Methyl 5-(chloromethyl)-2-furoate → HCID 21962618, compound

HRID 2211931Notes

Reaction equation

HRID 2211931 reaction equation
[CH3:1][C:2]1([CH3:15])[C:11]2[C:6](=[CH:7][C:8]([CH3:12])=[CH:9][CH:10]=2)[C:5]([CH3:14])([CH3:13])[CH2:4][CH2:3]1.Cl[CH2:17][C:18]1[O:22][C:21]([C:23]([O:25][CH3:26])=[O:24])=[CH:20][CH:19]=1.[Cl-].[Cl-].[Cl-].[Al+3]>C(Cl)Cl>[CH3:12][C:8]1[C:9]([CH2:17][C:18]2[O:22][C:21]([C:23]([O:25][CH3:26])=[O:24])=[CH:20][CH:19]=2)=[CH:10][C:11]2[C:2]([CH3:15])([CH3:1])[CH2:3][CH2:4][C:5]([CH3:14])([CH3:13])[C:6]=2[CH:7]=1

Participants

5

Reactant 3

HCID 75065Methyl 5-(chloromethyl)-2-furoateHCID 811871,2,3,4-Tetrahydro-1,1,4,4,6-pentamethylnaphthaleneHCID 6451240Aluminum(III) Chloride

Product 1

HCID 21962618HCID 21962618, compoundYield 46%

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent2×

Procedure

To a solution containing 1,1,4,4,6-pentamethyl-1,2,3,4-tetrahydronaphtalene 4 (20 g, 99 mmol) and methyl 5-(chloromethyl)-2-furoate 5 (17.28 g, 99 mmol) in methylene chloride (500 mL, 0.2 M), aluminum trichloride (16.46 g, 124 mmol) is added slowly as a solid at the reflux temperature of methylene chloride. The solution is refluxed for an additional two hours. The reaction is monitored by tlc in 10% ethyl acetate/hexanes solution. The reaction is cooled to room temperature and the unreacted aluminum trichloride is quenched with water over 15 minutes. The crude product is extracted with methylene chloride and passed through silica gel (80 g) and eluted with methylene chloride. The solvent is evaporated in vacuo to syrup. The crude product us purified with silica gel (300 g) via a plug filtration column. Methyl 5-[(3,5,5,8,8-pentamethyl-5,6,7,8-tetrahydro-2-naphthalenyl)methyl]-2-furoate 6 is eluted with 2% ethyl acetate/hexanes to afford 15.4 g (46% yield). NMR 1.25 (s, 6H), 1.28 (s, 6H), 1.67 (s, 4H), 2.23 (s, 3H), 3.89 (s, 3H), 3.97 (s, 2H), 5.95 (d, 1H), 7.09 (m, 3H).

Workup

  1. temperatureThe solution is refluxed for an additional two hours
  2. customthe unreacted aluminum trichloride is quenched with water over 15 minutes
  3. extractionThe crude product is extracted with methylene chloride
  4. washeluted with methylene chloride
  5. customThe solvent is evaporated in vacuo to syrup
  6. filtrationThe crude product us purified with silica gel (300 g) via a plug filtration column
  7. washMethyl 5-[(3,5,5,8,8-pentamethyl-5,6,7,8-tetrahydro-2-naphthalenyl)methyl]-2-furoate 6 is eluted with 2% ethyl acetate/hexanes
  8. customto afford 15.4 g (46% yield)

Sources & evidence

ORD record
ord-8fba10417794417a96df2d07b5f80543
Source dataset
uspto-grants-2006_09
Patent number
US07101878B1

Reaction notes

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