Sodium hydride → (E)-3-(2'-tert-butoxycarbonyl-ethenyl)-4,6-dichloro-1H-indole-2-carboxylic acid isopropyl ester

HRID 581060

Reaction equation

HRID 581060 reaction equation
[H-].[Na+].[Br-].[C:4]([O:8][C:9]([CH2:11][P+](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1)=[O:10])([CH3:7])([CH3:6])[CH3:5].[H][H].[CH2:33]([O:35][C:36]([C:38]1[NH:39][C:40]2[C:45]([C:46]=1[CH:47]=O)=[C:44]([Cl:49])[CH:43]=[C:42]([Cl:50])[CH:41]=2)=[O:37])[CH3:34].[C:51](OC(C=P(C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1)=O)(C)(C)C>C(O)(C)C.O>[CH:33]([O:35][C:36]([C:38]1[NH:39][C:40]2[C:45]([C:46]=1/[CH:47]=[CH:11]/[C:9]([O:8][C:4]([CH3:7])([CH3:6])[CH3:5])=[O:10])=[C:44]([Cl:49])[CH:43]=[C:42]([Cl:50])[CH:41]=2)=[O:37])([CH3:51])[CH3:34]

Participants

8

Reactant 5

HCID 24758Sodium hydrideHCID 256127tert-Butyl (triphenylphosphoranylidene) acetate2×HCID 2733853(tert-Butoxycarbonylmethyl)triphenylphosphonium BromideHCID 2794948ethyl 4,6-dichloro-3-formyl-1H-indole-2-carboxylateHCID 178418361HCID 178418361, compound

Product 1

HCID 67558194(E)-3-(2'-tert-butoxycarbonyl-ethenyl)-4,6-dichloro-1H-indole-2-carboxylic acid isopropyl esterYield 207.9%

Reagents, catalysts & solvents 2

HCID 962WaterSolventHCID 3776IsopropanolSolvent

Procedure

Sodium hydride (1 g; 95%) was added in two 0.5 g portions to a solution of (tert-butoxycarbonylmethyl)-triphenylphosphonium bromide (8.4 g) in isopropanol (100 ml). After the evolution of hydrogen ceased ethyl-3-formyl-4,6-dichloro-indole-2-carboxylate (5 g) was added and the reaction mixture was refluxed for 2 h. (tert-Butoxycarbonylmethylene)-triphenylphosphorane (1 g) was added and the reflux was continued for 8 h. An other amount of (tert-butoxycarbonylmethylene)-triphenylphosphorane (3.5 g) was added and the reaction mixture was refluxed for additional 3 h. After cooling to r.t. the solution was poured into water and extracted with ethyl acetate. The organic extracts were dried and evaporated under reduced pressure. The residue was purified by flash chromatography using cyclohexane/ethyl acetate 3:1 as eluant to give the title compound (2.2 g) as a white solid.

Workup

  1. additionwas added
  2. additionwas added
  3. temperaturethe reaction mixture was refluxed for additional 3 h
  4. extractionextracted with ethyl acetate
  5. customThe organic extracts were dried
  6. customevaporated under reduced pressure
  7. customThe residue was purified by flash chromatography

Sources & evidence

ORD record
ord-69d1d42198544a6ca32a38130fded35b
Source dataset
uspto-grants-1999_07
Patent number
US05919811

Linked notes

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