Lithium hydroxide, monohydrate → 4-METHYLTETRAHYDRO-2H-PYRAN-4-CARBOXYLIC ACID

HRID 1049310Notes

Reaction equation

HRID 1049310 reaction equation
[CH3:1][C:2]1([C:8]([O:10]C)=[O:9])[CH2:7][CH2:6][O:5][CH2:4][CH2:3]1.O.[OH-].[Li+]>O1CCOCC1.O.CO>[CH3:1][C:2]1([C:8]([OH:10])=[O:9])[CH2:7][CH2:6][O:5][CH2:4][CH2:3]1

Participants

4

Reactant 2

HCID 168937Lithium hydroxide, monohydrateHCID 11019135Methyl 4-methyloxane-4-carboxylate

Product 1

HCID 115718204-METHYLTETRAHYDRO-2H-PYRAN-4-CARBOXYLIC ACIDYield 101.2%

Reagents, catalysts & solvents 1

HCID 22592949Dioxane methanol waterSolvent

Procedure

A solution of methyl 4-methyltetrahydro-2H-pyran-4-carboxylate (5.00 g, 31.6 mmol) in 1:1:1 dioxane/water/MeOH (60 mL) was treated with lithium hydroxide hydrate (5.31 g, 126 mmol) and stirred at RT overnight. The mixture was partially concentrated, diluted with water and EtOAc and acidified to pH=1 with 6M HCl. The layers were separated, the aqueous layer extracted with additional EtOAc (50 mL) and the combined organics were washed with brine, dried over Na2SO4 and concentrated to dryness to afford 4-methyltetrahydro-2H-pyran-4-carboxylic acid (4.61 g, 100%). 1H NMR (400 MHz, DMSO-d6): δ 12.29 (s, 1H), 3.65 (dt, J=11.8, 4.3 Hz, 2H), 3.33-3.32 (m, 2H), 1.87-1.86 (m, 2H), 1.35 (ddd, J=13.5, 9.9, 4.1 Hz, 2H), 1.13 (s, 3H).

Workup

  1. concentrationThe mixture was partially concentrated
  2. additiondiluted with water and EtOAc
  3. customThe layers were separated
  4. extractionthe aqueous layer extracted with additional EtOAc (50 mL)
  5. washthe combined organics were washed with brine
  6. dry with materialdried over Na2SO4
  7. concentrationconcentrated to dryness

Sources & evidence

ORD record
ord-4cf8477cbd414b63a2170ecea93a2e3a
Source dataset
uspto-grants-2016_07
Patent number
US09382228B2

Reaction notes

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