Dimethylformamide → 3-Chloro-3-(2-chlorophenyl)prop-2-enenitrile
Reaction equation
O=P(Cl)(Cl)[Cl:3].Cl[CH2:7][C:8]([C:10]1[CH:15]=[CH:14][CH:13]=[CH:12][CH:11]=1)=O.[ClH:16].NO.C[N:20]([CH:22]=O)C>>[Cl:16][C:8]([C:10]1[CH:15]=[CH:14][CH:13]=[CH:12][C:11]=1[Cl:3])=[CH:7][C:22]#[N:20]Participants
Conditions
- Temperature
- 0 °C
Procedure
25 ml of DMF were cooled to 0° C. and POCl3 (4.95 g, 32.3 mmol, 2 eq.) added dropwise. The reaction was stirred 30 min at 0° C. and a solution of 2-chloro-acetophenone (2.5 g, 16.17 mmol, 1 eq.) in 15 ml of DMF was added. Once all added the reaction was warmed to 50° C. and stirred for 8 h. The mixture was cooled to 0° C. and hydroxylamine hydrochloride (4.49 g, 6.68 mmol, 4 eq.) was added by portions very carefully (exothermic). Once all added the reaction was stirred at r.t. for 2 h and quenched with H2O. The medium was basified until pH 2-3 was reached with 1N aq. NaOH and extracted with ethylacetate. The organic layer was washed with brine and dried over MgSO4. Removal of all volatiles under reduced pressure afforded 3-chloro-3-(2-chlorophenyl)acrylonitrile (2.01 g, 60% yield) as a mixture of isomers which was used without further purification.
Workup
- additionOnce all added the reaction
- temperaturewas warmed to 50° C.
- stirringstirred for 8 h
- temperatureThe mixture was cooled to 0° C.
- additionOnce all added the reaction
- stirringwas stirred at r.t. for 2 h
- customquenched with H2O
- extractionextracted with ethylacetate
- washThe organic layer was washed with brine
- dry with materialdried over MgSO4
- customRemoval of all volatiles under reduced pressure
Sources & evidence
- ORD record
- ord-7c3fda468da94444bf46cec8dc41e254
- Source dataset
- uspto-grants-2016_05
- Patent number
- US09351489B2
Reaction notes
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