Reaction with antimony chloride

A number of routes to thiocarbonyl fluoride that do not involve tetrafluoro-dithietane have been developed. In one (50), phosgene is chlorinated to give tri-chlorosulfenyl chloride, which is converted to chlorodifluorosulfenyi chloride by reaction with antimony trifluoride, and the fluorinated compound is then dehalogenated by reaction with tin. 

Bromo-l-chloro-l,l-difluoroethane (3) is prepared from l,2-dibromo-l,l-dichloroethane (1) in good yield when the fluorination reaction with antimony(III) fluoride/antimony(V) chloride is conducted in two steps. 

Hydrogen fluoride alone undergoes exchange reactions only with very reactive organic halides. However,. because it reacts with antimony chloride to form antimony fluoride and hydrogen chloride,34 it can be used to transform a large amount of organic halide to the fluoride with the aid of only small.amounts of antimony salts. This is the method used in industry for the preparation of dichlorodifluoromethane.34-36... 

Derivation Reaction of chloroform with anhydrous hydrogen fluoride with antimony chloride catalyst. 

How did the action differ from the corresponding experiment with antimony chloride (9) Write an equation for the reaction. 

On spraying with 2,6-dichloro-p-benzoquinone-4-chloroimine, ceric sulfate reagent (Seher, 1960, 1961) and especially with antimony penta-chloride (BoUiger, 1962), the tocopherols give different colors which vary also with the adsorbant, as shown in Table IX and Figs. 7 and 8. The reaction with antimony pentachloride (20% in chloroform) depends on the number and position of the methyl gi-oup on the benzene ring and on the nature of the side chain. These color complexes are not stable, however. 

Dichloroethylarsine is produced from ethylarsine by reaction with the chlorides of mercury, tin, phosphorus, arsenic, or antimony (58). Dimethyl-arsine reacts with hydrogen iodide or bromide to give the halodimethylarsine (293). 

Fig. 182. Thin-layer chromatogram (SRS-technique) of a pyrethin concentrate according to Stahl [93]. The irradiation (shaded area) was carried out after separation in direction 1. The colour reactions with antimony(III)chloride, with 2,4-dinitrophenylhydrazine and with iodide/starch, are superimposed on the single diagram (for details see text and original article)...

The regiochemistry of the reaction is strongly influenced by the identity of the Lewis acid catalyst employed as well as by the reaction temperature. For example, with indium chloride in place of aluminum chloride, compound 5 is obtained in higher selectivity (total yield 58%, 5 6 7=88 9 3). On increasing the temperature in the reaction with indium chloride, the product composition is changed and compound 6 is the predominant one (total yield 57%, 5 6 7=0 84 16). Quite similar results are achieved with iron trichloride, tin tetrachloride, and zinc chloride, while in the case of antimony pentachloride and titanium tetrachloride, compound 5 is the major product. 

The requirement for photoinitiation indicates that a radical-chain mechanism must be involved. Chlorination of 1-pentyne carried out in a gas phase reactor at higher temperatures and with higher chlorine alkyne ratios gives both the trans dichloroalkene and the saturated tetrachloro compound derived from addition of a second mole of chlorine.Fair yields of dichloroalkenes, predominantly the cis dihalide, can be obtained from acetylenes by reaction with antimony penta-chloride... 

Reaction with Aluminum Chloride or Antimony Pentachloride in Chloroform Solution... 

This reaction gives fair-to-good yields of monoorganotin tribromides and trichlorides when quaternary ammonium or phosphonium catalysts are used (149). Better yields are obtained with organic bromides and staimous bromide than with the chlorides. This reaction is also catalyzed by tri alkyl antimony compounds at 100—160°C, bromides are more reactive than chlorides in this preparation (150,151). a,C0-Dihaloalkanes also react in good yield giving CO-haloalkyltin trihaHdes when catalyzed by organoantimony compounds (152). 

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 reactions of some fluorinated ethers may result in the elimination of alkyl fluorides In the case of 2-methoxyperfluoro-2-butene, treatment with antimony pentafluoride gives perfluoro-3-buten-2-one and methylfluoride [107] By reacting 2-chloro-l,l,2-trifluorodiethyl ether with boron trifluoride etherate or with aluminum chloride, chlorofluoroacetyl fluoride can be obtained with the elimination of ethyl fluonde [108] (equations 76 and 77)... 

Antimony phthalocyanine can be prepared in a melt of antimony(III) chloride and phthalonitrile. The obtained product is of the formula [PcSb(Cl)2] SbClfi.164 PcSbX is formed by the reaction of metal-free phthalocyanine with antimony(III) chloride in l-chloronaphthalene59 or by the reaction of metal-free phthalocyanine with antimony(III) fluoride.165... 

Few 1-benzothiophene-S-oxides 218 were obtained in moderate yields by treatment of 1-arylacetylenes 219 with sulfur dioxide and benzene in the presence of antimony pentafluoride (equation 127). A series of cyclic sulphoxides have been prepared by hydrolysis of the corresponding alkoxy sulphonium salts 220 " (equation 128). Syn-sulphoxide 221 was obtained in a low yield (15-20%) in the reaction of the dianion of cyclooctatetraene 222 with thionyl chloride (equation 129). 

In view of the high toxicity of (II), it seemed that the sulphur analogue, dimethylaminosulphonyl fluoride (VI), might be of some interest. We therefore studied the fluorination of dimethylaminosulphonyl chloride. The reaction with potassium fluoride was incomplete, and that with zinc fluoride unsatisfactory, but that with antimony trifluoride using benzene as a solvent proved to be very satisfactory, and an 80 per cent yield of (VI) was obtained. Physiological examination showed that (VI) caused no irritation when small animals were exposed to a concentration of 1 mg./l. for 10 min., and no deaths took place. With the sulphonyl chloride at the same concentration, lacrimation and nasal irritation were caused no deaths were recorded, and all the animals recovered almost immediately on being removed from the chamber. 

Exchange studies were carried out by solvolysing a series of butyl chlorides in 2m solutions of antimony pentafluoride in fluoro-sulfonic acid at —50° and —78°. The acid contained tracer levels of TjO and small amounts of water to provide sufficient nucleophiles to catalyse proton exchange reactions with some of the intermediates formed in the butyl system (Kramer, 1970, 1973). 

Sb reacts with chlorine or bromine forming antimony chloride or bromide with iodine, the reaction occurs in boiling benzene or halogenated organic solvent to form antimony truodide, Sbls. 

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. ... 

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