1,10-Phenanthroline → N-(4-Cyano-phenyl)-hydrazinecarboxylic Acid tert-butyl Ester

HRID 655867Notes

Reaction equation

HRID 655867 reaction equation
N1C2C(=CC=C3C=2N=CC=C3)C=CC=1.C(=O)([O-])[O-].[Cs+].[Cs+].I[C:22]1[CH:29]=[CH:28][C:25]([C:26]#[N:27])=[CH:24][CH:23]=1.[C:30]([O:34][C:35]([NH:37][NH2:38])=[O:36])([CH3:33])([CH3:32])[CH3:31]>[Cu](I)I.CN(C=O)C>[C:30]([O:34][C:35]([N:37]([C:22]1[CH:29]=[CH:28][C:25]([C:26]#[N:27])=[CH:24][CH:23]=1)[NH2:38])=[O:36])([CH3:33])([CH3:32])[CH3:31]

Participants

7

Reactant 4

HCID 13181,10-PhenanthrolineHCID 10796Cesium carbonateHCID 70091tert-Butyl carbazateHCID 764674-Iodobenzonitrile

Product 1

HCID 11230036N-(4-Cyano-phenyl)-hydrazinecarboxylic Acid tert-butyl EsterYield 54.1%

Reagents, catalysts & solvents 2

HCID 83717Copper iodideCatalystHCID 6228DimethylformamideSolvent

Conditions

Temperature
80 °C

Procedure

Copper iodide (18 mg, 0.05 eq, 0.09 mmol), 1,10-phenanthroline (67 mg, 0.2 eq, 0.37 mmol) and caesium carbonate (0.84 g, 1.4 eq, 2.6 mmol) were mixed in a RB flask, placed under vacuum and purged with N2 (g). 4-iodo-benzonitrile (0.5 g, 1.0 eq, 1.85 mmol), hydrazine carboxylic acid tert-butyl ester (0.3 g, 1.2 eq, 2.22 mmol) and DMF (25 ml) were added to the mixture which was then heated to 80° C. with stirring under an inert atmosphere for 16 hours. The reaction mixture was allowed to cool and the solvent was removed in vacuo. The resultant residue was absorbed onto silica and purified by column chromatography using heptane/ethyl acetate (7:3) as eluent to yield the title compound as a pale orange solid (0.23 g, 1.0 mmol, 45%). LCMS: [M+H]+=234, rt=1.94 min, 97% purity.

Workup

  1. custompurged with N2 (g)
  2. temperatureto cool
  3. customthe solvent was removed in vacuo
  4. customThe resultant residue was absorbed onto silica
  5. custompurified by column chromatography

Sources & evidence

ORD record
ord-f9b04c8b2db244ebbe6aefc2242c4bde
Source dataset
uspto-grants-2011_12
Patent number
US08071607B2

Reaction notes

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