Triethylamine → HCID 76759590, compound

HRID 444704Notes

Reaction equation

HRID 444704 reaction equation
[Cl:1][C:2]1[C:6]([CH3:7])=[CH:5][S:4][C:3]=1[C:8](=O)[CH:9]([C:15]#[N:16])[C:10]([O:12][CH2:13][CH3:14])=[O:11].O=P(Cl)(Cl)[Cl:20].CCN(CC)CC>C(Cl)(Cl)Cl>[Cl:20][C:8]([C:3]1[S:4][CH:5]=[C:6]([CH3:7])[C:2]=1[Cl:1])=[C:9]([C:15]#[N:16])[C:10]([O:12][CH2:13][CH3:14])=[O:11]

Participants

5

Reactant 3

HCID 8471TriethylamineHCID 24813Phosphorus oxychlorideHCID 67115664HCID 67115664, compound

Product 1

HCID 76759590HCID 76759590, compoundYield 66.9%

Reagents, catalysts & solvents 1

HCID 6212ChloroformSolvent

Conditions

Temperature
5 °C

Procedure

To a solution of ethyl 3-(3-chloro-4-methyl-2-thienyl)-2-cyano-3-oxopropanoate (15.40 g, 56.67 mmol, 1 eq.) in 200 ml of CHCl3 was added POCl3 (86.9 g, 566 mmol, 10 eq.). Et3N (14.33 g, 141.6 mmol, 2.5 eq.) was added dropwise with stirring at 5° C., and the mixture was refluxed for 4 h. The mixture was evaporated. After evaporation, the mixture was diluted with DCM (CH2Cl2) and with ice water and was extracted with DCM (CH2Cl2) and washed with brine. The organic layers were combined and dried over MgSO4 before concentration under reduced pressure. The residue was subjected to column chromatography on silica gel to give ethyl 3-chloro-3-(3-chloro-4-methyl-2-thienyl)-2-cyanoacrylate (11 g, 66% yield) as a mixture of 2 isomers

Workup

  1. temperaturethe mixture was refluxed for 4 h
  2. customThe mixture was evaporated
  3. customAfter evaporation
  4. additionthe mixture was diluted with DCM (CH2Cl2) and with ice water
  5. extractionwas extracted with DCM (CH2Cl2)
  6. washwashed with brine
  7. dry with materialdried over MgSO4 before concentration under reduced pressure

Sources & evidence

ORD record
ord-4847b81d5f864422aa202a73eb9b298b
Source dataset
uspto-grants-2013_07
Patent number
US08476197B2

Reaction notes

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