Tert-Butyl nitrite → HCID 58531353, compound

HRID 1889702Notes

Reaction equation

HRID 1889702 reaction equation
[NH2:1][C:2]1[CH:7]=[CH:6][C:5]([C:8]2[CH:13]=[CH:12][CH:11]=[C:10]([CH2:14][N:15]([CH2:28][C:29]3[CH:34]=[CH:33][C:32]([F:35])=[CH:31][CH:30]=3)[S:16]([C:19]3[CH:24]=[C:23]([Cl:25])[CH:22]=[C:21]([Cl:26])[C:20]=3[OH:27])(=[O:18])=[O:17])[CH:9]=2)=[CH:4][CH:3]=1.N(OC(C)(C)C)=O.[N:43]([Si](C)(C)C)=[N+:44]=[N-]>C(#N)C.C1COCC1>[N:1]([C:2]1[CH:3]=[CH:4][C:5]([C:8]2[CH:13]=[CH:12][CH:11]=[C:10]([CH2:14][N:15]([CH2:28][C:29]3[CH:30]=[CH:31][C:32]([F:35])=[CH:33][CH:34]=3)[S:16]([C:19]3[CH:24]=[C:23]([Cl:25])[CH:22]=[C:21]([Cl:26])[C:20]=3[OH:27])(=[O:18])=[O:17])[CH:9]=2)=[CH:6][CH:7]=1)=[N+:43]=[N-:44]

Participants

6

Reactant 3

HCID 10906Tert-Butyl nitrite2×HCID 78378Azidotrimethylsilane2×HCID 58531635HCID 58531635, compound

Product 1

HCID 58531353HCID 58531353, compoundYield 50%

Reagents, catalysts & solvents 2

HCID 6342AcetonitrileSolventHCID 8028TetrahydrofuranSolvent

Procedure

To an ice cold mixture of N-((4′-aminobiphenyl-3-yl)methyl)-3,5-dichloro-N-(4-fluoro-benzyl)-2-hydroxybenzenesulfonamide (0.08 g, 0.15 mmol) in anhydrous acetonitrile (1 mL) and anhydrous THF (1 mL) was added tert-butyl nitrite (0.03 mL, 0.22 mmol) followed by the dropwise addition of azidotrimethylsilane (0.02 mL, 0.17 mmol). The ice bath was removed and the reaction stirred at room temperature. After 1 h, anhydrous THF (0.5 mL) and anhydrous acetonitrile (0.5 mL) were added. After an additional 16 h, the reaction mixture was cooled to 0° C. before tert-butyl nitrite (0.06 mL, 0.44 mmol) and azidotrimethylsilane (0.07 mL, 0.52 mmol) were added. Two hours later, the reaction was quenched with water and extracted twice with chloroform. The combined organic layers were dried over anhydrous sodium sulfate, filtered and concentrated in vacuo. The residue was dissolved in CHCl3 then passed through a RediSep normal phase silica flash column (4 g) eluting with hexane, followed by CHCl3. The appropriate fractions were concentrated in vacuo to afford the title compound (0.04 g, 50%) as a brown glass. 1H NMR (DMSO-d6) δ 7.80-7.75 (m, 1H), 7.57 (d, J=2.5 Hz, 1H), 7.56-7.45 (m, 3H), 7.32 (t, J=7.7 Hz, 1H), 7.28-7.18 (m, 5H), 7.15-7.03 (m, 3H), 4.51 (s, 2H), 4.49 (s, 2H). MS (ESI): 555.3 (M−H)−.

Workup

  1. customThe ice bath was removed
  2. additionanhydrous THF (0.5 mL) and anhydrous acetonitrile (0.5 mL) were added
  3. waitAfter an additional 16 h
  4. additionwere added
  5. customTwo hours later, the reaction was quenched with water
  6. extractionextracted twice with chloroform
  7. dry with materialThe combined organic layers were dried over anhydrous sodium sulfate
  8. filtrationfiltered
  9. concentrationconcentrated in vacuo
  10. dissolutionThe residue was dissolved in CHCl3
  11. washeluting with hexane
  12. concentrationThe appropriate fractions were concentrated in vacuo

Sources & evidence

ORD record
ord-ad92af5a10324688aba32e22298ee264
Source dataset
uspto-grants-2013_08
Patent number
US08501992B2

Reaction notes

Loading…