Methyl thiophene-2-carbimidothioate hydroiodide → HCID 178464027, compound

HRID 1668441Notes

Reaction equation

HRID 1668441 reaction equation
[CH2:1]([N:3]([CH2:30][CH3:31])[CH2:4][CH2:5][N:6]1[C:14]2[C:9](=[CH:10][C:11]([N+:15]([O-])=O)=[CH:12][CH:13]=2)[CH:8]=[C:7]1[CH2:18][C:19]1[CH:24]=[CH:23][C:22]([O:25][C:26]([F:29])([F:28])[F:27])=[CH:21][CH:20]=1)[CH3:2].I.CS[C:35]([C:37]1[S:38][CH:39]=[CH:40][CH:41]=1)=[NH:36]>C(O)C.C(OCC)C.[Pd]>[CH2:1]([N:3]([CH2:30][CH3:31])[CH2:4][CH2:5][N:6]1[C:14]2[C:9](=[CH:10][C:11]([NH:15][C:35]([C:37]3[S:38][CH:39]=[CH:40][CH:41]=3)=[NH:36])=[CH:12][CH:13]=2)[CH:8]=[C:7]1[CH2:18][C:19]1[CH:24]=[CH:23][C:22]([O:25][C:26]([F:29])([F:28])[F:27])=[CH:21][CH:20]=1)[CH3:2]

Participants

6

Reactant 2

HCID 66704664Methyl thiophene-2-carbimidothioate hydroiodideHCID 67340621HCID 67340621, compound

Product 1

HCID 178464027HCID 178464027, compoundYield 53.1%

Reagents, catalysts & solvents 3

HCID 23938PalladiumCatalystHCID 702EthanolSolventHCID 3283Diethyl EtherSolvent

Procedure

Compound 9 (75 mg, 0.172 mmol) was dissolved in anhydrous ethanol (5 mL) in a dry argon purged flask. Palladium, 10wt % on activated carbon (18.3 mg, 0.0172 mmol) is quickly added and the atmosphere from the flask evacuated by vacuum pump and replaced with hydrogen from a balloon. The atmosphere is evacuated from the flask and replaced with hydrogen twice more and the mixture stirred under a hydrogen atmosphere at room temperature. After 3 hours, thin layer chromatography (2M NH3 in MeOH:CH2Cl2, 2.5:97.5) shows complete conversion to 10, which is utilized without isolation. The mixture is filtered through a pad of celite to remove insolubles, the pad washed with anhydrous ethanol (5 mL) and the ethanolic solution of the amine 10 is charged to a small, argon purged flask fitted with a magnetic stirbar. Thiophene-2-carboximidothioic acid methyl ester hydroiodide (63.8 mg, 0.224 mmol) is added to the flask and the reaction was stirred under argon at ambient temperature for 45 hours. The solution was diluted with diethyl ether (100 ml) and cooled in an ice bath. No precipitate formed thus the solvent was evaporated. The residue was purified using silica gel column chromatography (2M NH3 in MeOH:CH2Cl2, 2.5:97.5 to 5:95) to afford a pale yellow residue 11 (47 mg, 53.0%). 1H NMR (MeOD) δ 0.98 (t, 6H, J=7.1 Hz), 2.47-2.56 (2×m, 6H), 4.13 (t, 2H, J=7.1 Hz), 4.24 (s, 2H), 6.24 (s, 1H), 6.84 (dd, 1H, J=8.4, 1.6 Hz), 7.09-7.13 (m, 2H), 7.17-7.24 (m, 2H), 7.33-7.39 (m, 3H), 7.56 (d, 1H, J=5.2 Hz), 7.64 (d, 1H, J=3.7 Hz); ESI-MS (m/z, %): 515 (MH+, 100%).

Workup

  1. customthe atmosphere from the flask evacuated by vacuum pump
  2. customThe atmosphere is evacuated from the flask
  3. filtrationThe mixture is filtered through a pad of celite
  4. customto remove insolubles
  5. washthe pad washed with anhydrous ethanol (5 mL)
  6. additionthe ethanolic solution of the amine 10 is charged to a small, argon purged flask
  7. customfitted with a magnetic stirbar
  8. stirringthe reaction was stirred under argon at ambient temperature for 45 hours
  9. temperaturecooled in an ice bath
  10. customNo precipitate formed thus the solvent
  11. customwas evaporated
  12. customThe residue was purified

Sources & evidence

ORD record
ord-d8c2ec32a8af48ee8f3d28615c0962f4
Source dataset
uspto-grants-2011_08
Patent number
US07989447B2

Reaction notes

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