3-Phenoxyphenylmethyltriphenylphosphonium chloride → 1-(4-Chlorophenyl)-1-cyclopropyl-4-(3-phenoxyphenyl)1,3-butadiene

HRID 1383228Notes

Reaction equation

HRID 1383228 reaction equation
C([Li])CCC.[Cl-].[O:7]([C:14]1[CH:15]=[C:16]([CH2:20][P+](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)[CH:17]=[CH:18][CH:19]=1)[C:8]1[CH:13]=[CH:12][CH:11]=[CH:10][CH:9]=1.[Cl:40][C:41]1[CH:46]=[CH:45][C:44]([C:47]([CH:51]2[CH2:53][CH2:52]2)=[CH:48][CH:49]=O)=[CH:43][CH:42]=1>O1CCCC1>[Cl:40][C:41]1[CH:46]=[CH:45][C:44]([C:47]([CH:51]2[CH2:53][CH2:52]2)=[CH:48][CH:49]=[CH:20][C:16]2[CH:17]=[CH:18][CH:19]=[C:14]([O:7][C:8]3[CH:9]=[CH:10][CH:11]=[CH:12][CH:13]=3)[CH:15]=2)=[CH:43][CH:42]=1

Participants

5

Reactant 3

HCID 212741653-Phenoxyphenylmethyltriphenylphosphonium chlorideHCID 571914023-(4-Chlorophenyl)-3-cyclopropylpropenalHCID 178418339Butyllithium

Product 1

HCID 541076381-(4-Chlorophenyl)-1-cyclopropyl-4-(3-phenoxyphenyl)1,3-butadieneYield 85.8%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent2×

Conditions

Temperature
-78 °C

Procedure

A stirred solution of 4.4 mL (0.011 mole) of n-butyllithium (2.5 molar in hexane) in 100 mL of dry tetrahydrofuran was cooled to -78° C., and 4.6 grams (0.01 mole) of 3-phenoxyphenylmethyltriphenylphosphonium chloride was quickly added. Upon completion of addition, the reaction mixture was stirred at -78° C. for one hour and then was allowed to warm to -20° C. where it stirred for one hour. The reaction mixture was cooled to -78° C., and 2.1 grams (0.01 mole) of 3-(4-chlorophenyl)-3-cyclopropylpropenal (prepared in Step B) in 10 mL of tetrahydrofuran was added during a 15 minute period. Upon completion of addition, the reaction mixture was allowed to warm to ambient temperature where it stirred for two hours. The reaction was quenched with the addition of 15 mL of aqueous 10% hydrochloric acid solution. The mixture was extracted with diethyl ether. The combined extracts were 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% diethyl ether in hexane. The appropriate fractions were combined and concentrated under reduced pressure, yielding 3.2 grams of 1-(4-chlorophenyl)-1-cyclopropyl-4-(3-phenoxyphenyl)1,3-butadiene.

Workup

  1. additionUpon completion of addition
  2. temperatureto warm to -20° C. where it
  3. stirringstirred for one hour
  4. temperatureThe reaction mixture was cooled to -78° C.
  5. additionUpon completion of addition
  6. temperatureto warm to ambient temperature where it
  7. stirringstirred for two hours
  8. customThe reaction was quenched with the addition of 15 mL of aqueous 10% hydrochloric acid solution
  9. extractionThe mixture was extracted with diethyl ether
  10. dry with materialThe combined extracts were dried with sodium sulfate
  11. filtrationfiltered
  12. concentrationThe filtrate was concentrated under reduced pressure to a residue
  13. washElution
  14. concentrationconcentrated under reduced pressure

Sources & evidence

ORD record
ord-a14bd42400834727a732f56da2561a21
Source dataset
uspto-grants-1989_02
Patent number
US04808762

Reaction notes

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