Sodium Carbonate → 2-Nitro-4-(thiophen-2-yl)aniline

HRID 392616Notes

Reaction equation

HRID 392616 reaction equation
Br[C:2]1[CH:8]=[CH:7][C:5]([NH2:6])=[C:4]([N+:9]([O-:11])=[O:10])[CH:3]=1.C([O-])([O-])=O.[Na+].[Na+].[S:18]1[CH:22]=[CH:21][CH:20]=[C:19]1B(O)O>CN(C=O)C.O.CN(C=O)C.C1C=CC(P(C2C=CC=CC=2)[C-]2C=CC=C2)=CC=1.C1C=CC(P(C2C=CC=CC=2)[C-]2C=CC=C2)=CC=1.Cl[Pd]Cl.[Fe+2]>[N+:9]([C:4]1[CH:3]=[C:2]([C:19]2[S:18][CH:22]=[CH:21][CH:20]=2)[CH:8]=[CH:7][C:5]=1[NH2:6])([O-:11])=[O:10]

Participants

7

Reactant 3

HCID 10340Sodium CarbonateHCID 701324-Bromo-2-nitroanilineHCID 27339602-Thiopheneboronic acid

Product 1

HCID 226648312-Nitro-4-(thiophen-2-yl)aniline

Reagents, catalysts & solvents 3

HCID 178418228Bis(cyclopenta-1,4-dien-1-yl(diphenyl)phosphane);dichloropalladium;iron(2+)CatalystHCID 6228DimethylformamideSolventHCID 21962138N,N-Dimethylformamide--water (1/1)Solvent

Conditions

Temperature
23 °C

Procedure

4-Bromo-2-nitroaniline (1.0 eq) and Na2CO3 (2.0 eq) were dissolved in DMF/H2O (5:1) at room temperature. Nitrogen was bubbled through the reaction mixture for 5 minutes and PdCl2(dppf)2 (0.1 eq) was added. After stirring at 23° C. for approximately 10 minutes, 2-thiopeneboronic acid (1.1 eq) in DMF was added and the reaction was heated at 90° C. for 12 hours. After this time, the solution was concentrated and partitioned between EtOAc and H2O. The layers were separated and the aqueous layer was extracted with EtOAc. The combined organic layers were dried over MgSO4 and concentrated under reduced pressure. The resulting black residue was purified by silica gel chromatography (0-20% EtOAc:hexanes) to yield an orange solid. LC/MS m/z 221.1 (MH+), Rf 2.67 minutes.

Workup

  1. customNitrogen was bubbled through the reaction mixture for 5 minutes
  2. temperaturethe reaction was heated at 90° C. for 12 hours
  3. concentrationAfter this time, the solution was concentrated
  4. custompartitioned between EtOAc and H2O
  5. customThe layers were separated
  6. extractionthe aqueous layer was extracted with EtOAc
  7. dry with materialThe combined organic layers were dried over MgSO4
  8. concentrationconcentrated under reduced pressure
  9. customThe resulting black residue was purified by silica gel chromatography (0-20% EtOAc:hexanes)
  10. customto yield an orange solid

Sources & evidence

ORD record
ord-c8443d2d8d014df4a881cd592a214d3d
Source dataset
uspto-grants-2004_10
Patent number
US06800760B2

Reaction notes

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