Ethyl Acetate → 3-Amino-9-chloro-2-oxo-5-phenyl-1-(2,2,2-trifluoroethyl)-2,3-dihydro-1H-1,4-benzodiazepine

HRID 459896Notes

Reaction equation

HRID 459896 reaction equation
[N:1]([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]=[CH:18][CH:19]=[C:20]([Cl:21])[C:7]=2[N:6]([CH2:22][C:23]([F:26])([F:25])[F:24])[C:5]1=[O:27])=[N+]=[N-].C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.C(OCC)(=O)C.C(=O)(O)[O-].[Na+]>O1CCCC1.O.[Cl-].[Na+].O>[NH2:1][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]=[CH:18][CH:19]=[C:20]([Cl:21])[C:7]=2[N:6]([CH2:22][C:23]([F:26])([F:24])[F:25])[C:5]1=[O:27]

Participants

8

Reactant 4

HCID 8857Ethyl AcetateHCID 11776TriphenylphosphineHCID 516892Sodium BicarbonateHCID 184442503-Azido-9-chloro-2-oxo-5-phenyl-1-(2,2,2-trifluoroethyl)-2,3-dihydro-1H-1,4-benzodiazepine

Product 1

HCID 184442493-Amino-9-chloro-2-oxo-5-phenyl-1-(2,2,2-trifluoroethyl)-2,3-dihydro-1H-1,4-benzodiazepineYield 51.9%

Reagents, catalysts & solvents 3

HCID 962WaterSolventHCID 8028TetrahydrofuranSolventHCID 57417360Sodium chloride; waterSolvent

Procedure

A solution of 3-azido-9-chloro-2-oxo-5-phenyl-1-(2,2,2-trifluoroethyl)-2,3-dihydro-1H-1,4-benzodiazepine (0.320 g, 0.812 mmol) and triphenylphosphine (0.426 g, 1.62 mmol) in tetrahydrofuran (13 mL) and water (1.5 mL) was stirred at room temperature for 48 h. Workup with ethyl acetate and saturated sodium bicarbonate, followed by saturated brine and drying over sodium sulfate gave the product. The crude product was purified by chromatography (silica gel, 0–5% methanol in methylene chloride gradient elution), giving the title compound (0.155 g). 1H NMR (500 MHz, CDCl3) δ 7.65 (d, J=8 Hz, 2H), 7.49 (tt, J=2,7 Hz, 1H), 7.42 (t, J=8 Hz, 2H), 7.32 (t, J=8 Hz, 1H), 7.26 (d, J=7 Hz, 1H), 5, 22 (m, 1H), 4.56 (s, 1H), 4.30 (m, 1H), 2.15 (br s, 2H).

Workup

  1. dry with materialdrying over sodium sulfate
  2. customgave the product
  3. customThe crude product was purified by chromatography (silica gel, 0–5% methanol in methylene chloride gradient elution)

Sources & evidence

ORD record
ord-f41423c6ae02483f81a2d839fcdb4be1
Source dataset
uspto-grants-2007_03
Patent number
US07196079B2

Reaction notes

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