Rearranged reactions with hydrogen

Other Reactions. Primary amyl alcohols can be halogenated to the corresponding chlorides by reaction with hydrogen chloride in hexamethylphosphoramide (87). Neopentyl chloride [753-89-9] is formed without contamination by rearrangement products. A convenient method for preparing / f/-amyl bromide and iodide involves reaction of / f/-amyl alcohol with hydrobromic or hydroiodic acid in the presence of Li or Ca haUde (88). The metal haUdes increase the yields (85 —95%) and product purity. 

Cg Aromatic Reactions with Hydrogen. The mild acid nature of the family of aluminophosphate based sieves renders them selective for a number of rearrangements as observed in the reactions of olefins and paraffins described above. This property as well as their apparent low disproportionation activity observed in the alkylation of toluene suggests that they be evaluated as the acid function in bifunctional Cg aromatic isomerization. As described above, cyclo-olefins are most likely involved in the conversion of ethylbenzene to xylenes. Strong acid functions, such as in mordenite, actively isomerize cyclo-olefinic intermediates but also catalyze ring-opening reactions which lead to loss of aromatics. A more selective acid function must still effectively interconvert ethyl cyclohexene to dimethylcyclohexenes but must leave the cyclohexene rings intact. 

It is believed that this process involves the following steps (a) formation of dicobaltoc-tacarbonyl from cobalt and CO, which equilibrates with cobalt hydrocarbonyl by reaction with hydrogen (b) substitution of one carbon monoxide by olefin to form a jr-complex (c) conversion of a yr-complex to cobalt alkyltetracarbonyl via a cobalt tricarbonyl intermediate after the addition of carbon monoxide and (d) fast rearrangement of the cobalt alkyltetracarbonyl compound into the acyl cobalt tricarbonyl compound, which reacts with hydrogen to give aldehyde and cobalt hydrocarbonyls. A detailed mechanism is shown below. 

In papers on the mechanism of hydroformylation, it has been suggested that alkyltetracarbonylcobalt compounds may rearrange to acyltricarbonyl-cobalt compounds followed by formation of HCo(CO)3 by reaction with hydrogen or alcohols without CO being taken up from the gas phase [35] (see Eq. 6). 

Our belief that carbocations are intermediates m the addition of hydrogen halides to alkenes is strengthened by the fact that rearrangements sometimes occur For example the reaction of hydrogen chloride with 3 methyl 1 butene is expected to produce 2 chloro 3 methylbutane Instead a mixture of 2 chloro 3 methylbutane and 2 chloro 2 methylbutane results... 

The reactions of alcohols with hydrogen halides to give alkyl halides (Chapter 4) are nucleophilic substitution reactions of alkyloxonium ions m which water is the leaving group Primary alcohols react by an 8 2 like displacement of water from the alkyloxonium ion by halide Sec ondary and tertiary alcohols give alkyloxonium ions which form carbo cations m an S l like process Rearrangements are possible with secondary alcohols and substitution takes place with predominant but not complete inversion of configuration... 

Electrochemical fluorination leads to fragmentation, coupling, and rearrangement reactions as well as giving the perfluorinated product. In addition, small amounts of hydrogen can be retained in the cmde product. The products are purified by treatment with base to remove the hydrogen-containing species and subsequently distilled. 

Squalene is also an intermediate in the synthesis of cholesterol. StmcturaHy, chemically, and biogeneticaHy, many of the triterpenes have much in common with steroids (203). It has been verified experimentally that squalene is the precursor in the biosynthesis of all triterpenes through a series of cyclization and rearrangement reactions (203,204). Squalene is not used much in cosmetics and perfumery formulations because of its light, heat, and oxidative instabiUty however, its hydrogenated derivative, squalane, has a wide use as a fixative, a skin lubricant, and a carrier of Hpid-soluble dmgs. 

Caprolactam [105-60-2] (2-oxohexamethyleiiiiriiQe, liexaliydro-2J -a2epin-2-one) is one of the most widely used chemical intermediates. However, almost all of the aimual production of 3.0 x 10 t is consumed as the monomer for nylon-6 fibers and plastics (see Fibers survey Polyamides, plastics). Cyclohexanone, which is the most common organic precursor of caprolactam, is made from benzene by either phenol hydrogenation or cyclohexane oxidation (see Cyclohexanoland cyclohexanone). Reaction with ammonia-derived hydroxjlamine forms cyclohexanone oxime, which undergoes molecular rearrangement to the seven-membered ring S-caprolactam. 

Maltol. Otsuka Chemical Co. in Japan has operated several electroorganic processes on a small commercial scale. It has used plate and frame and aimular cells at currents in the range of 4500—6000 A (133). The process for the synthesis of maltol [118-71 -8], a food additive and flavor enhancer, starts from furfural [98-01-1] (see Food additives Flavors and spices). The electrochemical step is the oxidation of a-methylfurfural to give a cycHc acetal. The remaining reaction sequence is acid-catalyzed ring expansion, epoxidation with hydrogen peroxide, and then acid-catalyzed rearrangement to yield maltol, ie ... 

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