Dehydrochlorination mechanisms

Figure 6. Dehydrochlorination mechanisms and products of isomeric chhrdans and nonachhrs...

In the free radical copolymerization of vinyl chloride with 3%-10% propylene, the propylene must be added regularly during the copolymerization in order to reduce the constitutional inhomogeneity. Propylene incorporation hinders the unzipping dehydrochlorination mechanism. These... 

Acrylate and methacrylate co-monomers participate in the nitrile reaction [182] but styrene type monomers act as a blocking agent. Chlorinated co-monomers degrade the AN units at lower temperatures [184] by a dehydrochlorination mechanism (Scheme XXV) ... 

Samples which contain chlorinated polyenes (3.73) can be further completely dehydrochlorinated by laser radiation (488 nm from an argon ion laser) by the zip-dehydrochlorination mechanism induced by chlorine (Cl radicals) [552, 554-557, 1965] ... 

Dehydrochlorination of 1,1,2-trichloroethane at 500°C in the presence of a copper catalyst gives a different product, ie, cis- and /n7 j -l,2-dichloroethylene. Addition of small amounts of a chlorinating agent, such as chlorine, promotes radical dehydrochlorination in the gas phase through a disproportionation mechanism that results in loss of hydrogen chloride and formation of a double bond. The dehydrochlorination of 1,2-dichloroethane in the presence of chlorine, as shown in equations 19 and 20, is a typical example. 

Physical properties of pentachloroethane are Hsted in Table 10. The kinetics and mechanism of the pyrolysis of pentachloroethane in the temperature ranges of 407—430°C and 547—592°C have been studied (133—135). Tetrachloroethylene and hydrogen chloride are the two primary pyrolysis products, showing that dehydrochlorination is the primary reaction. 

There is a great deal of uncertainty as to the mechanism of PVC degradation but certain facts have emerged. Firstly dehydrochlorination occurs at an early stage in the degradation process. There is some infrared evidence that as hydrogen chloride is removed polyene structures are formed (Figure 12.18). 

Starnes and Plitz [51], in their studies of PVC stabilization with di( -butyl)tin bis ( -dodecyl mercaptide) or with mixtures of the mercaptide and di( -butyl)tin dichloride, found that the rate of dehydrochlorination was inversely related to the amount of sulphur content of approximately 0.9%. The following mechanism of allyl chloride substitution was proposed [Eq. (12)]. 

Naqvi [134] has proposed an alternative model to the Frye and Horst mechanism for the degradation and stabilization of PVC. At room temperature, PVC is well below its glass transition temperature (about 81°C). The low thermal stability of the polymer may be due to the presence of undesirable concentrations of like-poles in the more or less frozen matrix with strong dipoles. Such concentrations, randomly distributed in the polymer matrix, may be considered to constitute weak or high energy spots in the polymer, the possible sites of initiation of thermal dehydrochlorination. 

The mechanisms of degradation and the mode of action of the various PVC stabilisers have both been widely studied. Often at least one aspect of their operation is some sort of reaction with the first trace of hydrogen chloride evolved. This removes what would otherwise act as the catalyst for further dehydrochlorination, and hence significantly retards the degradation process. In addition, many stabilisers are themselves capable of reacting across any double bonds formed, thereby reversing the process that causes discoloration and embrittlement. 

Roberts AL, PM Gschwend (1991) Mechanism of pentachloroethane dehydrochlorination to tetrachloroethyl-ene. Environ Sci Technol 25 76-86. 

These quantum yield values appear to be much higher than unity and therefore demonstrate that carbonization occurs by a chain reaction process. The mechanism of the laser-induced dehydrochlorination of photodegraded C-PVC can be schematically represented by the follo-... 

These remarks represent only the barest outline of at least two aspects of PVC degradation which have been the focus of attention for several years and remain incompletely understood namely the mechanism involved and the related problem of the involvement of HC1. Several excellent reviews give more comprehensive summaries of the earlier work (10, 11, 12). More recent work has made it clear that under appropriate conditions the presence of HC1 can affect the initiation, propagation and termination steps as well as influencing the distribution of polyene sequence lengths. In addition it can undergo photochemical addition reactions with the polyenes, i.e. the reverse of the dehydrochlorination process, as well as forming colored polyene/HCl complexes. These various possibilities will be considered in turn. 

The mechanism of the formation of compound 67 has been studied by Higa and Krubsack [41] in detail, as shown in Scheme 15. Namely, the initial step of the reaction of the cinnamic acid derivative 66 with thionyl chloride is an electrophilic addition of thionyl chloride across the double bond of cin-namoyl chloride to form the sulfinyl chloride intermediate (66a), which is then converted to 68 by the Pummerer reaction. Dehydrochlorination of 68... 

Cristol, S. J. (1947) The kinetics of the alkaline dehydrochlorination of the benzene hexachloride isomers. The mechanisms of second-order elimination reactions. Journal of the American Chemical Society, 69, 338-342. 

In addition, Nakagawa et al. (1JL) have shown that dehydrochlorination of PVC was suppressed extremely by incorporation of DTC or MDTC group, while the mechanism was not fully obvious. 

Also other Type B and C series from Table II are consistent with the above elimination mechanisms. The dehydration rate of the alcohols ROH on an acid clay (series 16) increased with the calculated inductive effect of the group R. For the dehydrochlorination of polychloroethanes on basic catalysts (series 20), the rate could be correlated with a quantum-chemical reactivity index, namely the delocalizability of the hydrogen atoms by a nucleophilic attack similar indices for a radical or electrophilic attack on the chlorine atoms did not fit the data. The rates of alkylbenzene cracking on silica-alumina catalysts have been correlated with the enthalpies of formation of the corresponding alkylcarbonium ions (series 24). Similar correlations have been obtained for the dehydrosulfidation of alkanethiols and dialkyl sulfides on silica-alumina (series 36 and 37) in these cases, correlation by the Taft equation is also possible. The rate of cracking of 1,1-diarylethanes increased with the increasing basicity of the reactants (series 33). 

Of the general methods for the generation of transient nitrile imines for use in synthesis (19), perhaps the most convenient are the base-induced dehydrochlorination of hydrazonyl chlorides and the oxidation of hydrazones. Developments in both of these areas have either increased the convenience of the method or given a deeper insight into the reaction mechanism. 

Silver carbonate, when used as the base in the dehydrochlorination of hydrazonyl chlorides, has a unique effect in enhancing yields and favoring particular modes of reaction, for example, in the promotion of the tandem intermolecular-intramolecular synthesis of macrocycles 302 discussed in Section 7.3.2.4 (73). Such differences have led to some investigations into the mechanism of its reaction. In this work (74), the hydrazonyl chloride 134 was reacted with 2 M equiv of silver carbonate in the presence of various allylic alcohols. 

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