4-Nitrobenzaldehyde → HCID 89534604, compound

HRID 2176040Notes

Reaction equation

HRID 2176040 reaction equation
[Br-].[CH2:2]([O:9][C:10]([C:12]1[S:16][C:15]([CH2:17][P+](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)=[CH:14][CH:13]=1)=[O:11])C1C=CC=CC=1.[N+:37]([C:40]1[CH:47]=[CH:46][C:43]([CH:44]=O)=[CH:42][CH:41]=1)([O-])=O.C1COCC1.C[O-].[Na+].CO>O>[NH2:37][C:40]1[CH:47]=[CH:46][C:43]([CH2:44][CH2:17][C:15]2[S:16][C:12]([C:10]([O:9][CH3:2])=[O:11])=[CH:13][CH:14]=2)=[CH:42][CH:41]=1

Participants

6

Reactant 4

HCID 5414-NitrobenzaldehydeHCID 8028TetrahydrofuranHCID 23694274Sodium methanolate methanolHCID 90370141HCID 90370141, compound

Product 1

HCID 89534604HCID 89534604, compoundYield 58.3%

Reagents, catalysts & solvents 1

HCID 962WaterSolvent

Procedure

To a mixture of 2.88 g of ({5-[(benzyloxy)carbonyl]-2-thienyl}methyl)(triphenyl)phosphonium bromide, 823 mg of 4-nitrobenzaldehyde and 30 mL of THF was added dropwise 1.0 mL of a 5.0 M sodium methoxide/methanol solution, followed by stirring overnight at room temperature. Water was added to the reaction mixture, followed by extraction with ethyl acetate. The organic layer was washed sequentially with 1.0 M hydrochloric acid, a saturated aqueous sodium hydrogen carbonate solution, and saturated brine and then dried over anhydrous sodium sulfate, and the solvent was removed under reduced pressure. The residue was purified by silica gel column chromatography (hexane:ethyl acetate=4:6). 10 mL of methanol and 10 mL of THF were added to the obtained residue, and 98 mg of 10% palladium carbon was added thereto under an argon flow, followed by stirring overnight at room temperature in a hydrogen atmosphere. The reaction mixture was filtered using celite, and the solvent was removed under reduced pressure. The residue was purified by silica gel column chromatography (hexane:ethyl acetate=1:1), thereby obtaining 765 mg of methyl 5-[2-(4-aminophenyl)ethyl]thiophene-2-carboxylate.

Workup

  1. extractionfollowed by extraction with ethyl acetate
  2. washThe organic layer was washed sequentially with 1.0 M hydrochloric acid
  3. dry with materiala saturated aqueous sodium hydrogen carbonate solution, and saturated brine and then dried over anhydrous sodium sulfate
  4. customthe solvent was removed under reduced pressure
  5. customThe residue was purified by silica gel column chromatography (hexane:ethyl acetate=4:6)
  6. addition10 mL of methanol and 10 mL of THF were added to the obtained residue, and 98 mg of 10% palladium carbon
  7. additionwas added
  8. stirringby stirring overnight at room temperature in a hydrogen atmosphere
  9. filtrationThe reaction mixture was filtered
  10. customthe solvent was removed under reduced pressure
  11. customThe residue was purified by silica gel column chromatography (hexane:ethyl acetate=1:1)

Sources & evidence

ORD record
ord-2be884c14ad246239286503196b44a35
Source dataset
uspto-grants-2015_06
Patent number
US09062032B2

Reaction notes

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