Sodium Sulfite → 1-[2-(2-Isopropyl-2H-[1,2,4]triazol-3-yl)-4,5-dihydro-6-oxa-3-thia-1-aza-benzo[e]azulen-8-yl]-ethane-1,2-diol

HRID 708031Notes

Reaction equation

HRID 708031 reaction equation
[CH:1]([N:4]1[C:8]([C:9]2[S:10][C:11]3CC[O:14][C:15]4[CH:22]=[C:21](C=C)[CH:20]=[CH:19][C:16]=4[C:17]=3[N:18]=2)=[N:7][CH:6]=[N:5]1)([CH3:3])[CH3:2].C[N+]1([O-])[CH2:31][CH2:30][O:29][CH2:28][CH2:27]1.S([O-])([O-])=[O:34].[Na+].[Na+]>CC(C)=O.C1COCC1.O>[CH:1]([N:4]1[C:8]([C:9]2[S:10][C:11]3[CH2:31][CH2:30][O:29][C:28]4[CH:27]=[C:21]([CH:22]([OH:34])[CH2:15][OH:14])[CH:20]=[CH:19][C:16]=4[C:17]=3[N:18]=2)=[N:7][CH:6]=[N:5]1)([CH3:3])[CH3:2]

Participants

7

Reactant 3

HCID 24437Sodium SulfiteHCID 82029Methyl morpholine oxideHCID 582037962-(2-Isopropyl-2H-[1,2,4]triazol-3-yl)-8-vinyl-4,5-dihydro-6-oxa-3-thia-1-aza-benzo[e]azulene

Product 1

HCID 582040341-[2-(2-Isopropyl-2H-[1,2,4]triazol-3-yl)-4,5-dihydro-6-oxa-3-thia-1-aza-benzo[e]azulen-8-yl]-ethane-1,2-diolYield 46%

Reagents, catalysts & solvents 3

HCID 180AcetoneSolventHCID 962WaterSolventHCID 8028TetrahydrofuranSolvent

Procedure

A solution of 2-(2-Isopropyl-2H-[1,2,4]triazol-3-yl)-8-vinyl-4,5-dihydro-6-oxa-3-thia-1-aza-benzo[e]azulene (1.28 mmol) in acetone, THF and water (15 mL, 1:1:1) was treated with N-methylmorpholine-N-oxide (299 mg, 2.56 mmol) then potassium osmate dihydrate (14 mg, 0.04 mmol). The reaction mixture was stirred at room temperature overnight. Solid sodium sulfite was added and the reaction mixture was extracted with EtOAc. The combined organics were dried over sodium sulfate, concentrated and the residue purified by reverse phase HPLC to give 286 as a colorless solid (222 mg, 46%). LCMS: 373.1. 1H NMR (400 MHz, DMSO) δ 8.28 (d, J=8.2 Hz, 1H), 8.09 (s, 1H), 7.16 (d, J=8.1 Hz, 1H), 7.04 (s, 1H), 5.82 (dt, J=13.3, 6.5 Hz, 1H), 5.26 (d, J=4.4 Hz, 1H), 4.70 (t, J=5.8 Hz, 1H), 4.54 (dd, J=10.4, 5.6 Hz, 1H), 4.36 (t, J=5.0 Hz, 2H), 3.53-3.35 (m, 4H), 1.55 (d, J=6.6 Hz, 6H)

Workup

  1. extractionthe reaction mixture was extracted with EtOAc
  2. dry with materialThe combined organics were dried over sodium sulfate
  3. concentrationconcentrated
  4. customthe residue purified by reverse phase HPLC

Sources & evidence

ORD record
ord-ecece42db7ff48ee986d2871b8cbf895
Source dataset
uspto-grants-2015_11
Patent number
US09175009B2

Reaction notes

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