SINTEZA, STRUKTURA I SVOJSTVA 3-BENZIL-CIKLOPENTANSPIRO-5-HIDANTOINA

Abstract

Derivati hidantoina se uveliko primenjuju u medicini. Poznati su kao antikonvulzivi, antidepresivi i antikancerogeni agensi 1. U okviru proučavanja uticaja strukture na biološku aktivnost derivata cikloalkanspiro-5-hidantoina, sintetisan je 3-benzil-cikloalkanspiro-5-hidantoin. Jedinjenje je dobijeno Bučerer-Libovom metodom polazeći od ciklopentanona, kalijum-cijanida i amonijum-karbonata u 50%-nom rastvoru etanola, posle čega je izvršena nukleofilna supstitucija benzil-bromidom. Monokristali odgovarajućih dimenzija dobijeni su prekristalizacijom iz etil-acetata posle 24 h na sobnoj temperaturi. Jedinjenje je okarakterisano rendgenskom strukturnom analizom i UV-vis, FT-IR, 1H i 13C NMR spektroskopskim metodama. Asimetrična jedinica 3-benzil-ciklopentanspiro-5-hidantoina sastoji se od dva molekula, u kojima ciklopentanski prsten ima konformaciju koverte. Dve jake vodonične veze N–HO između NH-grupa iz hidantoinskih prstenova jednog molekula i O=C-grupa iz hidantoinskih prstenova susednih molekula [d(N···O) iznose 2,869(4) i 2,913(4) Å; uglovi iznose 174 i 160 °], dovode do formiranja centrosimetričnih R22(8) dimera (slika). Dimeri su dalje povezani u 3D mrežu slabim C–H··· interakcijama između H-atoma u ciklopentanskom prstenu i benzenskog prstena (dužina H–Cg iznosi 2,960 Å). Kristalografski podaci: C28H32N4O4, Mr = 488,58, trikliničan sistem, prostorna grupa P1, a = 5,976(1), b = 12,801(3), c = 17,604(4) Å, α = 106,51(3), β = 91,33(3), γ = 92,01(3) °, V = 1289,6(4) Å3, R1 = 0,0569 za 2252 refleksija sa I  2σ(I).

Hydantoin derivatives are widely used in medicine. They are known as anticonvulsants, antidepressants and anticancer agents 1. Within the study of the hydantoins, a new 3-benzyl-cycloalkanespiro-5-hydantoin has been synthesized. Titled compound has been prepared using Bucherer-Lieb method starting from cyclopentanone, potassium cyanide and ammonium carbonate in 50 % ethanol solution, followed by nuclephilic substitution with benzyl bromide. The single crystals of the suitable size were formed by recrystallization from ethyl acetate after 24 h standing at room temperature. The characterization of the compound was made by the single-crystal X-ray diffraction analysis and UV-vis, FT-IR, 1H and 13C NMR spectroscopic methods. The asymmetric unit of the 3-benzyl-cyclopentane-5-hydantoin consists of two molecules, in which a cyclopentane rings adopt the envelope conformation. Molecules form R22(8) centrosymmetric dimers through two strong N–HO hydrogen bonds between hydrogen bond donor NH group and hydrogen bond acceptor O=C group from hydantoin rings belonging to adjacent molecules [d(N···O) are 2.869(4) and 2.913(4) Å; angle values are 174 and 160 °] (Figure). By weak C–H··· interactions between H atoms of the cyclopentane and benzene rings (H–Cg distance is 2.960 Å), the dimmers are further connected into the 3D network. Crystal data: C28H32N4O4, Mr = 488.58, triclinic, space group P1, a = 5.976(1), b = 12.801(3), c = 17.604(4) Å, α = 106.51(3), β = 91.33(3), γ = 92.01(3) °, V = 1289.6(4) Å3, R1 = 0.0569 for 2252 observed reflections with I  2σ(I).