General Description
A colorless liquid with a fruity odor. Flash point 185°F. Boiling point 365°F. May cause adverse health effects if ingested or inhaled. May irritate to skin, eyes and mucous membranes. Used in organic synthesis and in lacquers and paints.
Reactivity Profile
ETHYL ACETOACETATE(141-97-9), a beta-keto ester, is more reactive than many esters. Undergoes an exothermic cleavage reaction in the presence of concentrated base. Reacts with acids to liberate heat along with alcohols and acids. Strong oxidizing acids may cause a vigorous reaction that is sufficiently exothermic to ignite the reaction products. Flammable hydrogen is generated by mixing esters with alkali metals and hydrides. Mixing with 2,2,2-tris(bromomethyl)ethanol and zinc led to an explosion [US Patent 3 578 619, Crotonaldehyde may rapidly polymerize with ETHYL ACETOACETATE(141-97-9) (Soriano, D.S. et al. 1988. Journal of Chemical Education 65:637.).1971].
Air & Water Reactions
Flammable.
Hazard
Toxic by ingestion and inhalation; irritant
to skin and eyes.
Health Hazard
Liquid may cause mild irritation of eyes.
Description
The organic compound ethyl acetoacetate (EAA) is the ethyl ester of acetoacetic acid. It is mainly used as a chemical intermediate in the production of a wide variety of compounds, such as amino acids, analgesics, antibiotics, antimalarial agents, antipyrine and amino pyrine, and vitamin B1; as well as the manufacture of dyes, inks, lacquers, perfumes, plastics, and yellow paint pigments. Alone, it is used as a flavoring for food.
Chemical Properties
Ethyl 3-Oxobutanoate is a colorless liquid with
a fruity, ethereal, sweet odor reminiscent of green apples. It is used to create fresh, fruity top notes in feminine fine fragrances. Ethyl acetoacetate occurs in flavors of
natural materials such as coffee, strawberries, and yellow passion fruits.
Chemical Properties
Ethyl acetoacetate has a characteristic ether-like, fruity, pleasant, refreshing odor.
Occurrence
Naturally occurring in strawberry, coffee, sherry, passion fruit juice (yellow), babaco fruit (Carica pentagona
Heilborn) and bread.
Uses
Ethyl acetoacetate (EAA) is used as starting material for the syntheses of alpha-substituted acetoacetic esters and cyclic compounds, e.g. pyrazole, pyrimidine and coumarin derivatives as well as intermediate for vitamins and pharmaceuticals. Product Data Sheet
Application
Ethyl acetoacetate can be used as a potential bio-based diluent for improving the cold flow properties of biodiesel from waste cooking oil[1]. Ethyl acetoacetate reacts with glycosylamines to form ethyl 3-(glycosylamino)crotonate, which is further transformed into ethyl 2-methyl-4-(polyhydroxyalkyl)pyrrole-3-carboxylates under conditions that promote the Amadori rearrangement of glycosylamines. It also reacts with ketohexylamines (D-fructosylamine, L-sorbosylamine) to form ethyl 2-methyl-5-(tetrahydroxybutyl)pyrrole-3-carboxylates[2].
Preparation
Ethyl acetoacetate is produced industrially by treatment of diketene with ethanol.
The preparation of ethyl acetoacetate is a classic laboratory procedure . It is prepared via the Claisen condensation of ethyl acetate. Two moles of ethyl acetate condense to form one mole each of ethyl acetoacetate and ethanol.
Production Methods
Ethyl acetoacetate is manufactured through a reaction of
high-purity ethyl acetate with sodium, followed by neutralization
with sulfuric acid.
Aroma threshold values
Detection: 520 ppb. Aroma characteristics at 10%: sweet fruity apple, fermented, slightly fusel-like and
rummy, fruity banana with tropical nuances.
Taste threshold values
Taste characteristics at 100 ppm: fruity banana, apple and white grape with slightly green estry and tropical
nuances.Taste characteristics at 300 ppm: estery, fatty, fruity and tutti-frutti
Flammability and Explosibility
Nonflammable
Chemical Reactivity
Ethyl acetoacetate is subject to Keto - enol tautomerism. Ethyl acetoacetate is often used in the acetoacetic ester synthesis similar to diethyl malonate in the malonic ester synthesis or the Knoevenagel condensation. The protons alpha to carbonyl groups are acidic, and the resulting carbanion can undergo nucleophilic substitution. A subsequent thermal decarboxylation is also possible.Similar to the behavior of acetylacetone, the enolate of ethyl acetoacetate can also serve as a bidentate ligand. For example, it forms purple coordination complexes with iron (III) salts :
Ethyl acetoacetate can also be reduced to ethyl 3-hydroxy butyrate.
Chemical Reactivity
Reactivity with Water No reaction; Reactivity with Common Materials: No reaction; Stability During Transport: Stable; Neutralizing Agents for Acids and Caustics: Not pertinent; Polymerization: Not pertinent; Inhibitor of Polymerization: Not pertinent.
Synthesis
Ethyl acetoacetate is a mixture of two tautomer forms: the enolic and the ketonic; the liquid ester at equilibrium contains
approximately 70% of the enolic form. It is prepared by Claisen condensation of ethyl acetate in the presence of sodium ethylate;
also by reacting diketene with ethanol in the presence of sulfuric acid or triethylamine and sodium acetate, with or without solvent.
Purification Methods
Shake the ester with small amounts of saturated aqueous NaHCO3 (until no further effervescence), then with water. Dry it with MgSO4 or CaCl2 and distil it under reduced pressure. [Beilstein 3 IV 1528.]
References
[1] LEICHANG CAO. Ethyl acetoacetate: A potential bio-based diluent for improving the cold flow properties of biodiesel from waste cooking oil[J]. Applied Energy, 2014, 114: Pages 18-21. DOI:10.1016/j.apenergy.2013.09.050.
[2] A.GóMEZ SáNCHEZ; J. V del P. Reaction of glycosylamines with ethyl acetoacetate[J]. Carbohydrate Research, 1966, 1 6: Pages 421-434. DOI:10.1016/S0008-6215(00)81220-3.
