Sodium hydride → [3-Chloro-5-(trifluoromethyl)-2-pyridinyl][(diphenylmethylene)amino]acetonitrile

HRID 987001Notes

Reaction equation

HRID 987001 reaction equation
[H-].[Na+].[CH:3]1[CH:8]=[CH:7][C:6]([C:9]([C:14]2[CH:19]=[CH:18][CH:17]=[CH:16][CH:15]=2)=[N:10][CH2:11][C:12]#[N:13])=[CH:5][CH:4]=1.Cl[C:21]1[C:26]([Cl:27])=[CH:25][C:24]([C:28]([F:31])([F:30])[F:29])=[CH:23][N:22]=1.[Cl-].[NH4+]>CN(C)C=O.C(OCC)C.C(O)C>[Cl:27][C:26]1[C:21]([CH:11]([N:10]=[C:9]([C:14]2[CH:19]=[CH:18][CH:17]=[CH:16][CH:15]=2)[C:6]2[CH:7]=[CH:8][CH:3]=[CH:4][CH:5]=2)[C:12]#[N:13])=[N:22][CH:23]=[C:24]([C:28]([F:31])([F:30])[F:29])[CH:25]=1

Participants

8

Reactant 4

HCID 24758Sodium hydrideHCID 25517Ammonium ChlorideHCID 1122342,3-Dichloro-5-(trifluoromethyl)pyridineHCID 612957[(Diphenylmethylene)amino]acetonitrile

Product 1

HCID 22988174[3-Chloro-5-(trifluoromethyl)-2-pyridinyl][(diphenylmethylene)amino]acetonitrile

Reagents, catalysts & solvents 3

HCID 702EthanolSolventHCID 3283Diethyl EtherSolventHCID 6228DimethylformamideSolvent3×

Conditions

Temperature
0 °C

Procedure

To a suspension of 60% sodium hydride (4.0 g) in dry dimethylformamide at 0-2° C. under nitrogen was dropwise added a solution of N-(diphenylmethylene)aminoacetonitrile (11.1 g) in dry dimethylformamide (60 ml) and the mixture was stirred for 1 hour at 0° C., 2,3-Dichloro-5-trifluoromethyl pyridine (7 ml) in dry dimethylformamide (20 ml) was added dropwise over 10 minutes. The mixture was stirred at 0° C. for 30 minutes and then warmed to 22° C. over 3 hours. The mixture was re-cooled to less than 10° C., and ethanol (3 ml) was added dropwise and stirring continued for 15 minutes. The mixture was poured as a thin stream into a stirred mixture of diethyl ether (500 ml) and 20% saturated aqueous ammonium chloride solution. The phases were separated and the organic phase was washed with 20% saturated aqueous ammonium chloride solution (2×150 ml). The organic phase was dried over anhydrous magnesium sulphate, filtered and evaporated onto flash silica (50 g). Chromatography over silica eluting with 5-20% diethyl ether in 40/60° Bp petrol gave the title compound, m.p. 108-110° C.

Workup

  1. stirringThe mixture was stirred at 0° C. for 30 minutes
  2. temperaturewarmed to 22° C. over 3 hours
  3. temperatureThe mixture was re-cooled to less than 10° C.
  4. stirringstirring
  5. waitcontinued for 15 minutes
  6. customThe phases were separated
  7. washthe organic phase was washed with 20% saturated aqueous ammonium chloride solution (2×150 ml)
  8. dry with materialThe organic phase was dried over anhydrous magnesium sulphate
  9. filtrationfiltered
  10. customevaporated onto flash silica (50 g)

Sources & evidence

ORD record
ord-ed8a08e7b2384837b451ee68103ec218
Source dataset
uspto-grants-2003_10
Patent number
US06630495B1

Reaction notes

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