Ammonium Chloride → HCID 178498378, compound

HRID 1846152Notes

Reaction equation

HRID 1846152 reaction equation
[CH3:1][O:2][C:3](=[O:12])[C:4](=[C:9]([NH2:11])[CH3:10])[C:5](OC)=[O:6].C[C:14]1(C)[CH2:18][CH2:17][CH2:16][N:15]1[CH3:19].CC(C)([O-])C.[Na+].[Cl-].[NH4+]>C1(C)C=CC=CC=1.C(O)(C)(C)C>[CH3:1][O:2][C:3]([C:4]1[C:5]([OH:6])=[C:18]2[CH2:17][CH2:16][N:15]([CH3:19])[C:14]2=[N:11][C:9]=1[CH3:10])=[O:12]

Participants

7

Reactant 4

HCID 25517Ammonium ChlorideHCID 264792HCID 264792, compoundHCID 12518841HCID 12518841, compoundHCID 23676156Sodium t-butoxide

Product 1

HCID 178498378HCID 178498378, compound

Reagents, catalysts & solvents 2

HCID 1140TolueneSolventHCID 6386tert-ButanolSolvent

Conditions

Temperature
90 °C

Procedure

A mixture of 100 mg of 2-(1-Amino-ethylidene)-malonic acid dimethyl ester (57.7 μmol) and 168 mg of 2,2-dimethyl-1-methylpyrrolidine (115.4 μmol) in 2 mL of toluene was heated at reflux for 3 h then 160 mg of sodium tert butoxide (2.9 eq) and 1 mL of tert butanol was added. The resulting reaction mixture was heated at 90° C. and stirred for 16 h then cooled to room temperature. To this solution was added 5 mL of aqueous saturated ammonium chloride and was extracted with three portions of 10 mL of ethyl acetate. The combined organic layer was washed with brine and dried (MgSO4). After the solvent was removed under diminished pressure, the residue was purified by flash chromatography on a silica gel column (15×2 cm). Elution with 1:20 to 1:10 EtOAc-hexanes gave product 28 as white solid: yield 115 mg, (90%); Silica gel TLC Rf 0.46 (1:4 EtOAc-Hexane); 1H NMR (CDCl3, ppm): δ 2.62 (s, 3H), 2.93 (t, J=8.4 Hz, 2H), 2.98 (s, 3H), 3.55 (t, J=9.0 Hz, 2H), 3.90 (s, 3H), 11.79 (s, 1H). 13C NMR (CDCl3, ppm): δ 22.48, 27.82, 31.90, 51.98, 52.35, 101.09, 102.20, 162.20, 163.75, 165.64, 172.38; HRMS (ESI+) calculated for C11H14N2O3 223.1077. found 223.1082.

Workup

  1. temperaturewas heated
  2. temperatureat reflux for 3 h
  3. customThe resulting reaction mixture
  4. temperaturethen cooled to room temperature
  5. extractionwas extracted with three portions of 10 mL of ethyl acetate
  6. washThe combined organic layer was washed with brine
  7. dry with materialdried (MgSO4)
  8. customAfter the solvent was removed under diminished pressure
  9. customthe residue was purified by flash chromatography on a silica gel column (15×2 cm)
  10. washElution with 1:20 to 1:10 EtOAc-hexanes

Sources & evidence

ORD record
ord-02ee21dbe99846f8a65a29bbe44e76d9
Source dataset
uspto-grants-2015_02
Patent number
US08952025B2

Reaction notes

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