5-Chloro-2-methylbenzonitrile → 5-Chloro-N-hydroxy-2-methyl-benzamidine

HRID 714237Notes

Reaction equation

HRID 714237 reaction equation
[Cl:1][C:2]1[CH:3]=[CH:4][C:5]([CH3:10])=[C:6]([CH:9]=1)[C:7]#[N:8].Cl.[NH2:12][OH:13].C(=O)(O)[O-].[Na+]>CO>[Cl:1][C:2]1[CH:3]=[CH:4][C:5]([CH3:10])=[C:6]([CH:9]=1)[C:7](=[N:12][OH:13])[NH2:8]

Participants

5

Reactant 3

HCID 1427435-Chloro-2-methylbenzonitrileHCID 443297Hydroxyamine hydrochlorideHCID 516892Sodium Bicarbonate

Product 1

HCID 52391465-Chloro-N-hydroxy-2-methyl-benzamidineYield 98.6%

Reagents, catalysts & solvents 1

HCID 887MethanolSolvent2×

Procedure

A solution of 5-chloro-2-methylbenzonitrile (1.5 g, 9.89 mmol), hydroxylamine hydrochloride (1.38 g, 19.79 mmol) and sodium bicarbonate (3.33 g, 39.6 mmol) in methanol (100 mL) was heated to 70° C. for 6 h. The mixture was cooled to room temperature and diluted with methanol (100 mL). The mixture was filtered, and the filtrate was concentrated, diluted with water and extracted with EtOAc (100 mL, 3×). The EtOAc extract was dried over MgSO4, filtered and concentrated under reduced pressure to obtain crude 5-chloro-N′-hydroxy-2-methylbenzimidamide (1.8 g, 99% crude yield). LC/MS: m/e 185.0 (M+H)+. 1H NMR (400 MHz, CD3OD) δ ppm 7.30-7.29 (2 H, m), 7.23 (1 H, d), 2.36 (3H, s).

Workup

  1. filtrationThe mixture was filtered
  2. concentrationthe filtrate was concentrated
  3. additiondiluted with water
  4. extractionextracted with EtOAc (100 mL, 3×)
  5. extractionThe EtOAc extract
  6. dry with materialwas dried over MgSO4
  7. filtrationfiltered
  8. concentrationconcentrated under reduced pressure

Sources & evidence

ORD record
ord-5a5e2bac7d864265b36a47b185e8d51f
Source dataset
uspto-grants-2015_11
Patent number
US09187437B2

Reaction notes

Loading…