Hydrochloric Acid → HCID 15475386, compound

HRID 566882Notes

Reaction equation

HRID 566882 reaction equation
[N+:1]([C:4]1[CH:5]=[C:6]2[C:11](=[C:12]([CH3:18])[C:13]=1[O:14][CH2:15][CH:16]=[CH2:17])[O:10][C:9](=[O:19])[CH:8]=[C:7]2[CH3:20])([O-])=O.[Sn].[Sn](Cl)Cl.Cl>C(O)C>[NH2:1][C:4]1[CH:5]=[C:6]2[C:11](=[C:12]([CH3:18])[C:13]=1[O:14][CH2:15][CH:16]=[CH2:17])[O:10][C:9](=[O:19])[CH:8]=[C:7]2[CH3:20]

Participants

6

Reactant 4

HCID 313Hydrochloric AcidHCID 24479Stannous ChlorideHCID 5352426Tin atom2×HCID 15475385HCID 15475385, compound

Product 1

HCID 15475386HCID 15475386, compoundYield 82%

Reagents, catalysts & solvents 1

HCID 702EthanolSolvent

Procedure

To a round bottom flask was added finely ground 6-nitro-4,8-dimethyl-7-allyloxycoumarin of Example 2 (3.00 g, 10.9 mmoles), tin (3.24 g, 27.3 mmoles), tin (II) chloride (3.04 g, 16.0 mmoles) and 9 ml concentrated hydrochloric acid in 200 ml ethanol. The mixture was stirred overnight during which all tin dissolved. Most of the ethanol was removed in vacuo. As the solution was allowed to cool, a gel formed which was filtered to recover a small amount of pearlized crystals (the hydrochloride salt). Water was added and a drop of iso-amyl alcohol was added to prevent frothing as solid sodium bicarbonate was added with stirring until the solution was basic. Ether was added to the filtrate arid a precipitate formed which was filtered and rinsed with ether to remove tin (II) chloride. The solids were dried and extracted with hot ethanol on the funnel of a filtration flask. Evaporation of the ethanol gave a crude product that was recrystallized from ethanol to provide 2.20 grams (82% yield) bright mustard yellow crystals: mp 145.6-147.4° C.; 1H-nmr (dimethyl sulfoxide-d6):δ 2.28 (s, 3H), 2.49 (s, 3H), 4.54 (d, 2H), 5.28 (d, 1H), 5.48 (d, 1H), 5.98-6.32 (m, 1H), 6.39 (s, 1H), 7.58 (s, 1H); 13C-nmr (dimethyl sulfoxide-d6):δ 9.4, 18.1, 74.6, 113.6, 115.1, 116.0, 118.7, 120.1, 125.5, 133.5, 147.0, 151.5, 152.5, 159.6.

Workup

  1. dissolutiondissolved
  2. customMost of the ethanol was removed in vacuo
  3. temperatureto cool
  4. customa gel formed which
  5. filtrationwas filtered
  6. customto recover a small amount of pearlized crystals (the hydrochloride salt)
  7. additionWater was added
  8. additiona drop of iso-amyl alcohol was added
  9. additionwas added
  10. additionEther was added to the filtrate
  11. customformed which
  12. filtrationwas filtered
  13. washrinsed with ether
  14. customto remove tin (II) chloride
  15. customThe solids were dried
  16. extractionextracted with hot ethanol on the funnel of a filtration flask
  17. customEvaporation of the ethanol

Sources & evidence

ORD record
ord-81faaf298bb047c0932049dce0fd0b34
Source dataset
uspto-grants-2001_01
Patent number
US06177424B1

Reaction notes

Loading…