Sinteza derivatov (+)-izokamfolenske kisline kot potencialnih dišav

magistrsko delo

Tjaša Koželj (Avtor), Uroš Grošelj (Mentor), Matija Strlič (Član komisije za zagovor), Bogdan Štefane (Član komisije za zagovor)

Povzetek

Skozi zgodovino in dandanes v parfumski industriji obstaja stalno zanimanje za razvoj novih snovi, ki izboljšajo ali spremenijo dišavne note ter omogočijo proizvodnjo novih parfumskih olj. Takšne snovi se uporabljajo za nadomestitev naravnih surovin, ki so omejene in drage za proizvodnjo, ali za ustvarjanje novih dišavnih not, ki še niso na voljo. Ker so lesne dišeče spojine nepogrešljive sestavine v parfumeriji, smo se odločili za dišečo kafro, katere izdelki so iskani že od antičnih časov. Ugotovljeno je bilo, da so nekateri derivati kamfolenske kisline, kot so estri, ketoni in alkoholi s podaljšano stransko verigo, izjemno stabilne spojine z zelo individualno dišavnimi lastnostmi, ki so vsestransko uporabne, predvsem lesne, sadne in cvetlične dišave. Nasprotno pa dišave, pridobljene iz (+)-izokamfolenske kisline, še niso bile opisane v literaturi. Zato je bila v magistrski nalogi izvedena sinteza različnih derivatov (+)-izokamfolenske kisline s potencialnimi olfaktornimi lastnostmi. Priprava derivatov (+)-izokamfolenske kisline se je začela s komercialno dostopno (1S)-(+)-10-kamforsulfonsko kislino, ki smo jo v dveh sinteznih korakih pretvorili v izhodno (+)-izokamfolensko kislino. V prvem delu smo izvedli zaestritev (+)-izokamfolenske kisline z različnimi primarnimi organohalidi v prisotnosti K2CO3, izolirani estri pa so imeli prijeten vonj po lesu, najbolj presenetljiv pa je bil vonj estra po morju. V tem prvem delu smo izvedli tudi Steglichevo zaestrenje (+)-izokamfolenske kisline z različnimi alkoholi, EDC kot aktivacijskim reagentom in DMAP kot katalizatorjem. Vonj estrov je bil rahlo saden, lesen in cvetličen. Naslednji korak je bila redukcija (+)-izokamfolenske kisline v primarni alkohol z LiAlH4. Različni kislinski anhidridi so reagirali s pripravljenim primarnim alkoholom in tvorili estre s sadnim vonjem. Majhna knjižnica etrov z lesnimi vonjavami je bila sintetizirana z Williamsonovo sintezo z uporabo deprotoniranega primarnega alkohola in različnih alkil halogenidov. Iz primarnega alkohola in TFA je bil sintetiziran ciklični eter, ki je imel prijeten vonj po poprovi meti. V magistrskem delu smo izvedli tudi olfaktorno analizo sintetiziranih ketonov, pripravljenih iz Weinrebovega amida in različnih Grignardovih reagentov, pri čemer so bile prisotne sladke vonjave. Iz nekaterih izoliranih ketonov smo z metilmagnezijevim bromidom pripravili terciarne alkohole, pri katerih smo zaznali vonj po gozdu. Z epoksidacijo metilenske skupine smo nakazali možnost nadaljnjih funkcionalizacij derivatov (+)-izokamfolenske kisline. V zadnjem delu smo testirali citotoksično delovanje sintetiziranih dišav.

Ključne besede

derivati kafre;(+)-izokamfolenska kislina;dišave;olfaktorne lastnosti;magistrska dela;

Podatki

Jezik:	Slovenski jezik
Leto izida:	2022
Tipologija:	2.09 - Magistrsko delo
Organizacija:	UL FKKT - Fakulteta za kemijo in kemijsko tehnologijo
Založnik:	[T. Koželj]
UDK:	547.599.057(043.2)
COBISS:	135266051
Št. ogledov:	78
Št. prenosov:	29
Ocena:	0 (0 glasov)
Metapodatki:

Ostali podatki

Sekundarni jezik:	Angleški jezik
Sekundarni naslov:	Synthesis of (+)-isocampholenic acid derivatives as potential fragrances
Sekundarni povzetek:	Throughout history, and even today, there has been an ongoing interest in the perfume industry to develop new substances that enhance, alter, or improve olfactory notes to enable the production of new perfume oils. Such substances are used either to replace costly natural substances that are in limited supply and costly to produce, or to create new fragrance notes of perfume types that were previously unavailable. Since woody-smelling compounds are indispensable ingredients in perfumery, we decided to work with fragrant camphor, whose products have been sought since ancient times. It has been found that some derivatives of campholenic acid, such as esters, ketones, and alcohols with extended side chain, are extremely stable compounds with a very individual scent property and are fragrances that are versatile, especially woody, sandalwood, fruity and floral scents. In contrast, fragrances derived from (+)-isocampholenic acid have not yet been described in the literature and in this master thesis, the synthesis of various (+)-isocampholenic acid derivatives with potential olfactory properties, was carried out. The preparation of the (+)-isocampholenic acid derivatives started from commercially available (1S)-(+)-10-camphorsulfonic acid, which gave, in two synthestic steps, the starting (+)-isocampholenic acid. In the first part, the esterification of (+)-isocampholenic acid with various organohalides in the presence of K2CO3 was carried out, and the isolated esters had a pleasant woody odor, but the most surprising odor we detected was that of an ester with a marine odor. In this part, we also performed Steglich esterification of (+)-isocampholenic acid with different alcohols, EDC as coupling reagent and DMAP as catalyst. The odor of the esters was mildly fruity, woody and floral. The next step was the reduction of (+)-isocampholenic acid to primary alcohol with LiAlH4. Various acid anhydrides reacted with the prepared primary alcohol to form esters with a fruity odor. A small library of woody ethers was synthesized with Williamson synthesis using depronated primary alcohol and various organohalides. A cyclic ether was synthesized from primary alcohol and TFA, which exhibited a very pleasant peppermint odor. In this master's thesis, we also performed olfactory evaluation of the synthesized ketones, prepared from Weinreb amide and various Grignard reagents. The odor of the ketones was woody with a pleasant sweet smell. From some of the isolated ketones we prepared tertiary alcohols using methylmagnesium bromide, where we perceived the smell of forest. By epoxidation of the methylene group, we demonstrated the possibility of further functionalization of (+)-isocampholic acid derivatives. In the last part, we tested the cytotoxic activity of the synthesized fragrances.
Sekundarne ključne besede:	fragrances;camphor;(+)-isocampholenic acid;olfactory properties;Kafra;Organska sinteza (kemija);Univerzitetna in visokošolska dela;
Vrsta dela (COBISS):	Magistrsko delo/naloga
Študijski program:	1000375
Konec prepovedi (OpenAIRE):	1970-01-01
Komentar na gradivo:	Univ. v Ljubljani, Fak. za kemijo in kemijsko tehnologijo, smer Kemija
Strani:	125 str.
ID:	17179915