Dichloromethane methanol → HCID 16042898, compound

HRID 1186105Notes

Reaction equation

HRID 1186105 reaction equation
[N+:1]([C:4]1[CH:19]=[CH:18][CH:17]=[CH:16][C:5]=1[CH2:6][N:7]([CH2:13][C:14]#[N:15])[C:8](=[O:12])[O:9][CH2:10][CH3:11])([O-])=O.CO.C(Cl)Cl>C(O)(=O)C.[Fe]>[CH2:10]([O:9][C:8]([N:7]1[CH2:6][C:5]2[CH:16]=[CH:17][CH:18]=[CH:19][C:4]=2[N:1]=[C:14]([NH2:15])[CH2:13]1)=[O:12])[CH3:11]

Participants

5

Reactant 2

HCID 21226129Dichloromethane methanolHCID 59862492HCID 59862492, compound

Product 1

HCID 16042898HCID 16042898, compoundYield 26%

Reagents, catalysts & solvents 2

HCID 23925IronCatalystHCID 176Acetic AcidSolvent

Conditions

Temperature
90 °C

Procedure

To a solution of ethyl-2-nitrobenzyl-(cyanomethyl)carbamate (2) (227 mg, 0.862 mmol) dissolved in acetic acid (5 mL) under a nitrogen atmosphere was added Fe (289 mg, 5.17 mmol). The reaction mixture was heated to 90° C. for 4 hours, then cooled to room temperature and concentrated under reduced pressure. The resulting brown oil was diluted with EtOAc (20 mL) and filtered over GF/F paper (rinsing with 10 mL of EtOAc). The organic phase was washed with saturated Na2CO3 (20 mL) and brine (20 mL), dried over Na2SO4, and concentrated. The resulting brown oil was purified by column chromatography (5% MeOH/CH2Cl2, then 20% MeOH/CH2Cl2) to provide 52 mg (0.223 mmol, 26% yield) of (E)-ethyl-2-amino-3H-benzo[e][1,4]diazepine-4(5H)-carboxylate (3) as a tan solid. 1H NMR (400 MHz, DMSO-d6) δ 1.17-1.25 (m, 3H), 3.81 (s, 2H), 4.02-4.12 (m, 2H), 4.23 (s, 2H), 6.79 (br s, 1H), 6.85-6.92 (m, 2H), 7.18-7.24 (m, 2H).

Workup

  1. temperaturecooled to room temperature
  2. concentrationconcentrated under reduced pressure
  3. additionThe resulting brown oil was diluted with EtOAc (20 mL)
  4. filtrationfiltered over GF/F paper (rinsing with 10 mL of EtOAc)
  5. washThe organic phase was washed with saturated Na2CO3 (20 mL) and brine (20 mL)
  6. dry with materialdried over Na2SO4
  7. concentrationconcentrated
  8. customThe resulting brown oil was purified by column chromatography (5% MeOH/CH2Cl2

Sources & evidence

ORD record
ord-d830c7812aca42a8b604a016a29ebfdc
Source dataset
uspto-grants-2014_03
Patent number
US08673898B2

Reaction notes

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