(Diethylamino)sulfur trifluoride → 3-fluoro-1,3-dihydro-7-nitro-5-phenyl-2H-1,4-benzodiazepin-2-one

HRID 1112103Notes

Reaction equation

HRID 1112103 reaction equation
O[CH:2]1[N:8]=[C:7]([C:9]2[CH:14]=[CH:13][CH:12]=[CH:11][CH:10]=2)[C:6]2[CH:15]=[C:16]([N+:19]([O-:21])=[O:20])[CH:17]=[CH:18][C:5]=2[NH:4][C:3]1=[O:22].C(N(S(F)(F)[F:29])CC)C>C(Cl)Cl>[F:29][CH:2]1[N:8]=[C:7]([C:9]2[CH:14]=[CH:13][CH:12]=[CH:11][CH:10]=2)[C:6]2[CH:15]=[C:16]([N+:19]([O-:21])=[O:20])[CH:17]=[CH:18][C:5]=2[NH:4][C:3]1=[O:22]

Participants

4

Reactant 2

HCID 123472(Diethylamino)sulfur trifluorideHCID 616119Nitroxazepam

Product 1

HCID 131259943-fluoro-1,3-dihydro-7-nitro-5-phenyl-2H-1,4-benzodiazepin-2-oneYield 83.5%

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent

Procedure

A well stirred suspension of 3.6 g (0.012 mole) of 1,3-dihydro-3-hydroxy-7-nitro-5-phenyl-2H-1,4-benzodiazepin-2-one in 200 ml methylene chloride was cooled to -70°, and 5 ml (0.04 mole) of diethylaminosulfur trifluoride was added dropwise. The reaction mixture was allowed to warm slowly to -10°, at which temperature all of the solid went into solution. The reaction mixture was poured into 400 ml of ice water, and the organic layer was separated, washed with water, dried (MgSO4) and evaporated to dryness under reduced pressure. The residue was recrystallized from benzene-heptane to give 3.0 g (83%) of 3-fluoro-1,3-dihydro-7-nitro-5-phenyl-2H-1,4-benzodiazepin-2-one as colorless crystals: mp 174°-175° (dec.); 1H nmr (DMSO-d6) δ 5.90 ppm (d, J = 57 Hz, 1H), 7.3-7.7 ppm (m, 6H), 8.07 ppm (d, J = 2.5 Hz, 1H) and 8.45 ppm (d, d, J = 9.0, 2.5 Hz, 1H); 19F nmr (DMSO-d6) δ -161.4 ppm (d, J = 57 Hz).

Workup

  1. temperaturewas cooled to -70°
  2. temperatureto warm slowly to -10°, at which temperature all of the solid
  3. customthe organic layer was separated
  4. washwashed with water
  5. dry with materialdried (MgSO4)
  6. customevaporated to dryness under reduced pressure
  7. customThe residue was recrystallized from benzene-heptane

Sources & evidence

ORD record
ord-e8e0835ea16f455b805a209236ccf2cb
Source dataset
uspto-grants-1978_10
Patent number
US04120856

Reaction notes

Loading…