Tetrachloride, titanium groups

The chemistry of hafnium has not received the same attention as that of titanium or zirconium, but it is clear that its behaviour follows that of zirconium very closely indeed with only minor differences in such properties as solubility and volatility being apparent in most of their compounds. The most important oxidation state in the chemistry of these elements is the group oxidation state of +4. This is too high to be ionic, but zirconium and hafnium, being larger, have oxides which are more basic than that of titanium and give rise to a more extensive and less-hydrolysed aqueous chemistry. In this oxidation state, particularly in the case of the dioxide and tetrachloride, titanium shows many similarities with tin which is of much the same size. A large... 

Figure 20.16 schematically illustrates the process of titania film growth by ALD. The substrate is hydroxylated first, prior to the introduction of titanium precursor, titanium tetrachloride. Titanium tetrachloride reacts with the surface hydroxyl groups through a surface condensation reaction ... 

Another catalyst system found in the patent literature involves the deposition of halides such as zirconium tetrachloride, vanadium tetrachloride, titanium tetraiodide, or oxyhalides such as chromium oxychloride or vanadium oxychloride on a finely divided particulate inorganic substrate having surface hydroxyl groups. Among such solids are alumina, zirconia, silica (particularly a pyrogenic silica such as Cab-O-SiF ), or a carbon black such as channel black or furnace black. A toluene slurry of this material is added, under dry nitrogen, to a toluene solution of A -vinyl-pyrrolidone containing a small amount of triisobutylaluminum. After 24 hr at 80°C, a 25% yield of polymer is produced [73]. 

As indicated by the title, these processes are largely due to the work of Ziegler and coworkers. The type of polymerisation involved is sometimes referred to as co-ordination polymerisation since the mechanism involves a catalyst-monomer co-ordination complex or some other directing force that controls the way in which the monomer approaches the growing chain. The co-ordination catalysts are generally formed by the interaction of the alkyls of Groups I-III metals with halides and other derivatives of transition metals in Groups IV-VIII of the Periodic Table. In a typical process the catalyst is prepared from titanium tetrachloride and aluminium triethyl or some related material. 

A study of alkylations with a group of substituted benzyl halides and a range of Friedel-Crafts catalysts has provided insight into the trends in selectivity and orientation that accompany changes in both the alkyl group and the catalysts. There is a marked increase in substrate selectivity on going from / -nitrobenzyl chloride to /i-methoxybenzyl chloride. For example, with titanium tetrachloride as the catalyst, Aitoi Abenz increases from 2.5 to 97. This increase in substrate selectivity is accompanied by an increasing preference for para substitution. With /i-nitrobenzyl chloride, the ortho para ratio is 2 1 (the... 

Nitroalkenes are also reactive Michael acceptors under Lewis acid-catalyzed conditions. Titanium tetrachloride or stannic tetrachloride can induce addition of silyl enol ethers. The initial adduct is trapped in a cyclic form by trimethylsilylation.316 Hydrolysis of this intermediate regenerates the carbonyl group and also converts the ad-nitro group to a carbonyl.317... 

With co-catalysts other than water, a part of the co-catalyst may also form an end-group by a termination reaction. When trichloroacetic acid was used as co-catalyst with titanium tetrachloride, trichloroacetate end-groups were found on the polyisobutenes [9, 10]. 

The only solid acidic catalyst which has given high polymers at an appreciable rate at low temperatures, and which has been studied in some detail, is that described by Wichterle [41, 42]. This was prepared as follows A 10 per cent solution in hexane of aluminium tri-(s- or t-butoxide) was saturated with boron fluoride at room temperature, and excess boron fluoride was removed from the precipitate by pumping off about half the hexane. Two moles of boron fluoride were absorbed per atom of aluminium, and butene oligomers equivalent to two-thirds of the alkoxy groups were found in the solution the resulting solid had hardly any catalytic activity. When titanium tetrachloride was added to the suspension in hexane, an extremely active catalyst was formed but the supernatant liquid phase had no catalytic activity. The DP of the polymers formed by the catalyst prepared from the s-butoxide was much lower than that of polymers formed with a catalyst prepared from the r-butoxidc. 

In the latest paper from Marek s group [29] they once again introduce the self-ionisation of titanium tetrachloride in order to explain their photo-initiation results. Unfortunately, their reaction scheme is very obscure, but evidently it does not involve addition of a metal-containing cation to the monomer. 

Titanium tetrachloride promoted reactions of 1-methyl-1-trimethylsilylallene with qui-nones 25 afforded products derived from a reaction with one of the carbonyl groups on the quinones. Besides the substitution pattern on the allene, the higher activity of titanium tetrachloride has to be considered to play a role in this abnormal product formation. 

Oki and his co-workers (177) also found that these halogenated compounds (107) exhibited enormous differences in reactivity when they were treated with Lewis acids. The sc form undergoes a Friedel-Crafts type cyclization in the presence of titanium tetrachloride, which is a weak Lewis acid, whereas the ap form survives these conditions. The latter reacts in the presence of the stronger Lewis acid antimony pentachloride. This difference is apparently caused by a chloro group in proximity to the site where a cationic center develops during the reaction (Scheme 12). 

Once the methoxy group has been installed and nucleophilic capture of the intermediate has occurred, the product (132) can be treated with an enol ether (e.g. 133) and titanium tetrachloride to affect C-C bond formation adjacent to nitrogen. This sequence served nicely in syntheses of both indolizidine alkaloids elaeokanine A (135) and C (136). 

Presently there are two main processes for manufacturing this important white pigment. The main one involves reaction of rutile ore (about 95% Ti02) with chlorine to give titanium tetrachloride. For this reason we have chosen to group this key chemical under chlorine and sodium chloride. The titanium tetrachloride is a liquid and can be purified by distillation, bp 136°C. It is then oxidized to pure titanium dioxide and the chlorine is regenerated. Approximately 94% of all titanium dioxide is made by this process. 

An example of ring enlargement is the intramolecular Schmidt reaction of azidoalkyl ketone 53 that gives, by the action of titanium tetrachloride, through intermediate azidohydrin, lactam 20 (95JA10449). Because of the large distance between keto and azido groups, the usual catalyst trifluoroacetic acid does not work. 

The metal halide catalysts include aluminum chloride, aluminum bromide, ferric chloride, zinc chloride, stannic chloride, titanium tetrachloride and other halides of the group known as the Friedel-Crafts catalysts. Boron fluoride, a nonmetal halide, has an activity similar to that of aluminum chloride. 

Another way of ensuring that a glass surface is free of water or hydroxyl groups is to cover it with a film of sodium. This method was used when the melting point phase diagram for the system isobutene + titanium tetrachloride was determined (Longworth, Plesch and Rutherford, 1959 Plesch, 1972), but it cannot be used on silane-treated glass as the sodium will not spread on the waxy surface. 

Notes This alcohol protecting is easily attached and readily removed by Lewis acids such as zinc bromide and titanium tetrachloride. Phenols can be protected (reaction of the sodium salt with MEMC1) and deprotected with TFA. More easily removed than the MOM group. 

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