Toluene → Ethyl 2-(1-nonen-1-yl)-3,3-dimethylcyclopropanecarboxylate

HRID 354696

Reaction equation

HRID 354696 reaction equation
C([Li])CCC.[Br-].[CH2:7]([P+](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1)[CH2:8][CH2:9][CH2:10][CH2:11][CH2:12][CH2:13][CH3:14].[CH:34]([CH:36]1[C:38]([CH3:40])([CH3:39])[CH:37]1[C:41]([O:43][CH2:44][CH3:45])=[O:42])=O.C1(C)C=CC=CC=1>CCCCCC.O1CCCC1.O>[CH:34]([CH:36]1[C:38]([CH3:40])([CH3:39])[CH:37]1[C:41]([O:43][CH2:44][CH3:45])=[O:42])=[CH:7][CH2:8][CH2:9][CH2:10][CH2:11][CH2:12][CH2:13][CH3:14]

Participants

8

Reactant 4

HCID 1140TolueneHCID 566079Ethyl 3-formyl-2,2-dimethylcyclopropane-1-carboxylateHCID 3084855Octyltriphenylphosphonium bromideHCID 178418339Butyllithium

Product 1

HCID 54188881Ethyl 2-(1-nonen-1-yl)-3,3-dimethylcyclopropanecarboxylateYield 57%

Reagents, catalysts & solvents 3

HCID 962WaterSolventHCID 8028TetrahydrofuranSolventHCID 8058HexaneSolvent

Procedure

64.5 g of a 15% strength solution of butyl-lithium in n-hexane were added dropwise to a suspension of 68.3 g (0.15 mol) of n-octyl-triphenylphosphonium bromide in 300 ml of absolute tetrahydrofuran at 0°-5° C., with the exclusion of air. After one hour, 25.5 g (0.15 mol) of ethyl 2-formyl-3,3-dimethylcyclopropanecarboxylate were slowly added, and the mixture was further stirred for 18 hours at room temperature. The mixture was shaken after the addition of 400 ml of toluene and 300 ml of water, the water was separated off and the organic phase was washed once again with 200 ml of water. The toluene solution was then dried over sodium sulphate and the solvent was distilled off in vacuo. The residue was stirred with 300 ml of petroleum ether (40°-60° C.), the solution was filtered off from the undissolved triphenylphosphine oxide, and the filtrate was again concentrated by evaporation in vacuo. The residue was distilled in vacuo. 22.6 g (57% of theory) of ethyl 2-(1-nonen-1-yl)-3,3-dimethylcyclopropanecarboxylate with a boiling point of 90° C./0.01 mm Hg were thus obtained.

Workup

  1. stirringThe mixture was shaken
  2. customthe water was separated off
  3. washthe organic phase was washed once again with 200 ml of water
  4. dry with materialThe toluene solution was then dried over sodium sulphate
  5. distillationthe solvent was distilled off in vacuo
  6. stirringThe residue was stirred with 300 ml of petroleum ether (40°-60° C.)
  7. filtrationthe solution was filtered off from the undissolved triphenylphosphine oxide
  8. concentrationthe filtrate was again concentrated by evaporation in vacuo
  9. distillationThe residue was distilled in vacuo

Sources & evidence

ORD record
ord-180eb195a3fc49f1b48ad354030375a7
Source dataset
uspto-grants-1983_03
Patent number
US04376786

Linked notes

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