20.500.12556/RUL-148948 Študija nukleofilnega fluoriranja alkoholov z imidazolnim tipom reagenta Study of nucleophilic fluorination of alcohols with imidazole type of reagent Fluorove organske molekule so pomembne zaradi njihove vloge v farmaciji, agrokemiji, materialih ter medicini. V okviru diplomske naloge smo študirali reakcijo fluorodehidroksiliranja z novim fluorirnim reagentom imidazolnega tipa (1,3-bis(2,6-diizopropilfenil)-2-kloro-1H-imidazol-3-ijev divodikov trifluorid), katerega prednost sta predvsem obstojnost na zraku in reaktivnost ob prisotnosti vode, poleg tega pa se lahko regenerira z vodno raztopino vodikovega fluorida. Na modelnih substratih različno substituiranih benzilnih alkoholov smo proučevali reakcijske pogoje deoksifluoriranja. Osredotočili smo se na čas, temperaturo, topilo, vrsto baze ter razmerji med substratom, reagentom in bazo. Pri glavnem modelnem substratu 4-terc-butilbenzil alkoholu smo s spreminjanjem pogojev dosegli 76-% pretvorbo v 4-terc-butilbenzil fluorid. Raziskovali smo tudi reakcijsko pot in 4-terc-butilbenzil klorid identificirali kot vmesni produkt dvostopenjskega deoksifluorirnega mehanizma. S Hammetovo enačbo smo določili konstanto reakcije ρ in iz nje sklepali o SN2 mehanizmu nukleofilne substitucije. Nekatere substituirane benzilne alkohole smo z reagentom pretvorili v pripadajoče fluoride, prav tako pa smo delovanje reagenta pokazali na nekaterih drugih tipih substratov (karboksilna kislina, alifatski alkoholi). Fluorinated organic molecules are important for their role in pharmaceuticals, agrochemicals, materials and medicine. In this thesis we have studied reaction of fluorodehydroxylation with the imidazole-type reagent (2-chloro-1,3-bis(2,6-diisopropylphenyl)-1H-imidazol-3-ium dihydrogen trifluoride), which has the advantage of being stable under ambient conditions and reactive in the presence of water, while it can be regenerated using aqueous solution of hydrogen fluoride. The deoxyfluorination was studied on model substrates of differently substituted benzyl alcohols. The focus was on time, temperature, solvent, type of base, and the ratio of substrate, reagent and base. For the main model substrate 4-tert-butylbenzyl alcohol, 76% conversion to 4-tert-butylbenzyl fluoride was achieved by varying the conditions. The reaction pathway was also investigated and 4-tert-butylbenzyl chloride was identified as an intermediate product of the two-step deoxyfluorination mechanism. The Hammett equation was used to determine the reaction constant ρ and the SN2 mechanism of the nucleophilic substitution was derived. Some other substituted benzylic alcohols were converted to the corresponding fluorides with the reagent, and the activity of the reagent was also demonstrated on some other types of substrates (carboxylic acid, aliphatic alcohols). nukleofilno fluoriranje deoksifluoriranje reagent imidazolnega tipa benzilni alkoholi Hammetova korelacija nucleophilic fluorination deoxyfluorination imidazole-type reagent benzylic alcohols Hammet correlation true false false Slovenski jezik Angleški jezik Diplomsko delo/naloga 2023-09-01 12:25:00 2023-09-01 12:25:04 2023-11-14 10:42:48 0000-00-00 00:00:00 2023 0 0 0000-00-00 NiDoloceno NiDoloceno NiDoloceno 0000-00-00 0000-00-00 0000-00-00 22049 165247491 Omahen_Blaz_-_Studija_nukleofilnega_fluoriranja_alkoholov_z_imidazolnim_tipom_reagenta.pdf Omahen_Blaz_-_Studija_nukleofilnega_fluoriranja_alkoholov_z_imidazolnim_tipom_reagenta.pdf 1 53EC0C34266AB59F972DEC362444E9AF 51384a3679a2b199e57dc500a504ef5a4f7b26080cc159ef9a2ef33c29e9cddc d02dd64f-48b1-11ee-af86-0050569b8976 https://repozitorij.uni-lj.si/Dokument.php?lang=slv&id=173323 Fakulteta za kemijo in kemijsko tehnologijo 0 0 0