Ceric ammonium nitrate → Ethyl 6-chloro-7b-methyl-2-oxo-1,3-dihydrocyclopropa[c]quinoline-1a-carboxylate

HRID 1745854Notes

Reaction equation

HRID 1745854 reaction equation
[CH2:1]([O:3][C:4]([C:6]12[CH2:27][C:7]1([CH3:28])[C:8]1[C:13]([N:14](CC3C=CC(OC)=CC=3)[C:15]2=[O:16])=[CH:12][CH:11]=[C:10]([Cl:26])[CH:9]=1)=[O:5])[CH3:2].O=[N+]([O-])[O-].[O-][N+](=O)[O-].[O-][N+](=O)[O-].[O-][N+](=O)[O-].[O-][N+](=O)[O-].[O-][N+](=O)[O-].[Ce+4].[NH4+].[NH4+]>C(#N)C.O>[CH2:1]([O:3][C:4]([C:6]12[CH2:27][C:7]1([CH3:28])[C:8]1[C:13]([NH:14][C:15]2=[O:16])=[CH:12][CH:11]=[C:10]([Cl:26])[CH:9]=1)=[O:5])[CH3:2]

Participants

4

Reactant 2

HCID 180504Ceric ammonium nitrateHCID 210202446-Chloro-3-(4-methoxy-benzyl)-7b-methyl-2-oxo-1,2,3,7b-tetrahydro-3-aza-cyclo-propa[a]naphthalene-1a-carboxylic acid ethyl ester

Product 1

HCID 15959175Ethyl 6-chloro-7b-methyl-2-oxo-1,3-dihydrocyclopropa[c]quinoline-1a-carboxylateYield 86%

Reagents, catalysts & solvents 1

HCID 18373917Acetonitrile--water (1/1)Solvent

Procedure

A solution of 4 (20.0 mg, 0.050 mmol) in acetonitrile/H2O (9:1, 0.300 mL) was cooled to 0° C. in an ice-water bath and treated with CAN (82.0 mg, 0.150 mmol). The reaction mixture was stirred at ambient temperature for 12 h and quenched with Na2S2O5 to remove anisaldehyde. The resulting suspension was diluted with H2O, extracted with CH2Cl2, dried (Na2SO4), filtered, and concentrated in vacuo. Chromatography afforded 5 (12.0 mg, 86%) as a white solid. 1H NMR (CDCl3, 400 MHz) δ 8.55 (br s, 1H), 7.43 (d, J=2.2 Hz, 1H), 7.15 (dd, J=2.2, 9 Hz, 1H), 6.72 (d, J=9 Hz, 1H), 4.31 (m, 2H), 2.12 (d, J=6.6 Hz, 1H), 1.55 (s, 3H), 1.29 (t, J=7.2 Hz, 3H), 1.11 (d, J=6.6 Hz, 1H).

Workup

  1. customquenched with Na2S2O5
  2. customto remove anisaldehyde
  3. additionThe resulting suspension was diluted with H2O
  4. extractionextracted with CH2Cl2
  5. dry with materialdried (Na2SO4)
  6. filtrationfiltered
  7. concentrationconcentrated in vacuo

Sources & evidence

ORD record
ord-0deb792108ad40159400c5beaa6ccdc8
Source dataset
uspto-grants-2006_03
Patent number
US07019141B2

Reaction notes

Loading…