Trimethylsilyl cyanide → 3-Chloro-2-cyano-2-(2-hydroxyethoxy)propyl acetate

HRID 28376

Reaction equation

HRID 28376 reaction equation
[C:1]([O:4][CH2:5][C:6]1([CH2:11][Cl:12])[O:10][CH2:9][CH2:8][O:7]1)(=[O:3])[CH3:2].C[Si]([C:17]#[N:18])(C)C>C(Cl)Cl.[I-].[Zn+2].[I-]>[C:1]([O:4][CH2:5][C:6]([C:17]#[N:18])([O:10][CH2:9][CH2:8][OH:7])[CH2:11][Cl:12])(=[O:3])[CH3:2]

Participants

5

Reactant 2

HCID 82115Trimethylsilyl cyanideHCID 57426437(2-(Chloromethyl)-1,3-dioxolan-2-yl)methyl acetate

Product 1

HCID 574264383-Chloro-2-cyano-2-(2-hydroxyethoxy)propyl acetate

Reagents, catalysts & solvents 2

HCID 9883512zinc(II)iodideCatalystHCID 6344DichloromethaneSolvent

Conditions

Temperature
40 °C

Procedure

A mixture of (2-(chloromethyl)-1,3-dioxolan-2-yl)methyl acetate (67.8 mmol), trimethylsilyl cyanide (20.29 g, 204 mmol, TCI America) and zinc iodide (3.65 g, 11.4 mmol) was heated (40° C., oil bath) for 6 hrs, then at ambient temperature for 16 hrs. The mixture was diluted with CH2Cl2 (100 mL) and stirred with silica gel (50 g) for several hours. The mixture was loaded onto a flash silica gel column (350 g silica) and eluted with CH2Cl2 then increasing amounts of Et2O to a final eluent of 30% Et2O in CH2Cl2. Product fractions were pooled and concentrated in-vacuo to give the title compound as an amber oil: 1H NMR (500 MHz, CDCl3) δ ppm 4.44 (1H, d, J=-11.90 Hz), 4.35 (1H, d, J=11.90 Hz), 3.83-3.88 (2H, m), 3.79-3.84 (4H, m), 2.13-2.16 (3H, m); LC/MS m/z 222.16 (M+H).

Workup

  1. washeluted with CH2Cl2
  2. concentrationconcentrated in-vacuo

Sources & evidence

ORD record
ord-99a368140e46451989d82193f02a1eef
Source dataset
uspto-grants-2008_09
Patent number
US07419969B2

Linked notes

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