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Physical Data: t-BuCl: bp 51-52 °C; AlCl3: sublimes at 178 °C.
Solubility: both t-BuCl and AlCl3 sol organic solvents such as CH2Cl2 and CHCl3 as well as CS2.
Form Supplied in: t-BuCl: liquid; AlCl3: solid. Both are commercially available.
Preparative Method: prepared by mixing equimolar amounts of t-BuCl and AlCl3 at -78 °C.2 This compound is a white or pale yellow needle-like crystal, which is stable and can be stored indefinitely at -78 °C. However, it decomposes at about -30 °C to yield a reddish liquid and HCl. In most reactions involving the use of t-BuCl.AlCl3, both t-BuCl and AlCl3 are generally added to the reaction solution independently without premixing. The ratio between t-BuCl and AlCl3 may also vary, depending on the requirement of the specific reaction.
Handling, Storage, and Precautions: t-butyl chloride-aluminum chloride is corrosive and moisture sensitive. Thus it should be handled in an anhydrous atmosphere.
t-Butyl chloride-Aluminum Chloride (1:1 molar ratio) is prepared at -78 °C, but is not stable at -30 °C and decomposes into a reddish liquid,2 which belongs to a family of catalysts called aluminum chloride sludges.3 The sludges are valuable catalysts for commercial-scale alkylation reactions since the liquid state of the catalysts ensures continuous flow operations.3 Sludge catalysts have also found application in hydrocarbon isomerization.3,27 Reagents derived from t-BuCl.AlCl3 are not limited to the 1:1 molar ratio of the components. In many reactions, varying ratios of t-BuCl and AlCl3 may be used, depending on the need of the specific reaction, and the addition of t-BuCl and AlCl3 is generally performed without premixing the two components.
Friedel-Crafts alkylation with t-BuCl.AlCl3 as a t-butylating agent has been well studied.1 Early interest in this reaction was directed toward the mechanism of ionization.1,5 The practical importance of the t-butylation in the perfume industry for the preparation of xylene musk also provided further impetus for examination.1a Recently, this reaction has been employed in organic synthesis to protect certain positions of arenes.6 The t-butyl group introduced can be readily removed later.7 Two important features have been established regarding the use of t-BuCl.AlCl3 as an alkylating agent in aromatic substitution.1a It is difficult to achieve ortho substitution of substituted aromatic compounds, with the exception of fluorine substituted compounds. This is due to the steric bulk of the t-butyl group. Further, due to the strong Lewis acidic character of AlCl3, t-butylation of aromatic compounds using t-BuCl.AlCl3 is always accompanied by isomerization and disproportionation. These side reactions can be suppressed by employing solvents such as MeNO2 and varying the reaction conditions.
Reaction between t-BuCl.AlCl3 and chloroamines was also investigated.21 When trichloroamine is used, 90% t-butylamine is obtained, along with 8% of 2,2-dimethylaziridine as a minor product (eq 12). However, the use of monochloroamine decreased the yield of t-butylamine to a range of only 7-20%.
t-Butyl chloride-aluminum chloride is also found to facilitate the methylation of methylcyclohexane with tetramethylsilane (eq 17).28 Only 5% 1,1-dimethylcyclohexane is obtained when methylcyclohexane was treated with Me4Si.AlCl3. In contrast, 85% 1,1-dimethylcyclohexane was obtained when t-BuCl was added to the reaction system.
t-Butyl chloride interacts with AlCl3 to eliminate HCl to form isobutene, which can be polyacetylated by Acetyl Chloride.30 Upon treatment of the reaction mixture with aqueous Ammonia, 2,4,6-trimethylpyridine, 4-acetonyl-2,6-dimethylpyridine, and 1,3,6,8-tetramethyl-2,7-naphthyridine were obtained in total 92% yield with a ratio of 36:40:24, respectively. If liquid ammonia is used, the yield of the reaction remained the same, but the proportion of 1,3,6,8-tetramethyl-2,7-naphthyridine increased to 63%, while only traces of 4-acetonyl-2,6-dimethylpyridine could be detected. The amount of 2,4,6-trimethylpyridine obtained was essentially the same (eq 19).
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