Calcium complexes pyridines

Calcium-binding proteins, 6, 564, 572, 596 intestinal, 6, 576 structure, 6, 573 Calcium carbonate calcium deposition as, 6, 597 Calcium complexes acetylacetone, 2, 372 amides, 2,164 amino acids, 3, 33 arsine oxides, 3, 9 biology, 6, 549 bipyridyl, 3, 13 crown ethers, 3, 39 dimethylphthalate, 3, 16 enzyme stabilization, 6, 549 hydrates, 3, 7 ionophores, 3, 66 malonic acid, 2, 444 peptides, 3, 33 phosphines, 3, 9 phthalocyanines, 2,863 porphyrins, 2, 820 proteins, 2, 770 pyridine oxide, 3,9 Schiff bases, 3, 29 urea, 3, 9... 

Calcium complexes amino acids, 33 arsine oxides, 9 bipyridyl, 13 crown ethers, 39 dimethylphthalate, 16 hydrates, 7, ionophores, 66 peptides, 33 phosphines, 9 pyridine oxide, 9 Schiff bases, 29 urea,9 Calixarenes... 

Nickel halide complexes with amines give mixtures of linear polymer and cychc trimers (30). Nickel chelates give up to 40% of linear polymer (31). When heated with ammonia over cadmium calcium phosphate catalysts, propargyl alcohol gives a mixture of pyridines (32). 

Another feature ofthe spore is the presence of pyridine 2,6-dicarboxylic acid (DPA) (Fig. 1.10) occurring as a complex with calcium, which at one time was implicated in heat resistance. The isolation of heat-resistant spores containing no Ca-DPA has refuted this hypothesis. 

Phenylcalcium iodide and pyridine give 2-phenylpyridine and either 2,5- (119) or 2,6-diphenylpyridine, depending on conditions.264 Scheme V was tentatively proposed to account for the results. Phenylation of 2-phenylpyridine by phenylcalcium iodide gave only the 2,6-isomer. As was appreciated by the authors,264 the replacement of a hydride ion at C-5 by a phenyl anion is a controversial stage and seems, at first sight, mechanistically improbable. If the nitrogen atom is assumed to form a relatively stable complex with the calcium atom,... 

REDUCTION, REAGENTS Bis(triphenyl-phosphine)copper tetrahydroborate. Borane-Pyridine. Calcium-Methylamine/ ethylenediaminc. Chlorobis(cyclopenta-dienyl)tetrahydroboratozirconium(IV). Chromium(II)-Amine complexes. Copper(0)-lsonitrile complexes. 2,2-Dihydroxy-l, 1-binaphthyl-Lithium aluminum hydride. Di-iododimethylsilane. Diisobutyl-aluminum 2,6-di-/-butylphenoxide. Diisobutyl aluminum hydride. Dimethyl sulfide-Trifluoroacetic anhydride. Disodium tetracarbonylferrate. Lithium-Ammonia. Lithium-Ethylenediamine. Lithium bronze. Lithium aluminum hydride. Lithium triethylborohydride. Potassium-Graphite. 1,3-Propanedithiol. Pyridine-Sulfur trioxide complex. 

All reactions and sample preparations are carried out in an inert-atmosphere enclosure under dry nitrogen. Solvents and reagents are dried in the following manner. Benzene, tetrahydrofuran, and n-pentane are freshly distilled from lithium aluminum hydride pyridine is distilled over barium oxide and tetramethylethylenediamine is distilled over calcium hydride. Solvents used in preparing nmr and infrared samples are degassed by a freeze-thaw technique. Nmr spectra are obtained with torch-sealed nmr tubes. The commercial transition metal carbonyl complexes are recrystallized and vacuum-dried before use. Glassware is routinely flame-dried. 

An early X-ray structure of 8 crystallized from pyridine indicated it to have a pleated loop conformation (see ref. 1, p. 70), and rather similar conformations have been observed for its complexes with calcium and uranyl cations. In a more recent study, however, the X-ray structure of a complex of 8 with eight pyridine molecules showed it to assume a twisted conformation, something approaching the pinched conformation suggested in the early 1980s before an X-ray structure had been obtained. Complexes of 8 " with various metal ions, including lanthanides, thorium, and molybdenum, also reveal a conformation different from a pleated loop and approximately described as a 1,2,3,4-alternate. 

A very convenient method for the synthesis of (158) consists in the side-chain bromination of 2-thienyl ethyl ketone followed by reaction with sodium methoxide in methanol and with methanesulphonyl chloride in pyridine, which gave (157) in 88% yield. Treatment of (157) with calcium carbonate led to 1,2-rearrangement of the thienyl group to give (158). Metal complexes of s> -thiophen-2-aldoxime, thiophen-2-carbaldehyde 2-benzothiazolylhydrazone, and thiophen-2-carbaldehyde thiosemicarba-zone have been studied. 

Caprolactone (CL) (Acros, 99%) was dried over calcium hydride at r.t. for 48h and then distilled under reduced pressure. 2-(N,N-dimethylamino)ethyl methaciylate (DMAEMA) (Aldrich, 98%) was deprived of its inhibitor by filtration through a basic alumina column, and depending on samples (see text) dried over calcium hydride at r.t. for 24h and then distilled under reduced pressme. Butane-1,4-diol (Acros, > 99%) was dried over calcium hydride for 48h at r.t. and distilled at 70°C under reduced pressure. Triethylamine (NEts, Fluka, 99%) was dried over barium oxide for 48h at r.t. and distilled under reduced pressure. Copper bromide (CuBr, Fluka, 98%) was purified in acetic acid and recrystallized in ethanol under inert atmosphere until a white powder is obtained. Tin(ll) bis-2-ethyl hexanoate (Sn(Oct)2, Aldrich, 95%), methacrylic anhydride (Aldrich, 94%), N,N-dimethylamino-4-pyridine (DMAP, Acros 99%), 1,1,4,7,10,10-hexamethyltriethylene tetramine (HMTETA, Aldrich, 97%), ethyl-2-bromoisobutyrate (E BBr, Aldrich, 98%), N,N-dicyclohexylcarbodiimide (DCC, Acros, 99%), were used as received. Tetrahydrofuran (THF, Labscan, 99%) was dried over molecular sieves (4A) and distilled over polystyryl lithium (PS LC) complex under reduced pressure just before use. Toluene (Labscan, 99%) was dried by refluxing over CaH2. 

Perchlorates are powerful oxidizing substances. These compounds explode when mixed with combustible, organic, or other easily oxidizable compounds and subjected to heat or friction. Perchlorates explode violently at ambient temperatures when mixed with mineral acids, finely divided metals, phosphorus, trimethylphosphite, ammonia, or ethylenediamine. Explosions may occur when perchlorates are mixed with sulfur, or hydride of calcium, strontium, or barium and are subjected to impact or ground in a mortar. Perchlorates react with fluorine to form fluorine perchlorate, an unstable gas that explodes spontaneously. Heating perchlorates to about 200°C (392°F) with charcoal or hydrocarbons can produce violent explosions. Metal perchlorates from complexes with many organic solvents, which include benzene, toluene, xylenes, aniline, diozane, pyridine, and acetonitrile. These complexes are unstable and explode when dry. Many metal perchlorates explode spontaneously when recrystaUized from ethanol. Saturated solution of lead perchlorate in mathanol is shock sensitive. 

The prerequisite for the toxic effect of heavy metals is penetration of the cell wall. For this, certain carriers are needed to transport the heavy metals through lipophilic centres in the cell membrane. Oxines, 2-mercapto-pyridine-N-oxides (III. 11) and dialkyl-dithiocarbamates (III.9) are examples of compounds capable of complexing heavy metal ions such as Cu ions and transporting them into the microbe cell. The carriers named are also toxic, as such, to micro-organisms. But, as a copper carrier, copper-8-hydroxyquinoline is about 100 times more effective than 8-hydroxyquinoline (oxine III. 11.4). Once heavy metal ions have overcome the cell wall with the aid of the carrier molecules, they may compete with magnesium, calcium and potassium ions for receptor sites, inhibit enzymes and cause non-specific precipitation of proteins. 

Cation exchangers based on PBDMA-coated silica are offered by a number of companies. Metrohm (Herisau, Switzerland), for example, offers two columns under the trade names Metrosep Cl and C4. The 5 pm Metrosep Cl is considered to be the high-performance column for the simultaneous analysis of mono-and divalent cations with an analysis time of less than 20 min. It can also be used for the separation of various amines, which are typically eluted with a nitric acid eluent. Figure 4.41 shows an example chromatogram obtained under standard chromatographic conditions with an eluent mixture of tartaric acid and pyridine-2,6-dicarboxyiic acid (PDCA) (dipicohnic acid). Under these chromatographic conditions, calcium elutes ahead of magnesium, followed by strontium and barium. This unusual retention behavior can be attributed to the complex-ing properties of pyridine-2,6-dicarboxylic acid. With a pure tartaric acid eluent. 

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