3. filtrationfiltered through Celite
  4. washThe filtrate was washed with saturated NaCl, water
  5. dry with materialdried over anhydrous sodium sulfate
  6. concentrationconcentrated
  7. customThe residue was purified by column chromatography on silica gel using 20% ethyl acetate—hexane

Sources & evidence

ORD record
ord-06f4a06bd57840ad81225f7f47346f27
Source dataset
uspto-grants-2014_06
Patent number
US08741942B2

Reaction notes

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