Ethane ethyl chloride from

Chlorination of Ethane. Ethane [74-84-0] maybe chlorinated thermally, catalyticaHy, photochemicaHy, or electrolyticaHy. Monochlorination is favored because ethyl chloride chlorinates at about one-fourth of the rate at which it is itself produced from ethane. 

Much later (Marcinkowsky and Berty 1973) it was proven that ethane did indeed have an effect. In the study of the inhibitor action of chlorinated hydrocarbons it was discovered that these compounds chlorinate the silver catalyst and ethane removes the chlorine from the catalyst by forming ethyl chloride. Since the inhibitor was in the 10 ppm range and similar quantities were used from the ethane present in about one volume percent, the small difference could not be calculated from material balance. The effect of ethane was only noticed as significant by the statistics, which justifies the statement made by Aris (1966) that, The need for sophistications should not be rejected unsophisticatedly. ... 

Large volumes of gas are generated, primarily ethane and ethylene, from the disproportionation of the ethyl radicals produced in the reaction of ethylmagnesium bromide with ferric chloride. The reaction should be carried out in an efficient hood, or else a tube should be run from the top of the reflux condenser to a hood. 

To a solution of N-methyl-4-nitrophenethylamine (1.5 g) (J.O.C., [1956], 21, 45) and 2-[4-nitrophenoxy]ethyl chloride (1.55 g) (C.A., [1955], 49, 3163e) in acetonitrile (50 ml) was added potassium carbonate (1.25 g) and sodium iodide (1.2 g) and the suspension was stirred at reflux for 72 hours. After evaporation to dryness, the residual oily solid was partitioned between a 2 N aqueous sodium bicarbonate solution and ethyl acetate. After two further extractions with ethyl acetate, the organic portions were combined, washed with a saturated aqueous brine solution, dried over magnesium sulfate, filtered and evaporated. The resultant orange solid (2.7 g) was crystallised from ethanol to give l-(4-nitrophenoxy)-2-[N-methyl-N-(4-nitrophenethyl)amino]ethane (1.9 g), m.p. 74°C. 

Small amounts of ethylene dichloride (b.p. 83.5°C) are also recovered as a by-product from the direct chlorination of ethane to ethyl chloride (chlor-oethane). 

The Grignard reaction is a two-step reaction used to prepare pure hydrocarbons. Consider the preparation of pure ethane, CH3CH3, from ethyl chloride, CH3CH2CI. 

As in steam cracking, a large number of by-products is produced. Some of them result from the consecutive reactions of the chlorination of vinyl chloride and of its derivatives obtained by dehydrochlorination (tri-, tetra-, pentachloroethane, perchloro-ethane, di-, trichloroethylene. perchloroethyleneX and the others from the hydrochlorination of vinyl chloride il.l-dichloroethane), while others result from decomposition reactions (acetylene, cokei or conversion of impurities initially present (hydrocarbons such as ethylene, butadiene and benzene, chlorinated derivatives such as chloroprene, methyl and ethyl Chlorides, chloroform, carbon tetrachloride, eta, and hydrogen) ... 

Reaction 9 shows that the major portion of the reacting ethylene ions interact with ethyl chloride by discrete transfer steps including H" transfer, H2" transfer, and possibly Cl" transfer. Also, as discussed later, the total cross section for reaction of ethylene ions in this system is quite large (> 100 sq. A.). This may be compared with the corresponding reaction of ethylene ions with ethane, for which extremely small cross-sections have been found (44). In the latter case, however, the H" transfer reaction is endothermic, and the H2" transfer process would not have been detected in the previous experiments. These facts may explain the low reactivity reported. With ethyl chloride, H" transfer to ethylene ions is also indicated to be endothermic by the usual calculations. This suggests that the reactant ethylene ions in this system may well be vibra-tionally excited. It would also account for the chloride ion transfer to this ion, mentioned above. The ratio of rate constants observed for C2H4+ reaction with ethyl chloride is kU2-/ku- = 1.4. In addition to the reactions just discussed, part of the ethylene ion reactant forms a complex intermediate with CoH5C1, and elimination of HC1 and DC1 from this intermediate occurs with about equal probability. 

The radiolysis product yields in the presence of ion scavenger (Table III) also show that ethane is not formed from neutralization of stable ions. Therefore, the remainder of the ethane product (above that indicated to result from neutral decomposition) must be produced by an ion-molecule process—i.e., a yield of G = 1.47. The ion-molecule reactions previously listed show that ethylene ions react with ethyl chloride to form ethane. From the relative rates indicated for Reactions 3a-3d and the ethane yield just derived, a relative yield of 2.46 may be deduced for the ionic fragmentation to ethylene ion in the radiolysis. 

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