Allyl aluminium

Hydroboration proceeds without a catalyst, but hydroboration with less active catecholborane (225) is accelerated by catalysts. Usually 1,2-addition to conjugated dienes takes place, but the Pd-catalysed reaction of catecholborane (225) gives the 1,4-adduct 226. This reaction is not catalysed by Rh complexes [98], Hydroalumination of conjugated dienes catalysed by Cp2TiCl2 affords the allylic aluminium compounds 227 by 1,4-addition. The Pd-catalysed hydrostannation of isoprene with HSnBu3 affords the (Z)-2-alkenylstannane 228 with high regio- and stereoselectivities [99],... 

Prior to tlie advent of tripbenylpbospbine-stab dized CuH [6a, b, 11], Tsuda and Saegusa described use of Gve mole percent MeCu/DtBAL in THE/HMPA to effect bydtoaluminaiion of conjugated ketones and esters [26], Hie likely aluminium etiolate intermediate could be quendied witli water ot TMSCl, ot alkylated/acylated widi various electrophiles fsudi as Mel, allyl bromide, etc. Sdieme 5.5). Mote... 

Chlor-. of or combined with chlorine, chloro (as Chlorbenzoeadure, chlorobenzoic acid), chloride of (as Chlorzink, zinc chloride), chlorahnlich, a. like chlorine, chlorinous. Chlor-alaun, m. chloralum, -alkalien, n.pl. alkali-metal chlorides, -allyl, n, allyl chloride, -aluminium, n. aluminum chloride, -ammon, m., -ammonium, n. ammonium chloride, -amyl, n, amyl chloride, -antimon, n, antimony chloride, -arsenlk, n. chloride of arsenic, -arsenikldsung, /, (Pkarm.) solution of arsenious add, hydrochloric solution of arsenic, -arsinkampfstoff, m. chlorodi-phenylarsine, adamsite, chlorartig, a. like chlorine, chlorinous,... 

Allylic sulfones and a, /5-unsaturated sulfones are known to be in equilibrium314-319. Allylic sulfones, such as 242, isomerize to a, /5-unsaturated sulfones 243 upon treatment with a catalytic amount of potassium t-butoxide in dry THF. The a, /5-unsaturated sulfones can be converted to the corresponding olefins upon desulfonation with sodium amalgam320 or aluminium amalgam294,321. Since treatment of allylic sulfones with potassium-graphite gives 2-alkenes, alkylation of allylic sulfones and subsequent desulfonation is a useful process for the synthesis of olefins, as shown in Scheme 6. 

Allyl propyl disulphide a-Alumina, see Aluminium oxide Aluminium as Al Metal dust Pyro powders Welding (umes Soluble salts Alkyls (NOC)... 

Finally, in an aromatic series, the effect of allyl chloride on benzene or toluene in the presence of ethyl aluminium dichloride (Friedel-Crafts catalysts) at -70 C is very violent and has led to a large number of accidents. It is thought that the exothermicity of the reaction below (in the case of benzene) caused these accidents, but one can not exclude a violent polymerisation of allyl chloride. 

A new route to the tetrahydroTTF system is provided by reaction of oxalyl chloride with ethanedithiol followed by dehydration to give 35. When this is treated with aluminium chloride the salt 36 is formed and its X-ray structure is reported <00ZN(B)597>. The preparation of new simple benzoditelluroles 37 has been described <00MI1127>. Treatment of allyl dithiocarbamates 38 with bromine affords the 2-amino-l,3-dithiolanylium salts 39 <97MIP112282, 98MIP113243>. 

Although lithium aluminium hydride does not reduce alkenes or acetylene hydrocarbons, it reduces allylic alcohols and their acetylenic counterparts. Thus cinnamic acid is reduced to dihydrocinnamyl alcohol. 

In order to find out what R+ is, we consider first the common experience that when a tert- mty halide is treated with an aluminium halide under ordinary conditions, there is a brisk evolution of hydrogen halide and a coloured solution containing oligo-isobutylenes and condensed allylic ions is formed. In the present experiments the solutions were colourless, no hydrogen halide was evolved, and the conductivity was stable and behaved reversibly. Further, the rectilinearity of the k-[A1X3] plots in Figures 9 and 10, and the smallness of the intercepts on the K-axis, showed that ions generated by reactions other than those of type (viii) must have been very scarce, and for the experiment with tert-butyl bromide this was borne out by the absence of any byproducts. 

The benzotriazole 109 reacts with alkyl or allyl halides in the presence of bismuth(III) chloride and metallic aluminium to give the homoalkylated amines 110 in high yields119. 

O-Methanesulphonyloximes of a,/i-unsaturated ketones yield allylic amines on reduction with lithium aluminium hydride (equation 78)207. 

Other polymerisation incidents are f Acrylaldehyde, 1145 Acrylamide, 1180 Acrylic acid, 1148 Acrylic acid, Initiator, Water, 1148 f Acrylonitrile, 1107 f Acrylonitrile, Initiators, 1107 f Acrylonitrile, Silver nitrate, 1107 f Acryloyl chloride, 1093 Allyl 4-toluenesulfonate, 3315 Aluminium chloride, Alkenes, 0062 3 - Aminopropiononitrile f Aziridine, Acids, 0863... 

Reduction of a range of allyl and benzyl chlorides at a stainless steel cathode in dimethylformamide in the presence of carbonyl compounds and using a sacrificial anode of aluminium or zinc, leads to a Reformatsky-type reaction in 40-80 % yields. Allyl halide give products by reaction at both the a- and y-positions. Tetra-chioromethane and bromotrifluoromethane take part in similar reactions provided a... 

Reformatsky reactions between allyl chloride and carbonyl cortqiounds are also effected in protic solvents using aluminium and a catalytic amount of tin chloride. Finely divided tin is formed and organotin reagents are involved as intermediates. These react with the carbonyl compound releasing tin ions, which are recycled by the dissolving aluminium [189],... 

The dissolving aluminium, lead bromide system has been combined with a Lewis acid in tetrahydrofuran to effect the combination of an allyl bromide with an acetal or an a-acetoxyamide, Altuninium chloride is employed as the Lewis acid to... 

A combination of dissolving aluminium and titanium tetrachloride in tetrahycko-furan promotes the allylation of imines. Here titanium is reduced to titaniumfo),... 

S)-[ F]fluoroethylcarazolol 8, 111 subtypes of, 100 Adriamycine (doxorubicine), 589 Agrochemical agents, 215 AIF. See Aluminium monofluoride Aliphatic nucleophilic substitution, 28 Alkenes, as amide bond substitutes, 702-703 Alkenes fluorination, 18 Allyl hydrazines as SSAO inhibitors, 674 Aluminium monofluoride, 534 Alumino-fluoride complexes, 364 Alzheimer s disease (AD)... 

The use of other metal cations such as those derived from zinc, lithium, or aluminium proved less effective (136). Treatment of allyl alcohol with diethyl zinc in the presence of a catalytic amount of diisopropyl (/ ,/ )-(+ )-tartrate (DIPT) in 1,4-dioxane, however, afforded the corresponding (5/f)-2-isoxazolines with excellent selectivity er >92 8) (178). Addition of dioxane was necessary in order to avoid precipitation of the complex of zinc salts containing the DIPT moiety. Without this solvent, lower stereoselectivity was found, probably due to the precipitation mentioned above, which prevents the favorable catalytic cycle proposed (Scheme 6.32) (178). 

The procedure described in this experiment exemplifies a general method [225] for the reduction of propargylic alcohols to -allylic alcohols. The first step in the reaction is the formation of the aluminium alkoxide -C=C-C-OAlH3. Subsequently one of the three hydrogen atoms attached to aluminum is transferred to the triple bond with formation of a 5-membered cyclic aluminum compound. Hydrolysis affords the -allylic alcohol. In the present case an -enyne alcohol is formed. 

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