Allyltrimethylsilane → HCID 58237930, compound

HRID 1192919Notes

Reaction equation

HRID 1192919 reaction equation
[Cl:1][CH2:2][CH2:3][C:4](O)([C:11]1[CH:16]=[CH:15][CH:14]=[CH:13][CH:12]=1)[CH2:5][C:6]([O:8][CH2:9][CH3:10])=[O:7].[CH2:18]([Si](C)(C)C)[CH:19]=[CH2:20]>C(Cl)Cl.Cl[Ti](Cl)(Cl)Cl>[Cl:1][CH2:2][CH2:3][C:4]([C:11]1[CH:16]=[CH:15][CH:14]=[CH:13][CH:12]=1)([CH2:20][CH:19]=[CH2:18])[CH2:5][C:6]([O:8][CH2:9][CH3:10])=[O:7]

Participants

5

Reactant 2

HCID 69808AllyltrimethylsilaneHCID 58237933HCID 58237933, compound

Product 1

HCID 58237930HCID 58237930, compoundYield 45.7%

Reagents, catalysts & solvents 2

HCID 24193Titanium TetrachlorideCatalystHCID 6344DichloromethaneSolvent2×

Conditions

Temperature
-78 °C

Procedure

To a solution of ethyl 5-chloro-3-hydroxy-3-phenylpentanoate (1.0 g, 3.9 mmol) in anhydrous CH2Cl2 (20 mL) cooled to −78° C. under nitrogen was added allyltrimethylsilane (4.5 g, 39 mmol) followed by a solution of TiCl4 in CH2Cl2 (16 mL, 1 mol/L) dropwise. The solution was stirred at −78° C. for 30 min, and then was heated to reflux overnight. The reaction was quenched with aqueous Na2CO3 solution. The organic phase was separated and concentrated to give the crude product, which was purified by column chromatography to afford the ethyl 3-(2-chloroethyl)-3-phenylhex-5-enoate (0.5 g, 45%). 1H NMR (CDCl3): δ=1.08 (t, 3H), 2.24 (m, 2H), 2.54 (m, 2H), 2.68 (d, 2H), 3.19 (m, 1H), 3.26 (m, 1H), 3.96 (q, 2H), 5.01 (m, 2H), 5.51 (m, 1H), 7.14 (m, 1H), 7.19 (m, 2H), 7.29 (m, 2H).

Workup

  1. temperaturewas heated
  2. temperatureto reflux overnight
  3. customThe reaction was quenched with aqueous Na2CO3 solution
  4. customThe organic phase was separated
  5. concentrationconcentrated
  6. customto give the crude product, which
  7. customwas purified by column chromatography

Sources & evidence

ORD record
ord-11ccadad413b4867b8d217248abf0750
Source dataset
uspto-grants-2014_03
Patent number
US08680281B2

Reaction notes

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