Methanesulfonyl chloride → HCID 11576899, compound

HRID 1173479Notes

Reaction equation

HRID 1173479 reaction equation
[NH2:1][C:2]1[CH:7]=[CH:6][C:5]([S:8][CH2:9][CH2:10][N:11]([CH2:24][C:25]([F:28])([F:27])[F:26])[C:12]2[CH:19]=[CH:18][C:15]([C:16]#[N:17])=[C:14]([C:20]([F:23])([F:22])[F:21])[CH:13]=2)=[CH:4][CH:3]=1.[CH3:29][S:30](Cl)(=[O:32])=[O:31]>C(Cl)Cl>[C:16]([C:15]1[CH:18]=[CH:19][C:12]([N:11]([CH2:24][C:25]([F:28])([F:26])[F:27])[CH2:10][CH2:9][S:8][C:5]2[CH:6]=[CH:7][C:2]([NH:1][S:30]([CH3:29])(=[O:32])=[O:31])=[CH:3][CH:4]=2)=[CH:13][C:14]=1[C:20]([F:21])([F:22])[F:23])#[N:17]

Participants

4

Reactant 2

HCID 31297Methanesulfonyl chloride4×HCID 86623739HCID 86623739, compound

Product 1

HCID 11576899HCID 11576899, compoundYield 55.2%

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent

Procedure

A solution of 4-[{2-[(4-aminophenyl)thio]ethyl}(2,2,2-trifluoroethyl)amino]-2-(trifluoromethyl)benzonitrile (0.038 g, 0.091 mmol; see Example 74A) in CH2Cl2 (4 mL) was treated under N2 with TEA (0.010 g, 0.099 mmol) and MsCl (0.011 g, 0.099 mmol) and stirred at rt. After 4 h, additional TEA (0.0046 g, 0.046 mmol) and MsCl (0.0052 g, 0.046 mmol) were added and stirred at rt. After 1 h, the mixture was concentrated in vacuo and the residue taken up in CHCl3 (4 mL) and heated at 70° C. for 2 h. Upon cooling, additional TEA (0.0046 g, 0.046 mmol) and MsCl (0.0052 g, 0.046 mmol) were added and heated at 70° C. for 12 h. Upon cooling, additional TEA (0.0092 g, 0.091 mmol) and MsCl (0.0104 g, 0.091 mmol) were added and heated at 70° C. for 4 h. The mixture was partitioned between EtOAc and 0.1N HCl. The organic phase was washed with 0.1N HCl and brine, dried (Na2SO4) and concentrated in vacuo. The residue was purified by silica gel chromatography (5-80% EtOAc/hexanes gradient) to give the title compound (0.025 g, 55% yield): MS (ES) m/z 496 (M−1).

Workup

  1. stirringstirred at rt
  2. waitAfter 1 h
  3. concentrationthe mixture was concentrated in vacuo
  4. temperatureheated at 70° C. for 2 h
  5. temperatureUpon cooling
  6. temperatureheated at 70° C. for 12 h
  7. temperatureUpon cooling
  8. temperatureheated at 70° C. for 4 h
  9. customThe mixture was partitioned between EtOAc and 0.1N HCl
  10. washThe organic phase was washed with 0.1N HCl and brine
  11. dry with materialdried (Na2SO4)
  12. concentrationconcentrated in vacuo
  13. customThe residue was purified by silica gel chromatography (5-80% EtOAc/hexanes gradient)

Sources & evidence

ORD record
ord-972f9558e13e40808d526e215a682781
Source dataset
uspto-grants-2010_11
Patent number
US07834063B2

Reaction notes

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