Antimony pentachloride, reaction with

Explosive reaction with chlorosulfuric acid, hydroiodic acid, magnesium perchlorate, chromyl chloride. Forms sensitive explosive mixtures with metal halogenates (e.g., chlorates, bromates, or iodates of barium, calcium, magnesium, potassium, sodium, zinc), ammonium nitrate, mercury(1) nitrate, silver nitrate, sodium nitrate, potassium permanganate. Violent reaction or ignition with alkalies + heat, fluorine, chlorine, liquid bromine, antimony pentachloride. Reacts with hot alkalies or hydroiodic acid to form... 

Antimony pentachloride reacts with a-chloro isocyanates to form l-oxa-3-azabutatriene salts, R2C=N+=C=0 SbCle, 26, which undergo [2+2+2] cycloaddition reactions with disubstituted cyanamides to give 1,3,5-oxadiazinium salts 27. ... 

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. 

Carbon tetrachloride is used to produce chlorofluorocarbons by the reaction with hydrogen fluoride using an antimony pentachloride (SbCls) catalyst ... 

Bromates, chlorates or iodates ignite in contact with phosphonium iodide at ambient temperature if dry, or in presence of acid to generate bromic acid, etc. Ignition also occurs with nitric acid, and reaction with dry silver nitrate is very exothermic. Interaction with antimony pentachloride at ambient temperature proceeds explosively. 

Diselenium dication 145a was formed by the reaction of the corresponding bis-selenide 144 with a 1 2 mixture of sulfuryl chloride and antimony pentachloride (see Equation 41) <1997JS01006>. 

Unlike the reaction of alkyl aryl ketoximes with tetrasulfur tetranitride <1996CHEC-II(4)355>, the treatment of alkyl methyl ketoximes 189 with tetrasulfur tetranitride antimony pentachloride complex in either benzene or toluene at 50-80°C gave low yields (3-37%) of 3-alkyl-4-methyl-l,2,5-thiadiazoles 190 (Equation 39) <1999H(50)147>. Compounds 190 were volatile and the low yields are in part attributed to their loss as the solvent was removed in vacuo. Suprisingly, only single regioisomers were obtained. 3-Heptanone oxime 191 did, however, give a mixture of two isomers 192 and 193 (Equation 40). 

Reaction of tetrasulphur tetranitride antimony pentachloride complex (S4N4.SbCl5) with a series of primary (3-enaminones and P-enamino esters 79 in toluene at 100 °C gave reasonable yields of 3,4-disubstituted 1,2,5-thiadiazoles 80. The formation of 80 was explained by the same mechanism as that proposed for the formation of 1,2,5-thiadiazoles from 3,5-disubstituted isoxazoles with S4N4.SbCl5 complex <00H159>. 

Oki and his co-workers (177) also found that these halogenated compounds (107) exhibited enormous differences in reactivity when they were treated with Lewis acids. The sc form undergoes a Friedel-Crafts type cyclization in the presence of titanium tetrachloride, which is a weak Lewis acid, whereas the ap form survives these conditions. The latter reacts in the presence of the stronger Lewis acid antimony pentachloride. This difference is apparently caused by a chloro group in proximity to the site where a cationic center develops during the reaction (Scheme 12). 

Hydrocarbons undergo related reaction.s in the super-acid media, such as fluorosuiphuric acid and antimony pentachloride. It has been suggested that the initial one-electron processes during the electrochemical oxidation of alkanes in fluorosuiphuric acid involve a protonated carbon-hydrogen bond with formation of a carbon radical and release of two protons [15]. 

Also, the extremely labile trichloride 101 of Viehe salt 100 is reversibly and quantitatively obtained in the solid state [9]. This latter reaction is related to the solid-solid syntheses of the extremely reactive hexachloroantimonates or -phosphates (102) of the Viehe salt by its milling with antimony pentachloride or phosphorus pentachloride [9] (Scheme 11). Furthermore, the labile adduct of chlorine to benzylidene aniline is obtained at -20 °C in a solid-state reaction. 

THF can be polymerized only with cationic initiators, for example, boron trifluoride or antimony pentachloride. The initial step consists of the formation of a cyclic oxonium ion one of two activated methylene groups in the a-position to the oxonium ion is then attacked by a monomer molecule in an S 2-reaction, resulting in the opening of the ring. Further chain growth proceeds again via tertiary oxonium ions and not, as formerly assumed, via free carbonium ions ... 

It may also be prepared by the reaction of antimony pentachloride in HCl with hydrogen sulfide and removing any free sulfur by extraction with carbon disulfide ... 

Heating with chlorine, or passing the gas into the molten trichloride yields antimony pentachloride, SbCls. Reaction with HF produces trifluoride, SbF3. 

Since N-nitrosoimmonium ions seem to be involved in the hydrolysis of a-acetates, it should be possible to isolate such species as stable salts. For this purpose, we selected a system such as XVII in which the phenyl group should provide further stabilization of such a carbonium ion. After the reaction of nitrosyl chloride with the corresponding imines, addition of antimony pentachloride resulted in the precipitation of pale yellow solids these could be isolated and stored under nitrogen for several days at room temperature. ... 

A series of 3-acyl and 3-aroyl-4-substituted 1,2,5-thiadiazoles 82 have been synthesised by reaction of 3,S-disubstituted isoxazoles 81 with tetrasulfur tetranitride antimony pentachloride (S4N4.SbCl5) in toluene at 90 C to reflux temperature. Compounds 82 are produced regioselectively and a plausible mechanism for their formation discussed. Under the same conditions, 3,4-dialkyl and 5-alkyl(aryl)-isoxazoles furnished chloroketones of type 83 <98JCS(P1)2175>. 

Tetrakis(phenyldifluorophosphine)nickel-(0) could also be obtained, using arsenic trifluoride in the presence of catalytic amounts of antimony pentachloride, or zinc fluoride as fluorinating agents. Yields as high as 50% could be obtained, but sizable decomposition on the process of fluorination of the chlorophosphine nickel-(0) complexes in solution could not be entirely suppressed. The marked instability of zerovalent nickel-phosphine complexes in solution in organic solvents, even under strictly anhydrous and anaerobic conditions, has been noted by several workers (16,20), but is still lacking a detailed explanation. A closer examination of the system carbon tetrachloride-tetrakis(trichlorophosphine)nickel-(0) (23) showed the main pa h of the reaction to consist in the formation of hexachloro-ethane with conversion of zerovalent into bivalent nickel, while the coordinated... 

In the presence of antimony pentachloride, titanium tetrachloride, stannic chloride, and tellurium tetrachloride, the decomposition reaction follows a second-order rate law, first order with respect to each component. Equation 3 is in accordance with these results. With antimony trichloride and... 

Isolation of salts of both the cation radicals and dications has been achieved for a number of systems. Thus, reaction of 2,3,4,5-tetraphenyl-l,4-dioxin with antimony pentachloride in chloroform gives the cation radical (63) as blue-violet crystals, and this can be oxidized by voltammetry to the green dication salt (64). Tetraphenyl-l,4-dithiin with antimony pentachloride in benzene affords the dication salt (65) directly as dark violet crystals (70ZC147). 6-Methyl-1,4-benzodithiin reacts with the same reagent to give a cation radical salt, which decomposes in air to a black resin (62JCS4963). 

Replacement of either one or two of the chlorines of carbon tetrachloride by fluorine can be achieved readily with antimony trifluoride containing some antimony pentachloride. The reaction stops after two chlorines have been replaced. The antimony trifluoride can be regenerated continuously from the antimony chloride by addition of anhydrous hydrogen fluoride ... 

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