Acetic acid, phosphono-, 1-(1,1-dimethylethyl) ester, diammonium salt → HCID 67313493, compound

HRID 1011647Notes

Reaction equation

HRID 1011647 reaction equation
P([CH2:5][C:6]([O:8][C:9]([CH3:12])([CH3:11])[CH3:10])=[O:7])(O)(O)=O.C([Li])CCC.[CH2:18]([O:20][C:21]([C:23]1[S:27][C:26]2[CH:28]=[C:29]([CH:32]=O)[CH:30]=[CH:31][C:25]=2[CH:24]=1)=[O:22])[CH3:19]>C1COCC1>[CH2:18]([O:20][C:21]([C:23]1[S:27][C:26]2[CH:28]=[C:29]([CH:32]=[CH:5][C:6]([O:8][C:9]([CH3:12])([CH3:11])[CH3:10])=[O:7])[CH:30]=[CH:31][C:25]=2[CH:24]=1)=[O:22])[CH3:19]

Participants

5

Reactant 3

HCID 431492Acetic acid, phosphono-, 1-(1,1-dimethylethyl) ester, diammonium saltHCID 57443969Ethyl 6-formylbenzo[b]thiophene-2-carboxylateHCID 178418339Butyllithium

Product 1

HCID 67313493HCID 67313493, compoundYield 71%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent

Procedure

To a stirred solution of tert-butyl phosphonoacetate (1.7 g, 7.27 mmol) in THF (20 mL) was slowly added n-butyllithium (1.6 M, 5 mL) with cooling to −78 degrees Celsius. After stirring for 30 minutes at −78 degrees Celsius, this solution was added into a solution of 6-formyl-benzo[b]thiophene-2-carboxylic acid ethyl ester (1.83 g, 7.27 mmol). The resulting solution was stirred at −78 degrees Celsius for 30 minutes before being allowed to warm to room temperature. The solution was subsequently cooled back to −78 degrees Celsius and quenched with sat. aq NH4Cl. The mixture was extracted with ethyl acetate, and the combined organic extracts were dried over anhydrous sodium sulfate. After being filtrated and concentrated, the residue was purified by flash column chromatography to give 1.7 g (71%) of 6-(2-tert-butoxycarbonyl-vinyl)-benzo[b]thiophene-2-carboxylic acid ethyl ester. MS: calc'd 333 (MH+), exp 333 (MH+). 1H NMR (d6-DMSO, 400 MHz), 8.38 (s, 1H), 8.18 (s, 1H), 8.02 (d, 1H, J=8.4 Hz), 7.82 (d, 1H, J=8.4 Hz), 7.66 (d, 1H, J=16.0 Hz), 6.66 (d, 1H, J=16.0 Hz), 4.36 (q, 2H, J=7.2 Hz), 1.49 (s, 9H), 1.34 (t, 3H, J=7.2 Hz).

Workup

  1. temperaturewith cooling to −78 degrees Celsius
  2. stirringThe resulting solution was stirred at −78 degrees Celsius for 30 minutes
  3. temperatureThe solution was subsequently cooled back to −78 degrees Celsius
  4. customquenched with sat. aq NH4Cl
  5. extractionThe mixture was extracted with ethyl acetate
  6. dry with materialthe combined organic extracts were dried over anhydrous sodium sulfate
  7. filtrationAfter being filtrated
  8. concentrationconcentrated
  9. customthe residue was purified by flash column chromatography

Sources & evidence

ORD record
ord-a5975a060a4648df9f6d7125da400db6
Source dataset
uspto-grants-2011_07
Patent number
US07977372B2

Reaction notes

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