Hydrocarbons, with Halogenated olefins

Additions of halogen fluorides to the more electrophilic perfluonnated olefins generally require different conditions Reactions of iodine fluoride, generated in situ from iodine and iodine pentafluoride [62 102 103, /05] or iodine, hydrogen fluoride, and parapeiiodic aud [104], with fluormated olefins (equations 8-10) are especially well studied because the perfluoroalkyl iodide products are useful precursors of surfactants and other fluorochemicals Somewhat higher temperatures are required compared with reactions with hydrocarbon olefins Additions of bromine fluoride, from bromine and bromine trifluonde, to perfluonnated olefins are also known [lOti]... 

Infrared chemiluminescence measurements [581] of the HF products from the reactions of fluorine atoms with a wide range of pure and halogenated olefinic and aromatic hydrocarbons (see list in Table 7)... 

Certain halogenated compounds will condense with paraffinic, olefinic, or aromatic hydrocarbons. Catalysts for these reactions are of the Ftiedel-Crafts type. Thus, the condensation of alkyl halides with ethylene in the presence of aluminum chloride, zinc chloride, iron chloride, etc., furnishes higher alkyl halides. An example is the reaction of /-butyl chloride and ethylene to form l-chloro-3,3-dimethylbutane (75%). ... 

When the hydrogen halides are similarly allowed to react with olefinic hydrocarbons, the halogen, in accordance with Markownikofif s rule, ordinarily attaches itself preponderantly to that carbon with which are combined the least number of hydrogen atoms, while the hydrogen adds on to the terminal carbon atom. 

The unsaturated open-chain hydrocarbons include the alkene or olefin series, the diene series, and the alkyne series. The alkene series is made up of chain hydrocarbons in which a double bond exists between two carbon atoms. The general formula for the series is CnH2n, where n is the number of carbon atoms. As in the paraffin series, the lower members are gases, intermediate compounds are liquids, and the higher members of the series are solids. The alkene series compounds are more active chemically than the saturated compounds. They react easily with substances such as halogens by adding atoms at the double bonds. 

Finally, binuclear lanthanide(III)-silver(I) shift reagents are noteworthy. These form complexes with olefins, aromatic rings, halogenated saturated hydrocarbons, and phosphines. Due to the lack of polar groups, these functionalities do not give significant LIS with common mononuclear LSR. Applications of this binuclear technique have been reviewed261 for example, the Z- and E-isomers of 2-octene can be differentiated. 

These hydrocarbons are characterised by the facility with which they combine with the halogens, forming oils they have, therefore, been termed olefines, or oil-makers. They also unite with nascent hydrogen, and are converted into paraffins, as the members of the former group are termed. The equations which follow illustrate this —... 

Two reviews of isomerization reactions should be referred to as sources of information on Russian researches in the field. The book by Petrov (291) on isomerization of paraffins, olefins, diolefins, and acetylenes with up to 34 carbon atoms gives information based on Russian and non-Russian researches and was written by an author who has carried out with co-workers numerous studies of isomerization of olefins in the presence of various catalysts. The review by Danilov (55) was confined to Russian contributions to the field of isomerization during the period of 1917-1947 and covers isomerization of hydrocarbons of all classes, their halogenated derivatives, oxygenated compounds and heterocyclics. In view of these detailed publications, the discussion below is limited to highlights of the field. 

A group of substances which are closely associated with the gas hydrates, are the compounds of urea (and thiourea) with a large number of organic substances with long-chain molecules, such as normal saturated hydrocarbons and olefins, alcohols, acids, esters, ketones, halogenated hydrocarbons, etc.3, which were discovered accidentally by Bengen in 1940. These compounds are only produced with unbranched, non-cyclic molecules4. This is even so very specific that a method of separation can be based on it for normal and iso hydrocarbons in mixtures. 

Halogenation of saturated hydrocarbon polymers can hardly be controlled and is frequently assodated with chain degradation phenomena In contrast, the presence of randomly distributed olefinic unsaturations, allows selective halogenation reactions by adopting appropriate conditions. For instance, butyl rubber can be chiorinated or brominated in allylic positions and chloro-butyl or bromo-butyl rubber results The latter polymers are very interesting since they exhibit fast curing rates when sulfur and ZnO are introduced in the formulations. 

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