Ethyl Acetate → 1-benzyl-4-tert-butyloxycarbonyl-7-methylene-2-oxo-2,3,4,5,6,7-hexahydro-1H-1,4-benzodiazonine

HRID 1106924Notes

Reaction equation

HRID 1106924 reaction equation
[CH2:1]([N:8]1[C:16]2[CH:17]=[CH:18][CH:19]=[CH:20][C:15]=2[C:14](=O)[CH2:13][CH2:12][N:11]([C:22]([O:24][C:25]([CH3:28])([CH3:27])[CH3:26])=[O:23])[CH2:10][C:9]1=[O:29])[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1.[C:30](OCC)(=O)C>O1CCCC1>[CH2:1]([N:8]1[C:16]2[CH:17]=[CH:18][CH:19]=[CH:20][C:15]=2[C:14](=[CH2:30])[CH2:13][CH2:12][N:11]([C:22]([O:24][C:25]([CH3:26])([CH3:27])[CH3:28])=[O:23])[CH2:10][C:9]1=[O:29])[C:2]1[CH:3]=[CH:4][CH:5]=[CH:6][CH:7]=1

Participants

4

Reactant 2

HCID 8857Ethyl AcetateHCID 187882101-benzyl-4-tert-butyloxycarbonyl-2,7-dioxo-2,3,4,5,6,7-hexahydro-1H-1,4-benzodiazonine

Product 1

HCID 187881551-benzyl-4-tert-butyloxycarbonyl-7-methylene-2-oxo-2,3,4,5,6,7-hexahydro-1H-1,4-benzodiazonine

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent

Procedure

μ-Chloro-μ-methylene-[bis(cyclopentadienyl)titanium]dimethylaluminium (0.5M in toluene/15 ml, 7.5 mmol) was added to a solution of 1-benzyl-4-tert-butyloxycarbonyl-2,7-dioxo-2,3,4,5,6,7-hexahydro-1H-1,4-benzodiazonine (2.95 g, 7.5 mmol) in tetrahydrofuran (23 ml) at -5° C. The resultant suspension was stirred at -5° C. for 15 minutes then allowed to warm to room temperature. Stirring was continued for a further 30 minutes followed by the addition of ethyl acetate (50 ml) and the mixture was washed with 0.2M sodium hydroxide solution (1.5 ml), and dried (MgSO4). The mixture was filtered through a pad of celite and evaporated to dryness. The crude product was purified by chromatography on silica gel with ethyl acetate-hexane (1:3) as eluant. (981 mg, 33%).

Workup

  1. washthe mixture was washed with 0.2M sodium hydroxide solution (1.5 ml)
  2. dry with materialdried (MgSO4)
  3. filtrationThe mixture was filtered through a pad of celite
  4. customevaporated to dryness
  5. customThe crude product was purified by chromatography on silica gel with ethyl acetate-hexane (1:3) as eluant

Sources & evidence

ORD record
ord-332f7280fa984a239c383fbfcb08222c
Source dataset
uspto-grants-2000_05
Patent number
US06057311

Reaction notes

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