141-97-9 Usage
Description
Ethyl acetoacetate (EAA) is an organic compound, specifically the ethyl ester of acetoacetic acid. It is a colorless liquid with a fruity odor and a characteristic ether-like, fruity, and pleasant refreshing scent. It is a tautomer at room temperature, consisting of about 93% keto form and 7% enol form. Ethyl acetoacetate is naturally occurring in various fruits and beverages such as strawberry, coffee, sherry, passion fruit juice, and bread.
Uses
1. Used in Pharmaceutical and Chemical Industries:
Ethyl acetoacetate is used as a starting material for the syntheses of alpha-substituted acetoacetic esters and cyclic compounds, including pyrazole, pyrimidine, and coumarin derivatives. It also acts as an intermediate in the synthesis of vitamins and pharmaceuticals.
2. Used in Organic Synthesis:
Ethyl acetoacetate is utilized 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.
3. Used in Dyes, Inks, and Plastics Industries:
It is widely used in the production of dyes, inks, perfumes, plastics, and flavoring agents.
4. Used in Lacquers and Paints:
Ethyl acetoacetate is employed as a co-promoter for unsaturated polyester resins, making it useful in the manufacturing of lacquers and paints.
5. Used as a Flavoring Agent:
It is used as a flavoring for food, providing fruity banana, apple, and white grape notes with slightly green estry and tropical nuances.
6. Used as a Formaldehyde Scavenger:
Ethyl acetoacetate finds application as a formaldehyde scavenger, which is beneficial in various industrial processes.
7. Used in Fragrance Industry:
Ethyl acetoacetate is used to create fresh, fruity top notes in feminine fine fragrances, with aroma characteristics of sweet fruity apple, fermented, slightly fusel-like, and rummy, fruity banana with tropical nuances.
Production Methods
Ethyl acetoacetate is manufactured through a reaction of
high-purity ethyl acetate with sodium, followed by neutralization
with sulfuric acid.
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.
Synthesis Reference(s)
The Journal of Organic Chemistry, 58, p. 793, 1993 DOI: 10.1021/jo00055a046
Air & Water Reactions
Flammable.
Reactivity Profile
Ethyl acetoacetate, 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 (Soriano, D.S. et al. 1988. Journal of Chemical Education 65:637.).1971].
Hazard
Toxic by ingestion and inhalation; irritant
to skin and eyes.
Health Hazard
Liquid may cause mild irritation of eyes.
Flammability and Explosibility
Nonflammable
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.
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.
Safety Profile
eye irritant.
Combustible liquid when exposed to heat
or flame; can react with oxidzing materials.
Explosive reaction when heated with Zn +
tribromoneopentyl alcohol or 2,2,2
tris(bromomethy1)ethanol. To fight fire, use
alcohol foam, CO2, dry chemical. When
heated to decomposition it emits acrid
smoke and irritating fumes. See also
ESTERS.
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.]
Check Digit Verification of cas no
The CAS Registry Mumber 141-97-9 includes 6 digits separated into 3 groups by hyphens. The first part of the number,starting from the left, has 3 digits, 1,4 and 1 respectively; the second part has 2 digits, 9 and 7 respectively.
Calculate Digit Verification of CAS Registry Number 141-97:
(5*1)+(4*4)+(3*1)+(2*9)+(1*7)=49
49 % 10 = 9
So 141-97-9 is a valid CAS Registry Number.
InChI:InChI=1/C6H10O3/c1-3-5(4(2)7)6(8)9/h5H,3H2,1-2H3,(H,8,9)/p-1
141-97-9Relevant articles and documents
-
Roberts,McElvain
, p. 2007 (1937)
-
-
Cristol,Ragsdale,Meek
, p. 1863 (1949)
-
-
McElvain
, p. 3124 (1929)
-
-
Frampton,Nobis
, p. 404 (1953)
-
-
Susuki,Tsuji
, p. 1954,1957 (1968)
-
-
Dauben,Bradlow
, p. 5204 (1952)
-
-
Wasserman,H.H.,Wentland,S.H.
, p. 1 - 2 (1970)
-
-
Tanimoto et al.
, p. 665 (1978)
-
Revisiting ageless antiques; synthesis, biological evaluation, docking simulation and mechanistic insights of 1,4-Dihydropyridines as anticancer agents
Sidhom, Peter A.,El-Bastawissy, Eman,Salama, Abeer A.,El-Moselhy, Tarek F.
supporting information, (2021/06/21)
The historic DHP nucleus was serendipitously discovered by Arthur Hantzsch about 130 years ago and is still considered a hidden treasure for various pharmacological activities. Twenty-one DHP analogues were synthesized using the expedient one pot Hantzsch synthesis for screening as anticancer agents. Initially, the in vitro anti-proliferative single dose against a panel of 18 cancer cell lines showed that compounds 11b and 8f were the superlative candidates regarding their antitumor effect (GI% mean = 66.40% and 50.42%, correspondingly) compared to cisplatin (GI% mean = 65.58%) and doxorubicin (GI% mean = 74.56%). Remarkably, compound 11b showed a remarkable MDA-MB-468 anticancer activity (GI%=80.81%), higher than cisplatin (64.44%) and doxorubicin (76.72%), as well as strong antitumor activity against lung cancer A549 (GI%= 83.02%), more powerful than both cisplatin and doxorubicin. Compound 11b exhibited an exceptional anticancer activity against lung cancer cell line (A549) as its GI50 in nanomolar was (540 nM) with a 9-fold increase greater than cisplatin (GI50 = 4.93 μM) and with a selectivity index = 131 to cancer cells over normal cells. Further mechanistic investigations proved that DHPs anticipate simultaneously TOPI and RTKs (VEGFR-2, HER-2 and BTK) which can stimulate BAX/BAK and the executioner caspases via rtPCR studies.
A straightforward synthesis of 5-sulfonamidomethyl substituted 4,7-dihydroazolo[1,5-a]pyrimidines
Shvets, Elena H.,Pidvorotnia, Anastasiia V.,Kulyk, Olesia G.,Mazepa, Alexander V.,Kolosov, Maksim A.
, p. 114 - 122 (2020/10/02)
4,7-Dihydroazolo[1,5-a]pyrimidin-5-ylmethanesulfonamides are side-products of the three-component Biginelli-like reaction of aminoazoles, aldehydes and N,N-dialkyl-2-ketomethanesulfonamides. Herein, we report a straightforward synthesis of 5-sulfonamidomethyl substituted 4,7-dihydroazolo[1,5-a]pyrimidines by a two-component condensation of aminoazoles and N,N-dialkyl(cinnamoyl)methanesulfonamides in DMF at reflux. The starting N,N-dialkyl-2-ketomethanesulfonamides can be obtained by either lithiation of N,N-dialkylmethanesulfonamides and reaction with aldehydes followed by oxidation of the resulting alcohols or by Claisen condensation of N,N-dialkylmethanesulfonamides with the corresponding esters. The chemical structures of all synthesized compounds are supported by 1H and 13C NMR-spectroscopy, mass spectrometry and elemental analysis.