4-Bromo-2-nitroaniline → HCID 86682384, compound

HRID 1465833Notes

Reaction equation

HRID 1465833 reaction equation
[CH3:1][N:2]1[CH2:7][CH2:6][N:5]([C:8]2[CH:16]=[C:15]3[C:11]([CH:12]=[C:13]([Sn](CCCC)(CCCC)CCCC)[N:14]3[S:17]([C:20]3[CH:25]=[CH:24][C:23]([CH3:26])=[CH:22][CH:21]=3)(=[O:19])=[O:18])=[CH:10][CH:9]=2)[CH2:4][CH2:3]1.Br[C:41]1[CH:47]=[CH:46][C:44]([NH2:45])=[C:43]([N+:48]([O-:50])=[O:49])[CH:42]=1>CN(C=O)C.C1C=CC([P]([Pd]([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)[P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1>[CH3:1][N:2]1[CH2:7][CH2:6][N:5]([C:8]2[CH:16]=[C:15]3[C:11]([CH:12]=[C:13]([C:41]4[CH:47]=[CH:46][C:44]([NH2:45])=[C:43]([N+:48]([O-:50])=[O:49])[CH:42]=4)[N:14]3[S:17]([C:20]3[CH:25]=[CH:24][C:23]([CH3:26])=[CH:22][CH:21]=3)(=[O:18])=[O:19])=[CH:10][CH:9]=2)[CH2:4][CH2:3]1

Participants

5

Reactant 2

HCID 701324-Bromo-2-nitroanilineHCID 86682383HCID 86682383, compound

Product 1

HCID 86682384HCID 86682384, compound

Reagents, catalysts & solvents 2

HCID 178418397HCID 178418397, compoundCatalystHCID 6228DimethylformamideSolvent

Conditions

Temperature
100 °C

Procedure

6-(4-Methyl-piperazin-1-yl)-1-(toluene-4-sulfonyl)-2-tributylstannanyl-1H-indole (crude) (5.0 g, 7.6 mmol) and 4-bromo-2-nitroaniline (2.05 g, 9.5 mmol) in DMF (50 mL) were placed in a RB flask followed by evacuating and flushing with nitrogen. Pd(PPh3)4 (0.22 g, 0.19 mmol) was added and under nitrogen was heated to 100° C., overnight. Analysis after this period indicated that all starting material had been consumed. Workup was by diluting with EtOAc (200 ml) and repeatedly washing with sat NH4Cl (5×50 ml). Crude NMR spectrum was complex, attributed to the product nitrogen atoms being in various oxidation states. The crude was chromatographically purified (16 cm×6 cm silicagel column, gradient eluting with dichloromethane to 10% methanol in dichloromethane), and all related fractions were pooled together (orange thick oil) 3.0 g, was taken directly to the next step without further purification or attempting to assign the chemical shifts.

Workup

  1. customby evacuating
  2. customflushing with nitrogen
  3. waitAnalysis after this period indicated that all starting material
  4. customhad been consumed
  5. additionby diluting with EtOAc (200 ml)
  6. washrepeatedly washing with sat NH4Cl (5×50 ml)
  7. customThe crude was chromatographically purified
  8. wash(16 cm×6 cm silicagel column, gradient eluting with dichloromethane to 10% methanol in dichloromethane)
  9. customwas taken directly to the next step without further purification

Sources & evidence

ORD record
ord-902256e53c234aca970f64c396e646ae
Source dataset
uspto-grants-2015_04
Patent number
US08999993B2

Reaction notes

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