Hydrochloric Acid → HCID 178527117, compound

HRID 1161118Notes

Reaction equation

HRID 1161118 reaction equation
[NH2:1][OH:2].C([SiH2][O:8][C:9](C)(C)[C:10]1[CH:11]=[C:12]([CH:15]=[CH:16][CH:17]=1)[C:13]#[N:14])(C)(C)C.N1C=CC=CC=1.[S:26](Cl)(Cl)=[O:27].Cl>C(O)(C)C.[Cl-].[Na+].O.O1CCCC1.ClCCl>[O:27]=[S:26]1[NH:14][C:13]([C:12]2[CH:11]=[C:10]([CH2:9][OH:8])[CH:17]=[CH:16][CH:15]=2)=[N:1][O:2]1

Participants

10

Reactant 5

HCID 313Hydrochloric AcidHCID 787HydroxylamineHCID 1049PyridineHCID 24386Thionyl ChlorideHCID 178455426HCID 178455426, compound

Product 1

HCID 178527117HCID 178527117, compoundYield 91%

Reagents, catalysts & solvents 4

HCID 3776IsopropanolSolventHCID 6344DichloromethaneSolventHCID 8028TetrahydrofuranSolventHCID 57417360Sodium chloride; waterSolvent

Procedure

Add hydroxylamine (50% aqueous solution, 5.34 g, 80.8 mmol) dropwise to a refluxing solution of 3-(tert-butyl-dimethyl-silanyloxymethyl)-benzonitrile (5.00 g, 20.2 mmol) in isopropanol (0.1 M). After 2 hours, concentrate the reaction under reduced pressure and azeotrope with toluene. Add dichloromethane (0.1 M) and pyridine (1.92 g, 24.3 mmol) and cool reaction to −78° C. Add thionyl chloride (2.64 g, 22.2 mmol) via syringe. After 4 hours, warm the reaction to room temperature. Concentrate the reaction under reduced pressure. Add tetrahydrofuran (0.1M) and 10% hydrochloric acid (0.1M) and stir. After 18 hours, add brine and extract with 25% isopropyl alcohol:75% dichloromethane. Combine organic layers, dry with sodium sulfate, filter and concentrate under reduced pressure to yield the title product as a yellow solid (3.90 g, 91%): 1H NMR (DMSO-d6) δ 4.63 (s, 2H), 5.42 (bs, 1H), 7.59 (m, 2H), 7.75 (dt, 1H), 7.88 (s, 1H), 12.23 (bs, 1H).

Workup

  1. concentrationconcentrate
  2. customthe reaction under reduced pressure and azeotrope with toluene
  3. customreaction to −78° C
  4. waitAfter 4 hours
  5. temperaturewarm
  6. customthe reaction to room temperature
  7. concentrationConcentrate
  8. customthe reaction under reduced pressure
  9. waitAfter 18 hours
  10. extractionextract with 25% isopropyl alcohol
  11. dry with materialCombine organic layers, dry with sodium sulfate
  12. filtrationfilter
  13. concentrationconcentrate under reduced pressure

Sources & evidence

ORD record
ord-902147da017548a0bfab0188a19eca92
Source dataset
uspto-grants-2010_10
Patent number
US07816523B2

Reaction notes

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