Hydrochloric Acid → Dimethyl(2-chloro-4-cyanophenyl)malonate

HRID 1866086Notes

Reaction equation

[H-].[Na+].[C:3]([O:11][CH2:12]C)(=[O:10])[CH2:4][C:5]([O:7][CH2:8]C)=[O:6].[Cl:14][C:15]1[CH:16]=[C:17]([CH:20]=[CH:21][C:22]=1Br)[C:18]#[N:19].Cl>O1CCOCC1.[Cu]Br.O>[CH3:8][O:7][C:5](=[O:6])[CH:4]([C:22]1[CH:21]=[CH:20][C:17]([C:18]#[N:19])=[CH:16][C:15]=1[Cl:14])[C:3]([O:11][CH3:12])=[O:10]

Participants

Conditions

Temperature: 50 °C

Procedure

7.6 g (0.191 mol) of 60% strength sodium hydride in paraffin oil were initially charged in 300 ml of dioxane. At from 55° C. to 60° C., 22.9 g (0.173 mol) of diethyl malonate were added dropwise, and the mixture was stirred at 50° C. for 1-2 hours. 9.9-g (0.069 mol) of copper(1) bromide were added. At 80° C., 15 g (0.069 mol) of 3-chloro-4-bromobenzonitrile were then added dropwise, and the mixture was subsequently stirred at 100° C. for 14 hours. The reaction mixture was then cooled and acidified by dropwise addition of concentrated hydrochloric acid at from 15° C. to 20° C. Water was added, the mixture was extracted with dichloromethane, the organic phase was dried over sodium sulphate and the solvent was removed. The residue was distilled at 1 mbar, giving 17.5 g of dimethyl(2-chloro-4-cyanophenyl)malonate.

Workup

stirringthe mixture was subsequently stirred at 100° C. for 14 hours
temperatureThe reaction mixture was then cooled
extractionthe mixture was extracted with dichloromethane
dry with materialthe organic phase was dried over sodium sulphate
customthe solvent was removed
distillationThe residue was distilled at 1 mbar

Sources & evidence

ORD record: ord-eb4ad380124f472fbedda80532c3e92a
Source dataset: uspto-grants-2009_12
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US07629294B2

Reaction notes

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