Nitric Acid → HCID 13406828, compound

HRID 461819Notes

Reaction equation

HRID 461819 reaction equation
Cl.[CH2:2]([O:4][C:5]([CH:7]1[CH2:16][C:15]2[C:10](=[CH:11][CH:12]=[CH:13][CH:14]=2)[CH2:9][NH:8]1)=[O:6])[CH3:3].S(=O)(=O)(O)O.[N+:22]([O-])([OH:24])=[O:23]>[OH-].[Na+]>[CH2:2]([O:4][C:5]([C@@H:7]1[CH2:16][C:15]2[C:10](=[CH:11][C:12]([N+:22]([O-:24])=[O:23])=[CH:13][CH:14]=2)[CH2:9][NH:8]1)=[O:6])[CH3:3]

Participants

5

Reactant 3

HCID 944Nitric AcidHCID 1118Sulfuric AcidHCID 6603637ethyl 1,2,3,4-tetrahydroisoquinoline-3-carboxylate hydrochloride

Product 1

HCID 13406828HCID 13406828, compound

Reagents, catalysts & solvents 1

HCID 14798Sodium HydroxideSolvent

Conditions

Temperature
-30 °C

Procedure

3-Ethoxycarbonyl-1,2,3,4-tetrahydroisoquinoline hydrochloride (50 g.) is added in small portions, at -20° C., whilst stirring, to concentrated sulphuric acid (d = 1.83; 325 cc.). After 10 minutes, a limpid solution is obtained. The mixture is cooled to -30° C., and concentrated nitric acid (d = 1.49; 10 cc.) is then added over the course of 15 minutes. The reaction mixture is left, whilst being stirred, at -40° C., for 30 minutes and is then poured onto ice (1 kg.) and rendered alkaline by adding sodium hydroxide solution (d = 1.33; 1,000 cc.) whilst maintaining the temperature at between 15° and 20° C. The batch is extracted with methylene chloride (3 × 500 cc.). The organic extracts are combined, dried over potassium carbonate, filtered and evaporated under reduced pressure (30 mm.Hg) at 40° C. A pinkish solid (34 g.) is obtained, which is recrystallised from diisopropyl ether (300 cc.). (S)-3-Ethoxycarbonyl-7-nitro-1,2,3,4-tetrahydroisoquinoline is thus obtained in the form of pale pink crystals (17.5 g.) melting at 94°-95° C. are thus obtained.

Workup

  1. customa limpid solution is obtained
  2. waitThe reaction mixture is left
  3. additionis then poured onto ice (1 kg.)
  4. temperaturewhilst maintaining the temperature at between 15° and 20° C
  5. extractionThe batch is extracted with methylene chloride (3 × 500 cc.)
  6. dry with materialdried over potassium carbonate
  7. filtrationfiltered
  8. customevaporated under reduced pressure (30 mm.Hg) at 40° C
  9. customA pinkish solid (34 g.) is obtained
  10. customwhich is recrystallised from diisopropyl ether (300 cc.)

Sources & evidence

ORD record
ord-baf0346c2501429c92ff383940f3db6b
Source dataset
uspto-grants-1977_12
Patent number
US04064247

Reaction notes

Loading…