Ammonia → Ethyl 2-(carbamothioylamino)-4,5-dimethylthiophene-3-carboxylate

HRID 471510Notes

Reaction equation

HRID 471510 reaction equation
[N:1]([C:4]1[S:5][C:6]([CH3:15])=[C:7]([CH3:14])[C:8]=1[C:9]([O:11][CH2:12][CH3:13])=[O:10])=[C:2]=[S:3].[NH3:16]>ClCCl>[CH3:14][C:7]1[C:8]([C:9]([O:11][CH2:12][CH3:13])=[O:10])=[C:4]([NH:1][C:2]([NH2:16])=[S:3])[S:5][C:6]=1[CH3:15]

Participants

4

Reactant 2

HCID 222AmmoniaHCID 3419522Ethyl 2-isothiocyanato-4,5-dimethylthiophene-3-carboxylate

Product 1

HCID 777992Ethyl 2-(carbamothioylamino)-4,5-dimethylthiophene-3-carboxylateYield 3%

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent

Procedure

To a solution of ethyl 2-isothiocyanato-4,5-dimethylthiophene-3-carboxylate (Example 50b) (1.21 g, 5.27 mmol) in dichloromethane (10 mL) was added ammonia (7 M in MeOH, 1.12 mL, 7.91 mmol) at 0° C. The reaction mixture was then stirred at room temperature for 3 h, quenched with water and extracted with dichloromethane (3×). The combined organic layers were washed with brine, dried over MgSO4, filtered and concentrated. The dark orange residue was purified by chromatography on silica gel (Gradient 0-50% EtOAc in Hexanes) to give the title compound (37.1 mg, 3%). 1H NMR (400 MHz, DMSO-d6) δ 1.32 (t, 3H, J=7.1 Hz), 2.18 (s, 3H), 2.19 (s, 3H), 4.30 (q, 2H, J=7.1 Hz), 8.43 (s, 2H), 11.38 (s, 1H). MS 259 (MH+).

Workup

  1. customquenched with water
  2. extractionextracted with dichloromethane (3×)
  3. washThe combined organic layers were washed with brine
  4. dry with materialdried over MgSO4
  5. filtrationfiltered
  6. concentrationconcentrated
  7. customThe dark orange residue was purified by chromatography on silica gel (Gradient 0-50% EtOAc in Hexanes)

Sources & evidence

ORD record
ord-647731cea6f84fd8b1b8b3724fee061f
Source dataset
uspto-grants-2014_01
Patent number
US08633186B2

Reaction notes

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