Hydrochloric Acid → Diethyl 2-aminononane-1,9-dioate

HRID 1153820Notes

Reaction equation

HRID 1153820 reaction equation
C([NH:4][CH:5]([C:11]([O:13][CH2:14][CH3:15])=[O:12])[C:6](OCC)=O)(=O)C.BrC[CH2:18][CH2:19][CH2:20][CH2:21][CH2:22][C:23]([O:25][CH2:26][CH3:27])=[O:24].Cl>[O-]CC>[NH2:4][CH:5]([CH2:6][CH2:18][CH2:19][CH2:20][CH2:21][CH2:22][C:23]([O:25][CH2:26][CH3:27])=[O:24])[C:11]([O:13][CH2:14][CH3:15])=[O:12]

Participants

5

Reactant 3

HCID 313Hydrochloric AcidHCID 14041Acetamidomalonic acid diethyl esterHCID 122490Ethyl 7-bromoheptanoate

Product 1

HCID 6455180Diethyl 2-aminononane-1,9-dioateYield 55%

Reagents, catalysts & solvents 1

HCID 1194401-Hydroxyethyl radicalSolvent

Procedure

Diethyl acetamidomalonate (16.7 g) and ethyl 7-bromoheptanoate (16.6 g) were dissolved in ethanolic ethoxide (prepared from sodium (1.51 g) and absolute ethanol (30 ml)) and the mixture was refluxed for 27 hours. The cooled solution was poured into ice-water, the product was extracted into ether, and the dried extract was evapoated to give crude diethyl acetamido-(6-ethoxycarbonylhexyl) malonate as a pale yellow oil, δ2.2(3H, singlet, --COCH3), 4.17(6H, multiplet, 3×--OCH2 --CH3). This amide was refluxed with concentrated hydrochloric acid (111 ml) for 51/2 hours, the cooled solution was washed with ether, and the aqueous layer was decolorised with activated charcoal and evaporated to dryness in vacuo. The residual colourless glass was dissolved in the minimum quantity of absolute ethanol and added dropwise to a stirred, cooled (-10° C.) mixture of absolute ethanol (125 ml) and thionyl chloride (15.7 g). The resulting solution was set aside at room temperature for 1 hour, refluxed for 11/2 hours, cooled, and poured into ice-water, adjusting the pH to 9 with aqueous sodium hydroxide. The mixture was extracted with ether, and the dried extract was concentrated and distilled, giving diethyl 2-aminononanedioate (55% yield) as a colourless oil, b.p. 114°-115°/0.02-03 mm.

Workup

  1. temperaturethe mixture was refluxed for 27 hours
  2. extractionthe product was extracted into ether
  3. extractionthe dried extract
  4. customto give crude diethyl acetamido-(6-ethoxycarbonylhexyl) malonate as a pale yellow oil, δ2.2(3H
  5. washthe cooled solution was washed with ether
  6. customevaporated to dryness in vacuo
  7. dissolutionThe residual colourless glass was dissolved in the minimum quantity of absolute ethanol
  8. additionadded dropwise to a stirred
  9. temperaturecooled
  10. addition(-10° C.) mixture of absolute ethanol (125 ml) and thionyl chloride (15.7 g)
  11. temperaturerefluxed for 11/2 hours
  12. temperaturecooled
  13. additionpoured into ice-water
  14. extractionThe mixture was extracted with ether
  15. extractionthe dried extract
  16. concentrationwas concentrated
  17. distillationdistilled

Sources & evidence

ORD record
ord-f46396c85f4e443187e7c8be36a17f6a
Source dataset
uspto-grants-1984_12
Patent number
US04486443

Reaction notes

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