Ethyl cyanoacetate → HCID 15734965, compound

HRID 2050535Notes

Reaction equation

HRID 2050535 reaction equation
[H-].[Na+].[C:3]([CH2:5][C:6]([O:8][CH2:9][CH3:10])=[O:7])#[N:4].[H][H].CS(O[CH2:18][CH2:19][CH2:20][C:21]([C:23]1[CH:32]=[CH:31][C:26]([C:27]([O:29][CH3:30])=[O:28])=[CH:25][CH:24]=1)=[CH2:22])(=O)=O.[Cl-].[NH4+]>O1CCCC1>[C:6]([CH:5]([C:3]#[N:4])[CH2:18][CH2:19][CH2:20][C:21]([C:23]1[CH:24]=[CH:25][C:26]([C:27]([O:29][CH3:30])=[O:28])=[CH:31][CH:32]=1)=[CH2:22])([O:8][CH2:9][CH3:10])=[O:7]

Participants

7

Reactant 5

HCID 7764Ethyl cyanoacetate2×HCID 24758Sodium hydrideHCID 25517Ammonium ChlorideHCID 15734964HCID 15734964, compoundHCID 178418361HCID 178418361, compound

Product 1

HCID 15734965HCID 15734965, compound

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent3×

Conditions

Temperature
0 °C

Procedure

A 1 liter three neck round bottomed-flask was equipped with a reflux condenser, addition funnel, and gas inlet, and charged with a mixture of 0.10 g (5.0 eq) of 80% sodium hydride in 40 ml of anhydrous tetrahydrofuran. This mixture was cooled to 0° C. and a solution of 0.39 ml (5.5 eq) of ethyl cyanoacetate in anhydrous tetrahydrofuran was added dropwise under a nitrogen atmosphere. The mixture was vigorously stirred and allowed to attain room temperature until hydrogen evolution was no longer observed. To the mixture was then added 0.40 g (1.0 eq) of methyl 4-(5-methylsulfonyloxy-pent-1-en-2-yl)benzoate in 5 ml of anhydrous tetrahydrofuran. The mixture was then refluxed for 15 hours, saturated ammonium chloride solution was added, and the solution extracted three times with diethylether. The extracts were dried over magnesium sulfate, and concentrated under reduced pressure to give the product (containing some unreacted ethyl cyanoacetate which can be removed by Kugelrohr distillation at 40° C./1 mm Hg). Further purification of the product was accomplished by flash chromatography, eluting with 1:3 ethylacetate:hexanes. M.S.:m/z=315.1458 (M+, calc. for C18H21O4N: 315.1470), 284 (M+ --CH3O), 202 (M+ --EtO2C--CH2 --CN), 176, 143 (100%). 1H-N M.R.(CDCl3, 300 MHz): δ=1.28(t, 3H, CH3 --CH2O, J=7.5 Hz); 1.64(quin, 2H, CH2 --CH2 --CH2, J=7.5 Hz); 1.96(dt, 2H, CH2 --CH, J=7.5 Hz); 2.60(t, 2H, CH2 --C=, J=7.5Hz); 3.44(t, 1H, CH--CN, J=7.5 Hz); 3.92(s, 3H, CH3O); 4.22(q, 2H, CH3 --CH2O, J=7.5 Hz); 5.19(s, 1Holef.); 5.41(s, 1Holef.); 7.42 (d, 2Harom., J=9 Hz); 8.00(d, 2Harom., J=9 Hz).

Workup

  1. temperatureThe mixture was then refluxed for 15 hours
  2. extractionthe solution extracted three times with diethylether
  3. dry with materialThe extracts were dried over magnesium sulfate
  4. concentrationconcentrated under reduced pressure
  5. customto give the product (
  6. customcan be removed by Kugelrohr distillation at 40° C./1 mm Hg)
  7. customFurther purification of the product
  8. washeluting with 1:3 ethylacetate

Sources & evidence

ORD record
ord-2bf22dfd83974b899e71ede74de28321
Source dataset
uspto-grants-1991_05
Patent number
US05013738

Reaction notes

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