Higher alkenes alkylation with

C-Alkylations may be discussed under the headings of alkene reactions and A/-alkyl rearrangements. The isopropylation of benzene and naphthalene are two important examples of alkylation with alkenes (see Alkylation). Manufacture of j butylaniline, by heating /V-butylaniline with 2inc chloride, typifies the rearrangement reaction appropriate to and higher alkyl derivatives. 

Alkyl halides and tosylates react with Na2pe(CO)4 in the presence of ethylene to give alkyl ethyl ketones. The reaction was not successful for higher alkenes, except that where the double bond and the tosylate group are in the same molecule, five- and six-membered rings can be closed. ... 

The catalytic enantioselective addition of vinylmetals to activated alkenes is a potentially versatile but undeveloped class of transformations. Compared to processes with arylmetals and, particularly alkylmetals, processes with the corresponding vinylic reagents are of higher synthetic utility but remain scarce, and the relatively few reported examples are Rh-catalysed conjugate additions. In this context, Hoveyda et al. reported very recently an efficient method for catalytic asymmetric allylic alkylations with vinylaluminum reagents that were prepared and used in Thus, stereoselective reactions... 

Mitsubishi has patented a triphenylphosphine oxide-modified rhodium catalyst for the hydroformylation of higher alkenes with both alkyl branches and internal bonds. [19] Reaction conditions are 50-300 kg/cm2 of CO/H2 and 100-150 degrees C. The high CO/H2 partial pressures provide stabilization for rhodium in the reactor, but rhodium stability in the vaporizer separation system is a different matter. Mitsubishi adds triphenylphosphine to stabilize rhodium in the vaporizer. After separation, triphenylphosphine is converted to its oxide before the catalyst is returned to the reactor. 

A similar type of catalyst including a supported noble metal for regeneration was described extensively in a series of patents assigned to UOP (209-214). The catalysts were prepared by the sublimation of metal halides, especially aluminum chloride and boron trifluoride, onto an alumina carrier modified with alkali or rare earth-alkali metal ions. The noble metal was preferably deposited in an eggshell concentration profile. An earlier patent assigned to Texaco (215) describes the use of chlorinated alumina in the isobutane alkylation with higher alkenes, especially hexenes. TMPs were supposed to form via self-alkylation. Fluorinated alumina and silica samples were also tested in isobutane alkylation,... 

In alkylation of benzene with both ethylene and propylene di- and polyalkylates are also formed. In alkylation with propylene 1,2,4,5-tetraisopropylbenzene is the most highly substituted product steric requirements prevent formation of penta-and hexaisopropylbenzene. On the other hand, alkylation of benzene with ethylene readily even yields hexaethylbenzene. Alkylation with higher alkenes occurs more readily than with ethylene or propylene, particularly when the alkenes are branched. Both promoted metal chlorides and protic acids catalyze the reactions. 

Alkylation processes usually combine isobutane with an alkene or with mixed alkene streams (C3-C5 olefins from FCC units). The best octane ratings are attained when isobutane is alkylated with butylenes. Alkylation of higher-molecular-weight hydrocarbons (>C5) is less economic because of increased probability of side reactions. Phillips developed a technology that combines its triolefin process (metathesis of propylene to produce ethylene and 2-butenes) with alkylation since 2-butenes yield better alkylate than propylene.290 Since ethylene cannot be readily used in protic acid-catalyzed alkylations, a process employing AICI3 promoted by water was also developed.291... 

It is advantageous to pretreat butene feeds before alkylation.294-298 1,3-Butadiene is usually hydrogenated (to butenes or butane) since it causes increased acid consumption. The additional benefit of this process is that under hydrogenation conditions alkene isomerization (hydroisomerization) takes place, too. Isomerization, or the transformation of 1-butene to 2-butenes, is really attractive for HF alkylation since 2-butenes give better alkylate (higher octane number) in HF-cata-lyzed alkylation. Excessive 1,3-butadiene conversion, therefore, ensuring 70-80% isomerization, is carried out for HF alkylation. In contrast, approximately 20% isomerization is required at lower butadiene conversion for alkylation with H2SO4. 

Most titanium(IV) alkyls tend to be reduced by aluminum alkyls in a complicated sequence of reactions accompanied by evolution of alkane and alkene. The catalytic activity of the bis(cyclopentadienyl)titanium-aluminum complexes is associated with the titanium alkyl. Hence, it is very interesting to investigate the mechanism of any reductive reaction. In order to study side reactions in the absence of polymerization, highly alkylated systems completely free of halogen are preferred. Moreover, reduction takes place much faster, the higher the alkyl-group content of the added aluminum alkyl. 

The reaction of I2/A1203 with alkenes even in the presence of NaCl does not result in iodo chlorides but in alkyl iodides. Evidently HI is generated by reaction of I2 with surface hydroxyls. This reaction can even take place with nonactivated alumina, but yields are higher (30-85%) with activated A1203. This reaction does not occur on silica gel. 

In contrast to Group 4 catalysts, lanthanide alkyl complexes tend to react with higher alkenes under tr-bond metathesis to give alkane and Ln-vinyl species, rather than insertion products.116... 

The extra steric bulk of HCo(CO)4 (compared to HCo(CO)3) should favor addition of the alkene to give hnear alkyls. The lower probability of alkene reaction with the saturated HCo(CO)4 catalyst is consistent with the reduced activity at higher CO partial pressures. One can also explain all these features with the 16e HCo(CO)3 catalyst by proposing that alkene isomerization is more facile with the resulting 16e RCo(CO)3 species that results after reaction with alkene (Scheme 2). 

Reduction of an alkyl halide, either via the Grignard reagent or directly with metal and acid, involves simply the replacement of a halogen atom by a hydrogen atom the carbon skeleton remains intact. This method has about the same applicability as the previous method, since, like alkenes, alkyl halides are generally prepared from alcohols. Where either method could be used, the hydrogenation of alkenes would probably be preferred because of its simplicity and higher yield. 

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