(4-Fluoro-3-phenoxyphenyl)methyltriphenylphosphonium chloride → 1-Cyclopropyl-1-(4-chlorophenyl)-4-(4-fluoro-3-phenoxyphenyl)-1,3-butadiene

HRID 1110412Notes

Reaction equation

HRID 1110412 reaction equation
C([Li])CCC.[Cl-].[F:7][C:8]1[CH:13]=[CH:12][C:11]([CH2:14][P+](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)=[CH:10][C:9]=1[O:34][C:35]1[CH:40]=[CH:39][CH:38]=[CH:37][CH:36]=1.[CH:41]1([C:44]([C:48]2[CH:53]=[CH:52][C:51]([Cl:54])=[CH:50][CH:49]=2)=[CH:45][CH:46]=O)[CH2:43][CH2:42]1>O1CCCC1>[CH:41]1([C:44]([C:48]2[CH:49]=[CH:50][C:51]([Cl:54])=[CH:52][CH:53]=2)=[CH:45][CH:46]=[CH:14][C:11]2[CH:12]=[CH:13][C:8]([F:7])=[C:9]([O:34][C:35]3[CH:36]=[CH:37][CH:38]=[CH:39][CH:40]=3)[CH:10]=2)[CH2:43][CH2:42]1

Participants

5

Reactant 3

HCID 19754846(4-Fluoro-3-phenoxyphenyl)methyltriphenylphosphonium chlorideHCID 571914023-(4-Chlorophenyl)-3-cyclopropylpropenalHCID 178418339Butyllithium

Product 1

HCID 543787091-Cyclopropyl-1-(4-chlorophenyl)-4-(4-fluoro-3-phenoxyphenyl)-1,3-butadieneYield 35.8%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent2×

Conditions

Temperature
-78 °C

Procedure

A stirred solution of 0.71 gram (4.4 mL-0.011 mole) of n-butyllithium (2.5M in hexane) in 50 mL of dry tetrahydrofuran was cooled to -78° C., and 4.98 grams (0.01 mole) of 4-fluoro-3-phenoxyphenylmethyltriphenylphosphonium chloride (prepared in Steps C-E) was quickly added. Upon completion of addition the reaction mixture was stirred at -78° C. for one hour, and then a solution of 2.03 grams (0.01 mole) of 3-cyclopropyl-3-(4-chlorophenyl)-2-propenal (prepared in Steps A and B) in 10 mL of dry tetrahydrofuran was added dropwise during a 10 minute period. Upon completion of addition the reaction mixture was stirred at -78° C. for one hour and then was allowed to warm to ambient temperature where it was stirred for two hours. The reaction was quenched with 10 mL of aqueous dilute hydrochloric acid, and the reaction mixture was extracted with diethyl ether. The ether extract was dried with sodium sulfate and filtered. The filtrate was concentrated under reduced pressure to a residue. The residue was subjected to column chromatography on silica gel. Elution was accomplished using 5% ethyl acetate in hexane. The appropriate fractions were combined and concentrated under reduced pressure yielding 1.4 grams of 1-cyclopropyl-1-(4-chlorophenyl)-4-(4-fluoro-3-phenoxyphenyl)-1,3-butadiene. The nmr spectrum was consistent with the proposed structure.

Workup

  1. additionUpon completion of addition the reaction mixture
  2. additionUpon completion of addition the reaction mixture
  3. stirringwas stirred at -78° C. for one hour
  4. temperatureto warm to ambient temperature where it
  5. stirringwas stirred for two hours
  6. customThe reaction was quenched with 10 mL of aqueous dilute hydrochloric acid
  7. extractionthe reaction mixture was extracted with diethyl ether
  8. extractionThe ether extract
  9. dry with materialwas dried with sodium sulfate
  10. filtrationfiltered
  11. concentrationThe filtrate was concentrated under reduced pressure to a residue
  12. washElution
  13. concentrationconcentrated under reduced pressure

Sources & evidence

ORD record
ord-db4e57cca75e47f7b23228c2e10fac52
Source dataset
uspto-grants-1990_12
Patent number
US04975451

Reaction notes

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