Acetic Acid → 3-Azido-9-chloro-2-oxo-5-phenyl-1-(2,2,2-trifluoroethyl)-2,3-dihydro-1H-1,4-benzodiazepine

HRID 459895Notes

Reaction equation

HRID 459895 reaction equation
[Cl:1][C:2]1[C:12]2[N:11]([CH2:13][C:14]([F:17])([F:16])[F:15])[C:10](=[O:18])[CH2:9][N:8]=[C:7]([C:19]3[CH:24]=[CH:23][CH:22]=[CH:21][CH:20]=3)[C:6]=2[CH:5]=[CH:4][CH:3]=1.CC(C)([O-])C.[K+].C(C1C=C(C(C)C)C=C(C(C)C)C=1S([N:49]=[N+:50]=[N-:51])(=O)=O)(C)C.C(O)(=O)C.C(=O)(O)[O-].[Na+]>O1CCCC1.[Cl-].[Na+].O.C(OCC)(=O)C>[N:49]([CH:9]1[N:8]=[C:7]([C:19]2[CH:20]=[CH:21][CH:22]=[CH:23][CH:24]=2)[C:6]2[CH:5]=[CH:4][CH:3]=[C:2]([Cl:1])[C:12]=2[N:11]([CH2:13][C:14]([F:15])([F:17])[F:16])[C:10]1=[O:18])=[N+:50]=[N-:51]

Participants

9

Reactant 5

HCID 176Acetic AcidHCID 3717072,4,6-Triisopropylbenzenesulfonyl azideHCID 516892Sodium BicarbonateHCID 184442569-Chloro-2-oxo-5-phenyl-1-(2,2,2-trifluoroethyl)-2,3-dihydro-1H-1,4-benzodiazepineHCID 23665647Potassium tert-butoxide

Product 1

HCID 184442503-Azido-9-chloro-2-oxo-5-phenyl-1-(2,2,2-trifluoroethyl)-2,3-dihydro-1H-1,4-benzodiazepine

Reagents, catalysts & solvents 3

HCID 8028TetrahydrofuranSolvent2×HCID 8857Ethyl AcetateSolventHCID 57417360Sodium chloride; waterSolvent

Procedure

A solution of 9-chloro-2-oxo-5-phenyl-1-(2,2,2-trifluoroethyl)-2,3-dihydro-1H-1,4-benzodiazepine (0.287 g, 0.813 mmol) in tetrahydrofuran (10 mL) was cooled to −78° C., and potassium t-butoxide (0.905 mL, 1 M in tetrahydrofuran) was added. After 15 min, 2,4,6-triisopropylbenzenesulfonylazide (0.976 mL, 1M in tetrahydrofuran) was added. After 15 min, acetic acid (0.186 mL, 3.2 mmol) was added and the reaction warned to room temperature and stirred for 3.5 h. Workup with ethyl acetate and saturated sodium bicarbonate solution, followed by saturated brine and drying gave a solid. Tetrahydrofuran (30 mL) was added, the solid filtered, and the filtrate concentrated to obtain the title compound. MS 394 (M+1) 1H NMR (500 MHz, CDCl3) δ 7.77–7.20 (m, 8H), 6.40 (s, 1H), 5.20 (m, 1H), 4.30 (m, 1H).

Workup

  1. waitAfter 15 min
  2. customwarned to room temperature
  3. customdrying
  4. customgave a solid
  5. filtrationthe solid filtered
  6. concentrationthe filtrate concentrated

Sources & evidence

ORD record
ord-b6639f5144d14e7c9804ee600101cdd3
Source dataset
uspto-grants-2007_03
Patent number
US07196079B2

Reaction notes

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