Water → HCID 178519296, compound

HRID 1256216Notes

Reaction equation

HRID 1256216 reaction equation
[Br:1][C:2]1[C:6]2[N:7]=[C:8]([C:17]3[C:22]([F:23])=[CH:21][CH:20]=[CH:19][C:18]=3[F:24])[C:9]3[CH:10]=[C:11]([CH:15]=C)[CH:12]=[CH:13][C:14]=3[C:5]=2[NH:4][N:3]=1.O.I([O-])(=O)(=O)=[O:27].[Na+]>C1COCC1.CC(O)(C)C.[Os](=O)(=O)(=O)=O>[Br:1][C:2]1[C:6]2[N:7]=[C:8]([C:17]3[C:22]([F:23])=[CH:21][CH:20]=[CH:19][C:18]=3[F:24])[C:9]3[CH:10]=[C:11]([CH:15]=[O:27])[CH:12]=[CH:13][C:14]=3[C:5]=2[NH:4][N:3]=1

Participants

7

Reactant 3

HCID 962Water2×HCID 23667635Sodium periodateHCID 178435467HCID 178435467, compound

Product 1

HCID 178519296HCID 178519296, compoundYield 68.3%

Reagents, catalysts & solvents 3

HCID 30318Osmium TetroxideCatalystHCID 6386tert-ButanolSolvent2×HCID 8028TetrahydrofuranSolvent

Procedure

A 150 ml round-bottomed flask equipped with a magnetic stirrer and with a septum having a top-mounted argon intake is charged with 1 g of 3-bromo-5-(2,6-difluorophenyl)-7-vinyl-1H-pyrazolo[4,3-c]isoquinoline in 13 ml of THF and then 7 ml of water, 13 ml of tert-butanol, 0.79 ml of a solution of osmium tetroxide at 2.5% in 2-methyl-2-propanol, and 17 g of sodium periodate are added. The mixture is stirred at RT for 3 h and then poured into water, extracted with AcOEt, washed with saturated NaCl solution, dried over MgSO4, filtered and concentrated under RP. This gives 1.047 g of a crude product, which is purified by chromatography on silica gel (20-45 μm), eluting with a mixture of DCM and methanol (95/5 by vol.), to give 686 mg of 3-bromo-5-(2,6-difluorophenyl)-1H-pyrazolo[4,3-c]isoquinoline-7-carbaldehyde (cream solid). MS (E/I): m/z=388 (M+); 1H NMR: 7.41 (d, J=7.9 Hz, 2H); 7.77 (m, 1H); 8.34 (broad s, 1H); 8.47 (dd, J=8.5, 1.2 Hz, 1H); 8.69 (d, J=8.5 Hz, 1H); 10.15 (s, 1H); 14.89 (broad m, 1H).

Workup

  1. customA 150 ml round-bottomed flask equipped with a magnetic stirrer and with a septum
  2. extractionextracted with AcOEt
  3. washwashed with saturated NaCl solution
  4. dry with materialdried over MgSO4
  5. filtrationfiltered
  6. concentrationconcentrated under RP
  7. customThis gives 1.047 g of a crude product, which is purified by chromatography on silica gel (20-45 μm)
  8. washeluting with a mixture of DCM and methanol (95/5 by vol.)

Sources & evidence

ORD record
ord-aa843537c27e4d8489c45168d2203f7b
Source dataset
uspto-grants-2013_06
Patent number
US08461175B2

Reaction notes

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