2-Aminothiophenol → HCID 69994767, compound

HRID 1357370Notes

Reaction equation

HRID 1357370 reaction equation
[H-].[Na+].[NH2:3][C:4]1[CH:9]=[CH:8][CH:7]=[CH:6][C:5]=1[SH:10].[CH3:11][O:12][C:13](=[O:27])[C:14]1[C:15](=[CH:20][C:21]([N+]([O-])=O)=[CH:22][CH:23]=1)[C:16]([O:18][CH3:19])=[O:17]>CN(C=O)C>[CH3:19][O:18][C:16](=[O:17])[C:15]1[C:14](=[CH:23][C:22]([S:10][C:5]2[CH:6]=[CH:7][CH:8]=[CH:9][C:4]=2[NH2:3])=[CH:21][CH:20]=1)[C:13]([O:12][CH3:11])=[O:27]

Participants

5

Reactant 3

HCID 87132-AminothiophenolHCID 24758Sodium hydrideHCID 691191,2-Benzenedicarboxylic acid, 4-nitro-, 1,2-dimethyl ester

Product 1

HCID 69994767HCID 69994767, compoundYield 51%

Reagents, catalysts & solvents 1

HCID 6228DimethylformamideSolvent2×

Conditions

Temperature
-25 °C

Procedure

Sodium hydride, 60% dispersion in mineral oil, (0.18 g, 4.5 mmol) was added to a solution of 2-aminothiophenol (0.59 ml, 4.0 mmol) in dry DMF (5 ml) at −20° C. The mixture was stirred at −20 to −30° C. for 10 minutes. A solution of 4-nitrophthalic acid dimethyl ester (0.83 g, 3.5 mmol) in dry DMF (5 ml) was added dropwise. The reaction mixture was stirred at −30° C.±5° C. for 1 hour and then at room temperature for 20 hours, poured into icewater (20 ml) and finally extracted with ethyl acetate (3×25 ml). The combined organic phase was washed with water (25 ml), dried over magnesium sulphate, and evaporated to dryness in vacuo. The crude product was purified on silica gel (eluent: methylene chloride) to give 4-(2-aminophenylsulfenyl)phthalic acid dimethyl ester (yield: 0.56 g (51%)) as a golden oil. 1H—NMR (CDCl3) in ppm: δ 3.85 (3H,s); 3.87 (3H,s); 4.29 (2H,broad s); 6.72-685 (2H,m); 7.07 (1H,d.d.); 7.23-7.34 (2H,m); 7.43 (1H,d.d.): 7.63 (1H,d).

Workup

  1. stirringThe reaction mixture was stirred at −30° C.±5° C. for 1 hour
  2. waitat room temperature for 20 hours
  3. additionpoured into icewater (20 ml)
  4. extractionfinally extracted with ethyl acetate (3×25 ml)
  5. washThe combined organic phase was washed with water (25 ml)
  6. dry with materialdried over magnesium sulphate
  7. customevaporated to dryness in vacuo
  8. customThe crude product was purified on silica gel (eluent: methylene chloride)

Sources & evidence

ORD record
ord-de5363c1b7a54d06b300719f686f044e
Source dataset
uspto-grants-2003_07
Patent number
US06590118B1

Reaction notes

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