Methane → HCID 178527798, compound

HRID 439468Notes

Reaction equation

HRID 439468 reaction equation
[NH2:1][C:2]1[CH:7]=[C:6]([Cl: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:8][C:6]1[C:5]([Cl:9])=[CH:4][C:3]2[N:10]=[C:13]([SH:14])[NH:1][C:2]=2[CH:7]=1

Participants

7

Reactant 4

HCID 297Methane2×HCID 6348Carbon DisulfideHCID 14797Potassium HydroxideHCID 792974,5-Dichloro-1,2-phenylenediamine

Product 1

HCID 178527798HCID 178527798, compoundYield 86.4%

Reagents, catalysts & solvents 2

HCID 702EthanolSolventHCID 962WaterSolvent

Procedure

The procedure of Van Allan, J. A. V. and Deacon, B. D., Organic Synthesis. IV:569 was adapted. A mixture of 1,2-diamino-4,5-dichlorobenzene (510 mg, 2.88 mMol, Aldrich), potassium hydroxide (190 mg, 3.40 mMol), carbon disulfide (260 mg, 3.40 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 overnight. The mixture was placed in a refrigerator for 3 h to get two crystals (brown and white). The brown crystals were removed by washing with chloroform (5 mL). Recrystallization from hot EtOH/H2O gave pure 5,6-dichloro-2-mercaptobenzimidazole (545 mg, 86%) as white long needles. Mp was measured: the color of 5,6-dichloro-2-mercaptobenzimidazole changed to yellow at 303° C.; the decomposition of 5,6-dichloro-2-mercaptobenzimidazole is obvious at 305° C. and it melted to a black liquid at 308°-10° C. IR (KBr, cm-1): 3447; 3107; 3043; 1607; 1496; 1461. NMR (1H, DMSO-d6): δ7.305 (s, 2H); 12.781 (s, 2H). HRMS: calcd for C7H4Cl2N2S (M+) m/z: 217.9425, Found: 217.9482.

Workup

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

Sources & evidence

ORD record
ord-7008a62a6def4daab43e4f37c3e72a72
Source dataset
uspto-grants-1996_05
Patent number
US05514680

Reaction notes

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