Ethanol → HCID 178511914, compound

HRID 1668457Notes

Reaction equation

HRID 1668457 reaction equation
[N+:1]([C:4]1[CH:5]=[C:6]2[C:10](=[CH:11][CH:12]=1)[N:9]([CH2:13][CH2:14][CH2:15][N:16]1[CH2:21][CH2:20][O:19][CH2:18][CH2:17]1)[CH:8]=[CH:7]2)([O-])=O.C(O)C.[H][H].I.[S:28]1[CH:32]=[CH:31][CH:30]=[C:29]1[C:33](SC)=[NH:34]>[Pd].CCOCC>[O:19]1[CH2:20][CH2:21][N:16]([CH2:15][CH2:14][CH2:13][N:9]2[C:10]3[C:6](=[CH:5][C:4]([NH:1][C:33]([C:29]4[S:28][CH:32]=[CH:31][CH:30]=4)=[NH:34])=[CH:12][CH:11]=3)[CH:7]=[CH:8]2)[CH2:17][CH2:18]1

Participants

7

Reactant 4

HCID 702EthanolHCID 59004671HCID 59004671, compoundHCID 66704664Methyl thiophene-2-carbimidothioate hydroiodideHCID 178418361HCID 178418361, compound

Product 1

HCID 178511914HCID 178511914, compoundYield 62.6%

Reagents, catalysts & solvents 2

HCID 23938PalladiumCatalystHCID 3283Diethyl EtherSolvent

Procedure

To an argon purged round bottom flask containing compound 39 (153 mg, 0.529 mmol) was added 10% by weight palladium on carbon (56 mg, 0.053 mmol) and a magnetic stirbar, followed by the addition of absolute ethanol (10 mL). The system was fitted with a hydrogen filled balloon. The argon atmosphere was removed using a water aspirator and replaced with hydrogen. The atmosphere was removed twice more and replaced with hydrogen a total of 3 times and was stirred for 17.5 hours. TLC (2M NH3 in methanol:CH2Cl2, 5:95) revealed the reaction was complete. The reaction was filtered through a 5 um PTFE frit. The frit washed with absolute ethanol (5 mL). The filtrate was transferred to a reaction vial fitted with a magnetic stirbar, and was purged with argon. Methyl thiophene-2-carbimidothioate hydroiodide (226 mg, 0.793 mmol) was added as a solid and the reaction was stirred at room temperature for 18 hours. The reaction was complete by TLC and was diluted with ether (40 mL) and the reaction was filtered to collect the precipitate. The precipitate washed with ether. The precipitate was dissolved in ethanol and stirred at room temperature with DOWES-66 resin (3.00 g). The mixture was stirred at room temperature for 2 hours. The reaction was filtered and the filtrate concentrated. The material was purified by silica gel column chromatography (2M NH3 in methanol:CH2Cl2, 2.5:97.5 to 5:95) to obtain compound 40 (122 mg) as a brown oil. 1H NMR (DMSO-d6) δ 7.72 (d, J=3.6 Hz, 1H), 7.58 (d, J=3.6 Hz, 1H), 7.41 (d, J=8.7 Hz, 1H), 7.29 (d, J=3.0 Hz, 1H), 7.09 (t, J=4.5 Hz, 1H), 6.97 (s, 1H), 6.69 (d, J=9.0 Hz, 1H), 6.32 (d, J=3.0 Hz, 1H), 6.22 (brs, 2H), 4.17 (t, J=6.6 Hz, 2H), 3.58 (t, J=4.5 Hz, 4H), 2.31 (m, 4H), 2.21 (t, J=6.9 Hz, 2H), 1.90 (m, 2H); ESI-MS (m/z, %): 369 (M+1); ESI-HRMS calculated for C20H25N4OS (MH+): 369.1743, Observed: 369.1754.

Workup

  1. customThe argon atmosphere was removed
  2. customThe atmosphere was removed twice more
  3. filtrationThe reaction was filtered through a 5 um PTFE frit
  4. washThe frit washed with absolute ethanol (5 mL)
  5. customThe filtrate was transferred to a reaction
  6. customvial fitted with a magnetic stirbar
  7. customwas purged with argon
  8. stirringthe reaction was stirred at room temperature for 18 hours
  9. filtrationthe reaction was filtered
  10. customto collect the precipitate
  11. washThe precipitate washed with ether
  12. dissolutionThe precipitate was dissolved in ethanol
  13. stirringstirred at room temperature with DOWES-66 resin (3.00 g)
  14. stirringThe mixture was stirred at room temperature for 2 hours
  15. filtrationThe reaction was filtered
  16. concentrationthe filtrate concentrated
  17. customThe material was purified by silica gel column chromatography (2M NH3 in methanol:CH2Cl2, 2.5:97.5 to 5:95)

Sources & evidence

ORD record
ord-fe2ea965a7eb436bb0be519485b3b296
Source dataset
uspto-grants-2011_08
Patent number
US07989447B2

Reaction notes

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