KCo(H2O)2BP2O8·0.48H2O and K0.17Ca0.42Co(H2O)2BP2O8·H2O: two cobalt borophosphates with helical ribbons and disordered (K,Ca)/H2O schemes

The two title compounds, potassium diaquacobalt(II) borodiphosphate 0.48‐hydrate and potassium–calcium(0.172/0.418) diaquacobalt(II) borodiphosphate monohydrate, were synthesized hydrothermally. They are new members of the borophosphate family characterized by _∞[BP₂O₈]³⁻ helices running along [001] and constructed of boron (Wyckoff position 6b, twofold axis) and phosphorus tetrahedra. The [CoBP₂O₈]⁻ anionic frameworks in the two materials are structurally similar and result from a connection in the ab plane between the CoO₄(H₂O)₂ coordination octahedra (6b position) and the helical ribbons. Nevertheless, the two structures differ in the disorder schemes of the K,Ca and H₂O species. The alkali cations in the structure of the pure potassium compound are disordered over three independent positions, one of them located on a 6b site. Its framework is characterized by double occupation of the tunnels by water molecules located on twofold rotation axes (6b) and a fraction of alkali cations; its cell parameters, compared with those for the mixed K,Ca compound, show abnormal changes, presumably due to the disorder. For the K,Ca compound, the K and Ca cations are on twofold axes (6b) and the channels are occupied only by disordered solvent water molecules. This shows that it is possible, due to the flexibility of the helices, to replace the alkali and alkaline earth cations while retaining the crystal framework.     

Synthesis and biological screening of some chromonyl-substituted heterocycles derived from 2(3H)-furanone derivative

A 2(3H)-furanone bearing chromonyl moiety at position-3 was synthesized and utilized for the construction of N-heterocycles such as pyrrolone, N-aminoquinolone, and pyridazinone derivatives. The reactivity of the chromonylfuranone toward some nitrogen nucleophiles such as ammonia, benzylamine, hydrazine, and phenylhydrazine was studied. On the other hand, thiation of the starting chromonylfuranone interestingly provides mono- and di-thiated products. The chemoselectivity of these reactions is discussed. The structures of all products obtained were elucidated from their analytical and spectral data. The antimicrobial activities of selected examples of the synthesized compounds were examined against two strains of bacteria and two fungus strains. Some of them showed promising antimicrobial activities.     

SYNTHÉSE DE THIOÉTHERS D'ACIDES PROPYLBORONIQUES S - BENZYLÉS

The protection of the hydroxy group of p-cresol 1 by o-silylation gives derivatives 2 and 3 , the methyl group of which can be brominated by NBS. The phase transfer catalysis applied to 4 and 5 is a good way which permits the mild introduction of the allylthio group ( 6 and 7 ). Hydroboration applied to silylated compounds 8 and 9 , followed by methanolysis and hydrolysis leads to target acids 10 and 11 in a good yield.

La protection du groupement hydroxy du p-crésol 1 par o-silylation donne les dérivés 2 et 3 ce qui permet de bromer le substituant méthyle par le N-bromosuccinimide (NBS). La catalyse par transfert de phase (CTP) appliquée aux produits 4 et 5 est une bonne méthode pour introduire un groupement allylthio (composés 6 , 7 ). L'hydroboration des composés silylés 8 et 9 , suivie d'une méthanolyse et d'une hydrolyse permet d'accéder aux acides cibles 10 et 11 avec de bons rendements.     

REACTION OF ORGANOCADMIUM REAGENTS WITH SULFONYL HALIDES III. ACTION OF ALKANESULFONYL CHLORIDES ON SELECTED DIARYLCADMIUM COMPOUNDS

Abstract

The reaction of methane- and ethanesulfonyl chloride with selected diarylcadmium compounds was investigated. In contrast with arenesulfonyl chlorides which react with diarylcadmium to give sulfones in appreciable yields, ethanesulfonyl chloride did not yield sulfones. Methane-sulfonyl chloride gave sulfones in very poor yields. The major products were haloarenes, alkane-sulfinic acids and biaryls.

Cross-over experiments revealed that the formation of biaryls involve an inter-not intra-molecular reaction (cf. eq. 4).     

Synthesis of 3-Substituted Pyrido[4′,3′:4,5]thieno[2,3-d]pyrimidines and Related Fused Thiazolo Derivatives

New ethyl 3-(substituted)-4-oxo-2-thioxo-1,2,3,4,5,6,7,8-octahydropyrido[4',3':4,5]thieno-[2,3-d]pyrimidine-7-carboxylates ( 3a , b ), ( 6 ),( 11-13 ), ethyl 3-methyl-5-oxo-2,3,6,9-tetrahydro 5 H -pyrido[4',3':4,5]thieno[2,3-d][1,3]thiazolo[3,2-a]pyrimidine-8(7H)-carboxylate ( 4 ), and ethyl 2-methyl-5-oxo-2,3,6,9-tetrahydro-5 H -pyrido[4',3':4,5]thieno[2,3-d][1,3]thiazolo[3,2-a]-pyrimidine-8(7H)-carboxylate ( 8 ) have been synthesized from diethyl 2-isothiocyanato-4,5,6,7-tetrahydrothieno[2,3-c]pyridine-3,6-dicarboxylate 1. The structure of these compounds as well as their intermediates have been established by their spectral data.     

Novel Synthesis of Condensed Pyridin-2(1H)-one and Pyrimidine Derivatives

The reaction of N-chloroacetyl derivatives 6-10 with morpholine yielded N-morpholin-1-yl acetyl derivatives 11-15 , which were subjected to Thorpe-Zieler cyclization with sodium tert -butoxide to produce the corresponding condensed pyridin-2(1H)-one derivatives 16-20 . Treatment of compounds 1 , 6-10 with either malononitrile or p -chlorobenzylidinemalononitrile in presence of triethylamine, afforded the corresponding pyrimidines 21-25 , 27 and pyridine derivative 26 respectively. Moreover compound 1 a was treated with ethyl isothiocyanoacetate to give the corresponding piprazine derivative 28 .     

On the Reaction of 3-Acetyl Coumarin with Alkyl Phosphites. Structural Confirmations Based on X-Ray Crystallography

3-Acetyl coumarin ( 1 ) reacts with dialkyl phosphites at 100°;C for 8 h to give the phosphonates 2 . Under the same experimental conditions, 1 reacts with trialkyl phosphites to form a mixture of the phosphonates 2 and 3 . The molecular structures of these products were elucidated by x-ray crystallography.