Stereoselektivnost sinteza 1,1'-bi-2-naftola u reakcijama s FeCl3

master's thesis

• Title (english): Stereoselectivity of 1,1'-bi-2-naphthol syntheses using FeCl3
• Author: Ivana Križić
• Mentor: Ines Primožič (mentor)
• Committee member: Ines Primožič (predsjednik povjerenstva)
• Committee member: Iva Juranović Cindrić (član povjerenstva)
• Committee member: Biserka Prugovečki (član povjerenstva)
• Committee member: Ivana Biljan (član povjerenstva)
• Granter: University of Zagreb; Faculty of Science; (Department of Chemistry); Zagreb
• Defense date and country: 2016-09-27, Croatia
• Scientific / art field, discipline and subdiscipline: NATURAL SCIENCES; Chemistry; Organic Chemistry

Abstract

Enantiomerno čisti 1,1bi2naftol te njegovi derivati imaju široku primjenu kao kiralni katalizatori u stereoselektivnim organskim sintezama. U ovom radu istražena je priprava 1,1bi2naftola u reakciji oksidativnog fenolnog povezivanja 2-naftola uz Fe(III) klorid uz prisustvo zraka, u organskim otapalima i mehanokemijski, uz katalitičku količinu otapala. Optimirani su uvjeti reakcije u metanolu, acetonu i acetonitrilu. Reakcija je bitno ubrzana dodatkom di-tert-butilperoksida. Mehanokemijska sinteza (LAG) nije se pokazala kao dobra metoda za izvođenje reakcije. Sintetiziranom racemičnom 1,1bi2naftolu razdvojeni su enantiomeri kemijskom metodom s Nbenzilcinhonidinijevim kloridom. Da bi istražili moguće postizanje stereoselektivnosti reakcije (acetonitril/di-tert-butilperoksid) u reakcijsku smjesu dodan je niz kiralnih spojeva (cinchonidin, cinhonin, Nbenzilcinhoninijev klorid, (S)()1feniletilamin, Nbenzil(S)3-hidroksikinuklidinijev bromid, (S)1feniletanol, metilDglukopiranozid, cikodekstrin) te HPLC metodom na kiralnoj koloni praćena inducirana stereoselektivnost reakcije. Najbolja stereoselektivnost pokazala se u reakciji s (S)-1-feniletilaminom (e.v. 14,4 %). Reakcija priprave 1,1bi2naftola izvedena je i uz dodatak jednog od produkata reakcije, (S)enantiomera. Dobiven je stereospecifično kao produkt (R)enantiomer.

Abstract (english)

Enantiomerically pure 1,1bi2naphthol and its derivatives have a wide usage as chiral catalysts in stereoselective organic synthesis. In this thesis aerobic oxidative fenolic coupling of 2naphthol with Fe(III) chloride in organic solvents was investigated. Reaction was performed in methanol, acetonitrile and acetone successfully. Addition of di-tert-butylperoxide significantly speeded up the reaction. Mechanochemical synthesis (LAG) was investigated as well, but under the used experimental conditions no product was observed. Chemical resolution of racemic 1,1bi2naphthol using Nbenzylcinchonidinium chloride was performed to gain pure enantiomers. To evaluate possible stereoselectivity of the reaction (acetonitrile/di-tert-butylperoxide), a series of chiral compounds were added as well: cinchonidine, cinchonine, Nbenzylcinchoninium chloride, (S)()1phenylethylamine, Nbenzyl(S)3-hydroxyquinuclidium bromide, (S)1phenylethanol, methylDglucopyranozide, cyclodextrin. Chiral HPLC method was used to detect induced stereoselectivity of reactions. In the reaction with (S)-1-feniletilamine, the best stereoselectivity was observed (ee 14.4 %). When the stereoselective reaction was conducted in the presence of the product, (S)- 1,1bi2naphthol, the reaction proceeded stereospecifically toward the (R)-enantiomer.

• Keywords: naftol; kiralna HPLC analiza; stereoselektivna sinteza
• Keywords (english): naphtol; chiral HPLC analysis; stereoselective synthesis
• Language: croatian
• URN:NBN: urn:nbn:hr:217:983365
• Study programme: Title: Graduate Studies in Chemistry; specializations in: Research (scientific-professional) programme; Course: Research (scientific-professional) 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
• Created on: 2017-01-26 09:31:08