Tert-Butylamine → N-(tert-butyl)-5-cyanofuran-2-sulfonamide

HRID 2388798Notes

Reaction equation

HRID 2388798 reaction equation
[Na+].[CH:2]([C:4]1[O:8][C:7]([S:9]([O-:12])(=[O:11])=O)=[CH:6][CH:5]=1)=O.Cl.[NH2:14]O.[C:16]([NH2:20])([CH3:19])([CH3:18])[CH3:17]>O.C(O)(=O)C.P(Cl)(Cl)(Cl)=O.C(Cl)Cl>[C:16]([NH:20][S:9]([C:7]1[O:8][C:4]([C:2]#[N:14])=[CH:5][CH:6]=1)(=[O:11])=[O:12])([CH3:19])([CH3:18])[CH3:17]

Participants

8

Reactant 3

HCID 6385Tert-ButylamineHCID 443297Hydroxyamine hydrochlorideHCID 3772036Sodium 5-formylfuran-2-sulphonate

Product 1

HCID 53628367N-(tert-butyl)-5-cyanofuran-2-sulfonamide

Reagents, catalysts & solvents 4

HCID 176Acetic AcidSolventHCID 962WaterSolventHCID 6344DichloromethaneSolventHCID 24813Phosphorus oxychlorideSolvent

Procedure

A solution of 5-formylfuran-2-sulfonic acid sodium salt (2.97 g), and hydroxylamine hydrochloride (1.05 g) in H2O (1.35 mL) and acetic acid (21 mL) was heated at 60° C. for 4 h. After cooling to room temperature the solvent was removed in vacuo. The crude residue was triturated with Et2O (3×50 mL) and dried under high vacuum to give a crude pale brown solid. A solution of this material (3.7 g) in phosphorusoxychloride (100 mL) was heated at 60° C. for 18 h. After cooling to room temperature the mixture was partitioned between ice-water (100 mL) and EtOAc (100 mL). The aqueous layer was separated and further extracted with EtOAc (2×100 mL). The combined organic phases were washed with brine (100 mL), dried (MgSO4), filtered and evaporated to dryness in vacuo to give a crude brown oil. To a solution of this crude oil (1.6 g) in DCM (85 mL) was added tert-butylamine (1.8 mL). After stirring at room temperature for 2 days the mixture was filtered through celite, washing with DCM (2×20 mL). The filtrate was evaporated to dryness in vacuo. The resulting crude material was purified by column chromatography using EtOAc/isohexane (2:8) as eluent to give the subtitle compound as a pale yellow oil. Yield: 1.0 g.

Workup

  1. customwas removed in vacuo
  2. customThe crude residue was triturated with Et2O (3×50 mL)
  3. customdried under high vacuum
  4. customto give a crude pale brown solid
  5. temperatureAfter cooling to room temperature the mixture
  6. customwas partitioned between ice-water (100 mL) and EtOAc (100 mL)
  7. customThe aqueous layer was separated
  8. extractionfurther extracted with EtOAc (2×100 mL)
  9. washThe combined organic phases were washed with brine (100 mL)
  10. dry with materialdried (MgSO4)
  11. filtrationfiltered
  12. customevaporated to dryness in vacuo
  13. customto give a crude brown oil
  14. filtrationwas filtered through celite
  15. washwashing with DCM (2×20 mL)
  16. customThe filtrate was evaporated to dryness in vacuo
  17. customThe resulting crude material was purified by column chromatography

Sources & evidence

ORD record
ord-3da66eade15949f0bee150d823319b7a
Source dataset
uspto-grants-2012_09
Patent number
US08269002B2

Reaction notes

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