A. Omran

The synthesis of tetracarbonyl derivatives of thiacalix(4)arene in different conformations and their complexation properties towards alkali metal ions

Abstract The three conformations of 5,11,17,23-tetra-tert-butyl-25,26,27,28-tetrakis[(benzoyl)methoxy]-2,8,14,20-tetrathiacalix[4]arene 1 : cone, partial cone and 1,3-alternate, were prepared by the treatment of 5,11,17,23-tetra-tert-butyl-2,8,14,20-tetrathiacalix[4]arene-25,26,27,28-tetraol (TCA) with α-bromo acetophenone in the presence of appropriate alkali carbonate M2CO3 (M=Na, K, Cs) as base catalyst in acetonitrile. Structure of the conformers were established by 1H NMR, 1H–1H COSY, 1D NOE, 2D ROESY and X-ray experiments. The alkali cation binding selectivity of the obtained macrocycles was investigated by the ion-pair extraction method.

Synthesis of tetrathioesters and tetrathioamides based p-tert-butylthiacalix[4]arene and studying their recognition abilities towards different metals by extraction

Abstractp-tert-Butylthiacalix[4]arene tetrathioesters 2a–c and tetrathioamides 4a–c in three different conformers (cone, partial cone and 1,3-alternate respectively) have been synthesized. The later were characterized by different physical methods IR, 1H NMR, 13C NMR and X-ray crystallography. Their recognition abilities towards different alkali, earth alkaline and transition metals such as (Na+, K+, Cs+, Ba2+, Pb2+, Ag+, Cd2+, Hg2+ and Co2+) cations have been examined by metal picrate extraction from aqueous solutions into dichloromethane.Graphical Abstract

Crystal structure of the inclusion complex 25-benzo-ylmeth-oxy-5,11,17,23-tetra-tert-butyl-26,27,28-trihy-droxy-2,8,14,20-tetra-thia-calix[4]arene-tetra-ethyl-ammonium chloride (1/1).

The asymmetric unit of the title compound, C48H54O5S4·N(C2H5)4 +·Cl−, contains two tetra-tert-butyl-[(benzoyl)methoxy]-trihydroxy-tetrathiacalix[4]arene molecules, two tetraethylammonium cations and two chloride anions. The two calixarene molecules in the asymmetric unit each display a cone conformation. There are no significant differences between the two independent molecules. The guest species do not sit within the calixarene ‘buckets’. In the crystal, extensive O—H⋯O, O—H⋯S and O—H⋯Cl hydrogen bonds and weak C—H⋯O, C—H⋯S and C—H⋯Cl interactions link the thiacalixarene molecules, tetraethylammonium cations and chloride anions, forming a three-dimensional network encompassing channels running parallel to the a-axis direction. The structure contains a solvent-accessible void of 76 (3) Å3, but no solvent molecule could reasonably be located. The crystal studied was an inversion twin with a 0.57 (8):0.43 (8) domain ratio.

Crystal structure of 1-(2-amino-phen-yl)-3-phenyl-urea.

In the title compound, C13H13N3O, the phenyl ring makes a dihedral angle of 47.0 (1)° with the mean plane of the –NC(=O)N– unit, while the dihedral angle between the latter mean plane and the aminophenyl ring is 84.43 (7)°. In the crystal, molecules are linked via N—H⋯O hydrogen bonds involving the central –NHC(=O)NH– units, forming chains running parallel to the b axis. These chains associate with one another via N—H⋯O and N—H⋯N hydrogen bonds, from the pendant amino groups to the –NHC(=O)NH– units of adjacent molecules, forming columns propagating along [010]. The structure was refined as a two-component twin with a 0.933 (3):0.067 (3) domain ratio.

Synthesis, Separation and Characterization of Thiacalix[4]arenes Diastereomers

Two different 1 , 3-Distal thiacalix[4]arenas were prepared by the reaction of thiacalix[4]arene with phenacyl and/or p-nitro phenacyl bromide in acetone or acetonitrile in the presence of dry CsOH. The prepared 1, 3-distal disubstituted thiacalixarenes afforded two pairs of diastereomers upon brominating in chloroform. The obtained diastereomers were separated by fractional crystallization in a mixture dichloromethane-acetone.

Crystal structure of ethyl 2-[2-((1E)-{(1E)-2-[2-(2-eth­oxy-2-oxoeth­oxy)benzyl­idene]hydrazin-1-yl­idene}meth­yl)phen­oxy]acetate

The complete molecule of the title compound, C22H24N2O6, is generated by crystallographic inversion symmetry and is approximately planar (r.m.s. deviation of the non-H atoms = 0.134 Å). The packing consists of inter-digitated sheets inclined at 25.9 (4)° to one another and linked by short C—H⋯O hydrogen bonds.

Utility of Hydrazinopiperidinomethanethione in Synthesis of Thiadiazole, Thiadiazine, and Pyrazole Derivatives

Hydrazinopiperidinomethanethione 2 was prepared and reacted with active halo compounds, carbon disulfide, phenyliso-thiocyanate, ylidenenitriles, and N,S-acetyls to give thiadiazine 4–7 , thiadiazole 8–10 , and pyrazole 11,13 , 14–17 derivatives, respectively.

Crystal structure of tetra­ethyl 27,30-dioxo-7,12,20,25-tetra-tert-but­yl-3,16-dioxa-9,22,28,31-tetra­thia­hepta­cyclo­[21.3.1.11,5.14,8.110,14.114,18.117,21]dotriaconta-4,6,8(29),10,12,17,19,21(32),23,25-deca­ene-2,2,15,15-tetra­carboxyl­ate

The asymmetric unit of the title compound, C54H64O12S4, consists of one half of the molecule, which is located on an inversion centre. The heterocyclic six-membered ring adopts a distorted envelope conformation with the spiro C atom as the flap. In the crystal, molecules are linked by weak C—H⋯O hydrogen bonds with an R 2 2(14) motif, forming a chain along the b-axis direction.