Verfahren zur Herstellung von halogenierten organischen Verbindungen

摘要

Organic compounds are halogenated by electrolyzing an anhydrous fluid electrolyte containing an organic compound and an electrolytically available halogen other than fluorine. As described chlorination is effected using fused salt baths e.g. at temperatures of 90 to 270 DEG C., typically of alkaline metal halides and/or alkaline earth metal halides, mainly chlorides but including minor amounts of bromides or fluorides, which may also include halides, preferably chlorides, of one or more of Al,B,Ga,Mg,Zn,Fe,Hg. The organic compounds may be alkanes, cycloalkanes, aromatic hydrocarbons, ethers, ketones or may be incompletely halogenated derivatives of such compounds. Anodes of Pt, Ni, Fe, Al, carbon or graphite may be used while cathodes may be of Fe, V, W, Ni, Pt, carbon or graphite. Apparatus for carrying out the process may comprise a glass U-tube, the anolyte and catholyte being separated by a sintered glass diaphragm, or a rectangular cell may be used consisting of outer side walls of steel and nickel forming cathode and anode respectively between which are sandwiched PTFE gaskets and a glass cloth diaphragm (Fig. 1 not shown). Alternatively, Fig. 2, 3, the cell may comprise an outer steel container cathode 1 provided with sight glasses 11 with an anode formed of nickel rods 6 engaging nickel discs 7 and separated from a glass cloth sock diaphragm 8 by PTFE spacers 16. In another arrangement, Fig.4, the cell is formed by a spherical glass flash 1 provided with a stirrer 4, a nickel helix anode 5 and a glass cloth diaphragm sleeve 10 within which is located a glass coil former 8 on which is wound the cathode in the form of iron wire. Supply tubes reaching to the bottom of the catholyte and anolyte supply HCl gas and gaseous or easily vaporized organic compounds to be halogenated respectively. In examples the electrolyte is NaAlCl4 with or without excess AlCl3 and the catholyte is fed with HCl gas and the anolyte with ethane. Depending on the operating conditions, the anoidic gaseous product may be chiefly ethyl chloride with small amounts of 1:2 dichloroethane, hexachloroethane, tetrachloroethylene, and trans-dichloroethylene, together with some unreacted ethane and hydrogen chloride (Example 1); tetrachlorothylene and hexachloroethane without chlorine (Examples 2, 3 and 6); rexachloroethane with chlorine at higher electrolyzing current (Example 4); chlorine, hexachloroethane, sym-tetrachloroethane and tetrachloroethylene at higher current and temperature, 200 DEG C. (Example 5). If a mixture of commercial ethane and hydrogen chloride is fed to the analyte, the product is 1:2-dichloroethane and sym-tetrachloroethane together with chlorine (Example 9). In a modification (Example 7) using an anolyte of anhydrous ferric chloride and sodium chloride and a catholyte of NaAlCl4, a Pt wire anode and iron wire cathode, the anode gas product from pure ethane comprises chlorines 1:2-dichloroethane with a trace of ethyl chloride. By using as electrolyte an equimolar melt of HgCl2 and KCl at 270 DEG C. with a Pt wire anode and iron gauze cathode the anode product was free of chlorine and comprised mainly ethyl chloride with traces of dichloroethanes, 1:1:2-trichloroethane, tetrachloroethylene and probably vinyl chloride and trans-1:2-dichloroethylene.