Hydrochloric Acid → 4-(Chloromethyl)-N-hydroxybenzimidoyl chloride

HRID 81375Notes

Reaction equation

HRID 81375 reaction equation
[Cl:1][CH2:2][C:3]1[CH:11]=[CH:10][C:6]([CH:7]=[N:8][OH:9])=[CH:5][CH:4]=1.C1C(=O)N([Cl:19])C(=O)C1.Cl.O1CCOCC1>CN(C=O)C>[Cl:1][CH2:2][C:3]1[CH:11]=[CH:10][C:6]([C:7]([Cl:19])=[N:8][OH:9])=[CH:5][CH:4]=1

Participants

6

Reactant 4

HCID 313Hydrochloric AcidHCID 312751,4-DioxaneHCID 31398ChlorosuccinimideHCID 762257374-Chloromethylbenzaldehyde oxime

Product 1

HCID 766866014-(Chloromethyl)-N-hydroxybenzimidoyl chlorideYield 113.9%

Reagents, catalysts & solvents 1

HCID 6228DimethylformamideSolvent

Procedure

4-(chloromethyl)benzaldehyde oxime 5 (15.8 g, 93.16 mmol) was dissolved in DMF (300 mL). NCS (13.69 g, 102.5 mmol) was added in portions and then HCl in dioxane (100 mL of 4 M, 400.0 mmol) was added slowly, cooling the mixture with an ice water bath to moderate the exotherm, keeping internal temperature below 33° C. The mixture was then stirred at room temperature for 1 hour. The solution was partitioned between EtOAc and water and the organic extract was washed with water and brine (5×200 ml), dried over MgSO4 and concentrated under reduced pressure to give a colourless solid (21.65 g, 95%). 1H NMR (400 MHz, CDCl3) δ 4.63 (2H, s), 7.45 (2H, d, J=8 Hz), 7.86 (2H, d, J=8 Hz), 8.36 (1H, s).

Workup

  1. temperaturecooling the mixture with an ice water bath
  2. customtemperature below 33° C
  3. customThe solution was partitioned between EtOAc and water
  4. extractionthe organic extract
  5. washwas washed with water and brine (5×200 ml)
  6. dry with materialdried over MgSO4
  7. concentrationconcentrated under reduced pressure

Sources & evidence

ORD record
ord-20972544c6a147f59e18b4913de17036
Source dataset
uspto-grants-2014_09
Patent number
US08846686B2

Reaction notes

Loading…