Methyl iodide → 1-methyl-3-fluoro-5-phenyl-7-nitro-2,3-dihydro-1H-1,4-benzodiazapin-2-one

HRID 1112104Notes

Reaction equation

HRID 1112104 reaction equation
[H-].[Na+].[F:3][CH:4]1[N:10]=[C:9]([C:11]2[CH:16]=[CH:15][CH:14]=[CH:13][CH:12]=2)[C:8]2[CH:17]=[C:18]([N+:21]([O-:23])=[O:22])[CH:19]=[CH:20][C:7]=2[NH:6][C:5]1=[O:24].[CH3:25]I>O1CCCC1>[F:3][CH:4]1[N:10]=[C:9]([C:11]2[CH:12]=[CH:13][CH:14]=[CH:15][CH:16]=2)[C:8]2[CH:17]=[C:18]([N+:21]([O-:23])=[O:22])[CH:19]=[CH:20][C:7]=2[N:6]([CH3:25])[C:5]1=[O:24]

Participants

5

Reactant 3

HCID 6328Methyl iodideHCID 24758Sodium hydrideHCID 131259943-fluoro-1,3-dihydro-7-nitro-5-phenyl-2H-1,4-benzodiazepin-2-one

Product 1

HCID 128110131-methyl-3-fluoro-5-phenyl-7-nitro-2,3-dihydro-1H-1,4-benzodiazapin-2-oneYield 60%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent2×

Procedure

A slurry of 0.20 g (0.08 mole) of sodium hydride in 10 ml of tetrahydrofuran was added to a solution of 1.74 g (0.0058 mole) of 3-fluoro-1,3-dihydro-7-nitro-5-phenyl-2H-1,4-benzodiazepin-2-one and 10 ml methyl iodide in 100 ml of tetrahydrofuran at 25°. The reaction mixture was stirred for 3 hr at 25°, and then poured into 300 ml of ice water. The aqueous mixture was extracted with methylene chloride, and the extracts were dried (MgSO4) and then evaporated to dryness under reduced pressure. The residue was dissolved in hot benzene and then fractionally precipitated by the addition of hexane. The first dark fractions of solid were discarded. The remaining fractions were collected on a filter and dried in vacuum to give 1.10 g (60%) of 3-fluoro-1,3-dihydro-1-methyl-7-nitro-5-phenyl-2H-1,4-benzodiazepin-2-one as a light tan amorphous solid with no distinct melting point: 1H nmr (CDCl3) δ 3.53 ppm (s, 3H), 5.59 ppm (d, J = 57 Hz, 1H), 7.2-7.9 ppm (m, 6H) and 8.2-8.9 ppm (m, 2H); 19F nmr (CDCl3) δ -161.7 ppm (d, J = 57 Hz).

Workup

  1. extractionThe aqueous mixture was extracted with methylene chloride
  2. dry with materialthe extracts were dried (MgSO4)
  3. customevaporated to dryness under reduced pressure
  4. dissolutionThe residue was dissolved in hot benzene
  5. customfractionally precipitated by the addition of hexane
  6. customThe remaining fractions were collected on
  7. filtrationa filter
  8. customdried in vacuum

Sources & evidence

ORD record
ord-c321ffe35be3497b8578a3a4e71c98cd
Source dataset
uspto-grants-1978_10
Patent number
US04120856

Reaction notes

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