Acetonitrile → HCID 11554304, compound

HRID 2221106Notes

Reaction equation

HRID 2221106 reaction equation
[CH2:1]([N:8]1[C:13]2[N:14]=[N:15][C:16]([C:18]3[CH:23]=[CH:22][CH:21]=[CH:20][CH:19]=3)=[CH:17][C:12]=2[CH2:11][CH:10]([NH:24]C(=O)OCC2C=CC=CC=2)[CH2:9]1)[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1.C(#N)C.I[Si](C)(C)C.[C:43]1([S:49](Cl)(=[O:51])=[O:50])[CH:48]=[CH:47][CH:46]=[CH:45][CH:44]=1>C(=O)([O-])[O-].[Na+].[Na+].C1COCC1.O.Cl>[CH2:1]([N:8]1[C:13]2[N:14]=[N:15][C:16]([C:18]3[CH:23]=[CH:22][CH:21]=[CH:20][CH:19]=3)=[CH:17][C:12]=2[CH2:11][CH:10]([NH:24][S:49]([C:43]2[CH:48]=[CH:47][CH:46]=[CH:45][CH:44]=2)(=[O:51])=[O:50])[CH2:9]1)[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1

Participants

9

Reactant 4

HCID 6342AcetonitrileHCID 7369Benzenesulfonyl chlorideHCID 85247Trimethylsilyl iodideHCID 58671545HCID 58671545, compound

Product 1

HCID 11554304HCID 11554304, compoundYield 71%

Reagents, catalysts & solvents 4

HCID 313Hydrochloric AcidCatalystHCID 962WaterSolventHCID 8028TetrahydrofuranSolventHCID 10340Sodium CarbonateSolvent

Procedure

To a stirred solution of 5G (0.023 g, 0.051 mmol) in 0.3 ML of acetonitrile at room temperature under argon was added iodotrimethylsilane (0.020 mL, 0.144 mmol). The yellow solution was stirred 20 min and then quenched with methanol (2 mL). After stirring for 30 min, the reaction mixture was evaporated and then re-evaporated from dichloromethane/hexanes. The solid residue was slurried twice with ether, decanting each time. The remaining solid was slurried in 10% sodium carbonate solution (1.0 mL) at room temperature while a solution of benzenesulfonyl chloride (0.020 mL, 0.157 mmol) in 1.0 mL of THF was added. After rapid stirring for 15 h, the reaction mixture was diluted with water. The solution was adjusted to pH 8 with a few drops of hydrochloric acid and then extracted twice with EtOAc. The organic extracts were dried (MgSO4), filtered, evaporated and purified by chromatography on silica gel (1:5 Ether/CH2Cl2) to give the title compound as a yellow solid (16.5 mg, 71% yield). MS [M+H]+: found 457. HPLC (Method C): retention time, 7.33 min; 98.3% purity. 1H NMR (CDCl3, 400 MHz) δ7.90 (m, 2H), 7.77 (m, 2H), 7.54 (m, 1H), 7.49-7.37 (m, 5H), 7.32-7.21 (m, 6H), 5.61 (d, 1H, J=8.0 Hz), 5.09 (d, 2H, J=14.9 Hz), 4.59 (d, 2H, J=14.9 Hz), 3.84 (m, 1H), 3.33 (dd, 1H, J=2.6, 11.3 Hz), 3.09 (m, 1H), 2.90 (dd, 2H, J=4.4, 17.1 Hz), 2.77 (dd, 2H, J=3.1, 17.1 Hz); 13C NMR (CDCl3, 101 MHz) δ155.5, 151.2, 140.7, 137.3, 136.3, 132.7, 129.2, 128.8, 128.7, 128.3, 127.6, 126.9, 125.9, 125.9, 124.9, 51.3, 51.0, 44.8, 33.6.

Workup

  1. customquenched with methanol (2 mL)
  2. stirringAfter stirring for 30 min
  3. customthe reaction mixture was evaporated
  4. customre-evaporated from dichloromethane/hexanes
  5. customdecanting each time
  6. additionwas added
  7. stirringAfter rapid stirring for 15 h
  8. extractionextracted twice with EtOAc
  9. dry with materialThe organic extracts were dried (MgSO4)
  10. filtrationfiltered
  11. customevaporated
  12. custompurified by chromatography on silica gel (1:5 Ether/CH2Cl2)

Sources & evidence

ORD record
ord-8dffc38e25b64dabbe395e8eaddfc1f5
Source dataset
uspto-grants-2008_05
Patent number
US07368458B2

Reaction notes

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