Potassium Carbonate → Ethyl 7,7-dimethyl-4,5,6,7-tetrahydrothieno[3,2-c]pyridine-2-carboxylate hydrochloride

HRID 468670Notes

Reaction equation

HRID 468670 reaction equation
C([N:8]1[CH2:13][C:12]([CH3:15])([CH3:14])[C:11]2[S:16][C:17]([C:19]([O:21][CH2:22][CH3:23])=[O:20])=[CH:18][C:10]=2[CH2:9]1)C1C=CC=CC=1.C([O-])([O-])=O.[K+].[K+].[Cl:30]C(OC(Cl)C)=O>C(Cl)Cl.CCO>[ClH:30].[CH3:14][C:12]1([CH3:15])[CH2:13][NH:8][CH2:9][C:10]2[CH:18]=[C:17]([C:19]([O:21][CH2:22][CH3:23])=[O:20])[S:16][C:11]1=2

Participants

6

Reactant 3

HCID 11430Potassium CarbonateHCID 5213051-Chloroethyl chloroformateHCID 66931877Ethyl 5-benzyl-7,7-dimethyl-4,5,6,7-tetrahydrothieno[3,2-c]pyridine-2-carboxylate

Product 1

HCID 66932164Ethyl 7,7-dimethyl-4,5,6,7-tetrahydrothieno[3,2-c]pyridine-2-carboxylate hydrochlorideYield 79.1%

Reagents, catalysts & solvents 2

HCID 702EthanolSolventHCID 6344DichloromethaneSolvent2×

Procedure

A solution of ethyl 5-benzyl-7,7-dimethyl-4,5,6,7-tetrahydrothieno[3,2-c]pyridine-2-carboxylate (14.6 g, 0.044 mol) in anhydrous DCM was cooled to 0° C. whereupon K2CO3 (6.1 g, 0.044 mmol) and α-chloroethyl chloroformate (6.97 g, 0.049 mol) were added. Upon complete addition, the reaction was heated at reflux overnight. The reaction was cooled to room temperature and diluted with DCM, then washed with saturated aqueous NaHCO3 and brine respectively. The organic layer was dried over anhydrous Na2SO4 and evaporated to afford an oily residue which was taken up in EtOH and refluxed for 2 hours. The solvent was evaporated to dryness and the residue was washed with ethyl acetate to afford the desired product (9.6 g, 79%). 1H NMR (400 MHz, DMSO) δ 9.82 (s, 2H), 7.64 (s, 1H), 4.28 (q, J=7.2 Hz, 2H), 4.15 (s, 2H), 3.26 (s, 2H), 1.42 (s, 6H), 1.28 (t, J=7.2 Hz, 3H).

Workup

  1. additionwere added
  2. additionUpon complete addition
  3. temperaturethe reaction was heated
  4. temperatureat reflux overnight
  5. washwashed with saturated aqueous NaHCO3 and brine respectively
  6. dry with materialThe organic layer was dried over anhydrous Na2SO4
  7. customevaporated
  8. customto afford an oily residue which
  9. temperaturerefluxed for 2 hours
  10. customThe solvent was evaporated to dryness
  11. washthe residue was washed with ethyl acetate

Sources & evidence

ORD record
ord-ec6adcc987144b67816e9d8452b3af4f
Source dataset
uspto-grants-2014_01
Patent number
US08624040B2

Reaction notes

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