Dechlorinated

Apparatus 250-ml three-necked flask (see Pig. 1) for the addition of dichloro-carbene and the dechlorination. 

Apparatus Ketene generator (500 ml distillation flask) (see Ref. 20, p. 529) for. the preparation of tetramethylallene 1-1 round-bottomed, three-necked flask, provided with a mechanical stirrer, a thermometer and a vent for the addition of dichlorocarbene 500-ml flask (see Fig. 1) for the dechlorination. 

Formate is an excellent hydride source for the hydrogenolysis of aryl halides[682]. Ammonium or triethylammonium formate[683] and sodium formate are mostly used[684,685]. Dechlorination of the chloroarene 806 is carried out with ammonium formate using Pd charcoal as a catalyst[686]. By the treatment of 2,4,6-trichloroamline with formate, the chlorine atom at the /iiara-position is preferentially removed[687]. The dehalogenation of 2,4-diha-loestrogene is achieved with formic acid, KI, and ascorbic acid[688]. 

An alternative use of added readily degradable substrates is to drive the local environment toward anaerobiosis so that reactions such as reductive dechlorinations or reductive removal of nitro-groups are promoted. 

Mercury cells are operated to maintain a 21—22 wt % NaCl concentration in the depleted brine and thus preserve good electrical conductivity. The depleted brine is dechlorinated and then resaturated with soHd salt prior to recycling back to the electroly2er. 

Removal of brine contaminants accounts for a significant portion of overall chlor—alkali production cost, especially for the membrane process. Moreover, part or all of the depleted brine from mercury and membrane cells must first be dechlorinated to recover the dissolved chlorine and to prevent corrosion during further processing. In a typical membrane plant, HCl is added to Hberate chlorine, then a vacuum is appHed to recover it. A reducing agent such as sodium sulfite is added to remove the final traces because chlorine would adversely react with the ion-exchange resins used later in the process. Dechlorinated brine is then resaturated with soHd salt for further use. 

Certain CFCs are used as raw materials to manufacture key fluorinated olefins to support polymer apphcations. Thermolysis of HCFC-22 affords tetrafluoroethylene and hexafluoropropylene [116-15 ] under separate processing conditions. Dechlorination of CFC-113 forms chlorotrifluoroethylene [79-38-9]. Vinyhdene fluoride [75-38-7] is produced by the thermal cracking of HCFC-142b. 

The chlorofluorocarbons react with molten alkah metals and CCI2F2 reacts vigorously with molten aluminum, but with most metals they do not react below 200°C. An exception is the dechlorination of chlorofluorocarbons with two or more carbon atoms in the presence of Zn, Mg, or A1 in polar solvents. A commercial synthesis of chlorotriduoroethylene [79-38-9] employs this reaction ... 

Pentafluorobenzene. Pentafluoroben2ene has been prepared by several routes multistage saturation—rearomati2ation process based on fluorination of ben2ene with cobalt trifluoride reductive dechlorination of chloropentafluoroben2ene with 10% pabadium-on-carbon in 82% yield (226,227) and oxidation of penta uorophenylbydra2ine in aqueous copper sulfate at 80°C in 77% yield (228). Its ioni2ation potential is 9.37 V. One measure of toxicity is LD q = 710 mg/kg (oral, mouse) (127). 

DDT is slowly converted in vivo by reductive dechlorination to DDD and by further dechlorinations to 4,4 -dichlorodiphenylacetic acid [83-05-6] (DDA), the predominant excretory metaboUte. Anaerobically, it may form 4,4 -dichlorodiphenyiacetonitrile [20968-04-1] (DDCN). However, most DDT that enters the environment is sequestered as DDE, which is ubiquitously present in the body Hpids of invertebrate and vertebrate animals. In humans. 

Reductive DechIorina.tion. Such reduction of chlorinated aUphatic hydrocarbons, eg, lindane, has been known since the 1960s. More recentiy, the dechlorination of aromatic pesticides, eg, 2,4,5-T, or pesticide products, eg, chlorophenols, has also been documented (eq. 10) (20). These reactions are of particular interest because chlorinated compounds are generally persistent under aerobic conditions. 

Reductive reactions typically occur in anaerobic environments where there is an abundant supply of electron donors. Electron donors are typically of microbial origin, eg, porphyrins or cysteine, which sometimes leads to confusion regarding the nature, ie, chemical vs enzymatic, of the reductive reaction. By definition, all reductive reactions which are not enzymatically catalyzed are chemical. The most significant chemical reductive reaction is reductive dechlorination. 

Reductive dechlorination of chlorinated aUphatic hydrocarbons, eg, lindane (11) (eq. 17) is extremely facile and occurs almost exclusively via chemical mechanisms, although microorganisms are typically the source of electron donors (30). 

The reductive dechlorination of chlorinated aromatics is more compHcated in that the initial dechlorination of more highly chlorinated compounds may be either chemical or enzymatic, eg, PGP, whereas the dechlorination of less chlorinated compounds or dechlorinated products is typically enzymatic. For example, the first dechlorination of 2,4-dichlorophenol (ortho position) can occur either chemically or enzymatically the second dechlorination (para position) is enzymatic (eq. 10). 

Makeup. Makeup treatment depends extensively on the source water. Some steam systems use municipal water as a source. These systems may require dechlorination followed by reverse osmosis (qv) and ion exchange. Other systems use weUwater. In hard water areas, these systems include softening before further purification. Surface waters may require removal of suspended soHds by sedimentation (qv), coagulation, flocculation, and filtration. Calcium may be reduced by precipitation softening or lime softening. Organic contaminants can be removed by absorption on activated carbon. Details of makeup water treatment may be found in many handbooks (22—24) as well as in technical Hterature from water treatment chemical suppHers. 

Dechlorination Using Sufur Products, Technical Information Bulletin TlR-17, Rhtjane-Poulenc Basic Chemicals Co., Shelton, Conn., 1992. 

Uses. The use distribution of ammonium thiosulfate in 1995 was estimated to be photography, 48% agricultural appHcations, 50% and others, including dechlorination, 2%. 

Dechlorination of head-to-head, tail-to-tail stmcture can be expected to go to 100% completion. If dechlorination of head-to-tail stmcture starts at random positions, then 13.5% of the chlorine should remain at the end of reaction. Dilute solutions of PVC treated with zinc removes 87% of the chlorine, proving the head-to-tail stmcture of PVC (71). 

Sodium bicarbonate is generally added to increase alkalinity and muriatic acid (HCl) or sodium bisulfate (NaHSO ) to reduce it. In general, with acidic sanitizers such as chlorine gas or trichloroisocyanuric acid, ideal total alkalinity should be in the 100—120 ppm range, whereas, with alkaline products such as calcium, lithium, or sodium hypochlorite, a lower ideal total alkalinity of 80—100 ppm is recommended (14). Alkalinity is deterrnined by titration with standard sulfuric acid using a mixed bromcresol green—methyl red indicator after dechlorination of the sample with thiosulfate. Dechlorination with thiosulfate causes higher readings due to formation of hydroxyl ion (32) ... 

Methane, chlorine, and recycled chloromethanes are fed to a tubular reactor at a reactor temperature of 490—530°C to yield all four chlorinated methane derivatives (14). Similarly, chlorination of ethane produces ethyl chloride and higher chlorinated ethanes. The process is employed commercially to produce l,l,l-trichloroethane. l,l,l-Trichloroethane is also produced via chlorination of 1,1-dichloroethane with l,l,2-trichloroethane as a coproduct (15). Hexachlorocyclopentadiene is formed by a complex series of chlorination, cyclization, and dechlorination reactions. First, substitutive chlorination of pentanes is carried out by either photochemical or thermal methods to give a product with 6—7 atoms of chlorine per mole of pentane. The polychloropentane product mixed with excess chlorine is then passed through a porous bed of Fuller s earth or silica at 350—500°C to give hexachlorocyclopentadiene. Cyclopentadiene is another possible feedstock for the production of hexachlorocyclopentadiene. 

Further dechlorination may occur with the formation of substituted diphenyhnethanes. If enough aluminum metal is present, the Friedel-Crafts reactions involved may generate considerable heat and smoke and substantial amounts of hydrogen chloride, which reacts with more aluminum metal, rapidly forming AlCl. The addition of an epoxide inhibits the initiation of this reaction by consuming HCl. Alkali, alkaline-earth, magnesium, and zinc metals also present a potential reactivity hazard with chlorinated solvents such as methylene chloride. 

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