Trialkylaluminums

Epichlorohydrin Elastomers without AGE. Polymerization on a commercial scale is done as either a solution or slurry process at 40—130°C in an aromatic, ahphatic, or ether solvent. Typical solvents are toluene, benzene, heptane, and diethyl ether. Trialkylaluniinum-water and triaLkylaluminum—water—acetylacetone catalysts are employed. A cationic, coordination mechanism is proposed for chain propagation. The product is isolated by steam coagulation. Polymerization is done as a continuous process in which the solvent, catalyst, and monomer are fed to a back-mixed reactor. Pinal product composition of ECH—EO is determined by careful control of the unreacted, or background, monomer in the reactor. In the manufacture of copolymers, the relative reactivity ratios must be considered. The reactivity ratio of EO to ECH has been estimated to be approximately 7 (35—37). 

The most important reaction with Lewis acids such as boron trifluoride etherate is polymerization (Scheme 30) (72MI50601). Other Lewis acids have been used SnCL, Bu 2A1C1, Bu sAl, Et2Zn, SO3, PFs, TiCU, AICI3, Pd(II) and Pt(II) salts. Trialkylaluminum, dialkylzinc and other alkyl metal initiators may partially hydrolyze to catalyze the polymerization by an anionic mechanism rather than the cationic one illustrated in Scheme 30. Cyclic dimers and trimers are often products of cationic polymerization reactions, and desulfurization of the monomer may occur. Polymerization of optically active thiiranes yields optically active polymers (75MI50600). 

Aluminum phthalocyanine (PcAlX) can be prepared from the phthalonitrile and aluminum trichloride either in refluxing quinoline138 13g or without a solvent under addition of ammonium molybdate(VI).137 The chloro compound can be transformed to a hydroxy derivative by treatment with sulfuric acid.58-140 Also, the insertion of aluminum in a metal-free phthalocyanine is possible, for example trialkylaluminum can be used.141,142... 

Trialkylaluminum and diethyl ether - triorganoaluminum complexes undergo addition to l-ni-trocycloalkenes in hexane at 0°C or 60°C, respectively to give adducts in good yield23. 

Growth reaction of triethylaluminum and ethylene forming higher molecular weight trialkylaluminum... 

Oxidation of the trialkylaluminum to aluminum alcoholates and subsequent hydrolysis into the wanted alcohols and aluminum hydroxide... 

The MOCVD of chromium is based on the decomposition of dicumene chromium, (C9Hj2)2Cr, at 320-545°C.[ ]f ] However, the reaction tends to incorporate carbon or hydrogen in the deposit. It can also be deposited by the decomposition of its carbonyl which is made by dissolvingthe halide in an organic solvent such as tetrahydrofuran with CO at 200-300 atm and at temperatures up to 300°C in the presence of a reducing agent such as an electropositive metal (Na, Al, or Mg), trialkylaluminum, and others. 

Sn 1 mechanism. The reaction can also be applied to primary and secondary alcohols if these contain an aryl group in the a position. Higher trialkylaluminums are far less suitable, because reduction competes with alkylation (see also reactions of Me3Al with ketones, 16-27, and with carboxylic acids, 16-33). The compound Me2TiCl2... 

Nickel(O) reacts with the olefin to form a nickel(0)-olefin complex, which can also coordinate the alkyl aluminum compound via a multicenter bond between the nickel, the aluminum and the a carbon atom of the trialkylaluminum. In a concerted reaction the aluminum and the hydride are transferred to the olefin. In this mechanistic hypothesis the nickel thus mostly serves as a template to bring the olefin and the aluminum compound into close proximity. No free Al-H or Ni-H species is ever formed in the course of the reaction. The adduct of an amine-stabihzed dimethylaluminum hydride and (cyclododecatriene)nickel, whose structure was determined by X-ray crystallography, was considered to serve as a model for this type of mechanism since it shows the hydride bridging the aluminum and alkene-coordinated nickel center [31]. 

S)-phenylglycine have been used in the copper-catalysed conjugate addition of MeLi to enones. Trialkylaluminum reagents were also involved in only a few reactions, but these represent an interesting alternative. 

The existence of ketenes was established over a hundred years ago, and, in recent years, asymmetric synthesis based on [2 + 2] cycloadditions of ketenes with carbonyl compounds to form chiral p-lactones has been achieved with high yields and high stereoselectivities. In 1994, Miyano et al. reported the use of Ca-symmetric bis(sulfonamides) as ligands of trialkylaluminum complexes to promote the asymmetric [2 + 2] cycloaddition of ketenes with aldehydes. The corresponding oxetanones were obtained in good yields and enantioselectivities... 

With trialkylaluminum compounds, the addition reaction is called carboalumination. As discussed below, this reaction requires a catalyst to proceed. 

A chiral indene derivative, structure K, has been most commonly used.222 The catalyst interacts with the trialkylaluminum to generate a bimetallic species that is the active catalyst. 

The detailed mechanism of the catalysis is not known, but it is believed that the Lewis acid character of the zirconium is critical.223 The reaction is further accelerated by inclusion of partially hydrolyzed trialkylaluminum reagents known as alumoxanes.224... 

The first, consisting of a uranium salt, trialkylaluminum, and a Lewis acid, had been developed at Goodyear ( 1 ). The other system, described by Snam Progetti (2), permits the polymerization of butadiene to give polymers with a cis content of up to... 

Polymer Preparation. A more recent modification in the molecular structure of styrene-butadiene copolymers has been obtained with the discovery of a new catalyst system (6). The catalyst consists of a barium t-alkoxide-hydroxide salt together with a complex of dialkylmagnesium and trialkylaluminum. 

The Ziegler-Natta catalysts are prepared from transition metal halides and a reducing agent => the catalysts most commonly used are prepared from titanium tetrachloride (TiCl4) and a trialkylaluminum (R3AI). 

Aluminum(III) complexes are amongst the most common Lewis acids. In particular, aluminum halide species (e.g., A1C13, AlBr3) are commercially available and are widely used for various reactions. Other types of Lewis acid such as aluminum alkoxides, alkylaluminum halides, and trialkylaluminum species are also used for many kinds of Lewis-acid-mediated reactions. 

Thus, in the presence of macrocycles, trialkylaluminum and even diorganozinc compounds have been used as alkide and halide abstractors to generate macrocycle-chelated organozinc cations (Scheme 45).108,109... 

Organoaluminum reagents are inexpensive and readily available in large quantities. However, only a few examples of conjugate additions using trialkylaluminum nucleophiles have been reported. 

These glycals react with trialkylaluminums to give C-glycosides (5), in which the /ram-isomer predominates. 

The use of bulky trialkylaluminum reagents, such as Al( Bu)3, with various group 4 metallocenes led to olefin-polymerization catalysts that rivaled those formed with MAO as the co-catalyst. 

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