Ethyl cyanoacetate → HCID 14796094, compound

HRID 2350865Notes

Reaction equation

HRID 2350865 reaction equation
[H-].[Na+].[C:3]([CH2:5][C:6]([O:8][CH2:9][CH3:10])=[O:7])#[N:4].[H][H].C1(C)C=C(C)C=C(C)C=1[CH2:21][CH2:22][CH2:23][CH2:24][C:25]1[CH:34]=[CH:33][C:28]([C:29]([O:31][CH3:32])=[O:30])=[CH:27][CH:26]=1>O1CCCC1>[C:6]([CH:5]([C:3]#[N:4])[CH2:21][CH2:22][CH2:23][CH2:24][C:25]1[CH:26]=[CH:27][C:28]([C:29]([O:31][CH3:32])=[O:30])=[CH:33][CH:34]=1)([O:8][CH2:9][CH3:10])=[O:7]

Participants

6

Reactant 4

HCID 7764Ethyl cyanoacetateHCID 24758Sodium hydrideHCID 19847612HCID 19847612, compoundHCID 178418361HCID 178418361, compound

Product 1

HCID 14796094HCID 14796094, compound

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent

Conditions

Temperature
0 °C

Procedure

A mixture of 10.30 g (1.1 eq) of 80% sodium hydride in mineral oil is washed twice with anhydrous tetrahydrofuran (to remove the mineral oil) and 400 mL of tetrahydrofuran are then added. This is cooled to 0° C. and a solution of 35.29 g (1.0 eq) of ethyl cyanoacetate in anhydrous tetrahydrofuran is added dropwise under nitrogen. The mixture is stirred vigorously at ambient temperatures until the evolution of hydrogen ceases and an anhydrous solution of 89.33 g (1.0 eq) of methyl 4-(4-mesitylbutyl)benzoate is then added in a dropwise fashion. The mixture is stirred at ambient temperatures for 12 hours, then at reflux temperatures for 6 hours, and then cooled. The solvent is removed under reduced pressure and diethyl ether is added. The organic phase is separated, washed with water and brine, dried over magnesium sulfate, filtered and concentrated. The residue is chromatographed with 1:4 ethyl acetate:hexane and the homogeneous fractions are combined and concentrated to yield methyl 4-(5-carboethoxy-5-cyanopentyl)benzoate as a liquid, IR (film) vmax 2915, 2860, 2255, 1730, 1609, 1571, 1432, 1413, 1368, 1320, 1178, 1105, 1019, 962, 853, 759, and 602 cm-1 ; 1H NMR (CDCl3) delta 7.95 (d, J=8.1 Hz, 2H, Ar), 7.24 (d, J=8.1 Hz, 2H, Ar), 4.25 (q, J=7.2 Hz, 2H, CH2CH3), 3.90 (s, 3H, CO2CH3), 3.46 (t, J=6.8 Hz, 1H, CHCN), 2.69 (t, J=7.5 Hz, 2H, benzyl), 1.93-2.00 (m, 2H, CH2CH), 1.54-1.72 (m, 4H, 2° aliphatic), 1.30 (t, J=7.3 Hz, 3H, CH2CH3).

Workup

  1. washis washed twice with anhydrous tetrahydrofuran (
  2. customto remove the mineral oil) and 400 mL of tetrahydrofuran
  3. additionare then added
  4. temperatureat reflux temperatures for 6 hours
  5. temperaturecooled
  6. customThe solvent is removed under reduced pressure and diethyl ether
  7. additionis added
  8. customThe organic phase is separated
  9. washwashed with water and brine
  10. dry with materialdried over magnesium sulfate
  11. filtrationfiltered
  12. concentrationconcentrated
  13. customThe residue is chromatographed with 1:4 ethyl acetate
  14. concentrationconcentrated

Sources & evidence

ORD record
ord-09513d0ab7664ee8bf5468dde3edb4f8
Source dataset
uspto-grants-1989_10
Patent number
US04871743

Reaction notes

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