Triethylamine → HCID 67899429, compound

HRID 654425Notes

Reaction equation

HRID 654425 reaction equation
[H-].[Al+3].[Li+].[H-].[H-].[H-].C(N(CC)CC)C.O[C:15]1[CH:16]=[C:17]([CH:22]=[CH:23][CH:24]=1)[C:18]([O:20][CH3:21])=O.[CH:25]12[CH2:34][CH:29]3[CH2:30][CH:31]([CH2:33][CH:27]([CH2:28]3)[CH2:26]1)[CH2:32]2.C12CC3CC(CC(C3)C1=[O:45])C2>C1COCC1>[OH:45][C:25]12[CH2:34][CH:29]3[CH2:30][CH:31]([CH2:33][CH:27]([CH2:28]3)[C:26]1=[CH:21][O:20][CH2:18][C:17]1[CH:22]=[CH:23][CH:24]=[CH:15][CH:16]=1)[CH2:32]2

Participants

6

Reactant 4

HCID 8471TriethylamineHCID 88068Methyl 3-HydroxybenzoateHCID 19887292HCID 19887292, compoundHCID 21226445Aluminium lithium hydride

Product 1

HCID 67899429HCID 67899429, compoundYield 10%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent2×

Procedure

A 500 ml three-neck, round bottom flask is fit with a reflux condenser, 125 ml addition funnel, and a nitrogen inlet line with a two-way valve control. After the addition of 200 ml of dry THF, the solution is stirred and cooled under nitrogen on an ice bath. TiCl3 (156 mmol) is added rapidly followed by lithium aluminum hydride (75 mmol) in portions. The ice bath is removed and the solution is permitted to warm to ambient temperature. Upon the addition of triethylamine (86 mmol), the solution is refluxed for 1 h. At this time, a solution of 15-20 mmol of methyl 3-hydroxybenzoate and approximately a 10-20% excess of 2-adamantanone adamantane in about 50 ml of THF are added dropwise over several hours by means of the addition funnel. Refluxing is continued for another several hours. After completion, the cooled solution is quenched by the slow addition of about 50 ml of methanol, then about 100 ml of water. The black mixture is diluted in ether and repeatedly extracted with water until the aqueous phase is no longer colored. The solution is dried over Na2SO4 and concentrated in vacuo. Silica column chromatography is used to purify the desired product, 3-hydroxylphenylmethoxymethylene-adamantane. Ethyl acetate/hexane or methanol/CH2Cl2 solvent systems could be employed. The product (anticipated 10-30% yield; probably an oil) is characterized by NMR.

Workup

  1. additionA 500 ml three-neck, round bottom flask is fit with a reflux condenser, 125 ml addition funnel, and a nitrogen inlet line with a two-way valve control
  2. temperaturecooled under nitrogen on an ice bath
  3. customThe ice bath is removed
  4. temperaturethe solution is refluxed for 1 h
  5. temperatureRefluxing
  6. waitis continued for another several hours
  7. customAfter completion, the cooled solution is quenched by the slow addition of about 50 ml of methanol
  8. additionThe black mixture is diluted in ether
  9. extractionrepeatedly extracted with water until the aqueous phase
  10. dry with materialThe solution is dried over Na2SO4
  11. concentrationconcentrated in vacuo
  12. customto purify the desired product, 3-hydroxylphenylmethoxymethylene-adamantane

Sources & evidence

ORD record
ord-1d81bd0901104ceaaf7b496b4feb6303
Source dataset
uspto-grants-1992_07
Patent number
US05132204

Reaction notes

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