Water → HCID 22260273, compound

HRID 412402Notes

Reaction equation

HRID 412402 reaction equation
[C:1]([C:3]1[N:7]([CH3:8])[C:6]([C:9]2[CH:10]=[CH:11][C:12]3[N:17]([C:18]([O:20][C:21]([CH3:24])([CH3:23])[CH3:22])=[O:19])[C:16](=[O:25])[O:15][C:14]([CH3:27])([CH3:26])[C:13]=3[CH:28]=2)=[CH:5][CH:4]=1)#[N:2].[Br:29]N1C(=O)CCC1=O.N1C=CC=CC=1.O>C1COCC1>[Br:29][C:5]1[CH:4]=[C:3]([C:1]#[N:2])[N:7]([CH3:8])[C:6]=1[C:9]1[CH:10]=[CH:11][C:12]2[N:17]([C:18]([O:20][C:21]([CH3:22])([CH3:23])[CH3:24])=[O:19])[C:16](=[O:25])[O:15][C:14]([CH3:27])([CH3:26])[C:13]=2[CH:28]=1

Participants

6

Reactant 4

HCID 962WaterHCID 1049PyridineHCID 67184N-bromobutanimideHCID 22260275HCID 22260275, compound

Product 1

HCID 22260273HCID 22260273, compound

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent

Procedure

To a solution of tert-butyl 6-(5-cyano-1-methyl-1H-pyrrol-2-yl)-4,4-dimethyl-2-oxo-2H-3,1-benzoxazine-1(4H)-carboxylate (1 eq, 1.94 g, 5.10 mmol) in THF (150 mL) at −78° C. was added N-bromosuccinimide (1.1 eq, 1.0 g, 5.61 mmol). The solution was allowed to warm and stir for 16 hours Pyridine (1 mL) was added and the mixture was poured into water (150 mL), the layers were separated, the aqueous layer was extracted with ethyl acetate (3×10 mL) and the combined organic layer was washed with brine, dried over MgSO4 and concentrated in vacuo. The product, tert-butyl 6-(3-bromo-5-cyano-1-methyl-1H-pyrrol-2-yl)-4,4-dimethyl-2-oxo-2H-3,1-benzoxazine-1(4H)-carboxylate was obtained by crystallization from 20% ethyl acetate/hexane as a white crystalline solid. 1H NMR (300 MHz, d6-DMSO) δ 1.56 (s, 9H), 1.71 (s, 6H), 3.65 (s, 3H), 7.30 (s, 1H), 7.44 (d, 1H, J=8.4 Hz), 7.52 (d, 1H, J=8.4 Hz), 7.55 (s, 1H). M/z (ESI (+)) 461 (M+H)+. Anal. calcd for C21H22N3O4, C, 54.8,H, 4.82, N, 9.13. Found, C, 54.9, H, 4.86, N, 9.1.

Workup

  1. temperatureto warm
  2. additionwas added
  3. customthe layers were separated
  4. extractionthe aqueous layer was extracted with ethyl acetate (3×10 mL)
  5. washthe combined organic layer was washed with brine
  6. dry with materialdried over MgSO4
  7. concentrationconcentrated in vacuo

Sources & evidence

ORD record
ord-4df33f4826d74c66b312f4ff8bd6b1f9
Source dataset
uspto-grants-2003_05
Patent number
US06562857B2

Reaction notes

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