Vinylidene chloride → 3,3-Dichloro-1-[2,6-dichloro-4-(trifluoromethyl)-3-pyridinyl]-2-propen-1-one

HRID 1839358Notes

Reaction equation

HRID 1839358 reaction equation
[Cl:1][C:2]1[N:10]=[C:9]([Cl:11])[CH:8]=[C:7]([C:12]([F:15])([F:14])[F:13])[C:3]=1[C:4](Cl)=[O:5].[Al+3].[Cl-].[Cl-].[Cl-].[C:20]([Cl:23])([Cl:22])=[CH2:21]>C(Cl)Cl>[Cl:22][C:20]([Cl:23])=[CH:21][C:4]([C:3]1[C:2]([Cl:1])=[N:10][C:9]([Cl:11])=[CH:8][C:7]=1[C:12]([F:15])([F:14])[F:13])=[O:5]

Participants

5

Reactant 3

HCID 6366Vinylidene chlorideHCID 6451240Aluminum(III) ChlorideHCID 219482122,6-Dichloro-4-(trifluoromethyl)nicotinoyl chloride

Product 1

HCID 219481413,3-Dichloro-1-[2,6-dichloro-4-(trifluoromethyl)-3-pyridinyl]-2-propen-1-one

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent2×

Conditions

Temperature
0 °C

Procedure

A solution of the 2,6-dichloro-4-(trifluoromethyl)nicotinoyl chloride from the previous reaction in CH2Cl2 (14 mL) was added slowly to a cooled (0° C.) and stirred slurry solution of AlCl3 (4.4 g, 33.0 mmol) in CH2Cl2 (14 mL). After 15 min, vinylidene chloride (2.6 mL, 33.0 mmol) was added to the mixture dropwise. The reaction was allowed to warm to room temperature and was stirred overnight. The mixture was poured over ice and partitioned with CH2Cl2. The organic layer was collected and cooled to 0° C. before TEA (4.6 mL, 33 mmol)was added. After 15 min, the ice bath was removed and the reaction was allowed to warm to room temperature and stirred for an additional 30 min. The solution was washed with 1N HCl, NaHCO3, and water. The organic layer was passed through a pad of silica gel and concentrated in vacuo to afford 3,3-dichloro-1-[2,6-dichloro-4-(trifluoromethyl)-3-pyridinyl]-2-propen-1-one: (4.3 g, 95%) as a brown oil: LCMS RT: 3.59, MH+: 488.1, Rf=0.44 (EtOAc).

Workup

  1. additionwas added slowly to
  2. temperatureto warm to room temperature
  3. additionThe mixture was poured over ice
  4. custompartitioned with CH2Cl2
  5. customThe organic layer was collected
  6. additionwas added
  7. waitAfter 15 min
  8. customthe ice bath was removed
  9. temperatureto warm to room temperature
  10. stirringstirred for an additional 30 min
  11. washThe solution was washed with 1N HCl, NaHCO3, and water
  12. concentrationconcentrated in vacuo

Sources & evidence

ORD record
ord-907bb7d9b16c489e903ad755eeb56f9f
Source dataset
uspto-grants-2004_01
Patent number
US06677352B1

Reaction notes

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