Dehydrogenation reversible

Note that reaction (1) is a dehydrogenation (reverse of hydrogenation) and that its AH is positive. 

It is interesting that the 17-oxygenase will not attack a C-21 hydroxy compound. If a hydroxyl is first introduced at C-21, then further conversion stops at corticosterone and cortisol will not be produced (diagram of formulas above). The 11-hydroxy compounds can be dehydrogenated reversibly to the 11-keto compounds. 

Reverse osmosis is used for desalination of seawater, treatment of recycle water in chemical plants and separation of industrial wastes. More recently the technique has been applied to concentration and dehydrogenation of food products such as milk and fruit juices. See ultrafiltralion. 

Oxidation can also occur at the central metal atom of the phthalocyanine system (2). Mn phthalocyanine, for example, can be produced ia these different oxidation states, depending on the solvent (2,31,32). The carbon atom of the ring system and the central metal atom can be reduced (33), some reversibly, eg, ia vattiag (34—41). Phthalocyanine compounds exhibit favorable catalytic properties which makes them interesting for appHcations ia dehydrogenation, oxidation, electrocatalysis, gas-phase reactions, and fuel cells (qv) (1,2,42—49). 

Research is also being conducted in Japan to aromatize propane in presence of carhon dioxide using a Zn-loaded HZSM-5 catalyst/ The effect of CO2 is thought to improve the equilibrium formation of aromatics by the consumption of product hydrogen (from dehydrogenation of propane) through the reverse water gas shift reaction. 

Examples of reverse spillover (or backspillover) are the dehydrogenation of isopentane and cyclohexane on active carbon. Deposition of a transition metal on the active carbon accelerates the recombination of H to H2 due to a reverse spillover or backspillover effect.72... 

Annular flow reactors, such as that illustrated in Figure 3.2, are sometimes used for reversible, adiabatic, solid-catalyzed reactions where pressure near the end of the reactor must be minimized to achieve a favorable equilibrium. Ethylbenzene dehydrogenation fits this situation. Repeat Problem 3.7 but substitute an annular reactor for the tube. The inside (inlet) radius of the annulus is 0.1m and the outside (outlet) radius is 1.1m. 

The above-described reverse reaction (viz. the Fe-catalyzed dehydrogenation of alcohols to ketones/aldehydes) has been reported by Williams in 2009 (Table 9) [58]. In this reaction, the bicyclic complex 16 shows a sluggish activity, whereas the dehydrogenation of l-(4-methoxyphenyl)ethanol catalyzed by the phenylated complex 17 affords the corresponding ketone in 79% yield when 1 equiv. (relative to 17) of D2O as an additive was used. For this oxidation reaction, l-(4-methoxyphenyl) ethanol is more suitable than 1-phenylethanol and the reaction rate and the yield of product are higher. 

Ruthenium NHC dihydride complex 26 was found to exhibit interesting reversible hydrogenation/dehydrogenation activity (Scheme 10.11) [35,36]. When excess acetone was used as a hydrogen acceptor, dehydrogenation of several alcohols was achieved (Table 10.5). 

In 2004, Whittlesey and Williams demonstrated that the reversible C-H activation of Ru-NHC complexes (e.g. 32a, Scheme 13.14) provides an effective manifold for tandem dehydrogenation/Wittig reaction/hydrogenation of alcohols, thus generating alkanes from alcohols and phosphorus ylides [56]. 

The dehydrogenation reaction was generally monitored by taking samples for reversed phase H PLC analysis. Diode array detectors for H PLC were relatively new at that time and proved valuable for quickly getting structural information on products of the reaction produced under different conditions. Key reaction parameters for adduct formation, overall concentration, BSTFA, TfOH, and DDQ charges, were optimized using a thermostated HPLC autosampler to sample reactions directly for analysis. Comparison of reaction profiles provided rate and reaction time information that was used to select a more limited number of reaction conditions that were scaled up to compare yields. 

Gibbs energy change of reversible reaction pairs of dehydrogenation/hydrogenation as a function of temperature. 

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