Ethyl Acetoacetate → (4-nitrophenyl)methyl 3-oxobutanoate

HRID 2119197Notes

Reaction equation

HRID 2119197 reaction equation
[C:1]([O:7][CH2:8][CH3:9])(=[O:6])[CH2:2][C:3]([CH3:5])=[O:4].[N+:10]([C:13]1[CH:20]=[CH:19]C(CO)=[CH:15][CH:14]=1)([O-:12])=[O:11]>>[C:1]([O:7][CH2:8][C:9]1[CH:19]=[CH:20][C:13]([N+:10]([O-:12])=[O:11])=[CH:14][CH:15]=1)(=[O:6])[CH2:2][C:3]([CH3:5])=[O:4]

Participants

3

Reactant 2

HCID 8868Ethyl AcetoacetateHCID 692754-Nitrobenzyl alcohol

Product 1

HCID 2760918(4-nitrophenyl)methyl 3-oxobutanoateYield 76.6%

Procedure

A mixture of ethyl acetoacetate (140 g, 1.08 mole) and p-nitrobenzyl alcohol (153 g, 1.00 mole; was washed with diethyl ether prior to use) in toluene (1 L) was slowly distilled, 900 ml of the solvent being collected over a period of 15 hours. After cooling, any insoluble material was removed by filtration over Celite, washed with toluene and evaporated in vacuo to obtain 280 g of a crude oil. This oil was crystallized at 5° C. from diethyl ether (280 ml) to yield 181.55 g (0.766 mole, 76.6% yield) of the title compound as off-white crystals: mp 40°-42° C.; ir (film) νmax : 1740 (ester), 1715 (C=O), 1515 and 1345 (NO2) cm-1 ; 1Hmr (CDCl3) δ: 1.98 (s, impurity), 2.32 (3H, s, CH3), 3.62 (2H, s, --COCH2CO2R), 5.08 (s, impurity), 5.28 (2H, s, --CO2CH2Ar), 7.53 (2H, "d", J=9 Hz, ArH's), and 8.23 ppm (2H, "d", J=9 Hz, ArH's); Rf 0.45 (diethyl ether). An analytical sample was obtained by recrystallization from toluene-hexanes: mp 47°-49° C.

Workup

  1. washwas washed with diethyl ether
  2. distillationwas slowly distilled
  3. custom900 ml of the solvent being collected over a period of 15 hours
  4. temperatureAfter cooling
  5. customany insoluble material was removed by filtration over Celite
  6. washwashed with toluene
  7. customevaporated in vacuo
  8. customto obtain 280 g of a crude oil
  9. customThis oil was crystallized at 5° C. from diethyl ether (280 ml)

Sources & evidence

ORD record
ord-80a3cb26a1d241feb9ad63746eaa6bb1
Source dataset
uspto-grants-1987_07
Patent number
US04683296

Reaction notes

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