Vanillin → Allyl 4-[3-methoxy-4-(2-tetrahydropyranyloxy)cinnamoyl]-1-methyl-1-cyclohexanecarboxylate

HRID 2225495Notes

Reaction equation

HRID 2225495 reaction equation
[CH3:1][O:2][C:3]1[CH:4]=[C:5]([CH:8]=[CH:9][C:10]=1[O:11][CH:12]1[CH2:17][CH2:16][CH2:15][CH2:14][O:13]1)[CH:6]=O.O=CC1C=CC(O)=C(OC)C=1.[C:29]([CH:32]1[CH2:37][CH2:36][C:35]([CH3:44])([C:38]([O:40][CH2:41][CH:42]=[CH2:43])=[O:39])[CH2:34][CH2:33]1)(=[O:31])[CH3:30].C[Si](C)(C)[N-][Si](C)(C)C.[Na+].[Cl-].[NH4+]>C1COCC1>[CH3:1][O:2][C:3]1[CH:4]=[C:5]([CH:8]=[CH:9][C:10]=1[O:11][CH:12]1[CH2:17][CH2:16][CH2:15][CH2:14][O:13]1)[CH:6]=[CH:30][C:29]([CH:32]1[CH2:37][CH2:36][C:35]([CH3:44])([C:38]([O:40][CH2:41][CH:42]=[CH2:43])=[O:39])[CH2:34][CH2:33]1)=[O:31]

Participants

7

Reactant 5

HCID 1183VanillinHCID 25517Ammonium ChlorideHCID 2724254Sodium bis(trimethylsilyl)amideHCID 30218293-Methoxy-4-[(tetrahydro-2H-pyran-2-yl)oxy]benzaldehydeHCID 19004629Allyl 4-acetyl-1-methyl-1-cyclohexanecarboxylate

Product 1

HCID 67758353Allyl 4-[3-methoxy-4-(2-tetrahydropyranyloxy)cinnamoyl]-1-methyl-1-cyclohexanecarboxylateYield 39.2%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent

Procedure

A solution of 1.5 g of 3-methoxy-4-(2-tetrahydropyranyloxy)benzaldehyde, derived from vanillin by the introduction of tetrahydropyranyl group thereinto, 1.5 g of allyl 4-acetyl-1-methyl-1-cyclohexanecarboxylate (Example 37), and 8 ml of sodium hexamethyldisilazide (THF 1M solution), mixed in 50 ml of THF, was reacted for 4 hours under an argon stream, while it was refluxed. After reaction, 100 ml of an aqueous ammonium chloride solution was added to the reaction solution. The solution was extracted three times with 50 ml of ethyl acetate. The organic layer obtained was washed three times with an aqueous sodium chloride solution and dried over magnesium sulfate. Thereafter, the solvent was removed in vacuo. The oily substance obtained was subjected to column chromatography using 50 g of silica gel. From the fraction eluted with hexane and ethyl acetate=4:1, the solvent was removed in vacuo, yielding 1.1 g of allyl 4-[3-methoxy-4-(2-tetrahydropyranyloxy)cinnamoyl]-1-methyl-1-cyclohexanecarboxylate (a compound of the present invention) as a yellow oil, which had the following physiochemical properties:

Workup

  1. customwas reacted for 4 hours under an argon stream
  2. temperaturewhile it was refluxed
  3. additionwas added to the reaction solution
  4. extractionThe solution was extracted three times with 50 ml of ethyl acetate
  5. customThe organic layer obtained
  6. washwas washed three times with an aqueous sodium chloride solution
  7. dry with materialdried over magnesium sulfate
  8. customThereafter, the solvent was removed in vacuo
  9. customThe oily substance obtained
  10. washFrom the fraction eluted with hexane and ethyl acetate=4:1
  11. customthe solvent was removed in vacuo

Sources & evidence

ORD record
ord-d6d3ec0a1692470e85817a7deb6e43eb
Source dataset
uspto-grants-1994_09
Patent number
US05344845

Reaction notes

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