Acetic Acid → 7-Bromobenzo[b]thiophen-2-amine

HRID 1296779Notes

Reaction equation

HRID 1296779 reaction equation
[Br:1][C:2]1[C:10]2[S:9][C:8](C(O)=O)=[CH:7][C:6]=2[CH:5]=[CH:4][CH:3]=1.C([N:17](CC)C(C)C)(C)C.P(N=[N+]=[N-])(=O)(OC1C=CC=CC=1)OC1C=CC=CC=1.C(O)(=O)C>CN(C=O)C>[Br:1][C:2]1[C:10]2[S:9][C:8]([NH2:17])=[CH:7][C:6]=2[CH:5]=[CH:4][CH:3]=1

Participants

6

Reactant 4

HCID 176Acetic AcidHCID 81531DiisopropylethylamineHCID 123414Diphenylphosphoryl azideHCID 179795837-Bromo-1-benzothiophene-2-carboxylic acid

Product 1

HCID 121122087-Bromobenzo[b]thiophen-2-amineYield 92%

Reagents, catalysts & solvents 1

HCID 6228DimethylformamideSolvent

Procedure

156 mg (0.61 mmol) of 7-bromo-1-benzothiophene-2-carboxylic acid are mixed with 156.8 mg (1.21 mmol) of N,N-diisopropylethylamine in 4.0 ml of DMF. At 0° C., 183.7 mg (0.67 mmol) of diphenyl phosphorazidate are added. The reaction mixture is left to stand at 8° C. overnight and then stirred into ice-water. It is neutralized with acetic acid, and the resulting precipitate is filtered off with suction and carefully dried at 40° C. The solid is then suspended in xylene and heated under reflux for 1 h. The solvent is removed under reduced pressure, and the residue is put in water and heated for 3 h. The aqueous phase is extracted several times with ethyl acetate. The organic phase is dried over sodium sulfate and then the solvent is removed under reduced pressure. 128 mg of the title compound are isolated in a purity which is suitable for further reactions. The amine is reacted further without further purification.

Workup

  1. waitThe reaction mixture is left
  2. filtrationthe resulting precipitate is filtered off with suction
  3. customcarefully dried at 40° C
  4. temperatureheated
  5. temperatureunder reflux for 1 h
  6. customThe solvent is removed under reduced pressure
  7. temperatureheated for 3 h
  8. extractionThe aqueous phase is extracted several times with ethyl acetate
  9. dry with materialThe organic phase is dried over sodium sulfate
  10. customthe solvent is removed under reduced pressure

Sources & evidence

ORD record
ord-512f73a9b84f4a2bbe473c5fce6a09d3
Source dataset
uspto-grants-2007_07
Patent number
US07247728B2

Reaction notes

Loading…