Triphenylmethylphosphonium → Methyl 4-(5-Acetoxy-pent-1-en-2-yl)benzoate

HRID 2050533Notes

Reaction equation

HRID 2050533 reaction equation
[CH3:1][P+](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1.C[Si](C)(C)[N-][Si](C)(C)C.[Na+].[C:31]([O:34][CH2:35][CH2:36][CH2:37][C:38]([C:40]1[CH:49]=[CH:48][C:43]([C:44]([O:46][CH3:47])=[O:45])=[CH:42][CH:41]=1)=O)(=[O:33])[CH3:32]>O1CCCC1>[C:31]([O:34][CH2:35][CH2:36][CH2:37][C:38]([C:40]1[CH:49]=[CH:48][C:43]([C:44]([O:46][CH3:47])=[O:45])=[CH:42][CH:41]=1)=[CH2:1])(=[O:33])[CH3:32]

Participants

5

Reactant 3

HCID 74506TriphenylmethylphosphoniumHCID 2724254Sodium bis(trimethylsilyl)amideHCID 15734961Methyl 4-(4-Acetoxy-1-oxobutyl)benzoate

Product 1

HCID 15734962Methyl 4-(5-Acetoxy-pent-1-en-2-yl)benzoate

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent3×

Procedure

Methyl triphenylphosphonium (1.5 g, 1.1 eq) was suspended in 50 ml of anhydrous tetrahydrofuran and 4.0 ml of 1.0M solution of sodium hexamethyldisilazide (1.05 eq) in tetrahydrofuran were added via syringe. The mixture was stirred at room temperature for one hour and a solution of 1.0 g (1.0 eq) of methyl 4-(4-acetoxy-1-oxobutyl)benzoate in anhydrous tetrahydrofuran, was added dropwise. The resulting reaction mixture was stirred for 2 hours at room temperature. Sodium bromide/triphenylphosphineoxide precipitate was removed by filtration, and the filtrate washed with water. After extraction of the aqueous layer with diethyl ether, the organic layers were dried over magnesium sulfate and evaporated to dryness to yield the product which was further purified by flash chromatography eluting with 1:5 ethyl acetate:hexanes. M.S.:m/z=262 (M+,CI), 231.1020 (M+ --CH3O, calc. for C14H15O3 : 231.1021), 202 (M+ - AcOH), 176, 143 (100%). 1H-N.M.R. (CDCl3, 300 MHz): δ=1.80(quin, 2H, CH2 --CH2 --CH2, J=7.5 Hz); 2:04(s, 3H, CH3 --CO); 2.62 (t, 2H, CH2 --C=, J=7.5 Hz); 3.94(s, 3H, CH3O); 4.10(t, 2H, CH2O, J=7.5 Hz); 5.20 (s, 1Holef.); 5.41(s, 1Holef.); 7.48(d, 2Harom., J=9 Hz); 8.01(d, 2Harom., J=9 Hz).

Workup

  1. customThe resulting reaction mixture
  2. stirringwas stirred for 2 hours at room temperature
  3. customSodium bromide/triphenylphosphineoxide precipitate was removed by filtration
  4. washthe filtrate washed with water
  5. extractionAfter extraction of the aqueous layer with diethyl ether
  6. dry with materialthe organic layers were dried over magnesium sulfate
  7. customevaporated to dryness
  8. customto yield the product which
  9. customwas further purified by flash chromatography
  10. washeluting with 1:5 ethyl acetate

Sources & evidence

ORD record
ord-8f37289e833c4fde89ff93e7d311df16
Source dataset
uspto-grants-1991_05
Patent number
US05013738

Reaction notes

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