Aluminum compounds alkylation

Organochromium Catalysts. Several commercially important catalysts utilize organ ochromium compounds. Some of them are prepared by supporting bis(triphenylsilyl)chromate on siUca or siUca-alumina in a hydrocarbon slurry followed by a treatment with alkyl aluminum compounds (41). Other catalysts are based on bis(cyclopentadienyl)chromium deposited on siUca (42). The reactions between the hydroxyl groups in siUca and the chromium compounds leave various chromium species chemically linked to the siUca surface. The productivity of supported organochromium catalysts is also high, around 8—10 kg PE/g catalyst (800—1000 kg PE/g Cr). 

Dicyclopentadiene is also polymerized with tungsten-based catalysts. Because the polymerization reaction produces heavily cross-Unked resins, the polymers are manufactured in a reaction injection mol ding (RIM) process, in which all catalyst components and resin modifiers are slurried in two batches of the monomer. The first batch contains the catalyst (a mixture of WCl and WOCl, nonylphenol, acetylacetone, additives, and fillers the second batch contains the co-catalyst (a combination of an alkyl aluminum compound and a Lewis base such as ether), antioxidants, and elastomeric fillers (qv) for better moldabihty (50). Mixing two Uquids in a mold results in a rapid polymerization reaction. Its rate is controlled by the ratio between the co-catalyst and the Lewis base. Depending on the catalyst composition, solidification time of the reaction mixture can vary from two seconds to an hour. Similar catalyst systems are used for polymerization of norbomene and for norbomene copolymerization with ethyhdenenorbomene. 

Alkoxides of nonmetals are described in articles about the corresponding compounds (see Boron COMPOUNDS, Boron oxides Silicon compounds). Metal alkyls, in which the alkyl group is bound direcdy to the metal, are also discussed elsewhere (see Aluminum compounds). 

Organoaluminum Compounds. Apphcation of aluminum compounds in organic chemistry came of age in the 1950s when the direct synthesis of trialkylalurninum compounds, particularly triethylalurninum and triisobutylalurninum from metallic aluminum, hydrogen, and the olefins ethylene and isobutylene, made available economic organoalurninum raw materials for a wide variety of chemical reactions (see a-BONDED alkyls and aryls). 

Aluminum alkyls react by the Ziegler reaction with the least substituted double bond to give the tricitroneUyl aluminum compound. Oxidation of the iatermediate compound then produces the tricitroneUyl aluminate, which is easily hydroly2ed with water to give citroneUol (112,113). If the citroneUene is opticaUy active, opticaUy active citroneUol can be obtained (114). The (—)-citroneUol is a more valuable fragrance compound than the ( )-citroneUol. 

Al Ti in the range of 0.9—1.0 appeared optimum for i7j -l,4-polyisoprene yield (20). Other factors such as catalyst preparation temperature, influence of the R group in the alkyl aluminum compound (R Al), and catalyst aging have been extensively studied (16,17). Another variable studied was the effect of... 

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]. 

Anionic Association Polymer. Another type of lost circulation agent is a combination of an organic phosphate ester and an aluminum compound, for example, aluminum isopropoxide. The action of this system as a fluid loss agent seems to be that the alkyl phosphate ester becomes crosslinked by the aluminum compound to form an anionic association polymer, which serves as the gelling agent [1488]. 

Natta A process for polymerizing propylene and other higher olefins, catalyzed by crystalline titanium trichloride and an alkyl aluminum compound such as triethyl aluminum. The polymer can exhibit various types of stereoregularity, depending on the catalyst and the conditions. Invented in 1954 by G. Natta at the Istituto de Chimica Industrial del Politecnico di Milano, Italy, and commercialized in 1957. Now used widely, worldwide. See also Ziegler, Ziegler-Natta. 

Triethylaluminum can be economically prepared on an industrial scale from aluminum hydride and ethylene,124 so a successful alkylation using organo-aluminum compound will certainly open up a new area for active research. Asymmetric alkylation of aromatic aldehydes with triethylaluminum was carried out by Chan et al.125 In the presence of (R)- or (.S )-134 and Ti(OPr1)4, alkylation proceeded readily, yielding the alcohol with high ee (Scheme 2-52). 

The patent literature contains several references to the use of sulfoxide complexes, usually generated in situ, as catalyst precursors in oligomerization and polymerization reactions. Thus, a system based upon bis(acrylonitrile)nickel(0> with added Me2SO or EtgSO is an effective cyclotrimerization catalyst for the conversion of butadiene to cyclo-1,5,-9-dodecatriene (44). A similar system based on titanium has also been reported (407). Nickel(II) sulfoxide complexes, again generated in situ, have been patented as catalyst precursors for the dimerization of pro-pene (151) and the higher olefins (152) in the presence of added alkyl aluminum compounds. 

Aluminum compounds such as AlMe3 are well known to be highly air and moisture sensitive due to the strength of the Al-O bond (—350kjmol-1) versus the Al-C bond (—255 kj mol-1). Complete oxidation of 1ml of A1Mc3 in ambient air can produce a fireball 3 ft in diameter. Recent studies under controlled conditions have produced a better understanding of the reactivity of aluminum alkyls. 

Another interpretation that may be taken into consideration, kinetically equivalent to the former one, is a total substitution of the polymeric alkyl-aluminum compound which is bound to a catalytically active complex containing the transition metal, as follows ... 

C.S.Marvel et al, JACS 7% 5408-9( 1950) Alkyl-Aluminum Compounds. See Aluminum Alkyls... 

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