Mixture Of ZnCl Research Articles

Deprotonative Metalation of Functionalized Aromatics Using Mixed Lithium–Cadmium, Lithium–Indium, and Lithium–Zinc Species

In situ mixtures of CdCl(2)TMEDA (0.5 equiv; TMEDA = N,N,N',N'-tetramethylethylenediamine) or InCl(3) (0.33 equiv) with [Li(tmp)] (tmp = 2,2,6,6-tetramethylpiperidino; 1.5 or 1.3 equiv, respectively) were compared with the previously described mixture of ZnCl(2)TMEDA (0.5 equiv) and [Li(tmp)] (1.5 equiv) for their ability to deprotonate anisole, benzothiazole, and pyrimidine. [(tmp)(3)CdLi] proved to be the best base when used in tetrahydrofuran at room temperature, as demonstrated by subsequent trapping with iodine. The Cd-Li base then proved suitable for the metalation of a large range of aromatics including benzenes bearing reactive functional groups (CONEt(2), CO(2)Me, CN, COPh) or heavy halogens (Br, I), and heterocycles (from the furan, thiophene, pyrrole, oxazole, thiazole, pyridine, and diazine series). Five-membered heterocycles benefiting from doubly activated positions were similarly dideprotonated at room temperature. The aromatic lithium cadmates thus obtained were involved in palladium-catalyzed cross-coupling reactions or simply quenched with acid chlorides.

(C6H14N2){Zn[ZnB2P4O15(OH)2]·(C6H13N2)Cl}: A New Templated Zincoborophosphate

Colorless crystals of (C 6 H 14 N 2 ){Zn[ZnB 2 P 4 O 15 (OH) 2 ].(C 6 H 13 N 2 )Cl} (1) were prepared from mixtures of ZnCl 2 , B 2 O 3 , diaza-bicyclo[2.2.2]octane (DABCO), and 85% H 3 PO 4 under mild hydrothermal conditions (170 °C). The crystal structure was determined by single-crystal X-ray diffraction (monoclinic, P2 1 /c (No. 14), a = 1704.3(1) pm, b = 937.03(5) pm, c = 1619.75(8) pm, β = 96.894(3)°, Z = 2). The crystal structure contains tetrahedral zigzag ribbons, 1 ∞{[ZnB 2 P 4 O 15 (OH) 2 ] 4- }, running along [010]. Additional ZnO 2 NCl tetrahedra at the borders complete the ribbons by sharing common O-corners with the zincoborophosphate polymer. The nitrogen atoms of the quaternary ZnO 2 NCl tetrahedra belong to monoprotonated (HDABCO) + ions. A second (diprotonated) species, (H 2 DABCO) 2+ , acts as a pure template and is fixed to adjacent zincoborophosphate ribbons along [100] via hydrogen bonds. The title compound 1 can be described as an adduct of (C 6 H 14 N 2 ){Zn[ZnB 2 P 4 O 15 (OH) 2 ]} with diaza-bicyclo[2.2.2]octane-hydrochloride. Thermoanalytical and X-ray powder diffraction investigations to high temperatures (740 °C) show the decomposition of 1 and the formation of a NH 4 [ZnBP 2 O 8 ] polymorph as an intermediate.

Study of the Acylation Reaction of 2(3H)-Benzothiazolones in the Mixture of ZnCl 2 -DMF

The use of polyphosphoric acid and the complex AlCl 3 -DMF in 6-acylation of 2(3H)-benzothiazolones previously have been reported. Instead of the frequently used AlCl 3 as a catalyst in the Friedl-Crafts reactions, we conducted the acylation of 2(3H)-benzothiazones using zinc chloride as a catalyst in DMF as solvent and acid chlorides or anhydrides as acylating agents.

Two polymorphs of a piperazinium zincophosphate with different interrupted SOD-type frameworks

Two polymorphous forms of the piperazinium zincophosphate (ZnPO) (C 4N 2H 12)[Zn 2P 3O 12H 3] have been obtained under mild hydrothermal conditions from mixtures of ZnCl 2, H 3PO 4 piperazine and H 3BO 3 in ethylene glycol/water solvents. Single-crystal X-ray structure analyses revealed that both polymorphs possess an open-framework structure with sodalite (SOD) topology. While polymorph I (formulation (C 4N 2H 12)[Zn 2(HPO 4) 3], space group P2 1/c, Z=8) is reported for the first time, polymorph II (formulation (C 4N 2H 12)[Zn 2(PO 4)(H 1.5PO 4) 2], space group C2/c, Z=4) is a known phase. Its structure has been reinvestigated in order to unambiguously determine the hydrogen bonds. The interruptions in the ZnPO host structures possess the form of distorted tetrahedral [H 3O 4(P) 4] groupings (hydroxyl nests). A diprotonated piperazine molecule is enclosed in every [4 66 8] cage. The polymorphs differ in the host–guest N–H⋯O and C–H⋯O interactions, the degree of condensation of the distinct phosphate tetrahedra, the hydrogen-bonding systems in the interruptions, and the long-range ordering of interruptions in the host frameworks. Considerable differences are seen for the donor–acceptor O⋯O distances (ranging from 2.47 to 3. 14 Å) in the total of three distinct [H 3O 4(P) 4] groupings.

New heterometallic copper zinc alkoxides: synthesis, structure properties and pyrolysis to Cu/ZnO composites

The copper compound [(THF)KCu(O t Bu) 3] ∞ 1 was obtained by interaction of a 1:1 mixture of ZnCl 2/CuCl 2 with KO t Bu. Bi- and trifunctional aminoalcohols were used to synthesize the intramolecularly donor stabilized Cu(II) alkoxides Cu(OCH(R)CH 2NMe 2) 2 ( 3: R=Me, 4: =CH 2NMe 2) where 4 was structurally characterized. Lewis acid–base adduct formation with (Me 3Si) 3CZnCl gave the heterodinuclear compounds (Me 3Si) 3CZnCl · Cu(OCH(R)CH 2NMe 2) 2 ( 5: R=Me, 6: R=CH 2NMe 2), which were characterized by X-ray single-crystal structure analysis. The two metal centers Cu and Zn of 5 and 6 are bridged by two oxygen atoms to form a Cu–O–Zn core. Pyrolysis of compounds 5 and 6 in dry argon or a H 2/N 2 mixture at atmospheric pressure forms metallic copper and zinc oxide, whereas pyrolysis under O 2/Ar forms additionally oxidized copper species. Elemental analysis of the pyrolysis products showed carbon and nitrogen contamination. Scanning electron microscopy and energy dispersive X-ray analysis were performed to get information on the morphology and the chemical composition of the pyrolysis products.

Comparison of coal hydroliquefaction catalysed by ZnCl 2- MCl n (CuCl, CrCl 3 and MoCl 5) and ZnCl 2 melts

Hydrogenation of four bituminous coals impregnated with 5 wt% of either mixtures of ZnCl 2- MCl n (CuCl, CrCl 3 and MoCl 5) systems or ZnCl 2 was carried out using a batch autoclave system at 400° for 3 h at 9.8 MPa of initial hydrogen pressure. The ZnCl 2-MoCl 5 system showed the highest yield of the hexane-soluble (HS) fraction compared with the other systems irrespective of the coal used. The difference between the yields of HS fractions using the ZnCl 2-MoCl 5 and other systems was most marked for coals of fairly low volatile matter content, though the conversion was relatively low (47–66%), whilst for coals of high volatile matter content HS yields with the binary melt systems were high (86–91% conversion). Elemental analyses of the HS fractions indicated that the ZnCl 2-MoCl 5 system is most favourable in decreasing the average molecular weight and the heteroatom content of HS, this characteristic trend being confirmed also with five HS fractions separated by Chromatographic techniques. Both elemental analyses and molecular weights of asphaltene (benzene-soluble materials, BS) indicated that the ZnCl 2-MoCl 5 system is also most effective in cracking coal structure.