Aluminum chloride, with ethylene and

Allenylacetylenes, 50,101 ir-Allylnickel bromide, 52,199 Aluminum amalgam, 52, 7S Aluminum chloride, with ethylene and p-methoxyphenylacetyl chloride to give 6-methoxy-(3-tetralone, 51, 109... 

Dichloroethane is produced by the vapor- (28) or Hquid-phase chlorination of ethylene. Most Hquid-phase processes use small amounts of ferric chloride as the catalyst. Other catalysts claimed in the patent Hterature include aluminum chloride, antimony pentachloride, and cupric chloride and an ammonium, alkaU, or alkaline-earth tetrachloroferrate (29). The chlorination is carried out at 40—50°C with 5% air or other free-radical inhibitors (30) added to prevent substitution chlorination of the product. Selectivities under these conditions are nearly stoichiometric to the desired product. The exothermic heat of reaction vapori2es the 1,2-dichloroethane product, which is purified by distillation. 

Treatment of Decalin with acetyl chloride and aluminum chloride in ethylene chloride as solvent gives a complex mixture of products as shown (15). By variation of the reaction parameters, however, it is possible to maximize the yield of the remarkable reaction product, 10 j3-vinyl-/m j-Decalin l/8,r oxide (5). This vinyl ether undoubtedly... 

Ethylbenzene is manufactured by the alkylation process from ethylene and benzene feeds. The catalyst employed has mostly been aluminum chloride with a small addition of ethyl chloride promoter. Normally, aluminum chloride is somewhat corrosive and causes relatively high maintenance on the equipment. 

Properties Colorless liquid aromatic odor. Vapor heavier than air, bp 136.187C, refr index 1.49594 (20C), d 0.867 (20C), fp -95C, bulk d 7.21 lb/gal (25C), flash p 59F (15C), autoign temp 810F (432C), specific heat 0.41 cal/gal/K, viscosity 0.64 cP (25C). Soluble in alcohol, benzene, carbon tetrachloride, and ether almost insoluble in water. Derivation (1) By heating benzene and ethylene in the presence of aluminum chloride, with subsequent distillation (2) by fractionation directly from the mixed xylene stream in petroleum refining. Grade Technical, pure, research. 

Aluminum bromide has been finding increasing application as an acid catalyst in organic synthesis it has recently become of industrial importance in the alkylation of aromatic hydrocarbons with ethylene, and in the isomerization of normal hydrocarbons. It is also used in the polymerization of olefins, and to some extent in the Friedel-Crafts reaction. It has been found particularly useful in such reactions since it is not only more soluble in organic media, but also more active catalytically than aluminum chloride. Winter and Cramer have described a procedure for pre-... 

Alkenyl halides such as vinyl chloride (H2C=CHC1) do not form carbocations on treatment with aluminum chloride and so cannot be used m Friedel-Crafts reactions Thus the industrial preparation of styrene from benzene and ethylene does not involve vinyl chloride but proceeds by way of ethylbenzene... 

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. 

Benzotrichloride with zinc chloride as catalyst reacts with ethylene glycol to form 2-chloroethyl benzoate [7335-25-3] (35). Perchlorotoluene is formed by chlorination with a solution of sulfur monochloride and aluminum chloride in sulfuryl chloride (36). 

Alkylation. Ethylbenzene [100-41 -4] the precursor of styrene, is produced from benzene and ethylene. The ethylation of benzene is conducted either ia the Hquid phase ia the preseace of a Eriedel-Crafts catalyst (AlCl, BE, EeCl ) or ia the vapor phase with a suitable catalyst. The Moasanto/Lummus process uses an aluminum chloride catalyst that yields more than 99% ethylbenzene (13). More recently, Lummus and Union Oil commercialized a zeoHte catalyst process for Hquid-phase alkylation (14). Badger and Mobil also have a vapor-phase alkylation process usiag zeoHte catalysts (15). Almost all ethylbenzene produced is used for the manufacture of styrene [100-42-5] which is obtained by dehydrogenation ia the preseace of a suitable catalyst at 550—640°C and relatively low pressure, <0.1 MPa (<1 atm). 

Acyl halides may also be added to ethylene ia the presence of aluminum chloride to form halogenated ketones. At low temperatures, ethylene reacts with halogens to yield dihaloethanes. At high temperatures, trichloroethylene and perchloroethylene are formed. The most profitable route for chloroethylene is via ethylene dichloride (see Chlorocarbonsandchlorohydrocarbons). 

With Acyl Halides, Hydrogen Halides, and Metallic Halides. Ethylene oxide reacts with acetyl chloride at slightly elevated temperatures in the presence of hydrogen chloride to give the acetate of ethylene chlorohydrin (70). Hydrogen haUdes react to form the corresponding halohydrins (71). Aqueous solutions of ethylene oxide and a metallic haUde can result in the precipitation of the metal hydroxide (72,73). The haUdes of aluminum, chromium, iron, thorium, and zinc in dilute solution react with ethylene oxide to form sols or gels of the metal oxide hydrates and ethylene halohydrin (74). 

Phosphoms oxychloride reacts with ethylene oxide in the presence of aluminum chloride to give tris-2-chloroethyl phosphate, a valuable plasticizer (75). Phosgene reacts with ethylene oxide and other alkylene oxides to form esters of chlorocarbonic acid (76) (see Carbonic and carbonochloridic esters). 

Polymerization of ethylene oxide can occur duriag storage, especially at elevated temperatures. Contamination with water, alkahes, acids, amines, metal oxides, or Lewis acids (such as ferric chloride and aluminum chloride) can lead to mnaway polymerization reactions with a potential for failure of the storage vessel. Therefore, prolonged storage at high temperatures or contact with these chemicals must be avoided (9). 

Acylation of 1,4-dimethoxynaphthalene with acetic anhydride (1.2 equiv) and aluminum chloride (2.2 equiv) in ethylene dichloride (60°C, 3 h) gives two products, 6-acetyl-l,4-dimethoxynaphthalene (30%) and l-hydroxy-2-acetyl-4-methoxynaphtha-lene (50%). Suggest a rationalization for the formation of these two products and, in particular, for the differing site of substitution in the two products. 

The six-position may be functionalized by electrophilic aromatic substitution. Either bromination (Br2/CH2Cl2/-5°) acetylation (acetyl chloride, aluminum chloride, nitrobenzene) " or chloromethylation (chloromethyl methyl ether, stannic chloride, -60°) " affords the 6,6 -disubstituted product. It should also be noted that treatment of the acetyl derivative with KOBr in THF affords the carboxylic acid in 84% yield. The brominated crown may then be metallated (n-BuLi) and treated with an electrophile to form a chain-extender. To this end, Cram has utilized both ethylene oxide " and dichlorodimethyl-silane in the conversion of bis-binaphthyl crowns into polymer-bound resolving agents. The acetylation/oxidation sequence is illustrated in Eq. (3.54). 

Acylation of norephedrine (56) with the acid chloride from benzoylglycolic acid leads to the amide (57), Reduction with lithium aluminum hydride serves both to reduce the amide to the amine and to remove the protecting group by reduction (58), Cyclization by means of sulfuric acid (probably via the benzylic carbonium ion) affords phenmetrazine (59), In a related process, alkylation of ephedrine itself (60) with ethylene oxide gives the diol, 61, (The secondary nature of the amine in 60 eliminates the complication of dialkylation and thus the need to go through the amide.) Cyclization as above affords phendimetra-zine (62), - Both these agents show activity related to the parent acyclic molecule that is, the agents are CNS stimulants... 

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