Ethylenediamine → 6-Nitro-1,2,3,4-tetrahydro-benzo[e][1,4]diazepin-5-one

HRID 1687039Notes

Reaction equation

HRID 1687039 reaction equation
CO[C:3](=[O:14])[C:4]1[C:9]([N+:10]([O-:12])=[O:11])=[CH:8][CH:7]=[CH:6][C:5]=1F.[CH2:15]([NH2:18])[CH2:16][NH2:17].C(N(C(C)C)CC)(C)C.[Cl-].[NH4+]>O1CCOCC1>[N+:10]([C:9]1[C:4]2[C:3](=[O:14])[NH:18][CH2:15][CH2:16][NH:17][C:5]=2[CH:6]=[CH:7][CH:8]=1)([O-:12])=[O:11]

Participants

6

Reactant 4

HCID 3301EthylenediamineHCID 25517Ammonium ChlorideHCID 81531DiisopropylethylamineHCID 597752Methyl 2-fluoro-6-nitrobenzoate

Product 1

HCID 578538616-Nitro-1,2,3,4-tetrahydro-benzo[e][1,4]diazepin-5-oneYield 25.9%

Reagents, catalysts & solvents 1

HCID 312751,4-DioxaneSolvent

Procedure

2-fluoro-6-nitrobenzoic acid methyl ester (4.54 g, 22.8 mmol), ethylenediamine (1.50 mL, 22.4 mmol) and diisopropylethylamine (8.71 mL, 50 mmol) were dissolved in 1,4-dioxane (40 mL). The reaction mixture was then irradiated at 140° C. for 40 minutes. After cooling, the reaction mixture was poured over saturated ammonium chloride (50 mL), and organics were extracted with ethyl acetate (3×50 mL). The combined organic extracts were dried over Na2SO4, filtered and reduced. The residue was then purified by flash column chromatography (0% MeOH/DCM-20% MeOH/DCM over 35 minutes) to afford 1.2 grams of 6-Nitro-1,2,3,4-tetrahydro-benzo[e][1,4]diazepin-5-one as a yellow oil. LC/MS (ESI)=208.24 (M+H).

Workup

  1. customThe reaction mixture was then irradiated at 140° C. for 40 minutes
  2. temperatureAfter cooling
  3. extractionorganics were extracted with ethyl acetate (3×50 mL)
  4. dry with materialThe combined organic extracts were dried over Na2SO4
  5. filtrationfiltered
  6. customThe residue was then purified by flash column chromatography (0% MeOH/DCM-20% MeOH/DCM over 35 minutes)

Sources & evidence

ORD record
ord-6d915b5e8fd14439b863f278d993298f
Source dataset
uspto-grants-2012_04
Patent number
US08148391B2

Reaction notes

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