Bromine → HCID 66977175, compound

HRID 712355Notes

Reaction equation

HRID 712355 reaction equation
[NH2:1][C:2]1[CH:7]=[CH:6][C:5]([C:8]2[CH:9]=[N:10][C:11]([N:14]3[CH2:19][CH2:18][C:17]([CH2:25][CH3:26])([C:20]([O:22][CH2:23][CH3:24])=[O:21])[CH2:16][CH2:15]3)=[N:12][CH:13]=2)=[CH:4][C:3]=1[N+:27]([O-:29])=[O:28].[Br:30]Br>C(O)(=O)C>[NH2:1][C:2]1[C:3]([N+:27]([O-:29])=[O:28])=[CH:4][C:5]([C:8]2[CH:9]=[N:10][C:11]([N:14]3[CH2:19][CH2:18][C:17]([CH2:25][CH3:26])([C:20]([O:22][CH2:23][CH3:24])=[O:21])[CH2:16][CH2:15]3)=[N:12][CH:13]=2)=[CH:6][C:7]=1[Br:30]

Participants

4

Reactant 2

HCID 24408BromineHCID 66977122HCID 66977122, compound

Product 1

HCID 66977175HCID 66977175, compoundYield 78%

Reagents, catalysts & solvents 1

HCID 176Acetic AcidSolvent

Procedure

To solution of ethyl 1-(5-(4-amino-3-nitrophenyl)pyrimidin-2-yl)-4-ethylpiperidine-4-carboxylate (6.0 g, 15.02 mmol) in acetic acid (60.0 mL) was added bromine (0.85 mL, 16.52 mmol) dropwise at rt and the mixture then stirred at rt for 16 h. After completion of reaction the mixture was poured into 100 mL of ice-cold water, extracted with EtOAc (3×150 mL) and the combined organic layer washed with brine, dried over anhydrous Na2SO4, filtered and evaporated under reduced pressure. The crude residue was purified over 100-200 M silica-gel column chromatography using 10% EtOAc:Hexane to obtain the product as a beige solid (5.60 g, 78%). 1H NMR (CDCl3): δ 8.66 (s, 2H), 8.18 (s, 2H), 7.21 (br s, 2H), 4.39-4.43 (m, 2H), 4.13-4.18 (m, 2H), 3.06-3.11 (m, 2H), 2.04-2.08 (m, 2H), 1.50-1.52 (m, 2H), 1.38-1.39 (m, 2H), 1.21 (t, J=7.60 Hz, 3H) and 0.75 (t, J=7.60 Hz, 3H). MS: 478.11 [M+H]+, 81%.

Workup

  1. customAfter completion of reaction the mixture
  2. extractionextracted with EtOAc (3×150 mL)
  3. washthe combined organic layer washed with brine
  4. dry with materialdried over anhydrous Na2SO4
  5. filtrationfiltered
  6. customevaporated under reduced pressure
  7. customThe crude residue was purified over 100-200 M silica-gel column chromatography

Sources & evidence

ORD record
ord-6bcb97cbb23343259ade24b87423cdc8
Source dataset
uspto-grants-2015_11
Patent number
US09181234B2

Reaction notes

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