1,10-Phenanthroline → N-(3-morpholin-4-yl-phenyl)-hydrazinecarboxylic acid tert-butyl ester

HRID 1179208Notes

Reaction equation

HRID 1179208 reaction equation
I[C:2]1[CH:3]=[C:4]([N:8]2[CH2:13][CH2:12][O:11][CH2:10][CH2:9]2)[CH:5]=[CH:6][CH:7]=1.[C:14]([O:18][C:19](=[O:22])[NH:20][NH2:21])([CH3:17])([CH3:16])[CH3:15].N1C2C(=CC=C3C=2N=CC=C3)C=CC=1.C(=O)([O-])[O-].[Cs+].[Cs+]>CN(C=O)C.[Cu]I.O>[C:14]([O:18][C:19]([N:20]([C:2]1[CH:7]=[CH:6][CH:5]=[C:4]([N:8]2[CH2:13][CH2:12][O:11][CH2:10][CH2:9]2)[CH:3]=1)[NH2:21])=[O:22])([CH3:17])([CH3:16])[CH3:15]

Participants

8

Reactant 4

HCID 13181,10-PhenanthrolineHCID 10796Cesium carbonateHCID 70091tert-Butyl carbazateHCID 545364344-(3-Iodophenyl)morpholine

Product 1

HCID 58977018N-(3-morpholin-4-yl-phenyl)-hydrazinecarboxylic acid tert-butyl esterYield 62.1%

Reagents, catalysts & solvents 3

HCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)CatalystHCID 962WaterSolventHCID 6228DimethylformamideSolvent

Conditions

Temperature
80 °C

Procedure

To a solution of 4-(3-iodo-phenyl)-morpholine (1.81 g, 6.26 mmol) in DMF (6.5 mL) under nitrogen was added tert-butylcarbazate (993 mg, 7.52 mmol), copper (I) iodide (59.5 mg, 0.313 mmol), 1,10-phenanthroline (113 mg, 0.626 mmol) and cesium carbonate (2.85 g, 8.77 mmol). The mixture was heated at 80° C. for 18 h and then cooled to room temperature. Water (100 mL) was added and the mixture was extracted with ethyl acetate. The organic layer was dried over MgSO4, concentrated. The residue was purified by silica gel column chromatograghy eluted with EtOAc:hexanes (25 to 50% EtOAc) to give N-(3-morpholin-4-yl-phenyl)-hydrazinecarboxylic acid tert-butyl ester (1.14 g, 62%) as a yellowi oil. MS (ES+): m/z=294.2. 1H NMR (DMSO-d6, 500 MHz): δ 1.44 (s, 9H), 3.06 (t, 4H), 3.73 (t, 4H), 4.97 (s, 2H), 6.66 (dd, 1H), 6.91 (d, 1H), 7.01-7.05 (m, 1H), 7.09-7.14 (m, 1H).

Workup

  1. temperaturecooled to room temperature
  2. extractionthe mixture was extracted with ethyl acetate
  3. dry with materialThe organic layer was dried over MgSO4
  4. concentrationconcentrated
  5. customThe residue was purified by silica gel column chromatograghy
  6. washeluted with EtOAc

Sources & evidence

ORD record
ord-da03d006c47644c286ce0ee4ea01cc53
Source dataset
uspto-grants-2007_10
Patent number
US07279469B2

Reaction notes

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