Carbon tetrachloride, alkylation with

In dilute solutions in non-polar solvents, such as carbon tetrachloride, two carbonyl frequencies corresponding to the monomer and dimer are found. The frequency difference between the two bands is always close to 45 cm . Studies on the intensity changes in these bands on dilution can be carried out in the same way as on the OH frequencies to determine equilibrium coefficients [65]. The monomer frequency measured in this way is usually a little lower than that obtained from the vapour. In trifluoroacetic acid, for example, the monomer in the vapour absorbs at 1820 cm and falls to 1810 cm in carbon tetrachloride [66]. With unflorinated alkyl acids the monomer frequency in carbon tetrachloride has an average value [17] of 1760 cm ... 

Aluminum chloride dissolves readily in chlorinated solvents such as chloroform, methylene chloride, and carbon tetrachloride. In polar aprotic solvents, such as acetonitrile, ethyl ether, anisole, nitromethane, and nitrobenzene, it dissolves forming a complex with the solvent. The catalytic activity of aluminum chloride is moderated by these complexes. Anhydrous aluminum chloride reacts vigorously with most protic solvents, such as water and alcohols. The ability to catalyze alkylation reactions is lost by complexing aluminum chloride with these protic solvents. However, small amounts of these "procatalysts" can promote the formation of catalyticaHy active aluminum chloride complexes. 

Although in the dry state carbon tetrachloride may be stored indefinitely in contact with some metal surfaces, its decomposition upon contact with water or on heating in air makes it desirable, if not always necessary, to add a smaH quantity of stabHizer to the commercial product. A number of compounds have been claimed to be effective stabHizers for carbon tetrachloride, eg, alkyl cyanamides such as diethyl cyanamide (39), 0.34—1% diphenylamine (40), ethyl acetate to protect copper (41), up to 1% ethyl cyanide (42), fatty acid derivatives to protect aluminum (43), hexamethylenetetramine (44), resins and amines (45), thiocarbamide (46), and a ureide, ie, guanidine (47). 

The a alkylation of enamines has also been extended to photochemical and thermal reactions of carbon tetrachloride with enamines (292,293). 

The present procedure seems to be a general one for producing alkyl halides from acids. To aid in isolating higher-boiling or solid products, solvents such as carbon tetrachloride and cyclohexane can be used.7 In preparing a solid, the mercuric halide can be removed by extraction with 5% potassium iodide. 

Similar monoadducts were also obtained, when more simple chloroalkanes such as dichloromethane, chloroform, carbon tetrachloride were used (Figure 4, Table I). In the case of dichloromethane the product was a mixture of the 1,4 and 1,2 adducts. DFT calculations (B3LYP/3-21G ) showed that the 1,2 adduct is slightly more stable than the 1,4 adduct in this case, but becomes less stable when the alkyl group is bulkier, in agreement with the experimental results. 

Allenylcobaloximes, e.g. 26, react with bromotrichloromethane, carbon tetrachloride, trichloroacetonitrile, methyl trichloroacetate and bromoform to afford functionalized terminal alkynes in synthetically useful yields (Scheme 11.10). The nature of the products formed in this transformation points to a y-specific attack of polyhaloethyl radicals to the allenyl group, with either a concerted or a stepwise formation of coba-loxime(II) 27 and the substituted alkyne [62, 63]. Cobalt(II) radical 27 abstracts a bromine atom (from BrCCl3) or a chlorine atom (e.g. from C13CCN), which leads to a regeneration of the chain-carrying radical. It is worth mentioning that the reverse reaction, i.e. the addition of alkyl radicals to stannylmethyl-substituted alkynes, has been applied in the synthesis of, e.g., allenyl-substituted thymidine derivatives [64],... 

The need for great care to avoid the possibility of detonation of perchloryl compounds by exposure to shock, overheating or sparks is stressed. The compounds are generally more sensitive to impact than mercury fulminate and are of comparable sensitivity to lead azide [1], A range of highly explosive alkyl perchlorates [2] and perchlorylamines [3] have been prepared by interaction of dichlorine heptaoxide with alcohols or amines in carbon tetrachloride solution. The solutions of the products were not sensitive to mechanical shock and could... 

This includes bioremediation cases of contaminated sites with several toxic and carcinogenic pollutants, such as petroleum hydrocarbons, PAHs, dichlorobenzene, chlorinated hydrocarbons, carbon tetrachloride, Dicamba, methyl bromide, trinitrotoluene, silicon-based organic compounds, dioxins, alkyl-phenol polyethoxylates, nonylphenol ethoxylates, and polychlorinated biphenyls. The following is a brief summary of each case. 

Hundsdieke reaction org chem Production of an alkyl halide by boiling a silver carboxylate with an equivalent weight of bromine in carbon tetrachloride. honz.dek-o re,ak-sh3n ... 

The tertiary amine thus obtained was dissolved in absolute ethanol and was refluxed for two days with five molar percent excess of the appropriate bromoalkane (97% Humphrey Chemical, North Haven, Conn.). Solvent was removed and the residue in aqueous Na2C03 solution was extracted with hexane to remove any unreacted bromoalkane. Next, the N-alkyl N-benzyl N-methylglycine was extracted into chloroform from the aqueous layer. Solvent was stripped off and the crude material was recrystallized thrice from carbon tetrachloride and twice from THF/CHCl3 (60 40 v/v) mixture. The yields of the purified betaines were about 75% of the theoretical. 

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