Synthesis of 2-aminopyrrole-3-carboxylates via zinc perchlorate mediated annulation of alpha-cyano-gamma-ketoesters with amines

Download

index.pdf

Date

2008

Author

Akca, Nazmiye Bihter

Metadata

Show full item record

Item Usage Stats

127
views

28
downloads

2-Aminopyrrole-3-carboxylate derivatives are important starting materials for biologically active compounds like pyrrolotriazole, pyrrolotriazine so their synthese has great importance in the synthetic organic chemistry. There are only two methods for the synthesis of 2-aminopyrrole-3-carboxylates in the literature. Therefore, there is a great need for the design and development of a new method for the synthesis of 2-aminopyrrole-3-carboxylates. In this work, 2-aminopyrrole-3-carboxylate derivatives were synthesized starting from cyano acetic acid ethyl ester with a new method. In the first step, cyanoacetic acid ethyl ester was alkylated with bromo acetone in the presence of NaH. Then, obtained gamma-ketoester was reacted with primary amines in the presence of catalytic amount of zincpechlorate (Zn(ClO4)2). As a result, 2-aminopyrrole-3-carboxylate derivatives were obtained. Cyanoacetic acid ethyl ester was also alkylated with various bromo acetophenone derivatives in the presence of DBU (1,8-Diazabicycloundec-7-ene). As a result of these reactions, different gamma-ketoesters were obtained. The reaction of these gamma-ketoesters with primary amines in the presence of catalytic amount of Zn(ClO4)2 concluded with 2-aminopyrrole-3-carboxylate derivatives.

Subject Keywords

Chemistry., Catalytic reaction.

URI

http://etd.lib.metu.edu.tr/upload/3/12609715/index.pdf
https://hdl.handle.net/11511/17706

Collections

Graduate School of Natural and Applied Sciences, Thesis

Suggestions

OpenMETU
Core

Synthesis of Functionalized Novel alpha-Amino-beta-alkoxyphosphonates through Regioselective Ring Opening of Aziridine-2-phosphonates Polat-Cakir, Sidika; Beksultanova, Nurzhan; Doğan, Özdemir (Wiley, 2019-11-01) Aziridines are highly useful compounds as building blocks for the synthesis of important organic compounds. Amino acid synthesis by aziridine ring opening reaction is a good example to the use of aziridines. Although this reaction is studied by many groups, the synthesis of amino phosphonic acids is less explored. In this study, we have carried out the ring opening reaction of aziridinyl phosphonates with a variety of alcohols including the more functional propargylic and allylic alcohols. These reactions p...
Oxidative ring opening reactions of a-hydroxy ketones Aybey, Ayşe; Demir, Ayhan Sıtkı; Department of Chemistry (2008) Chiral polyfunctionalized 1,5-dicarbonyl compounds are important synthetic intermediates and starting materials for many biologically active compounds so their synthesis has a great importance in the literature. In the first step, 1,3-cyclohexandione and other b-diketone derivatives are protected under acid catalyzation and their corresponding b-keto enol ether derivatives are obtained. These b-keto enol ethers are then converted to a-acetoxy enones in racemic form by Mn(OAc)3 mediated oxidation. Enzymatic ...
Synthesis of chiral lactones via the baeyer villiger oxidation of cyclic aromatic acetoxy ketones novel annulation reactions of 2-propynyl-1,3-dicarbonyl compounds to form pyrroles addition of acyl phosphonates to diethyl cyanophosphonate (depc) Aybey, Asuman; Demir, Ayhan Sıtkı; Department of Chemistry (2009) Chiral Baeyer-Villiger (BV) oxidation of cyclic ketones allows rapid access to asymmetric lactones as valuable intermediates in organic chemistry and frequently encountered precursors in enantioselective synthesis. In the first part, BV oxidation of functionalized ketones, especially cyclic -hydroxy and acetoxy ketones is described which could be a straightforward route to the -hydroxy lactones and -hydroxyalkanoic acid derivatives. The -acetoxylation of indanone, tetralone and chromanone derivatives by usi...
Synthesis and enzymatic resolution of various cyclopentenoid and cyclohexenoid type compounds İyigün, Çiğdem; Tanyeli, Cihangir; Department of Chemistry (2005) The aim of this thesis is to synthesize enantiomerically enriched cyclopentenoid and cyclohexenoid type of compounds with quaternary carbon stereocenters that are the simplest precursors of the complex natural products. The first part of the study involves the preparation of ?'-acetoxy ?'-substituted ?,β-unsaturated cyclic ketones. Methylation, ethylation, benzylation and allylation of cyclohexenone and cyclopentenone derivatives are performed. Then, these compounds are regioselectively oxidized at the ?'-p...
Chemoenzymatic synthesis of 2-ethyl-5-hydroxy-3- methoxy-cyclopent-2-enone Dalfidan, Çağla; Demir, Ayhan Sıtkı; Department of Chemistry (2005) Chiral hydroxylated cyclopentane derivatives are important precursors for biologically active compounds. Synthesis of these types of compounds in optically pure form found increased interest in pharmaceutical chemistry. 2-ethyl-cyclopentane-1.3-dione was acetoxylated using manganese III acetate at preferred positions. Enzyme catalyzed enantioselective hydrolysis or enantioselective acetoxylation of hydrolyzed acetoxy derivatives gives the corresponding hydroxylated diketones in optically pure form.

Citation Formats

N. B. Akca, “Synthesis of 2-aminopyrrole-3-carboxylates via zinc perchlorate mediated annulation of alpha-cyano-gamma-ketoesters with amines,” M.S. - Master of Science, Middle East Technical University, 2008.