Tributylvinyltin → HCID 59946906, compound

HRID 1532573Notes

Reaction equation

HRID 1532573 reaction equation
[F:1][C:2]1[C:3]([C:10]2[C:14]([Cl:15])=[C:13]([O:16][CH:17]([F:19])[F:18])[N:12]([CH3:20])[N:11]=2)=[N:4][C:5](Cl)=[C:6]([Cl:8])[CH:7]=1.[CH:21]([Sn](CCCC)(CCCC)CCCC)=[CH2:22]>CN(C)C=O>[F:1][C:2]1[C:3]([C:10]2[C:14]([Cl:15])=[C:13]([O:16][CH:17]([F:19])[F:18])[N:12]([CH3:20])[N:11]=2)=[N:4][C:5]([CH:21]=[CH2:22])=[C:6]([Cl:8])[CH:7]=1

Participants

4

Reactant 2

HCID 81998TributylvinyltinHCID 21712133HCID 21712133, compound

Product 1

HCID 59946906HCID 59946906, compoundYield 287%

Reagents, catalysts & solvents 1

HCID 6228DimethylformamideSolvent

Conditions

Temperature
67 °C

Procedure

30 g of 3-(3-fluoro-5,6-dichloro-2-pyridyl)-4-chloro-5-difluoromethoxy-1-methyl-[1H]-pyrazole (Example H21) are dissolved in 200 ml of N,N-dimethylformamide (DMF). After addition of 32.9 g of vinyltributyltin, the mixture is twice evacuated and gassed with argon. A little (i.e. a spatula-tip) 2,6-di-tert-butyl-p-cresol and 3.0 g of bistriphenylphosphinepalladium dichloride (PdCl2(PPh3)2) are then added and the mixture is stirred at a temperature of 67° C. for 24 hours. After cooling to 22° C., the reaction mixture is filtered over Hyflo and partitioned between dilute hydrochloric acid and diethyl ether. The ether phase which has been separated off is washed with water, dried over sodium sulfate, filtered and concentrated in vacuo. 84 g of a black oil are obtained, and this is purified over a silica gel flash column (eluting agent: n-hexanelethyl acetate 6/1). The resulting solid is stirred with 100 ml of n-hexane for a further 2 hours, filtered off, washed and dried. 16.4 g of the desired title compound are obtained as a white solid of melting point 75-77° C.

Workup

  1. customthe mixture is twice evacuated
  2. additionA little (i.e. a spatula-tip) 2,6-di-tert-butyl-p-cresol and 3.0 g of bistriphenylphosphinepalladium dichloride (PdCl2(PPh3)2) are then added
  3. temperatureAfter cooling to 22° C.
  4. filtrationthe reaction mixture is filtered over Hyflo
  5. custompartitioned between dilute hydrochloric acid and diethyl ether
  6. customThe ether phase which has been separated off
  7. washis washed with water
  8. dry with materialdried over sodium sulfate
  9. filtrationfiltered
  10. concentrationconcentrated in vacuo

Sources & evidence

ORD record
ord-11ff9a9d212a4337b021b62e1148b33d
Source dataset
uspto-grants-2001_03
Patent number
US06204221B1

Reaction notes

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