Tetrahydrofuran → (Z)-methyl 4-(pent-2-en-2-yl)benzoate

HRID 2170490Notes

Reaction equation

HRID 2170490 reaction equation
C[Si]([N-][Si](C)(C)C)(C)C.[K+].[C:11]([C:14]1[CH:23]=[CH:22][C:17]([C:18]([O:20][CH3:21])=[O:19])=[CH:16][CH:15]=1)(=O)[CH3:12].O1C[CH2:27][CH2:26][CH2:25]1>[Br-].C([P+](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1)C.C1(C)C=CC=CC=1>[CH3:12]/[C:11](/[C:14]1[CH:23]=[CH:22][C:17]([C:18]([O:20][CH3:21])=[O:19])=[CH:16][CH:15]=1)=[CH:25]/[CH2:26][CH3:27]

Participants

6

Reactant 3

HCID 8028Tetrahydrofuran2×HCID 137990Methyl 4-acetylbenzoateHCID 3251421Potassium bis(trimethylsilyl)amide

Product 1

HCID 89581156(Z)-methyl 4-(pent-2-en-2-yl)benzoateYield 56%

Reagents, catalysts & solvents 2

HCID 73727Phosphonium, ethyltriphenyl-, bromide (1:1)CatalystHCID 1140TolueneSolvent

Conditions

Temperature
110 °C

Procedure

Ethyltriphenylphosphonium bromide (4.2 g, 11.2 mmol) was dissolved in tetrahydrofuran (15 mL), and then potassium bis(trimethylsilyl)amide (11.2 mmol, 11.2 mL of a 1M solution in tetrahydrofuran) was added dropwise in the mixture at room temperature under stirring. After 10 minute, methyl 4-acetylbenzoate (1 g, 5.6 mmol) dissolved in toluene (30 mL) was dropwise and heated to 110° C. for 3 hours. The mixture was cooled and evaporated, the residue was purified by column chromatography (silica gel, petroleum ether/ethyl acetate=5:1) to get (Z)-methyl 4-(pent-2-en-2-yl)benzoate (610 mg, 56%). LRMS (M+H+) m/z: calcd 204.12. found 204.

Workup

  1. temperatureThe mixture was cooled
  2. customevaporated
  3. customthe residue was purified by column chromatography (silica gel, petroleum ether/ethyl acetate=5:1)

Sources & evidence

ORD record
ord-629d74e4d29449e9aa0b8d55da6003ed
Source dataset
uspto-grants-2015_06
Patent number
US09051269B2

Reaction notes

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