Allyl bromide → Dimethyl 2-(2-propenyl)-2-(4-phenoxyphenyl)malonate

HRID 1386645

Reaction equation

HRID 1386645 reaction equation
[O:1]([C:8]1[CH:13]=[CH:12][C:11]([CH:14]([C:19]([O:21][CH3:22])=[O:20])[C:15]([O:17][CH3:18])=[O:16])=[CH:10][CH:9]=1)[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1.[CH:23]([N-]C(C)C)([CH3:25])[CH3:24].[Li+].C(Br)C=C>C1COCC1>[CH2:25]([C:14]([C:11]1[CH:12]=[CH:13][C:8]([O:1][C:2]2[CH:3]=[CH:4][CH:5]=[CH:6][CH:7]=2)=[CH:9][CH:10]=1)([C:19]([O:21][CH3:22])=[O:20])[C:15]([O:17][CH3:18])=[O:16])[CH:23]=[CH2:24]

Participants

5

Reactant 3

HCID 7841Allyl bromideHCID 2724682Lithium diisopropylamideHCID 15540880Dimethyl 2-(4-phenoxyphenyl)malonate

Product 1

HCID 21183038Dimethyl 2-(2-propenyl)-2-(4-phenoxyphenyl)malonate

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent

Conditions

Temperature
-78 °C

Procedure

A solution of dimethyl 2-(4-phenoxyphenyl)malonate (2.56 g, 8.54 mmol) in dry THF (50 mL) was cooled to −78° C. and then lithium diisopropylamide (4.7 mL of a 2M solution in ThF, 9.8 mmol) was added. The reaction was stirred at −78° C. for 1 hour and then allyl bromide (11.4 mg, 9.4 mmol) was added. The reaction was stirred at −78° C. for 3 hours and then allowed to warm to room temperature and heated in a 75° C. oil bath until the reaction was shown to be complete by TLC. The reaction was cooled to room temperature and quenched with 1N HCl. Extraction with ether and drying of the ether extracts (MgSO4) gave crude product. Purification by filtration through silica gel 60 (70-230 mesh) using EtOAc, followed by HPLC (porasil) using 11% EtOAc/hexanes gave 1.8 g of dimethyl 2-(2-propenyl)-2-(4-phenoxyphenyl)malonate as a viscous oil: 1H NMR (200 mHz, CDCl3) δ 7.4-6.85 (9H, m), 5.75 (1H, m), 5.05 (2H, m), 3.75 (6H, s), 3.1 (2H, d).

Workup

  1. stirringThe reaction was stirred at −78° C. for 3 hours
  2. temperatureto warm to room temperature
  3. temperatureheated in a 75° C. oil bath until the reaction
  4. temperatureThe reaction was cooled to room temperature
  5. customquenched with 1N HCl
  6. extractionExtraction with ether
  7. dry with materialdrying of the ether
  8. customgave crude product
  9. customPurification
  10. filtrationby filtration through silica gel 60 (70-230 mesh)

Sources & evidence

ORD record
ord-bfcd020f4cdc42d3a898790a91afa2b4
Source dataset
uspto-grants-2001_07
Patent number
US06265578B1

Linked notes

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