Hydrochloric Acid → Ethyl(2-chloro-2-nitrophenyl)(cyano)acetate

HRID 2167918Notes

Reaction equation

HRID 2167918 reaction equation
[CH2:1]([O:3][C:4](=[O:8])[CH2:5][C:6]#[N:7])[CH3:2].CC(C)([O-])C.[K+].Cl[C:16]1[C:21](Cl)=[CH:20][CH:19]=[CH:18][C:17]=1[N+:23]([O-:25])=[O:24].[ClH:26]>C1COCC1.C(OCC)(=O)C.CCCCCC.O>[CH2:1]([O:3][C:4](=[O:8])[CH:5]([CH:16]1[CH:21]=[CH:20][CH:19]=[CH:18][C:17]1([Cl:26])[N+:23]([O-:25])=[O:24])[C:6]#[N:7])[CH3:2]

Participants

9

Reactant 4

HCID 313Hydrochloric AcidHCID 7764Ethyl cyanoacetateHCID 185552,3-DichloronitrobenzeneHCID 23665647Potassium tert-butoxide

Product 1

HCID 131728954Ethyl(2-chloro-2-nitrophenyl)(cyano)acetate

Reagents, catalysts & solvents 4

HCID 962WaterSolventHCID 8028TetrahydrofuranSolventHCID 8058HexaneSolventHCID 8857Ethyl AcetateSolvent

Procedure

To an ice cold solution of ethylcyanoacetate (10.9 mL, 102.4 mmol) in anhydrous THF (170 mL) under nitrogen, was added potassium tert-butoxide (12.7 g, 107.5 mmol). The formed white suspension was stirred for 15 min, then treated with 2,3-dichloronitrobenzene (9.83 g, 51.2 mmol). The suspension was heated at reflux for 48 hours. The resulting reddish brown solution was poured in to water, and the aqueous-mixture was acidified to pH 2 with cone. HCl. The mixture was extracted with ether (3×150 mL) and then the combined organic phase was dried (using Na2SO4) and concentrated to give a dark oil. Flash chromatography using 10:1 hexane:ethyl acetate in a column packed with silica gel, 10 times the weight of the dark oil, provided a viscous yellow liquid 4, which was used without further purification for the next step. TLC Rf 0.23 (hexane-ethyl acetate 3:1). 1H NMR δ 1.33-1.38 (t, 3H, CH3); 4.29-4.35 (q, 2H, CH2); 7.59-8.14 (m, 3H, phenyl).

Workup

  1. temperatureThe suspension was heated
  2. temperatureat reflux for 48 hours
  3. extractionThe mixture was extracted with ether (3×150 mL)
  4. dry with materialthe combined organic phase was dried (using Na2SO4)
  5. concentrationconcentrated
  6. customto give a dark oil

Sources & evidence

ORD record
ord-df6d1c90da13435589bcbcbb6a70a836
Source dataset
uspto-grants-2015_06
Patent number
US09045489B2

Reaction notes

Loading…