Primary from olefins

Silylated primary allylic amines, e.g. CH2=CHCH2N(SiMe3)2, are produced from allylic chlorides and the mixed reagent AgI/LiN(SiMe3)2205. The formation of allylic amines from olefins by the ene reaction is shown in equation 77. The ene adducts 205 from bis(2,2,2-trichloroethyl) azodicarboxylate are converted into 206 by zinc dust in acetone/acetic acid206. 

Aqueous organometalHc catalysis allows the use of NH3-solutions in water for the direct synthesis of amines from olefins in a combined hydroformylation/reductive amination procedure (Scheme 4.19). The hydroformylation step was catalyzed by the proven Rh/TPPTS or Rh/BINAS (44) catalysts, while the iridium complexes formed from the same phosphine ligands and [ IrCl(COD) 2] were found suitable for the hydrogenation of the intermediate imines. With sufficiently high NH3/olefin ratios (8/1) high selectivity towards the formation of primary amines (up to 90 %) could be achieved, while in an excess of olefin the corresponding... 

Modification of the zeolite appears to have affected the selectivity of Ru in these hydrogenation reactions. Exchange of K cations for Na cations in Y zeolite increases the basicity of the support (ref. 9). In Fischer-Tropsch reactions over similar catalysts, Ru/Y catalysts so modified yielded significant increases in the olefinic product fraction at the expense of paraffins. Olefins are believed to be primary products in F-T synthesis, with paraffins being produced from olefins in secondary hydrogenation reactions. In an analogous fashion, the Ru/KY catalyst used in the present study might also be expected to... 

Systemization of experimental data on the syntheses of heterocyclic compounds with perfluoroalkyl groups from perfluoroolefins is based on reactions with various 1,1-, 1,2-, 1,3-, and 1,4-binucleophilic reagents. While the main features of nucleophilic reactions are preserved, further transformations of the primary products (or adducts, or the products of substitution of the functional groups at the internal multiple bond) occur under the influence of the added functional group containing a heteroatom. Here one can expect dramatic differences in the effect of the nature of the nucleophilic reagent between cyclizations by new nucleophilic centers and centers already available in the molecule. Another important aspect is isomerization of the primary internal olefin into the terminal olefin or internal olefin with a different structure under the action of the nucleophilic agent. This may be critical to the structure of the heterocycle formed. 

Cyclocarbonylation (9, 205-206). McMurry and Andrus have examined the scope of the reaction of Collman s reagent with unsaturated tosylates as a route to cycloalkanones and have concluded that the reaction is useful for preparation only of cyclopentanones and cyclohexanones from olefinic tosylates in which the double bond is monosubstituted. Yields are higher with primary tosylates than with secondary tosylates. 

All primary products isolated from olefin photo-oxygenations contain the unsaturation in a position adjacent to the original position, as illus-... 

Figure 1. Primary products from olefin photo-oxygenations, showing unsaturation in position adjacent to original position...

Formation of carbonium ions from olefins alkenes). Many industrial reactions of olefins involve protonation to give a carbonium ion, which is subject to nucleophilic attack, followed by proton transfer from the product to olefin. The ease of protonation follows the stability of the carbonium ion formed in the sequence tertiary > secondary > primary. Additional proton exchanges can occur at any stage in the overall process, leading to doublebond shifts in the olefinic feedstock and mixed products in some cases. (At high temperatures, products with terminal substituents may also be detectable). 

If the a-olefin CH2=CH—R involved in the primary insertion into the Ni-H bond (reaction 77) has an even number of carbon atoms, the products formed in the co-oligomerization reaction are indistinguishable from linear a-olefins formed in ethylene homooligomerization (reactions 71-73), which always proceed parallel with co-oligomerization. However, existence of the primary a-olefin insertion into the Ni-H bond is obvious from the product analysis in the case of co-oligomerization of a-olefins with odd numbers of carbon atoms (propylene, 1-pentene, 1-heptene, etc.). 

The regiospecific C-alkylation of primary benzylamines cf. Vol. 4, p. 174) has now been simplified by the use of a solid-liquid phase-transfer system. Vicinal diamines are not easily prepared directly from olefins, and although two new methods were recently reported (cf. Vol. 3, p. 170 and Vol. 4, p. 175) these have not been applicable to the preparation of primary diamines. A new method for this transformation involves the use of the cyclopentadienylnitrosyl-cobalt dimer (7), and is considered to be of general applicability. Some stereoselectivity was observed. 

Process Technology. In a typical oxo process, primary alcohols are produced from monoolefins in two steps. In the first stage, the olefin, hydrogen, and carbon monoxide [630-08-0] react in the presence of a cobalt or rhodium catalyst to form aldehydes, which are hydrogenated in the second step to the alcohols. 

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