Nitric Acid → HCID 16061668, compound

HRID 2035423Notes

Reaction equation

HRID 2035423 reaction equation
[F:1][C:2]([F:33])([F:32])[C:3]([NH:5][C@@H:6]1[CH2:31][CH2:30][N:9]2[C:10]3[CH:23]=[CH:22][C:21](C4N=NN(C)N=4)=[CH:20][C:11]=3[C@H:12]([CH3:19])[C:13]3[CH:18]=[CH:17][CH:16]=[CH:15][C:14]=3[C@H:8]2[CH2:7]1)=[O:4].[N+:34]([O-])([OH:36])=[O:35]>C(Cl)Cl>[F:1][C:2]([F:32])([F:33])[C:3]([NH:5][C@@H:6]1[CH2:31][CH2:30][N:9]2[C:10]3[CH:23]=[CH:22][C:21]([N+:34]([O-:36])=[O:35])=[CH:20][C:11]=3[C@H:12]([CH3:19])[C:13]3[CH:18]=[CH:17][CH:16]=[CH:15][C:14]=3[C@H:8]2[CH2:7]1)=[O:4]

Participants

4

Reactant 2

HCID 944Nitric AcidHCID 16063296HCID 16063296, compound

Product 1

HCID 16061668HCID 16061668, compound

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent

Procedure

A solution of 10 (8═H, R2═COCF3; 76 mg, 0.2 mmol) in DCM (1.5 mL) was cooled to 0° C. and fuming nitric acid (21 μl, 0.5 mmol) was added in portions. The ice/water bath was removed and the reaction mixture turned red. After 10 min the reaction was quenched with aqueous NaHCO3, extracted with DCM, dried (Na2SO4) and concentrated under reduced pressure. The crude product was purified by column chromatography on silica (Heptane:Ethyl acetate=7:3) followed by preparative HPLC. Freeze-drying from acetonitrile/H2O afforded rel-2,2,2-trifluoro-N-[(2R,10R,14bR)-1,2,3,4,10,14b-hexahydro-10-methyl-8-nitrodibenzo[c,f]pyrido[1,2-a]azepin-2-yl]acetamide) (10, R8═NO2, R2═COCF3; 6 mg, 7%. Data: (m/z)=420 (M+H)+.

Workup

  1. customThe ice/water bath was removed
  2. customAfter 10 min the reaction was quenched with aqueous NaHCO3
  3. extractionextracted with DCM
  4. dry with materialdried (Na2SO4)
  5. concentrationconcentrated under reduced pressure
  6. customThe crude product was purified by column chromatography on silica (Heptane:Ethyl acetate=7:3)
  7. dry with materialFreeze-drying from acetonitrile/H2O

Sources & evidence

ORD record
ord-906e362d771a4333b17915d4cc444c96
Source dataset
uspto-grants-2013_11
Patent number
US08575152B2

Reaction notes

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