Synthesis and investigation of solvent effects on the ultraviolet absorption spectra of 1, 3-bis-substituted-5, 5-dimethylhydantoins

Abstract

A series of 1,3-bis-substituted-5,5-dimethylhydantoins was synthesized using the reaction of 5,5-dimethylhydantoin with the corresponding alkyl halide in the presence of trimethylamine as catalyst and sodium hydroxide, according to a modified literature procedure. The experimental investigation included modification of the synthetic procedure in terms of starting materials solvent, temperature, isolation techniques, as well as purification and identification of the products. The absorption spectra of the 1,3-bis-substituted-5,5-dimethylhydantoins were recorded in twelve solvents in the range 200–400 nm. The effects of the solvent polarity and hydrogen bonding on the absorption spectra were interpreted by means of linear solvation energy relationships using a general equation of the form ν = ν0 s¶* + aα + bβ and by two-parameter models presented by the equation ν = ν0 s¶* + aα, where ¶* is a measure of the solvent polarity/polarisability, α is the scale of the solvent hydrogen bond donor acidities and β is the scale of the solvent hydrogen bond acceptor basicities. The solvent and substituent effects on the electronic absorption spectra of the investigated hydantoins is discussed.

U okviru rada je izvršena sinteza serije 1,3-bis-supstituisanih-5,5-dimetilhidantoina iz 5,5-dimetilhidantoina i odgovarajućeg alkilhalogenida u prisustvu trimetilamina kao katalizatora i natrijum-hidroksida, po modifikovanom postupku iz literature. Sintetizovani hidantoini su identifikovani na osnovu tačke topljenja, FTIR, 1H-NMR i UV spektroskopskih podataka. Apsorpcioni spektri 1,3-bis-supstituisanih-5,5-dimetilhidantoina su određeni u dvanaest rastvarača različite polarnosti u opsegu 200–400 nm. Uticaj polarnosti rastvarača kao i efekat vodonične veze proučavani su metodom linearne korelacije solvatacionih energija odnosno jednačinama oblika νmax = ν0 s¶*+aα + bβ i νmax = ν0 + s¶* + aα, u kojima je ν apsorpciona frekvencija ¶* mera efekata solvatacije vezana za polarnost rastvarača, α mera uspostavljanja vodonične veze sa proton-donorskim rastvarač ima, a β mera vodonične veze ostvarene sa protonakceptorskim rastvaračima. Rezultati prezentovani u ovom radu su veoma značajni za sagledavanje karakteristika 1,3-bis-supstituisanih- 5,5-dimetilhidantoina zbog njihove velike primene u kompozitnim materijalima kao vezujućih agenasa.