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

HRID 1584617Notes

Reaction equation

HRID 1584617 reaction equation
C=O.[C:3]([O:11][CH2:12][CH3:13])(=[O:10])[CH2:4][C:5]([O:7][CH2:8][CH3:9])=[O:6].[C:14]1(=O)[CH2:19][CH2:18]C[CH2:16][CH2:15]1.[CH:21](OC)([O:24][CH3:25])[O:22][CH3:23]>C(O)C.CC[O-].[Na+].S(=O)(=O)(O)O.S([O-])(O)(=O)=O.[Na+]>[O:24]1[C:21]2([CH2:18][CH2:19][CH2:14][CH2:15][CH2:16]2)[O:22][CH2:23][C:4]([C:5]([O:7][CH2:8][CH3:9])=[O:6])([C:3]([O:11][CH2:12][CH3:13])=[O:10])[CH2:25]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 65.9%

Reagents, catalysts & solvents 4

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

Conditions

Temperature
50 °C

Procedure

A suspension, stirred at room temperature, of 60.0 g of paraformaldehyde (2.0 mol) and 0.25 g of sodium ethylate in 50.0 g of ethanol had 160.2 g of diethyl malonate (1.0 mol) added to it gradually over a period of one hour, the internal temperature being kept, by cooling, between 20° C. and 30° C. The reaction was allowed to continue for 2 hours at 50° C., before 0.4 g of sulfuric acid and 1.0 g of sodium hydrogen sulfate were added and 98 g of cyclohexanone (1.0 mol) were gradually added over a period of 5 minutes. The mixture was heated to 50° C. for one hour, 112.2 g of trimethyl orthoformate were added gradually over a period of one hour, after which the reaction was allowed to continue for a further 2 hours at 50° C. Subsequent heating caused 159.6 g of low-boiling components to distill over. The remaining residue was fractionated in an oil pump vacuum, 213.8 g of target product [lacuna] column gave 197.8 g of colorless target product (74.1% of the theoretical yield, based on diethyl malonate used). The purity, determined by gas chromatography, was 96 FID percent by area.

Workup

  1. additionadded to it gradually over a period of one hour
  2. temperatureby cooling, between 20° C. and 30° C
  3. additionwere added
  4. temperatureSubsequent heating
  5. distillationto distill over

Sources & evidence

ORD record
ord-6fb932e07e28410886b10039f8eaef03
Source dataset
uspto-grants-1999_08
Patent number
US05932747

Reaction notes

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