Sulfuric Acid → Ethyl 1-methyl-2-(2-morpholinoethyl)pyrrole-3-carboxylate

HRID 515877Notes

Reaction equation

HRID 515877 reaction equation
C(O[CH:4](OCC)[CH2:5][C:6]1[N:7]([CH3:16])[CH:8]=[CH:9][C:10]=1[C:11]([O:13][CH2:14][CH3:15])=[O:12])C.S(=O)(=O)(O)O.[NH:25]1[CH2:30][CH2:29][O:28][CH2:27][CH2:26]1.ClC(Cl)C.O1CCOCC1.C(O[BH-](OC(=O)C)OC(=O)C)(=O)C.[Na+]>O1CCCC1.C(OCC)(=O)C.O.ClCCl.C([O-])(O)=O.[Na+]>[CH3:16][N:7]1[CH:8]=[CH:9][C:10]([C:11]([O:13][CH2:14][CH3:15])=[O:12])=[C:6]1[CH2:5][CH2:4][N:25]1[CH2:30][CH2:29][O:28][CH2:27][CH2:26]1

Participants

12

Reactant 6

HCID 1118Sulfuric AcidHCID 63651,1-DichloroethaneHCID 8083MorpholineHCID 312751,4-DioxaneHCID 5049666Sodium triacetoxyborohydrideHCID 117833716Ethyl 2-(2,2-diethoxyethyl)-1-methyl-pyrrole-3-carboxylate

Product 1

HCID 117833886Ethyl 1-methyl-2-(2-morpholinoethyl)pyrrole-3-carboxylate

Reagents, catalysts & solvents 5

HCID 962WaterSolventHCID 6344DichloromethaneSolventHCID 8028TetrahydrofuranSolventHCID 8857Ethyl AcetateSolventHCID 516892Sodium BicarbonateSolvent

Procedure

To a solution of 3.8 g of the compound obtained in Step C (14.05 mmol) in 28 mL of tetrahydrofuran there are added 58 mL of aqueous 10% sulphuric acid solution. The reaction mixture is stirred at ambient temperature for 2 hours and then diluted with a mixture of ethyl acetate and water. After separation, the organic phase is washed with brine, dried over MgSO4 and concentrated to dryness. To a solution of the residue thereby obtained in 70 mL of dichloroethane there are added a solution of 13.5 mL of morpholine (14.5 mmol) in a mixture composed of 30 mL of dichloroethane and 3.6 mL of 4N aqueous HCL solution in dioxane (14.5 mmol), and then 7.4 g of sodium triacetoxyborohydride (NaBH(OAc)3) (35.13 mmol). The reaction mixture is stirred at ambient temperature for 3 hours and then diluted with a mixture of dichloromethane and saturated aqueous NaHCO3 solution. After separation of the phases and extraction of the aqueous phase with dichloromethane, the organic phases are dried over MgSO4 and concentrated to dryness. The crude product thereby obtained is purified by chromatography over silica gel using dichloromethane and methanol as eluants. The title product is isolated in the form of an oil.

Workup

  1. customAfter separation
  2. washthe organic phase is washed with brine
  3. dry with materialdried over MgSO4
  4. concentrationconcentrated to dryness
  5. customTo a solution of the residue thereby obtained in 70 mL of dichloroethane
  6. stirringThe reaction mixture is stirred at ambient temperature for 3 hours
  7. customAfter separation of the phases and extraction of the aqueous phase with dichloromethane
  8. dry with materialthe organic phases are dried over MgSO4
  9. concentrationconcentrated to dryness
  10. customThe crude product thereby obtained
  11. customis purified by chromatography over silica gel

Sources & evidence

ORD record
ord-4555c36905fe408c90e29a1774672b99
Source dataset
uspto-grants-2015_08
Patent number
US09108983B2

Reaction notes

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