Formaldehyde → Methyl 3-hydroxypivalate

HRID 1904436Notes

Reaction equation

HRID 1904436 reaction equation
C(N(CC)CC)C.C=O.C(=O)C(C)C.[OH:15][CH2:16][C:17]([CH3:28])([CH3:27])[C:18]([O:20][CH2:21]C(C)(C)CO)=[O:19]>CO.C[O-].[Na+]>[OH:15][CH2:16][C:17]([CH3:28])([CH3:27])[C:18]([O:20][CH3:21])=[O:19]

Participants

7

Reactant 4

HCID 712FormaldehydeHCID 6561IsobutyraldehydeHCID 8471TriethylamineHCID 142183-Hydroxy-2,2-dimethylpropyl hydroxypivalate

Product 1

HCID 84152Methyl 3-hydroxypivalateYield 88.3%

Reagents, catalysts & solvents 2

HCID 10942334Sodium MethoxideCatalystHCID 887MethanolSolvent

Procedure

120 g (1.18 mol) of triethylamine were added with vigorous stirring under reflux to a hot mixture at 50° C. of 975 g (12 mol) of 37% strength formaldehyde solution and 865 g (12 mol) of isobutyraldehyde, and the mixture was allowed to rise to 92° to 94° C. in the course of 10 minutes. Triethylamine and water were then distilled off at from 150 to 30 mbar in the course of from 15 to 20 minutes and at a maximum bottom of column temperature of from 70° to 75° C. The remaining mixture was then heated under atmospheric pressure to 160° C. in the course of 15 minutes, during which, essentially, further residues of water came off, and was stirred at that temperature for a further 160 minutes. Distillation of the mixture gave 180 g of a fraction of boiling range 80°-95° C. at 8-10 mbar, which contained 119 g (1.17 mol) of hydroxypivalinaldehyde, corresponding to 9.75%, based on the starting materials. This left a residue of 305 g which, according to analysis by gas chromatography, comprised 96% (869 g; 4.26 mol) of 2,2-dimethylpropane-1,3-diol hydroxypivalate, corresponding to a 71% yield, based on the starting materials (overall selectivity 80.75%). The residue was taken up in 1,100 ml of methanol, 15 g (0.28 mol) of sodium methanolate were added, and the mixture was stirred at room temperature for 15 hours. Neutralization with acetic acid and fractional distillation gave 496.5 g (3.76 mol) of methyl hydroxypivalate, corresponding to 88.34% yield, based on esterdiol III, and also 375.4 g (3.68 mol) of 2,2-dimethyl-1,3-propanediol, corresponding to an 86.4% yield.

Workup

  1. customto rise to 92° to 94° C. in the course of 10 minutes
  2. distillationTriethylamine and water were then distilled off at from 150 to 30 mbar in the course of from 15 to 20 minutes
  3. customof from 70° to 75° C
  4. temperatureThe remaining mixture was then heated under atmospheric pressure to 160° C. in the course of 15 minutes, during which
  5. stirringwas stirred at that temperature for a further 160 minutes
  6. distillationDistillation of the mixture
  7. customgave 180 g of a fraction of boiling range 80°-95° C. at 8-10 mbar, which
  8. waitThis left a residue of 305 g which
  9. stirringthe mixture was stirred at room temperature for 15 hours
  10. distillationNeutralization with acetic acid and fractional distillation

Sources & evidence

ORD record
ord-167d551c40fa4af2b07a54feb89cee06
Source dataset
uspto-grants-1989_06
Patent number
US04837357

Reaction notes

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