Methane → HCID 178505401, Verbindung

HRID 235295

Reaktionsgleichung

Reaktionsgleichung von HRID 235295
[NH2:1][C:2]1[CH:7]=[C:6]([F:8])[C:5]([Cl:9])=[CH:4][C:3]=1[NH2:10].[OH-].[K+].[C:13](=S)=[S:14].C>O.C(O)C>[Cl:9][C:5]1[C:6]([F:8])=[CH:7][C:2]2[N:1]=[C:13]([SH:14])[NH:10][C:3]=2[CH:4]=1

Komponenten

7

Edukt 4

HCID 297Methane2×HCID 6348Carbon DisulfideHCID 14797Potassium HydroxideHCID 7357734-Chloro-5-fluoro-1,2-phenylenediamine

Produkt 1

HCID 178505401HCID 178505401, VerbindungAusbeute 575,7 %

Reagenzien, Katalysatoren, Lösungsmittel 2

HCID 702EthanolLösungsmittelHCID 962WaterLösungsmittel

Versuchsvorschrift

The procedure of Van Allan and Deacon, Org. Synth. Coll. Vol. IV, 569, was adapted. A mixture of 1,2-diamino-4-chloro-5-fluorobenzene (528 mg, 3.29 mmol, Aldrich), potassium hydroxide (202 mg, 0.36 mmol), carbon disulfide (280 mg, 0.36 mmol), 95% ethanol (3 mL) and water (0.45 mL) was heated under reflux for 3 h. Activated charcoal (120 mg) was then added cautiously, and after the mixture has been heated at the refluxing temperature for 10 min the activated charcoal was removed by filtration. The filtrate was heated to 60°-70° C., warm water (3 mL) was added, and then acetic acid (0.25 mL) in water (0.5 mL) was added with good stirring for 4 h. The mixture was placed in a refrigerator overnight to give a mixture of brown and white crystals. The brown crystals were removed by washing with chloroform (5 mL). Recrystallization from hot EtOH/H2O gave pure title compound (420 mg, 63.5%, purity >99.57% by HPLC) as a white cubic crystals; top: 294°-6° C. (sub. from 250° C.). IR (KBr, cm-1): 3443, 3131, 3075, 1618, 1506, 1487, 1462. 1H NMR (DMSO-d6): δ 7.169 (d, J=9 Hz, 1H); 7.245 (d, J=6.6 Hz, 1H); 12.758 (s, 2H). HRMS: calcd for C7H4ClFN2S (M+) m/z: 201.9766, Found: 201.9779.

Aufarbeitung

  1. temperaturewas heated
  2. temperatureunder reflux for 3 h
  3. customwas removed by filtration
  4. temperatureThe filtrate was heated to 60°-70° C.
  5. temperaturewarm water (3 mL)
  6. additionwas added
  7. additionacetic acid (0.25 mL) in water (0.5 mL) was added
  8. customwas placed in a refrigerator overnight
  9. customto give
  10. additiona mixture of brown and white crystals
  11. customThe brown crystals were removed
  12. washby washing with chloroform (5 mL)
  13. customRecrystallization from hot EtOH/H2O

Quellen und Nachweise

ORD-Eintrag
ord-cef5c72db3c94602a83a49021181bf9b
Quelldatensatz
uspto-grants-1997_01
Patentnummer
US05597922

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