1-Bromo-2,4,6-triisopropylbenzene → HCID 178506714, compound

HRID 1797232Notes

Reaction equation

HRID 1797232 reaction equation
C1([Mg]Br)CCCCC1.C(C1C=CC=C(C(C)C)C=1N=CC(C)C)(C)C.ClC(P)Cl.[Li:30]CCCC.Br[C:36]1[C:41]([CH:42]([CH3:44])[CH3:43])=[CH:40][C:39]([CH:45]([CH3:47])[CH3:46])=[CH:38][C:37]=1[CH:48]([CH3:50])[CH3:49]>C(OCC)C.C1COCC1>[CH:48]([C:37]1[CH:38]=[C:39]([CH:45]([CH3:47])[CH3:46])[CH:40]=[C:41]([CH:42]([CH3:44])[CH3:43])[C:36]=1[Li:30])([CH3:50])[CH3:49]

Participants

8

Reactant 5

HCID 1408461-Bromo-2,4,6-triisopropylbenzeneHCID 14511949Dichloromethyl-phosphaneHCID 71400953(1E)-N-[2,6-Di(propan-2-yl)phenyl]-2-methylpropan-1-imineHCID 178418339ButyllithiumHCID 178419651HCID 178419651, compound

Product 1

HCID 178506714HCID 178506714, compound

Reagents, catalysts & solvents 2

HCID 3283Diethyl EtherSolventHCID 8028TetrahydrofuranSolvent3×

Procedure

Cyclohexylmagnesium bromide (1.05 mL of a 2.0 M solution in ethyl ether, 2.1 mmol, Aldrich) was added to a solution of isobutyraldehyde 2,6-diisopropylphenylimine (0.462 g, 2.0 mmol) in THF (5 mL) at −78° C. The yellowish solution was warmed to RT, stirred for 1 h and then added to a solution of dichloromethylphosphine (0.19 mL, 2.1 mmol, Strem) in THF (5 mL) at −78° C. The solution was stirred for 10 min at −78° C., warmed to RT and stirred for 30 min. Assay by 31P-NMR (crude reaction mixture) showed the presence of a single major product (+110.4 ppm). The solution of 2,4,6-triisopropylphenyllithium was prepared by addition of BuLi (1.6 mL of a 1.6 M solution in hexanes, 2.6 mmol, Aldrich) to a solution of 1-bromo-2,4,6-triisopropylbenzene (0.63 mL, 2.5 mmol, Lancaster) in THF (8 mL) at −78° C. followed by stirring for 2 h. The solution of arylLi thus formed was added to the solution of chlorophosphine keeping both flasks at −78° C. The solution was stirred for 20 min at −78° C., warmed to RT and stirred for 30 min. Assay by 31P-NMR (crude reaction mixture) showed the presence of a single major product (−37.9 ppm). The solution was evaporated and CH2Cl2 (10 mL) was added to the residue. Filtration through a 2.2×2 cm plug of silica gel using CH2Cl2 (20 mL) and then ethyl ether (10 mL) as an eluent followed by evaporation of the solvent afforded crude product as a yellowish oil. To the crude ligand was added NiBr2(DME) (0.124 g, 0.40 mmol) and CH2Cl2 (10 mL). The red-brown solution was stirred for 1 h at RT, solution was evaporated and the residue washed with diethyl ether (3×20 mL) and hexanes (20 mL). A brown, insoluble solid (0.310 g, 107% based on Ni) was obtained.

Workup

  1. stirringThe solution was stirred for 10 min at −78° C.
  2. temperaturewarmed to RT
  3. stirringstirred for 30 min
  4. customAssay by 31P-NMR (crude reaction mixture)
  5. stirringby stirring for 2 h

Sources & evidence

ORD record
ord-bda09fa39c694ca48e746c9d47574b16
Source dataset
uspto-grants-2006_04
Patent number
US07034093B2

Reaction notes

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