HCID 12651433, compound → HCID 12651440, compound

HRID 354614Notes

Reaction equation

HRID 354614 reaction equation
C([Li])CCC.[Cl-].[CH3:7][O:8][C:9]1[CH:34]=[C:33]([CH3:35])[C:12]([CH2:13][P+](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)=[C:11]([CH3:36])[C:10]=1[CH3:37].[F:38]/[C:39](=[CH:48]\[CH:49]=[C:50](/[CH3:53])\[CH:51]=O)/[C:40](/[CH3:47])=[CH:41]/[C:42]([O:44][CH2:45][CH3:46])=[O:43]>O1CCCC1>[CH3:7][O:8][C:9]1[CH:34]=[C:33]([CH3:35])[C:12](/[CH:13]=[CH:53]/[C:50](/[CH3:51])=[CH:49]/[CH:48]=[C:39](\[F:38])/[C:40](/[CH3:47])=[CH:41]/[C:42]([O:44][CH2:45][CH3:46])=[O:43])=[C:11]([CH3:36])[C:10]=1[CH3:37]

Participants

5

Reactant 3

HCID 12651433HCID 12651433, compoundHCID 86736272HCID 86736272, compoundHCID 178418339Butyllithium

Product 1

HCID 12651440HCID 12651440, compound

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent2×

Conditions

Temperature
-30 °C

Procedure

A solution of 6.06 ml. (14.4 mmol) of n-butyllithium (2.3 M in hexane) was added dropwise under argon, at -72° C., to a stirred suspension of 4.61 g. (10 mmol) of 4-methoxy-2,3,6-trimethylbenzyl triphenylphosphonium chloride in 25 ml. of dry tetrahydrofuran. After addition of reagent was complete the mixture was stirred at -30° C. until an orange solution was formed. The resulting solution was first cooled to -72° C. and then treated dropwise with a solution of 2.03 g. (9.0 mmol) of ethyl (E,Z,E)-4-fluoro-3,7-dimethyl-8-oxo-2,4,6-octatrienoate in 10 ml. of dry tetrahydrofuran. The reaction mixture was gradually allowed to come to 25° C. and further stirred at this temperature under argon for 2.0 hours. It was poured onto 100 ml. of cold water and extracted with methylene chloride (4×100 ml.). The combined organic extracts were washed with water (2×100 ml.) dried over anhydrous magnesium sulfate and concentrated to give 6.4 g. of oily crude product. This material was filtered through 300 g. of florisil and eluted with methylene chloride to yield 2.97 g. of yellow crystalline substance, which on crystallization from ether-petroleum ether (~1:9) afforded ethyl (E,Z,E,E)-9-(4-methoxy-2,3,6-trimethylphenyl)-4-fluoro-3,7-dimethyl-2,4,6,8-nonatetraenoate as yellow crystals, mp 92°-96° C.

Workup

  1. additionAfter addition of reagent
  2. customwas formed
  3. temperatureThe resulting solution was first cooled to -72° C.
  4. additiontreated dropwise with a solution of 2.03 g
  5. customto come to 25° C.
  6. stirringfurther stirred at this temperature under argon for 2.0 hours
  7. additionIt was poured onto 100 ml
  8. extractionof cold water and extracted with methylene chloride (4×100 ml.)
  9. washThe combined organic extracts were washed with water (2×100 ml.)
  10. dry with materialdried over anhydrous magnesium sulfate
  11. concentrationconcentrated
  12. customto give 6.4 g
  13. filtrationThis material was filtered through 300 g
  14. washof florisil and eluted with methylene chloride
  15. customto yield 2.97 g
  16. customof yellow crystalline substance, which on crystallization from ether-petroleum ether (~1:9)

Sources & evidence

ORD record
ord-0094d29107dd4fc2925de56836ea8ef9
Source dataset
uspto-grants-1983_03
Patent number
US04375563

Reaction notes

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