Tributyltin azide → HCID 178420013, compound

HRID 1349707Notes

Reaction equation

HRID 1349707 reaction equation
[N:1]1([CH2:7][CH2:8][O:9][C:10]2[CH:15]=[CH:14][C:13]([C:16]3[C:24]4[C:19](=[CH:20][CH:21]=[C:22]([C:25]#[N:26])[CH:23]=4)[NH:18][N:17]=3)=[CH:12][CH:11]=2)[CH2:6][CH2:5][O:4][CH2:3][CH2:2]1.[N:27]([Sn](CCCC)(CCCC)CCCC)=[N+:28]=[N-:29]>C1(C)C=CC=CC=1>[NH:27]1[C:25]([C:22]2[CH:23]=[C:24]3[C:19](=[CH:20][CH:21]=2)[NH:18][N:17]=[C:16]3[C:13]2[CH:12]=[CH:11][C:10]([O:9][CH2:8][CH2:7][N:1]3[CH2:6][CH2:5][O:4][CH2:3][CH2:2]3)=[CH:15][CH:14]=2)=[N:26][N:29]=[N:28]1

Participants

4

Reactant 2

HCID 4984872Tributyltin azideHCID 224800663-{4-[2-(Morpholin-4-yl)ethoxy]phenyl}-1H-indazole-5-carbonitrile

Product 1

HCID 178420013HCID 178420013, compoundYield 8.9%

Reagents, catalysts & solvents 1

HCID 1140TolueneSolvent

Procedure

A mixture of 3-[4-(2-morpholin-4-ylethoxy)phenyl]-1H-indazole-5-carbonitrile (290 mg, 0.832 mmol), azidotributyltin (Bu3SnN3, 1.56 g, 4.70 mmol, 5.65 equiv.), and 9.0 mL toluene was refluxed for 17.5 h and concentrated to an oil. To the oil was added 6.5 mL of dioxane and 6.5 mL of 6.0 N aq. HCl. The mixture was stirred at room temperature for 4 h and then added to 25 mL of 6.0 N aq. NaOH. The mixture was extracted with 3× hexanes, and 3×Et2O. The aqueous layer was filtered to remove particulates. The pH was adjusted with 6.0 N aq. HCl to give maximum visual turbidity (approximately pH 5.0–5.5) and then the mixture was extracted with 2×EtOAc. The combined organics were dried (Na2SO4), filtered, and concentrated. The product was triturated in 5% EtOAc in hexanes. Filtration and drying of the solid afforded the title compound (29.0 mg, 8.90% yield): 1H NMR (CDCl3/CD3OD) δ 8.75 (s, 1H), 8.08 (d, 1H), 7.95 (d, 2H), 7.70 (m, 1H), 7.13 (d, 2H), 4.30 (t, 2H), 3.85–3.79 (m, 4H), 3.07 (t, 2H), 2.89–2.80 (m, 4H); ES-MS (m/z) 392 [M+1]+.

Workup

  1. temperaturewas refluxed for 17.5 h
  2. concentrationconcentrated to an oil
  3. additionTo the oil was added 6.5 mL of dioxane and 6.5 mL of 6.0 N aq. HCl
  4. additionadded to 25 mL of 6.0 N aq. NaOH
  5. extractionThe mixture was extracted with 3× hexanes, and 3×Et2O
  6. filtrationThe aqueous layer was filtered
  7. customto remove particulates
  8. customto give maximum visual turbidity (approximately pH 5.0–5.5) and then the mixture
  9. extractionwas extracted with 2×EtOAc
  10. dry with materialThe combined organics were dried (Na2SO4)
  11. filtrationfiltered
  12. concentrationconcentrated
  13. customThe product was triturated in 5% EtOAc in hexanes
  14. filtrationFiltration
  15. customdrying of the solid

Sources & evidence

ORD record
ord-f25b213d802c44c8b3e94c0dc3099dc9
Source dataset
uspto-grants-2007_05
Patent number
US07211594B2

Reaction notes

Loading…