Dodecane → 1-(3,5-Dimethylphenyl)-2-(diphenylmethylene)hydrazine

HRID 984558Notes

Reaction equation

HRID 984558 reaction equation
[C:1](=[N:14][NH2:15])([C:8]1[CH:13]=[CH:12][CH:11]=[CH:10][CH:9]=1)[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1.CC(C)([O-])C.[Na+].[C@@H]1(N)CCCC[C@H]1N.CCCCCCCCCCCC.I[C:43]1[CH:44]=[C:45]([CH3:50])[CH:46]=[C:47]([CH3:49])[CH:48]=1>[Cu]I.O1CCOCC1>[CH3:50][C:45]1[CH:44]=[C:43]([NH:15][N:14]=[C:1]([C:8]2[CH:9]=[CH:10][CH:11]=[CH:12][CH:13]=2)[C:2]2[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=2)[CH:48]=[C:47]([CH3:49])[CH:46]=1

Participants

8

Reactant 5

HCID 8182DodecaneHCID 438061,2-Diaminocyclohexane, trans-HCID 79304DiphenylmethylidenehydrazineHCID 1409241-Iodo-3,5-dimethylbenzeneHCID 23676156Sodium t-butoxide

Product 1

HCID 207408531-(3,5-Dimethylphenyl)-2-(diphenylmethylene)hydrazineYield 80.3%

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 (2.0 mg, 0.0105 mmol, 1.0 mol %), benzophenone hydrazone (245 mg, 1.25 mmol), sodium tert-butoxide (145 mg, 1.51 mmol), evacuated and backfilled with argon. trans-1,2-Cyclohexanediamine (13 μL, 0.108 mmol, 11 mol %), dodecane (235 μL), 5-iodo-m-xylene (150 μL, 1.04 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 dark brown suspension was cooled to room temperature and filtered through a 0.5×1 cm pad of silica gel eluting with 10 mL of hexane-ethyl acetate 5:1. The filtrate was concentrated and the residue was purified by flash chromatography on silica gel (2×20 cm; hexane-ethyl acetate 40:1; 15 mL fractions). Fractions 10-12 provided 251 mg (80% yield) of the product as a bright yellow solid. The 1H NMR spectrum was in accord with that reported by Buchwald et al. Wagaw, S.; Yang, B. H.; Buchwald, S. L. J. Am. Chem. Soc. 1999, 44, 10251.

Workup

  1. customevacuated
  2. customThe Schlenk tube was sealed
  3. temperatureThe resulting dark brown suspension was cooled to room temperature
  4. filtrationfiltered through a 0.5×1 cm pad of silica gel eluting with 10 mL of hexane-ethyl acetate 5:1
  5. concentrationThe filtrate was concentrated
  6. customthe residue was purified by flash chromatography on silica gel (2×20 cm; hexane-ethyl acetate 40:1; 15 mL fractions)

Sources & evidence

ORD record
ord-06ace967446c4df680e771077e03ba8e
Source dataset
uspto-grants-2005_03
Patent number
US06867298B2

Reaction notes

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