Ethyl cyanoacetate → Ethyl 2-ethoxyethylidene-cyanoacetate

HRID 1374857Notes

Reaction equation

HRID 1374857 reaction equation
[C:1]([CH2:3][C:4]([O:6][CH2:7][CH3:8])=[O:5])#[N:2].[C:9](OCC)(OCC)([O:11][CH2:12][CH3:13])[CH3:10]>CC(O)=O>[CH2:9]([O:11][CH2:12][CH:13]=[C:3]([C:1]#[N:2])[C:4]([O:6][CH2:7][CH3:8])=[O:5])[CH3:10]

Participants

4

Reactant 2

HCID 7764Ethyl cyanoacetateHCID 66221Triethyl orthoacetate

Product 1

HCID 57299996Ethyl 2-ethoxyethylidene-cyanoacetateYield 82.6%

Reagents, catalysts & solvents 1

HCID 176Acetic AcidCatalyst2×

Conditions

Temperature
135 °C

Procedure

To a stirred solution of Ethyl cyanoacetate (46.8 g, 414 mMol) and Triethyl orthoacetate (84.4 g, 520 mMol), in a 250 mL round bottom flask fitted with a short path distillation head, was added HOAc (1.2 mL, 21 mMol). The reaction was slowly heated to 135° C. and maintained at that temperature to distill off the ethyl alcohol that was produced. (Distillation started at ˜106° C.) At 15 min. intervals HOAc (1.2 mL, 21 mMol) was added to the reaction for an additional three times. The reaction was then slowly heated to 150° C. then cooled back down to ˜80° C. The title product (62.64 g, 82%) was obtained by short path distillation under high vacuum (bp 128° C., HV) as a pale yellow crystalline solid. (Note; Cooling to the condenser was shut off to prevent plugging.): 1H NMR (400 MHz, CDCl3) δ 4.27 (q, 2H), 4.22 (q, 2H), 2.61 (s, 3H), 1.43 (t, 3H), 1.31 (t, 3H).

Workup

  1. temperaturemaintained at that temperature
  2. distillationto distill off the ethyl alcohol that
  3. customwas produced
  4. additionwas added to the reaction for an additional three times
  5. temperatureThe reaction was then slowly heated to 150° C.
  6. temperaturethen cooled back down to ˜80° C

Sources & evidence

ORD record
ord-7db0819026ee433b952c5a9805deda49
Source dataset
uspto-grants-2007_01
Patent number
US07166595B2

Reaction notes

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