Water → HCID 13366427, compound

HRID 1632469Notes

Reaction equation

HRID 1632469 reaction equation
[Cl-].[F:2][C:3]([F:35])([F:34])[O:4][C:5]1[CH:10]=[C:9]([CH3:11])[C:8]([CH2:12][P+](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)=[C:7]([CH3:32])[C:6]=1[CH3:33].C([Li])CCC.[CH2:41]([O:43][C:44](=[O:55])/[CH:45]=[C:46](\[CH3:54])/[CH:47]=[CH:48]/[CH:49]=[C:50](\[CH3:53])/[CH:51]=O)[CH3:42].O>C1COCC1>[CH2:41]([O:43][C:44](=[O:55])/[CH:45]=[C:46](\[CH3:54])/[CH:47]=[CH:48]/[CH:49]=[C:50](\[CH3:53])/[CH:51]=[CH:12]/[C:8]1[C:9]([CH3:11])=[CH:10][C:5]([O:4][C:3]([F:2])([F:34])[F:35])=[C:6]([CH3:33])[C:7]=1[CH3:32])[CH3:42]

Participants

6

Reactant 4

HCID 962WaterHCID 12875232HCID 12875232, compoundHCID 20442920HCID 20442920, compoundHCID 178418339Butyllithium

Product 1

HCID 13366427HCID 13366427, compoundYield 59.1%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent2×

Conditions

Temperature
45 °C

Procedure

A suspension of 12.2 g (24 mmol) of (4-trifluoromethoxy-2,3,6-trimethylphenyl)methyltriphenylphosphonium chloride in 490 ml of dry THF was cooled to 45° C. and treated rapidly (over ~5 minutes) with 11.1 ml (25.5 mmol) of n-butyl lithium (2.3M in hexane) at -35° to -45° C. The reaction mixture was maintained at that temperature for 15 minutes, allowed to warm slowly to -25° C. at which time it became a slightly turbid orange solution. The mixture was cooled to -45° to -50° C. and 7.0 g (33 mmol) of ethyl-(2E,4E,6E)-3,7-dimethyl-8-oxo-octatrienoate in 50 ml of dry THF was added rapidly. The orange color disappeared; the reaction mixture was stirred at -25° C. for 2 hours, then allowed to warm to 0° C. over 1 hour and maintained at that temperature for 2 hours. The mixture was then poured into 1 liter of cold water and extracted with 250-ml portions of hexane. The organic phase was combined, washed successively with 500 ml of cold water, 2×500 ml of a 60% by volume methanol-water solution, and 500 ml of saturated NaCl solution, dried (MgSO4), filtered and concentrated. The resulting yellow oil was purified by HPLC (2 silica gel columns, 2% ethyl acetate in hexane as elutant) to give 5.79 g of ethyl-(2E,4E,6E,8E)-3,7-dimethyl-9-[2,3,6-trimethyl-4-(trifluoromethoxy)phenyl]-nonatetraenoate; mp 47°-49° C.

Workup

  1. temperatureThe reaction mixture was maintained at that temperature for 15 minutes
  2. temperatureto warm slowly to -25° C. at which time it
  3. temperatureThe mixture was cooled to -45° to -50° C.
  4. temperatureto warm to 0° C. over 1 hour
  5. temperaturemaintained at that temperature for 2 hours
  6. extractionextracted with 250-ml portions of hexane
  7. washwashed successively with 500 ml of cold water, 2×500 ml of a 60% by volume methanol-water solution, and 500 ml of saturated NaCl solution
  8. dry with materialdried (MgSO4)
  9. filtrationfiltered
  10. concentrationconcentrated
  11. customThe resulting yellow oil was purified by HPLC (2 silica gel columns, 2% ethyl acetate in hexane as elutant)

Sources & evidence

ORD record
ord-24ccef9f3f914866acb387793ecfe68f
Source dataset
uspto-grants-1984_10
Patent number
US04476056

Reaction notes

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