Malonic Acid → (2E)-3-(4-Bromo-2-thienyl)-2-propenoic acid

HRID 920926Notes

Reaction equation

HRID 920926 reaction equation
N1CCCCC1.[Br:7][C:8]1[CH:9]=[C:10]([CH:13]=O)[S:11][CH:12]=1.C(O)(=O)[CH2:16][C:17]([OH:19])=[O:18]>C(Cl)Cl.C(OC(C)C)(C)C>[Br:7][C:8]1[CH:9]=[C:10](/[CH:13]=[CH:16]/[C:17]([OH:19])=[O:18])[S:11][CH:12]=1

Participants

6

Reactant 3

HCID 867Malonic AcidHCID 8082PiperidineHCID 877924-Bromothiophene-2-carbaldehyde

Product 1

HCID 5708462(2E)-3-(4-Bromo-2-thienyl)-2-propenoic acidYield 50.4%

Reagents, catalysts & solvents 2

HCID 6344DichloromethaneSolventHCID 7914Diisopropyl EtherSolvent

Conditions

Temperature
100 °C

Procedure

Piperidine (1.036 mL, 10.47 mmol) was added to a mixture of 4-bromothiophene-2-carbaldehyde (20 g, 105 mmol) and malonic acid (13.07 g, 126 mmol) at 80° C. under nitrogen atmosphere. The reaction mixture was stirred for 2 h at 100° C. The reaction mixture was cooled to room temperature and extracted with EA/water. The organic phase was washed with 2N NaOH. The aqueous phase was acidified and a precipitate was formed. The solid was stirred in a mixture of DCM and diisopropyl ether (1:1). The solid was sucked off and dried under reduced pressure to give a bright beige solid (12.3 g, 50.4%).

Workup

  1. temperatureThe reaction mixture was cooled to room temperature
  2. extractionextracted with EA/water
  3. washThe organic phase was washed with 2N NaOH
  4. customa precipitate was formed
  5. customdried under reduced pressure

Sources & evidence

ORD record
ord-0a3b9d6ddc9b42979106d409f3a8abf7
Source dataset
uspto-grants-2016_03
Patent number
US09273068B2

Reaction notes

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