2-Ethylhexanol → 2-Ethylhexyl cyanoacetate

HRID 1015693Notes

Reaction equation

HRID 1015693 reaction equation
[C:1]([CH2:3][C:4]([OH:6])=[O:5])#[N:2].[CH2:7]([CH:9]([CH2:12][CH2:13][CH2:14][CH3:15])[CH2:10]O)[CH3:8].O.C1(C)C=CC(S(O)(=O)=O)=CC=1>O>[C:1]([CH2:3][C:4]([O:6][CH2:10][CH:9]([CH2:7][CH3:8])[CH2:12][CH2:13][CH2:14][CH3:15])=[O:5])#[N:2]

Participants

5

Reactant 3

HCID 77202-EthylhexanolHCID 9740Cyanoacetic acidHCID 521998p-Toluenesulfonic acid monohydrate

Product 1

HCID 963592-Ethylhexyl cyanoacetateYield 92%

Reagents, catalysts & solvents 1

HCID 962WaterSolvent3×

Conditions

Temperature
110 °C

Procedure

To a 1000 ml four neck flask fitted with mechanical agitator, thermometer, Dean and Stark apparatus and water condenser, add 237.5 g (2.23 mol on pure substance) 80 wt.-% cyanoacetic acid in water, 440 g (3.38 mol) 2-ethylhexanol and 1.2 g (6.3 mmol) p-toluenesulfonic acid monohydrate. Afterwards, the mixture is heated to reflux (110° C.) under atmospheric pressure for 1 hour and the water (both initial and formed) is azeotropically distilled out using a Dean and Stark apparatus returning the upper organic layer to the reactor. After 1 hour and at a temperature of 130° C. gradually a vacuum of 400 mbar is applied using a water respirator. The azeotropic distillation is maintained for further 6 hours while gradually increasing the vacuum from 400 mbar to 30 mbar in order to maintain a temperature of 130° C. until no further water is removed. After releasing the vacuum the reaction mixture is cooled to 90° C. After the addition of about 100 ml water (pre heated to 90° C.), the mixture is stirred at 85-90° C. for 10 minutes before separation of the phases. The upper organic layer is transferred to a 1000 ml four neck flask fitted with mechanical agitator, thermometer, packed column (ID=30 mm, H=1200 mm, packing metal raschid rings D=7 mm), water condenser and distillate flasks. Excess 2-Ethylhexanol is distilled out at 130-140° C. under a vacuum of 10-30 mbar. When complete increase the vacuum to 1.5 mbar and distilled out 2-ethylhexyl cyanoacetate at 130-140° C. 2-Ethylhexyl cyanoacetate is obtained as a colourless liquid. The reaction yield is 92% (based on cyanoacetic acid).

Workup

  1. temperatureAfterwards, the mixture is heated
  2. distillationis azeotropically distilled out
  3. customat a temperature of 130° C.
  4. distillationThe azeotropic distillation
  5. temperatureis maintained for further 6 hours
  6. temperaturewhile gradually increasing the vacuum from 400 mbar to 30 mbar in order
  7. temperatureto maintain a temperature of 130° C. until no further water
  8. customis removed
  9. temperatureis cooled to 90° C
  10. additionAfter the addition of about 100 ml water (pre heated to 90° C.)
  11. customfitted with mechanical agitator
  12. distillationExcess 2-Ethylhexanol is distilled out at 130-140° C. under a vacuum of 10-30 mbar
  13. temperatureWhen complete increase the vacuum to 1.5 mbar
  14. distillationdistilled out 2-ethylhexyl cyanoacetate at 130-140° C

Sources & evidence

ORD record
ord-80c16c649b444f0c97cdf045af5f45b9
Source dataset
uspto-grants-2011_07
Patent number
US07985870B2

Reaction notes

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