Stannous Chloride → HCID 86715465, compound

HRID 1403173Notes

Reaction equation

HRID 1403173 reaction equation
[Sn](Cl)Cl.[C:4]([O:8][C:9]([N:11]([C:19]1[C:24]([C:25]2[O:29][N:28]=[C:27]([C:30]3[CH:35]=[CH:34][C:33]([N+:36]([O-])=O)=[CH:32][CH:31]=3)[CH:26]=2)=[N:23][C:22]([C:39]2[CH:44]=[CH:43][C:42]([S:45]([CH:48]([CH3:50])[CH3:49])(=[O:47])=[O:46])=[CH:41][CH:40]=2)=[CH:21][N:20]=1)[C:12](=[O:18])[O:13][C:14]([CH3:17])([CH3:16])[CH3:15])=[O:10])([CH3:7])([CH3:6])[CH3:5]>C(O)C>[NH2:36][C:33]1[CH:32]=[CH:31][C:30]([C:27]2[CH:26]=[C:25]([C:24]3[C:19]([N:11]([C:12]([O:13][C:14]([CH3:15])([CH3:16])[CH3:17])=[O:18])[C:9](=[O:10])[O:8][C:4]([CH3:5])([CH3:6])[CH3:7])=[N:20][CH:21]=[C:22]([C:39]4[CH:40]=[CH:41][C:42]([S:45]([CH:48]([CH3:50])[CH3:49])(=[O:47])=[O:46])=[CH:43][CH:44]=4)[N:23]=3)[O:29][N:28]=2)=[CH:35][CH:34]=1

Participants

4

Reactant 2

HCID 24479Stannous ChlorideHCID 86715466HCID 86715466, compound

Product 1

HCID 86715465HCID 86715465, compoundYield 61%

Reagents, catalysts & solvents 1

HCID 702EthanolSolvent

Conditions

Temperature
60 °C

Procedure

Tin (II) chloride (499.4 mg, 2.213 mmol) was added to a stirred solution of tert-butyl N-tert-butoxycarbonyl-N-[5-(4-isopropylsulfonylphenyl)-3-[3-(4-nitrophenyl)isoxazol-5-yl]pyrazin-2-yl]carbamate (491 mg, 0.7376 mmol) in ethanol (15 mL) and the resulting solution heated at 60° C. for 16 h. The reaction mixture was cooled rt and concentrated in vacuo. The residue was partitioned between ethyl acetate (10 mL) and 1M NaOH(aq) (5 mL) and the residue that formed was filtered off. The layers were then separated and the aqueous layer was extracted further with ethyl acetate (2×10 mL) and the combined organic extracts were washed with brine (1×10 mL), dried over MgSO4 and concentrated in vacuo. The material was purified by column chromatography on silica (ISCO Companion, 12 g column) eluting with 0-100% EtOAc with petroleum ether. The product fractions were combined and concentrated in vacuo to leave the title compound as a yellow/orange solid (286 mg, 61% yield); 1H NMR (400 MHz, CDCl3) δ 1.37 (m, 6H), 1.42 (s, 18H), 3.28 (m, 1H), 3.95 (br s, 2H), 6.79 (m, 2H), 7.30 (s, 1H), 7.72 (d, J=8.0 Hz, 1H), 8.10 (m, 2H), 8.36 (m, 2H) and 9.06 (s, 1H) ppm; MS (ES+) 636.3 (M+H)

Workup

  1. temperatureThe reaction mixture was cooled rt
  2. concentrationconcentrated in vacuo
  3. customThe residue was partitioned between ethyl acetate (10 mL) and 1M NaOH(aq) (5 mL)
  4. customthe residue that formed
  5. filtrationwas filtered off
  6. customThe layers were then separated
  7. extractionthe aqueous layer was extracted further with ethyl acetate (2×10 mL)
  8. washthe combined organic extracts were washed with brine (1×10 mL)
  9. dry with materialdried over MgSO4
  10. concentrationconcentrated in vacuo
  11. customThe material was purified by column chromatography on silica (ISCO Companion, 12 g column)
  12. washeluting with 0-100% EtOAc with petroleum ether
  13. concentrationconcentrated in vacuo

Sources & evidence

ORD record
ord-1b6d7e8feb4241cb923d704767faf36b
Source dataset
uspto-grants-2014_12
Patent number
US08912198B2

Reaction notes

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