Ammonium Chloride → HCID 69341119, compound

HRID 1241477Notes

Reaction equation

HRID 1241477 reaction equation
[Cl-].[NH4+].[C:3]([O:7][C:8](=[O:46])[CH2:9][CH2:10][CH2:11][CH2:12][N:13]1[C:19]2[CH:20]=[CH:21][C:22]([I:24])=[CH:23][C:18]=2[C:17](=[O:25])[N:16]([CH:26]([C:28]2[CH:33]=[CH:32][C:31]([Cl:34])=[CH:30][C:29]=2[N+:35]([O-])=O)[CH3:27])[CH:15]([C:38]2[CH:43]=[CH:42][C:41]([Cl:44])=[CH:40][CH:39]=2)[C:14]1=[O:45])([CH3:6])([CH3:5])[CH3:4]>O.C(O)C.[Fe]>[C:3]([O:7][C:8](=[O:46])[CH2:9][CH2:10][CH2:11][CH2:12][N:13]1[C:19]2[CH:20]=[CH:21][C:22]([I:24])=[CH:23][C:18]=2[C:17](=[O:25])[N:16]([CH:26]([C:28]2[CH:33]=[CH:32][C:31]([Cl:34])=[CH:30][C:29]=2[NH2:35])[CH3:27])[CH:15]([C:38]2[CH:39]=[CH:40][C:41]([Cl:44])=[CH:42][CH:43]=2)[C:14]1=[O:45])([CH3:4])([CH3:5])[CH3:6]

Participants

6

Reactant 2

HCID 25517Ammonium ChlorideHCID 69341152HCID 69341152, compound

Product 1

HCID 69341119HCID 69341119, compoundYield 95%

Reagents, catalysts & solvents 3

HCID 23925IronCatalystHCID 702EthanolSolventHCID 962WaterSolvent

Conditions

Temperature
80 °C

Procedure

A solution of ammonium chloride (220 mg, 4.3 mmol) in water (2.5 mL) was added to a solution of 5-[3-(4-chlorophenyl)-4-[1-(4-chloro-2-nitrophenyl)ethyl]-7-iodo-2,5-dioxo-1,4-benzodiazepin-1-yl]valeric acid tert-butyl ester (230 mg, 0.306 mmol) in ethanol (5 mL). The resulting solution was heated to 80° C. and iron (200 mg, 3.58 mmol) was added. After 2 h at 80° C., the reaction mixture was cooled at room temperature, filtered through celite and evaporated. The residue was partitioned between ethyl acetat and water, dried (Na2SO4), and evaporated. Chromatography on silica (EtOAc/hexanes, 1:1) afforded the title compound (210 mg, 95%) as a colorless solid: 1H NMR (400 MHz, CDCl3) δ 1.44 (s, 9H, 3 CH2)), 1.57–1.63 (m, 4H, 2 CH2), 1.74 (d, J=7.2 Hz, 3H, CH3), 2.24 (t, J=7.2 Hz, 2H, CH2), 3.63–3.70 (m, 1H, CH), 4.28–4.35 (m, 1H, CH), 4.75 (br s, 2H, NH2), 5.28 (s, 1H, CH), 6.27 (q, J=7.2 Hz, 1H, CH), 6.60–6.69 (m, 5H, ArH), 6.90 (d, J=9.2 Hz, 2H, ArH), 7.20 (d, J=8.4 Hz, 1H, ArH), 7.49 (dd, J=8.8 Hz, J=2.4 Hz, 1H, ArH), 7.93 (d, J=2.0 Hz, 1H, ArH). Mass spectrum (LCMS, ESI pos.): Calcd for C32H34Cl2IN3O4: 721.0; found: 722.0 (M+H)+.

Workup

  1. temperaturethe reaction mixture was cooled at room temperature
  2. filtrationfiltered through celite
  3. customevaporated
  4. customThe residue was partitioned between ethyl acetat and water
  5. dry with materialdried (Na2SO4)
  6. customevaporated

Sources & evidence

ORD record
ord-311c810cef8a4dbb91423b0bedb18793
Source dataset
uspto-grants-2006_10
Patent number
US07115598B2

Reaction notes

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