Backside

The acoustical device component is placed in water and is configured like a conventional impulse echo equipment. The ultrasound wave passed the delay path and enters the specimen container through a very thin plastic window. The backside of the container is a steel plate and will also be used as a reference reflector to measure pn. 

EIR Enhanced IR [202] Reflection from backside of Enhanced sensitivity... 

Rotor Seals To balance the thrust on the rotor, usually there are one or two labyrinth-type seals on the rotor. These seals often are damaged if there is dust in the incoming fluid or gas, and wear on the backside seal causes serious upsets in thrust-bearing loads. Provisions are available for coUecting and disposing of the dust which tends to accumulate in the seal so as to protect the seal from serious erosion. 

If the addition of Br to the alkene results in a bromonium ion, the anti stereochemistry can be readily eiqilained. Nucleophilic ring opening by bromide ion would occur by backside attack at carbon, with rupture of one of the C—Br bonds, giving overall anti addition. 

Release coatings are important components of pressure sensitive adhesive (PSA) products such as tapes and labels [1]. Release materials are coated onto the backside of PSA tape backings (often called low adhesion backsizes or LABs in this form) to provide the desired tape roll unwind force. They are also coated onto various substrates to form release liners for PSA products such as labels and transfer tapes. Typically the thickness of the release coating is less than 1 p,m, and often times less than 0.1 jLm. Release coatings can be thought of as the PSA delivery system, providing a controlled unwind or release force and protecting the adhesive from contamination and unintentional contact until it is applied. 

The introduction of water, or air to a lesser extent, from the backside of flexible membranes reduces chamber volume and squeezes the cake yielding a further lowering of the moisture content. The filter press may be arranged as a mixed pack of flush and membrane plates, full flush or full membrane pack depending on the application. 

When pressure reaches 6-7 bars the cake is presqueezed for even distribution by pumping water to the backside of the membranes. 

Epoxidation of the A -enol acetate was originally carried out with per-benzoic acid. Monoperphthalic acid has also been used, but is apparently more susceptible to steric and conformational factors. The commercially available peracetic acid is generally most convenient. Based on the expected backside attack, the derived epoxides have the 17a configuration, and hydrolysis always produces the 17a-hydroxy group. 

Although this is a secondary substrate, complete shielding from backside attack by nucleophiles leads to S l solvolysis without solvent participation. The correspond-... 

One after the other, step through (or animate) the sequence of structures depicting the SN2 and proton transfer reactions shown above. Compare the two. From what direction does cyanide approach the hydrogen in HCl From the same side as Cl ( frontside ), or from the other side ( backside ) Does the Sn2 reaction follow a similar trajectory ... 

Sn2 reactions proceed with inversion at the electrophilic carbon. This suggests that the nucleophile attacks from the backside of carbon, i.e., the side of carbon furthest away from the leaving group. 

Backside attack may be favored for electrostatic reasons. Examine electrostatic potential maps fox bromide + methyl bromide frontside attack and bromide + methyl bromide backside attack, transition states involving frontside and backside attack of Br (the nucleophile) onto CHsBr, respectively. Which atoms in the transition states are most electron-rich Which trajectory better minimizes electrostatic repulsion ... 

Backside attack may be favored in order to facilitate transfer of nonbonding electrons from the nucleophile into the electrophile s lowest-unoccupied molecular orbital (LUMO). Efficient electron transfer requires maximal overlap of the LUMO and the donor orbital (usually a nonbonded electron pair on the nucleophile). Examine the LUMO of methyl bromide. How would a nucleophile have to approach in order to obtain the best overlap Is your answer more consistent with preferential backside or frontside attack ... 

Electrostatic potential map for bromide+methyl bromide backside attack shows most negatively-charged regions (in red) and less negatively-charged regions (in blue). 

Examine space-filling models of ethyl bromide and 2-methyl-2-propyl bromide. Given that Sn2 reactions require backside attack, which of these is more likely to react with EtO in an Sn2 fashion What will the product be What E2 products would be obtained from each alkyl bromide ... 

Electrostatic interactions can guide alkylation under certain conditions. Examine the electrostatic potential map of the potassium enolate of ethyl acetoacetate. Is carbon or oxygen more electron rich Are electrostatic interactions likely to favor addition of oxygen or carbon Examine atomic charges and electrostatic potential maps for diethylsulfate, ethyl chloride, ethyl bromide and ethyl iodide, pay attention to the backside of the electrophilic carbon. Order the systems from most to least electron poor. Which reaction is most likely to be guided by electrostatics Least likely Can the experimental results be fully explained on this basis ... 

Now, examine the orbital on cyclohexanone lithium enolate most able to donate electrons. This is the highest-occupied molecular orbital (HOMO). Identify where the best HOMO-electrophile overlap can occur. Is this also the most electron-rich site An electrophile will choose the best HOMO overlap site if it is not strongly affected by electrostatic effects, and if it contains a good electron-acceptor orbital (this is the lowest-unoccupied molecular orbital or LUMO). Examine the LUMO of methyl iodide and trimethylsilyl chloride. Is backside overlap likely to be successful for each The LUMO energies of methyl iodide and trimethylsilyl chloride are 0.11 and 0.21 au, respectively. Assuming that the lower the LUMO energy the more effective the interaction, which reaction, methylation or silylation, appears to be guided by favorable orbital interactions Explain. 

The synchronous bimolecular mechanism for aromatic nucleophilic substitution involves unfavorable geometry (bonds made and broken are both in the plane of the ring and backside attack is not possible) and unfavorable energetics (one high-energy step is required... 

Reducing the pressure acting on the fluid behind the impeller can be accomplished by two different methods, or a combination of both, on an open-impeller unit. One method is where small pumping vanes are cast on the backside of the impeller. The other method is for balance holes to be drilled through the impeller to the suction eye. 

Cause of failure Belt has evenly spaced deep bottom cracks from use of substandard backside idler (Figure 58.13). 

Action required Replace backside idler with one that is in accordance with the minimum size recommendation. 

The one general exception to the rule that ethers don t typically undergo Sn2 reactions occurs with epoxides, the three-membered cyclic ethers that we saw in Section 7.8. Epoxides, because of the angle strain in the three-membered ring, are much more reactive than other ethers. They react with aqueous acid to give 1,2-diols, as we saw in Section 7.8, and they react readily with many other nucleophiles as well. Propene oxide, for instance, reacts with HC1 to give l-chloro-2-propanol by Snj2 backside attack on the less hindered primary carbon atom. We ll look at the process in more detail in Section 18.6. 

How- does this reaction take place Although it appears superficially similar to the SN1 and S 2 nucleophilic substitution reactions of alkyl halides discussed in Chapter 11, it must be different because aryl halides are inert to both SN1 and Sj 2 conditions. S l reactions don t occur wdth aryl halides because dissociation of the halide is energetically unfavorable due to tire instability of the potential aryl cation product. S]sj2 reactions don t occur with aryl halides because the halo-substituted carbon of the aromatic ring is sterically shielded from backside approach. For a nucleophile to react with an aryl halide, it would have to approach directly through the aromatic ring and invert the stereochemistry of the aromatic ring carbon—a geometric impossibility. 

Backside displacement is sterically blocked therefore, no SN2 reaction. 

Epoxides are cleaved by treatment with acid just as other ethers are, but under much milder conditions because of ring strain. As we saw in Section 7.8, dilute aqueous acid at room temperature is sufficient to cause the hydrolysis of epoxides to 1,2-diols, also called vicinal glycols. (The word vicinal means "adjacent/ and a glycol is a diol.) The epoxide cleavage takes place by SK2-like backside attack of a nucleophile on the protonated epoxide, giving a trans- 1,2-dio) as product. 

The mechanisms of these acid-catalyzed epoxide openings are more complex than they at first appear. They seem to be neither purely SN1 nor SN2 but instead to be midway between the two extremes and to have characteristics of both. Take the reaction of 1,2-epoxy-l-methylcyclohexane with HBr shown in Figure 18.2, for instance. The reaction yields only a single stereoisomer of 2-bromo-2-methyl-cyclohexanol in which the —Br and —OH groups are trans, an S 2-li.ke result caused by backside displacement of the epoxide oxygen. But the fact that Br attacks the more hindered tertiary side of the epoxide rather than the less hindered secondary side is an SN1 -like result in which the more stable, tertiary carbocation is involved. 

Evidently, the transition state for acid-catalyzed epoxide opening has an Sn2 -like geometry but also has a large amount of S]v-l-like carbocationic character- Since the positive charge in the protonated epoxide is shared by the more highly substituted carbon atom, backside attack of Br- occurs at the more highly substituted site. 

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