Oxygen → 1-(Diphenylmethylene)-2-(4-(perfluoroethoxy)phenyl)hydrazine

HRID 514747Notes

Reaction equation

HRID 514747 reaction equation
Br[C:2]1[CH:7]=[CH:6][C:5]([O:8][C:9]([F:15])([F:14])[C:10]([F:13])([F:12])[F:11])=[CH:4][CH:3]=1.[C:16](=[N:29][NH2:30])([C:23]1[CH:28]=[CH:27][CH:26]=[CH:25][CH:24]=1)[C:17]1[CH:22]=[CH:21][CH:20]=[CH:19][CH:18]=1.C1(P(C2C=CC=CC=2)C2C=CC3C(=CC=CC=3)C=2C2C3C(=CC=CC=3)C=CC=2P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.O=O.CC(C)([O-])C.[Na+]>C1(C)C=CC=CC=1.C([O-])(=O)C.[Pd+2].C([O-])(=O)C>[C:17]1([C:16]([C:23]2[CH:28]=[CH:27][CH:26]=[CH:25][CH:24]=2)=[N:29][NH:30][C:2]2[CH:7]=[CH:6][C:5]([O:8][C:9]([F:15])([F:14])[C:10]([F:13])([F:12])[F:11])=[CH:4][CH:3]=2)[CH:18]=[CH:19][CH:20]=[CH:21][CH:22]=1

Participants

8

Reactant 5

HCID 977OxygenHCID 79304DiphenylmethylidenehydrazineHCID 918531-Bromo-4-(pentafluoroethoxy)benzeneHCID 634876Binap, (A+-)-2×HCID 23676156Sodium t-butoxide

Product 1

HCID 904026491-(Diphenylmethylene)-2-(4-(perfluoroethoxy)phenyl)hydrazineYield 88.2%

Reagents, catalysts & solvents 2

HCID 167845palladium(II) acetateCatalystHCID 1140TolueneSolvent

Conditions

Temperature
100 °C

Procedure

To a dry 2 L round bottomed flask fitted with an overhead mechanical stirrer, nitrogen inlet, thermometer, and reflux condenser were added 1 bromo-4-(perfluoroethoxy)-benzene (100 g, 344 mmol), benzophenone hydrazone (74.2 g, 378 mmol), and (2,2′-bis(diphenylphosphino)-1,1′-binaphthyl) (BINAP, 4.28 g, 6.87 mmol), and the mixture was suspended in anhydrous toluene (500 mL). To exclude oxygen, argon was sparged into the mixture for ten minutes (min) prior to and during the addition of palladium (II) acetate (Pd(OAc)2, 1.54 g, 6.87 mmol) and sodium tert-butoxide (NaOtBu, 49.5 g, 515 mmol), which was added in portions. The argon sparge was halted and the brown mixture was warmed to 100° C. and stirred for 3 h. The reaction was cooled to RT and poured into water (500 mL) and the aqueous mixture was extracted with EtOAc (3×200 mL). The combined organic extracts were washed with water, washed with saturated aqueous NaCI, dried over anhydrous MgSO4, filtered, and concentrated under reduced pressure on a rotary evaporator. The crude product was purified by flash column chromatography using 0-100% (v/v) EtOAc/hexanes as eluent to give the title compound as a red oil (123.3 g, 88%): 1H NMR (400 MHz, CDCI3) δ 5 7.63-7.56 (m, 4H), 7.55 (t, J=1.5 Hz, 1H), 7.51 (d, J=4.7 Hz, 1H), 7.36-7.26 (m, 5H), 7.13-7.04 (m, 4H); 19F NMR (376 MHz, CDCI3) 5-85.94, −87.84; 13C NMR (101 MHz, CDCI3) δ 145.23, 143.46, 141.24, 138.06, 132.53, 129.74, 129.41, 129.03, 128.30, 128.23, 126.57, 122.82, 113.45.

Workup

  1. customTo a dry 2 L round bottomed flask fitted with an overhead mechanical stirrer, nitrogen inlet
  2. temperaturethermometer, and reflux condenser
  3. customwas sparged into the mixture for ten minutes (min)
  4. additionwas added in portions
  5. customThe argon sparge
  6. temperatureThe reaction was cooled to RT
  7. additionpoured into water (500 mL)
  8. extractionthe aqueous mixture was extracted with EtOAc (3×200 mL)
  9. washThe combined organic extracts were washed with water
  10. washwashed with saturated aqueous NaCI
  11. dry with materialdried over anhydrous MgSO4
  12. filtrationfiltered
  13. concentrationconcentrated under reduced pressure on a rotary evaporator
  14. customThe crude product was purified by flash column chromatography

Sources & evidence

ORD record
ord-70763c92a2834eafa7d333caf66602e2
Source dataset
uspto-grants-2015_08
Patent number
US09108932B2

Reaction notes

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