Basic catalysis

The classical model of solid acid and bifimctional heterogeneous catalysis basically assumed that the acid catalyzed reactions followed the laws known for liquid acids. It also assumed that catalysis over bifunctional catalysts, exposing both metal sites and acid sites, could be described by assuming simple additivity, reaction intermediates were thought to shuttle fi equently between metal sites and acid sites. More recent research has, however, shown that both assumptions are inadequate. Some reactions which are not catalyzed by liquid acids are fast over solid acids, moreover bifimctional catalysts display substantial deviations fi"om the additivity model. 

Liquid-Liquid Phase Transfer Catalysis Basic Principles and Synthetic Applications... 

Wang D, Astruc D. Dendritic catalysis basic concepts and recent trends. Coord Chem Rev 2013 257 2317-34. 

The surface (catalysis) Addo-basic Acid catalysis Basic catalysis Activation of alkanes and alcenes Breaking of C-C bonds in aUphatics Formation of C-C bonds in ahphatics Rearrangements of C-C bonds Reactions of isomerisation Reactions of nucleophUic substitution and addition CycUzation reactions Reactions of electrophilic substitution on aromatic rings Dehydrogenation of alcohols Isomerization of the double bonds of olefins... 

D. Albanese, Catalysis Reviews-Science and Engineering, 45, 369 (2003). Liquid-Liquid Phase Transfer Catalysis Basic Principles and Synthetic Applications(Reprinted from Interfacial Catalysis, p. 203-226, 2003). 

The solid-gas interface and the important topics of physical adsorption, chemisorption, and catalysis are addressed in Chapters XVI-XVIII. These subjects marry fundamental molecular studies with problems of great practical importance. Again the emphasis is on the basic aspects of the problems and those areas where modeling complements experiment. 

As an example, experimental kinetic data on the hydrolysis of amides under basic conditions as well as under acid catalysis were correlated with quantitative data on charge distribution and the resonance effect [13]. Thus, the values on the free energy of activation, AG , for the acid catalyzed hydrolysis of amides could be modeled quite well by Eq. (5)... 

A combination of the promoting effects of Lewis acids and water is a logical next step. However, to say the least, water has not been a very popular medium for Lewis-acid catalysed Diels-Alder reactions, which is not surprising since water molecules interact strongly with Lewis-acidic and the Lewis-basic atoms of the reacting system. In 1994, when the research described in this thesis was initiated, only one example of Lewis-acid catalysis of a Diels-Alder reaction in water was published Lubineau and co-workers employed lanthanide triflates as a catalyst for the Diels-Alder reaction of glyoxylate to a relatively unreactive diene . No comparison was made between the process in water and in organic solvents. 

In a second attempt to extend the scope of Lewis-acid catalysis of Diels-Alder reactions in water, we have used the Mannich reaction to convert a ketone-activated monodentate dienophile into a potentially chelating p-amino ketone. The Mannich reaction seemed ideally suited for the purpose of introducing a second coordination site on a temporary basis. This reaction adds a strongly Lewis-basic amino functionality on a position p to the ketone. Moreover, the Mannich reaction is usually a reversible process, which should allow removal of the auxiliary after the reaction. Furthermore, the reaction is compatible with the use of an aqueous medium. Some Mannich reactions have even been reported to benefit from the use of water ". Finally, Lewis-acid catalysis of Mannich-type reactions in mixtures of organic solvents and water has been reported ". Hence, if both addition of the auxiliary and the subsequent Diels-Alder reaction benefit from Lewis-acid catalysis, the possibility arises of merging these steps into a one-pot procedure. 

This really crazy looking method is one of them. There are a lot of things about it that make it very attractive. The first is the author of the article Rajender S. Varma. You will see in the Nitropropene section of this book (and in references from many other parts of the book) that this guy has been making a lot of strangely applicable advances in catalysis, amination, and reduction of amphetamines and related compounds. It is uncanny how often Strike has come across this person s work. It is like he is the Shulgin of basic precursor and amphetamine progress. Go figure ... 

As we ve just seen nucleophilic ring opening of ethylene oxide yields 2 substituted derivatives of ethanol Those reactions involved nucleophilic attack on the carbon of the ring under neutral or basic conditions Other nucleophilic ring openings of epoxides like wise give 2 substituted derivatives of ethanol but either involve an acid as a reactant or occur under conditions of acid catalysis... 

It would be difficult to over-estimate the extent to which the BET method has contributed to the development of those branches of physical chemistry such as heterogeneous catalysis, adsorption or particle size estimation, which involve finely divided or porous solids in all of these fields the BET surface area is a household phrase. But it is perhaps the very breadth of its scope which has led to a somewhat uncritical application of the method as a kind of infallible yardstick, and to a lack of appreciation of the nature of its basic assumptions or of the circumstances under which it may, or may not, be expected to yield a reliable result. This is particularly true of those solids which contain very fine pores and give rise to Langmuir-type isotherms, for the BET procedure may then give quite erroneous values for the surface area. If the pores are rather larger—tens to hundreds of Angstroms in width—the pore size distribution may be calculated from the adsorption isotherm of a vapour with the aid of the Kelvin equation, and within recent years a number of detailed procedures for carrying out the calculation have been put forward but all too often the limitations on the validity of the results, and the difficulty of interpretation in terms of the actual solid, tend to be insufficiently stressed or even entirely overlooked. And in the time-honoured method for the estimation of surface area from measurements of adsorption from solution, the complications introduced by... 

Useful thermosetting resins are obtained by interaction of furfural with phenol. The reaction occurs under both acidic and basic catalysis. Other large uses of furfural together with phenol are in the manufacture of resin-bonded grinding wheels and coated abrasives (5). 

High Carbon Yield. Furfuryl alcohol and furfural are reactive solvents (monomers) and are effective in producing high carbon yield (heat induced carbonization in a reducing atmosphere). They function as binders for refractory materials or carbon bodies. Furfuryl alcohol usually requires acidic catalysis and furfural basic catalysis. Mixtures of furfuryl alcohol and furfural are generally catalyzed with acid although some systems may be catalyzed with base. 

Furfuryl alcohol alone, or in combination with other cross-linkable binders such as phenoHc reins, chemical by-products and pitch, catalyzed with acid, gives carbon yields of 35—56%. Furfural together with cyclohexanone, pitch, or phenoHc resins gives, under acid catalysis, yields of 35—55% carbon under basic catalysis yields of 5—50% are achieved. FurfuryHdeneacetone resins (13 and 14), catalyzed by acid or base, give carbon yields of 48—56 and... 

Aldoketenes also form piedorninantly the lactone dimers, although the ratio of isomers can be influenced by base catalysis. Ketoketenes dimerize symmetrically, and at a slower rate, to 1,3-cyclobutanediones, unless acidic or basic catalysts are present. 

A hst of polyol producers is shown in Table 6. Each producer has a varied line of PPO and EOPO copolymers for polyurethane use. Polyols are usually produced in a semibatch mode in stainless steel autoclaves using basic catalysis. Autoclaves in use range from one gallon (3.785 L) size in research faciUties to 20,000 gallon (75.7 m ) commercial vessels. In semibatch operation, starter and catalyst are charged to the reactor and the water formed is removed under vacuum. Sometimes an intermediate is made and stored because a 30—100 dilution of starter with PO would require an extraordinary reactor to provide adequate stirring. PO and/or EO are added continuously until the desired OH No. is reached the reaction is stopped and the catalyst is removed. A uniform addition rate and temperature profile is required to keep unsaturation the same from batch to batch. The KOH catalyst can be removed by absorbent treatment (140), extraction into water (141), neutralization and/or crystallization of the salt (142—147), and ion exchange (148—150). 

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