Hydrochloric Acid → 2-Chlorobenzenesulfonic Acid 3-[(3-amidinophenyl)methoxy]-5-methylphenyl Ester Hydrochloride

HRID 368527Notes

Reaction equation

HRID 368527 reaction equation
[C:1]([C:3]1[CH:4]=[C:5]([CH2:9][O:10][C:11]2[CH:12]=[C:13]([O:18][S:19]([C:22]3[CH:27]=[CH:26][CH:25]=[CH:24][C:23]=3[Cl:28])(=[O:21])=[O:20])[CH:14]=[C:15]([CH3:17])[CH:16]=2)[CH:6]=[CH:7][CH:8]=1)#[N:2].Cl.C(=O)([O-])[O-].[NH4+:34].[NH4+]>C(Cl)Cl.C(O)C>[ClH:28].[C:1]([C:3]1[CH:4]=[C:5]([CH2:9][O:10][C:11]2[CH:12]=[C:13]([O:18][S:19]([C:22]3[CH:27]=[CH:26][CH:25]=[CH:24][C:23]=3[Cl:28])(=[O:21])=[O:20])[CH:14]=[C:15]([CH3:17])[CH:16]=2)[CH:6]=[CH:7][CH:8]=1)(=[NH:34])[NH2:2]

Participants

6

Reactant 3

HCID 313Hydrochloric AcidHCID 517111Ammonium CarbonateHCID 540597372-Chlorobenzenesulfonic acid 3-[(3-cyanophenyl)methoxy]-5-methylphenyl ester

Product 1

HCID 865837232-Chlorobenzenesulfonic Acid 3-[(3-amidinophenyl)methoxy]-5-methylphenyl Ester HydrochlorideYield 95.9%

Reagents, catalysts & solvents 2

HCID 702EthanolSolventHCID 6344DichloromethaneSolvent2×

Procedure

To a solution of 2-chlorobenzenesulfonic acid 3-[(3-cyanophenyl) methoxy]-5-methylphenyl ester (207 mg, 0.5 mmol), as prepared in the preceding step, in methylene chloride (10 mL) was added 37% HCl in ethanol (10 mL) at 0° C. The mixture was allowed to stand at 0° C. for 3 days. The solvent was evaporated in vacuo and the residue was co-evaporated with methylene chloride several times. The residue was dissolved in ethanol (10 mL) and ammonium carbonate (192 mg, 2.0 mmol) was added at 0° C. The mixture was stirred at room temperature overnight. Methylene chloride (150 mL) was added to the mixture. The methylene chloride solution was washed with 10% K2CO3 (2×50 mL) and dried over K2CO3. The solvent was removed in vacuo, HCl in methanol (30 mL) was added, and the solvent again removed in vacuo. The residue was purified by flash chromatography (10% methanol in methylene chloride) to give the title compound as a white solid (112 mg, 48%). 1H-NMR (300 MHz, DMSO-d6) δ 2.23 (s, 3 H), 5.11 (s, 2 H), 6.54 (s, 1 H), 6.56 (s, 1 H), 6.88 (s, 1 H), 7.58 (t, 1 H, J=6.5 Hz), 7.61 (t, 1 H, J=12.2 Hz), 7.66 (d, 1 H, J=3.9 Hz), 7.73-7.95 (m, 5 H), and 9.40 (br s, 4 H). Mass spectrum (MALDI-TOF, sinapinic acid matrix) calcd. for C21H19N2O4SCl: 431.1 (M+H), 453.1 (M+Na). Found: 431.0, 452.9.

Workup

  1. customThe solvent was evaporated in vacuo
  2. dissolutionThe residue was dissolved in ethanol (10 mL)
  3. washThe methylene chloride solution was washed with 10% K2CO3 (2×50 mL)
  4. dry with materialdried over K2CO3
  5. customThe solvent was removed in vacuo, HCl in methanol (30 mL)
  6. additionwas added
  7. customthe solvent again removed in vacuo
  8. customThe residue was purified by flash chromatography (10% methanol in methylene chloride)

Sources & evidence

ORD record
ord-2285c250b4814b3795f0032545e1bfd4
Source dataset
uspto-grants-2000_10
Patent number
US06133315

Reaction notes

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