Dichloromethane → HCID 178483702, compound

HRID 1668484Notes

Reaction equation

HRID 1668484 reaction equation
[CH3:1][N:2]([CH3:15])[CH2:3][CH2:4][N:5]1[C:13]2[C:8](=[CH:9][C:10]([NH2:14])=[CH:11][CH:12]=2)[CH:7]=[CH:6]1.I.[S:17]1[CH:21]=[CH:20][CH:19]=[C:18]1[C:22](SC)=[NH:23].ClCCl>C(O)C.C(=O)(O)[O-].[Na+]>[CH3:1][N:2]([CH3:15])[CH2:3][CH2:4][N:5]1[C:13]2[C:8](=[CH:9][C:10]([NH:14][C:22]([C:18]3[S:17][CH:21]=[CH:20][CH:19]=3)=[NH:23])=[CH:11][CH:12]=2)[CH:7]=[CH:6]1

Participants

6

Reactant 3

HCID 6344DichloromethaneHCID 11206483462649-11-2HCID 66704664Methyl thiophene-2-carbimidothioate hydroiodide

Product 1

HCID 178483702HCID 178483702, compoundYield 22%

Reagents, catalysts & solvents 2

HCID 702EthanolSolventHCID 516892Sodium BicarbonateSolvent

Procedure

A solution of compound 92 (0.104 g, 0.512 mmol) in absolute ethanol (3 mL) was treated with methyl thiophene-2-carbimidothioate hydroiodide (0.290 g, 1.02 mmol) at room temperature and the resulting mixture was stirred for 3 hours. The reaction was diluted with saturated aqueous sodium bicarbonate (5 mL) followed by dichloromethane (30 mL) and transferred to a separatory funnel. The aqueous was extracted twice more with dichloromethane (2×30 mL). The combined organics were washed with brine and dried (Na2SO4). Solvent was evaporated and crude was purified by column chromatography (2M ammonia in methanol:dichloromethane, 5:95). Product was dried under high vacuum. HPLC revealed a 10% impurity. A second purification by column chromatography using less polar solvent conditions (2M ammonia in methanol:dichloromethane, 0:100-2.5:97.5) afforded pure product 93 (35 mg, 22%) as a yellow oil. 1H NMR (CDCl3) δ 7.43 (d, J=4.5 Hz, 2H), 7.33 (d, J=8.7 Hz, 1H), 7.21 (d, J=1.2 Hz, 1H), 7.13 (d, J=3.0 Hz, 1H), 7.08 (t, J=4.2 Hz, 1H), 6.67 (dd, J=1.8, 8.7 Hz, 1H), 6.43 (d, J=3.0 Hz, 1H), 4.22 (t, J=7.5 Hz, 2H), 2.72 (t, J=7.5 Hz, 2H), 2.31 (s, 6H); ES-MS (m/z, %): 313 (M+1); ESI-HRMS calculated for C17H21N4S (MH+): 313.1481, Observed: 313.1467.

Workup

  1. customtransferred to a separatory funnel
  2. extractionThe aqueous was extracted twice more with dichloromethane (2×30 mL)
  3. washThe combined organics were washed with brine
  4. dry with materialdried (Na2SO4)
  5. customSolvent was evaporated
  6. customcrude was purified by column chromatography (2M ammonia in methanol:dichloromethane, 5:95)
  7. customProduct was dried under high vacuum
  8. customA second purification by column chromatography

Sources & evidence

ORD record
ord-d293c62a9e684771ae772b998d2e12d2
Source dataset
uspto-grants-2011_08
Patent number
US07989447B2

Reaction notes

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