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Question

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Answers

SYNTHETIC APPLICATIONS OF FRIEDEL-CRAFTS ACYLATIONS: THE CLEMMENSEN AND WOLFF-KISHNER REDUCTIONS Rearrangements of the carbon chain do not occur in Friedel-Crafts acylations. The acylium ion, because it is stabilized by resonance, is more stable than most other carbocations. Thus, there is no driving force for a rearrangement. Because rearrangements do not occur, Friedel-Crafts acylations followed by reduction of the carbonyl group to a $\mathrm{CH}_{2}$ group often give much better routes to unbranched alkylbenzenes than do FriedelCrafts alkylations. The carbonyl group of an aryl ketone can be reduced to a CH $_{2}$ group. (FIGURE CANNOT COPY) As an example, let us consider the problem of synthesizing propylbenzenc. If we attempt this synthesis through a Friedel-Crafts alkylation, a rearrangement occurs and the major product is isopropylbenzene (see also Practice Problem 15.4 ): (FIGURE CANNOT COPY) Isopropylbenzene (major product) Propylbenzene (minor product) By contrast, the Fricdel-Crafts acylation of benzene with propanoyl chloride produces a ketone with an unrearranged carbon chain in excellent yield: (FIGURE CANNOT COPY) Propanoyl chloride Ethyl phenyl ketone $(90 \%)$ This ketone can then be reduced to propylbenzenc by scveral methods, including the Clemmensen reduction (Sect. $15.7 \mathrm{A}$ ) and the Wolff-Kishner reduction (Sect. $15.7 \mathrm{B}$ ). A The Clemmensen Reduction One general method for reducing a ketone to a methylene group-called the Clemmensen reduction- consists of refluxing the ketone with hydrochloric acid containing amalgamated zinc. [Caution: As we shall discuss later (Scction $20.4 \mathrm{B}$ ), zinc and hydrochloric acid will also reduce nitro groups to amino groups.] A Clemmensen reduction (FIGURE CANNOT COPY) Ethyl phenyl ketone Propylbenzene $(80 \%)$ In general, (FIGURE CANNOT COPY) B The Wolff-Kishner Reduction Another method for reducing a ketone to a methylene group is the Wolff-Kishner reduction, which involves heating the ketone with hydrazine and base. The Wolff-Kishner reduction complements the Clemmensen reduction in that it is conducted under basic conditions, whereas the Clemmensen reduction involves acidic conditions. The WolffKishner reduction proceeds via a hydrazone intermediate (Section $16.8 \mathrm{B}$ ) that is not isolated during the reaction. Ethyl phenyl ketone can be reduced to propylbenzene by the Wolff-Kishner reduction as follows, for example. A Wolff-Kishner reduction
(FIGURE CANNOT COPY) Hydrazone intermediate (see Section $16.8 B)$ When cyclic anhydrides are used as one component, the Fricdel-Crafts acylation providcs a means of adding a new ring to an aromatic compound. One illustration is shown here. Note that only the ketone is reduced in the Clemmensen reduction step. The carboxylic acid is unaffected. The same result can be achicved using the Wolff-Kishner reduction. (FIGURE CANNOT COPY) Benzene (excess) Succinic anhydride 3-Benzoylpropanoic acid (FIGURE CANNOT COPY) 4-Phenylbutanoic acid 4-Phenylbutanoyl chloride $\alpha$ -Tetralone Starting with benzene and the appropriate acyl chloride or acid anhydride, outline a synthesis of each of the following: a. Butylbenzene b. (FIGURE CANNOT COPY) c. (FIGURE CANNOT COPY) Diphenylmethane d. (FIGURE CANNOT COPY) 9,10 -Dihydroanthracene THE CHEMISTRY OF... DDT Aryl Halides as Insecticides Insects, especially mosquitoes, fleas, and lice, have been responsible for innumerable human deaths throughout history. The bubonic plague or "black death" of medieval times that killed nearly one-third of Europe's population was borne by fleas. Malaria and yellow fever, diseases that were responsible for the loss of millions of lives in the twentieth century alone, are mosquito-borne diseases. One compound widely known for its insecticidal properties and environmental effects is DDT $[1,1,1$ -trichloro-2, 2-bis(4-chlorophenyl)ethane]. (FIGURE CANNOT COPY) DDT $[1,1,1$ -trichloro-2, 2- bis(4-chlorophenyl)ethane] From the early 1940 s through the early 1970 s, when its use was banned in the United States, vast quantities of DDT were sprayed over many parts of the world in an effort to destroy insects. These efforts rid large areas of the world of disease-carrying insects, especially those responsible for malaria, yellow fever, sleeping sickness (caused by tsetse flies), and typhus. Though it has since re surged, by $1970,$ malaria had been largely eliminated from the developed world. According to estimates by the National Academy of Sciences, the use of DDT during that time had prevented more that 500 million deaths from malaria alone. (IMAGE CANNOT COPY) DDT Eventually it began to become clear that the prodigious use of DDT had harmful side effects. Aryl halides are usually highly stable compounds that are only slowly destroyed by natural processes. As a result they remain in the environment for years; they are what we now call "persistent insecticides" or "hard insecticides." The U.S. Environmental Protection Agency banned the use of DDT beginning in 1973. Aryl halides are also fat soluble and tend to accumulate in the fatty tissues of most animals. The food chain that runs from plankton to small fish to birds and to larger animals, including humans, tends to magnify the concentrations of aryl halides at each step. The chlorohydrocarbon DDT is prepared from inexpensive starting materials, chlorobenzene and trichloroacetaldehyde. The reaction, shown here, is catalyzed by acid. (FIGURE CANNOT COPY) DDT [1.1,1-trichloro-2,2bis(4-chlorophenyl)ethane] Estimates indicate that nearly 1 billion pounds of DDT were spread throughout the world ecosystem. One pronounced environmental effect of DDE, after conversion from DDT, has been in its action on eggshell formation in many birds. DDE inhibits the enzyme carbonic anhydrase that controls the calcium supply for shell formation. As a consequence, the shells are often very fragile and do not survive to the time of hatching. During the late 1940 s the populations of eagles, falcons, and hawks dropped dramatically. There can be little doubt that DDT was primarily responsible. DDE also accumulates in the fatty tissues of humans. Although humans appear to have a short-range tolerance to moderate DDE levels, the long-range effects are uncertain. Study Problem 1
The mechanism for the formation of DDT from chlorobenzene and trichloroacetaldehyde in sulfuric acid involves two electrophilic aromatic substitution reactions. In the first electrophilic substitution reaction, the electrophile is protonated trichloroacetaldehyde. In the second, the electrophile is a carbocation. Propose a mechanism for the formation of DDT. Study Problem 2 What kind of reaction is involved in the conversion of DDT to DDE?

Explain why the connection without good excites and we've been excited. It's two different products. Let's look at the mechanism with our without backsides but the Nation actress first step and it produces Benzie like Come Pick a Time which is further stabilized by untraditional. Were fifteens in it in, for instance. Oh, structure was shows conjugation and this camera car time is most stable with public art time at this common, which is making conjugation with the benzene in. That's why this the assured direction off the reaction and a combination with BR minus gives you the major product in the prisons or both sides they have taken. Spacious is different. That's the radical of woman and unethical of woman. Also wants toe form Benzia political fishhook, and it's, ah, most able than medical at this carbon. For the same reason that would be liking education off the benzene green. And then on the next step over chain propagation, the medical reacts with them. HBR Junior is another. They are dark and gives the product

So this is a long problems, so I'll throw on some basic first. So what this is going on about is there are different combinations of proteins that they are testing. In this experiment, thes exists as timers, meaning that the T one are one is a single protein, and we're saying it's bound to another single protein, and these come as a complex. So these are an example of the kind of die MERS we're talking about. Will say It's a T one R one protein, and it's bound to a T. One are, too. There's, too, so it makes a single diver. The response. Onley happens because thes two proteins air together, and they do not exist in the membrane as a single protein, eliciting a response. The other thing they're doing is they are knocking out the presence of these proteins in the mice. So what they're doing is there finding the genes that produce these proteins. It's a one, and they're making different kinds of mice that don't have these proteins. So what they're doing is they're knocking out, so they're preventing these proteins from being made. One of each of t one are won t one are two and T one r three, and they have a special fourth mouse where they knock out both t two t one are two and t one r three. So in problem A, they're proposing to different models for how our taste receptors work. They're saying that there is a cell model and that there's a receptor based model based on how our tastes work. The cell model is saying that we have taste cells, and each of these taste cells has one specific type of dime. Er. So we're saying this first cell has a t one are one and we'll see a T one are two receptor and no other kind of diver. A different tastes cell. We'll say we'll have ah t one are one and a T one r three. These each has specific different types of cells. So we're saying that the tastes thes different cells react. Thio will be different and independent. The other kind of model they're proposing is that each of our taste cells have multiple sets of those dime er's. So they're gonna have each combination of these, and the signal it sends out is going to change based on which receptor for which timer is activated. So it's gonna have the whole mixture of these reactions. It's going to be the whole compilation of these different proteins in their giant reforms. So it's They're noting that in previous work they took individual cells and they isolated them, and they probably ran a gel electrophoresis to see what kind of proteins they could find from each cell. So they ran multiple gels, and they found out that between different cells taste cells, they had different proteins. So we're going to say this one did not have the t one are, too, and this one do not have the t one r three. So since we're finding cells that do not have a mixture of all of the proteins, and they each Onley have certain types of proteins, the previous research they've done supports the cell theory where each taste cell is different in their protein contents, rather than containing all the dimmer combinations at once. Problem being, they're testing the different types of taste. They're testing salt. They're testing bitter. They're tasting you, mommy, which is kind of like the flavorful nous you find your needs and they're tasting sweet. So they're testing them on knockout mice. Um, you'll remember that the t two t one are too 21 r three is responsible for sweet and the t one are one. T one r three is responsible for you, Mommy. So in the knockout mice they've had where they've knocked out, say the combinations of these proteins all those knockout mice. Even if they don't have these special combinations of diners in them, they can still taste salt and bitter. This is kind of proposing that even without those special dimmers, you're still able toe perceived those different tastes of salt and bitter. This means that all our tastes aren't dependent on the timer's that were knocked out in this representation and experiment in part C. They're showing us a graph of the response for a new mommy taste and knock out mice where if you eliminate either t one r three or if you knock out t one our wine, you're not going to get any response our extra licking from an umami flavor. You'll also note that for the controls and the experiment, they used I m p to increase the flavor of umami, and they used a melon I'd to reduce the salty flavor. This is just toe help control the licking the mice might dio for the ingredient they used to prevent the vice from liking it due to a salty flavor. They're controlling it so that Onley the umami flavors what the mice are gonna lick for. So for this model, it's more representing that mommy has to exist in the dime. Reform of tea one are one T. One R three To get any sense of umami flavor. If you knock out either of these proteins, you can't taste umami. So this is applicant to both cell models because regardless of whether the actual sell, your experimenting on has just the t one are won t one r three for a mommy or has the mixture of all the different dime er's. If you knock out either of these two proteins that make up the dime. Er, you're not going to get any response of umami from either of them. So you know that Mommy has to come in the diamond form, and regardless of whether the diamond exists in just one type of cell or exists in all type of taste, cells. You're not going to get a response if you remove that diamond. Okay, Part E were given another model for a sweet taste. This one's a little bit different than your mommy. Um, here you have the wild type or the t one are one wild type. Just means none of the proteins have been removed, so they have all the different types to u one R one t one are two and t one are three, so they're just normally born, not genetically modified. The other lines represent the removal of t. One are two on lee T one are three on lee and both t one are too t one are three that make up the sweet flavor timer. This model is more representing that. If you remove any of these processes, T one are two or tty one r three. You're still not going to get as much of a sweet flavor. So again, you pretty much have to have the dime er to get that full sweet flavor taste. And if you knock out either one of those proteins, your ability to check tech these flavors is greatly reduced. The only difference here is that the X axis measures the concentration of the material and at very high concentrations, you can perceive the flavor of sweet to a small extent as long as you have either the T one are two or the t. One are three present. So even if for some reason you can't make the diamond for it if you have t one are too. You can still purse. We've seat suite, which is unexpected. That kind of it's a lot different than the umami, where you must have both in order to perceive the taste. So moving on to part F here we have perceiving the taste of sucrose as sweet. Um, this was what I was referring to earlier. If you don't have both of the proteins, T one are two and t one are three. You can't persuade sweet it all, but it's unusual that if you have just a single of one of the proteins, it doesn't have to exist in the diet reform. It can somehow exist, probably with a T. One are, too, and some other sort of protein that they're not testing in this experiment. Lastly, in part G there, substituting kind of the flavors that are being perceived. They're using tetracycline, which is an antibiotic, so it's not gonna have any kind of particular flavor. They're using it to substitute a sweet taste, and they're not going to use any kind of sweet ingredient. Instead, what they're doing is they're altering the protein so that when you apply Tetra cycling to the dime er you're going to purse, we've it perceive it as a sweet flavor rather than no flavor at all. In this circumstance, it is kind of proving that you don't need specific substrates. Are substances to stimulate the diner protein to get the response you'd expect? And it's saying that you can use other substances instead to trigger the response. That's kind of not what they're going for the experiment. But it still manages to prove what the scientists are thinking because as long as you stimulate the dime er, regardless of what you give to it, it's going to trigger response that your brain perceives as flavor. So it's saying that although our dime er's may not need a certain sweet flavor in order to send a signal, it's saying that you need a signal to perceive the taste of sweet. If there's no signal sent by the protein, you're not going to get that flavor being perceived


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