Sodium Bicarbonate → tert-butyl 2-formyl-4H,5H,6H,7H-thieno[3,2-c]pyridine-5-carboxylate

HRID 2388687Notes

Reaction equation

HRID 2388687 reaction equation
[OH:1][CH2:2][C:3]1[S:11][C:10]2[CH2:9][CH2:8][N:7]([C:12]([O:14][C:15]([CH3:18])([CH3:17])[CH3:16])=[O:13])[CH2:6][C:5]=2[CH:4]=1.C(=O)([O-])O.[Na+].CC1(C)N([O])C(C)(C)CCC1.[O-]Cl.[Na+]>ClCCl.O.C(OCC)(=O)C.CCCCCC>[CH:2]([C:3]1[S:11][C:10]2[CH2:9][CH2:8][N:7]([C:12]([O:14][C:15]([CH3:18])([CH3:17])[CH3:16])=[O:13])[CH2:6][C:5]=2[CH:4]=1)=[O:1]

Participants

8

Reactant 4

HCID 516892Sodium BicarbonateHCID 2724126TempoHCID 118456061,1-Dimethylethyl 6,7-dihydro-2-(hydroxymethyl)thieno[3,2-c]pyridine-5(4H)-carboxylateHCID 23665760Sodium Hypochlorite

Product 1

HCID 11845085tert-butyl 2-formyl-4H,5H,6H,7H-thieno[3,2-c]pyridine-5-carboxylate

Reagents, catalysts & solvents 3

HCID 962WaterSolvent2×HCID 6344DichloromethaneSolvent2×HCID 21226206Ethyl acetate hexaneSolvent

Conditions

Temperature
0 °C

Procedure

To a solution of tert-butyl 6,7-dihydro-2-(hydroxymethyl)thieno[3,2-c]pyridine-5(4H)-carboxylate (1.6 g, 0.006 mol) in dichloromethane (18 ml), sodium hydrogen carbonate (1.06 g) dissolved in water was added and the resulting mixture was cooled to 0° C. Then a catalytic amount of TEMPO followed by NaOCl (18 ml, 10×) were added at 0° C. and the reaction mixture was stirred for 1-2 h at room temperature. Progress of the reaction was monitored by TLC (30% ethyl acetate/hexane). Upon completion of the reaction, the reaction mixture were diluted with water (20 ml) and dichloromethane (20 ml). Then the dichloromethane layer was separated and the aqueous layer was extracted with dichloromethane. The combined extract was dried over sodium sulfate, concentrated under reduced pressure and the crude so obtained was purified by column chromatography (silica, 7% ethyl acetate/hexane) to yield the titled compound as a pale yellow solid.

Workup

  1. additionwas added
  2. additionwere added at 0° C.
  3. customUpon completion of the reaction
  4. customThen the dichloromethane layer was separated
  5. extractionthe aqueous layer was extracted with dichloromethane
  6. extractionThe combined extract
  7. dry with materialwas dried over sodium sulfate
  8. concentrationconcentrated under reduced pressure
  9. customthe crude so obtained
  10. customwas purified by column chromatography (silica, 7% ethyl acetate/hexane)

Sources & evidence

ORD record
ord-c2e8789803044782be10b80d7a5f1f79
Source dataset
uspto-grants-2012_09
Patent number
US08268814B2

Reaction notes

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