Methanesulfonic Acid → 1-Ethyl-3-[5-hydroxy-7-(2-pyridyl)-1,3-benzothiazol-2-yl]urea

HRID 712153Notes

Reaction equation

HRID 712153 reaction equation
C([O:8][C:9]1[CH:10]=[C:11]([C:24]2[CH:29]=[CH:28][CH:27]=[CH:26][N:25]=2)[C:12]2[S:16][C:15]([NH:17][C:18]([NH:20][CH2:21][CH3:22])=[O:19])=[N:14][C:13]=2[CH:23]=1)C1C=CC=CC=1.CS(O)(=O)=O>C(Cl)Cl.CCOCC>[CH2:21]([NH:20][C:18]([NH:17][C:15]1[S:16][C:12]2[C:11]([C:24]3[CH:29]=[CH:28][CH:27]=[CH:26][N:25]=3)=[CH:10][C:9]([OH:8])=[CH:23][C:13]=2[N:14]=1)=[O:19])[CH3:22]

Participants

5

Reactant 2

HCID 6395Methanesulfonic AcidHCID 727246171-[5-Benzyloxy-7-(2-pyridyl)-1,3-benzothiazol-2-yl]-3-ethyl-urea

Product 1

HCID 727246181-Ethyl-3-[5-hydroxy-7-(2-pyridyl)-1,3-benzothiazol-2-yl]ureaYield 97%

Reagents, catalysts & solvents 2

HCID 3283Diethyl EtherSolventHCID 6344DichloromethaneSolvent

Procedure

To a stirred solution of 1-[5-benzyloxy-7-(2-pyridyl)-1,3-benzothiazol-2-yl]-3-ethyl-urea (76 g, 0.187 mol) in DCM (1.7 L) was added methane sulfonic acid (270 mL, 4.17 mol) dropwise over 30 min. The reaction mixture was then stirred at rt for 3 h. After the completion of reaction (by TLC), the reaction mass was concentrated under reduced pressure. EtOAc (1 L) was added to the residue and the solution poured carefully onto crushed ice. The pH of the solution was maintained to 8-9 by addition of saturated NaHCO3 solution followed by extraction with EtOAc (3×5 L). The combined organics were washed with water, brine, dried (anhydrous Na2SO4), filtered and concentrated under reduced pressure. The residue thus obtained was stirred in Et2O (1.0 L) for 1 h at rt then filtered to obtain the desired product (57.0 g, 97%). 1H-NMR (DMSO-d6): δ 1.08 (t, J=7.20 Hz, 3H), 3.20 (m, 2H), 6.86 (br s, 1H), 7.0 (s, 1H), 7.46 (s, 2H), 7.96 (m, 1H), 8.10 (m, 1H), 8.76 (m, 1H), 9.59 (br s, 1H) and 10.41 (br s, 1H). LCMS: 315.06 [M+H]+.

Workup

  1. customAfter the completion of reaction (by TLC)
  2. concentrationthe reaction mass was concentrated under reduced pressure
  3. additionEtOAc (1 L) was added to the residue
  4. additionthe solution poured carefully
  5. customonto crushed ice
  6. temperatureThe pH of the solution was maintained to 8-9 by addition of saturated NaHCO3 solution
  7. extractionfollowed by extraction with EtOAc (3×5 L)
  8. washThe combined organics were washed with water, brine
  9. dry with materialdried (anhydrous Na2SO4)
  10. filtrationfiltered
  11. concentrationconcentrated under reduced pressure
  12. customThe residue thus obtained
  13. filtrationthen filtered

Sources & evidence

ORD record
ord-3864ffe345124098a2ee75d4e98bf9ef
Source dataset
uspto-grants-2015_11
Patent number
US09181234B2

Reaction notes

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