Sulfuric Acid → 2-(2,6-Dichloro-4-trifluoromethylphenylhydrazono)succinonitrile

HRID 2287648Notes

Reaction equation

HRID 2287648 reaction equation
N([O-])=O.[Na+].S(=O)(=O)(O)O.[Cl:10][C:11]1[CH:16]=[C:15]([C:17]([F:20])([F:19])[F:18])[CH:14]=[C:13]([Cl:21])[C:12]=1[NH:22]C1C=CC=CC=1.[K].OC=[C:32]([CH2:35][C:36]#[N:37])[C:33]#[N:34].C([O-])(=O)C.[Na+].[OH-].[NH4+:44]>O.C(O)(=O)C.ClCCl>[Cl:21][C:13]1[CH:14]=[C:15]([C:17]([F:18])([F:19])[F:20])[CH:16]=[C:11]([Cl:10])[C:12]=1[NH:22][N:44]=[C:32]([CH2:35][C:36]#[N:37])[C:33]#[N:34]

Participants

10

Reactant 6

HCID 1118Sulfuric Acid2×HCID 14923Ammonium HydroxideHCID 517045Sodium AcetateHCID 23668193Sodium Nitrite2×HCID 544907242,6-Dichloro-4-trifluoromethylphenylanilineHCID 867554972-Hydroxymethylenesuccinonitrile potassium salt

Product 1

HCID 853091952-(2,6-Dichloro-4-trifluoromethylphenylhydrazono)succinonitrile

Reagents, catalysts & solvents 3

HCID 176Acetic AcidSolvent4×HCID 962WaterSolventHCID 6344DichloromethaneSolvent

Conditions

Temperature
80 °C

Procedure

Sodium nitrite (3.9 g) was added to stirred concentrated sulfuric acid (12.8 ml) and heated at 80° C. until dissolved. Acetic acid (25 ml) was added at 30° C. A mixture of 2,6-dichloro-4-trifluoromethylphenylaniline (10.0 g) and acetic acid (25 ml) was added over 10 minutes at 20° C. maintaining below 25° C. The mixture was heated at 55° C. for 50 minutes, and further sodium nitrite (0.65 g) and acetic acid (10 ml) added, and after 20 minutes heated to 70° C. and sulfuric acid (2.8 ml) added. After 20 minutes the cooled mixture was added to a mixture of 2-hydroxymethylenesuccinonitrile potassium salt (7.6 g) and sodium acetate (35.6 g) in water and acetic acid (70 ml) at 10° C. After warming to 20° C. during 1 hour, dichloromethane was added followed by ammonium hydroxide solution (210 ml) to give a pH of 8. The organic phase was separated, washed (water and brine), dried (sodium sulfate) and evaporated to give the title compound as a red-brown solid (18.1 g). Recrystallization from hexane/t-butyl methyl ether) gave the pure title compound (6.85 g), m.p. 80-82° C., NMR 3.6 (s, 2H), 7.66 (s, 2H), 9.03 (s, 1H exchangeable with D2O).

Workup

  1. dissolutionuntil dissolved
  2. additionwas added over 10 minutes at 20° C.
  3. temperaturemaintaining below 25° C
  4. temperatureThe mixture was heated at 55° C. for 50 minutes
  5. temperatureafter 20 minutes heated to 70° C.
  6. temperatureAfter warming to 20° C. during 1 hour
  7. customto give a pH of 8
  8. customThe organic phase was separated
  9. washwashed (water and brine)
  10. dry with materialdried (sodium sulfate)
  11. customevaporated

Sources & evidence

ORD record
ord-82dbe3ec955e4daf933054f09ad76716
Source dataset
uspto-grants-2000_07
Patent number
US06084105

Reaction notes

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