2-Methyl-2-thiopseudourea → HCID 178473457, compound

HRID 900017Notes

Reaction equation

HRID 900017 reaction equation
CS[C:3](=[NH:5])[NH2:4].[CH2:6]([O:8][C:9](Cl)=[O:10])[CH3:7].[OH-].[Na+].O.O.O.C([O-])(=O)C.[Na+].[N:22]1[CH:27]=[CH:26][CH:25]=[C:24]([C:28]2[CH:34]=[CH:33][C:31](N)=[C:30]([N+:35]([O-])=O)[CH:29]=2)[CH:23]=1.C1(C)C=CC(S(O)(=O)=O)=CC=1>O.C(O)C.C(OCC)(=O)C.C(O)(=O)C>[CH2:6]([O:8][C:9](=[O:10])[NH:4][C:3]1[NH:5][C:31]2[CH:33]=[CH:34][C:28]([C:24]3[CH:23]=[N:22][CH:27]=[CH:26][CH:25]=3)=[CH:29][C:30]=2[N:35]=1)[CH3:7]

Participants

11

Reactant 6

HCID 51422-Methyl-2-thiopseudoureaHCID 6101p-Toluenesulfonic acidHCID 10928Ethyl chloroformateHCID 14798Sodium HydroxideHCID 104658594-(Pyridin-3-yl)-2-nitroanilineHCID 23665404Sodium Acetate Trihydrate

Product 1

HCID 178473457HCID 178473457, compound

Reagents, catalysts & solvents 4

HCID 176Acetic AcidSolventHCID 702EthanolSolventHCID 962WaterSolventHCID 8857Ethyl AcetateSolvent

Procedure

To a solution of 2-methyl-2-thiopseudourea (151 mg, 0.54 mmol) and ethylchloroformate (0.103 mL, 1.08 mmol) in water (2 mL) at 0° C. was added 25% aqueous sodium hydroxide in a dropwise fashion over 1 hour until the pH stabilized at 8. Enough acetic acid was then added to achieve pH 5 then sodium acetate trihydrate (74 mg, 0.54 mmol) and a solution of 2 (0.54 mmol) in ethanol (3 mL) were added. A catalytic amount of p-toluenesulfonic acid was added and the resulting mixture was heated at reflux for 1 hour. The reaction mixture was then cooled to ambient temperature and diluted with ethyl acetate (50 mL). The organic solution was washed with aqueous NaOH, water, and brine then dried over magnesium sulfate and concentrated in vacuo. The crude product was purified by preparative HPLC to afford compound Ia-11. 1H NMR (CDCl3) δ 9.1 (s, 1H), 8.75 (d, 1H), 8.5 (d, 1H), 7.9 (s, 1H), 7.8 (m, 1H), 7.65 (m, 2H), 4.3 (q, 2H), 1.3 (t, 3H). (M+1)283.

Workup

  1. temperaturethe resulting mixture was heated
  2. temperatureat reflux for 1 hour
  3. washThe organic solution was washed with aqueous NaOH, water, and brine
  4. dry with materialthen dried over magnesium sulfate
  5. concentrationconcentrated in vacuo
  6. customThe crude product was purified by preparative HPLC
  7. customto afford compound Ia-11

Sources & evidence

ORD record
ord-5082138f1b504eeeaceaba81e62f04de
Source dataset
uspto-grants-2008_04
Patent number
USRE040245E1

Reaction notes

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