Sulfuric acid magnesium salt (1:1) → HCID 67404927, compound

HRID 2366558Notes

Reaction equation

HRID 2366558 reaction equation
[O-]S([O-])(=O)=O.[Mg+2].[O:7]1[C:11]2([CH2:16][CH2:15][C:14](=O)[CH2:13][CH2:12]2)[O:10][CH2:9][CH2:8]1.Cl.[F:19][C:20]1[CH:25]=[CH:24][C:23]([NH:26]N)=[CH:22][CH:21]=1>C(Cl)Cl.[Cl-].[Cl-].[Zn+2]>[F:19][C:20]1[CH:21]=[C:22]2[C:23](=[CH:24][CH:25]=1)[NH:26][C:14]1[CH2:15][CH2:16][C:11]3([O:10][CH2:9][CH2:8][O:7]3)[CH2:12][C:13]2=1

Participants

6

Reactant 3

HCID 24083Sulfuric acid magnesium salt (1:1)HCID 699814-Fluorophenylhydrazine hydrochlorideHCID 5674151,4-Dioxaspiro[4.5]decan-8-one

Product 1

HCID 67404927HCID 67404927, compound

Reagents, catalysts & solvents 2

HCID 3007855ZincchlorideCatalystHCID 6344DichloromethaneSolvent

Procedure

To a suspension of MgSO4 (18.4 g, 0.154 mol) in DCM (500 ml) were added 1,4-dioxaspiro[4.5]decan-8-one (48.0 g, 0.308 mol) and 4-fluorophenylhydrazine hydrochloride (50.0 g, 0.308 mol). Then, TEA (43.8 ml, 0.308 mol) was added dropwise over 5 min. The internal temperature went up from 17° C. to 25° C. upon addition of TEA. The resulting suspension was allowed to stir at rt for 4 h and filtered. The white solid was washed twice with DCM and the filtrate was concentrated in reduced pressure. The orange slurry was suspended in toluene (500 ml) and ZnCl2 (38.6 g, 0.283 mol) was added. The resulting dark orange solution was stirred at reflux using a Dean-Stark apparatus for 12 h. After cooling to rt, the resulting black mixture was filtered over celite. The solid was washed with isopropyl acetate, the organic filtrate was basified with 1N NaOH (until pH ˜12). The aqueous phase was extracted with isopropyl acetate, the combined organic extracts were passed through celite, dried over Na2SO4, filtered and concentrated in vacuo to yield the titled compound as a dark brown solid.

Workup

  1. additionThe internal temperature went up from 17° C. to 25° C. upon addition of TEA
  2. filtrationfiltered
  3. washThe white solid was washed twice with DCM
  4. concentrationthe filtrate was concentrated in reduced pressure
  5. stirringThe resulting dark orange solution was stirred
  6. temperatureat reflux
  7. customfor 12 h
  8. temperatureAfter cooling to rt
  9. filtrationthe resulting black mixture was filtered over celite
  10. washThe solid was washed with isopropyl acetate
  11. extractionThe aqueous phase was extracted with isopropyl acetate
  12. dry with materialdried over Na2SO4
  13. filtrationfiltered
  14. concentrationconcentrated in vacuo

Sources & evidence

ORD record
ord-cdccfb7d3a9344368107e27f9c20c62b
Source dataset
uspto-grants-2014_04
Patent number
US08697869B2

Reaction notes

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