1,10-Phenanthroline → HCID 69146517, compound

HRID 1271708Notes

Reaction equation

HRID 1271708 reaction equation
I[C:2]1[CH:11]=[CH:10][C:5]([C:6]([O:8][CH3:9])=[O:7])=[CH:4][CH:3]=1.[C:12]1(=[O:19])[NH:18][CH2:17][CH2:16][CH2:15][CH2:14][CH2:13]1.C([O-])([O-])=O.[K+].[K+].N1C2C(=CC=C3C=2N=CC=C3)C=CC=1>[Cu]I.CCOC(C)=O.O>[CH3:9][O:8][C:6](=[O:7])[C:5]1[CH:10]=[CH:11][C:2]([N:18]2[CH2:17][CH2:16][CH2:15][CH2:14][CH2:13][C:12]2=[O:19])=[CH:3][CH:4]=1

Participants

7

Reactant 4

HCID 13181,10-PhenanthrolineHCID 7768CaprolactamHCID 11430Potassium CarbonateHCID 69273Methyl 4-iodobenzoate

Product 1

HCID 69146517HCID 69146517, compoundYield 51.8%

Reagents, catalysts & solvents 2

HCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)CatalystHCID 22728543Water ethylacetateSolvent

Procedure

A mixture of methyl 4-iodobenzoate (5.24 g, 20.0 mmol), caprolactam (2.26 g, 20.0 mmol), K2CO3 (3.58 g, mmol), CuI (1.53 g, mmol), and 1,10-phenantroline (1.45 g, 35 mmol, 3.3 eq) was heated at 120–125° C. for 15 h. To the cooled mixture was added EtOAc/H2O. The organic layer was washed with H2O and brine, dried over MgSO4, filtered, and concentrated to dryness. The residue was purified by flash chromatography (hexanes:EtOAc=1:1 to 0:1) to give pure 4-(2-oxo-azepan-1-yl)-benzoic acid methyl ester as a white solid (2.56 g, yield: 51.8%). 1H NMR (DMSO-d6) δ 8.01 (d, J=8.6 Hz, 2H), 7.31 (d, J=8.6 Hz, 2H), 3.87 (s, 3H), 3.76 (m, 2H), 2.68 (m, 2H), 1.79 (m, 4H) ppm. LC-MS (ESI) 248.28 (M+H), tR=2.69 min (10–90% MeOH in H2O with 10 mM NH4OAc in a 4-min run).

Workup

  1. temperaturewas heated at 120–125° C. for 15 h
  2. washThe organic layer was washed with H2O and brine
  3. dry with materialdried over MgSO4
  4. filtrationfiltered
  5. concentrationconcentrated to dryness
  6. customThe residue was purified by flash chromatography (hexanes:EtOAc=1:1 to 0:1)

Sources & evidence

ORD record
ord-39351a73e7c14ba38b59c9c734977297
Source dataset
uspto-grants-2007_04
Patent number
US07205318B2

Reaction notes

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