Diethyl Ether → N,N-Diphenyl-4-(prop-2-en-1-yl)aniline

HRID 2354311Notes

Reaction equation

HRID 2354311 reaction equation
CCOCC.Br[C:7]1[CH:12]=[CH:11][C:10]([N:13]([C:20]2[CH:25]=[CH:24][CH:23]=[CH:22][CH:21]=2)[C:14]2[CH:19]=[CH:18][CH:17]=[CH:16][CH:15]=2)=[CH:9][CH:8]=1.[CH2:26]([Li])[CH2:27][CH2:28]C.C(Br)C=C>CCCCCC.C(Cl)Cl>[CH2:28]([C:7]1[CH:12]=[CH:11][C:10]([N:13]([C:20]2[CH:25]=[CH:24][CH:23]=[CH:22][CH:21]=2)[C:14]2[CH:19]=[CH:18][CH:17]=[CH:16][CH:15]=2)=[CH:9][CH:8]=1)[CH:27]=[CH2:26]

Participants

6

Reactant 4

HCID 3283Diethyl EtherHCID 7841Allyl bromideHCID 6428384-BromotriphenylamineHCID 178418339Butyllithium

Product 1

HCID 16218147N,N-Diphenyl-4-(prop-2-en-1-yl)anilineYield 35%

Reagents, catalysts & solvents 1

HCID 21226440Methylenechloride HexaneSolvent

Conditions

Temperature
-50 °C

Procedure

To a stirring, anhydrous ether solution (20 mL) of 16 (0.58 g, 1.8 mmol) under inert atmosphere, n-butyl lithium (1.6 M in hexanes, 1.2 mL, 1.92 mmol) was added slowly at −50° C., and the mixture was stirred at −50° C. for 15 min, and gradually warmed up to 25° C. After 3 h, copper iodide(I) (0.51 g, 2.7 mmol) was added followed by dropwise addition of allyl bromide (0.32 g, 2.7 mmol). The solution was stirred for 12 h, followed by quenching with 100 mL saturated aqueous NH4+Cl− solution and extraction with ether (3×100 mL). The combined ether extracts were washed with water (2×100 mL) and brine (2×100 mL), and dried over anhydrous Na2SO4. Following filtration, solvent was removed in vacuum to yield an oil. Chromatography on silica gel with hexane:methylene chloride (4:1) afforded 0.18 g of 17 as a colorless-oil. Yield, 35%. 1H NMR (CDCl3): δ 3.40 (d, J=7.5 Hz, 2H), 5.11-5.32 (m, 2H), 5.98-6.07 (m, 1H), 6.98-7.15 (m, 8H), 7.22-7.37 (m, 6H). Anal. Calcd for C21H19N: C, 88.36; H, 6.72; N, 4.91. Found, C, 88.34; H, 6.10; N, 4.24.

Workup

  1. temperaturegradually warmed up to 25° C
  2. waitAfter 3 h
  3. stirringThe solution was stirred for 12 h
  4. customby quenching with 100 mL saturated aqueous NH4+Cl− solution and extraction with ether (3×100 mL)
  5. washThe combined ether extracts were washed with water (2×100 mL) and brine (2×100 mL)
  6. dry with materialdried over anhydrous Na2SO4
  7. filtrationfiltration, solvent
  8. customwas removed in vacuum
  9. customto yield an oil

Sources & evidence

ORD record
ord-f6973ab84a794cca845c7e160abfadc2
Source dataset
uspto-grants-2010_07
Patent number
US07750175B2

Reaction notes

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