Titanium tetrachloride, complex formation

An older, equally interesting industrial route involves condensing 2-aminoan-thraquinone in nitrobenzene in the presence of antimony pentachloride or titanium tetrachloride. Complex 97 prevents any undesirable formation of anthrim-ide (98). 

W. R. Longworth, P. H. Plesch, P. P. Rutherford, Complex Formation between Isobutene and Titanium Tetrachloride, International Conference on Coordination Chemistry, 1959, Chem. Soc. Special Publ., No. 13, 115. 

The formation of complexes between olefins and metal halides is particularly well documented for titanium tetrachloride [10, 11, 12] thus my theory can be applied with some confidence to systems which involve this metal halide. I will show that it provides a simple qualitative explanation for observations which have so far remained obscure and affords also a quantitative interpretation which is open to testing once the necessary... 

It seems to me that we can understand these apparent contradictions by means of the ideas which are implicit in my earlier arguments. If the monomer concentration is not so high that all the titanium tetrachloride is complexed, and if the solvent is of suitable polarity, and if the system is sufficiently pure, then a rate of formation of TiCl+3 adequate for initiation by it can be expected. 

These experiments provide the most direct evidence so far for the formation of complexes between A1X3 and isobutylene. The formation of such complexes was of course to be expected on the basis of the complex formation between aluminium halides and other olefins [29-33] and between titanium tetrachloride and isobutylene [34], and numerous other examples of complexes formed by an olefin and a metal halide it can be objected... 

The regioselectivity of Michael additions of thiolates to 2,4-dienones can be altered drastically by variation of the reaction conditions and addition of Lewis acids to the reaction mixture. Lawton and coworkers examined the reaction of 2-mercaptoethanol with l-(3-nitrophenyl)-2,4-pentadien-l-one and observed a high regioselectivity in favor of the 1,6-addition product at 45 °C (equation 42)123,124. Lowering of the reaction temperature caused an increase in the amount of 1,4-adduct, and at —40°C, a product ratio of 40 60 was found. These events suggest that kinetic control favors the 1,4-addition product whereas the 1,6-adduct is thermodynamically more stable. If, however, the reaction was carried out with a complex of the dienone and titanium tetrachloride, only the 1,4-adduct was isolated after hydrolytic workup123. Obviously, this product is trapped as a metal chelate which prevents formation of the 1,6-adduct by retro-Michael/Michael addition. In the absence of the chelating Lewis acid, the 1,4-addition product can indeed be converted... 

Titanium forms three series of salts in which the element is respectively tetra-, tri-, and mono-valent. Thus, titanium and chlorine form titanium tetrachloride, TiCl4, titanium trichloride, TiCl3, and titanium monochloride, TiCl. The two last are unstable and readily pass into the higher chloride. Titanium tetrachloride shows a marked resemblance to tin tetrachloride it unites easily with hydrochloric acid in solution, with formation of the complex acid, ehloro-titanic acid, [TiCl6]tI2, and forms many crystalline products with other chlorides. It also unites with ammonia, forming ammines. 

In Section III, A the catalytic action of A1C13 and BBr3 on the thermal decomposition of thiatriazoles was mentioned. This effect is evidently connected with complex formation between a thiatriazole and a Lewis acid since the catalytic activity is lost on addition of compounds that complex more effectively with the Lewis acid.19 It is remarkable that titanium tetrachloride, in contrast to this, does not catalyze decomposition, but instead forms a thermally stable, orange 1 1 complex with 5-phenylthiatriazole.19 The complex is sensitive to atmospheric moisture and is hydrolyzed in high yield to the starting thiatriazole on addition of water. 

The principal use for the tetrachloride is in pyrots as a smoke agent (called FM ), Ref 5 reports that the tetrachloride. . is extremely reactive resulting in the formation of hydrated oxides, or with atmospheric moisture and, when used for screening, is often disseminated from aircraft spray tanks. Its reaction with water vapor is relatively complex. First, the titanium tetrachloride is hydrated. This reaction is followed by further hydrolysis yielding, finally, titanium hydroxide and HC1. The smoke consists of a mixture of fine particles of solid titanium hydroxide, Ti(0H)4 the hydrated oxide, Ti02-H20 intermediate hydroxychlorides of titanium and dilute HC1 droplets. The sequence of reaction is ... 

Complex formation between olefins and Lewis acids has been demonstrated in a number of cases, e.g., isobutene and titanium tetrachloride (66), butene-2 and boron trifluoride (67—69), propylene and aluminum bromide (70), stflbene and various Lewis acids (71), styrene and stannic chloride (72), and in similar systems (73). Monomer-catalyst Ji-complex formation occurs during the polymerization of styrene or a-methyl styrene with chloroacetic acids (74,75). All these complexes are usually very weak and only stable at low temperatures. Evans contends (76) that isobutene and boron trifluoride do not interact because no polymerization occurs in the absence of moisture and therefore he postulates that BF3 HaO is the primary species. This does not rule out the possibility of a weak interaction between isobutene and the Lewis acid. Indeed, Nakana et al. (77) found direct evidence for the existence of boron trifluoride-propene complexes at low temperatures. 

The formation of halohydrins can be promoted by peroxidase catalysts.465 Recently 466 it has been shown that photocatalysis reactions of hydrogen peroxide decomposition in the presence of titanium tetrachloride can produce halohydrins. The workers believe that titanium(IV) peroxide complexes are formed in situ, which act as the photocatalysts for hydrogen peroxide degradation and for the synthesis of the chlorohydrins from the olefins. The kinetics of chlorohydrin formation were studied, along with oxygen formation. The quantum yield was found to be dependent upon the olefin concentration. The mechanism is believed to involve short-lived di- or poly-meric titanium(IV) complexes. 

Protection of phenols by the foregoing methods is complicated by the rapid Friedel-Crafts rearrangement of the nascent rm-butyl ether. By using trifluoro-methanesulfonic add at -78 PC, the rate of /erf-butyl ether formation is fast and the Friedel-Crafts alkylation does not compete [Scheme 4.126].226 Similarly, attempts to deprotect phenol ferf-butyl ethers with trifluoroacetic acid or titanium tetrachloride may give complex mixtures, again as a result of Friedel-Crafts alkylation of the phenol but this side reaction can be suppressed by using a catalytic amount of trifluoromethanesulfonic acid in 2.2,2-trifluoroethanol as solvent at -5 DC. 

As previously mentioned, 1-alkynyltrialkylborates (18) have become increasingly important in the formation of carbon-carbon bonds via attack of electrophiles. However, such complexes cannot react with simple Qc,P-unsaturated carbonyl compounds such as methyl vinyl ketone, because of their weak electrophilicity. Recently it was ascertained that ,P-unsaturated carbonyl compounds react with 18 via a Michael-type reaction in the presence of titanium tetrachloride, and the usual alkaline hydrogen peroxide oxidation leads to the synthesis of 5-dicarbonyl compounds... 

Because olefins are soft bases and most Friedel-Crafts halides are hard acids, the primary interaction between these two types of compounds must be regarded as a weak one, the outcome of which is nerally limited to the equilibrium formation of the relatively feeble rr-complex. Only with the softer of the strong Lewis acids would one expect this interaction to proceed further and give direct Hunter-Yohe initiation titanium tetrachloride seems to comply with such a requirement, as suggested by the experimental evidence discussed in Sect. IV-B4-b). 

Other Lewis acids that complex with thietane are titanium tetrachloride or bromide,boron trifluoride,trimethylaluminum, and tin tetrachloride. The enthalpies of formation of the aluminum complex (— 16.04 kcal/mole) and the tin complex (— 14.2 kcal/mole) and the wavelength of the charge transfer band of the tin complex (270 nm) have been determined. The titanium tetrahalides form both a 1 1 and a 1 2 adduct (titanium halide thietane). °° Treatment of 3-methyl-thietane with aluminum chloride or tin tetrachloride yields a rubbery white soUd." "... 

The first step of the mechanism involves the initial complexation of titanium tetrachloride to the carbonyl group of the electron-deficient alkene (enone) to give an alkoxy-substituted allylic carbocation. The allylic carbocation attacks the (trimethylsilyl)allene regiospecifically at C3 to generate vinyl cation I, which is stabilized by the interaction of the adjacent C-Si bond. The allylic Ji-bond is only coplanar with the C-Si bond in (trimethylsilyl)allenes, so only a C3 substitution can lead to the formation of a stabilized cation. A[1,2]-shift of the silyl group follows to afford an isomeric vinyl cation (II), which is intercepted by the titanium enolate to produce the highly substituted five-membered ring. Side products (III - V) may be formed from vinyl cation I. 

The formation of linear isotactic or syndiotactic polymers can be achieved by metal-catalysed polymerisation. This employs Ziegler-Natta catalysts, made from triethylaluminium (Et3Al) and titanium tetrachloride (TiCl4), which react with alkenes by a complex mechanism. The polymerisation of ethylene (CH2=CH2) leads to the formation of (linear) high-density polyethylene, which is of greater strength than the (branched) low-density polyethylene produced on radical polymerisation. 

An even better nucleophile is nitrogen. The incompatibility of basic amines for almost every one of these reactions catalyzed by these coordinatively unsaturated Ru complexes led us to examine sulfonamides and carboxamides. However, no productive results ensued. A basic amino group was also examined to verify its incompatibility. In contrast to that expectation, cyclization proceeded without problems as summarized in Equation 1.70 [61]. A Lewis acid was required as a cocatalyst. For formation of pyrrolidines, titanium tetrachloride proved most efficacious whereas for formation of piperidines, methylaluminum dichloride proved best. In principle, any nucleophile, such as carbon, that satisfactorily reacts in ruthenium-catalyzed allylic alkylations should function here also. 

The effectiveness of Ziegler-Natta catalysts of the triethylaluminum-titanium tetrachloride type seems to be the subject of some controversy. One patent describes the formation of poly(vinyl fluoride) with such a catalytic system in THF in a bottle polymerization at 30 C and autogenous pressure for 6 hr [57]. A complex of triisobutylaluminum, vanadium oxytrichloride, and THF is said to be particularly effective at 30°C both for the homo- and copolymerizations of vinyl fluoride [58, 59]. The processes are said to resemble typical Ziegler-Natta systems and are independent of the THF concentration when the mole ratio of THF to VOCI3 was greater than 2.3 1. The use of triisobutylaluminum with tetraisopropoxytitanium at 30°C for 15 min is said to lead to a process with an ionic-coordination mechanism [60]. 

Titanium. Catalyses of hydrogenation of alkenes, alkynes, carbonyl-, and nitro-compounds have been described. The effect of the nature of the ligand L and of the alkene to be reduced on reactivity in catalytic hydrogenation by Ti(7r-C5H5)2L2 has been quantitatively studied. The dependence of rate constants on solvent for reduction of decene in the presence of Ti(7r-C5H5)Me+ is interpreted in terms of electrostatic interaction between the active ionic species and the solvent. There is also a thermochemical report relevant here, and that is of a determination of the heats of mixing of cyclohexene and of hex-l-ene with titanium tetrachloride. The heats of mixing are close to zero, which implies very small heats of complex formation between these alkenes and titanium. ... 

Philip Kocienski published an elegant synthesis of racemic olean. The starting material is the THP ether of 4,4-dibromobutanol. In spite of the acid-sensitivity of the acetal, the formation of a carbene complex with titanium tetrachloride and zinc can be achieved. Its reaction with a corresponding ester leads to an enol ether, which cyclises to olean under acidic conditions. [217]... 

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