4-Propylcyclohexanone → HCID 23443725, compound

HRID 1840697Notes

Reaction equation

HRID 1840697 reaction equation
[CH2:1]([Li])CCC.[CH2:6]([CH:9]1[CH2:14][CH2:13][C:12](=O)[C:11](=[CH:16][C:17]2[CH:22]=[C:21]([F:23])[C:20]([F:24])=[C:19]([F:25])[CH:18]=2)[CH2:10]1)[CH2:7][CH3:8].C(C1CCC(=O)CC1)CC.FC1C=C(C=C(F)C=1F)C=O>[Br-].C[P+](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1.O1CCCC1.O>[CH2:6]([CH:9]1[CH2:14][CH2:13][C:12]2[C:11](=[CH:16][C:17]3[C:22]([CH:1]=2)=[C:21]([F:23])[C:20]([F:24])=[C:19]([F:25])[CH:18]=3)[CH2:10]1)[CH2:7][CH3:8]

Participants

8

Reactant 4

HCID 1424824-PropylcyclohexanoneHCID 27769543,4,5-TrifluorobenzaldehydeHCID 69880937HCID 69880937, compoundHCID 178418339Butyllithium

Product 1

HCID 23443725HCID 23443725, compound

Reagents, catalysts & solvents 3

HCID 74505Methyltriphenyliphosphonium bromideCatalystHCID 962WaterSolventHCID 8028TetrahydrofuranSolvent2×

Procedure

A mixture of 5 mmol of methyltriphenylphosphonium bromide and 5 mmol of butyllithium in 25 ml of tetrahydrofuran which has been reacted to completion at 0° C. was treated over the course of 10 minutes with a solution of 4.5 mmol of 4-propyl-2-(3,4,5-trifluorobenzylidene)cyclohexanone [prepared from 4-propyl-cyclohexanone and 3,4,5-trifluorobenzaldehyde analogously to Walton, J. Org. Chem. 22, 1161 (1957)] in 5 ml of tetrahydrofuran. After 4 hours at room temperature, 50 ml of water were added, the mixture was extracted twice with 25 ml of tert-butyl methyl ether each time, the extract was washed with water and evaporated in a rotary evaporator, and the residue was chromatographed over silica gel with heptane. The resultant crude product [(Z2) from Scheme 1 with R1=propyl, L2=L3=F, X═F) was dissolved in 1 l of benzene and irradiated with a 450 W UV lamp with cooling in a circulation apparatus. After 8 hours, the reaction solution was evaporated in a rotary evaporator, and the residue was chromatographed over silica gel with heptane/ethyl acetate 9:1. Recrystallization from acetonitrile gave colorless crystals.

Workup

  1. customhas been reacted to completion at 0° C.
  2. extractionthe mixture was extracted twice with 25 ml of tert-butyl methyl ether each time
  3. washthe extract was washed with water
  4. customevaporated in a rotary evaporator
  5. customthe residue was chromatographed over silica gel with heptane
  6. dissolution=F, X═F) was dissolved in 1 l of benzene
  7. customirradiated with a 450 W UV lamp
  8. temperaturewith cooling in a circulation apparatus
  9. waitAfter 8 hours
  10. customthe reaction solution was evaporated in a rotary evaporator
  11. customthe residue was chromatographed over silica gel with heptane/ethyl acetate 9:1
  12. customRecrystallization from acetonitrile
  13. customgave colorless crystals

Sources & evidence

ORD record
ord-cd182115c02b40079f6d94f16f387e29
Source dataset
uspto-grants-2004_01
Patent number
US06682785B2

Reaction notes

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