Hydrochloric Acid → 2-Chlorobenzenesulfonic acid 3-[(4-amidinophenyl)methoxy]-5-methylphenyl ester hydrochloride

HRID 368540Notes

Reaction equation

HRID 368540 reaction equation
[C:1]([C:3]1[CH:8]=[CH:7][C:6]([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:5][CH:4]=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:8]=[CH:7][C:6]([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:5][CH:4]=1)(=[NH:34])[NH2:2]

Participants

6

Reactant 3

HCID 313Hydrochloric AcidHCID 517111Ammonium CarbonateHCID 543888062-Chlorobenzenesulfonic acid 3-[(4-cyanophenyl)methoxy]-5-methylphenyl ester

Product 1

HCID 867552142-Chlorobenzenesulfonic acid 3-[(4-amidinophenyl)methoxy]-5-methylphenyl ester hydrochlorideYield 147.6%

Reagents, catalysts & solvents 2

HCID 702EthanolSolventHCID 6344DichloromethaneSolvent

Procedure

To a solution of 2-chlorobenzenesulfonic acid 3-[(4-cyanophenyl)methoxy]-5-methylphenyl ester (414 mg, 1.0 mmol), as prepared in the preceding step, in methylene chloride (10 mL) was added 37% HCl in ethanol (20 mL) at 0° C. The mixture was stirred at room temperature for 2 days. The solvent was evaporated and the residue was co-evaporated with methylene chloride several times. The residue was then dissolved in ethanol (20 mL) and ammonium carbonate (385 mg, 4.0 mmol) was added at 0° C. The mixture was stirred at room temperature overnight. The reaction mixture was partitioned between methylene chloride and 10% K2CO3 (50 mL). The organic phase was washed with 50 mL of 10% K2CO3 and dried over K2CO3. The solvent was removed in vacuo. The residue was diluted with CH2Cl2, treated with HCl in methanol (30 mL), and concentrated. The residue was then purified by crystallization (methanol and ethyl acetate) to give the title compound as a white solid (345 mg, 74%). 1H-NMR (300 MHz, DMSO-d6) δ 2.21 (s, 3H), 5.16 (s, 2H), 6.53 (t, 2 H, J=9.3 Hz)), 6.86 (s, 1H), 7.55-7.62 (m, 3H), 7.82-7.89 (m, 4 H), 7.93 (d, 1H, J=4.0 Hz), 9.24 (br s, 2 H) and 9.44 (br s, 2 H). Mass spectrum (MALDI-TOF, sinapinic acid matrix) calcd. for C21H19N2ClO4S: 431.1 (M+H). Found: 431.1.

Workup

  1. customThe solvent was evaporated
  2. dissolutionThe residue was then dissolved in ethanol (20 mL)
  3. stirringThe mixture was stirred at room temperature overnight
  4. customThe reaction mixture was partitioned between methylene chloride and 10% K2CO3 (50 mL)
  5. washThe organic phase was washed with 50 mL of 10% K2CO3
  6. dry with materialdried over K2CO3
  7. customThe solvent was removed in vacuo
  8. additionThe residue was diluted with CH2Cl2
  9. additiontreated with HCl in methanol (30 mL)
  10. concentrationconcentrated
  11. customThe residue was then purified by crystallization (methanol and ethyl acetate)

Sources & evidence

ORD record
ord-fa5cd422d289415db3f372bacc7d096a
Source dataset
uspto-grants-2000_10
Patent number
US06133315

Reaction notes

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