Potassium,calcium, and strontium complexes with diphenyloxo-18-crown-6. Synthesis and vibrational spectra

New K, Ca, and Sr complexes with diphenyloxo-18-crown-6 (2,3,5,6-dibenzo-1,4,7,10,13,16-hexaoxocyclooctadecadiene-2,5, DPO18C6) were prepared and isolated as solids. Their IR spectra (400–4000 cm^–1) were studied. On the basis of spectroscopic data, a structure was proposed for these compounds. In the complexes, DPO18C6 occurs in the inner sphere of K, Ca, and Sr. Only five oxygen atoms of the crown ether are involved in coordination, and the macrocycle conformation does not depend on the nature of the metal.Translated from Koordinatsionnaya Khimiya, Vol. 31, No. 2, 2005, pp. 98–103.Original Russian Text Copyright © 2005 by Ivanova, Dorokhov, Kireeva, Pyatova, Yakshin, Tsivadze.     

Synthesis of 4-(trifluoromethyl)pyrido[4,3-<Emphasis Type="Italic">d</Emphasis>]pyrimidine derivatives

Earlier unknown 4-alkoxy-and 4-hydroxy-5-methyl-4-trifluoromethyl-1,4-dihydropyri-do[4,3-d]pyrimidines were obtained by the reaction of 5-acetyl-4-dimethylaminovinyl-6-(trifluoromethyl)pyrimidine with alcoholic (aqueous) solutions of NH₃. The former eliminate alcohol (water) on sublimation in vacuo to be converted to 5-methyl-4-(trifluoromethyl)-pyrido[4,3-d]pyrimidine. The latter upon the action of alcohols (water) under mild conditions were reverted to the corresponding 4-alkoxy-and 4-hydroxydihydropyrido[4,3-d]pyrimidines.     

Synthesis of 1-arylcytosine-5-carboxylic acid esters

A reaction of alkyl 2-(diaminomethylidene)-3-oxoalkanoates with arylisocyanates leads to the formation of the corresponding ureas, which upon the action of Na alkoxides cyclize to 1-aryl-6-R-cytosine-5-carboxylates. The latter reacting with arylisocyanates according to the similar scheme give rise to 3,6-diaryl-5-methylpyrimido[4,5-d]pyrimidine-2,4,7(1H,3H,6H)-triones.     

Reactivity of metal-containing monomers 66. Hydrogenation of nitrotoluene derivatives in the presence of polymer-immobilized Pd nanoparticles

A new approach to the synthesis of immobilized catalysts of the mixed type was developed: frontal polymerization of metal-containing monomers in the presence of a highly dispersed inorganic support. The synthesis of the acrylamide complex of Pd^II nitrate on the SiO₂ surface followed by polymerization and reduction results in the formation of a polymer-inorganic composite with inclusions of Pd nanoparticles stabilized by the polymer matrix on the support surface. The study of the catalytic properties in the hydrogenation of nitrotoluene derivatives showed that the polymer-immobilized Pd nanoparticles on the inorganic support are efficient catalysts for the reduction of the nitrocompounds.     

Synthesis of N-(1,2,4-triazol-5-yl)amidines from 5-amino-1,2,4-triazole and nitriles using tributylborane

A method is proposed for the synthesis of N-(1,2,4-triazol-5-yl)amidines not previously described in the literature from 5-amino-1,2,4-triazole and nitriles using tributylborane as an auxiliary reagent. The structures of the products were indicated by physicochemical methods.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 10, pp. 2353–2355, October, 1989.     

"Codimers" of N-(pyrid-2-yl) amides and ethyl cyanoacetate

Potential chelating-forming ligands and reagents for heterocyclization — ethyl esters of 4-[N-(R-pyrid-2-yl)carbamoyl]-3-amino-2-cyanobuten-2-oic acids ["codimers" of cyanoacetic acid ethyl ester (EECA) and the corresponding (pyrid-2-yl) amides of this same acid) — were synthesized in two ways: by condensation of 2-dialkylborylamidopyridines (picolines) with EECA (via chelate compounds of boron) and by the reaction of EECA dimer with 2-aminopyridines (picolines).N. D. Zelinskii Institute of Organic Chemistry, Russian Academy of Sciences, 117913 Moscow. Translated from Izvestiya Akademii Nauk, Seriya Khimicheskaya, No. 2, pp. 371–376, February, 1992.     

Potassium and cesium thiocyanate complexes with diphenyloxa-21-crown-7: Synthesis and vibration spectra. Selective properties of dipnehyloxa-21-crown-7

Novel K and Cs complexes with diphenyloxa-21-crown-7 (2,3,5,6-dibenzo-1,4,7,10,13,16,19-heptaoxacyclo-heneicosadiene-2,5; DPO21C7) are synthesized and isolated in a solid state, and their IR spectra (4000–400 cm^–1) are studied. Only four ether O atoms of crown ether are involved in coordination. Conformation of a macrocycle in the complexes depends on the cation size. The potentiometric selectivity of diphenyloxa-21-crown-7 toward Cs⁺ ions was found to be the greatest.Translated from Koordinatsionnaya Khimiya, Vol. 31, No. 3, 2005, pp. 163–167.Original Russian Text Copyright © 2005 by Ivanova, Dorokhov, Pyatova, Galkina, Yakshin, Tsivadze.This revised version was published online in April 2005 with a corrected cover date.This revised version was published online in April 2005 with a corrected cover date.     

Alkalli Metal Complexes with <Emphasis Type="Italic">N</Emphasis>-(4′-Benzo-15-Crown-5)-2-(Amino-<Emphasis Type="Italic">N</Emphasis>-tosyl)-phenylaldimine

Complexes of Li, Na, and K with N-(4′-benzo-15-crown-5)-2-(amino-N-tosyl)-phenylaldimine (L) are synthesized and their IR spectra are studied with assignment of the basic vibration frequencies of the ligand and complexes. The conformation states of macrocycles in the title complexes are analyzed. The macrocycle conformation in complexes of L with the Li, Na, and K salts is not influenced by the nature of a metal or acido ligands. The structures of the synthesized compounds are suggested on the basis of the spectral and elemental analysis data.__________Translated from Koordinatsionnaya Khimiya, Vol. 31, No. 7, 2005, pp. 512–517.Original Russian Text Copyright © 2005 by Ivanova, Dorokhov, Pyatova, Bicherov, Burlov, Garnovskii, Tsivadze.     

Synthesis of pyrido[2,3-<Emphasis Type="Italic">d</Emphasis>]pyrimidin-7(8<Emphasis Type="Italic">H</Emphasis>)-one derivatives from 5-acetyl-4-aminopyrimidines and β-dicarbonyl compounds

Heating of 5-acetyl-4-aminopyrimidine derivatives with ethyl acetoacetate, ethyl benzoylacetate, and diethyl acetone-1, 3-dicarboxylate in the absence of a base gave the corresponding 6-acylpyrido[2, 3-d]pyrimidin-7(8H)-ones. Under analogous conditions, the reaction with ethyl malonate afforded ethyl 7-oxo-7, 8-dihydropyrido[2, 3-d]pyrimidine-6-carboxylates. The pyridone (rather than hydroxypyridine) structures of the pyridopyrimidines obtained were confirmed by IR spectroscopy.__________Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 3, pp. 770–773, March, 2005.