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Aluminums alkenes

The organometallic chemistry of aluminum is dominated by the chemistry of aluminum(lll), but lower oxidation state compounds are now accessible. The first examples of this class of compounds are carbonyl complexes such as Al(CO), A1(C0)2, and Al3(CO), which were generated upon exposure of aluminum atoms to CO in matrix-isolation experiments near 20 K. The number, relative intensities, and frequency of the carbonyl stretches in the IR spectra, along with isotopic labeling and EPR studies were used to verify these compositions. These complexes exhibit vco values of 1868, 1985 and 1904, and 1715 cm , respectively, indicative of Al- CO 7t backbonding. The carbonyl species are unstable at higher temperatures and no stable carbonyl complex of aluminum, in any oxidation state, has been reported. The monomeric aluminum-alkene adducts A1( -C2H4) and k rf-CeHe) were similarly identified in inert matrices at low temperature. No room-stable alkene complexes of aluminum have been reported. [Pg.155]

Epoxidation of an alkene followed by lithium aluminum hydride reduction of the result mg epoxide gives the same alcohol that would be obtained by acid catalyzed hydration (Section 610) of the alkene... [Pg.681]

ALKYLATION OF ALIPHATIC COMPOUNDS The first reported alkylation of branched-chain alkanes by ethylene, over aluminum chloride (69), made it possible to alkylate alkanes (except methane and ethane) with straight chain or branched alkenes. [Pg.556]

Uses. Magnesium alkyls are used as polymerization catalysts for alpha-alkenes and dienes, such as the polymerization of ethylene (qv), and in combination with aluminum alkyls and the transition-metal haUdes (16—18). Magnesium alkyls have been used in conjunction with other compounds in the polymerization of alkene oxides, alkene sulfides, acrylonitrile (qv), and polar vinyl monomers (19—22). Magnesium alkyls can be used as a Hquid detergents (23). Also, magnesium alkyls have been used as fuel additives and for the suppression of soot in combustion of residual furnace oil (24). [Pg.340]

The alkylation of phenol with an alkene using either acid or aluminum catalysis probably accounts for 95% of the commercially produced alkylphenols with alkyl groups of three carbons or larger. The alkenes are commercially available and environmentally kind. They do not produce by-products as do alkylations which use alcohols or alkyl haUdes. Together with an acid catalyst and the appropriate amount of phenol, mono-, di-, and trialkylphenols can be produced. [Pg.59]

Ring All lation. Ortho alkylation of IDA has taken on increasing commercial importance. Ortho ethylation, the first commercial process, is carried out (5—8) using an alkyl aluminum haUde or an aluminum anilide. The alkylation rate decreases for higher alkenes (1). [Pg.237]

Lithium aluminum hydride normally reacts with thiiranes via nucleophilic attack on carbon, but where that process is hindered sulfur is attacked to give the alkene, usually in good yield, and lithium sulfide (70JPR421). [Pg.155]

As for boron catalysts, the aluminum catalysts have exclusively been applied for the inverse electron-demand 1,3-dipolar cycloaddition between alkenes and nitrones. The first contribution to this field was published by j0rgensen et al. in... [Pg.219]

The enantioselective inverse electron-demand 1,3-dipolar cycloaddition reactions of nitrones with alkenes described so far were catalyzed by metal complexes that favor a monodentate coordination of the nitrone, such as boron and aluminum complexes. However, the glyoxylate-derived nitrone 36 favors a bidentate coordination to the catalyst. This nitrone is a very interesting substrate, since the products that are obtained from the reaction with alkenes are masked a-amino acids. One of the characteristics of nitrones such as 36, having an ester moiety in the a position, is the swift E/Z equilibrium at room temperature (Scheme 6.28). In the crystalline form nitrone 36 exists as the pure Z isomer, however, in solution nitrone 36 have been shown to exists as a mixture of the E and Z isomers. This equilibrium could however be shifted to the Z isomer in the presence of a Lewis acid [74]. [Pg.233]

The reactions of nitrones constitute the absolute majority of metal-catalyzed asymmetric 1,3-dipolar cycloaddition reactions. Boron, aluminum, titanium, copper and palladium catalysts have been tested for the inverse electron-demand 1,3-dipolar cycloaddition reaction of nitrones with electron-rich alkenes. Fair enantioselectivities of up to 79% ee were obtained with oxazaborolidinone catalysts. However, the AlMe-3,3 -Ar-BINOL complexes proved to be superior for reactions of both acyclic and cyclic nitrones and more than >99% ee was obtained in some reactions. The Cu(OTf)2-BOX catalyst was efficient for reactions of the glyoxylate-derived nitrones with vinyl ethers and enantioselectivities of up to 93% ee were obtained. [Pg.244]

The function of the tetraethyltin is to create vacant sites so that coordination of alkene molecules becomes possible, and to change the oxidation state of the tungsten atom from +6 to +4. Similar behavior of the aluminum compound in the system WCL-CgHsAlCb is not probable, because it has been demonstrated that WCle-AlClg is also an active catalyst (22, 44), which suggests that C2H5AICI2 functions as a Lewis acid. Vacant sites can be created by a Lewis acid as follows ... [Pg.152]

An important use of the Friedel-Crafts alkylation reaction is to effect ring closure. The most common method is to heat with aluminum chloride an aromatic compound having a halogen, hydroxy, or alkene group in the proper position, as, for example, in the preparation of tetralin ... [Pg.710]

Magnesium alkoxides (formed by ROH- -Me2Mg —>ROMgMe) have been decomposed thermally, by heating at 195-340°C to give the alkene, CEU, and MgO. Syn elimination is found and an Ei mechanism is likely. Similar decomposition of aluminum and zinc alkoxides has also been accomplished. ... [Pg.1328]

Halogenation of 106 with triphenylphosphine, iodine, and imidazole provided the iodo derivative 109. On treatment with lithium aluminum hydride, 109 was converted into two endocyclic alkenes, 110 and di-O-isopro-pylidenecyclohexanetetrol, in the ratio of 2 1. Oxidation of 110 with dimethyl sulfoxide - oxalyl chloride afforded the enone 111.1,4-Addition of ethyl 2-lithio-l,3-dithiane-2-carboxylate provided compound 112. Reduction of 112 with lithium aluminum hydride, and shortening of the side-chain, gave compound 113, which was converted into 114 by deprotection. ... [Pg.40]

Kuzuhara and his coworkers synthesized (+)-205 by hydroxylation of the alkene 304, which was prepared from the chiral azidocyclohexene derivative (303) derived from D-glucose, in which a novel rearrangement of the C - C double bond accompanying reduction of the azido group with lithium aluminum hydride was observed. [Pg.65]

The earliest reported Fxs were the result of the reaction of nitrous acid with naturally occurring alkenes being the identified intermediate a a-nitrooxime that suffers dehydration with cyclization. Apart from these conditions, the most recent Fxs synthesis descriptions have involved reactions between alkenes and dinitrogen trioxide (Fig. 3), nitroalkanes and aluminum trichlo-... [Pg.269]

In 1968, Eisch and Foxton showed that nickel(II) salts enhance the rate of BU2AIH addition to internal alkynes by a factor of ca. 1000 compared to the process in the absence of a catalyst [26]. Similar catalytic activity of nickel compounds was found for the addihon of aluminum hydrides to alkenes. [Pg.51]

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]. [Pg.52]


See other pages where Aluminums alkenes is mentioned: [Pg.308]    [Pg.551]    [Pg.328]    [Pg.59]    [Pg.40]    [Pg.953]    [Pg.88]    [Pg.277]    [Pg.739]    [Pg.82]    [Pg.224]    [Pg.12]    [Pg.1028]    [Pg.87]    [Pg.708]    [Pg.709]    [Pg.1206]    [Pg.1425]    [Pg.23]    [Pg.148]    [Pg.28]    [Pg.47]    [Pg.49]    [Pg.50]    [Pg.50]    [Pg.51]    [Pg.52]    [Pg.53]    [Pg.54]    [Pg.54]   
See also in sourсe #XX -- [ Pg.2 , Pg.3 , Pg.3 , Pg.5 , Pg.10 ]

See also in sourсe #XX -- [ Pg.2 , Pg.3 , Pg.3 , Pg.5 ]




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