Hydrochloric Acid → Ethyl 2-cyano-3-(2,3-dichlorophenyl)propanoate

HRID 510433Notes

Reaction equation

Br[CH2:2][C:3]1[CH:8]=[CH:7][CH:6]=[C:5]([Cl:9])[C:4]=1[Cl:10].[C:11]([CH2:13][C:14]([O:16][CH2:17][CH3:18])=[O:15])#[N:12].C([O-])([O-])=O.[K+].[K+].Cl>C1COCC1.O>[C:11]([CH:13]([CH2:2][C:3]1[CH:8]=[CH:7][CH:6]=[C:5]([Cl:9])[C:4]=1[Cl:10])[C:14]([O:16][CH2:17][CH3:18])=[O:15])#[N:12]

Participants

Conditions

Temperature: 60 °C

Procedure

A mixture of 1-(bromomethyl)-2,3-dichlorobenzene (82 g, 0.34 mol), ethyl 2-cyanoacetate (82 g, 0.34 mol) and K2CO3 (187.7 g, 1.36 mol) in THF (1.5 L), was stirred at 60° C. for 16 h. The reaction mixture was cooled and adjusted pH to 2-3 with 4N aq. HCl. The mixture was diluted with water (1 L) and extracted with ethyl acetate (400 mL*3). The combined organic layers were washed with brine, dried over Na2SO4, filtered and the filtrate was concentrated. The resulting residue was purified by silica gel chromatography eluted with PE:EA=15:1 to provide the titled compound (45 g, 48%), as a white solid; 1H NMR (300 MHz, CDCl3) δ ppm 1.32 (t, J=7.2 Hz, 3H), 3.23 (dd, J=9.6, 13.8 Hz, 1H), 3.56 (dd, J=6.0, 13.8 Hz, 1H), 3.91 (dd, J=6.0, 9.6 Hz, 1H), 4.28 (q, J=7.2 Hz, 2H), 7.21 (t, J=7.8 Hz, 1H), 7.28 (dd, J=1.8, 7.5 Hz, 1H), 7.45 (dd, J=1.8, 7.8 Hz, 1H).

Workup

temperatureThe reaction mixture was cooled
extractionextracted with ethyl acetate (400 mL*3)
washThe combined organic layers were washed with brine
dry with materialdried over Na2SO4
filtrationfiltered
concentrationthe filtrate was concentrated
customThe resulting residue was purified by silica gel chromatography
washeluted with PE

Sources & evidence

ORD record: ord-9b700d9e3fcb498b80beacd8dfc4a3c3
Source dataset: uspto-grants-2015_08
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US09096605B2

Reaction notes

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