Acetic Acid → Methyl 4-(5,5-dicyanopentyl)benzoate

HRID 2259442Notes

Reaction equation

HRID 2259442 reaction equation
[C:1]([C:5]1[CH:10]=[CH:9][C:8]([CH2:11][CH2:12][CH2:13][CH:14]=O)=[CH:7][CH:6]=1)([O:3][CH3:4])=[O:2].[C:16](#[N:20])[CH2:17][C:18]#[N:19].NC(C(O)=O)C.C(O)(=O)C>O.C1C=CC=CC=1>[C:18]([CH:17]([C:16]#[N:20])[CH2:14][CH2:13][CH2:12][CH2:11][C:8]1[CH:9]=[CH:10][C:5]([C:1]([O:3][CH3:4])=[O:2])=[CH:6][CH:7]=1)#[N:19]

Participants

7

Reactant 4

HCID 176Acetic AcidHCID 602DL-alanineHCID 8010MalononitrileHCID 9859111Methyl 4-(4-oxobutyl)benzoate

Product 1

HCID 19003541Methyl 4-(5,5-dicyanopentyl)benzoate

Reagents, catalysts & solvents 2

HCID 241BenzeneSolventHCID 962WaterSolvent2×

Procedure

A mixture of 3.36 g (1.0 eq) of 4-(4-carbomethoxyphenyl)butanal, 1.29 g (1.2 eq) of malononitrile, 0.05 g of D,L-alanine, 1 mL of glacial acetic acid, and 60 mL of benzene is refluxed with azeotropic removal of water. After 3 hours, about 85% of the theoretical amount of water should be formed and removed. The mixture then is cooled to room temperature and poured into water. The aqueous layer is extracted twice with benzene and the combined organic layers are dried over sodium sulfate, filtered and concentrated under reduced pressure. Chromatography with 1:1 ethyl acetate:hexanes and concentration of the eluant yield methyl 4-(5,5-dicyanopentyl)benzoate as an oil. IR (film) max ν max 2240, 1718, 1615, 1280, and 1110 cm-1 ; 1H NMR (CDCl3) delta 7.99 (d, J=8.1 Hz, 2H, Ar), 7.24-7.29 (m, 3H, Ar, vinyl), 3.90 (s, 3H, --CH3), 2.79 (t, J=7.4 Hz, 2H, benzyl), 2.60-2.64 (m, 2H, --CH2C=C), 1.94-1.97 (m, 2H, --CH2 --).

Workup

  1. customremoved
  2. additionpoured into water
  3. extractionThe aqueous layer is extracted twice with benzene
  4. dry with materialthe combined organic layers are dried over sodium sulfate
  5. filtrationfiltered
  6. concentrationconcentrated under reduced pressure

Sources & evidence

ORD record
ord-edd21f3fb3d743439f7fb4eb7a4c9bc1
Source dataset
uspto-grants-1995_12
Patent number
US05473071

Reaction notes

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