Water → (2,6-Diisopropylphenyl)[1-(2'-methoxybiphenyl-3-yl)ethylidene]amine

HRID 45478Notes

Reaction equation

HRID 45478 reaction equation
Br[C:2]1[CH:3]=[C:4]([C:8](=[N:10][C:11]2[C:16]([CH:17]([CH3:19])[CH3:18])=[CH:15][CH:14]=[CH:13][C:12]=2[CH:20]([CH3:22])[CH3:21])[CH3:9])[CH:5]=[CH:6][CH:7]=1.[Li]CCCC.Br[C:29]1[CH:34]=[CH:33][CH:32]=[CH:31][C:30]=1[O:35][CH3:36].O>C1COCC1.[Cl-].[Cl-].[Zn+2].CC(C)([P](C(C)(C)C)([Pd][P](C(C)(C)C)(C(C)(C)C)C(C)(C)C)C(C)(C)C)C>[CH:20]([C:12]1[CH:13]=[CH:14][CH:15]=[C:16]([CH:17]([CH3:19])[CH3:18])[C:11]=1[N:10]=[C:8]([C:4]1[CH:3]=[C:2]([C:29]2[CH:34]=[CH:33][CH:32]=[CH:31][C:30]=2[O:35][CH3:36])[CH:7]=[CH:6][CH:5]=1)[CH3:9])([CH3:22])[CH3:21]

Participants

8

Reactant 4

HCID 962WaterHCID 113582-BromoanisoleHCID 58238584N-[1-(3-Bromophenyl)ethylidene]-2,6-diisopropylanilineHCID 178418339Butyllithium

Product 1

HCID 58238573(2,6-Diisopropylphenyl)[1-(2'-methoxybiphenyl-3-yl)ethylidene]amineYield 79%

Reagents, catalysts & solvents 3

HCID 3007855ZincchlorideCatalystHCID 178418851HCID 178418851, compoundCatalystHCID 8028TetrahydrofuranSolvent2×

Conditions

Temperature
-70 °C

Procedure

To a solution of 2.78 g (7.75 mmol) of 13 in 30 mL of THF, 3.10 mL (7.75 mmol) of 2.5 M nBuLi in hexanes was added at −100° C. The reaction mixture was stirred for 1 hr at −70° C., then cooled to −100° C., and 8.35 mL (8.35 mmol) of 1M ZnCl2 in THF was added. The resulting mixture was slowly warmed to room temperature, stirred for 12 hr at this temperature, and then 1.45 g (7.75 mmol) of 2-bromoanisole and 85 mg (0.15 mmol) of Pd(PtBu3)2 were added. The resulting mixture was refluxed for 3 hr, and then 5 mL of water was added. This mixture was passed through short layer of silica gel 60 (40-63 um) which was then additionally washed with 30 mL of dichloromethane. The combined organic filtrate was evaporated to dryness, and the product was isolated by flash chromatography on silica gel 60(40-63 um, eluent: from hexanes to hexanes-diethyl ether=20:1, vol.). This procedure gave 2.36 g (79%) of the title product.

Workup

  1. temperaturecooled to −100° C.
  2. temperatureThe resulting mixture was slowly warmed to room temperature
  3. stirringstirred for 12 hr at this temperature
  4. temperatureThe resulting mixture was refluxed for 3 hr
  5. washwas then additionally washed with 30 mL of dichloromethane
  6. customThe combined organic filtrate was evaporated to dryness
  7. customthe product was isolated by flash chromatography on silica gel 60(40-63 um, eluent: from hexanes to hexanes-diethyl ether=20:1, vol.)

Sources & evidence

ORD record
ord-48ce2117ca204564bb083007c42e29cc
Source dataset
uspto-grants-2013_09
Patent number
US08541522B2

Reaction notes

Loading…