Silica chlorination

Dichlorourethane and tert-butyl hypochlorite (TBH) were even more reactive in the presence of silica, chlorination of toluene with TBH being complete in just one hour at ambient temperature with 3.8g of BDH silica for a 5 mmol reaction in 10 ml of tetrachloromethane solvent Intrigued by these observations, we decided to undertake a more systematic investigation of the potential of solid catalysts for organic synthesis. 

Silica chlorine tube Feed inlet and gas outlet... 

Silica gel is again obtained but silicon does not form the corresponding hexachlorosilicic acid since the small silicon atom is unable to coordinate six chlorine atoms. 

Anhydrous hydrogen fluoride (as distinct from an aqueous solution of hydrofluoric acid) does not attack silica or glass. It reacts with metals to give fluorides, for example with heated iron the anhydrous iron(II) fluoride is formed the same product is obtained by displacement of chlorine from iron(II) chloride ... 

Both the Toth and Alcoa processes provide aluminum chloride for subsequent reduction to aluminum. Pilot-plant tests of these processes have shown difficulties exist in producing aluminum chloride of the purity needed. In the Toth process for the production of aluminum chloride, kaolin [1332-58-7] clay is used as the source of alumina (5). The clay is mixed with sulfur and carbon, and the mixture is ground together, pelletized, and calcined at 700°C. The calcined mixture is chlorinated at 800°C and gaseous aluminum chloride is evolved. The clay used contains considerable amounts of silica, titania, and iron oxides, which chlorinate and must be separated. Silicon tetrachloride and titanium tetrachloride are separated by distillation. Resublimation of aluminum chloride is requited to reduce contamination from iron chloride. 

Methane, chlorine, and recycled chloromethanes are fed to a tubular reactor at a reactor temperature of 490—530°C to yield all four chlorinated methane derivatives (14). Similarly, chlorination of ethane produces ethyl chloride and higher chlorinated ethanes. The process is employed commercially to produce l,l,l-trichloroethane. l,l,l-Trichloroethane is also produced via chlorination of 1,1-dichloroethane with l,l,2-trichloroethane as a coproduct (15). Hexachlorocyclopentadiene is formed by a complex series of chlorination, cyclization, and dechlorination reactions. First, substitutive chlorination of pentanes is carried out by either photochemical or thermal methods to give a product with 6—7 atoms of chlorine per mole of pentane. The polychloropentane product mixed with excess chlorine is then passed through a porous bed of Fuller s earth or silica at 350—500°C to give hexachlorocyclopentadiene. Cyclopentadiene is another possible feedstock for the production of hexachlorocyclopentadiene. 

It is known that not all reactions proceed in the same manner on all adsorbent layers because the material in the layer may promote or retard the reaction. Thus, Ganshirt [209] was able to show that caffeine and codeine phosphate could be detected on aluminium oxide by chlorination and treatment with benzidine, but that there was no reaction with the same reagent on silica gel. Again the detection of amino acids and peptides by ninhydrin is more sensitive on pure cellulose than it is on layers containing fluorescence indicators [210]. The NBP reagent (. v.) cannot be employed on Nano-Sil-Ci8-100-UV2S4 plates because the whole of the plate background becomes colored. 

Zebiihr et al. (29) developed an automated system for determining PAHs, PCBs and PCDD/Fs by using an aminopropyl silica column coupled to a porous graphitic carbon column. This method gives five fractions, i.e. aliphatic and monoaromatic hydrocarbons, polycyclic aromatic hydrocarbons, PCBs with two or more ortho-chlorines, mono-ort/io PCBs, and non-ortho PCBs and PCDD/Fs. This method employed five switching valves and was successfully used with extracts of sediments, biological samples and electrostatic filter precipitates. 

The only recorded example using this method in the sugar series is the chlorination of l,2 3,4-di-0-isopropylidene-D-galactopyranose (73) which affords in addition to the expected 6-chloro-6-deoxy derivative 74a, a 5,6-unsaturated derivative 75 as well. These products were separated by silica gel column chromatography no yields were given. 

Discussion. This method is based upon the precipitation of lead chlorofluoride, in which the chlorine is determined by Volhard s method, and from this result the fluorine content can be calculated. The advantages of the method are, the precipitate is granular, settles readily, and is easily filtered the factor for conversion to fluorine is low the procedure is carried out at pH 3.6-5.6, so that substances which might be co-predpitated, such as phosphates, sulphates, chromates, and carbonates, do not interfere. Aluminium must be entirely absent, since even very small quantities cause low results a similar effect is produced by boron ( >0.05 g), ammonium (>0.5 g), and sodium or potassium ( > 10g) in the presence of about 0.1 g of fluoride. Iron must be removed, but zinc is without effect. Silica does not vitiate the method, but causes difficulties in filtration. 

Thin film composite (TFC) is an ultrathin barrier membrane on polysulfone support layer, of good chemical stability. It has a wide operating pH range of 2.0 to 12.0 at 0 to 40 °C, but cannot tolerate chlorine. TFC membranes are better at rejecting silica than CA membranes. 

The silica gel surface is extremely polar and, as a result, must often be deactivated with a polar solvent such as ethyl acetate, propanol or even methanol. The bulk solvent is usually an n-alkane such as n-heptane and the moderators (the name given to the deactivating agents) are usually added at concentrations ranging from 0.5 to 5% v/v. Silica gel is very effective for separating polarizable materials such as the aromatic hydrocarbons, nitro hydrocarbons (aliphatic and aromatic), aliphatic ethers, aromatic esters, etc. When separating polarizable substances as opposed to substances with permanent dipoles, mixtures of an aliphatic hydrocarbon with a chlorinated hydrocarbon such as chlorobutane or methylene dichloride are often used as the mobile... 

Our own earlier work on the chlorination of toluene had been subject to similar constraints. In this case, chlorination with ferf-butyl hypochlorite had proved to be advantageous. In the presence of silica gel as catalyst the yield of chlorotoluenes was quantitative but the regioselectivity was more or less statistical (ref. 8). However, the use of proton-exchanged zeolite X allowed the production of chlorotoluenes with a para-selectivity of more than 90 % (Fig. 4) (ref. 9). No HCl is generated in this process since the by-product is tert-butanol, and there is no inhibition of the catalyst. Indeed, the catalyst can be reused if necessary. 

In addition the role played by the sorbent on which the chromatography is carried out must not be neglected. For instance, it is only on aluminium oxide layers and not on silica gel that it is possible to detect caffeine and codeine by exposure to chlorine gas and treatment with potassium iodide — ben2idine [37]. The detection limits can also depend on the sorbent used. The detection limit is also a function of the h/ f value. The concentration of substance per chromatogram zone is greater when the migration distance is short than it is for components with high h/ f values. Hence, compounds with low h/ f values are more sensitively detected. 

TLC Analysis. Samples were examined by TLC using standard procedures. Rf values were determined and compared with those of authentic reference materials. Radioactive components were located by scanning (Vanguard Instrument Corp., North Haven, Conn., Model 885) or by autoradiography (Eastman Kodak, Rochester, N. Y., type AA film). The relative Rf value of DCDD on silica gel plates (Brinkmann Instruments, Inc., Westbury, N. Y., type For,4) when developed with n-hexane dioxane acetic acid, 90 10 4, V/V/V, was 0.90. The observed impurity had a relative Rf value of 0.40. On Brinkmann alumina plates, developed with n-hexane, DCDD had a relative Rf of 0.32. Neither system separated the chlorinated dibenzodioxin isomers. 

To prepare pure silicon, silica is first converted to SiClq. A redox reaction between coke and chlorine gas is coupled with a metathesis reaction to give SiClq, which liquefies on cooling ... 

Although cracking also occurs on chlorine-treated clays and amorphous silica-aluminas, the application of zeolites has resulted in a significant improvement in gasoline yield. The finite size of the zeolite micropores prohibits the formation of large condensed aromatic molecules. This beneficial shape-selectivity improves the carbon efficiency of the process and also the lifetime of the catalyst. 

Titanium dioxide (E171, Cl white 6) is a white, opaque mineral occurring naturally in three main forms rutile, anatase, and brookite. More than 4 million tons of titanium dioxide are produced per year and it is widely used for industrial applications (paints, inks, plastics, textiles) and in small amounts as a food colorant. ° "° Production and properties — Titanium oxide is mainly produced from ilmenite, a titaniferous ore (FeTiOj). Rutile and anatase are relatively pure titanium dioxide (Ti02) forms. Titanium oxide pigment is produced via chloride or sulfate processes via the treatment of the titanium oxide ore with chlorine gas or sulfuric acid, followed by a series of purification steps. High-purity anatase is preferred for utilization in the food industry. It may be coated with small amounts of alumina or silica to improve technological properties. 

Since iron phthalocyanine complexes can be activated and stabilized by a chlorine ring substitution (12), the activity of iron hexadecachlorophthalocyanine (7b) immobilized on silica was examined for the synthesis of 4, 5, and 6 with TBHP as oxidant. 

Polymerization of triphenylmethyl methacrylate in the presence of a chiral anion catalyst results in a polymer with a helical structure that can be coated onto macroporous silica [742,804). Enantioselectivity in this case results from insertion and fitting of the analyte into the helical cavity. Aromatic compounds and molecules with a rigid nonplanar structure are often well resolved on this phase. The triphenylmethyl methacrylate polymers are normally used with eluents containing methanol or mixtures of hexane and 2-propanol. The polymers are soluble in aromatic hydrocarbons, chlorinated hydrocarbons and tetrahydrofuran which, therefore, are not suitable eluents. 

An extension of the reduction-chlorination technique described so far, wherein reduction and chlorination occur simultaneously, is a process in which the oxide is first reduced and then chlorinated. This technique is particularly useful for chlorinating minerals which contain silica. The chlorination of silica (Si02) by chlorine, in the presence of carbon, occurs above about 1200 °C. However, the silica present in the silicate minerals readily undergoes chlorination at 800 °C. This reaction is undesirable because large amounts of chlorine are wasted to remove silica as silicon tetrachloride. Silica is, therefore, removed by other methods, as described below, before chlorination. Zircon, a typical silicate mineral, is heated with carbon in an electric furnace to form crude zirconium carbide or carbonitride. During this treatment, the silicon in the mineral escapes as the volatile oxide, silicon monoxide. This vapor, on contact with air, oxidizes to silica, which collects as a fine powder in the furnace off-gas handling system ... 

Apart from chlorine (without or with carbon), carbon tetrachloride, phosgene, hydrogen chloride, and sulfur dioxide-chlorine mixtures, some of the metal chlorides can also function as chlorinating agents. The chlorinating action of metal chlorides is dramatically illustrated by the behavior of the silica lining in reactors used for the chlorination of titanium dioxide and beryllium dioxide. 

Titanium tetrachloride is produced on an industrial scale by the chlorination of titanium dioxide-carbon mixtures in reactors lined with silica. During the reactor operation, the lining comes into contact not only with chlorine but also with titanium tetrachloride. There appears to be no attack on silica by either of these as the lining remains intact. However, the use of such a reactor for chlorinating beryllium oxide by the carbon-chlorine reduction chlorination procedure is not possible because the silica lining is attacked in this case. This corrosion of silica can be traced to the attack of beryllium chloride on silica. The interaction of beryllium chloride with silica results in the formation of silicon tetrachloride in accordance with the reaction... 

It follows that titanium tetrachloride can not chlorinate silica because at all temperatures the free energy change for that reaction has a large positive value. In general, in the interaction between the oxide (MO) of one metal (M) and the chloride (M C12) of a different metal (M ) ... 

In the case of methyloxirane, however, on Pt and Pd catalysts the extent of the rupture of the sterically hindered bond is indicative of the electrophilic character of the catalyst. Unsupported or silica-supported ion-exchanged catalysts cleave the sterically less hindered bond, whereas on the impregnated catalysts, the rupture of the more hindered C-O bond is dominant.290 It is likely that Pt or Pd surface metal ions are responsible for the rupture of the sterically more hindered bond and residual chlorine from the catalyst preparation can stabilize these ions in the hydrogen atmosphere. 

A chiral diphosphine ligand was bound to silica via carbamate links and was used for enantioselective hydrogenation.178 The activity of the neutral catalyst decreased when the loading was increased. It clearly indicates the formation of catalytically inactive chlorine-bridged dimers. At the same time, the cationic diphosphine-Rh catalysts had no tendency to interact with each other (site isolation).179 New cross-linked chiral transition-metal-complexing polymers were used for the chemo- and enantioselective epoxidation of olefins.180... 

Heinisch et al. described methods for detecting drugs containing chlorine, bromine, or iodine that can be extracted from acidic solutions with ether, then identified with TLC using 12 solvent systems and silica gel F254 plates [66]. 

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