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E1cB Mechanism Reaction The E1cB mechanism has the same features as the E2 mechanism except that proton abstraction by the base proceeds essentially to completion prior to departure of the leaving group A variant of this mechanism may intervene whenever the leaving group is a poor leaving group or an exceptionally stable carbanion may be formed (ie, due to the presence of Z substituents in addition to the polar s bond and/or a hybridization e ect) The factors which lead to stabilization of carbanions have been discussed in 7 E1 Elimination Reaction The rate-determining step of the E1 elimination reaction is precisely the same as previously discussed for the SN 1 reaction The interaction diagram for the C H bond and an adjacent carbocationic center is shown in Figure 106b.



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Because the s and s C H bond orbitals are equally spaced relative to the energy of the p orbital at the cationic site, the LUMO energy is approximately the same as the energy of the unperturbed cationic p orbital Reactivity with Lewis bases remains very high but is reduced somewhat by delocalization of the orbital (smaller coe cient on the p orbital) Notice that the presence of the adjacent C H bond results in stabilization of the carbocation by a lowering of the energy of the sCH orbital Concomitant delocalization of the C H bonding electrons is accompanied by weakening of the C H bond and partial bond formation between the H and the C at the cationic site Hydride transfer may result if this is energetically favorable The most probable course of the reaction with a Lewis base is formation of a s bond at the cationic site.





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In nature, our eyes perceive pigments according to the subtractive color model. Sunlight contains every visible color found on Earth. When sunlight is projected on an object, the object absorbs (subtracts) some of the light and reflects the rest. The reflected light is the color you see. For example, a fire engine is bright red because it absorbs all non-red meaning all blue and green from the white-light spectrum. Pigments on a sheet of paper work the same way. You can even mix pigments to create other colors. Suppose you paint a red brush stroke, which absorbs green and blue light, over a blue brush stroke, which absorbs green and red light. You get a blackish mess with only a modicum of blue and red light left, along with a smidgen of green because the colors weren t absolutely pure. But wait every child knows red and blue mix to form purple. So what gives What gives is that what you learned in elementary school is only a rude approximation of the truth. Did you ever try mixing a vivid red with a canary yellow only to produce an ugly orange-brown glop The reason you didn t achieve the bright orange you wanted is because red starts out darker than bright orange, which means you must add a great deal of yellow before you arrive at orange. And even then, the yellow had better be an incredibly bright lemon yellow, not some deep canary yellow with a lot of red in it.

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However, there is a possibility of attack at the H end of the C H bond, and this mode may be enhanced if the base is a ``good'' Lowry Bronsted base (forms a strong bond to H) Both addition of the nucleophile to C and proton abstraction are reversible The equilibrium may often be channeled toward proton abstraction by removal of the more volatile ole n by distillation..

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Domain/Key Normal Form makes a database provably immune to data anomalies, but it can be tricky to implement and it s not usually necessary. The higher levels of normalization may also require you to split tables into many pieces, making it harder and more time-consuming to reassemble the pieces when you need them.

N o t all of the techniques for improving customer satisfaction rely on additional expense: online booksellers are a prime example of sites that effectively act as brokers. They may not physically o w n the millions of books available on the site (as a conventional bookstore would have to), but they can offer the product and a reliable, competitive service nonetheless. This example also highlights the advantage of thinking innovatively by focusing on customers.

FIGURE 9.26. Ronchi Hartmann null test, (a) Ronchi-Hartmann screen in front of the surface under test, (b) Observed null fringe pattern. (From Cordero-Davila, et al., 1990.)

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