Ethyl Methanesulfonate → HCID 178477475, compound

HRID 863463Notes

Reaction equation

HRID 863463 reaction equation
[C:1]1([CH2:7][N:8]([CH3:21])[CH2:9][CH2:10][C:11]2[CH:16]=[CH:15][C:14]([NH:17][C:18]([NH2:20])=[S:19])=[CH:13][CH:12]=2)[CH:6]=[CH:5][CH:4]=[CH:3][CH:2]=1.CS(O)(=O)=O.CS(O[CH2:32][CH3:33])(=O)=O.C([O-])(=O)C.[NH4+].C(=O)([O-])[O-].[Na+].[Na+].C(O)(=O)/C=C\C(O)=O>CO.C(OCC)(=O)C.C(OCC)C.O.C(O)C>[C:1]1([CH2:7][N:8]([CH3:21])[CH2:9][CH2:10][C:11]2[CH:12]=[CH:13][C:14]([NH:17][C:18]([S:19][CH2:32][CH3:33])=[NH:20])=[CH:15][CH:16]=2)[CH:2]=[CH:3][CH:4]=[CH:5][CH:6]=1

Participants

12

Reactant 6

HCID 6113Ethyl Methanesulfonate2×HCID 6395Methanesulfonic AcidHCID 10340Sodium CarbonateHCID 444266Maleic AcidHCID 517165Ammonium AcetateHCID 19696466HCID 19696466, compound

Product 1

HCID 178477475HCID 178477475, compound

Reagents, catalysts & solvents 5

HCID 702EthanolSolventHCID 887MethanolSolvent2×HCID 962WaterSolventHCID 3283Diethyl EtherSolventHCID 8857Ethyl AcetateSolvent2×

Conditions

Temperature
-20 °C

Procedure

1-(4-(2-((Phenylmethyl)(methyl)amino)ethyl)phenyl)-2-thiourea (step (f), 0.30 g) was suspended in 200 ethanol (2.5 ml), and the mixture was treated with methanesulfonic acid (0.065 ml) and then ethyl methanesulfonate (0.12 ml). After 3 hours at 100° C., TLC on C18 silica with 80% methanol/20% water with 0.8% ammonium acetate showed incomplete conversion to product. At this point additional ethyl methanesulfonate (0.20 g) was added and the mixture refluxed for one hour. After stirring overnight, the crude reaction product was treated with ethyl acetate (50 ml) and water (50 ml). The aqueous layer was treated with sodium carbonate (0.25 g) and extracted with diethyl ether (20 ml). The remaining aqueous layer was treated with sodium bicarbonate (1 g) and extracted with of diethyl ether (20 ml). The ether layers were identical by TLC and were combined, dried with sodium sulfate and evaporated to yield the free base which was then treated with maleic acid (0.24 g) in methanol (1 ml), then diluted with ethyl acetate (4 ml) followed by diethyl ether (25 ml), giving an oil. The solvents were decanted, and the resulting solids were dissolved in hot isopropanol (20 ml) and cooled to -20° C. The resulting solids were collected and air dried to provide N-(4-(2-((phenylmethyl)(methyl)amino)ethyl)phenyl) carbamimidothioic acid, ethyl ester, 0.34 g, m.p. 136°-137° C.

Workup

  1. temperaturethe mixture refluxed for one hour
  2. customthe crude reaction product
  3. extractionextracted with diethyl ether (20 ml)
  4. additionThe remaining aqueous layer was treated with sodium bicarbonate (1 g)
  5. extractionextracted with of diethyl ether (20 ml)
  6. dry with materialdried with sodium sulfate
  7. customevaporated
  8. customto yield the free base which
  9. customgiving an oil
  10. customThe solvents were decanted
  11. dissolutionthe resulting solids were dissolved in hot isopropanol (20 ml)
  12. customThe resulting solids were collected
  13. customair dried

Sources & evidence

ORD record
ord-62065a6484e94b249af33b89089d0479
Source dataset
uspto-grants-1998_02
Patent number
US05721247

Reaction notes

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