The dissertation is focused on the new approaches for the synthesis of new heteropolycyclic compounds based on the nitrogen-containing derivatives of Endic anhydride, investigation their chemical and physico-chemical properties.
Reduction of imide and epoxyimide norbornene derivatives by sodium borohydride has been investigated under different conditions, including various solvents, reagent’s ratio and reduction system. The method of synthesis of 5-endo-hydroxy-4-azatricyclo-[5.2.1.02,6]dec-8-en-3-ones based on 5-substituted imide norbornene derivatives was developed. It was found that reduction of imides proceeds stereochemically with formation of product where hydroxy-group is located only on the external side of norbornene frame (exo-position).
One-step transformation of the 4-aza-8,9-epoxybicyclo[5.2.1.02,6]undecane-3,5-
diones to the 2-hydroxy-9-(cycloalkylaminocarbonyl)-4-azatricyclo[4.2.1.03,7]nonan-5- ones in treatment with magnesium piperidin-1-ide and morpholin-4-ide bromides was developed. The proper selection of the experimental conditions allows the formation of hardly available polycyclic lactams.
It was found that the treatment of epoxyimides with sodium borohydride results in
formation of N-substituted 7-oxo-5-azatetracyclo[6.3.0.02,6.03,10]-undecan-4-ones or tricyclic dihydroxypirolidone derivatives. The structure of product depends on the substituent at the nitrogen atom of imide fragment and reduction reaction conditions. The selective method of synthesis for N-substituted 7-oxo-5-azatetracyclo[6.3.0.02,6.03,10]- undecan-4-ones was developed. It was found that treatment of epoxyimides with Grignard reagents, phenylacetylene magnesium bromide and phenyl lithium leads to one type of product - 6-substituted tetracyclic lactams with the structure of 3-oxo-4-aza-11- oxatetracyclo[5.2.1.15,8.02,6]-undecane. It was revealed that treatment of epoxyimide norbornene derivatives with piperidin-1-ide and morpholin-4-ide bromides leads to the tricyclic amidolactones (4-substituted 2-hudroxy-9-carbamoyl-4-azatricyclo[4.2.1.03,7]nonan-5-ones).
The formation of zwitterionic 5-(N,N-dialkyliminio)-exo-2-arylsulfonylamino-4-
oxatricyclo[4.2.1.03,7]nonane-endo-9-carboxylates as well as expected N,N-dialkyl-5-oxoexo-2-arylsulfonylamino-4-oxatricyclo[4.2.1.03,7]nonane-endo-9-carboxamides in the reaction of amidoacid norbornene derivatives with arenesunfonyl azides was observed.
It was established that the optimal catalyst for the reaction of oxidation and isomerization of 5-endo-hydroxy-4-azatricyclo[5.2.1.02,6]dec-8-en-3-ones by Lewis acids (MgBr2, AlCl3, CF3COOH, and NaH) is trifluoroacetic acid. The N-benzyl-3-(diphenylmethyl)bicyclo[2.2.1]hept-5-ene-2-carboxamide was unexpectedly isolated in the reaction of 4-benzyl-5-endo-hydroxy-4-azatricyclo-[5.2.1.02,6]dec-8-en-3-one with anhydrous AlCl3 in benzene. A convenient method for the synthesis of 5-exo-alkoxy-4-alkyl(aryl)-4-azatricyclo[5.2.1.02,6]dec-8-en-3-ones was developed. The intermolecular cyclization of 5-endo-hydroxy-4-azatricyclo[5.2.1.02,6]dec-8-en-3-ones was investigated.
The X-ray diffraction studies fully confirm the reliability of the obtained results for the most of classes of represented synthesized compounds.
