1,10-Phenanthroline → 1-tert-Butoxycarbonyl-1-(4-phenylphenyl)hydrazine

HRID 984556

Reaction equation

HRID 984556 reaction equation
N1C2C(=CC=C3C=2N=CC=C3)C=CC=1.I[C:16]1[CH:21]=[CH:20][C:19]([C:22]2[CH:27]=[CH:26][CH:25]=[CH:24][CH:23]=2)=[CH:18][CH:17]=1.C([O-])([O-])=O.[Cs+].[Cs+].[C:34]([O:38][C:39]([CH3:42])([CH3:41])[CH3:40])(=[O:37])[NH:35][NH2:36]>[Cu]I.O1CCOCC1>[C:39]([O:38][C:34]([N:35]([C:16]1[CH:21]=[CH:20][C:19]([C:22]2[CH:27]=[CH:26][CH:25]=[CH:24][CH:23]=2)=[CH:18][CH:17]=1)[NH2:36])=[O:37])([CH3:42])([CH3:41])[CH3:40]

Participants

7

Reactant 4

HCID 13181,10-PhenanthrolineHCID 10796Cesium carbonateHCID 153224-IodobiphenylHCID 70091tert-Butyl carbazate

Product 1

HCID 120323381-tert-Butoxycarbonyl-1-(4-phenylphenyl)hydrazineYield 88%

Reagents, catalysts & solvents 2

HCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)CatalystHCID 312751,4-DioxaneSolvent

Conditions

Temperature
110 °C

Procedure

An oven-dried resealable Schlenk tube was charged with CuI (50 mg, 0.263 mmol, 5.1 mol %), 1,10-phenanthroline (100 mg, 0.555 mmol, 11 mol %), 4-iodobiphenyl (1.45 g, 5.18 mmol), Cs2CO3 (2.30 g, 7.06 mmol), evacuated and backfilled with argon. tert-Butyl carbazate (825 mg, 6.24 mmol) and dioxane (1.0 mL) were added under argon. The Schlenk tube was sealed and the reaction mixture was stirred magnetically at 110° C. for 23 h. The resulting suspension was cooled to room temperature and filtered through a 1×1 cm pad of silica gel eluting with 50 mL of ethyl acetate. The filtrate was concentrated and the residue was purified by flash chromatography on silica gel (2×20 cm; hexane-ethyl acetate 4:1; 20 mL fractions). Fractions 9-20 provided 1.29 g (88% yield) of the product as a light yellow solid. 1H NMR (400 MHz, CDCl3): δ 7.64-7.59 (m, 2H), 7.57 (s, 4H), 7.48-7.43 (m, 2H), 7.38-7.33 (m, 1H), 4.50 (s, 2H), 1.56 (s, 9H).

Workup

  1. customevacuated
  2. customThe Schlenk tube was sealed
  3. temperatureThe resulting suspension was cooled to room temperature
  4. filtrationfiltered through a 1×1 cm pad of silica gel eluting with 50 mL of ethyl acetate
  5. concentrationThe filtrate was concentrated
  6. customthe residue was purified by flash chromatography on silica gel (2×20 cm; hexane-ethyl acetate 4:1; 20 mL fractions)

Sources & evidence

ORD record
ord-99c5b2f12c964f51b0024fafc96a6fe2
Source dataset
uspto-grants-2005_03
Patent number
US06867298B2

Linked notes

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