Toluene → HCID 178527321, compound

HRID 520533Notes

Reaction equation

HRID 520533 reaction equation
[C:1]([C:3]1[CH:11]=[C:10]([C:12]2[CH:20]=[CH:19][CH:18]=[C:17]3[C:13]=2[CH:14]=[CH:15][N:16]3C(OC(C)(C)C)=O)[CH:9]=[C:8]2[C:4]=1[CH:5]=[N:6][N:7]2[S:28]([C:31]1[CH:36]=[CH:35][CH:34]=[CH:33][CH:32]=1)(=[O:30])=[O:29])#[N:2].C1(C)C=CC=CC=1.C([Sn](CCCC)=O)CCC.C[Si]([N:58]=[N+:59]=[N-:60])(C)C>O.C(O)(=O)C>[NH:16]1[C:17]2[C:13](=[C:12]([C:10]3[CH:9]=[C:8]4[C:4]([CH:5]=[N:6][N:7]4[S:28]([C:31]4[CH:32]=[CH:33][CH:34]=[CH:35][CH:36]=4)(=[O:29])=[O:30])=[C:3]([C:1]4[NH:2][N:60]=[N:59][N:58]=4)[CH:11]=3)[CH:20]=[CH:19][CH:18]=2)[CH:14]=[CH:15]1

Participants

7

Reactant 4

HCID 1140TolueneHCID 61221Dibutyltin oxideHCID 78378AzidotrimethylsilaneHCID 667768451,1-Dimethylethyl 4-[4-cyano-1-(phenylsulfonyl)-1H-indazol-6-yl]-1H-indole-1-carboxylate

Product 1

HCID 178527321HCID 178527321, compoundYield 33%

Reagents, catalysts & solvents 2

HCID 176Acetic AcidSolventHCID 962WaterSolvent

Conditions

Temperature
90 °C

Procedure

To a round bottomed flask was charged 1,1-dimethylethyl 4-[4-cyano-1-(phenylsulfonyl)-1H-indazol-6-yl]-1H-indole-1-carboxylate (6.16 g, 12.36 mmol) followed by toluene (250 ml). The resulting solution was then treated with dibutyl(oxo)stannane (0.554 g, 2.224 mmol) and trimethylsilyl azide (3.3 ml, 25.09 mmol). The mixture was heated to 90° C. overnight, then cooled to room temperature and concentrated in vacuo. The residue was dissolved in methanol/DCM and preabsorbed onto silica (20 g). This was placed on the top of a silica cartridge (750 g) and eluted with 0-40% methanol in DCM. The product containing fraction was evaporated to give a green foam which was placed into acetic acid (50 ml) and the mixture heated to 100° C. overnight. The mixture was heated for a further 24 h, then cooled to room temperature and water (250 ml) added. A precipitate formed, which was collected by filtration and air dried over the weekend to give the title compound as a pale grey solid (1.8 g).

Workup

  1. temperaturecooled to room temperature
  2. concentrationconcentrated in vacuo
  3. dissolutionThe residue was dissolved in methanol/DCM
  4. custompreabsorbed onto silica (20 g)
  5. washeluted with 0-40% methanol in DCM
  6. additionThe product containing fraction
  7. customwas evaporated
  8. customto give a green foam which
  9. temperaturethe mixture heated to 100° C. overnight
  10. temperatureThe mixture was heated for a further 24 h
  11. temperaturecooled to room temperature
  12. customA precipitate formed
  13. filtrationwhich was collected by filtration and air
  14. customdried over the weekend

Sources & evidence

ORD record
ord-a83b838038d24908b51ef30444f71789
Source dataset
uspto-grants-2016_05
Patent number
US09326987B2

Reaction notes

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