Acrylonitrile → HCID 11447451, compound

HRID 505861Notes

Reaction equation

HRID 505861 reaction equation
[CH2:1]([CH:4]([C:10]([O:12][CH2:13][CH3:14])=[O:11])[C:5]([O:7][CH2:8][CH3:9])=[O:6])[CH:2]=[CH2:3].[C:15](#[N:18])C=C>C1(C)C=CC=CC=1>[C:15](/[CH:3]=[CH:2]\[CH2:1][CH:4]([C:10]([O:12][CH2:13][CH3:14])=[O:11])[C:5]([O:7][CH2:8][CH3:9])=[O:6])#[N:18]

Participants

4

Reactant 2

HCID 7855AcrylonitrileHCID 74900Diethyl allylmalonate

Product 1

HCID 11447451HCID 11447451, compoundYield 60.2%

Reagents, catalysts & solvents 1

HCID 1140TolueneSolvent

Procedure

A solution of 100.0 mg (0.48 mmol) diethyl allylmalonate, 77.4 mg (1.45 mmol) acrylonitrile and 35.0 mg (0.05 mmol) [RuCl2(ImH2Mes)((4-chloro-2-trifluoromethyl-8-quinolinyl)methylene)] in 5 ml toluene was stirred at 110° C. To monitor the conversion and selectivity, 0.05-ml samples were taken were taken after 3 h and 40 h. Each sample was filtered over a silica gel pad, the filtrate was evaporated to dryness and analyzed by GC (column: HP-5, 5% phenyl methyl siloxan (Agilent 19091-413); injector: 250° C.; detector: 250° C.; oven: 100 to 150° C./5° C. per min, 5 min at 150° C., 150 to 200° C./5° C. per min and 200 to 300° C./20° C. per min; carrier gas: He (0.46 bar); retention times: 9.2 min diethyl allylmalonate, 17.5 min (Z)-diethyl 2-[3-cyano-2-propenyl]malonate and 18.8 min (E)-diethyl 2-[3-cyano-2-propenyl]malonate). After 3 h (66% conversion), 57% of the title compound and after 40 h (94% conversion) 83% of the title compound as an (E):(Z) mixture of 1:2 was formed. After evaporation of the solvent under reduced pressure, the crude product was purified by silica gel chromatography (cyclohexane/ethyl acetate 8:2) to yield 65.1 mg (60%) of the title compound as a (E):(Z) mixture of 1:2. MS: 226.3 (M+). 1H-NMR of diethyl 2-[3-cyano-2-propenyl]malonate (300 MHz, C6D6): (Z)-isomer: 1.29 (t, J=7.1 Hz, 6H); 2.99 (td, J=7.1, 1.5 Hz, 2H); 3.51 (t, J=7.0 Hz, 1H); 4.20-4.24 (m, 4H); 5.40-5.42 (m, 1H); 6.54 (m, 1H). (E)-isomer: 1.28 (t, J=7.1 Hz, 6H); 2.79 (td, J=7.1, 1.5 Hz, 2H); 3.46 (t, J=7.1 Hz, 1H); 4.20-4.24 (m, 4H); 5.40-5.42 (m, 1H); 6.68 (m, 1H).

Workup

  1. filtrationEach sample was filtered over a silica gel pad
  2. customthe filtrate was evaporated to dryness
  3. customanalyzed by GC (column: HP-5, 5% phenyl methyl siloxan (Agilent 19091-413); injector: 250° C.; detector: 250° C.; oven: 100 to 150° C./5° C. per min, 5 min at 150° C., 150 to 200° C./5° C. per min and 200 to 300° C./20° C. per min; carrier gas: He (0.46 bar); retention times: 9.2 min diethyl allylmalonate, 17.5 min (Z)-diethyl 2-[3-cyano-2-propenyl]malonate and 18.8 min (E)-diethyl 2-[3-cyano-2-propenyl]malonate)
  4. waitAfter 3 h (66% conversion), 57% of the title compound
  5. waitafter 40 h (94% conversion) 83% of the title compound as an (E)
  6. addition(Z) mixture of 1:2
  7. customwas formed
  8. customAfter evaporation of the solvent under reduced pressure
  9. customthe crude product was purified by silica gel chromatography (cyclohexane/ethyl acetate 8:2)

Sources & evidence

ORD record
ord-1fa85cc19ce744c8976686cca95adcac
Source dataset
uspto-grants-2010_08
Patent number
US07781586B2

Reaction notes

Loading…