methyl 7-(2,2-dimethylpropionylamino)-10H-9-oxa-1,2-diazaphenanthrene-8-carboxylate → methyl 7-amino-10H-9-oxa-1,2-diazaphenanthrene-8-carboxylate

HRID 2200337Notes

Reaction equation

HRID 2200337 reaction equation
CC(C)(C)C([NH:5][C:6]1[C:19]([C:20]([O:22][CH3:23])=[O:21])=[C:18]2[C:9]([C:10]3[CH:11]=[CH:12][N:13]=[N:14][C:15]=3[CH2:16][O:17]2)=[CH:8][CH:7]=1)=O>CO.S(=O)(=O)(O)O>[NH2:5][C:6]1[C:19]([C:20]([O:22][CH3:23])=[O:21])=[C:18]2[C:9]([C:10]3[CH:11]=[CH:12][N:13]=[N:14][C:15]=3[CH2:16][O:17]2)=[CH:8][CH:7]=1

Participants

4

Reactant 1

HCID 89705397methyl 7-(2,2-dimethylpropionylamino)-10H-9-oxa-1,2-diazaphenanthrene-8-carboxylate2×

Product 1

HCID 89705423methyl 7-amino-10H-9-oxa-1,2-diazaphenanthrene-8-carboxylateYield 49.9%

Reagents, catalysts & solvents 2

HCID 887MethanolSolventHCID 1118Sulfuric AcidSolvent

Procedure

A solution of methyl 7-(2,2-dimethylpropionylamino)-10H-9-oxa-1,2-diazaphenanthrene-8-carboxylate (Intermediate 7, 0.702 g) in methanol (50 mL) and sulphuric acid (4 mL) was stirred and heated at reflux for 16 hours. After cooling, the solution was evaporated in vacuo and the residue was partitioned between ethyl acetate and water. The mixture was basified with 5M sodium hydroxide, then stirred and heated until all the solid had dissolved. The layers were separated and the aqueous layer was extracted six times with ethyl acetate. The combined extracts were dried (Na2SO4), filtered and the filtrate was evaporated in vacuo. The residue was triturated with DCM and the solid was collected by filtration to give methyl 7-amino-10H-9-oxa-1,2-diazaphenanthrene-8-carboxylate (0.264 g) as a yellow solid.

Workup

  1. temperatureheated
  2. temperatureat reflux for 16 hours
  3. temperatureAfter cooling
  4. customthe solution was evaporated in vacuo
  5. customthe residue was partitioned between ethyl acetate and water
  6. temperatureheated until all the solid
  7. dissolutionhad dissolved
  8. customThe layers were separated
  9. extractionthe aqueous layer was extracted six times with ethyl acetate
  10. dry with materialThe combined extracts were dried (Na2SO4)
  11. filtrationfiltered
  12. customthe filtrate was evaporated in vacuo
  13. customThe residue was triturated with DCM
  14. filtrationthe solid was collected by filtration

Sources & evidence

ORD record
ord-15687075b13f4ce3a64a954afdc28b6d
Source dataset
uspto-grants-2016_06
Patent number
US09359369B2

Reaction notes

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