Priprava i razdvajanje enantiomera (±)-ektoina

master's thesis

• Title (english): Synthesis and enantioseparation of (±)-ectoine
• Author: Marcela Šišić
• Mentor: Marin Roje (mentor)
• Committee member: Ines Primožič (predsjednik povjerenstva)
• Committee member: Nives Galić (član povjerenstva)
• Committee member: Željka Soldin (član povjerenstva)
• Committee member: Željka Car (član povjerenstva)
• Granter: University of Zagreb; Faculty of Science; (Department of Chemistry); Zagreb
• Defense date and country: 2021, Croatia
• Scientific / art field, discipline and subdiscipline: NATURAL SCIENCES; Chemistry

Abstract

Optimiran je sintetski put priprave (±)-2-metil-1,4,5,6-tetrahidropirimidin-4-karboksilne
kiseline, odnosno (±)-ektoina. Sintetski put započinje bromiranjem dihidrofuran-2(3H)-ona.
Nastali 3-bromdihidrofuran-2(3H)-on prevodi se u nekoliko reakcijskih koraka u dihidroklorid
2,4-diaminobutanske kiseline. Dobivena 2,4-diaminobutanska kiselina kompleksira se s
bakrovim(II) kationom kako bi se u reakciji s 4-nitrofenil-acetatom postigla selektivna
acetilacija samo terminalne aminoskupine. Pripravljena 4-acetamido-2-aminobutanska kiselina
u zadnjem sintetskom koraku termički se ciklizira u konačni spoj, (±)-ektoin. Odvajanje
enantiomera (±)-ektoina provedeno je tekućinskom kromatografijom visoke djelotvornosti i
postignuto je primjenom ChiralT kolone uz nekoliko različitih analitičkih metoda. Osim toga,
ispitana je prisutnost (+)-ektoina tekućinskom kromatografijom visoke djelotvornosti na
Synergi polar – RP koloni u hranjivom mediju u kojem su rasli različiti sojevi bakterija
Streptomyces sp. Utvrđena je prisutnost izlučenog (+)-ektoina u hranjivim medijima koji su
sadržavali različite koncentracije natrijevog klorida.

Abstract (english)

The synthetic route of preparation of (±)-2-methyl-1,4,5,6-tetrahydropyrimidine-4-carboxylic
acid or (±)-ectoine was optimized. The synthetic pathway begins with the bromination of
dihydrofuran-2-(3H)-one. The resulting 3-bromodihydrofuran-2-(3H)-one is converted in
several reaction steps to 2,4-diaminobutanoic acid dihydrochloride. The resulting 2,4-
diaminobutanoic acid dihydrochloride is complexed with a copper(II) cation to achieve
selective acetylation of only the terminal amino group by reaction with 4-nitrophenyl acetate.
The prepared 4-acetamido-2-aminobutanoic acid in the last synthetic step is thermally cyclized
to the final compound, (±)-ectoine. Separation of the (±)-ectoine enantiomers is achieved by
high-performance liquid chromatography on a ChiralT column using several analytical
methods. In addition, the presence of (+)-ectoine was determined by high-performance liquid
chromatography on a Synergi polar - RP column in a fermentation broths inoculated with
different strains of bacteria Streptomyces sp., and different NaCl concentrations.

• Keywords: ektoin; odvajanje enantiomera; osmoprotektant
• Keywords (english): ectoine; enantioseparation; osmoprotectant
• Language: croatian
• URN:NBN: urn:nbn:hr:217:929787
• Project: Number: N/A; Title: Znanstveni centar izvrsnosti za bioprospecting mora; Title: Scientific Center of Excellence for Bioprospecting of the sea; Acronym: BioProCro; Leader: Rozelinda Čož-Rakovac; Jurisdiction: Croatia; Funder: MZOS; Funding stream: ZCI
• Study programme: Title: Graduate university studies in chemistry; specializations in: Research programme; Course: Research programme; Study programme type: university; Study level: graduate; Academic / professional title: magistar/magistra kemije (magistar/magistra kemije)
• Type of resource: Text
• File origin: Born digital
• Access conditions: Open access; Embargo expiration date: 2022-09-23
• Created on: 2021-10-20 09:09:44