Double product definition

Very little is known about the structure of the cured polyester resin. The products definitely belong in the thermoset class. There is some correlation between maximum physical properties a nd a molar ratio of 1 1 between double bonds in the alkyd and monomer. However, this is not critical and simple cross-linking does not tell the full story. The styrene monomer can be present in twice the molar amount needed, and yet complete copolymerization takes place without apparent formation of styrene polymer. 

It was anticipated all along that the vinylsilane residue could serve as a vinyl iodide surrogate. After protection of the C-14 secondary hydroxyl in 180 in the form of a triisopropylsilyl ether, the vinyltrimethylsilyl function can indeed be converted to the requisite vinyl iodide with AModosuccinimide (NIS) (see 180—>181, Scheme 43). Vinyl iodide 181 is produced stereospecifically with retention of the A17,18 double bond geometry. This transformation is stereospecific since the stereochemistry of the starting vinylsilane and the vinyl iodide product bear a definite relationship to each other.67b 75... 

The study of optical isomers has shown a similar development. First it was shown that the reduction potentials of several meso and racemic isomers were different (Elving et al., 1965 Feokstistov, 1968 Zavada et al., 1963) and later, studies have been made of the ratio of dljmeso compound isolated from electrolyses which form products capable of showing optical activity. Thus the conformation of the products from the pinacolization of ketones, the reduction of double bonds, the reduction of onium ions and the oxidation of carboxylic acids have been reported by several workers (reviewed by Feokstistov, 1968). Unfortunately, in many of these studies the electrolysis conditions were not controlled and it is therefore too early to draw definite conclusions about the stereochemistry of electrode processes and the possibilities for asymmetric syntheses. 

Since Huisgen s definition of the general concepts of 1,3-dipolar cycloaddition, this class of reaction has been used extensively in organic synthesis. Nitro compounds can participate in 1,3-dipolar cycloaddition as sources of 1,3-dipoles such as nitronates or nitroxides. Because the reaction of nitrones can be compared with that of nitronates, recent development of nitrones in organic synthesis is briefly summarized. 1,3-Dipolar cycloadditions to a double bond or a triple bond lead to five-membered heterocyclic compounds (Scheme 8.12). There are many excellent reviews on 1,3-dipolar cycloaddition, in particular, the monograph by Torssell covers this topic comprehensively. This chapter describes only recent progress in this field. Many papers have appeared after the comprehensive monograph by Torssell. Here, the natural product synthesis and asymmetric 1,3-dipolar cycloaddition are emphasized.630 Synthesis of pyrrolidine and -izidine alkaloids based on cycloaddition reactions are also discussed in this chapter. 

An interesting pericyclic-anionic-pericyclic domino reaction showing a high stereoselectivity is the cycloaddition-aldol-retro-ene process depicted in scheme 20.1581 The procedure presumably starts with a [4+2]-cycloaddition of diene 98 and S02 in presence of a Lewis acid. After opening of the formed adduct reaction with (Z)-silyl vinyl ether 99 leads to a mixture of alk-2-enesulfinic acids 101. It follows a retro-ene reaction which affords a 7 3 mixture of the products 102 and 103. The reaction described by Vogel et al is a nice example for the efficient generation of polypropionate chains with the stereoselective formation of three stereogenic centers and one (0-double bond in a three-component domino reaction in its strict definition. 

Oxidation indices, 656-72 peroxide determination, 762-3 peroxide value, 656, 657-64 colorimetry, 658-61 definition, 657 direct titration, 657 electrochemical methods, 663-4 IR spectrophotometry, 661-3 NIR spectrophotometry, 663 UV-visible spectrophotometry, 658-61 secondary oxidation products, 656, 665-72 tests for stability on storage, 664-5, 672 thermal analysis, 672 Oxidative amperometiy, hydroperoxide determination, 686 Oxidative cleavage alkenes, 1094-5 double bonds, 525-7 Oxidative couphng, hydrogen peroxide determination, 630, 635 Oxidative damage... 

Enantioselective (enzymatic) cyclization of 1 could lead to either enantiomer 2 a or 3 a, depending on which face of the internal double bond is attacked at C-6 by the cation derived from the allylic pyrophosphate unit. Re- or Si-face cyclization (see the detailed discussion in Section 4.3.4.1.2.1., p 442 of 1 b would, however, lead to the diastereomers 2b and 3b. respectively. A thorough analysis of the NMR spectrum of the cyclization product of 1 b definitely showed that 2b was formed thus proving the absolute configuration of (-)-fl-irans-berga-motene to be 2a185. 

This is a simple double replacement reaction (see Chapter 8 for an introduction to these types of reactions). A hydrogen ion from water switches places with the sodium of sodium carbonate to form the products carbonic acid and sodium hydroxide. By the Bronsted-Lowry definition, water is the acid because it donates its hydrogen to Na2COj. This makes Na2C03 the base because it accepts the hydrogen from H2O. 

Note that reactions 2.14, 2.15, and 2.23 involve fractional stoichiometric coefficients on the left-hand sides. This is because we wanted to define conventional enthalpies of formation (etc.) of one mole of each of the respective products. However, if we are not concerned about the conventional thermodynamic quantities of formation, we can get rid of fractional coefficients by multiplying throughout by the appropriate factor. For example, reaction 2.14 could be doubled, whereupon AG° becomes 2AG, AH° = 2AH , and AS° = 2ASf, and the right-hand sides of Eqs. 2.21 and 2.22 must be squared so that the new equilibrium constant K = K2 = 1.23 x 1083 bar-3. Thus, whenever we give a numerical value for an equilibrium constant or an associated thermodynamic quantity, we must make clear how we chose to define the equilibrium. The concentrations we calculate from an equilibrium constant will, of course, be the same, no matter how it was defined. Sometimes, as in Eq. 2.22, the units given for K will imply the definition, but in certain cases such as reaction 2.23 K is dimensionless. 

Olefins can add to double bonds in a reaction different from those discussed in 5-15, which, however, is still formally the addition of RH to a double bond. This reaction is called the ene synthesis44,1 and bears a certain similarity to the Diels-Alder reaction (5-47). For the reaction to proceed without a catalyst, one of the components must be a reactive dienophile (see 5-47 for a definition of this word) such as maleic anhydride, but the other (which supplies the hydrogen) may be a simple alkene such as propene. There has been much discussion of the mechanism of this reaction, and both concerted pericyclic (as shown above) and stepwise mechanisms have been suggested. The reaction between maleic anhydride and optically active PhCHMeCH=CH2 gave an optically active product,441 which is strong evi-... 

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