1,1-Dimethylethyl 6-formyl-2,2-dimethyl-1,3-dioxane-4-acetate → 1,1-Dimethylethyl 6-[3-difluoromethyl-4,4-bis(4-fluorophenyl)-1,3-butadienyl]-1,3-dioxane-4-acetate

HRID 1086100Notes

Reaction equation

HRID 1086100 reaction equation
C([Li])CCC.[F:6][C:7]1[CH:12]=[CH:11][C:10]([C:13]([C:25]2[CH:30]=[CH:29][C:28]([F:31])=[CH:27][CH:26]=2)=[C:14]([CH:22]([F:24])[F:23])[CH2:15]P(=O)(OC)OC)=[CH:9][CH:8]=1.[CH:32]([CH:34]1[O:39][C:38](C)(C)[O:37][CH:36]([CH2:42][C:43]([O:45][C:46]([CH3:49])([CH3:48])[CH3:47])=[O:44])[CH2:35]1)=O>O1CCCC1>[F:23][CH:22]([F:24])[C:14](=[C:13]([C:10]1[CH:9]=[CH:8][C:7]([F:6])=[CH:12][CH:11]=1)[C:25]1[CH:26]=[CH:27][C:28]([F:31])=[CH:29][CH:30]=1)[CH:15]=[CH:32][CH:34]1[O:39][CH2:38][O:37][CH:36]([CH2:42][C:43]([O:45][C:46]([CH3:47])([CH3:49])[CH3:48])=[O:44])[CH2:35]1

Participants

5

Reactant 3

HCID 156146011,1-Dimethylethyl 6-formyl-2,2-dimethyl-1,3-dioxane-4-acetateHCID 54009116Dimethyl [3,3-bis(4-fluorophenyl)-2-difluoromethyl-2-propen-1-yl]phosphonateHCID 178418339Butyllithium

Product 1

HCID 536982541,1-Dimethylethyl 6-[3-difluoromethyl-4,4-bis(4-fluorophenyl)-1,3-butadienyl]-1,3-dioxane-4-acetateYield 46.9%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent

Procedure

Butyl lithium (1.04 mL of 2.5M solution, 2.6 mmol) was added to a solution of dimethyl [3,3-bis(4-fluorophenyl)-2-difluoromethyl-2-propen-1-yl]phosphonate (1.0 g, 2.6 mmol) in 10 mL of tetrahydrofuran at -78° C. After stirring for 30 minutes, 1,1-dimethylethyl 6-formyl-2,2-dimethyl-1,3-dioxane-4-acetate (0.82 g, 3.2 mmol) was added and the mixture stirred for 64 hrs. at room temperature. The mixture was quenched with saturated ammonium chloride solution and extracted with diethyl ether. The extracts were dried over magnesium sulfate and conentrated in vacuo. The residue was purified by chromatography on silica eluting with 5% ethyl acetate in hexane to give an oil. Crystallization from pentane gave 0.6 g of the title compound; m.p. =124°-125° C.

Workup

  1. stirringthe mixture stirred for 64 hrs
  2. customat room temperature
  3. customThe mixture was quenched with saturated ammonium chloride solution
  4. extractionextracted with diethyl ether
  5. dry with materialThe extracts were dried over magnesium sulfate
  6. customThe residue was purified by chromatography on silica eluting with 5% ethyl acetate in hexane
  7. customto give an oil
  8. customCrystallization from pentane

Sources & evidence

ORD record
ord-f6efdf4cc3df4b71b32c6117ddb89c79
Source dataset
uspto-grants-1991_04
Patent number
US05011947

Reaction notes

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