Nitrogen → HCID 13558282, compound

HRID 637563Notes

Reaction equation

HRID 637563 reaction equation
N#N.[NH2:3][C:4]1[CH:9]=[C:8]([O:10][CH3:11])[C:7]([O:12][CH3:13])=[CH:6][C:5]=1[C:14](=[O:16])[CH3:15].Br[CH2:18][CH2:19][C:20]([O:22][CH2:23][CH3:24])=[O:21].C([O-])(O)=O.[Na+]>C(N(CC)CC)C>[C:20]([CH2:19][CH2:18][NH:3][C:4]1[CH:9]=[C:8]([O:10][CH3:11])[C:7]([O:12][CH3:13])=[CH:6][C:5]=1[C:14](=[O:16])[CH3:15])([O:22][CH2:23][CH3:24])=[O:21]

Participants

6

Reactant 4

HCID 947NitrogenHCID 68320Ethyl 3-bromopropionateHCID 516892Sodium BicarbonateHCID 602085Ethanone, 1-(2-amino-4,5-dimethoxyphenyl)-

Product 1

HCID 13558282HCID 13558282, compoundYield 35.2%

Reagents, catalysts & solvents 1

HCID 8471TriethylamineSolvent

Procedure

Triethylamine (3.88 g, 5.34 mL, 38.44 mM) was added at once under N2 to a stirred mixture of 2'-amino-4',5'-dimethoxyacetophenone (2.5 g, 12.8 mM) and ethyl 3-bromopropionate (17.43 mL, 96.2 mM) at room temperature. Immediately the reaction mixture solified. This was heated under N2 to 140°-150° C. (bath temp.) for a period of 4 hours during which the reaction mixture had partially liquified into a red-brown, viscous slurry. After cooling to room temperature it was treated with 5% NaHCO3 solution (50 mL) and then extracted with CH2Cl2 (3×60 mL). The combined organic extracts were washed with H2O, dried (Na2SO4) and evaporated in vacuo to remove CH2Cl2 (low vacuum) and excess 3-bromopropionate (under high vacuum at 50°-60° C.). The dark oily residue was chromatographed on a column of SilicAR CC-7 (300 g, 55.5×6 cm) packed in hexane. The sample was applied to the column in CH2Cl2 (50 mL) followed by elution with hexane and then with increasing proportions of ethyl acetate/hexane, collecting 1 L fractions. Fractions 10 and 11, afforded, upon evaporation to dryness 2'-(N-2-carbethoxyethylamino)-4',5'-dimethoxyacetophenone as a waxy crystalline solid (1.33 g, 35.2%), mp 73°-75° C.

Workup

  1. temperatureThis was heated under N2 to 140°-150° C. (bath temp.) for a period of 4 hours during which the reaction mixture
  2. extractionextracted with CH2Cl2 (3×60 mL)
  3. washThe combined organic extracts were washed with H2O
  4. dry with materialdried (Na2SO4)
  5. customevaporated in vacuo
  6. customto remove CH2Cl2 (low vacuum) and excess 3-bromopropionate (under high vacuum at 50°-60° C.)
  7. customThe dark oily residue was chromatographed on a column of SilicAR CC-7 (300 g, 55.5×6 cm)
  8. washfollowed by elution with hexane
  9. customwith increasing proportions of ethyl acetate/hexane, collecting 1 L fractions

Sources & evidence

ORD record
ord-0e6eb1c16bd74df5a7fa2e91623f1fe0
Source dataset
uspto-grants-1985_12
Patent number
US04556739

Reaction notes

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