Dehydroxylation

The 7a-dehydroxylation is the most important bacterial transformation of bile acids, rapidly forming secondary from primary bile acids and is seemingly 

These deconjugated secondary bile acids are lipophilic and are believed to passively diffuse across the colon and enter the blood supply for return to the liver. Little is known of the mechanism, although in ASBT knockout mice there is an increase in OSTa/OSTp mRNA within the proximal colon.This could simply reflect reduced bile-acid uptake in the terminal ileum and a response to increased bile-acid levels entering the colon. 

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One of the factors responsible for the rather wide variation in a values for benzene is the presence of ji-clectrons in the molecule, which can cause its adsorption to acquire a specific character if the adsorbent is polar (Chapter 1, p. 11). On hydroxylated silica, for example, the heat of adsorption is much higher than on the dehydroxylated material - on the latter solid indeed the interaction is so weak that a Type HI isotherm results (Fig. 2.19). Unfortunately c-values are rarely quoted in the literature, but... 

Rehydroxylation as a cause of low-pressure hysteresis is exemplified in the isotherm of Fig. 4.26, where the adsorbent was a partially dehydroxylated... 

A completely dehydroxylated surface consists essentially of an array of oxygen atoms the Si-0 linkages are essentially covalent so that the silicon atoms are almost completely screened by the much larger oxygen atoms. Such a surface represents the extreme case and, even on samples ignited at 1100°C, a minute residue of isolated hydroxyl groups will be present. 

When a partially dehydroxylated silica is exposed to water vapour it undergoes slow rehydroxylation. This process will occur during the course... 

The hydrophobic character exhibited by dehydroxylated silica is not shared by the metal oxides on which detailed adsorption studies have been made, in particular the oxides of Al, Cr, Fe, Mg, Ti and Zn. With these oxides, the progressive removal of chemisorbed water leads to an increase, rather than a decrease, in the affinity for water. In recent years much attention has been devoted, notably by use of spectroscopic and adsorption techniques, to the elucidation of the mechanism of the physisorption and chemisorption of water by those oxides the following brief account brings out some of the salient features. 

The microcalorimetric measurements of Della Gatta and his co-workers in their investigation of the interaction of water vapour with highly dehydroxylated y-alumina confirm that in this system also, the nondissocia-tive chemisorption of water is nonactivated, whilst the dissociative chemisorption is always activated. Thus the pseudo-equilibrium between the two chemisorbed states is displaced towards dissociative chemisorption as the temperature is increased above 150 C. 

For a ceUulosic material containing hydroxyl groups, the reactions might consist of dehydroxylation and depolymerization by hydrogenolysis, during which there is a transition from soHd to Hquid to gas. 

Novel aromatic carboxylation reactions have been observed in the anaerobic transformation of phenols to ben2oates (82). A mixed anaerobic microbial consortium apparentiy transforms phenol (33) through an intermediate to ben2oic acid (34) via dehydroxylation. This reaction has not yet been widely exploited for its obvious synthetic value. 

Cl y Conversion. The starting material for this process is kaolin, which usually must be dehydroxylated to y /i7-kaolin by air calcination. At 500—600°C, yW /t -kaohn forms, followed by a mulliti2ed kaolin at 1000—1050°C. 

Allyl Complexes. Allyl complexes of thorium have been known since the 1960s and are usually stabilized by cyclopentadienyl ligands. AEyl complexes can be accessed via the interaction of a thorium haUde and an aHyl grignard. This synthetic method was utilized to obtain a rare example of a naked aHyl complex, Th(Tj -C2H )4 [144564-74-9] which decomposes at 0°C. This complex, when supported on dehydroxylated y-alumina, is an outstanding heterogeneous catalyst for arene hydrogenation and rivals the most active platinum metal catalysts in activity (17,18). 

Degradation Decarboxylation, deamination, dehalogenation, dehydroxylation, ring fission, demethoxylation, deacetylation... 

After the blends have been prepared (either in the dry or wet process), these materials are fed at a uniform rate into a long rotary kiln. The materials are gradually heated to a liquid state. At temperatures up to about I,600°F the free water evaporates, the clay minerals dehydroxylate and crystallize, and CaCO, decomposes. At temperatures above 1,600°F the CaCO, and CaO react with aluminosilicates and the materials become liquids. Heating is continued to as high as 2,800°F. 

Release of water from the crystalline hydroxides (dehydroxylation) differs from the dehydration of a crystalline hydrate (Sect. 1) in that product release must be preceded by chemical interaction between anions. 

Rate parameters [(da/df), A, E measured for dehydroxylations are frequently sensitive to the availability of water vapour in the vicinity of the reactant and this accounts for the apparent variations in kinetic data sometimes found between different reports concerned with the same reaction. Water adsorbed on product adjoining the reaction interface could be expected to participate in the reversible proton transfer step, the precursor to water elimination. Despite this influence of PH2o on reaction rate, we are aware of no reported instance of S—T behaviour in dehydroxylations. 

The most intensively investigated dehydroxylation is probably the reaction of Mg(OH)2, though detailed results are also available for the hydroxides of certain other divalent cations. Several summaries of the mechanistic deductions obtained from such work, including literature sources, were presented at a conference at Dijon in 1974 [87]. The extensive literature concerned with the thermal analysis of hydroxides has been reviewed by Dollimore [79] who has also included the behaviour of oxides. Water elimination can be regarded as the first in a sequence of structurally related steps through which the hydroxide is converted into the thermally most stable oxide. 

Less detailed information is available concerning the rates of reactions of most hydroxy salts of inorganic acids indeed, the qualitative changes occurring during stepwise or overall removal of water have not been established for many systems. The behaviour characteristics of a number of hydroxy halides are mentioned below, as are the dehydroxylations of representative minerals. Some aspects of the relationships between the reactions of minerals and structurally similar metal hydroxides are critically discussed by Brett et al. [92]. 

In a detailed mechanistic study of Mg(OH)2 dehydroxylation, Gordon and Kingery [245] precede consideration of their kinetic data with an... 

Several other hydroxides of divalent metals crystallize in the same Cdl2 type structure as brucite, notably [610] those of Ca2+,Mn2+, Fe2+, Co2+, Ni2+ and Cd2+. The rates of dehydroxylation of these solids have, how-... 

Giovanoli and Briitsch [264] studied the kinetics of vacuum dehydroxylation of 7-FeO 0H(- -7 Fe203). It was not possible to demonstrate satisfactory obedience to a single kinetic expression. Microscopic examinations detected the occurrence of random nucleation over reactant surfaces and crystallographic indications of the specific structural reorganization steps, which occur at the reaction interface, are discussed. 

The initial stage of vacuum dehydroxylation of 3-Be(OH)2 (408— 493 K) [620] was deceleratory (E 59 kj mole-1), ascribed to diffusion control. During the subsequent main stage of reaction, interface penetration (E = 115 kJ mole-1) was rate-determining. 

Interest in the dehydroxylation of metal hydroxy salts has hitherto largely centred on the hydroxyhalides. Studies of the relative reactivities of comparable salts of this type have included measurements of the influences of the constituent halide and of variations in the ratio of... 

Analyses of rate measurements for the decomposition of a large number of basic halides of Cd, Cu and Zn did not always identify obedience to a single kinetic expression [623—625], though in many instances a satisfactory fit to the first-order equation was found. Observations for the pyrolysis of lead salts were interpreted as indications of diffusion control. More recent work [625] has been concerned with the double salts jcM(OH)2 yMeCl2 where M is Cd or Cu and Me is Ca, Cd, Co, Cu, Mg, Mn, Ni or Zn. In the M = Cd series, with the single exception of the zinc salt, reaction was dehydroxylation with concomitant metathesis and the first-order equation was obeyed. Copper (=M) salts underwent a similar change but kinetic characteristics were more diverse and examples of obedience to the first order, the phase boundary and the Avrami—Erofe ev equations [eqns. (7) and (6)] were found for salts containing the various cations (=Me). 

Dehydroxylation of the clay mineral kaolinite [71,626—629] is predominantly deceleratory and sensitive to PH2o (Table 11). Sharp and co-workers [71,627] conclude that water evolution is diffusion controlled and that an earlier reported obedience to the first-order equation is incorrect. A particularly critical comparison of a—time data is required to distinguish between these possibilities. Anthony and Garn [629] detected a short initial acceleratory stage in the reaction and concluded that at low Ph2o there is random nucelation, which accounts for the reported... 

Kinetic data for dehydroxylation of representative clay minerals (See also ref. 36.)... 

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