Tert-Butyl nitrite → HCID 69001380, compound

HRID 1453984Notes

Reaction equation

HRID 1453984 reaction equation
N[C:2]1[O:7][CH:6]2[C:8]3[C:12](=[CH:13][CH:14]=[C:5]2[CH:4]([C:15]2[CH:20]=[C:19]([O:21][CH3:22])[C:18]([O:23][CH3:24])=[C:17]([Br:25])[CH:16]=2)[C:3]=1[C:26]#[N:27])[N:11]=[CH:10][CH:9]=3.C(ON=O)(C)(C)C.[BH4-].[Na+]>C1COCC1>[Br:25][C:17]1[CH:16]=[C:15]([CH:4]2[C:3]([C:26]#[N:27])=[CH:2][O:7][CH:6]3[C:8]4[C:12](=[CH:13][CH:14]=[C:5]23)[N:11]=[CH:10][CH:9]=4)[CH:20]=[C:19]([O:21][CH3:22])[C:18]=1[O:23][CH3:24]

Participants

5

Reactant 3

HCID 10906Tert-Butyl nitriteHCID 4311764Sodium borohydrideHCID 69002760HCID 69002760, compound

Product 1

HCID 69001380HCID 69001380, compoundYield 40.5%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent

Conditions

Temperature
-15 °C

Procedure

To a solution of 2-amino-4-(3-bromo-4,5-dimethoxy-phenyl)-3-cyano-4H-indolo[4,5-b]pyran (0.998 g, 2.34 mmol) in anhydrous THF (40 mL) kept at −30° C., was added tert-butylnitrite (1.0 mL, 7.58 mmol) via a syringe under argon. The light yellow solution was stirred between −20 to −10° C. for 4 h, then allowed to warm up to 0° C. The reaction mixture was cooled to −10° C. and sodium borohydride (NaBH4, 0.259 g, 6.84 mmol) was added in one portion. The reaction mixture was warmed up to room temperature slowly and stirred overnight (15 h). The THF solvent was evaporated and the residue was dissolved in EtOAc (100 mL). The mixture was washed with saturated NaHCO3 (15 mL) and brine (15 mL), dried over MgSO4, and evaporated to yield a brown residue. The residue was purified by flash column chromatography (silica gel, EtOAc:hexanes/1:2) to yield 0.390 g (40%) of the product as an off-white solid. 1H NMR (CDCl3): 8.30 (brs, 1H), 7.45 (d, J=0.6 Hz, 1H), 7.24 (t, J=2.7 Hz, 1H), 7.13 (dd, J=0.8, 8.6 Hz, 1H), 6.96 (d, J=2.1 Hz, 1H), 6.76 (d, J=1.8 Hz, 1H), 6.70 (J=8.1 Hz, 1H), 6.67 (m, 1H), 4.81 (s, 1H), 3.84 (s, 3H), 3.83 (s, 3H).

Workup

  1. customkept at −30° C.
  2. temperatureto warm up to 0° C
  3. temperatureThe reaction mixture was cooled to −10° C.
  4. temperatureThe reaction mixture was warmed up to room temperature slowly
  5. stirringstirred overnight (15 h)
  6. customThe THF solvent was evaporated
  7. dissolutionthe residue was dissolved in EtOAc (100 mL)
  8. washThe mixture was washed with saturated NaHCO3 (15 mL) and brine (15 mL)
  9. dry with materialdried over MgSO4
  10. customevaporated
  11. customto yield a brown residue
  12. customThe residue was purified by flash column chromatography (silica gel, EtOAc:hexanes/1:2)

Sources & evidence

ORD record
ord-dc4137a0b37d4f8f9daf5d911ff006e0
Source dataset
uspto-grants-2009_01
Patent number
US07476741B2

Reaction notes

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