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

HRID 1389814Notes

Reaction equation

HRID 1389814 reaction equation
[Br:1][C:2]1[CH:3]=[CH:4][C:5]2[NH:11][C:10](=[O:12])[CH:9](O)[N:8]=[C:7]([C:14]3[CH:19]=[CH:18][CH:17]=[CH:16][CH:15]=3)[C:6]=2[CH:20]=1.C(N(S(F)(F)[F:27])CC)C>C(Cl)Cl>[F:27][CH:9]1[N:8]=[C:7]([C:14]2[CH:19]=[CH:18][CH:17]=[CH:16][CH:15]=2)[C:6]2[CH:20]=[C:2]([Br:1])[CH:3]=[CH:4][C:5]=2[NH:11][C:10]1=[O:12]

Participants

4

Reactant 2

HCID 123472(Diethylamino)sulfur trifluorideHCID 627325HCID 627325, compound

Product 1

HCID 131259917-Bromo-3-fluoro-5-phenyl-1,3-dihydro-2H-1,4-benzodiazepin-2-oneYield 88%

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent

Procedure

A well stirred suspension of 6.0 g (0.018 mole) of 7-bromo-1,3-dihydro-3-hydroxy-5-phenyl-2H-1,4-benzodiazepin-2-one in 250 ml methylene chloride was cooled to -70°, and 7.5 ml (0.06 mole) of diethylaminosulfur trifluoride was added dropwise. The reaction mixture was allowed to warm slowly to -10° over a period of 30 min., and held at -10° for 20 min., until most of the solid had dissolved. The reaction mixture was poured into 500 ml of ice water and stirred until the yellow color faded. The organic layer was separated, dried over MgSO4, and evaporated to dryness under reduced pressure. The residue was dissolved in 300 ml of hot benzene and filtered hot. The filtrate was mixed with 400 ml hexane and cooled. The crystals that separated were collected on a filter, washed with hexane, and dried in air to give 5.28 g (88%) of 3-fluoro-7-bromo-1,3-dihydro- 5-phenyl-2H-1,4-benzodiazepin-2-one as colorless crystals: mp 207°-209° (dec.); 19F nmr (acetone-d6) δ -162.6 ppm (d, J=57 Hz); 1H nmr (acetone-d6) δ 5.86 ppm (d, J=57 Hz, 1H), 7.2-8 ppm (m, 8H), 9.90 ppm (NH); ir (KBr) 5.84μ (C=O). A sample was dried in a vacuum oven for analysis.

Workup

  1. temperaturewas cooled to -70°
  2. temperatureto warm slowly to -10° over a period of 30 min.
  3. dissolutionuntil most of the solid had dissolved
  4. stirringstirred until the yellow color
  5. customThe organic layer was separated
  6. dry with materialdried over MgSO4
  7. customevaporated to dryness under reduced pressure
  8. dissolutionThe residue was dissolved in 300 ml of hot benzene
  9. filtrationfiltered hot
  10. additionThe filtrate was mixed with 400 ml hexane
  11. temperaturecooled
  12. customThe crystals that separated
  13. customwere collected on a filter
  14. washwashed with hexane
  15. customdried in air

Sources & evidence

ORD record
ord-dd1291c7aa9f4160a737ebf4f3238d0a
Source dataset
uspto-grants-1981_01
Patent number
US04246270

Reaction notes

Loading…