p-Bromochlorobenzene → HCID 12501054, compound

HRID 2413294Notes

Reaction equation

HRID 2413294 reaction equation
Br[C:2]1[CH:7]=[CH:6][C:5](Cl)=CC=1.[Cl:9][CH2:10][SiH2:11][CH:12](Cl)Cl.[CH2:15]([Li])[CH2:16][CH2:17][CH3:18]>O1CCCC1.C(=O)=O.CC(C)=O.CCCCCC.[Cl-].[Li+]>[Cl:9][CH2:10][Si:11]([CH2:2][CH2:7][CH2:6][CH3:5])([CH2:15][CH2:16][CH2:17][CH3:18])[CH3:12]

Participants

8

Reactant 3

HCID 7806p-BromochlorobenzeneHCID 57370169HCID 57370169, compoundHCID 178418339Butyllithium

Product 1

HCID 12501054HCID 12501054, compoundYield 12%

Reagents, catalysts & solvents 4

HCID 8028TetrahydrofuranSolventHCID 8058HexaneSolventHCID 433294Lithium ChlorideSolventHCID 18522661Acetone cardiceSolvent

Procedure

A solution of 14.4 g (0.075 mol) of 4-bromochlorobenzene and 9.5 ml (12.3 g, 0.075 mol) of chloromethyl(dichloro)methylsilane in 150 ml of tetrahydrofuran was stirred under nitrogen and cooled in dry ice-acetone while 94 ml (0.15 mol) of 1.6 molar n-butyllithium in hexane was added dropwise at a rate that held the mixture between -65° and -55°. The resulting slurry was allowed to warm to room temperature, giving a solution that was diluted with hexanes until no more lithium chloride precipitated. Filtration, evaporation of the filtrate, dissolution of the residue in hexanes, refiltration, and evaporation left 19.8 g of a pale orange liquid. Distillation gave first 1.8 g (12%) of chloromethyl(dibutyl)methylsilane, bp 45° (0.05 mm), followed by 6.8 g (35%) of the title compound as a colorless liquid: bp 90° (0.05 mm); nD21 1.5246; ir (neat) 2925, 1580, 1380, 1260, 1090, 1015, 820, 740 cm -1 ; nmr (CDCl3) 0.4 (3H, s), 0.6-1.5 (9H, m), 2.9 (2H, s), 7.0-7.4 (4H, q).

Workup

  1. additionwas added dropwise at a rate that
  2. customthe mixture between -65° and -55°
  3. customgiving a solution that
  4. customprecipitated
  5. filtrationFiltration, evaporation of the filtrate, dissolution of the residue in hexanes
  6. customrefiltration, and evaporation
  7. waitleft 19.8 g of a pale orange liquid
  8. distillationDistillation

Sources & evidence

ORD record
ord-b5f88e006c914109b6f9f118a507955e
Source dataset
uspto-grants-1985_01
Patent number
US04496551

Reaction notes

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