Sulfuric Acid → HCID 14280576, compound

HRID 1387708Notes

Reaction equation

HRID 1387708 reaction equation
[NH2:1]/[C:2](/[CH3:6])=[CH:3]\[C:4]#[N:5].[Cl:7][C:8]1[CH:13]=[C:12]([C:14]([F:17])([F:16])[F:15])[CH:11]=[C:10]([Cl:18])[C:9]=1[NH:19]N.S(=O)(=O)(O)O>C(O)C>[NH2:5][C:4]1[N:19]([C:9]2[C:10]([Cl:18])=[CH:11][C:12]([C:14]([F:17])([F:15])[F:16])=[CH:13][C:8]=2[Cl:7])[N:1]=[C:2]([CH3:6])[CH:3]=1

Participants

5

Reactant 3

HCID 1118Sulfuric Acid2×HCID 688223[2,6-Dichloro-4-(trifluoromethyl)phenyl]hydrazineHCID 5325263(2Z)-3-Amino-2-butenenitrile

Product 1

HCID 14280576HCID 14280576, compound

Reagents, catalysts & solvents 1

HCID 702EthanolSolvent

Procedure

3-Aminocrotononitrile (5.0 g) was added to a stirred solution of 2,6-dichloro-4-trifluoromethylphenylhydrazine (15.0 g) in ethanol (100 ml), then the resulting solution treated with concentrated sulphuric acid (1.0 ml) to produce a white solid precipitate. The mixture was heated under reflux for 6 hours, allowed to cool and stirred for a further 18 hours at room temperature; this cycle was repeated, then more concentrated sulphuric acid (4 ml) added. The reaction mixture was heated at 60° C. for 8 hours, allowed to cool, stirred at room temperature for 18 hours and evaporated under reduced pressure. The resulting orange oil was partitioned between dichloromethane (100 ml) and water (100 ml), then the organic phase dried, allowed to stand at room temperature for 18 hours and filtered to remove some white solid material. The filtrate was evaporated under reduced pressure to give an orange oil which was triturated with hot hexane. On cooling, the hexane solution deposited a yellow oil which slowly crystallised to furnish the title compound as a white solid, m.p. 80-83° C. Found: C, 42.73; H, 2.62; N, 13.58. C11H8Cl2F3N3 requires 42.61; H, 2.60; N, 13.55%. δ(CDCl3): 2.25 (s,3H), 3.48 (br.s,2H), 5.52 (s,1H), 7.70 (s,2H). MS (thermospray): M/Z [M] 310.0; C11H8Cl2F3N3 requires 310.12.

Workup

  1. customto produce a white solid precipitate
  2. temperatureThe mixture was heated
  3. temperatureunder reflux for 6 hours
  4. temperatureto cool
  5. temperatureThe reaction mixture was heated at 60° C. for 8 hours
  6. temperatureto cool
  7. stirringstirred at room temperature for 18 hours
  8. customevaporated under reduced pressure
  9. customThe resulting orange oil was partitioned between dichloromethane (100 ml) and water (100 ml)
  10. customthe organic phase dried
  11. waitto stand at room temperature for 18 hours
  12. filtrationfiltered
  13. customto remove some white solid material
  14. customThe filtrate was evaporated under reduced pressure
  15. customto give an orange oil which
  16. customwas triturated with hot hexane
  17. temperatureOn cooling
  18. customslowly crystallised

Sources & evidence

ORD record
ord-d0932070fa7241cb9da8888b8966b183
Source dataset
uspto-grants-2001_07
Patent number
US06268509B1

Reaction notes

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