Iodoethane → (+/-)-9-Ethyl-4-oxo-2-pyrimidin-4-yl-5,6,8,9-tetrahydro-4H-1,4-a,7-triaza-benzocycloheptene-7-carboxylic acid ethyl ester

HRID 1520426Notes

Reaction equation

HRID 1520426 reaction equation
[CH2:1]([O:3][C:4]([N:6]1[CH2:12][CH2:11][C:10]2=[N:13][C:14]([C:18]3[CH:23]=[CH:22][N:21]=[CH:20][N:19]=3)=[CH:15][C:16](=[O:17])[N:9]2[CH2:8][CH2:7]1)=[O:5])[CH3:2].C[Si]([N-][Si](C)(C)C)(C)C.[Li+].[CH2:34](I)[CH3:35]>O1CCCC1>[CH2:1]([O:3][C:4]([N:6]1[CH2:12][CH:11]([CH2:34][CH3:35])[C:10]2=[N:13][C:14]([C:18]3[CH:23]=[CH:22][N:21]=[CH:20][N:19]=3)=[CH:15][C:16](=[O:17])[N:9]2[CH2:8][CH2:7]1)=[O:5])[CH3:2]

Participants

5

Reactant 3

HCID 6340IodoethaneHCID 2733832Lithium HexamethyldisilazideHCID 668417894-Oxo-2-pyrimidin-4-yl-5,6,8,9-tetrahydro-4H-1,4a,7-triaza-benzocycloheptene-7-carboxylic acid ethyl ester

Product 1

HCID 44598875(+/-)-9-Ethyl-4-oxo-2-pyrimidin-4-yl-5,6,8,9-tetrahydro-4H-1,4-a,7-triaza-benzocycloheptene-7-carboxylic acid ethyl esterYield 18%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent

Conditions

Temperature
-78 °C

Procedure

To a solution of 10.00 g (41.27 mmol) of 4-oxo-2-pyrimidin-4-yl-5,6,8,9-tetrahydro-4H-1,4-a,7-triaza-benzocycloheptene-7-carboxylic acid ethyl ester in dry tetrahydrofuran (8 mL) under argon at −78° C. was added 2.00 mL (2.00 mmol) of lithium bis(trimethylsilyl)amide (1M in tetrahydrofuran). The solution was stirred at −78° C. for 10 min and 1.28 mL of ethyl iodide (15.86 mmol) was added. The reaction was stirred at −78° C. for 1 h and then at 0° C. for 2 h. The mixture was quenched with the addition of a saturated solution of ammonium chloride and extracted with ethyl acetate. The organic phase was dried over sodium sulfate and concentrated. The residue was purified by flash chromatography (dichloromethane with 1% of methanol) to afford 0.100 g of a white solid (18%).

Workup

  1. stirringThe reaction was stirred at −78° C. for 1 h
  2. waitat 0° C. for 2 h
  3. customThe mixture was quenched with the addition of a saturated solution of ammonium chloride
  4. extractionextracted with ethyl acetate
  5. dry with materialThe organic phase was dried over sodium sulfate
  6. concentrationconcentrated
  7. customThe residue was purified by flash chromatography (dichloromethane with 1% of methanol)

Sources & evidence

ORD record
ord-f893908a2582430d8e3378021ee61452
Source dataset
uspto-grants-2015_07
Patent number
US09073914B2

Reaction notes

Loading…