Methyl cyanoacetate → HCID 21218461, compound

HRID 1585459Notes

Reaction equation

HRID 1585459 reaction equation
[CH3:1][O:2][C:3]1[CH:8]=[CH:7][C:6]([CH2:9][CH2:10][CH:11]=O)=[CH:5][CH:4]=1.[C:13]([CH2:15][C:16]([O:18][CH3:19])=[O:17])#[N:14]>C(O)(=O)C.N1CCCCC1>[C:13](/[C:15](=[CH:11]\[CH2:10][CH2:9][C:6]1[CH:5]=[CH:4][C:3]([O:2][CH3:1])=[CH:8][CH:7]=1)/[C:16]([O:18][CH3:19])=[O:17])#[N:14]

Participants

5

Reactant 2

HCID 7747Methyl cyanoacetateHCID 111266073-(4-Methoxyphenyl)propanal

Product 1

HCID 21218461HCID 21218461, compoundYield 72.3%

Reagents, catalysts & solvents 2

HCID 8082PiperidineCatalystHCID 176Acetic AcidSolvent2×

Procedure

A solution of 13d (0.616 g, 3.75 mmol) in 0.51 mL glacial acetic acid was treated with NCCH2CO2CH3 (0.338 g, 3.75 mmol, 0.3 mL, 1.0 equiv), then a premixed solution of piperidine (0.0011 g, 0.128 mmol, 13 mL, 3.4 mol %) and 125 mL of acetic acid at room temperature (24 h). The reaction mixture was quenched by the addition of saturated aqueous NaHCO3 (15 mL, pH>7) and extracted with EtOAc (3×15 mL). The combined organic extracts were dried (MgSO4) and concentrated in vacuo. SGC chromatotron (SiO2, 1 mm, 0-10% EtOAc/hexanes) afforded 15d (0.665 g, 0.920 g theoretical, 72%). For 15d: 1H NMR (CDCl3, 400 MHz) d 7.63 (t, 1H, J=7.5 Hz, CH=C), 7.09 (d, 2H, J=8.5 Hz, Ar C2-H and C6-H), 6.83 (d, 2H, J=8.5 Hz, Ar C3-H and C5-H), 3.83 (s, 3H, OCH3), 3.78 (s, 3H, OCH3), 2.70-2.90 (m, 4H, ArCH2CH2); IR (neat) nmax 2955, 1837, 2359, 2341, 1732, 1612, 1513, 1436, 1270, 1248, 1178, 1116, 1061, 1039, 823, 761, 668 cm-1. See FIG. 19c.

Workup

  1. customat room temperature
  2. custom(24 h)
  3. customThe reaction mixture was quenched by the addition of saturated aqueous NaHCO3 (15 mL, pH>7)
  4. extractionextracted with EtOAc (3×15 mL)
  5. dry with materialThe combined organic extracts were dried (MgSO4)
  6. concentrationconcentrated in vacuo

Sources & evidence

ORD record
ord-35eee307cfcd40d0ada680db3966c541
Source dataset
uspto-grants-1999_08
Patent number
US05939268

Reaction notes

Loading…