1,2-Dichloroethane → (E)-5-(2,5-dimethoxy-3,4,6-trimethylphenyl)-3-methyl-2-penten-1-ol

HRID 1195468Notes

Reaction equation

HRID 1195468 reaction equation
C[Al](C)C.[CH2:5]([C:9]1[C:14]([O:15][CH3:16])=[C:13]([CH3:17])[C:12]([CH3:18])=[C:11]([O:19][CH3:20])[C:10]=1[CH3:21])[CH2:6]C#C.C([Li])C[CH2:24][CH3:25].C=[O:28].Cl[CH2:30][CH2:31]Cl>C1COCC1.[Cl-].[Cl-].[CH-]1C=CC=C1.[CH-]1C=CC=C1.[Zr+2]>[CH3:16][O:15][C:14]1[C:13]([CH3:17])=[C:12]([CH3:18])[C:11]([O:19][CH3:20])=[C:10]([CH3:21])[C:9]=1[CH2:5][CH2:6]/[C:30](/[CH3:31])=[CH:25]/[CH2:24][OH:28]

Participants

8

Reactant 5

HCID 111,2-Dichloroethane2×HCID 712FormaldehydeHCID 16682925TrimethylaluminumHCID 216084171-(3-Butynyl)-3,6-dimethoxy-2,4,5-trimethylbenzeneHCID 178418339Butyllithium

Product 1

HCID 15837167(E)-5-(2,5-dimethoxy-3,4,6-trimethylphenyl)-3-methyl-2-penten-1-ol

Reagents, catalysts & solvents 2

HCID 131716798Zirconocene dichiorideCatalystHCID 8028TetrahydrofuranSolvent

Conditions

Temperature
50 °C

Procedure

A suspension of zirconocene dichloride (2.61 g; 8.9 mmol) in 1,2-dichloroethane was treated firstly with trimethylaluminium (10.9 ml; 114 mmol), then with a solution of 1-(3-butynyl)-3,6-dimethoxy-2,4,5-trimethylbenzene (10.6 g; 45.7 mmol) in 1,2-dichloroethane (60 ml). The mixture was heated to 50° C. for 46 hours, thereafter cooled to -40°, diluted with THF (20 ml), treated with 40 ml of a 1.6 molar n-butyllithium solution (in hexane) and finally with 4.37 g of paraformaldehyde. The resulting reaction mixture was stirred at room temperature for 20 hours and subsequently introduced into ice-cold 2N hydrochloric acid solution. The mixture was extracted twice with ether and the combined extracts were washed with water and dried. The oil which remained after removal of the solvent was purified on silica gel (eluent: hexane/ethyl acetate=2.5/1), yielding (E)-5-(2,5-dimethoxy-3,4,6-trimethylphenyl)-3-methyl-2-penten-1-ol as a colourless oil which crystallized slowly at room temperature (m.p.: 46° C.).

Workup

  1. temperaturecooled to -40°
  2. customThe resulting reaction mixture
  3. extractionThe mixture was extracted twice with ether
  4. washthe combined extracts were washed with water
  5. customdried
  6. customafter removal of the solvent
  7. customwas purified on silica gel (eluent: hexane/ethyl acetate=2.5/1)

Sources & evidence

ORD record
ord-ee112cb0006f4e1d8956374b78581694
Source dataset
uspto-grants-1992_05
Patent number
US05110955

Reaction notes

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