1,4-Cyclohexanedicarboxylic acid, 2,5-dioxo-, 1,4-diethyl ester → rel-(1R,4S)-2,5-Bis(methylene)-1,4-cyclohexanediol

HRID 2120984Notes

Reaction equation

HRID 2120984 reaction equation
CCO[C:4]([CH:6]1[C:12](=[O:13])[CH2:11][CH:10]([C:14](OCC)=O)[C:8](=[O:9])[CH2:7]1)=O.[H-].[H-].[H-].[H-].[Li+].[Al+3]>O1CCCC1>[OH:9][C@H:8]1[CH2:7][C:6](=[CH2:4])[C@H:12]([OH:13])[CH2:11][C:10]1=[CH2:14]

Participants

4

Reactant 2

HCID 953101,4-Cyclohexanedicarboxylic acid, 2,5-dioxo-, 1,4-diethyl esterHCID 21226445Aluminium lithium hydride

Product 1

HCID 54436986rel-(1R,4S)-2,5-Bis(methylene)-1,4-cyclohexanediol

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent2×

Procedure

A warm solution of dry, recrystallized diethyl 1,4-cyclohexanedione-2,5-dicarboxylate (30.75 g, 120 mmol) in 350 ml anhydrous tetrahydrofuran (THF) was added to a refluxing solution of 1.0 M LAH in THF (600 mL) over a 2 hour period. After an additional 1.5 hours at reflux and subsequent cooling, a saturated solution of aqueous Rochelles's salt (app. 73 mL) was added dropwise to the reaction mixture. The tartrate complex was filtered, washed with THF and the filtrate was concentrated to a paste. The paste was recrystallized from hot ethyl acetate; yield 4.39 g (31.3 mmol, 26.1%). A second recrystallization yielded 3.81 g (27.2 mmol, 22.6%).

Workup

  1. customA warm solution of dry
  2. temperatureAfter an additional 1.5 hours at reflux
  3. additionsubsequent cooling, a saturated solution of aqueous Rochelles's salt (app. 73 mL) was added dropwise to the reaction mixture
  4. filtrationThe tartrate complex was filtered
  5. washwashed with THF
  6. concentrationthe filtrate was concentrated to a paste
  7. customThe paste was recrystallized from hot ethyl acetate
  8. customA second recrystallization
  9. customyielded 3.81 g (27.2 mmol, 22.6%)

Sources & evidence

ORD record
ord-1c161e8346a54de1be76800c382a67d5
Source dataset
uspto-grants-2004_02
Patent number
US06693190B1

Reaction notes

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