4-Hydroxybenzaldehyde → Diethyl 2-(4-hydroxybenzylidene)malonate

HRID 922189Notes

Reaction equation

HRID 922189 reaction equation
N1CCCCC1.C(O)(=O)C.[OH:11][C:12]1[CH:19]=[CH:18][C:15]([CH:16]=O)=[CH:14][CH:13]=1.[C:20]([O:28][CH2:29][CH3:30])(=[O:27])[CH2:21][C:22]([O:24][CH2:25][CH3:26])=[O:23]>C1(C)C=CC=CC=1>[OH:11][C:12]1[CH:19]=[CH:18][C:15]([CH:16]=[C:21]([C:22]([O:24][CH2:25][CH3:26])=[O:23])[C:20]([O:28][CH2:29][CH3:30])=[O:27])=[CH:14][CH:13]=1

Participants

6

Reactant 4

HCID 1264-HydroxybenzaldehydeHCID 176Acetic AcidHCID 7761Diethyl MalonateHCID 8082Piperidine

Product 1

HCID 576572Diethyl 2-(4-hydroxybenzylidene)malonateYield 46.2%

Reagents, catalysts & solvents 1

HCID 1140TolueneSolvent

Conditions

Temperature
125 °C

Procedure

To a 100 mL RB flask fitted with magnetic stirrer was charged with piperidine (0.426 g, 0.5 mL, 5 mmol) and acetic acid (0.3 g, 0.3 mL, 5 mmol). To this, toluene (25 mL) was added, followed by 4-hydroxybenzaldehyde (2 g, 16.4 mmol) and diethyl malonate (3.15 g, 19.7 mmol). The RM was heated at 125° C., by fitted with a dean-stark's apparatus for 5 h. After 5 h, the RM was concentrated; water (50 mL) was added and extracted with ethyl acetate (50 mL×2)). The organic layer was washed with saturated brine solution (50 mL). The organic layer was dried over anhydrous Na2SO4 and the solvent was removed under reduced pressure. The product was obtained as yellow solid. (2 g, yield: 46.2%); MS (ESI, 120 eV): m/z=263.1 (M−H)+; 1H NMR (300 MHz, DMSO-d6): δ 10.27 (s, 1H), 7.58 (s, 1H), 7.36-7.38 (d, 2H), 6.81-6.84 (d, 2H), 4.17-4.32 (m, 4H), 4.06-4.14 (q, 1H), 1.21-1.26 (t, 6H).

Workup

  1. customTo a 100 mL RB flask fitted with magnetic stirrer
  2. customby fitted with a dean-stark's apparatus for 5 h
  3. concentrationthe RM was concentrated
  4. additionwater (50 mL) was added
  5. extractionextracted with ethyl acetate (50 mL×2))
  6. washThe organic layer was washed with saturated brine solution (50 mL)
  7. dry with materialThe organic layer was dried over anhydrous Na2SO4
  8. customthe solvent was removed under reduced pressure
  9. customThe product was obtained as yellow solid

Sources & evidence

ORD record
ord-4a28720c153f4d64ae51d80deb1436f9
Source dataset
uspto-grants-2016_03
Patent number
US09278915B2

Reaction notes

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