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(E)-Methyl 2-(2-chloro-6-nitrophenyl)-3-hydroxybut-2-enoate → methyl 4-chloro-2-methyl-1H-indole-3-carboxylate

HRID 453853
Notes
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Reaction equation

HRID 453853 reaction equation
[Cl:1][C:2]1[CH:7]=[CH:6][CH:5]=[C:4]([N+:8]([O-])=O)[C:3]=1/[C:11](=[C:16](\O)/[CH3:17])/[C:12]([O:14][CH3:15])=[O:13]>C(O)(=O)C.O.C(Cl)Cl.CO>[Cl:1][C:2]1[CH:7]=[CH:6][CH:5]=[C:4]2[C:3]=1[C:11]([C:12]([O:14][CH3:15])=[O:13])=[C:16]([CH3:17])[NH:8]2
ParticipantsConditionsProcedureWorkupSources & evidenceReaction notes

Participants

5

Reactant 1

HCID 86761957(E)-Methyl 2-(2-chloro-6-nitrophenyl)-3-hydroxybut-2-enoate

Product 1

HCID 59473719methyl 4-chloro-2-methyl-1H-indole-3-carboxylateYield 91%

Reagents, catalysts & solvents 3

HCID 176Acetic AcidSolventHCID 962WaterSolventHCID 21226129Dichloromethane methanolSolvent

Conditions

Temperature
90 °C

Procedure

(E)-Methyl 2-(2-chloro-6-nitrophenyl)-3-hydroxybut-2-enoate (14.76 mmol, 1.0 equiv.) was dissolved in acetic acid (96 ml), and a solution of TiCl3 (20%-w/w in 2 N HCl, 71.6 ml) was added, with stirring. The mixture was then heated for 5-10 min at 90° C. The reaction mixture was cooled with an ice bath and diluted with water and DCM/methanol (9:1, 100 ml). The phases were separated and the organic phase was washed with water and sat. NaCl solution. Drying over Na2SO4 was then carried out, followed by concentration under reduced pressure. The product was crystallized from hexane. Yield: 91%

Workup

  1. temperatureThe reaction mixture was cooled with an ice bath
  2. customThe phases were separated
  3. washthe organic phase was washed with water and sat. NaCl solution
  4. dry with materialDrying over Na2SO4
  5. concentrationfollowed by concentration under reduced pressure
  6. customThe product was crystallized from hexane

Sources & evidence

ORD record
ord-b221d243f2524303bc50d79c785b5aca
Source dataset
uspto-grants-2013_07
DOI
10.6084/m9.figshare.5104873.v1
Patent number
US08492559B2

Reaction notes

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On this pageParticipantsConditionsProcedureWorkupSources & evidenceReaction notes