Ethyl acetate hexane → HCID 178514971, compound

HRID 1037995Notes

Reaction equation

HRID 1037995 reaction equation
C(OC([N:8]1[C:16]2[C:11](=[CH:12][C:13]([N+:17]([O-:19])=[O:18])=[CH:14][CH:15]=2)[C:10]([CH2:20]Br)=[N:9]1)=O)(C)(C)C.[C:22]1(=[O:32])[NH:26][C:25](=[O:27])[C:24]2=[CH:28][CH:29]=[CH:30][CH:31]=[C:23]12.[K].CCOC(C)=O.CCCCCC>CN(C=O)C.C(Cl)Cl.C(O)(C(F)(F)F)=O>[N+:17]([C:13]1[CH:12]=[C:11]2[C:16](=[CH:15][CH:14]=1)[NH:8][N:9]=[C:10]2[CH2:20][N:26]1[C:22](=[O:32])[C:23]2[C:24](=[CH:28][CH:29]=[CH:30][CH:31]=2)[C:25]1=[O:27])([O-:19])=[O:18]

Participants

7

Reactant 3

HCID 21226206Ethyl acetate hexane2×HCID 24194345Phthalimide potassium saltHCID 576861301H-Indazole-1-carboxylic acid, 3-(bromomethyl)-5-nitro-, 1,1-dimethylethyl ester

Product 1

HCID 178514971HCID 178514971, compound

Reagents, catalysts & solvents 3

HCID 6228DimethylformamideSolventHCID 6344DichloromethaneSolvent2×HCID 6422Trifluoroacetic acidSolvent

Procedure

3-Bromomethyl-5-nitro-indazole-1-carboxylic acid tert-butyl ester (0.63 g, 1.77 mmol) and potassium phthalimide (0.396 g, 1.2 eq) were stirred in DMF (1 mL) at 80° C. for two hours. TLC (20% EtOAc/hexane) showed starting material consumed and new products formed. After DMF was evaporated, a residue, 1.33 g, was obtained. The resulting residue was stirred in DCM and filtered. The filtration cake then washed with DCM followed by hexane. The evaporation of the filtrate gave 0.79 g of crude. Flash chromatograph (20-30% EtOAc/hexane) gave a mixture, two spots shown on TLC. During the sample preparation, solid precipitated and the solid was collected, 95 mg. MS showed de-Boc product, (M+H)+ at 323. An adequate amount of this mixture was treated with TFA in DCM for two hours. TLC showed one spot and MS gave (M+H)+ at 323. The remaining mixture was stirred in a mixture of TFA (6 mL) and DCM (10 mL) for two hours. Evaporation of TFA and DCM gave the desired product, 0.71 g, (quant. yield).

Workup

  1. customconsumed
  2. customnew products formed
  3. customAfter DMF was evaporated
  4. customa residue, 1.33 g, was obtained
  5. filtrationfiltered
  6. washThe filtration cake then washed with DCM
  7. customThe evaporation of the filtrate
  8. customgave 0.79 g of crude
  9. customDuring the sample preparation, solid
  10. customprecipitated
  11. customthe solid was collected
  12. additionAn adequate amount of this mixture was treated with TFA in DCM for two hours
  13. customgave (M+H)+ at 323
  14. customEvaporation of TFA and DCM

Sources & evidence

ORD record
ord-bf62197c840943c29fa672fda92842a1
Source dataset
uspto-grants-2013_10
Patent number
US08546404B2

Reaction notes

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