Butadiene telomerization technique

This technique was particularly successful for the introduction of aluminum alkyl halides into co-condensates of first-row transition metal vapors and butadiene/arene mixtures to catalyze butadiene telomerization reactions. The oligomers produced were significantly different from the products produced by heterogeneous catalyst slurry systems. 

Other Alkyl Ethers. Sucrose has been selectively etherified by electrochemical means to generate a sucrose anion followed by reaction with an alkyl halide (21,22). The benzylation of sucrose using this technique gives 2-O-benzyl- (49%), T-O-benzyl- (41%), and 3 -O-benzyl- (10%) sucrose (22). The benzylation of sucrose with benzyl bromide and silver oxide in DMF also produces the 2-O-benzyl ether as the principal product, but smaller proportions of T- and 3 -ethers (23). Octadienyl ether derivatives of sucrose, intermediates for polymers, have been prepared by a palladium-catalyzed telomerization reaction with butadiene in 2-propanol—water (24). 

An interesting variant of entry 5 is entry 11, in which one of the educts is a polar and the other a nonpolar reactant yielding organic products. Once again the catalyst is in the aqueous phase and thus easily separated from the products. This technique is used in the telomerization of butadiene with water (Kuraray process cf. Section 6.7) and the telomerization of butadiene with ammonia (see Section 4.2.2). 

An interesting new example is the two-phase telomerization of butadiene with ammonia, yielding octadienylamines [57]. When this reaction is carried out in homogeneous one-phase solution, a great amount of primary, secondary and tertiary amines is formed [56]. With the two-phase techniques using water, and toluene or pentane as the second phase, the consecutive reactions (Eq. 2) can be almost completely avoided, and the primary octodienylamines are the only main products. This reaction has not yet been realized industrially. 

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