Tributylamine → 4-Chloro-2-[[(2,3-difluorophenyl)methyl]thio]-6-[2-(2,2-dimethyl[1,3]dioxolan-4-yl)-vinyl]-pyrimidine

HRID 1958888Notes

Reaction equation

HRID 1958888 reaction equation
Cl[C:2]1[CH:7]=[C:6]([Cl:8])[N:5]=[C:4]([S:9][CH2:10][C:11]2[CH:16]=[CH:15][CH:14]=[C:13]([F:17])[C:12]=2[F:18])[N:3]=1.[CH3:19][C:20]1([CH3:27])[O:24][CH:23]([CH:25]=[CH2:26])[CH2:22][O:21]1.C(N(CCCC)CCCC)CCC>[Cl-].C([N+](CCCC)(CCCC)CCCC)CCC.CN(C)C=O.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.[Pd].[Pd]>[Cl:8][C:6]1[CH:7]=[C:2]([CH:26]=[CH:25][CH:23]2[CH2:22][O:21][C:20]([CH3:27])([CH3:19])[O:24]2)[N:3]=[C:4]([S:9][CH2:10][C:11]2[CH:16]=[CH:15][CH:14]=[C:13]([F:17])[C:12]=2[F:18])[N:5]=1

Participants

7

Reactant 3

HCID 7622TributylamineHCID 27350232,2-Dimethyl-4-vinyl-1,3-dioxolaneHCID 859280374,6-Dichloro-2-((2,3-difluorobenzyl)thio)pyrimidine

Product 1

HCID 866198624-Chloro-2-[[(2,3-difluorophenyl)methyl]thio]-6-[2-(2,2-dimethyl[1,3]dioxolan-4-yl)-vinyl]-pyrimidine

Reagents, catalysts & solvents 3

HCID 70681Tetrabutylammonium ChlorideCatalystHCID 9811564Bis(dibenzylideneacetone)palladiumCatalystHCID 6228DimethylformamideSolvent

Conditions

Temperature
90 °C

Procedure

A mixture of 4,6-dichloro-2-[(2,3-difluorobenzyl)thio]pyrimidine (product of example 1 step ii) (0.5 g), tris(dibenzylideneacetone)dipalladium(0) (45 mg), 2,2-dimethyl-4-vinyl-1,3-dioxolane (630 mg), tri-n-butylamine (610 mg) and tetra-n-butylammonium chloride (460 mg) in anhydrous N,N-dimethylformamide (6.5 ml) were heated at 90° C. for 3 h. then stirred at room temperature overnight. The reaction mixture was partitioned between ethyl acetate and water. The organic phase was washed with water and brine, dried (MgSO4) and the solvent evaporated under reduced pressure. The residue was purified by flash silica-gel chromatography eluting with 10% diethyl ether in iso-hexane to give the sub-title compound as a yellow viscous oil. Yield: 98 mg.

Workup

  1. customThe reaction mixture was partitioned between ethyl acetate and water
  2. washThe organic phase was washed with water and brine
  3. dry with materialdried (MgSO4)
  4. customthe solvent evaporated under reduced pressure
  5. customThe residue was purified by flash silica-gel chromatography
  6. washeluting with 10% diethyl ether in iso-hexane

Sources & evidence

ORD record
ord-9ea6a7f3bf1a45e581c1d1fcd4e6290f
Source dataset
uspto-grants-2013_04
Patent number
US08410123B2

Reaction notes

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