Copper(II) bromide complexes with acyclic and cyclic pyrimidine-containing phane ligands

Complexes of copper(II) bromide with cyclic and isostructural acyclic phane ligands containing derivatives of pyrimidine nucleobases (cytosine and uracil) were synthesized and characterized. In two cyclic pyrimidinophanes used, the macrocycles included two 6-methylthiocytosine and one 6-methyluracil units linked by polymethylene chains (L³) and two 6-methyluracil units linked by N-containing bridges (L⁵). Ligand L³ and its isostructural acyclic analogs are coordinated by the Cu²⁺ ion through the same donor sites (the ring N atoms of the thiocytosine units). The coordination polyhedra of the Cu atom in complexes with cyclic and acyclic ligands are different. Ligand L⁵ and its isostructural acyclic analog also form copper(II) complexes with different coordination polyhedra involving different donor sites. The acyclic ligand is coordinated by the Cu²⁺ ion via the bridging N atom, while cyclic ligand L⁵, via the uracil CO groups (the bridging N atoms become protonated). The resulting complexes are dielectrics.     

Reaction of 2-mercaptopyrimidines with some α,ω-dihaloalkanes

Conclusions In the reaction of some 2-mercapto-4,6-disubstituted pyrimidines with different,-dihaloalkanes, thiazolepyrimidine and pyrimidothiazine salts, 2-(-haloalkylthio)-4,6-disubstituted pyrimidines, and,-bis (4,6-disubstituted pyrimidinyl-2-thio) alkanes are formed. The structure of the products of the reactions is a function of the nature of the substituents in the pyrimidine ring, the number of methylene groups in the,-dihaloalkanes, and the ratio of the reagents.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 6, pp. 1396–1402, June, 1984.     

Two-fragment α-adrenolytics. 4. Synthesis of phosphorylated derivatives of 2-aryloxyethylamines and N-phenylpiperazine

The reactions of 3-chloropropylphosphonates, 3-chloropropylthiophosphonates, or 3-chloropropylphosphinates with 2-aryloxyethylamines or N-phenylpiperazine afford the corresponding 3-(2-aryloxyethylamino)propylphosphonates and -phosphinates or 3-(4-phenylpiperazin-1-yl)propylphosphonates and -phosphinates. The compounds obtained exhibit -adrenolytic and hypotensive activities, the latter being found to depend on the substituents at the P atom.     

Reaction of 2,4-dimercapto-6-methylpyrimidine with α,ω-dibromoalkanes

Conclusions The major products of the reaction of the disodium salt of 2,4-dimercapto-6-methylpyriniidine with ,-dibromoalkanes are 2,4-bis(-bromoalkylthio)-6-methylpyrimidines and trimacrocyclic compounds.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 4, pp. 930–932, April, 1982.     

α,ω-Bis(3,6-dimethyl-2,4-dioxo-1,2,3,4-tetrahydropyrimidin-1-yl)alkanes and products of their cyclization, pyrimidinophanes: intra- and intermolecular interaction in crystals and in solutions

Reaction of α,ω-bis(3,6-dimethyl-2,4-dioxo-1,2,3,4-tetrahydropyrimidin-1-yl)alkanes with paraformaldehyde leads to pyrimidinophanes, which contain four 3,6-dimethyluracil fragments, connected to each other by the methylene chains. A comparative study of intra- and intermolecular interactions of “open” and macrocyclic uracil derivatives in the crystal state and in solution was performed. According to the NMR spectroscopy data, there is no self-association of “open” and macrocyclic compounds in chloroform solutions, whereas the X-ray data revealed the intermolecular π-π contacts between the 3,6-dimethyluracil fragments in the crystals of these compounds. Conclusions on the presence of intramolecular interactions in chloroform solutions of α,ω-bis(3,6-dimethyl-2,4-dioxo-1,2,3,4-tetrahydropyrimidin-1-yl)alkanes and pyrimidinophanes were made based on the UV spectra, which were interpreted in terms of hypo- and hyperchromic effects relatively to the model uracil derivative. These conclusions correlate with the X-ray data: there are no intramolecular π-π contacts between the 3,6-dimethyluracil fragments both in the crystals and in solutions of “open” compounds, positions of these fragments relatively to each other in the molecules of pyrimidinophanes are defined by the lengths of the polymethylene bridges. The intramolecular stacking effect between the opposite uracil rings is observed for the macrocycles with trimethylene and hexamethylene chains, whereas there is no such interactions in pyrimidinophanes with tetramethylene chains. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 1, pp. 119–131, January, 2008.     

Reverse micellar catalysis of phosphorylation of pyrimidinophanes

The reaction of pyrimidinophanes with 4-nitrophenyl bis(chloromethyl)phosphinate in reverse micellar solutions of cetyltrimethylammonium bromide, polyethylene glycol 600 monolaurate, and their mixture was studied by spectrophotometry in chloroform. The catalytic activity of the micelles was found to depend on the macrocycle size and concentration and relative content of surfactants in the solution.