Trimethylolpropane → Trimethylolpropane tris(acetoacetate)

HRID 1740324Notes

Reaction equation

HRID 1740324 reaction equation
[CH2:1]([C:3]([CH2:8][OH:9])([CH2:6][OH:7])[CH2:4][CH3:5])[OH:2].[C:10]([O:16]C)(=[O:15])[CH2:11][C:12]([CH3:14])=[O:13].P(OC1C=CC=CC=1)(OC1C=CC=CC=1)OC1C=CC=CC=1.C([Sn](=O)CCCC)CCC>>[C:10]([OH:16])(=[O:15])[CH2:11][C:12]([CH3:14])=[O:13].[C:10]([OH:16])(=[O:15])[CH2:11][C:12]([CH3:14])=[O:13].[C:10]([OH:16])(=[O:15])[CH2:11][C:12]([CH3:14])=[O:13].[CH2:1]([C:3]([CH2:8][OH:9])([CH2:6][OH:7])[CH2:4][CH3:5])[OH:2]

Participants

5

Reactant 4

HCID 6510TrimethylolpropaneHCID 7540Triphenyl phosphiteHCID 7757Methyl acetoacetateHCID 61221Dibutyltin oxide

Product 1

HCID 18402738Trimethylolpropane tris(acetoacetate)

Procedure

A 1000 ml. four-necked flask fitted with overhead stirrer, nitrogen sparge tube, thermometer and Barrett trap on top of a 6" steam jacketed Vigreux column was charged with 134.2 g. trimethylolpropane (1.0 mol), 580.6 g. methyl acetoacetate (5.0 mols), 0.8 g. triphenyl phosphite and 0.8 g. dibutyltin oxide. Steam was turned on in the jacketed Vigreux and the mixture was stirred with a nitrogen sparge and heated. When the pot temperature reached 142° C. methanol began distilling rapidly from the mixture. Heating was continued for a total of 50 minutes to a maximum pot temperature of 185° C. Vacuum was then applied and the excess methyl acetoacetate was removed first at 20 mm. Hg then at 1 mm. Hg with a maximum pot temperature of 180° C. Yield of orange liquid product was 372.4 g., 96% of theory. A small amount of white solid formed in the sides of the flask after cooling to room temperature. This was removed by gravity filtration. Proton NMR showed 100% conversion based on integration of methylene adjacent to esterified oxygen relative to methyl of trimethylolpropane.

Workup

  1. customfour-necked flask fitted with overhead stirrer
  2. customnitrogen sparge tube
  3. additionwas charged with 134.2 g
  4. customsparge
  5. temperatureheated
  6. customreached 142° C.
  7. distillationbegan distilling rapidly from the mixture
  8. temperatureHeating
  9. customwas continued for a total of 50 minutes to a maximum pot temperature of 185° C
  10. customthe excess methyl acetoacetate was removed first at 20 mm. Hg
  11. customwith a maximum pot temperature of 180° C
  12. customA small amount of white solid formed in the sides of the flask
  13. customThis was removed by gravity filtration

Sources & evidence

ORD record
ord-9ca08c5935bc4c27a2bc43be004e38e4
Source dataset
uspto-grants-1999_10
Patent number
US05969046

Reaction notes

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