Bicyclo[2.2.1]heptane-1-methanesulfonic acid, 7,7-dimethyl-2-oxo-, (1S)- → HCID 66743923, compound

HRID 2364101Notes

Reaction equation

HRID 2364101 reaction equation
[NH2:1][C:2]1[CH:6]=[C:5]([C:7]2[CH:8]=[N:9][NH:10][C:11]=2[CH3:12])[S:4][C:3]=1[C:13]([NH2:15])=[O:14].[C:16]1([N:22]2[CH2:31][CH2:30][C:25]3(OCCO3)[CH2:24][CH2:23]2)[CH:21]=[CH:20][CH:19]=[CH:18][CH:17]=1.CC1(C)C2(CS(O)(=O)=O)C(CC1CC2)=O.[O-]S([O-])(=O)=O.[Mg+2].C([O-])(O)=O.[Na+]>CC(N(C)C)=O>[CH3:12][C:11]1[NH:10][N:9]=[CH:8][C:7]=1[C:5]1[S:4][C:3]2[C:13](=[O:14])[NH:15][C:25]3([CH2:30][CH2:31][N:22]([C:16]4[CH:21]=[CH:20][CH:19]=[CH:18][CH:17]=4)[CH2:23][CH2:24]3)[NH:1][C:2]=2[CH:6]=1

Participants

7

Reactant 5

HCID 18462Bicyclo[2.2.1]heptane-1-methanesulfonic acid, 7,7-dimethyl-2-oxo-, (1S)-HCID 24083Sulfuric acid magnesium salt (1:1)HCID 516892Sodium BicarbonateHCID 114700398-Phenyl-1,4-dioxa-8-azaspiro[4.5]decaneHCID 667430133-amino-5-(5-methyl-1H-pyrazol-4-yl)thiophene-2-carboxamide

Product 1

HCID 66743923HCID 66743923, compoundYield 27%

Reagents, catalysts & solvents 1

HCID 31374DimethylacetamideSolvent

Conditions

Temperature
100 °C

Procedure

A mixture of 3-amino-5-(5-methyl-1H-pyrazol-4-yl)thiophene -2-carboxamide (100 mg, 0.45 mmol), 8-phenyl-1,4-dioxa-8-azaspiro[4.5]decane (109 mg, 0.50 mmol), CSA (125 mg, 0.54 mmol), MgSO4 (108 mg, 0.90 mmol) and DMA (1 mL) was stirred at 100° C. for 1 h. Then, saturated aqueous NaHCO3 was added to quench the reaction. The organic materials were extracted with EtOAc/THF. The combined extracts were dried over Na2SO4 and filtered. After removal of the solvent at reduced pressure, the residue was purified by column chromatography (Purif, NH, 80:20 hexane/EtOAc to EtOAc then to 95:5 EtOAc/MeOH), then crystallized from MeOH/EtOAc/heptane to give the title compound (46 mg, 27%) as a yellow solid:

Workup

  1. customto quench
  2. customthe reaction
  3. extractionThe organic materials were extracted with EtOAc/THF
  4. dry with materialThe combined extracts were dried over Na2SO4
  5. filtrationfiltered
  6. customAfter removal of the solvent at reduced pressure
  7. customthe residue was purified by column chromatography (Purif, NH, 80:20 hexane/EtOAc to EtOAc
  8. customto 95:5 EtOAc/MeOH), then crystallized from MeOH/EtOAc/heptane

Sources & evidence

ORD record
ord-5bd1d07a189844119a899948daeff304
Source dataset
uspto-grants-2014_04
Patent number
US08691828B2

Reaction notes

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