609-14-3

Usage

Uses

Used in Organic Synthesis:
Ethyl 2-methylacetoacetate is used as a precursor in the Japp-Klingemann reaction, which involves the preparation of hydrazones from beta-keto acid and aryl diazonium salts. This reaction is significant in the synthesis of various organic compounds, including ethylpyruvate phenylhydrazone, which is produced by reacting ethyl 2-methylacetoacetate with benzenediazonium chloride.
Used in Pharmaceutical Industry:
Ethyl 2-methylacetoacetate is employed as a substrate in the rhenium-catalyzed synthesis of multisubstituted aromatic compounds. These compounds are essential in the development of pharmaceuticals, as they can be used as building blocks for the creation of new drugs with potential therapeutic applications.
Used in Chemical Research:
Ethyl 2-methylacetoacetate can be utilized in the synthesis of coumarin derivatives via Pechmann condensation. Coumarins are a class of organic compounds that have various applications, including their use as fragrances, flavorings, and in the pharmaceutical industry as anticoagulants and anti-inflammatory agents.
Used in Material Science:
Ethyl 2-methylacetoacetate undergoes dehydration to yield conjugated alkynyl and allenyl esters, which are important in the development of advanced materials with unique properties. These materials can be used in various applications, such as in the electronics industry for the creation of novel semiconductors or in the development of new polymers with specific characteristics.
Used in Total Synthesis:
Ethyl 2-methylacetoacetate is also used in the total synthesis of complex organic compounds, such as chlorotonil A, yangjinhualine A, (+)and (?)-saudin. These natural products have been found to possess various biological activities, making them valuable targets for the development of new drugs and therapeutic agents.

InChI:InChI=1/C7H12O3/c1-4-10-7(9)5(2)6(3)8/h5H,4H2,1-3H3/t5-/m1/s1

Upstream product

• 109-99-9 tetrahydrofuran 
• 2985-33-3 monoethyl methylmalonate 
• 920-39-8 isopropylmagnesium bromide 
• 75-36-5 acetyl chloride 
• 463-51-4 Ketene 
• 535-11-5 Ethyl 2-bromopropionate 
• 74-83-9 methyl bromide 
• 1007476-32-5 sodium ethyl acetylacetate enolate 
• 29397-21-5 Diacetyldiazomethan 
• 64-17-5 ethanol 
• 82515-48-8 2-hydroxymethyl-2-methyl-acetoacetic acid ethyl ester 
• 141-97-9 ethyl acetoacetate 
• 77-78-1 dimethyl sulfate 
• 141-52-6 sodium ethanolate 

Downstream Products

• 1679-47-6 3-methyltetrahydro-2-furanone 
• 1234-27-1 4,4'-(carbonylbis(azanediyl))dibenzoic acid 
• 107057-96-5 5-hydroxy-3,4,7-trimethylcoumarin 
• 133-13-1 ethyl diethyl malonate 
• 103986-39-6 5,7-dihydroxy-3,4-dimethylcoumarin 
• 16782-80-2 3,5,5,6-tetramethyl-2-cyclohexenone 
• 4792-57-8 ethyl 2-[2-(4-methoxyphenyl)hydrazinylidene]propanoate 
• 134747-25-4 ethyl 2-[2-(3-nitrophenyl)hydrazinylidene]propanoate 
• 408511-89-7 2,2,3-trimethyl-4,6-dioxo-cyclohexanecarboxylic acid ethyl ester 
• 5296-86-6 2-[(4-chlorophenyl)-hydrazono]-propionic acid ethyl ester 
• 16382-11-9 ethyl 2-[2-(4-bromophenyl)hydrazinylidene]propanoate 
• 16382-12-0 2-(4-ethoxy-phenylhydrazono)-propionic acid ethyl ester 
• 292853-66-8 2-(2-(2-nitrophenyl)hydrazono)propionic acid ethyl ester 
• 135065-47-3 6-chloro-7-hydroxy-3,4-dimethyl-2H-chromen-2-one 

Relevant academic research and scientific papers

Investigations into the biosynthesis of the antifungal strobilurins

The strobilurins are important antifungal metabolites isolated from a number of basidiomycetes and have been valuable leads for the development of commercially important fungicides. Isotopic labelling studies with early and advanced intermediates confirm for the first time that they are produced via a linear tetraketide, primed with the rare benzoate starter unit, itself derived from phenylalanine via cinnamate. Isolation of a novel biphenyl metabolite, pseudostrobilurin B, provides evidence for the involvement of an epoxide in the key rearrangement to form the β-methoxyacrylate moiety essential for biological activity. Formation of two bolineol related metabolites, strobilurins Y and Z, also probably involves epoxide intermediates. Time course studies indicate a likely biosynthetic pathway from strobilurin A, with the simplest non-subsubstituted benzoate ring, to strobilurin G with a complex dioxepin terpenoid-derived substituent. Precursor-directed biosynthetic studies allow production of a number of novel ring-halogenated analogues as well as a new pyridyl strobilurin. These studies also provide evidence for a non-linear biosynthetic relationship between strobilurin A and strobilurin B.

Merging aerobic oxidation and enamine catalysis in the asymmetric α-amination of β-ketocarbonyls using N-hydroxycarbamates as nitrogen sources

We describe herein an unprecedented asymmetric α-amination of β-ketocarbonyls under aerobic conditions. The process is enabled by a simple chiral primary amine through the coupling of a catalytic enamine ester intermediate and a nitrosocarbonyl (generated in situ) derived from N-hydroxycarbamate. The reaction features high chemoselectivity and excellent enantioselectivity for a broad range of substrates. Merging O and N: Enantioselective α-amination of β-ketocarbonyl compounds has been achieved by merging enamine catalysis and CuI-catalyzed aerobic oxidation of hydroxycarbamates. Excellent chemoselectivity and enantioselectivity are obtained with the aid of a simple primary/tertiary diamine catalyst. This presents a facile route for the asymmetric synthesis of unnatural amino acids.

Metal-Free Tandem Rearrangement/Lactonization: Access to 3,3-Disubstituted Benzofuran-2-(3H)-ones

A novel metal-free synthesis of 3,3-disubstituted benzofuran-2-(3H)-ones through reacting α-aryl-α-diazoacetates with triarylboranes is presented. Initially, triarylboranes were successfully investigated in α-arylations of α-diazoacetates, however in the presence of a heteroatom in the ortho position, the boron enolate intermediate undergoes an intramolecular rearrangement to form a quaternary center. The intermediate cyclizes to afford valuable 3,3-disubstituted benzofuranones in good yields.

Synthesis and fungicidal activities of perfluoropropan-2-yl-based novel quinoline derivatives

A series of novel perfluoropropan-2-yl-based quinoline derivatives was designed and synthesized utilizing tebufloquin as the lead compound. The structures of all the newly synthesized compounds were confirmed by spectroscopic data 1HNMR, MS and elemental analysis. The results of bioassay indicated that these compounds exhibited potent fungicidal activities against Erysiphe graminis. Especially, compound 8c displayed excellent activity with EC50 value at 1.48 mg / L, which was better than that of the commercialized fungicide-tebufloquin. The structure-activity relationship for these new compounds was also discussed.

Substituted phenyl pyrazolone derivatives and preparation and application (by machine translation)

The present invention provides a substituted phenyl pyrazolone derivatives, in particular to a 2 - phenyl - pyrazoline - 3 - ketone compound and its pharmaceutically acceptable salt, solvate. The substituted acetic acid ethyl ester with sodium hydroxide in aqueous solution in the [...] reflux reaction, then in the palladium-carbon and hydrogen under the action of the hydrogenolysis benzyl, phenyl [...] obtained, with the bromochlorodifluoromethane alkane reaction to obtain the chloro, finally with the secondary amine on the condensation to obtain the target compound. The invention substituted phenyl pyrazoline compounds in vitro exhibits excellent capability of eliminating the free radicals, and have more strongly inhibit H3 receptor activity, exhibits excellent penetration of the blood brain barrier capacity, has a unique dual active, therefore, its for cerebral apoplexy, Alzheimer's disease, Parkinson's disease, progressive neurodegenerative diseases such as frozen sickness treatment has a unique clinical effect. The compound of the invention for treating central system system related disease and inflammatory disease application of the medicament. The formula structure is as follows: (by machine translation)

Asymmetric Aza-Wacker-Type Cyclization of N-Ts Hydrazine-Tethered Tetrasubstituted Olefins: Synthesis of Pyrazolines Bearing One Quaternary or Two Vicinal Stereocenters

We have developed an asymmetric aza-Wacker-type cyclization of N-Ts hydrazine-tethered tetrasubstituted olefins, affording optically active pyrazolines bearing chiral tetrasubstituted carbon stereocenters. This reaction is tolerant to a broad range of substrates under mild reaction conditions, giving the desired chiral products with high enantioselectivities. Generation of two vicinal stereocenters on the C=C double bonds was also achieved with high selectivities, a process which has been rarely studied for Wacker-type reactions. A mechanistic study revealed that this aza-Wacker-type cyclization undergoes a syn-aminopalladation process. It was also found that for substrates bearing two linear alkyl substituents on the outer carbon atom of the olefin, both of which are larger than a methyl group, the alkyl substituent that is cis to the intranucleophilic group participates more readily in β-hydride elimination. When one of the two alkyl substituents on the outer carbon atom of the olefin is a methyl group, β-hydride elimination proceeds selectively at the methylene side, thus both diastereomers can be prepared via switching the configuration of the olefin. Furthermore, the product can be converted to a pharmaceutical compound in high yields over three steps.

Synthesis and Absolute Configuration of Natural 2-Pyrones

2-Pyrones are frequently produced by microorganisms and often exhibit interesting bioactivities. Therefore, a short and easy synthetic access to these natural products is desirable. Synthetic routes to nectriapyrone, gibepyrone A, racemic gulypyrone A, (+)-germicidin C, (ent)-desoxygermicidin C and (ent)-prolipyrone A via a modular approach are presented, allowing the assignment of the absolute configurations of the latter three chiral compounds. The method failed for the synthesis of (ent)-phomapyrone B that was thus synthesized via a different route, resulting in an assignment of the absolute configuration of natural phomapyrone B.

Iron-Catalyzed Carbene Insertion Reactions of α-Diazoesters into Si-H Bonds

An efficient iron-catalyzed carbene insertion reaction of α-diazo carbonyl compounds into the Si-H bond was developed. A wide range of α-silylesters was obtained in high yields (up to 99%) from α-diazoesters using a simple iron(II) salt as catalyst.

Tunable Aerobic Oxidative Hydroxylation/Dehydrogenative Homocoupling of Pyrazol-5-ones under Transition-Metal-Free Conditions

A practical and tunable transition-metal-free aerobic oxidation of pyrazol-5-ones preparing either 4-hydroxypyrazoles (via C-H hydroxylation) or bispyrazoles (via dehydrogenative homocoupling) is described. The K2CO3/dioxane reagent system predominately promoted hydroxylation to deliver the α-hydroxylated pyrazoles. In contrast, the formation of bispyrazoles was overwhelmingly preferred with CH3CN as the reaction medium without any additives.

Alkynylation of heterocyclic compounds using hypervalent iodine reagent

The alkynylation of various nitrogen- and/or sulphur-containing heterocyclic compounds using hypervalent iodine TMS-EBX by utilization of tertiary amines under mild conditions is described. The developed metal-free methodology furnishes the corresponding alkynylated heterocycles bearing quaternary carbon in high yields.