4-Chloroaniline → HCID 86698996, compound

HRID 63526Notes

Reaction equation

HRID 63526 reaction equation
[CH:1]1([C:4]2[C:5]([N+:15]([O-:17])=[O:16])=[CH:6][C:7]([N+:12]([O-:14])=O)=[C:8]([CH:11]=2)[CH:9]=O)[CH2:3][CH2:2]1.[Cl:18][C:19]1[CH:25]=[CH:24][C:22]([NH2:23])=[CH:21][CH:20]=1.[C-:26]#[N:27].[Na+].C(OC(=O)C)(=O)C>C(O)(=O)C.CO>[Cl:18][C:19]1[CH:25]=[CH:24][C:22]([N:23]2[C:9]([C:26]#[N:27])=[C:8]3[C:7]([CH:6]=[C:5]([N+:15]([O-:17])=[O:16])[C:4]([CH:1]4[CH2:2][CH2:3]4)=[CH:11]3)=[N+:12]2[O-:14])=[CH:21][CH:20]=1

Participants

7

Reactant 4

HCID 78124-ChloroanilineHCID 7918Acetic AnhydrideHCID 8929Sodium Cyanide2×HCID 866664205-Cyclopropyl-2,4-dinitrobenzaldehyde

Product 1

HCID 86698996HCID 86698996, compoundYield 108.4%

Reagents, catalysts & solvents 2

HCID 176Acetic AcidSolventHCID 887MethanolSolvent

Conditions

Temperature
60 °C

Procedure

To a stirred suspension of (iv) (20 g, 0.09 mol) in acetic acid (400 mL) was added 4-chloroaniline (21.6 g, 0.17 mol) and the reaction heated at 60° C. to obtain a complete solution. To this solution was added sodium cyanide (20 g, 0.41 mol) portionwise over 20 min. The reaction mixture was stirred for 5 min whereupon acetic anhydride (6 mL) was added. Upon the formation of a precipitate, an additional quantity of sodium cyanide (20 g, 0.41 mol) was added portionwise. After stirring for 1 h, the reaction mixture was cooled to RT, diluted with MeOH (30 ml) and the solids separated by filtration. The solid cake was dissolved in chloroform (400 ml) and the organics washed with water (2×100 ml), dried (MgSO4) and concentrated in vacuo to give the intermediate 2-(4-chlorophenyl)-5-cyclopropyl-6-nitro-2H-indazole-3-carbonitrile 1-oxide (34.6 g). ESI-MS m/z calculated for [M+H]+: 355.1. found: 355.2. 1H NMR (400 MHz, CDCl3) δ 8.32 (s, 1H), 7.72-7.50 (m, 5H), 2.44-2.30 (m, 1H), 1.18-1.05 (m, 2H), 0.85-0.71 (m, 2H).

Workup

  1. customto obtain a complete solution
  2. additionwas added
  3. temperaturethe reaction mixture was cooled to RT
  4. customthe solids separated by filtration
  5. dissolutionThe solid cake was dissolved in chloroform (400 ml)
  6. washthe organics washed with water (2×100 ml)
  7. dry with materialdried (MgSO4)
  8. concentrationconcentrated in vacuo

Sources & evidence

ORD record
ord-a03cd0f4f77c4da38332abab9ba21338
Source dataset
uspto-grants-2016_09
Patent number
US09447080B2

Reaction notes

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