1-Hexadecene oxidation, products

Homologous oxidation products of certain olefins have been isolated this evidence indicates that at least two routes of attack on the olefin molecule are possible. Bruyn (1954) isolated n-hexadecanediol-1,2 as a product of n-hexadecene-1 oxidation by the yeast Candida lipolytica. The primary attack in this case is at the double bond. Isotopic oxygen experiments with this system have not been reported. It may be surmized that the diol oxygen originates from O. The second route of olefin oxidation occurs on the terminal methyl carbon of the saturated end of the molecule, catalyzed by the ester bacterium of Stewart et al. (1960). Terminal hydroperoxide formation similar to that occurring during alkane oxidation undoubtedly occurs here since the double bond remains intact and appears in the alcohol moiety of the final ester product. It is too early to say if the above two mechanisms are characteristic of yeasts and bacteria, respectively. (See the Addendum.)... 

Cuprous chloride tends to form water-soluble complexes with lower olefins and acts as an IPTC catalyst, e.g., in the two-phase hydrolysis of alkyl chlorides to alcohols with sodium carboxylate solution [10,151] and in the Prins reactions between 1-alkenes and aqueous formaldehyde in the presence of HCl to form 1,3-glycols [10]. Similarly, water-soluble rhodium-based catalysts (4-diphenylphosphinobenzoic acid and tri-Cs-io-alkylmethylam-monium chlorides) were used as IPTC catalysts for the hydroformylation of hexene, dodecene, and hexadecene to produce aldehydes for the fine chemicals market [152]. Palladium diphenyl(potassium sulfonatobenzyl)phosphine and its oxide complexes catalyzed the IPTC dehalogenation reactions of allyl and benzyl halides [153]. Allylic substrates such as cinnamyl ethyl carbonate and nucleophiles such as ethyl acetoactate and acetyl acetone catalyzed by a water-soluble bis(dibenzylideneacetone)palladium or palladium complex of sulfonated triphenylphosphine gave regio- and stereo-specific alkylation products in quantitative yields [154]. Ito et al. used a self-assembled nanocage as an IPTC catalyst for the Wacker oxidation of styrene catalyzed by (en)Pd(N03) [155]. 

Fig. 14.4.1.1. Schematic diagram of a two-phase bioreactor system for continuous 1-octanol production. [After reference 7]. 1 -Octanol i s produced from n-octane in hexadecene by Pseudomonas oleovorans or recombinant strains containing the alkane oxidation genes.

---