1-Octene, hydration

Chitosan (Fig. 27) was deposited on sihca by precipitation. The palladium complex was shown to promote the enantioselective hydrogenation of ketones [80] with the results being highly dependent on the structure of the substrate. In the case of aromatic ketones, both yield and enantioselectiv-ity depend on the N/Pd molar ratio. Low palladium contents favored enan-tioselectivity but reduced the yield. Very high conversions were obtained with aliphatic ketones, although with modest enantioselectivities. More recently, the immobilized chitosan-Co complex was described as a catalyst for the enantioselective hydration of 1-octene [81]. Under optimal conditions, namely Co content 0.5 mmolg and 1-octene/Co molar ratio of 50, a 98% yield and 98% ee were obtained and the catalyst was reused five times without loss of activity or enantioselectivity. 

Condensation of 2-carbethoxycyclopentanone with tosylate 36 under basic conditions results in the introduction of a sidechain which can be hydrated and cycli-zed to give an acetylbicyclo[3.3.0]octene.6S This procedure, although rather classical, is capable of generating a highly functionalized substrate (Scheme 13). 

The passage from bicyclo[2.2.2]octane structures to the isomeric bicyclo[3.2.1]octanes is irreversible for all practical purposes in the CsHiz and C9H14 series (it was not investigated in the CioHie series) and this conclusion is substantiated by other facts the acid-catalyzed dehydration of 2-methylbicyclo[3.2.1]-2-octanols and 3-methylbicyclo-[3.2.1]-3-octanols gives small quantities of methylbicyclo[2.2.2]octenes 30), while the acid-catalyzed hydration of bicyclo[2.2.2]-2-octene forms the bicyclo[3.2.1]-2-octanol 27) the nitrous acid deamination of 2-aminobicyclo[2.2.2]-5-octene goes to bicyclo[3.2.1]octenols 31) and the solvolysis of bicyclo[2.2.2]-5-octen-2-ol esters to bicyclo[3.2.1]octenols 32). 

Oxytelluration of olefins with PhTeBrs or Ph2Te2-Br2 in aqueous THF generates (P-hydroxyalkyl)aryltelluiium dihalides. The reaction is tran -stereospecific in the case of cw-2-butene and cis- and trans-4-octenes and regiospecific in the cases of all terminal olefins. Their reactions with reducing agents in aqueous sodium hydroxide generate the Markovnikov hydration products. 

The influence of the hydration ratio and the physico-chemical properties of five supports in the hydroformylation of 1-octene was also studied [28]. The results confirm that the size of the pores and the amounts of water were found to be the determining factors contributing to SAPC effidency. 

Typical hydroformylation activity is illustrated in Table XII for a model, internal, linear-backbone, olefin mixture (2-, 3- and 4-octenes) using as catalyst precursor, a dispersion of ruthenium(IV) oxide, hydrate in tetrabutylphosphonium bromide (expt. 1). Optionally, a cobalt carbonyl-tertiary phosphine cocatalyst may be added (expt. 

Hexylketene diethyl mercaptal and monoperphthalic acid in ether kept 1 hr. at 0°, then 1 day at room temp. -> l,l-bis(ethanesulfonyl)-l-octene (Y 70-95%) dissolved in 90%-methanol, 85 %-hydrazine hydrate added, and the products isolated after 4-6 hrs. -> heptaldehyde hydrazone (Y 87%) and bis(ethane-sulfonyl) methane.—These are 2 steps of a sequence which may serve as a... 

In classical liquid-liquid systems, the rate of hydroformylation decreases in the order l-hejKne > 1-octene > 1-decene however, these olefins can react at virtually the same reaction rate with SAPC, because the solubility of the olefin in the aqueous phase is no longer the rate-determining factor [12]. SAPC highly depends on the intrinsic properties of the support such as particle size and surface area. Hanson has reported the preparation of SAPCs [38, 43]. Kalck et al. demonstrated that the hydration of the support is important for the hydroformylation of long-chain l-aUcenes [44]. Horvath found that the SAPC did not leach active rhodium species under hydroformylation conditions. 

---