Diethyl Ether → Ethyl 3-methyl-4-[2-methoxy-4-(2-methyl-1-propenyl)phenoxy]-2-butenoate

HRID 543341Notes

Reaction equation

HRID 543341 reaction equation
[I-].[CH:2]([P+](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1)([CH3:4])[CH3:3].C([Li])CCC.[CH3:29][C:30]([CH2:37][O:38][C:39]1[CH:44]=[CH:43][C:42]([CH:45]=O)=[CH:41][C:40]=1[O:47][CH3:48])=[CH:31][C:32]([O:34][CH2:35][CH3:36])=[O:33].CCOCC>O1CCCC1.O>[CH3:29][C:30]([CH2:37][O:38][C:39]1[CH:44]=[CH:43][C:42]([CH:45]=[C:2]([CH3:4])[CH3:3])=[CH:41][C:40]=1[O:47][CH3:48])=[CH:31][C:32]([O:34][CH2:35][CH3:36])=[O:33]

Participants

7

Reactant 4

HCID 3283Diethyl EtherHCID 2723783Isopropyltriphenylphosphonium iodideHCID 54099897Ethyl 3-methyl-4-(4-formyl-2-methoxyphenoxy)-2-butenoateHCID 178418339Butyllithium

Product 1

HCID 54014196Ethyl 3-methyl-4-[2-methoxy-4-(2-methyl-1-propenyl)phenoxy]-2-butenoate

Reagents, catalysts & solvents 2

HCID 962WaterSolventHCID 8028TetrahydrofuranSolvent2×

Procedure

Vanillin (3.43 g, 22.5 mmol) in 10 ml of DMF is added portionwise, at 0°, to sodium hydride (21.5 g, 23.6 mmol) in ml of DMF. The mixture is stirred for 10 min. and then ethyl 4-bromo-3-methyl-2-butenoate (4.87 g, 23.5 mmol) in 3 ml of DMF is added. After 3 hours, the reaction mixture is poured into ether and 5% sodium hydroxide solution. The aqueous layer is extracted with ether, and the organic layers are combined and washed with 5% sodium hydroxide, with water and with brine and dried. Solvent is removed in vacuo and the crude product is chromatographed to give ethyl 3-methyl-4-(4-formyl-2-methoxyphenoxy)-2-butenoate. To isopropyltriphenylphosphonium iodide (2.26 g, 5.23 mmol) in 15 ml of tetrahydrofuran (THF) is added n-butyllithium (1.6 M; 3.10 ml, 5.0 mmol) at -5°. The mixture is cooled to -60°, and ethyl 3-methyl-4-(4-formyl-2-methoxyphenoxy)-2-butenoate (0.70 g, 2.51 mmol) in 10 ml of THF is added. After 45 min. the reaction mixture is poured into ether and water, and the aqueous phase is extracted with ether. The combined ether layers are washed with water and with brine and dried. Solvent is removed in vacuo, and the crude product is triturated with hexane and the hexane-soluble fraction is purified by prep. TLC to give ethyl 3-methyl-4-[2-methoxy-4-(2-methyl-1-propenyl)phenoxy]-2-butenoate, MS m/e 304 (M+).

Workup

  1. temperatureThe mixture is cooled to -60°
  2. extractionthe aqueous phase is extracted with ether
  3. washThe combined ether layers are washed with water and with brine
  4. customdried
  5. customSolvent is removed in vacuo
  6. customthe crude product is triturated with hexane
  7. customthe hexane-soluble fraction is purified by prep

Sources & evidence

ORD record
ord-02ce67d8095149e185afb5960f5c38eb
Source dataset
uspto-grants-1987_04
Patent number
US04661617

Reaction notes

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