Ethylaluminium

Table 5.3-3 Solubilities of 1-butene and M-butane in the acidic mixture composed of l-butyl-3-methylimida-zolium ([BMIM]) chloride/alumini-um chloride/ ethylaluminium dichloride (1 1.22 0.06 molar ratio) as a function of temperature under atmospheric pressure.

The ethylaluminium dichloride-catalyzed reaction of p-toluenesulphinyl chloride with alkenes 136 successfully applied191 for the synthesis of allylic sulphoxides 137 (equation 74) may also be regarded formally as a reaction of sulphinyl chlorides with compounds containing active hydrogen atom. Treatment of an alkene 136 with one equivalent each of ethylaluminium dichloride and p-toluenesulphinyl chloride at room temperature gave the corresponding 137. This reaction is very general and proceeds in... 

Contact with RmMX (R is methyl, ethyl M is aluminium, zinc X is bromide, iodide) causes ignition. Diethylaluminium bromide, dimethylaluminium bromide, ethylaluminium bromide iodide, methylzinc iodide and methylaluminium diiodide are claimed as specially effective. 

Ethylaluminium diiodide [2938-73-0] EtAlI2 491M, 1975, 153 It ignites in air. See Other ALKYLALUMINIUM HALIDES c2h5aii2... 

Friedel-Crafts alkylation of benzene or toluene by allyl chloride in presence of ethylaluminium chlorides is vigorous even at — 70°C, and explosions have occurred. See Lewis acids, etc., next below... 

Interaction produces distillable ethylaluminium azide chloride, but the residue is explosive. 

Cyclization reactions of vinyl- and alkynylsilanes have been reviewed100. The course of the reaction of the cyclohexenone derivative 184 depends on the catalyst employed ethylaluminium dichloride gives solely the product 185 of 1,6-addition, whereas tetrabuty-lammonium fluoride yields a mixture containing 69% of the 1,4-adduct 186 and 31% of the bridged compound 187 (equation 89)101. Intramolecular addition reactions of allylic silanes102 may also be catalysed by Lewis acids (equation 90) or fluoride ions, and in this case an allyl anion or a pentavalent silicon intermediate may be involved (equation 91). Such reactions are exemplified by the formation of a 1 5 mixture of the diastereomers 189 and 190 when the cyclohexenone derivative 188 is treated with ethylaluminium dichloride (equation 92). In the presence of fluoride anion the ratio of the isomers is reversed103. 

Cyclization of the ally lie trimethylsilane 191 with ethylaluminium dichloride, followed by hydrolysis, gives solely the c -fused product 192 (equation 93)104. Under similar... 

The first organoaluminium complex that catalysed a Diels Alder reaction was formed from menthol and ethylaluminium dichloride. This finding was complemented by work of Corey who showed that the aluminium diamine complex (49) was effective for controlling the stereochemistry of Diels-Alder reactions involving cyclopentadiene and acryloyl and crotonyl amides (e.g. 

Diethylaluminium bromide, 1670 Diethylaluminium chloride, 1671 Diisobutylaluminium chloride, 3064 Dimethylaluminium bromide, 0882 Dimethylaluminium chloride, 0883 Ethylaluminium bromide iodide, 0841 Ethylaluminium dibromide, 0842 Ethylaluminium dichloride, 0843 Ethylaluminium diiodide, 0844 Hexaethyltrialmninimn trithiocyanate, 3695 Methylaluminium diiodide, 0423 Triethyldialuminium trichloride, 2556 Trimethyldialuminium trichloride, 2556 See Other ALKYLMETAL HALIDES... 

Diethylaluminium bromide, 1664 Diethylaluminium chloride, 1665 Diisobutylaluminium chloride, 3059 Dimethylaluminium bromide, 0878 Dimethylaluminium chloride, 0879 Ethylaluminium bromide iodide, 0837 Ethylaluminium dibromide, 0838 Ethylaluminium dichloride, 0839 Ethylaluminium diiodide, 0840 Hexaethyltrialuminium trithiocyanate, 3688 Methylaluminium diiodide, 0422 Triethyldialuminium trichloride, 2551 Trimethyldialuminium trichloride, 1288 See ALKYLALUMINIUM DERIVATIVES (references 1,2)... 

Some tricyclic 1,3-thiazetidines of type (51) are reported (95CPB63). Selective C-S bond cleavage of 3-aryl-fS-sultams (52) with ethylaluminium dichloride gives aryl ketones or aldehydes by a process involving 1,2-aryl shift, imine formation and hydrolysis of the imine (95TL245). 

The reaction of imines with 2-pyridyl thioesters in the presence of aluminium tribromide or ethylaluminium dichloride afforded /ra r-3,4-disubstituted azetidin-2-ones < 1996T2583>. Similar stereoselective addition of silylketene thioacetals to imines is known in the presence of Lewis acids <1996T2573>. An indium-mediated reaction of ethyl bromoacetate with imines yielded 3-unsubstituted azetidin-2-ones in reasonable yields (Equation 195) <2000J(P1)2179>. 

A variety of /3-sultams such as 65 with a poorly migratory substituent at C-3 have been treated with ethylaluminium dichloride to afford /ra r-l,2,3-oxathiazolidine-2-oxides 66 as 70 30 mixtures of isomers separable by preparative thin-layer chromatography (TLC) on silica gel. However, cA-aziridines 67 are obtained as the major products when the reaction is carried out in refluxing dichloromethane (Scheme 10) <1998T8941>. 

The 4-alkenyl /3-sultams 50 and 51 can be prepared by stereoselective alkylation of the 4-monosubstituted /3-sultams 68 with alkenyl halides. Reaction of product 50 with ethylaluminium dichloride in toluene gives the aldehyde 69. When /3-sultam 51 is used, a tandem cyclization is observed yielding the bicyclo[3.2.1] 7-sultam 70 (Scheme 12). In the... 

Treatment of 3-aryl-4-silyl /3-sultams 93 with ethylaluminium dichloride causes stereospecific C-N bond cleavage to provide (it)-styrylsulfonamides 94 (Equation 6). However, reaction of the corresponding 3-/-butyl /3-sultam proceeds at 40 °C, and its low reactivity is explained because of the weaker stabilization of the cationic intermediate by the /-butyl group than by the aromatic groups <1998CPB757>. 

Selective C-S bond cleavage of a /3-sultam ring bearing a variety of substituents at C-3 and C-4 can be achieved by reaction with Lewis acids and yields aryl ketones or aldehydes. A solution of ethylaluminium dichloride in hexane is easier to handle than solid aluminium chloride due to their relative moisture sensitivities (Scheme 25) <1998T8941>. 

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