Allyl Alcohol → 3-(1-Oxido-7,8-dihydro-6H-indeno[5,6-e][1,2,4]triazin-3-yl)-1-propanol

HRID 1669062Notes

Reaction equation

HRID 1669062 reaction equation
I[C:2]1[N:3]=[N+:4]([O-:15])[C:5]2[CH:14]=[C:13]3[C:9]([CH2:10][CH2:11][CH2:12]3)=[CH:8][C:6]=2[N:7]=1.[CH2:16]([OH:19])[CH:17]=[CH2:18].C([O-])(O)=O.[Na+].[BH4-].[Na+]>[Cl-].C([N+](CCCC)(CCCC)CCCC)CCC.C(#N)C.CO.CC([O-])=O.CC([O-])=O.[Pd+2].CC(O)=O>[O-:15][N+:4]1[C:5]2[CH:14]=[C:13]3[C:9](=[CH:8][C:6]=2[N:7]=[C:2]([CH2:18][CH2:17][CH2:16][OH:19])[N:3]=1)[CH2:10][CH2:11][CH2:12]3

Participants

10

Reactant 4

HCID 7858Allyl AlcoholHCID 516892Sodium BicarbonateHCID 4311764Sodium borohydrideHCID 16081315HCID 16081315, compound

Product 1

HCID 119516443-(1-Oxido-7,8-dihydro-6H-indeno[5,6-e][1,2,4]triazin-3-yl)-1-propanolYield 45.4%

Reagents, catalysts & solvents 5

HCID 70681Tetrabutylammonium ChlorideCatalystHCID 167845palladium(II) acetateCatalystHCID 176Acetic AcidSolventHCID 887MethanolSolventHCID 6342AcetonitrileSolvent

Conditions

Temperature
-40 °C

Procedure

Pd(OAc)2 (18 mg, 0.08 mmol) was added to a degassed solution of iodide 66 (250 mg, 0.80 mmol), allyl alcohol (0.27 mL, 3.40 mmol), tetrabutylammonium chloride (182 mg, 0.80 mmol) and NaHCO3 (147 mg, 1.76 mmol) in acetonitrile (12.5 mL) and the solution irradiated in a Milestone MicroSYNTH reactor for 15 min at 150° C. (max. 400 watt). After cooling, the mixture was quenched with saturated aqueous NH4Cl solution (10 ml) and filtered. The filtrate was extracted with EtOAc (3×20 ml), dried and the solvent evaporated. The crude residue was dissolved in MeOH (20 mL), cooled to −40° C. and NaBH4 (2×40 mg, 2.12 mmol) in MeOH (20 mL) added to it. The solution was stirred at −40° C. for 1, then HOAc (0.1 mL) added, warmed to 20° C. and the solvent evaporated. The residue was purified by chromatography, eluting with a gradient (80-100%) EtOAc/pet. ether, to give alcohol 70 (89 mg, 45%) as an off-white solid; spectroscopically identical to the sample prepared above.

Workup

  1. customthe solution irradiated in a Milestone MicroSYNTH reactor for 15 min at 150° C. (max. 400 watt)
  2. temperatureAfter cooling
  3. customthe mixture was quenched with saturated aqueous NH4Cl solution (10 ml)
  4. filtrationfiltered
  5. extractionThe filtrate was extracted with EtOAc (3×20 ml)
  6. customdried
  7. customthe solvent evaporated
  8. dissolutionThe crude residue was dissolved in MeOH (20 mL)
  9. temperaturewarmed to 20° C.
  10. customthe solvent evaporated
  11. customThe residue was purified by chromatography
  12. washeluting with a gradient (80-100%) EtOAc/pet. ether

Sources & evidence

ORD record
ord-43cd769c269342508c925e1bca6ff474
Source dataset
uspto-grants-2011_08
Patent number
US07989451B2

Reaction notes

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