Dehydrohalogenation thermal

In certain cases the fully conjugated polymer may not be soluble. It is then possible to use a precursor variant of the Gilch synthesis, where only one equivalent of base is used. This produces an intermediate soluble halide-substituted polymer that can be dehydrohalogenated thermally (Scheme 13) [104-107] or partially eliminated in an alcoholic solvent [108]. However, the intermediate halide-containing polymers may not be very stable, though this can depend on storage conditions [104]. 

Other Syntheses. Acryhc acid and other unsaturated compounds can also be made by a number of classical elimination reactions. Acrylates have been obtained from the thermal dehydration of hydracryhc acid (3-hydroxypropanoic acid [503-66-2]) (84), from the dehydrohalogenation of 3-halopropionic acid derivatives (85), and from the reduction of dihalopropionates (2). These studies, together with the related characterization and chemical investigations, contributed significantly to the development of commercial organic chemistry. 

Preparation. Thermal elimination of HCl from l-chloro-l,l-difluoroethane (HCFC-142b) [75-68-3] is the principal industrial route to VDF covered by numerous patents (8—19). Dehydrohalogenation of l-bromo-l,l-difluoroethane (20), or 1,1,1-trifluoroethane (HFC-143a) (21—25), or dehalogenation of l,2-dichloro-l,l-difluoroethane (26—28) are investigated alternative routes (see Fluorine compounds, organic-fluorinated aliphatic compounds). 

Thermal effects, including the dehydrohalogenation of polymers such as polyvinylchloride (PVC) can also occur. However, these effects are the exception and for the most part, XPS can be considered a non-destructive technique for surface characterization. 

From the results of the small scale thermal analysis experiments previously reported (23,25), it was concluded that the antimony volatilization and bromide release observed for ternary mixtures containing organobromine compounds, which did not undergo intermolecular dehydrohalogenation, could not be accounted for solely on the basis of HBr formation during degradation. 

The exothermic heat of reaction for PVC is relatively high, and thus so is the ceiling temperature. PVC resins, however, will dehydrohalogenate at temperatures considerably lower than the ceiling temperature, forming FICl gas and charred material. In this case, thermal degradation reactions occur at temperatures less than the ceiling temperature. 

Other degradation processes in addition to depolymerization can be initiated thermally. Thermal dehydrohalogenation of poly(vinyl chloride) is one such example [5]. 

Azirines are also made by carbene addition to nitriles (89 — 90) and by thermal or photochemical (68JA2869) elimination of N2 from vinyl azides (e.g. 91 — 92). Vinyl azides are prepared by the Hassner reaction (68JOC2686, 71ACR9), where iodine azide is first added to an alkene and the resultant (3-iodoazide is dehydrohalogenated with base (Scheme 37) (86RTC456). 

Treatment of PVC, suspended in chlorobenzene, with Et2AlCl followed by the addition of methanol greatly improved the thermal stability (6). This will be the subject of a separate publication. However, the nature of the improvement was different—i.e., film pressed in air at 200°C was yellow not colorless, but processing stability as determined by the torque rheometer test in the Brabender Plasticorder at 195°C was far superior and was measured in hours rather than minutes. The removal of labile chlorine atoms by Et2AlCl undoubtedly contributed to heat resistance. However, in the absence of a further reaction, such dehalo-genation probably became dehydrohalogenation, contributing to color development. 

In reaction (28) y-elimination of LiCl with the formation of an epoxide is obviously faster than P-elimination of Me3SiOLi (Peterson-olefination). Seyferth and his collaborators34) found that this reaction takes place when bis(trimethylsilyl)bromo-methyllithium is reacted with carbonyl compounds, albeit not stereoselectively (Eq. (30)). In contrast, thermal dehydrohalogenation of 1,1-dichloro-l-phenyl-dimethylsilyl-alkanes furnishes Z-olefins only (Eq. (31)) according to the results of Larson et al. 35) ... 

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