Methyl iodide → benzyl 1-methyl-2-oxo-5-phenyl-2,3-dihydro-1H-benzo[e][1,4]diazepin-3-ylcarbamate

HRID 2188600Notes

Reaction equation

HRID 2188600 reaction equation
[O:1]=[C:2]1[NH:8][C:7]2[CH:9]=[CH:10][CH:11]=[CH:12][C:6]=2[C:5]([C:13]2[CH:18]=[CH:17][CH:16]=[CH:15][CH:14]=2)=[N:4][CH:3]1[NH:19][C:20](=[O:29])[O:21][CH2:22][C:23]1[CH:28]=[CH:27][CH:26]=[CH:25][CH:24]=1.[H-].[Na+].[CH3:32]I.S([O-])(O)(=O)=O.[Na+]>CN(C=O)C.O>[CH3:32][N:8]1[C:7]2[CH:9]=[CH:10][CH:11]=[CH:12][C:6]=2[C:5]([C:13]2[CH:18]=[CH:17][CH:16]=[CH:15][CH:14]=2)=[N:4][CH:3]([NH:19][C:20](=[O:29])[O:21][CH2:22][C:23]2[CH:24]=[CH:25][CH:26]=[CH:27][CH:28]=2)[C:2]1=[O:1]

Participants

7

Reactant 4

HCID 6328Methyl iodideHCID 24758Sodium hydrideHCID 516919Sodium BisulfateHCID 2756242Benzyl (2-oxo-5-phenyl-2,3-dihydro-1h-benzo[e][1,4]diazepin-3-yl)carbamate

Product 1

HCID 18969006benzyl 1-methyl-2-oxo-5-phenyl-2,3-dihydro-1H-benzo[e][1,4]diazepin-3-ylcarbamateYield 91%

Reagents, catalysts & solvents 2

HCID 962WaterSolventHCID 6228DimethylformamideSolvent

Conditions

Temperature
0 °C

Procedure

To a solution of benzyl 2-oxo-5-phenyl-2,3-dihydro-1H-benzo[e][1,4]diazepin-3-ylcarbamate (13) (Sherril R. G.; Sugg, E. E. Improved Synthesis and Resolution of 3-Amino-1,3-dihydro-5-phenyl-2H-1,4-benzodiazepin-2-ones. J. Org. Chem. 1995, 60, 730-734) (1.00 g, 2.60 mmol) in anhydrous DMF (10 mL), kept at 0° C. under N2, NaH (60% dispersion in mineral oil, 0.10 g, 1 eq) was added in small portions. After 1.5 hr stirring at 0° C., methyl iodide (0.17 mL, 1.05 eq) was added at once; the mixture was stirred for additional 1.5 h at the same temperature, and then poured into a stirred solution of H2O (60 mL) containing aqueous sodium hydrogen sulphate (2 mL, 1 N). A solid precipitated, which was filtered, dried under vacuum, and then purified by flash chromatography (CH2Cl2/MeOH/NH3 99:1:0.1 as eluent) giving benzyl 1-methyl-2-oxo-5-phenyl-2,3-dihydro-1H-benzo[e][1,4]diazepin-3-ylcarbamate in 91% yield. M.p. 78-80° C.

Workup

  1. customkept at 0° C. under N2
  2. stirringthe mixture was stirred for additional 1.5 h at the same temperature
  3. customA solid precipitated
  4. filtrationwhich was filtered
  5. customdried under vacuum
  6. custompurified by flash chromatography (CH2Cl2/MeOH/NH3 99:1:0.1 as eluent)

Sources & evidence

ORD record
ord-e487b70145084a98adca5f29112fae17
Source dataset
uspto-grants-2012_12
Patent number
US08324202B2

Reaction notes

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