Hydrogenation 1-undecene

Monflier et al. (1997) have suggested Pd catalysed hydrocarboxylation of higher alpha olefins in which chemically modified P-cyclodextrin (especially dimethyl P-cyclodextrin) is u.sed in water in preference to a co-solvent like methanol, acetone, acetic acid, acetonitrile, etc. Here, quantitative recycling of the aqueous phase is possible due to easy phase separation without emulsions. A similar strategy has been adopted by Monflier et al. (1998) for biphasic hydrogenations for water-in.soluble aldehydes like undecenal using a water-soluble Ru/triphenylphosphine trisulphonate complex with a. suitably modified p-cyclodextrin. 

Given the /3-scission hypothesis, an examination of possible dodecenyl radicals indicates no reasonable mechanism of formation of Ci0H20 or CnH22. These products are formed only from the radical addition path. They can be used then to predict the relative importance of this path, XA. Decene is used to do this since it is better separated by GC from the corresponding diolefin than is undecene. XA is given by the ratio of the predicted value for decene from Table IV to the actual experimental yield. (Values for hydrogen atom addition are used here they are fairly close to those for CH3 and C2H5- addition, and available rate data (13, 14) indicate that H- atoms are the most likely radicals to add to dodecene.)... 

The selective hydrogenation of the disubstituted double bond of limonene (52) took place over a platinum catalyst at 60°C and 3 atmospheres pressure (Eqn. 15.33). 5 1,5-Undecadiene was hydrogenated to 5-undecene with 78% selectivity at 97% conversion over a Pt/A 2eolite catalyst that was treated with diphenyldiethoxysilane. 9... 

Yields of traw5-4-undecene of up to 68% have been reported in the hydrogenation of 4-undecyne using three types of palladium catalyst... 

CH2 = CH(CH2)8CHO, ChH20O, Mr 168.28, bp0,4kPa 103 °C, c%1 0.8496, < 1.4464, was identified, e.g., in coriander leaf extract [20]. It is a colorless liquid with a fatty-green, slightly metallic, heavy-flowery odor. The aldehyde can be synthesized from undecylenic acid, for example, by hydrogenation of the acid chloride (Rosen-mund reduction) or by reaction with formic acid in the vapor phase in the presence of titanium dioxide. In perfumery, 10-undecenal is one of the aldehydes essential for creating the aldehydic note. ... 

Phenyl-1-undecen-3-ol was converted into l-phenyl-3-undecanone (yield 25%) in the same way. Hydrogenation of the double bond was also achieved if the unsaturated ketone served as a substrate. Thus 0.4% (v/v) of l-tridecen-3-one was reduced to the saturated form by E. equi with a conversion rate of 73%. A similar reaction involving l-octen-3-ol and other allylic alcohols, with the aid of Pseudomonas oleovorans, has been reported43. In this case, formation of a considerable amount of saturated ketone, i.e., 3-octanone, was observed. 

The cuiTent process for producing aromatic and aliphatic aldehydes by direct hydrogenation of the corresponding carboxylic acids over Zr02 and Cr203 has been developed by the Mitsubishi Chemical Corporation. It has successfully commercialized the production of p-t-butylbenzaldehyde, m-phenoxybenzaldehyde, p-methylbenzaldehyde, 10-undecenal, and dodecanal by reduction of the corresponding acids. By use of this technology, ca. 2000 t y of aldehydes have been manufactured since 1988 [3]. 

Three different organic bases, imidazole (IM), triazole (TZ) and hydrogenated 1,8-diaza-bicyclo(5.4.0) undecene-7 (DBU) were immobilized on mesoporous materials. Immobilized state of organic bases and their catalytic activities in Knoevenagel condensation between ethylcyanoacetate and benzaldehyde was studied. Organic bases immobilized mainly on mesopore still retained their catalytic activities with an inevitable loss due to immobilization. Imidazole catalyst immobilized on KIT-1 disordered mesoporous material with three-dimensional channels showed a sufficient activity for multi-repeated use. 

The undecene methyl ester is saponified. The acid produced is converted to 11-bromoundecanoic acid in an anti-Markovnikov reaction under the influence of peroxides or light and hydrogen bromide. The bromoacid is converted to the ammonium salt of 11-amino undecanoic acid by ammonia and the free acid is liberated on lowering the pH. The free acid is polycondensed to polyamide (Nylon 11). 

Another divergent approach was demonstrated by the use of castor oil-derived platform chemicals. Here, 10-undecenal, 10-undecenoic acid, and 10-isocyanodec-1-ene served as components for the formation of the core unit via Passerini-3CR [59]. The resulting product, having three terminal olefins, was subsequently reacted with an excess of ferf-butyl acrylate in a cross-metathesis reaction, followed by hydrogenation of the newly formed double bonds. The introduced tert-hvXy esters were cleaved with trifiuoroacetic acid thus, three carboxylic acid groups were... 

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