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

HRID 1976087Notes

Reaction equation

HRID 1976087 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: 0 431.0, 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-ff3ff859fa1f4bc8bcabb686543f2c8d
Source dataset
uspto-grants-2001_05
Patent number
US06225302B1

Reaction notes

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