Aluminum trichloride

LABORATORY CHEMICAL SAFETY SUMMARY ALUMINUM TRICHLORIDE  

Substance Aluminum trichloride (Aluminum chloride, trichloroaluminium) CAS 7446-70-0 

Physical Properties White crystallme solid Sublimes at 181 °C Reacts violently with water (90 g/100 mL) 

Odor Hydrogen chloride odor detectable when exposed to moist air 

Toxicity Data LD50 oral (rat) 3730 mg/kg LD50 skin (rabbit) 2 g/kg TLV-TWA (ACGIH) 2 mg(Al)/m5 

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Ethylene Aluminum trichloride, carbon tetrachloride, chlorine, nitrogen oxides, tetrafluo-roethylene... 

In France, Compagnie Europnene du Zirconium (CEZUS) now owned jointly by Pechiney, Eramatome, and Cogema, uses a separation (14) based on the extractive distillation of zirconium—hafnium tetrachlorides in a molten potassium chloride—aluminum trichloride solvent at atmospheric pressure at 350°C. Eor feed, the impure zirconium—hafnium tetrachlorides from the zircon chlorination are first purified by sublimation. The purified tetrachlorides are again sublimed to vapor feed the distillation column containing the solvent salt. Hafnium tetrachloride is recovered in an enriched overhead fraction which is accumulated and reprocessed to pure hafnium tetrachloride. 

To avoid high resin chloride content associated with the use of high concentrations of aluminum trichloride, a ttialhylalurninum—water cocatalyst system in a 1.0 0.5 to 1.0 mole ratio has been used in conjunction with an organic chloride for the polymerization of P-pinene (95). Softening points up to 120°C were achieved with 1—3 Gardner unit improvement in color over AlCl produced resins. 

Isomerization of cyclohexane in the presence of aluminum trichloride catalyst with continuous removal of the lower boiling methylcyclopentane by distillation results in a 96% yield of the latter (54). The activity of AlCl -HCl catalyst has been determined at several temperatures. At 100°C, the molar ratio of methylcyclopentane to cyclohexane is 0.51 (55). 

Diketene is used to C-acetoacetylate aromatic compounds in the presence of aluminum trichloride [7446-70-0]. Benzene [71-43-2] and diketene react to produce acetoacet5lben2ene [93-91-4]. Pyrrole [109-97-7] and diketene react to produce 2-acetoacet5lpyrrole [22441-25-4]. The C-acetoacetyl derivatives of active methylene compounds such as cyanoacetates, malonodinitrile [109-77-3] and Meldmm s acid [2033-24-1], and olefins can be prepared using diketene. 

Prepa.ra.tlon, Diorganotin dichlorides are the usual precursors for all other diorganotin compounds three primary methods of manufacture are practiced. Dibutyltin dichloride is manufactured by Kocheshkov redistribution from cmde tetrabutyltin and stannic chloride and usually is cataly2ed with a few tenths of a percent aluminum trichloride ... 

A typical cationic polymeriza tion is conducted with highly purified monomer free of moisture and residual alcohol, both of which act as inhibitors, in a suitably dry unreactive solvent such as toluene with a Eriedel-Crafts catalyst, eg, boron triduoride, aluminum trichloride, and stannic chloride. Usually low temperatures (—40 to —70°C) are favored in order to prevent chain-transfer or sidereactions. 

The synthesis of adamantane (15), tricyclo[3.3.1.1 ]decane [281-23-2] by heating tetrahydrodicyclopentadiene (14) [6004-38-2] in the presence of aluminum trichloride illustrates another aspect of the synthetic utiHty of DCPD (80). Adamantane is the base for dmgs that control German measles and influenza (80-81) (see ANTIVIRAL AGENTS). 

Many reactions of fluorinated organics with metal halides result in the replacement of fluorine with halogen A general route to 1,1,1-trichloro- or tribromo-fluoroalkanes involves treating primary fluoroalkyl iodides with aluminum trichloride or aluminum tribromide [74], Benzylic [75, 76] or vinylic [72] fluorine can be exchanged for chlorine when treated with aluminum trichloride... 

In a related study, 161 was reported from a dimerization of a 3-vinylindole precursor (61JOC4254). Previously, a compound with the structure 162 had been suggested as a product originating from a dimerization of an alcohol precursor under acidic conditions (63G238). It has recently been demonstrated that the alcohol 163, when treated with aluminum trichloride in the presence of acetic anhydride, produced the indolocarbazole 160, which could be isolated in 41% yield as an 83 17 mixture of cis and trans isomers (98JOC2909). 

Modifications of this method, such as the use of the more stable diazonium trifluoroacetates and the decomposition of benzenedia-zonium zincichloride with zinc dust, have been used as sources of aryl radicals, although not in the arylation of heterocyclic compounds. Pyridine, quinoline, and thiophene can be phenylated by treatment with benzenediazonium chloride and aluminum trichloride. ... 

Pyridine has been phenylated with the following free-radical sources benzenediazonium chloride with aluminum trichloride the Gomberg reaction " phenylhydrazine and metal oxides A -nitroso-acetanilide dibenzoyl peroxide phenylazotriphenylmethane di-phenyliodonium hydroxide and electrolysis of benzoic acid. ° Although 2-phenylpyridine usually accounts for over 50% of the total phenylated product, each of the three phenyl derivatives can be obtained from the reaction by fractional recrystallization of the... 

There is an early report that thiophene reacts at the 3-position in phenylation with benzenediazonium chloride and aluminum trichloride, but in the Gomberg reaction thiophene has been found to substitute mainly at the 2-position both with p-tolyl and with p-chloro-phenyl radicals.Bcnzothiazole is phenylated at the 2-position in low yield by dibenzoyl peroxide a small quantity of the 4-isomcr is also obtained. ... 

The reaction is initiated by formation of a donor-acceptor complex 4 from acyl chloride 2, which is thereby activated, and the Lewis acid, e.g. aluminum trichloride. Complex 4 can dissociate into the acylium ion 5 and the aluminum tetrachloride anion 4 as well as 5 can act as an electrophile in a reaction with the aromatic substrate ... 

The branched oligo(arylene)s 37 and 40 can undeigo a further oxidative cyclization with copper(ll) chloride or triflate/aluminum trichloride leading to the formation of large, hitherto unknown polycyclic aromatic hydrocarbons PAHs 41 and 42. 

The synthesis of the right-wing sector, compound 4, commences with the prochiral diol 26 (see Scheme 4). The latter substance is known and can be conveniently prepared in two steps from diethyl malonate via C-allylation, followed by reduction of the two ethoxy-carbonyl functions. Exposure of 26 to benzaldehyde and a catalytic amount of camphorsulfonic acid (CSA) under dehydrating conditions accomplishes the simultaneous protection of both hydroxyl groups in the form of a benzylidene acetal (see intermediate 32, Scheme 4). Interestingly, when benzylidene acetal 32 is treated with lithium aluminum hydride and aluminum trichloride (1 4) in ether at 25 °C, a Lewis acid induced reduction takes place to give... 

Direct conversion of the 5/7-dibenz[i,/ ]azepin-10(l 177)-one 45 to the lO-(alkylsulfanyl) derivatives 46 has been achieved using an alkanethiol and aluminum trichloride.21-1... 

Dibenz[6,/][l,4]oxazepin-ll(10//)-ones 4 are formed in near quantitative yield by cycli-zation of aryl 2-isocyanatophenyl ethers 3 in the presence of aluminum trichloride. Exact yields were not reported.40... 

Dibenzothiazepinones 6 are formed in almost quantitative yield by the aluminum trichloride induced ring closure of 2-isocyanatophenyl phenyl sulfides, exactly as described for the dibenzo-oxazepinone analog (see Section 4.1.1.3.2.4.) (Method C). Exact yields were not reported.40... 

Aluminum trichloride catalyzes the reaction of benzopentathiepin with aromatic hydrocarbons to yield thianthrcncs. Thus, benzene, / -xylene and naphthalene give, respectively, 6 (44%), 7 (75 %) and 8 (93 %).409... 

The 1,2,4-triazole derivative 1 reacts in the presence of aluminum trichloride to provide the benzannulated 1,3-diazocine 2.6... 

Aluminum phthalocyanine (PcAlX) can be prepared from the phthalonitrile and aluminum trichloride either in refluxing quinoline138 13g or without a solvent under addition of ammonium molybdate(VI).137 The chloro compound can be transformed to a hydroxy derivative by treatment with sulfuric acid.58-140 Also, the insertion of aluminum in a metal-free phthalocyanine is possible, for example trialkylaluminum can be used.141,142... 

Inversion of the regioselectivity in the addition of 2-butenylmagnesium chloride to aldehydes in favor of the a-adducts is caused by aluminum trichloride. A typical experiment is shown24 ... 

The Lewis acid mediated addition of allylic tin reagents to nitroalkenes has been reported. The condensation reaction of tributyl[(Z)-2-butenyl]tin(IV) with (E)-(2-nitroethenyl)benzene or (L)-l-nitropropene catalyzed by titanium(IV) chloride proceeded with modest anti diastereoselectivity. Poorer diastereoselection resulted when diethyl ether aluminum trichloride complex was employed as the Lewis acid 18. 

The Friedel-Crafts reaction in the presence of anhydrous aluminum trichloride is one of the best methods for the manufacture of aromatic organophosphorus compounds see Eqs. (101) and (102) ... 

Using other alkylated benzene hydrocarbons, e.g., amyl-, hexyl-, octyl-, or nonylbenzene, similar surface-active phosphinic acids are formed by reaction with PC13 in the presence of anhydrous aluminum trichloride. The resulting alkylarylphosphinic acids form stable salts with primary, secondary, or tertiary hydroxy amines or aromatic amines [166,171]. 

A common reaction for the deposition of alumina is the hydrolysis of aluminum trichloride ... 

Aluminum trichloride, a cheap, abundant waste product of the chemical industry, forms a gel under certain conditions with carbonates and on mixing with alkalies. Laboratory and field tests showed that aluminum trichloride can be used as a gel-forming agent for reducing the permeability of waterconducting channels [673]. 

Aluminum Trichloride and Trisodium Phosphate as Sediment-Forming Material... 

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