Ethyl cyanoacetate → Ethyl 2-cyano-3-propylhex-2-enoate

HRID 3668

Reaction equation

HRID 3668 reaction equation
[CH3:1][CH2:2][CH2:3][C:4](=O)[CH2:5][CH2:6][CH3:7].[C:9]([CH2:11][C:12]([O:14][CH2:15][CH3:16])=[O:13])#[N:10].CC(OCC1C2C(=CC=CC=2)C(COC(C)=O)=C2C=1C=CC=C2)=O>C1CCCCC1.C(OCC)(=O)C>[C:9]([C:11](=[C:4]([CH2:5][CH2:6][CH3:7])[CH2:3][CH2:2][CH3:1])[C:12]([O:14][CH2:15][CH3:16])=[O:13])#[N:10]

Participants

6

Reactant 3

HCID 7764Ethyl cyanoacetateHCID 312464-HeptanoneHCID 613145Acetic acid 10-acetoxymethyl-anthracen-9-ylmethyl ester

Product 1

HCID 2058456Ethyl 2-cyano-3-propylhex-2-enoateYield 80,000%

Reagents, catalysts & solvents 2

HCID 8078CyclohexaneSolventHCID 8857Ethyl AcetateSolvent

Procedure

In a 100 mL round-bottom flask was dissolved 4-heptanone (11.4 g, 0.10 mmole) and ethyl cyanoacetate (11.30 g, 0.100 mole) in cyclohexane (25 mL). Acetic add (1.0 mL) and NH4OAc (2.0 g) were added. The solution was magnetically stirred and heated to reflux with a Dean-Stark trap in place overnight under N2. The reaction was cooled to ambient, diluted with ethyl acetate (100 mL) washed with H2O (2×50 mL) and brine (25 mL). The organic extracts were dried (Na2SO4, filtered and concentrated under vacuum to give an oil that was distilled (bp. 135°-137° C., 20 mmHg) to give Ethyl α-cyano-α-(4-heptylidene)acetate (16.65 g, 0.080 mole, 80%). IR (neat film) 2950, 2910, 2860, 2200, 1725, 1570, 1235, 1085 cm-1 ; 1H NMR (400 MHz, CDCl3 δ 4.15 (q, J=9 Hz, 2H), 2.60 (t, J=10 Hz, 2H), 2.38 (t, J=10 Hz, 2H), 1.25 (t, J=9 Hz, 2H), 1.40 (sextet, J=9 Hz, 2H), 1.25 (t, J=9 Hz, 3H), 0.88 (m, 6H); 13C NMR (100 MHz, CDCl3) δ 181.2, 161.5, 115.5, 104.6, 61.4, 40.2, 35.2, 21.9, 21.4, 14.1, 13.8 (one carbon not observed due to overlap); MS (CI) m/e 211 (14.5), 210 (100), 209 (3.59), 182 (3.5), 164 (2.8); HRMS (CI) calcd for C12H20NO2 (M+H) m/e 210.1484, found 210.1491.

Workup

  1. additionwere added
  2. temperatureheated
  3. temperatureto reflux with a Dean-Stark trap in place overnight under N2
  4. temperatureThe reaction was cooled to ambient,
  5. washwashed with H2O (2×50 mL) and brine (25 mL)
  6. dry with materialThe organic extracts were dried (Na2SO4
  7. filtrationfiltered
  8. concentrationconcentrated under vacuum
  9. customto give an oil that
  10. distillationwas distilled (bp. 135°-137° C., 20 mmHg)

Sources & evidence

ORD record
ord-58a8141f935a45458cf7a40ae4224d27
Source dataset
uspto-grants-1998_03
Patent number
US05734061

Linked notes

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