Formaldehyde → 1,5-Dioxaspiro[5.5]undecane-3,3-dicarboxylic acid, diethyl ester

HRID 1584616Notes

Reaction equation

HRID 1584616 reaction equation
[CH:1]([O:6][CH3:7])([O:4][CH3:5])OC.C=O.[C:10]([O:18][CH2:19][CH3:20])(=[O:17])[CH2:11][C:12]([O:14][CH2:15][CH3:16])=[O:13].[C:21]1(=O)[CH2:26][CH2:25]C[CH2:23][CH2:22]1>C([O-])C.[Na+].S(=O)(=O)(O)O.S([O-])(O)(=O)=O.[Na+].C(O)C>[O:4]1[C:1]2([CH2:25][CH2:26][CH2:21][CH2:22][CH2:23]2)[O:6][CH2:7][C:11]([C:12]([O:14][CH2:15][CH3:16])=[O:13])([C:10]([O:18][CH2:19][CH3:20])=[O:17])[CH2:5]1

Participants

9

Reactant 4

HCID 712FormaldehydeHCID 7761Diethyl MalonateHCID 7967CyclohexanoneHCID 9005Trimethyl orthoformate

Product 1

HCID 1171211,5-Dioxaspiro[5.5]undecane-3,3-dicarboxylic acid, diethyl esterYield 82%

Reagents, catalysts & solvents 4

HCID 1118Sulfuric AcidCatalystHCID 516919Sodium BisulfateCatalystHCID 2723922Sodium ethoxideCatalystHCID 702EthanolSolvent

Conditions

Temperature
50 °C

Procedure

A suspension, stirred at room temperature, of 148.4 g of trimethyl orthoformate (1.4 mol) and 63.0 g of paraformaldehyde (2.1 mol) was admixed with 10.0 g of ethanol and 0.25 g of sodium ethanolate. The mixture was then heated to 50° C., and 160.2 g of diethyl malonate (1.0 mol) were added gradually over a period of 1.75 hours. At first, the reaction mixture thus obtained was stirred for a further 2 hours at 50° C., followed by cooling to room temperature. With stirring, 0.37 g of sulfuric acid and 1.0 g of sodium hydrogen sulfate were added, after which the temperature was initially, for a further 2 hours, regulated to 50° C. In the course of subsequent heating to 80° C., 72.3 g of low-boiling components were taken off, and 98.0 g of cyclohexanone (1.0 mol) were then gradually added over a period of 1.75 hours, a further 74.4 g of low-boiling components distilling over. Subsequent fractional distillation without using a column gave 246.2 g of colorless target product (78.3% of the theoretical yield, based on diethyl malonate used) with a purity, determined by gas chromatography, of 95.4 FID percent by area.

Workup

  1. customAt first, the reaction mixture thus obtained
  2. temperatureby cooling to room temperature
  3. stirringWith stirring
  4. waitafter which the temperature was initially, for a further 2 hours
  5. customregulated to 50° C
  6. temperatureIn the course of subsequent heating to 80° C.
  7. distillationa further 74.4 g of low-boiling components distilling over
  8. distillationSubsequent fractional distillation

Sources & evidence

ORD record
ord-a2e33d34cc3c45b788fa619c78c1c57e
Source dataset
uspto-grants-1999_08
Patent number
US05932747

Reaction notes

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