Stille pyridine

Still another type of adsorption system is that in which either a proton transfer occurs between the adsorbent site and the adsorbate or a Lewis acid-base type of reaction occurs. An important group of solids having acid sites is that of the various silica-aluminas, widely used as cracking catalysts. The sites center on surface aluminum ions but could be either proton donor (Brpnsted acid) or Lewis acid in type. The type of site can be distinguished by infrared spectroscopy, since an adsorbed base, such as ammonia or pyridine, should be either in the ammonium or pyridinium ion form or in coordinated form. The type of data obtainable is illustrated in Fig. XVIII-20, which shows a portion of the infrared spectrum of pyridine adsorbed on a Mo(IV)-Al203 catalyst. In the presence of some surface water both Lewis and Brpnsted types of adsorbed pyridine are seen, as marked in the figure. Thus the features at 1450 and 1620 cm are attributed to pyridine bound to Lewis acid sites, while those at 1540... 

Acyl halides, both aliphatic and aromatic, react with the sodium derivative, but the product depends largely on the solvent used. Thus acetyl chloride reacts with the sodium derivative (E) suspended in ether to give mainly the C-derivative (t) and in pyridine solution to give chiefly the O-derivative (2). These isomeric compounds can be readily distinguished, because the C-derivative (1) can still by enolisation act as a weak acid and is therefore... 

Despite its V excessive character (340), thiazole, just as pyridine, is resistant to electrophilic substitution. In both cases the ring nitrogen deactivates the heterocyclic nucleus toward electrophilic attack. Moreover, most electrophilic substitutions, which are performed in acidic medium, involve the protonated form of thiazole or some quaternary thiazolium derivatives, whose reactivity toward electrophiles is still lower than that of the free base. 

The relationship between the stmcture of a molecule and its physical properties can be understood by finding a quantitative stmcture—property relation- ship (QSPR) (10). A basis set of similar compounds is used to derive an equation that relates the physical property, eg, melting poiat or boiling poiat, to stmcture. Each physical property requires its own unique QSPR equation. The compounds ia the basis set used for QSPRs with pyridines have sometimes been quite widely divergent ia respect to stmctural similarity or lack of it, yet the technique still seems to work well. The terms of the equation are composed of a coefficient and an iadependent variable called a descriptor. The descriptors can offer iasight iato the physical basis for changes ia the physical property with changes ia stmcture. 

The contents of the flask while still hot are poured into a 30-cm. evaporating dish and the alcohol is evaporated on a steam bath. The dry salt is pulverized and thoroughly mixed with 390 g. of calcium oxide, placed in a 2-I. copper retort (Note 3), and heated with the full flame of a Meker burner. The distillate is placed in a distilling flask and heated on a steam bath all material distilling under 90 is removed and discarded. The residue is then allowed to stand over solid potassium hydroxide for twelve hours and is finally fractionated. The dimethyl-pyridine distils at i42-i44°/743 mm. The yield is 35-36 g. or 62-64 per cent of the theoretical amount based on the 3,5-dicarb-ethoxy-2,6-dimethylpyridine, or 30-36 per cent based on the original ethyl acetoacetate. 

The acid/base interaction between the two polymers significantly increases the cohesive strength of the polymer blend at normal use temperatures but at elevated temperature the interaction can be interrupted and the polymer can still be melt processed. Other examples of basic polymers use for crosslinking include polyethylenimines, vinyl pyridine copolymers, and the like. 

In presence of platinum oxide as catalyst in methyl alcohol, it hydrogenates to dihydrowogermine, which darkens >265° and melts at 277-8° (dec.) [a]n ° — 61° (pyridine). The dihydro-base still contains eight... 

Androst-4-ene-3,17-dione. Testosterone (0.58 g, 2 mmoles) is dissolved in a solution prepared from 3 ml of benzene, 3 ml of dimethyl sulfoxide, 0.16 ml (2 mmoles) of pyridine and 0.08 ml (1 mmole) of trifluoroacetic acid. After addition of 1.24 g (6 mmoles) of dicyclohexylcarbodiimide, the sealed reaction flask is kept overnight at room temperature. Ether (50 ml) is added followed by a solution of 0.54 g (6 mmoles) of oxalic acid in 5 ml of methanol. After gas evolution has ceased ( 30 min) 50 ml of water is added and the insoluble dicyclohexylurea is removed by filtration. The organic phase is then extracted twice with 5 % sodium bicarbonate and once with water, dried over sodium sulfate and evaporated to a crystalline residue (0.80 g) which still contains a little dicyclohexylurea. Direct crystallization from 5 ml of ethanol gives androst-4-ene-3,17-dione (0.53 g, 92%) in two crops, mp 169-170°. 

We often speak of the PPP (Pariser-Parr-Pople) model in honour of these three authors. Thinking of the pyridine example above, we still divide the 42 electrons into two groups, the 6 7r-electrons and the 36 o--electrons. The spirit of the PPP model is that the cr-electrons and the atomic nuclei provide a potential for the TT-electrons. Attention focuses on the 7r-electrons. 

Despite the increasing information on the photochemistry of 2,4-dienones and other unsaturated ketones, as well as on the ring-chain valence isomerism of halogen-substituted pyran and dihydi opyran systems,the data are still very scarce. The intermediate formation of pyrans valence-isomeric with unsaturated carbonyl compounds in the pyridine syntheses based on reactions of ammonia with aldehydes or ketones, advocated by various authors (cf. Section II,B,2,f), is still rather speculative. (See also Section II,B,2,e for the valence isomerism of 5-chloro-2,4-dienones with pyrylium chlorides.)... 

The data show that in some cases basicity has a strong influence on reactivity. For example, the reaction of 2-chloropyridine derivatives with piperidine is about 3000 times as fast as that with pyridine the basicity change involved is in the order of 6 pA units. However, piperidine is only 4 times as reactive as morpholine with 2- or 4-chloropyrimidine as the substrate, although -dpAo in these cases is still fairly large, 2.5 units. Furthermore, even the qualitative correlation sometimes fails, and aniline is more reactive than pyridine in contrast to the expectations from their basicities. 

A similar kinetic effect was reported for the reaction of 4-chloro-pyridine 1-oxide with methoxide ion at 50°, and still larger effects were obtained with the 2- and 3-isomers at the same temperature. ... 

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