Transition anhydrides

The Acetaldehyde Oxidation Process. Liquid-phase catalytic oxidation of acetaldehyde (qv) can be directed by appropriate catalysts, such as transition metal salts of cobalt or manganese, to produce anhydride (26). Either ethyl acetate or acetic acid may be used as reaction solvent. The reaction proceeds according to the sequence... 

Free-radical reaction rates of maleic anhydride and its derivatives depend on polar and steric factors. Substituents added to maleic anhydride that decrease planarity of the transition state decrease the reaction rate. The reactivity decreases in the order maleic anhydride > fumarate ester > maleate ester. 

The performance of many metal-ion catalysts can be enhanced by doping with cesium compounds. This is a result both of the low ionization potential of cesium and its abiUty to stabilize high oxidation states of transition-metal oxo anions (50). Catalyst doping is one of the principal commercial uses of cesium. Cesium is a more powerflil oxidant than potassium, which it can replace. The amount of replacement is often a matter of economic benefit. Cesium-doped catalysts are used for the production of styrene monomer from ethyl benzene at metal oxide contacts or from toluene and methanol as Cs-exchanged zeofltes ethylene oxide ammonoxidation, acrolein (methacrolein) acryflc acid (methacrylic acid) methyl methacrylate monomer methanol phthahc anhydride anthraquinone various olefins chlorinations in low pressure ammonia synthesis and in the conversion of SO2 to SO in sulfuric acid production. 

Postulate a transition state structure for the formation of the acetylpyridinium ion from pyridine and acetic anhydride. 

Compare the geometry of maleic anhydride+propene, the ene transition state, to those of the reactants (maleic anhydride and propene). Is bond making and breaking occurring at once In particular, is the migrating hydrogen partially bonded to two carbons (rather than being fully bonded to one carbon ) Draw a Lewis structure to represent the transition state. Use dashed lines (.. and to represent partial bonds. 

Electrostatic potential map for maleic anhydride+propene, the transition state for the ene reaction, shows negatively-charged regions (in red) and positively-charged regions (in blue). 

Self-condensation of the substituted propiophenone, 15, by the pinacol reaction proceeds to give the glycol, 16, as the meso isomer. (If it is assumed that the transition state for this reaction resembles product, this stereoselectivity can be rationalized on the grounds of steric interaction compare A, which leads to the observed product, with B.) Dehydration under very specialized conditions (acetyl chloride, acetic anhydride) affords the bisstyrene-type diene (17). Removal of the acyl groups by means of base affords the synthetic estrogen, dien-... 

Note 1. Many of the possible conformations are not likely to contribute significantly to the chemistry of a particular monosaccharide, but must be stabilized by formation of additional rings, as in anhydrides or other derivatives. Some others may occur as transition-state intermediates. 

In a most recent paper [418] the preparation of corn fiber arabinoxylan esters by reaction of the polymer with C2-C4 anhydrides using methanesul-fonic acid as a catalyst is described. The water-insoluble derivatives with high molecular weight showed glass-transition temperatures from 61 to 138 °C, depending on the DS and substituent type. The products were thermally stable up to 200 °C. Above this temperature their stability rapidly decreased. 

The exo addition mode is expected to be preferred because it suffers fewer steric repulsive interactions than the endo approach however, the endo adduct is usually the major product because of stabilizing secondary orbital interactions in the transition state (Scheme 1.10). The endo preference is known as Alder s rule. A typical example is the reaction of cyclopentadiene with maleic anhydride which, at room temperature, gives the endo adduct which is then converted at... 

The cycloaddition between norbornadiene (23 in Scheme 1.12) and maleic anhydride was the first example of a /mmo-Diels-Alder reaction [55]. Other venerable examples are reported in Scheme 1.12 [56]. Under thermal conditions, the reaction is generally poorly diastereoselective and occurs in low yield, and therefore several research groups have studied the utility of transition metal catalysts [57]. Tautens and coworkers [57c] investigated the cycloaddition of norbornadiene and some of its monosubstituted derivatives with electron-deficient dienophiles in the presence of nickel-cyclo-octadiene Ni(COD)2 and PPhs. Some results are illustrated in Tables 1.4 and 1.5. 

The frontier orbital interactions at other than reaction sites can determine the selectivity [14]. The interaction between the HOMO of cyclopentadiene and the LUMO of maleic anhydride is illustrated in Scheme 26. The HOMO of cyclopentadiene has the same phase property as butadiene (Scheme 18). The LUMO of maleic anhydride is an in-phase combined orbital of and transition state for the... 

Table 4 PM3 calculation of 5-X-cyclopentadenes at the transition states of Diels-Alder reactions with maleic anhydride...

Table 5 AMI Calculation of the transition states in Diels-Alder reactions between 5-X-pentamethylcyclopentadiones and maleic anhydride...

Mataka and coworkers reported the studies of the Diels-Alder reactions of [3.3] orthoanthracenophanes 96 and 97, of which anthraceno unit, the potential diene, has two nonequivalent faces, inside and outside. The reactions of 96 with dien-ophiles gave the mixtures of inside and outside adducts with the ratios between 1 1 and 1 1.5. However, the ratio changes drastically, in favor of the inside adducts, when 97 reacts with dienophiles such as maleic anhydride, maleimide and naphto-quinone [55] (Scheme 46). Mataka suggested that the Jt-facial selectivity is controlled by an orbital interaction between the electron-poor dienophiles and the Jt-orbital of the facing aromatics, which would lead to a stabilization of the transition state, while Nishio suggested that the selectivity is due to the attractive k/k or CH/jt interaction [53]. 

Calculated Degree of Maleic Anhydride Grafting Required to Obtain a Solubility Parameter of 18.0 (J/cm ) , Assuming Full Conversion of the Grafted Anhydride with the Amines Listed, and Corresponding Glass Transition Temperatures (Tg)... 

For the mechanism of azolide hydrolysis under specific conditions like, for example, in micelles,[24] in the presence of cycloamyloses,[25] or transition metals,[26] see the references noted and the literature cited therein. Thorough investigation of the hydrolysis of azolides is certainly important for studying the reactivity of those compounds in chemical and biochemical systems.[27] On the other hand, from the point of view of synthetic chemistry, interest is centred instead on die potential for chemical transformations e.g., alcoholysis to esters, aminolysis to amides or peptides, acylation of carboxylic acids to anhydrides and of peroxides to peroxycarboxylic acids, as well as certain C-acylations and a variety of other preparative applications. 

Acetic anhydride, Organic materials, Transition metals Hikita, T. et al., J. Chem. Soc. Japan, Ind. Chem. Sect., 1951, 54, 253-255 The stability ranges of mixtures of the acid, anhydride and organic materials (ethanol, gelatine) used in electropolishing were studied. Presence of transition metals (chromium, iron, nickel) increases the possibility of explosion. (This is why such mixtures must not be stored after use for etching metals.)... 

Itoh and coworkers [223] have shown that fullerene derivatives as 6/2-113, which to date have been prepared in a stepwise procedure, can be obtained in a three-component domino process by treatment of diynes 6/2-109, dimethylphenylsilane 6/2-110 and fullerene (C60) in the presence of a Rh-catalyst [223]. Interestingly, using maleic anhydride as dienophile failed to give the desired cycloadduct, whereas Cso -in spite of its strong tendency to form complexes with various transition metals [224] - never suppressed the catalytic silylative cyclization step to give the diene 6/2-112 (Scheme 6/2.24). 

A,A -di(/>-dimethylamino-benzyl) derivatives of di(imidazolidinylidene)gold(i) salts were polymerized into polyimides by condensation with arene-tetracarboxylic anhydrides. The products are tough, but flexible, and have high glass transition temperatures and high thermal stability. Yellow films of the materials are transparent above 365 nm.279... 

Diorganoboryloxides, R2BO, bearing bulky organic substituents are quasi-alkoxide ligands for main group and transition metals. Because of the 7r-acceptor properties of boron, these anions are weaker 7r-donors than alkoxides, and this is reflected in their structural chemistry. Diethylzinc reacted with the borinic anhydride (9-BBN)20, Scheme 82, to afford the alkylzincboryloxide [EtZnO(9-BBN)]4 129, which also crystallizes in heterocubic form.187... 

The synthesis of poly(anhydride-co-amide)s (Table VII) of various chemistries was pursued by Hartmann and Schulz (1989) as a means of improving biocompatibility and extending the degradation times of polyanhydrides. This work also contains calorimetry data on the thermal transitions and spectroscopic characterization. 

Another important use of solubility parameters is in interpreting the effects of different solvents on the rates of reactions. In a chemical reaction, it is the concentration of the transition state that determines the rate of the reaction. Depending on the characteristics of the transition state, the solvent used can either facilitate or hinder its formation. For example, a transition state that is large and has little charge separation is hindered in its formation by using a solvent that has a high value of S. The volume of activation is usually positive for forming such a transition state which requires expansion of the solvent. A reaction of this type is the esterification of acetic anhydride with ethyl alcohol ... 

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