Trimethylolpropane → Trimethylolpropane tris(acetoacetate)

HRID 747071Notes

Reaction equation

HRID 747071 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(C)(C)C)(=[O:15])[CH2:11][C:12]([CH3:14])=[O:13]>C1(C)C=CC=CC=1>[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

4

Reactant 2

HCID 6510TrimethylolpropaneHCID 15538Tert-butyl acetoacetate3×

Product 1

HCID 18402738Trimethylolpropane tris(acetoacetate)

Reagents, catalysts & solvents 1

HCID 1140TolueneSolvent

Conditions

Temperature
111 °C

Procedure

A 1 liter, 4-neck round-bottom flask fitted with mechanical stirrer, pressure equalizing addition funnel (nitrogen inlet), thermocouple connected to a controller and mantle for heating, a 5-plate Oldershaw column and vacuum type distilling head with finger type condenser and stopcock to control the reflux ratio was charged with 201 g (1.50 mol) trimethylolpropane, 100 g (0.63 mol) tert.-butyl acetoacetate and 282 g of toluene. An additional 626.5 g (3.96 mol) of tert.-butyl acetoacetate was charged to the addition funnel. A slow nitrogen flow was maintained through the addition funnel and reactor and the mixture was heated to about 111° C. Reflux began when the flask contents reached about 111° C. and the reflux ratio/take-off was adjusted to keep the head temperature between 82-84° C. The additional tert.-butyl acetoacetate was gradually added over about 4 hr as 442 ml of distillate was collected. The pot temperature increased gradually to 117° C. during the addition. Distillation continued: the pot temperature gradually increased to 132° C. and the head temperature increased to 109° C. over an additional 2.3 hr. Total distillate collected was 472 g determined to be 70.59% tert.-butanol or 100.1% of theory.

Workup

  1. customA 1 liter, 4-neck round-bottom flask fitted with mechanical stirrer
  2. additionaddition funnel (nitrogen inlet)
  3. temperaturemantle for heating
  4. distillationa 5-plate Oldershaw column and vacuum type distilling head with finger type condenser
  5. temperatureA slow nitrogen flow was maintained through the addition funnel and reactor
  6. temperatureReflux
  7. customreached about 111° C.
  8. temperaturethe reflux ratio/take-off
  9. custombetween 82-84° C
  10. customwas collected
  11. temperatureThe pot temperature increased gradually to 117° C. during the addition
  12. distillationDistillation
  13. temperaturethe pot temperature gradually increased to 132° C.
  14. temperaturethe head temperature increased to 109° C. over an additional 2.3 hr
  15. distillationTotal distillate collected

Sources & evidence

ORD record
ord-4680c5edc92f4d5d89cc97c350278fde
Source dataset
uspto-grants-2008_07
Patent number
US07396429B2

Reaction notes

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