Aluminum chloride preparation

Polymeric BINOL aluminum chloride. Prepared by Ni(0)-catalyzed cross- coupling of chiral 6,6 -dibromo-BINOL diacetate, hydrolysis, and treatment with EtjAlCl, the chiral catalyst is effective for the Mukaiyama aldol reaction. 

FIGURE 34.36 Al MAS NMR spectra of silica-grafted aluminum chloride prepared at 300°C. a the sample was sealed with sealing tape, b exposed to air without sealing tape for 4 h. c for 48 h. d sample a hydrolyzed by contacting water vapor (180 mmol g-sample at 500°C for 1 h. Taken from reference 5v. With permission. 

Dipolystyryl aluminum chloride, prepared by stoichiometric reaction of 1 mol of AICI3 and 2 mol of living polystyrene, is used together with titanium halide catalyst to synthesize styrene-ethylene block copolymers (189). 

Recently, Koitai et al. (17) have shown that 5,5-diphenyl-2,4-thiazolidinedithione (15) with aluminum chloride in refluxing toluene gives 4,5-diphenyl-A-4-thia2oline-2-thione (16) (Scheme 7). 3-Methyl-4,5-diphenyl (17) and 4,5-diphenyl-A-4-thia2oline-2-thiones (16) are obtained in very low yields (1 to 5%) as by-products of the reaction between deoxybenzoin. benzoin. l,2-diphenyl-1.2-ethanediol. 1.2-diphenylethanol, or benzil, and Sg in hexamethylphosphoamide (18), The transformation of A-4-thiazoline-2-ones to the corresponding thiones by P2S5 (19) is of little synthetic value since the latter are more easily prepared. 

In an attempt to prepare propylbenzene a chemist alkylated benzene with 1 chloropropane and aluminum chloride However two isomeric hydrocarbons were obtained m a ratio of 2 1 the desired propylbenzene being the minor component What do you think was the major product How did it anse ... 

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... 

Isopropylbenzene is prepared by the Friedel-Crafts alkylation of benzene y using isopropyl chloride and aluminum chloride (Section 12 6) j... 

Aldehyde Synthesis. Formylation would be expected to take place when formyl chloride or formic anhydride reacts with an aromatic compound ia the presence of aluminum chloride or other Friedel-Crafts catalysts. However, the acid chloride and anhydride of formic acid are both too unstable to be of preparative iaterest. 

Preparation. Commercial manufacture of LiAlH uses the original synthetic method (44), ie, addition of a diethyl ether solution of aluminum chloride to a slurry of lithium hydride (Fig. 2). 

The reaction of HCl and silicon, germanium, and boron hydrides is cataly2ed by aluminum chloride and is useful for preparing chloro-substituted silanes andgermanes. 

Acetophenone. Acetophenone [98-86-2] (methyl phenyl ketone) is a colorless Hquid that forms laminar crystals at low temperature (mp 20°C). It has a characteristic sweet orange blossom odor, and is soluble in alcohols and ethers. It is found in nature in oil of casatoreum, obtained from beavers oil of labdanum, recovered from plants and in buds of balsam poplar. It can be prepared by the Friedel-Crafts reaction (qv) of acetyl chloride with benzene in the presence of aluminum chloride however, this route is of Htde commercial significance. 

Propiophenone. Propiophenone [93-55-0] (ethyl phenyl ketone) is a colorless Hquid with a flowery odor. It can be prepared by the Friedel-Crafts reaction of benzene and propionyl chloride in the presence of aluminum chloride (346), or by the catalytic reaction of benzoic acid and propionic acid in the presence of water (347). Propiophenone is commercially available (348), and is sold in Japan at 2700 Y/kg (349). It is used in the production of ephedrine, as a fragrance enhancer, and as a polymerization sensitizer. 

Isopropylnaphthalenes can be prepared readily by the catalytic alkylation of naphthalene with propjiene. 2-lsopropylnaphthalene [2027-17-0] is an important intermediate used in the manufacture of 2-naphthol (see Naphthalenederivatives). The alkylation of naphthalene with propjiene, preferably in an inert solvent at 40—100°C with an aluminum chloride, hydrogen fluoride, or boron trifluoride—phosphoric acid catalyst, gives 90—95% wt % 2-isopropylnaphthalene however, a considerable amount of polyalkylate also is produced. Preferably, the propylation of naphthalene is carried out in the vapor phase in a continuous manner, over a phosphoric acid on kieselguhr catalyst under pressure at ca 220—250°C. The alkylate, which is low in di- and polyisopropylnaphthalenes, then is isomerized by recycling over the same catalyst at 240°C or by using aluminum chloride catalyst at 80°C. After distillation, a product containing >90 wt % 2-isopropylnaphthalene is obtained (47). 

Derivatives. Oxidation of pyrogaHol trimethyl ether with nitric acid, followed by reduction ia acetic anhydride and treatment of the product with aluminum chloride, affords 3,6-dihydroxy-2,4-dimethoxyacetophenone (228). 3,4,5-Trimethoxyphenol (antiarol) has been prepared by treatment of... 

The first reported assignment of the PPS stmcture to reaction products prepared from benzene and sulfur in the presence of aluminum chloride was made by Genvresse in 1897 (8). These products were oligomeric and contained too much sulfur to be pure PPS. Genvresse isolated thianthrene and an amorphous, insoluble material that melted at 295°C. These early synthetic efforts have been reviewed (9—11). 

The class of compounds identified as basic aluminum chlorides [1327-41 -9] is used primarily ia deoderant, antiperspirant, and fungicidal preparations. They have the formula Al2(OH)g where x = 1 5, and are prepared by the reaction of an excess of aluminum with 5—15% hydrochloric acid at a temperature of 67—97°C (18). The same compounds are obtained by hydro1y2ing aluminum alkoxides with hydrochloric acid (19,20) (see Alkoxides, METAl). Basic aluminum chloride has also been prepared by the reaction of an equivalent or less of hydrochloric acid with aluminum hydroxide at 117—980 kPa (17—143 psi) (20). 

A quinoline—bromine adduct in hot carbon tetrachloride containing pyridine gives a 90% yield of 3-bromoquinoline (21) 3-chloroquinoline [612-59-9] is prepared by an analogous route, but in poorer yield. A quinoline—aluminum chloride complex heated with bromine gives a 78% yield of 5-bromoquinoline [165-18-3] (22). Equal quantities of 5- and 8-bromoquinoline [16567-18-3] are formed when quinoline is treated with one equivalent of bromine in concentrated sulfuric acid containing silver sulfate (23). 

Acid hahdes, eg, ben2oyl chloride, acetyl chloride, and ben2oyl bromide, have been used to prepare Si—Cl and Si—Br compounds from organosilanes. Acetyl chloride proceeds to higher yield when cataly2ed by aluminum chloride. 

The tetraaryl compounds can be prepared by employing anhydrous aluminum chloride (187) ... 

Friedel-Crafts Acylation. The Friedel-Crafts acylation procedure is the most important method for preparing aromatic ketones and thein derivatives. Acetyl chloride (acetic anhydride) reacts with benzene ia the presence of aluminum chloride or acid catalysts to produce acetophenone [98-86-2], CgHgO (1-phenylethanone). Benzene can also be condensed with dicarboxyHc acid anhydrides to yield benzoyl derivatives of carboxyHc acids. These benzoyl derivatives are often used for constmcting polycycHc molecules (Haworth reaction). For example, benzene reacts with succinic anhydride ia the presence of aluminum chloride to produce P-benzoylpropionic acid [2051-95-8] which is converted iato a-tetralone [529-34-0] (30). 

Addition Chlorination. Chlorination of olefins such as ethylene, by the addition of chlorine, is a commercially important process and can be carried out either as a catalytic vapor- or Hquid-phase process (16). The reaction is influenced by light, the walls of the reactor vessel, and inhibitors such as oxygen, and proceeds by a radical-chain mechanism. Ionic addition mechanisms can be maximized and accelerated by the use of a Lewis acid such as ferric chloride, aluminum chloride, antimony pentachloride, or cupric chloride. A typical commercial process for the preparation of 1,2-dichloroethane is the chlorination of ethylene at 40—50°C in the presence of ferric chloride (17). The introduction of 5% air to the chlorine feed prevents unwanted substitution chlorination of the 1,2-dichloroethane to generate by-product l,l,2-trichloroethane. The addition of chlorine to tetrachloroethylene using photochemical conditions has been investigated (18). This chlorination, which is strongly inhibited by oxygen, probably proceeds by a radical-chain mechanism as shown in equations 9—13. 

At 225—275°C, bromination of the vapor yields bromochloromethanes CCl Br, CCl2Br2, and CClBr. Chloroform reacts with aluminum bromide to form bromoform, CHBr. Chloroform cannot be direcdy fluorinated with elementary flourine fluoroform, CHF, is produced from chloroform by reaction with hydrogen fluoride in the presence of a metallic fluoride catalyst (8). It is also a coproduct of monochlorodifluoromethane from the HF—CHCl reaction over antimony chlorofluoride. Iodine gives a characteristic purple solution in chloroform but does not react even at the boiling point. Iodoform, CHI, may be produced from chloroform by reaction with ethyl iodide in the presence of aluminum chloride however, this is not the route normally used for its preparation. 

The properties of 1,1-dichloroethane are Hsted ia Table 1. 1,1-Dichloroethane decomposes at 356—453°C by a homogeneous first-order dehydrochlofination, giving vinyl chloride and hydrogen chloride (1,2). Dehydrochlofination can also occur on activated alumina (3,4), magnesium sulfate, or potassium carbonate (5). Dehydrochlofination ia the presence of anhydrous aluminum chloride (6) proceeds readily. The 48-h accelerated oxidation test with 1,1-dichloroethane at reflux temperatures gives a 0.025% yield of hydrogen chloride as compared to 0.4% HCl for trichloroethylene and 0.6% HCl for tetrachloroethylene. Reaction with an amine gives low yields of chloride ion and the dimer 2,3-dichlorobutane, CH CHCICHCICH. 2-Methyl-l,3-dioxaindan [14046-39-0] can be prepared by a reaction of catechol [120-80-9] with 1,1-dichloroethane (7). 

Tetrachloroethane is often an incidental by-product in the manufacture of chlorinated ethanes. It can be prepared by heating the 1,1,2,2-isomer with anhydrous aluminum chloride or chlorination of 1,1-dichloroethylene at 40°C (118). Hydrochlorination of trichloroethylene using a FeCl catalyst may also be used. 

FD C lakes were first approved for use ia 1959. Today, they are the most widely used type of lake. To make a lake, an alumina substrate is first prepared by adding sodium carbonate or sodium hydroxide to a solution of aluminum sulfate. Next, a solution of certified colorant is added to the resulting slurry, then aluminum chloride is added to convert the colorant to an aluminum salt, which then adsorbs onto the surface of the alumina. The slurry is then filtered, and the cake is washed, dried, and ground to an appropriate fineness, typically 0.1—4.0 p.m. 

Anthraquinone dyes are derived from several key compounds called dye intermediates, and the methods for preparing these key intermediates can be divided into two types (/) introduction of substituent(s) onto the anthraquinone nucleus, and (2) synthesis of an anthraquinone nucleus having the desired substituents, starting from benzene or naphthalene derivatives (nucleus synthesis). The principal reactions ate nitration and sulfonation, which are very important ia preparing a-substituted anthraquiaones by electrophilic substitution. Nucleus synthesis is important for the production of P-substituted anthraquiaones such as 2-methylanthraquiQone and 2-chloroanthraquiaone. Friedel-Crafts acylation usiag aluminum chloride is appHed for this purpose. Synthesis of quinizatia (1,4-dihydroxyanthraquiQone) is also important. 

Chloroanthraquinone [131-09-9] (65) is prepared by Friedel-Crafts reaction of chlorobenzene and phthaUc anhydride ia the presence of aluminum chloride followed by ring closure ia concentrated sulfuric acid (91). 

Indanthrene Khaki GG (158) is prepared from the corresponding pen tan th rim i de with aluminum chloride or aluminum chloride—sodium chloride... 

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