Sodium triacetoxyborohydride → 5-bromo-N-((2-(methylthio)benzo[d]thiazol-6-yl)methyl)-2-nitroaniline

HRID 1848094Notes

Reaction equation

HRID 1848094 reaction equation
[Br:1][C:2]1[CH:3]=[CH:4][C:5]([N+:9]([O-:11])=[O:10])=[C:6]([CH:8]=1)[NH2:7].[BH-](OC(C)=O)(OC(C)=O)OC(C)=O.[Na+].[CH3:26][S:27][C:28]1[S:29][C:30]2[CH:36]=[C:35]([CH:37]=O)[CH:34]=[CH:33][C:31]=2[N:32]=1>C(O)(C(F)(F)F)=O.C(Cl)Cl>[Br:1][C:2]1[CH:3]=[CH:4][C:5]([N+:9]([O-:11])=[O:10])=[C:6]([CH:8]=1)[NH:7][CH2:37][C:35]1[CH:34]=[CH:33][C:31]2[N:32]=[C:28]([S:27][CH3:26])[S:29][C:30]=2[CH:36]=1

Participants

6

Reactant 3

HCID 5049666Sodium triacetoxyborohydrideHCID 53147665-Bromo-2-nitroanilineHCID 547753816-Benzothiazolecarboxaldehyde, 2-(methylthio)-

Product 1

HCID 866810725-bromo-N-((2-(methylthio)benzo[d]thiazol-6-yl)methyl)-2-nitroanilineYield 73%

Reagents, catalysts & solvents 2

HCID 6344DichloromethaneSolventHCID 6422Trifluoroacetic acidSolvent

Procedure

To a stirred mixture of 5-bromo-2-nitroaniline (714 mg, 4.0 mmol) in TFA (7 mL) at −15° C. under argon, was added NaBH(OAc)3 (1.2 g, 5.4 mmol) in small portions. The mixture was stirred for 15 min, then a solution of 2-(methylthio)benzo[d]thiazole-6-carbaldehyde in CH2Cl2 (2 mL) was added dropwise. The mixture was stirred for 30 min then concentrated under reduced pressure to give a red oil. The oil was partitioned between EtOAc (200 mL) and saturated aq NaHCO3 (100 mL). The organic layer was separated and washed with brine (100 mL). The organic layer was separated, dried over Na2SO4, filtered, and concentrated under reduced pressure. The residue was purified by silica gel flash chromatography eluting with a gradient of 100% hexanes to 50% hexanes in EtOAc to afford 5-bromo-N-((2-(methylthio)benzo[d]thiazol-6-yl)methyl)-2-nitroaniline (1.1 g, 73%) as a yellow solid. LCMS (ESI) m/z 409, 411 (M+H)+.

Workup

  1. stirringThe mixture was stirred for 30 min
  2. concentrationthen concentrated under reduced pressure
  3. customto give a red oil
  4. customThe oil was partitioned between EtOAc (200 mL) and saturated aq NaHCO3 (100 mL)
  5. customThe organic layer was separated
  6. washwashed with brine (100 mL)
  7. customThe organic layer was separated
  8. dry with materialdried over Na2SO4
  9. filtrationfiltered
  10. concentrationconcentrated under reduced pressure
  11. customThe residue was purified by silica gel flash chromatography
  12. washeluting with a gradient of 100% hexanes to 50% hexanes in EtOAc

Sources & evidence

ORD record
ord-10e4397b61954dc79fd6e24d40645f4a
Source dataset
uspto-grants-2015_02
Patent number
US08952058B2

Reaction notes

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