Trifluoroacetic anhydride → HCID 67264401, compound

HRID 1040728Notes

Reaction equation

HRID 1040728 reaction equation
[CH3:1][CH:2]1[CH2:8][NH:7][C:6]2[CH:9]=[CH:10][CH:11]=[C:12]([N+:13]([O-:15])=[O:14])[C:5]=2[C:4](=[O:16])[NH:3]1.CC1NC2C=CC=C([N+]([O-])=O)[C:22]=2[C:21](=[O:32])NC1.C(N(C(C)C)CC)(C)C.FC(F)(F)C(OC(=O)C(F)(F)F)=O.[NH4+].[Cl-]>ClCCl>[C:21]([N:7]1[C:6]2[CH:9]=[CH:10][CH:11]=[C:12]([N+:13]([O-:15])=[O:14])[C:5]=2[C:4](=[O:16])[NH:3][CH:2]([CH3:1])[CH2:8]1)(=[O:32])[CH3:22]

Participants

7

Reactant 5

HCID 9845Trifluoroacetic anhydrideHCID 25517Ammonium ChlorideHCID 81531DiisopropylethylamineHCID 67263539HCID 67263539, compoundHCID 67263825HCID 67263825, compound

Product 1

HCID 67264401HCID 67264401, compound

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent

Procedure

A solution of 3-Methyl-6-nitro-1,2,3,4-tetrahydro-benzo[e][1,4]diazepin-5-one and 2-Methyl-6-nitro-1,2,3,4-tetrahydro-benzo[e][1,4]diazepin-5-one (350 mg, 1.58 mmol) was dissolved in dichloromethane (5 mL) and the solution was treated with diisopropylethylamine (0.330 mL, 1.89 mmol) and trifluoroacetic anhydride (332 mg, 1.58 mmol). The reactions were allowed to stir overnight at room temperature for approximately 3 hours. The mixture was then poured over saturated NH4Cl (30 mL) and extracted with dichloromethane (3×15 mL). Combined organic extracts were dried over Na2SO4, filtered and reduced. The crude product was then isolated and purified by flash column chromatography (0% ethyl acetate/hexanes—75% ethyl acetate hexanes) to afford 370 mg of 1-Acetyl-3-methyl-6-nitro-1,2,3,4-tetrahydro-benzo[e][1,4]diazepin-5-one and 1-Acetyl-2-methyl-6-nitro-1,2,3,4-tetrahydro-benzo[e][1,4]diazepin-5-one as a yellow oil. 229c) 1-Acetyl-6-amino-3-methyl-1,2,3,4-tetrahydro-benzo[e][1,4]diazepin-5-one and 1-Acetyl-6-amino-2-methyl-1,2,3,4-tetrahydro-benzo[e][1,4]diazepin-5-one. 1-Acetyl-3-methyl-6-nitro-1,2,3,4-tetrahydro-benzo[e][1,4]diazepin-5-one and 1-Acetyl-2-methyl-6-nitro-1,2,3,4-tetrahydro-benzo[e][1,4]diazepin-5-one (370 mg, 1.17 mmol) was dissolved in ethanol (10 mL) and the solution was treated with Raney Nickel (50% slurry in water) (2 mL) and hydrazine hydrate (0.584 mL, 11.7 mmol). The reaction was then allowed to stir overnight at room temperature. Catalyst was removed by filtering the reaction mixture through a Celite pad and washing the pad with methanol (3×25 mL). The filtrate was dried over Na2SO4, filtered and reduced to afford 140 mg of 1-Acetyl-6-amino-3-methyl-1,2,3,4-tetrahydro-benzo[e][1,4]diazepin-5-one and 1-Acetyl-6-amino-2-methyl-1,2,3,4-tetrahydro-benzo[e][1,4]diazepin-5-one as a clear oil. The crude mixture was used without further purification.

Workup

  1. extractionextracted with dichloromethane (3×15 mL)
  2. dry with materialCombined organic extracts were dried over Na2SO4
  3. filtrationfiltered
  4. customThe crude product was then isolated
  5. custompurified by flash column chromatography (0% ethyl acetate/hexanes—75% ethyl acetate hexanes)

Sources & evidence

ORD record
ord-2e9e0a2e112448ceb4b65db1d9068aab
Source dataset
uspto-grants-2013_10
Patent number
US08552186B2

Reaction notes

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