Oxidation with carbon tetrachloride

In contrast to phosphonic acids, H-phosphinic acids can be coupled with alcohols using carbodiimides to give H-phosphinates 83 (Scheme 31, Table 12).[63-1231 These H-phosphinates 83 afford the corresponding phosphonic acids 84 directly by oxidation with NaI04[123l or by treatment with bis(trimethylsilyl)amide followed by carbon tetrachloride, triethylamine, and waterJ63 Alternatively, as described above (Section 10.10.2.1.3), H-phosphinates may also be converted into the phosphonochloridates by oxidation with carbon tetrachloride and then coupled to nucleophiles other than water, f63-75-76 ... 

Hafnium Boride. Hafnium diboride [12007-23-7] HfB2, is a gray crystalline soHd. It is usually prepared by the reaction of hafnium oxide with carbon and either boron oxide or boron carbide, but it can also be prepared from mixtures of hafnium tetrachloride, boron trichloride, and hydrogen above 2000°C, or by direct synthesis from the elements. Hafnium diboride is attacked by hydrofluoric acid but is resistant to nearly all other reagents at room temperature. Hafnium dodecaboride [32342-52-2] has been prepared by direct synthesis from the elements (56). 

Hydroxybenzoic acid has been prepared by heating potassium phenoxide in a stream of carbon dioxide or with carbon tetrachloride, and by heating jfr-cresol with alkalies and various metallic oxides. The procedure described above is similar to one which appears in the early literature ... 

The identification and quantification of potentially cytotoxic carbonyl compounds (e.g. aldehydes such as pentanal, hexanal, traw-2-octenal and 4-hydroxy-/mAW-2-nonenal, and ketones such as propan- and hexan-2-ones) also serves as a useful marker of the oxidative deterioration of PUFAs in isolated biological samples and chemical model systems. One method developed utilizes HPLC coupled with spectrophotometric detection and involves precolumn derivatization of peroxidized PUFA-derived aldehydes and alternative carbonyl compounds with 2,4-DNPH followed by separation of the resulting chromophoric 2,4-dinitrophenylhydrazones on a reversed-phase column and spectrophotometric detection at a wavelength of378 nm. This method has a relatively high level of sensitivity, and has been successfully applied to the analysis of such products in rat hepatocytes and rat liver microsomal suspensions stimulated with carbon tetrachloride or ADP-iron complexes (Poli etui., 1985). 

Stability Unstable in air. Protect from water or moisture. Store away horn heat or ignition sources and sulfur compounds. Reacts with sulfur and sulfur compounds, producing highly toxic VX or VX-like compounds. It completely dissolves polymethylmethacrylate. It is incompatible with calcium hypochlorite (HTH), many chlorinated hydrocarbons, selenium, selenium compounds, moisture, oxidants, and carbon tetrachloride. 

Interaction with the oxide in carbon tetrachloride is vigorous, producing sparks. 

On the other hand, microsomes may also directly oxidize or reduce various substrates. As already mentioned, microsomal oxidation of carbon tetrachloride results in the formation of trichloromethyl free radical and the initiation of lipid peroxidation. The effect of carbon tetrachloride on microsomes has been widely studied in connection with its cytotoxic activity in humans and animals. It has been shown that CCI4 is reduced by cytochrome P-450. For example, by the use of spin-trapping technique, Albani et al. [38] demonstrated the formation of the CCI3 radical in rat liver microsomal fractions and in vivo in rats. McCay et al. [39] found that carbon tetrachloride metabolism to CC13 by rat liver accompanied by the formation of lipid dienyl and lipid peroxydienyl radicals. The incubation of carbon tetrachloride with liver cells resulted in the formation of the C02 free radical (identified as the PBN-CO2 radical spin adduct) in addition to trichoromethyl radical [40]. It was found that glutathione rather than dioxygen is needed for the formation of this additional free radical. The formation of trichloromethyl radical caused the inactivation of hepatic microsomal calcium pump [41]. 

Other N-silyIphosphinimines which are also suitably constructed phosphazene precursors, can be prepared by a second oxidation reaction of silylamino-phosphines. When these phosphines react with carbon tetrachloride, two types of P-chlorophosphiminines may be formed by essentially two pathways (eq 7) ( ). 

The reaction of superoxide ion with carbon tetrachloride is important for olefin epoxidations. This reaction includes the formation of the trichloromethyl peroxide radical Oj" + CCI4 —> Cl + CI3COO. The trichloromethyl peroxide radicals formed oxidize electron-rich olefins. The latter gives the corresponding epoxides. This peroxide radical is a stronger oxidizing agent than the superoxide ion itself (Yamamoto et al. 1986). 

Williams and coworkers preliminarily reported that CO oxidation on Pt/Al203 is faster in the presence of water solvent than in the presence of ethanol [141]. We then studied CO oxidation on platinum surface in the presence of different solvents, and identified obvious solvent effects, namely, CO oxidation takes place the most easily with water solvent, the least easily with carbon tetrachloride solvent, and follows the overall trend of water > ethanol > methanol > cyclohexane > benzene carbon tetrachloride [67]. We subsequently took advantage of the solvent effect to design a diagnosing tool to pin down low-coverage CO at the liquid-solid interface, by flushing the liquid-solid interface with water and carbon tetrachloride individually [67]. 

In a 1-1. three-necked round-bottomed flask, wrapped with aluminum foil to exclude light, and equipped with a mechanical stirrer, a reflux condenser, and an addition funnel, is suspended 37 g. (0.17 mole) of red mercuric oxide (Note 1) in 330 ml. of carbon tetrachloride (Note 2). To the flask is added 30.0 g. (0.22 mole) of 3-chlorocyclobutaneearboxylic acid (Note 3), and the mixture is heated to reflux while stirring. To the mixture is added dropwise a solution of 40 g. (0.25 mole) of bromine in 180 ml. of carbon tetrachloride as fast as possible (4-7 minutes) without loss of bromine from the condenser (Note 4). After a short induction period, carbon dioxide is evolved at a rate of 150-200 bubbles per minute (Note 5). The solution is allowed to reflux until the rate of carbon dioxide evolution slows to about 5 bubbles per minute. This will usually take 25-30 minutes (Note 6). The mixture is then cooled in an ice bath, and the precipitate is removed by filtration. The residue on the funnel is washed with carbon tetrachloride, and the filtrates are combined. The solvent is removed by distillation using a modified Claisen distillation apparatus with a 6-cm. Vigreux column, and vacuum distillation of the residual oil gives 13-17 g. (35-46%) of... 

Neptunium forms a number of halides in various oxidation states. These include tri-, tetra- and hexafluorides of compositions NpFs, NpF4, and NpFe, respectively trichloride, NpCF and tetrachloride, NpCh tribromide, NpBrs and the triiodide NpN. Neptunium fluorides are formed by heating neptunium dioxide at elevated temperatures with fluorine in the presence of hydrogen fluoride. The tetrachloride, NpCh is obtained similarly by heating the dioxide with carbon tetrachloride vapor at temperatures above 500°C. Neptunium tribromide and triiodide are prepared by heating the dioxide in a sealed vessel at 400°C with aluminum bromide and aluminum iodide, respectively. 

A sample of the methanolic oxidation product was treated directly with powdered sodium borohydride. Water was added, the solvent allowed to evaporate, and the aqueous solution extracted with carbon tetrachloride. Methyl vinyl carbinol was shown to be the major product, but about 10% impurities were present. Reduction by stirring overnight with 1.0 Af sodium sulfite followed by extraction with carbon tetrachloride produced a solution which analyzed as methyl vinyl carbinol with about 1% impurities. 

Volatile protactinium pentaehloride has been prepared in a vacuum by reaction of the oxide with phosgene at 550° C or with carbon tetrachloride at 200°C. Reduction of this at 600°C with hydrogen leads to protactinium(IV) tetrachloride, Pad. which is isostructural with uranium(IV) tetrachloride, UCI4. The pentaehloride can be converted into the bromide or iodide by heating with the corresponding hydrogen halide or alkali halide... 

Chlorine, determination of, in chlorine(I) oxide in carbon tetrachloride and hypochlorous acid solutions, 5 162, 164 Chlorine(I) compounds, 5 156 Chlorine(I) oxide, 5 156 in carbon tetrachloride solution, 5 158, 159 analysis of, 5 162 Chlorine(IV) oxide, 4 152 admixed with inert gas and chlorine, 4 153... 

Test for periodate (see note 1 below) This anion will give a positive test for oxidizing agents, but will not be detected in the systematic analysis. It will be necessary to remove first iodide or iodate by precipitation with silver nitrate in acid solution, and the excess silver ions with sodium chloride solution the resulting solution is strongly acidified with hydrochloric acid and an iron(II) salt is added. If a periodate is present, it will be reduced to iodine, which can be identified with carbon tetrachloride. 

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