Ethyl Acetate → Chloromethyl(2,4-dichlorophenyl)methyl(phenyl)silane

HRID 1980505

Reaction equation

HRID 1980505 reaction equation
[Cl:1][C:2]1[CH:7]=[C:6]([Cl:8])[CH:5]=[CH:4][C:3]=1Br.Cl[Si:11]([CH2:19][Cl:20])([CH3:18])[C:12]1[CH:17]=[CH:16][CH:15]=[CH:14][CH:13]=1.C([Li])CCC.C(OCC)(=O)C>O1CCCC1.CCCCCC>[Cl:20][CH2:19][Si:11]([C:3]1[CH:4]=[CH:5][C:6]([Cl:8])=[CH:7][C:2]=1[Cl:1])([CH3:18])[C:12]1[CH:17]=[CH:16][CH:15]=[CH:14][CH:13]=1

Participants

7

Reactant 4

HCID 8857Ethyl AcetateHCID 709471-Bromo-2,4-dichlorobenzeneHCID 12418873Chloro(chloromethyl)methyl(phenyl)silaneHCID 178418339Butyllithium

Product 1

HCID 13392380Chloromethyl(2,4-dichlorophenyl)methyl(phenyl)silaneYield 100.3%

Reagents, catalysts & solvents 2

HCID 8028TetrahydrofuranSolventHCID 8058HexaneSolvent

Procedure

A solution of 13.6 g (0.060 mol) of 2,4-dichlorobromobenzene and 12.3 g (0.060 mol) of chloro(chloromethyl)methyl(phenyl)silane (prepared as in Example 14) in 85 ml of dry tetrahydrofuran was chilled to -60° under nitrogen and stirred while 38 ml (0.060 mol) of 1.6 molar n-butyllithium in hexane was added dropwise at a rate that held the mixture below -55°. The resulting red solution was allowed to warm to room temperature, treated with 5 ml of ethyl acetate to quench any unreacted organolithium reagent, and poured into 170 ml of water. The organic layer was separated, the aqueous phase was washed with 50 ml of hexanes, and the combined organic phases were washed three times with water and once with brine, dried over magnesium sulfate, and evaporated to leave 19.0 g of bright yellow oil. Distillation gave 8.6 g (45%) of the title compound as a colorless liquid: b.p. 125°-130° (0.05 mm); nD21 1.5978; ir (neat) 3080, 3060, 2960, 2930, 1570, 1540, 1460, 1430, 1365, 1260, 1120, 1100, 1040, 820, 745, 735, 705 cm-1 ; nmr (CDCl3) 0.8 (3H, s), 3.4 (2H, s), 7.2-7.9 (8H, m).

Workup

  1. additionwas added dropwise at a rate that
  2. customthe mixture below -55°
  3. customto quench any unreacted organolithium reagent
  4. additionpoured into 170 ml of water
  5. customThe organic layer was separated
  6. washthe aqueous phase was washed with 50 ml of hexanes
  7. washthe combined organic phases were washed three times with water
  8. dry with materialonce with brine, dried over magnesium sulfate
  9. customevaporated

Sources & evidence

ORD record
ord-c9021bc7d5a34eb59db06ede24734291
Source dataset
uspto-grants-1985_04
Patent number
US04510136

Linked notes

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