Diethyl tetrahydropyran-4,4-dicarboxylate → Ethyl 4-(hydroxymethyl)oxane-4-carboxylate

HRID 1584417Notes

Reaction equation

HRID 1584417 reaction equation
[O:1]1[CH2:6][CH2:5][C:4]([C:12](OCC)=[O:13])([C:7]([O:9][CH2:10][CH3:11])=[O:8])[CH2:3][CH2:2]1.[H-].C([Al+]CC(C)C)C(C)C>C1(C)C=CC=CC=1>[OH:13][CH2:12][C:4]1([C:7]([O:9][CH2:10][CH3:11])=[O:8])[CH2:5][CH2:6][O:1][CH2:2][CH2:3]1

Participants

4

Reactant 2

HCID 239606Diethyl tetrahydropyran-4,4-dicarboxylateHCID 21225700Diisobutylaluminumhydride

Product 1

HCID 22439651Ethyl 4-(hydroxymethyl)oxane-4-carboxylate

Reagents, catalysts & solvents 1

HCID 1140TolueneSolvent

Conditions

Temperature
-25 °C

Procedure

A solution of diethyl tetrahydro-4H-pyran-4,4-dicarboxylate, the compound of Formula (7a), (12 Kg) in toluene (104 Kg) was cooled to between -30° C. to -35° C., and diisobutylaluminum hydride (69 Kg) was added at such a rate so as to maintain a reaction temperature of -25° C. After the addition was complete, the temperature was raised to 15° C. over 3 hours, and the reaction stirred until all starting material was consumed. The mixture was then recooled to -15° C. and allowed to stand overnight. The product was partitioned between ethyl acetate (54 Kg), ethanol (48 Kg), and saturated sodium sulfate solution (60 liters), and the mixture stirred overnight at 250C. The precipitated salts were filtered off, washed with tetrahydrofuran, and the filtrate washed with brine and separated. The organic layer was dried over magnesium sulfate and solvent removed under reduced pressure, to give ethyl 4-hydroxymethyltetrahydropyran-4-carboxylate (3.8 Kg), the compound of Formula (8a).

Workup

  1. additionwas added at such a rate so as
  2. additionAfter the addition
  3. temperaturethe temperature was raised to 15° C. over 3 hours
  4. customwas consumed
  5. customwas then recooled to -15° C.
  6. customThe product was partitioned between ethyl acetate (54 Kg), ethanol (48 Kg), and saturated sodium sulfate solution (60 liters)
  7. stirringthe mixture stirred overnight at 250C
  8. filtrationThe precipitated salts were filtered off
  9. washwashed with tetrahydrofuran
  10. washthe filtrate washed with brine
  11. customseparated
  12. dry with materialThe organic layer was dried over magnesium sulfate and solvent
  13. customremoved under reduced pressure

Sources & evidence

ORD record
ord-5935dfaaae3b4008948d984d5215bf56
Source dataset
uspto-grants-1999_08
Patent number
US05932595

Reaction notes

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