Chlorotrimethylsilane → HCID 10013095, compound

HRID 1700962Notes

Reaction equation

HRID 1700962 reaction equation
BrCCBr.Cl[Si](C)(C)C.[CH2:10]([C:12]([CH2:14][CH3:15])=[O:13])[CH3:11].Br[C:17]([CH3:24])([CH3:23])[C:18]([O:20][CH2:21][CH3:22])=[O:19]>C1COCC1.B(OC)(OC)OC.[Zn]>[CH3:23][C:17]([CH3:24])([C:12]([CH2:14][CH3:15])([OH:13])[CH2:10][CH3:11])[C:18]([O:20][CH2:21][CH3:22])=[O:19]

Participants

8

Reactant 4

HCID 6397ChlorotrimethylsilaneHCID 7288Ethyl ketoneHCID 78391,2-DibromoethaneHCID 11745Propanoic acid, 2-bromo-2-methyl-, ethyl ester

Product 1

HCID 10013095HCID 10013095, compoundYield 47%

Reagents, catalysts & solvents 3

HCID 23994ZincCatalyst2×HCID 8028TetrahydrofuranSolventHCID 8470Trimethyl borateSolvent

Procedure

A suspension of zinc dust (39.2 g, 0.6 mol) in 150 ml of THF and 150 ml of B(OCH3)3 is activated with 1,2 dibromoethane (3.0 ml) and chlorotrimethylsilane (3.0 ml). Diethyl ketone (95.7 ml, 0.9 mol) is added to the activated zinc suspension. Ethyl 2-bromo-2-methylpropanoate (Fuka, Buchs, Schweiz) is added dropwise within 90 min to the mixture. The mixture is stirred at r.t. for 20 h. The reaction is quenched by addition of concentrated aqueous ammonia solution (150 ml) at 0° C. Glycerine (150 ml) and diethyl ether (150 ml) is added and the organic layer is separated. The aqueous layer is extracted twice with diethyl ether. The combined organic layers are dried over magnesium sulfate and concentrated in vacuo. Purfication of the residue by vacuum distillation affords ethyl 2,2-dimethyl-3-ethyl-3-hydroxypentanoate 22 (56.65 g, 47%) as a colourless liquid (b.p. 108-110° C./10 mbar). 13C-NMR (100 MHz, CDCl3): δ=179.2; 76.2; 60.9; 50.3; 28.2; 21.6; 14.1; 8.9

Workup

  1. customThe reaction is quenched by addition of concentrated aqueous ammonia solution (150 ml) at 0° C
  2. additionGlycerine (150 ml) and diethyl ether (150 ml) is added
  3. customthe organic layer is separated
  4. extractionThe aqueous layer is extracted twice with diethyl ether
  5. dry with materialThe combined organic layers are dried over magnesium sulfate
  6. concentrationconcentrated in vacuo
  7. distillationPurfication of the residue by vacuum distillation

Sources & evidence

ORD record
ord-b652726571b3425e97c9c755355117bd
Source dataset
uspto-grants-2002_02
Patent number
US06350878B1

Reaction notes

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