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Ethyl Acetate → 2-[2-(5,5,8,8-Tetramethyl-5,6,7,8-tetrahydronaphth-2-yl)ethynyl]-5-hydroxymethylpyridine

HRID 5988
Notes
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Reaction equation

HRID 5988 reaction equation
[H-].[Al+3].[Li+].[H-].[H-].[H-].[CH3:7][C:8]1([CH3:33])[CH2:17][CH2:16][C:15]([CH3:19])([CH3:18])[C:14]2[CH:13]=[C:12]([C:20]#[C:21][C:22]3[CH:32]=[CH:31][C:25]([C:26](OCC)=[O:27])=[CH:24][N:23]=3)[CH:11]=[CH:10][C:9]1=2.[H-].C(OCC)(=O)C.[Cl-].[NH4+]>C(OCC)C>[CH3:7][C:8]1([CH3:33])[CH2:17][CH2:16][C:15]([CH3:18])([CH3:19])[C:14]2[CH:13]=[C:12]([C:20]#[C:21][C:22]3[CH:32]=[CH:31][C:25]([CH2:26][OH:27])=[CH:24][N:23]=3)[CH:11]=[CH:10][C:9]1=2
ParticipantsConditionsProcedureWorkupSources & evidenceReaction notes

Participants

7

Reactant 5

HCID 8857Ethyl AcetateHCID 25517Ammonium ChlorideHCID 166653HydrideHCID 15228883Ethyl 6-[2-(5,5,8,8-tetramethyl-5,6,7,8-tetrahydronaphth-2-yl)ethynyl]nicotinoateHCID 21226445Aluminium lithium hydride

Product 1

HCID 19372836
2-[2-(5,5,8,8-Tetramethyl-5,6,7,8-tetrahydronaphth-2-yl)ethynyl]-5-hydroxymethylpyridine

Reagents, catalysts & solvents 1

HCID 3283Diethyl EtherSolvent2×

Conditions

Temperature
-65 °C

Procedure

A 250 ml 3-necked flask is fitted with a stirrer, a dropping funnel, a nitrogen inlet and a thermometer. In the flask is placed a solution of 379.5 mg (10 mmol) of lithium aluminum hydride in 30 ml of dry diethyl ether. The solution is cooled to -65° C. under nitrogen and a solution of 3.6148 g (10 mmol) of ethyl 6-[2-(5,5,8,8-tetramethyl-5,6,7,8-tetrahydronaphth-2-yl)ethynyl]-nicotinoate in 15 ml of dry ether is added dropwise at a rate such that the temperature does not exceed -60° C. The mixture is stirred at -30° C. for 1 hour and the excess hydride is then destroyed by the addition of 300 mg (3.4 mmol) of ethyl acetate. The reaction mixture is then hydrolyzed by adding 3 ml of saturated ammonium chloride solution and allowing the temperature to rise to room temperature. The mixture is then filtered and the residue washed with ether. The ether layer is then washed with saturated sodium chloride solution, dried (MgSO4) and then concentrated in vacuo. The residue is purified by chromatography followed by recrystallization to give the title compound.

Workup

  1. customA 250 ml 3-necked flask is fitted with a stirrer, a dropping funnel, a nitrogen inlet
  2. customdoes not exceed -60° C
  3. customto rise to room temperature
  4. filtrationThe mixture is then filtered
  5. washthe residue washed with ether
  6. washThe ether layer is then washed with saturated sodium chloride solution
  7. dry with materialdried (MgSO4)
  8. concentrationconcentrated in vacuo
  9. customThe residue is purified by chromatography
  10. customfollowed by recrystallization

Sources & evidence

ORD record
ord-bbaaf1b0e141462ea39d5493141308d6
Source dataset
uspto-grants-1993_09
DOI
10.6084/m9.figshare.5104873.v1
Patent number
US05246962

Reaction notes

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On this pageParticipantsConditionsProcedureWorkupSources & evidenceReaction notes