Isopropyltriphenylphosphonium iodide → HCID 70361321, compound

HRID 543148Notes

Reaction equation

HRID 543148 reaction equation
[CH2:1]([Li])[CH2:2][CH2:3]C.[I-].CC([P+](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1)C.[CH3:29][C:30]([C:33]1[N:38]=[CH:37][C:36](/[CH:39]=[CH:40]/[C:41]([O:43][CH2:44][CH3:45])=[O:42])=[CH:35][N:34]=1)([CH3:32])[CH3:31]>CCCCCC.O1CCCC1>[CH3:1][C:2]1([CH3:3])[C@@H:39]([C:36]2[CH:35]=[N:34][C:33]([C:30]([CH3:29])([CH3:31])[CH3:32])=[N:38][CH:37]=2)[C@@H:40]1[C:41]([O:43][CH2:44][CH3:45])=[O:42]

Participants

6

Reactant 3

HCID 2723783Isopropyltriphenylphosphonium iodideHCID 13532899HCID 13532899, compoundHCID 178418339Butyllithium

Product 1

HCID 70361321HCID 70361321, compound

Reagents, catalysts & solvents 2

HCID 8028TetrahydrofuranSolvent2×HCID 8058HexaneSolvent

Procedure

A solution of n-butyllithium (10.6 cm3 of a 1.55M solution in hexane) was added slowly to a stirred solution of prop-2-yl triphenyl phosphonium iodide (7.1 g) in dry tetrahydrofuran (20 cm3) at the ambient temperature under a nitrogen atmosphere and the resultant mixture stirred for a further 15 minutes after which a solution of ethyl trans 3-[2-(2-methylprop-2-yl)pyrimidin-5-yl]propenoate (3.2 g) in dry tetrahydrofuran (25 cm3) was added dropwise at -5° C. After stirring for a further period of 30 minutes during which time the mixture warmed to the ambient temperature it was kept at the ambient temperature for 16 hours. The mixture was partitioned between water (300 cm3) and diethyl ether (200 cm3) and the aqueous phase extracted with ether (2×200 cm3) and the extracts combined with the ethereal phase. After washing with water (2×100 cm3) and drying over anhydrous magnesium sulphate, the ether was removed by evaporation under reduced pressure to yield a residual oil which was subjected to dry column chromatography using a silica column eluted first with dichloromethane (to remove triphenyl phosphine) and then with a mixture of dichloromethane (100 parts by volume) and ethyl acetate (5 parts by volume) to yield ethyl trans-2,2-dimethyl-3-[2-(2-methylprop-2-yl)pyrimidin-5-yl]cyclopropane carboxylate (2.8 g), the identity of which was confirmed by infra red and n.m.r. spectroscopy.

Workup

  1. additionwas added dropwise at -5° C
  2. waitwas kept at the ambient temperature for 16 hours
  3. customThe mixture was partitioned between water (300 cm3) and diethyl ether (200 cm3)
  4. extractionthe aqueous phase extracted with ether (2×200 cm3)
  5. washAfter washing with water (2×100 cm3)
  6. dry with materialdrying over anhydrous magnesium sulphate
  7. customthe ether was removed by evaporation under reduced pressure
  8. customto yield a residual oil which
  9. customto dry column chromatography
  10. washeluted first with dichloromethane (to remove triphenyl phosphine)
  11. additionwith a mixture of dichloromethane (100 parts by volume) and ethyl acetate (5 parts by volume)

Sources & evidence

ORD record
ord-e4186b47c27045a583fba236212ebe99
Source dataset
uspto-grants-1987_04
Patent number
US04661488

Reaction notes

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