A diacid
A polyester
There are two main classes of synthetic polymers: chain-growth polymers and step-growth polymers. The polyethylene and other alkene and diene polymers that we saw in Section 8.10 and Section 14.6 are called chain-growth polymers because they are produced in chain-reaction processes. An initiator adds to a $\mathrm{C}=\mathrm{C}$ bond to give a reactive intermediate, which adds to a second alkene molecule to produce a new intermediate, which adds to a third molecule, and so on. By contrast, polyamides and polyesters are step-growth polymers because each bond in the polymer is formed independently in a discrete step, often the nucleophilic acyl substitution reaction of a carboxylic acid derivative. Some commercially important step-growth polymers are shown in TABLE 21.2.


Acetyl CoA - 21.9 Polyamides and Polyesters: Step-Growth Polymers

TABLE 21.2 Some Common Step-Growth Polymers and Their Uses


| Monomers | Structure | Polymer | Uses |
| :---: | :---: | :---: | :---: |
| Adipic acid <br> Hexamethylenediamine | <smiles>O=CCCCCC[Ca]=O</smiles> $\mathrm{H}_{2} \mathrm{NCH}_{2} \mathrm{CH}_{2} \mathrm{CH}_{2} \mathrm{CH}_{2} \mathrm{CH}_{2} \mathrm{CH}_{2} \mathrm{NH}_{2}$ | Nylon 66 | Fibers, clothing, tire cord |
| Dimethyl terephthalate | <smiles>COC(=O)c1ccc(C(=O)OC)cc1</smiles> | Dacron, Mylar, Terylene | Fibers, clothing, films, tire cord |
| Ethylene glycol | $\mathrm{HOCH}_{2} \mathrm{CH}_{2} \mathrm{OH}$ |  |  |


TABLE 21.2 Some Common Step-Growth Polymers and Their Uses
Monomers


Polyamides (Nylons) -

The best known step-growth polymers are the polyamides, or nylons, first prepared in 1930 by Wallace Carothers at the DuPont Company by heating a diamine with a diacid. For instance, nylon 66 is prepared by reaction of adipic acid (hexanedioic acid) with hexamethylenediamine (1,6-hexanediamine) at $280{ }^{\circ} \mathrm{C}$. The designation " 66 " indicates the number of carbon atoms in the diamine (the first 6 ) and the diacid (the second 6).
![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-0763.jpg?height=459&width=1001&top_left_y=1619&top_left_x=562)


Polyamides (Nylons) -

Nylons are used both in engineering applications and in making fibers. A combination of high impact strength and abrasion resistance makes nylon an excellent metal substitute for bearings and gears. As fiber, nylon is used in a variety of applications, from clothing to tire cord to ropes.


Polyesters -

The most generally useful polyester is made by reaction between dimethyl terephthalate (dimethyl 1,4-benzenedicarboxylate) and ethylene glycol (1,2-ethanediol). The product is used under the trade name Dacron to make clothing fiber or tire cord and under the name Mylar to make recording tape. The tensile strength of poly(ethylene terephthalate) film is nearly equal to that of steel.
![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-0764.jpg?height=375&width=1387&top_left_y=187&top_left_x=369)


Polyesters -

Lexan, a polycarbonate prepared from diphenyl carbonate and bisphenol A, is another commercially valuable polyester. Lexan has an unusually high impact strength, making it valuable for use in bicycle helmets and laptop cases.
![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-0764.jpg?height=583&width=1218&top_left_y=695&top_left_x=448)


Sutures and Biodegradable Polymers -

Because plastics are too often thrown away rather than recycled, much work has been carried out on developing biodegradable polymers, which can be broken down rapidly in landfills by soil microorganisms. Among the most common biodegradable polymers are poly(glycolic acid) (PGA), poly(lactic acid) (PLA), and poly(hydroxybutyrate) (PHB). All are polyesters and are therefore susceptible to hydrolysis of their ester links. Copolymers of PGA with PLA have found a particularly wide range of uses. A 90/10 copolymer of poly(glycolic acid) with poly(lactic acid) is used to make absorbable sutures, for instance. The sutures are entirely hydrolyzed and absorbed by the body within 90 days after surgery.
<img class="imgSvg" id = "m6sn3p323m2zda2u629" src="data:image/svg+xml;base64,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"/>


Sutures and Biodegradable Polymers -

Glycolic acid
![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-0764.jpg?height=212&width=199&top_left_y=1932&top_left_x=589)


Sutures and Biodegradable Polymers -


Sutures and Biodegradable Polymers -

Poly(hydroxybutyrate)


Sutures and Biodegradable Polymers -

In Europe, interest has centered particularly on poly(hydroxybutyrate), which can be made into films for packaging as well as into molded items. The polymer degrades within four weeks in landfills, both by ester hydrolysis and by an E1cB elimination reaction of the oxygen atom $\beta$ to the carbonyl group. The use of poly(hydroxybutyrate) is limited at present by its cost-about four times that of polypropylene.


Sutures and Biodegradable Polymers -

PROBLEM Draw structures of the step-growth polymers you would expect to obtain from the following
21-23 reactions:
(a)
![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-0765.jpg?height=71&width=749&top_left_y=211&top_left_x=482)
(b)
![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-0765.jpg?height=75&width=826&top_left_y=296&top_left_x=484)
(c)
![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-0765.jpg?height=115&width=643&top_left_y=382&top_left_x=481)


Sutures and Biodegradable Polymers -

PROBLEM Kevlar, a nylon polymer prepared by reaction of 1,4-benzenedicarboxylic acid (terephthalic acid)
21-24 with 1,4 -benzenediamine ( $p$-phenylenediamine), is so strong that it's used to make bulletproof vests. Draw the structure of a segment of Kevlar.


Sutures and Biodegradable Polymers - 21.10 Spectroscopy of Carboxylic Acid Derivatives


Infrared Spectroscopy -

All carbonyl-containing compounds have intense IR absorptions in the range 1650 to $1850 \mathrm{~cm}^{-1}$. As shown in TABLE 21.3 the exact position of the absorption provides information about the specific kind of carbonyl group. For comparison, the IR absorptions of aldehydes, ketones, and carboxylic acids are included in the table, along with values for carboxylic acid derivatives.


Infrared Spectroscopy -

TABLE 21.3 Infrared Absorptions of Some Carbonyl Compounds


Infrared Spectroscopy -

| Carbonyl type | Example | Absorption $\left(\mathrm{cm}^{\mathbf{- 1}}\right)$ |
| :--- | :--- | :--- |
| Saturated acid chloride | Acetyl chloride | 1810 |
| Aromatic acid chloride | Benzoyl chloride | 1770 |
| Saturated acid anhydride | Acetic anhydride | 1820,1760 |
| Saturated ester | Ethyl acetate | 1735 |
| Aromatic ester | Ethyl benzoate | 1720 |
| Saturated amide | Acetamide | 1690 |
| $N$-Substituted amide | Benzamide | 1675 |
| $N, N$-Disubstituted amide | $N, N$-Dimethylacetamide | 1650 |
| Saturated aldehyde | Acetaldehyde | 1730 |
| Saturated ketone | Acetone | 1715 |
| Saturated carboxylic acid | Acetic acid | 1710 |

Acid chlorides are easily detected by their characteristic absorption near $1810 \mathrm{~cm}^{-1}$. Acid anhydrides can be identified by a pair of absorptions in the carbonyl region, one at $1820 \mathrm{~cm}^{-1}$ and another at $1760 \mathrm{~cm}^{-1}$. Note that each of these functional groups has a strong electron-withdrawing group attached to the carbonyl. The inductive withdrawal of electron density shortens the $\mathrm{C}=\mathrm{O}$ bond, thereby raising its stretching frequency. Esters are detected by their absorption at $1735 \mathrm{~cm}^{-1}$, a position somewhat higher than that for either aldehydes or ketones. Amides, by contrast, absorb near the low-wavenumber end of the carbonyl region, with the degree of substitution on nitrogen affecting the exact position of the IR band. That is, for amides, the delocalization of
electron density (resonance) from nitrogen into the carbonyl lengthens the $\mathrm{C}=\mathrm{O}$ bond and lowers its stretching frequency.


Infrared Spectroscopy -

PROBLEM What kinds of functional groups might compounds have if they show the following IR absorptions?
21-25 (a) Absorption at $1735 \mathrm{~cm}^{-1}$ (b) Absorption at $1810 \mathrm{~cm}^{-1}$
(c) Absorptions at 2500 to $3300 \mathrm{~cm}^{-1}$ and $1710 \mathrm{~cm}^{-1}$
(d) Absorption at $1715 \mathrm{~cm}^{-1}$

PROBLEM Propose structures for compounds that have the following formulas and IR absorptions:
21-26 (a) $\mathrm{C}_{6} \mathrm{H}_{12} \mathrm{O}_{2}, 1735 \mathrm{~cm}^{-1}$
(b) $\mathrm{C}_{4} \mathrm{H}_{9} \mathrm{NO}, 1650 \mathrm{~cm}^{-1}$
(c) $\mathrm{C}_{4} \mathrm{H}_{5} \mathrm{ClO}, 1780 \mathrm{~cm}^{-1}$


Nuclear Magnetic Resonance Spectroscopy -

Hydrogens on the carbon next to a carbonyl group are slightly deshielded and absorb near $2 \delta$ in the ${ }^{1} \mathrm{H}$ NMR spectrum, although the exact identity of the carbonyl group can't be determined. FIGURE 21.11 shows the ${ }^{1} \mathrm{H}$ NMR spectrum of ethyl acetate.
![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-0766.jpg?height=502&width=1397&top_left_y=779&top_left_x=359)

FIGURE 21.11 ${ }^{\mathbf{1}} \mathbf{H}$ NMR spectrum of ethyl acetate.
Although ${ }^{13} \mathrm{C}$ NMR is useful for determining the presence or absence of a carbonyl group in a molecule, the identity of the carbonyl group is difficult to determine. Aldehydes and ketones absorb near $200 \delta$, while the carbonyl carbon atoms of various acid derivatives absorb in the range 160 to $180 \delta$ (TABLE 21.4).


TABLE $21.4^{13} \mathrm{C}$ NMR Absorptions of Some Carbonyl Compounds


| Compound | Absorption (ס) |
| :--- | :--- |
| Acetic acid | 177.3 |
| Ethyl acetate | 170.7 |
| Acetyl chloride | 170.3 |
| Acetamide | 172.6 |
| Acetic anhydride | 166.9 |
| Acetone | 205.6 |
| Acetaldehyde | 201.0 |


$\boldsymbol{\beta}$-Lactam Antibiotics -

You should never underestimate the value of hard work and logical thinking, but it's also true that blind luck often plays a role in most real scientific breakthroughs. What has been called "the supreme example of luck in all scientific history" occurred in the late summer of 1928, when the Scottish bacteriologist Alexander Fleming went on vacation, leaving in his lab a culture plate recently inoculated with the bacterium Staphylococcus aureus.


While Fleming was away, an extraordinary chain of events occurred. First, a nine-day cold spell lowered the laboratory temperature to a point where the Staphylococcus in the culture plate could not grow. During this time, spores from a colony of the mold Penicillium notatum, being grown in a lab on the floor below, wafted up into Fleming's lab and landed in the culture plate. The temperature then rose, and both Staphylococcus and Penicillium began to grow. On returning from vacation, Fleming discarded the plate into a tray of antiseptic, intending to sterilize it. Evidently, though, the plate did not sink deeply enough into the antiseptic, because when Fleming happened to glance at it a few days later, what he saw changed the course of history. He noticed that the growing Penicillium mold appeared to dissolve the colonies of staphylococci.


Fleming realized that the Penicillium mold must be producing a chemical that killed the Staphylococcus bacteria, and he spent several years trying to isolate the substance. Finally, in 1939, the Australian pathologist Howard Florey and the German refugee Ernst Chain managed to isolate the active substance, called penicillin. The dramatic ability of penicillin to cure infections in mice was soon demonstrated, and successful tests in humans followed shortly thereafter. By 1943, penicillin was being produced on a large scale for military use in World War II, and by 1944 it was being used on civilians. Fleming, Florey, and Chain shared the 1945 Nobel Prize in Physiology or Medicine.


Now called benzylpenicillin, or penicillin G, the substance first discovered by Fleming is but one member of a large class of so-called $\boldsymbol{\beta}$-lactam antibiotics, compounds with a four-membered lactam (cyclic amide) ring. The four-membered lactam ring is fused to a five-membered, sulfur-containing ring, and the carbon atom next to the lactam carbonyl group is bonded to an acylamino substituent, RCONH-. This acylamino side chain can be varied in the laboratory to provide many hundreds of penicillin analogs with different biological activity profiles. Ampicillin, for instance, has an $\alpha$-aminophenylacetamido substituent [ $\left.\mathrm{PhCH}\left(\mathrm{NH}_{2}\right) \mathrm{CONH}-\right]$.
![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-0767.jpg?height=381&width=826&top_left_y=1661&top_left_x=647)


Closely related to the penicillins are the cephalosporins, a group of $\beta$-lactam antibiotics that contain an unsaturated, six-membered, sulfur-containing ring. Cephalexin, marketed under the trade name Keflex, is an example. Cephalosporins generally have much greater antibacterial activity than penicillins, particularly against resistant strains of bacteria.
<img class="imgSvg" id = "m6sn3p3lgih5vd7m2t" src="data:image/svg+xml;base64,<svg id="smiles-m6sn3p3lgih5vd7m2t" xmlns="http://www.w3.org/2000/svg" viewBox="0 0 350 208.2543267047978" style="width: 349.6871619136142px; height: 208.2543267047978px; overflow: visible;"><defs><linearGradient id="line-m6sn3p3lgih5vd7m2t-1" gradientUnits="userSpaceOnUse" x1="246.833896719773" y1="164.9804730940096" x2="269.1077703237328" y2="187.2543267047978"><stop stop-color="currentColor" offset="20%"></stop><stop stop-color="currentColor" offset="100%"></stop></linearGradient><linearGradient id="line-m6sn3p3lgih5vd7m2t-3" gradientUnits="userSpaceOnUse" x1="242.1723752526076" y1="160.47030484757397" x2="248.69460426471835" y2="136.12897109788844"><stop stop-color="currentColor" offset="20%"></stop><stop stop-color="currentColor" offset="100%"></stop></linearGradient><linearGradient id="line-m6sn3p3lgih5vd7m2t-5" gradientUnits="userSpaceOnUse" x1="246.833896719773" y1="164.9804730940096" x2="254.98668298491145" y2="134.55380590690265"><stop stop-color="currentColor" offset="20%"></stop><stop stop-color="currentColor" offset="100%"></stop></linearGradient><linearGradient id="line-m6sn3p3lgih5vd7m2t-7" gradientUnits="userSpaceOnUse" x1="216.40723685067476" y1="173.1332866703283" x2="246.833896719773" y2="164.9804730940096"><stop stop-color="currentColor" offset="20%"></stop><stop stop-color="currentColor" offset="100%"></stop></linearGradient><linearGradient id="line-m6sn3p3lgih5vd7m2t-9" gradientUnits="userSpaceOnUse" x1="254.98668298491145" y1="134.55380590690265" x2="285.41334285400967" y2="126.40099233058392"><stop stop-color="currentColor" offset="20%"></stop><stop stop-color="currentColor" offset="100%"></stop></linearGradient><linearGradient id="line-m6sn3p3lgih5vd7m2t-11" gradientUnits="userSpaceOnUse" x1="232.71280938095165" y1="112.27995229611442" x2="254.98668298491145" y2="134.55380590690265"><stop stop-color="currentColor" offset="20%"></stop><stop stop-color="currentColor" offset="100%"></stop></linearGradient><linearGradient id="line-m6sn3p3lgih5vd7m2t-13" gradientUnits="userSpaceOnUse" x1="194.133363246715" y1="150.8594330595401" x2="216.40723685067476" y2="173.1332866703283"><stop stop-color="currentColor" offset="20%"></stop><stop stop-color="currentColor" offset="100%"></stop></linearGradient><linearGradient id="line-m6sn3p3lgih5vd7m2t-15" gradientUnits="userSpaceOnUse" x1="288.1517446976525" y1="127.13473638864083" x2="296.3044564538404" y2="96.70804923705442"><stop stop-color="currentColor" offset="20%"></stop><stop stop-color="currentColor" offset="100%"></stop></linearGradient><linearGradient id="line-m6sn3p3lgih5vd7m2t-17" gradientUnits="userSpaceOnUse" x1="282.6749410103669" y1="125.667248272527" x2="290.8276527665548" y2="95.2405611209406"><stop stop-color="currentColor" offset="20%"></stop><stop stop-color="currentColor" offset="100%"></stop></linearGradient><linearGradient id="line-m6sn3p3lgih5vd7m2t-19" gradientUnits="userSpaceOnUse" x1="285.41334285400967" y1="126.40099233058392" x2="307.6871619136142" y2="148.67490048564284"><stop stop-color="currentColor" offset="20%"></stop><stop stop-color="currentColor" offset="100%"></stop></linearGradient><linearGradient id="line-m6sn3p3lgih5vd7m2t-21" gradientUnits="userSpaceOnUse" x1="224.55999580463296" y1="81.85329242701619" x2="232.71280938095165" y2="112.27995229611442"><stop stop-color="currentColor" offset="20%"></stop><stop stop-color="currentColor" offset="100%"></stop></linearGradient><linearGradient id="line-m6sn3p3lgih5vd7m2t-23" gradientUnits="userSpaceOnUse" x1="202.28614951185344" y1="120.43276587243315" x2="232.71280938095165" y2="112.27995229611442"><stop stop-color="currentColor" offset="20%"></stop><stop stop-color="currentColor" offset="100%"></stop></linearGradient><linearGradient id="line-m6sn3p3lgih5vd7m2t-25" gradientUnits="userSpaceOnUse" x1="194.133363246715" y1="150.8594330595401" x2="202.28614951185344" y2="120.43276587243315"><stop stop-color="currentColor" offset="20%"></stop><stop stop-color="currentColor" offset="100%"></stop></linearGradient><linearGradient id="line-m6sn3p3lgih5vd7m2t-27" gradientUnits="userSpaceOnUse" x1="227.01517846054043" y1="83.270791325122" x2="242.7651662172717" y2="55.990984037261356"><stop stop-color="currentColor" offset="20%"></stop><stop stop-color="currentColor" offset="100%"></stop></linearGradient><linearGradient id="line-m6sn3p3lgih5vd7m2t-29" gradientUnits="userSpaceOnUse" x1="222.1048131487255" y1="80.43579352891037" x2="237.85480090545678" y2="53.15598624104972"><stop stop-color="currentColor" offset="20%"></stop><stop stop-color="currentColor" offset="100%"></stop></linearGradient><linearGradient id="line-m6sn3p3lgih5vd7m2t-31" gradientUnits="userSpaceOnUse" x1="194.13333593553472" y1="90.0061060033349" x2="224.55999580463296" y2="81.85329242701619"><stop stop-color="currentColor" offset="20%"></stop><stop stop-color="currentColor" offset="100%"></stop></linearGradient><linearGradient id="line-m6sn3p3lgih5vd7m2t-33" gradientUnits="userSpaceOnUse" x1="194.13333593553472" y1="90.0061060033349" x2="202.28614951185344" y2="120.43276587243315"><stop stop-color="currentColor" offset="20%"></stop><stop stop-color="currentColor" offset="100%"></stop></linearGradient><linearGradient id="line-m6sn3p3lgih5vd7m2t-35" gradientUnits="userSpaceOnUse" x1="163.70667606643647" y1="98.15891957965363" x2="194.13333593553472" y2="90.0061060033349"><stop stop-color="currentColor" offset="20%"></stop><stop stop-color="currentColor" offset="100%"></stop></linearGradient><linearGradient id="line-m6sn3p3lgih5vd7m2t-37" gradientUnits="userSpaceOnUse" x1="185.98052235921602" y1="59.57944613423666" x2="194.13333593553472" y2="90.0061060033349"><stop stop-color="currentColor" offset="20%"></stop><stop stop-color="currentColor" offset="100%"></stop></linearGradient><linearGradient id="line-m6sn3p3lgih5vd7m2t-39" gradientUnits="userSpaceOnUse" x1="155.55385517210908" y1="51.426659869098216" x2="185.98052235921602" y2="59.57944613423666"><stop stop-color="currentColor" offset="20%"></stop><stop stop-color="currentColor" offset="100%"></stop></linearGradient><linearGradient id="line-m6sn3p3lgih5vd7m2t-41" gradientUnits="userSpaceOnUse" x1="150.13944098400918" y1="20.26624677813132" x2="158.29225456032793" y2="50.692906647229535"><stop stop-color="currentColor" offset="20%"></stop><stop stop-color="currentColor" offset="100%"></stop></linearGradient><linearGradient id="line-m6sn3p3lgih5vd7m2t-43" gradientUnits="userSpaceOnUse" x1="144.66264220757154" y1="21.73375322186868" x2="152.81545578389023" y2="52.1604130909669"><stop stop-color="currentColor" offset="20%"></stop><stop stop-color="currentColor" offset="100%"></stop></linearGradient><linearGradient id="line-m6sn3p3lgih5vd7m2t-45" gradientUnits="userSpaceOnUse" x1="133.28000156132083" y1="73.70053347305799" x2="155.55385517210908" y2="51.426659869098216"><stop stop-color="currentColor" offset="20%"></stop><stop stop-color="currentColor" offset="100%"></stop></linearGradient><linearGradient id="line-m6sn3p3lgih5vd7m2t-47" gradientUnits="userSpaceOnUse" x1="133.28000156132083" y1="73.70053347305799" x2="141.43281513763955" y2="104.12719334215623"><stop stop-color="currentColor" offset="20%"></stop><stop stop-color="currentColor" offset="100%"></stop></linearGradient><linearGradient id="line-m6sn3p3lgih5vd7m2t-49" gradientUnits="userSpaceOnUse" x1="102.85333437421392" y1="65.54774720791954" x2="133.28000156132083" y2="73.70053347305799"><stop stop-color="currentColor" offset="20%"></stop><stop stop-color="currentColor" offset="100%"></stop></linearGradient><linearGradient id="line-m6sn3p3lgih5vd7m2t-51" gradientUnits="userSpaceOnUse" x1="78.79756887579174" y1="81.58493980154148" x2="96.61665176442233" y2="63.76584091837364"><stop stop-color="currentColor" offset="20%"></stop><stop stop-color="currentColor" offset="100%"></stop></linearGradient><linearGradient id="line-m6sn3p3lgih5vd7m2t-53" gradientUnits="userSpaceOnUse" x1="80.57948076342569" y1="87.82162081187934" x2="102.85333437421392" y2="65.54774720791954"><stop stop-color="currentColor" offset="20%"></stop><stop stop-color="currentColor" offset="100%"></stop></linearGradient><linearGradient id="line-m6sn3p3lgih5vd7m2t-55" gradientUnits="userSpaceOnUse" x1="94.70052079789515" y1="35.12108733882128" x2="102.85333437421392" y2="65.54774720791954"><stop stop-color="currentColor" offset="20%"></stop><stop stop-color="currentColor" offset="100%"></stop></linearGradient><linearGradient id="line-m6sn3p3lgih5vd7m2t-57" gradientUnits="userSpaceOnUse" x1="50.15281357631875" y1="79.6688345467409" x2="80.57948076342569" y2="87.82162081187934"><stop stop-color="currentColor" offset="20%"></stop><stop stop-color="currentColor" offset="100%"></stop></linearGradient><linearGradient id="line-m6sn3p3lgih5vd7m2t-59" gradientUnits="userSpaceOnUse" x1="65.84901880177401" y1="33.26037979387597" x2="90.19035255145954" y2="39.78260880598668"><stop stop-color="currentColor" offset="20%"></stop><stop stop-color="currentColor" offset="100%"></stop></linearGradient><linearGradient id="line-m6sn3p3lgih5vd7m2t-61" gradientUnits="userSpaceOnUse" x1="64.27385361078822" y1="26.96830107368288" x2="94.70052079789515" y2="35.12108733882128"><stop stop-color="currentColor" offset="20%"></stop><stop stop-color="currentColor" offset="100%"></stop></linearGradient><linearGradient id="line-m6sn3p3lgih5vd7m2t-63" gradientUnits="userSpaceOnUse" x1="48.29208013406955" y1="50.81733422081514" x2="54.81433099512456" y2="75.1586621160937"><stop stop-color="currentColor" offset="20%"></stop><stop stop-color="currentColor" offset="100%"></stop></linearGradient><linearGradient id="line-m6sn3p3lgih5vd7m2t-65" gradientUnits="userSpaceOnUse" x1="42" y1="49.242174677642694" x2="50.15281357631875" y2="79.6688345467409"><stop stop-color="currentColor" offset="20%"></stop><stop stop-color="currentColor" offset="100%"></stop></linearGradient><linearGradient id="line-m6sn3p3lgih5vd7m2t-67" gradientUnits="userSpaceOnUse" x1="42" y1="49.242174677642694" x2="64.27385361078822" y2="26.96830107368288"><stop stop-color="currentColor" offset="20%"></stop><stop stop-color="currentColor" offset="100%"></stop></linearGradient></defs><mask id="text-mask-m6sn3p3lgih5vd7m2t"><rect x="0" y="0" width="100%" height="100%" fill="white"></rect><circle cx="293.56605461019757" cy="95.97430517899751" r="7.875" fill="black"></circle><circle cx="307.6871619136142" cy="148.67490048564284" r="7.875" fill="black"></circle><circle cx="232.71280938095165" cy="112.27995229611442" r="7.875" fill="black"></circle><circle cx="240.30998356136422" cy="54.57348513915554" r="7.875" fill="black"></circle><circle cx="163.70667606643647" cy="98.15891957965363" r="7.875" fill="black"></circle><circle cx="185.98052235921602" cy="59.57944613423666" r="7.875" fill="black"></circle><circle cx="147.40104159579036" cy="21" r="7.875" fill="black"></circle><circle cx="141.43281513763955" cy="104.12719334215623" r="7.875" fill="black"></circle><circle cx="194.133363246715" cy="150.8594330595401" r="7.875" fill="black"></circle></mask><style>
                .element-m6sn3p3lgih5vd7m2t {
                    font: 14px Helvetica, Arial, sans-serif;
                    alignment-baseline: 'middle';
                }
                .sub-m6sn3p3lgih5vd7m2t {
                    font: 8.4px Helvetica, Arial, sans-serif;
                }
            </style><g mask="url(#text-mask-m6sn3p3lgih5vd7m2t)"><line x1="246.833896719773" y1="164.9804730940096" x2="269.1077703237328" y2="187.2543267047978" style="stroke-linecap:round;stroke-dasharray:none;stroke-width:1.26" stroke="url('#line-m6sn3p3lgih5vd7m2t-1')"></line><line x1="242.1723752526076" y1="160.47030484757397" x2="248.69460426471835" y2="136.12897109788844" style="stroke-linecap:round;stroke-dasharray:none;stroke-width:1.26" stroke="url('#line-m6sn3p3lgih5vd7m2t-3')"></line><line x1="246.833896719773" y1="164.9804730940096" x2="254.98668298491145" y2="134.55380590690265" style="stroke-linecap:round;stroke-dasharray:none;stroke-width:1.26" stroke="url('#line-m6sn3p3lgih5vd7m2t-5')"></line><line x1="216.40723685067476" y1="173.1332866703283" x2="246.833896719773" y2="164.9804730940096" style="stroke-linecap:round;stroke-dasharray:none;stroke-width:1.26" stroke="url('#line-m6sn3p3lgih5vd7m2t-7')"></line><line x1="254.98668298491145" y1="134.55380590690265" x2="285.41334285400967" y2="126.40099233058392" style="stroke-linecap:round;stroke-dasharray:none;stroke-width:1.26" stroke="url('#line-m6sn3p3lgih5vd7m2t-9')"></line><line x1="232.71280938095165" y1="112.27995229611442" x2="254.98668298491145" y2="134.55380590690265" style="stroke-linecap:round;stroke-dasharray:none;stroke-width:1.26" stroke="url('#line-m6sn3p3lgih5vd7m2t-11')"></line><line x1="194.133363246715" y1="150.8594330595401" x2="216.40723685067476" y2="173.1332866703283" style="stroke-linecap:round;stroke-dasharray:none;stroke-width:1.26" stroke="url('#line-m6sn3p3lgih5vd7m2t-13')"></line><line x1="288.1517446976525" y1="127.13473638864083" x2="296.3044564538404" y2="96.70804923705442" style="stroke-linecap:round;stroke-dasharray:none;stroke-width:1.26" stroke="url('#line-m6sn3p3lgih5vd7m2t-15')"></line><line x1="282.6749410103669" y1="125.667248272527" x2="290.8276527665548" y2="95.2405611209406" style="stroke-linecap:round;stroke-dasharray:none;stroke-width:1.26" stroke="url('#line-m6sn3p3lgih5vd7m2t-17')"></line><line x1="285.41334285400967" y1="126.40099233058392" x2="307.6871619136142" y2="148.67490048564284" style="stroke-linecap:round;stroke-dasharray:none;stroke-width:1.26" stroke="url('#line-m6sn3p3lgih5vd7m2t-19')"></line><line x1="224.55999580463296" y1="81.85329242701619" x2="232.71280938095165" y2="112.27995229611442" style="stroke-linecap:round;stroke-dasharray:none;stroke-width:1.26" stroke="url('#line-m6sn3p3lgih5vd7m2t-21')"></line><line x1="202.28614951185344" y1="120.43276587243315" x2="232.71280938095165" y2="112.27995229611442" style="stroke-linecap:round;stroke-dasharray:none;stroke-width:1.26" stroke="url('#line-m6sn3p3lgih5vd7m2t-23')"></line><line x1="194.133363246715" y1="150.8594330595401" x2="202.28614951185344" y2="120.43276587243315" style="stroke-linecap:round;stroke-dasharray:none;stroke-width:1.26" stroke="url('#line-m6sn3p3lgih5vd7m2t-25')"></line><line x1="227.01517846054043" y1="83.270791325122" x2="242.7651662172717" y2="55.990984037261356" style="stroke-linecap:round;stroke-dasharray:none;stroke-width:1.26" stroke="url('#line-m6sn3p3lgih5vd7m2t-27')"></line><line x1="222.1048131487255" y1="80.43579352891037" x2="237.85480090545678" y2="53.15598624104972" style="stroke-linecap:round;stroke-dasharray:none;stroke-width:1.26" stroke="url('#line-m6sn3p3lgih5vd7m2t-29')"></line><line x1="194.13333593553472" y1="90.0061060033349" x2="224.55999580463296" y2="81.85329242701619" style="stroke-linecap:round;stroke-dasharray:none;stroke-width:1.26" stroke="url('#line-m6sn3p3lgih5vd7m2t-31')"></line><line x1="194.13333593553472" y1="90.0061060033349" x2="202.28614951185344" y2="120.43276587243315" style="stroke-linecap:round;stroke-dasharray:none;stroke-width:1.26" stroke="url('#line-m6sn3p3lgih5vd7m2t-33')"></line><line x1="163.70667606643647" y1="98.15891957965363" x2="194.13333593553472" y2="90.0061060033349" style="stroke-linecap:round;stroke-dasharray:none;stroke-width:1.26" stroke="url('#line-m6sn3p3lgih5vd7m2t-35')"></line><line x1="194.13333593553472" y1="90.0061060033349" x2="194.13333593553472" y2="90.0061060033349" style="stroke-linecap:round;stroke-dasharray:none;stroke-width:1.26" stroke="url('#line-m6sn3p3lgih5vd7m2t-37')"></line><line x1="192.69308061430763" y1="85.50034140565816" x2="193.12774718386618" y2="85.38387264028218" style="stroke-linecap:round;stroke-dasharray:none;stroke-width:1.26" stroke="url('#line-m6sn3p3lgih5vd7m2t-37')"></line><line x1="191.25282529308055" y1="80.99457680798142" x2="192.12215843219764" y2="80.76163927722945" style="stroke-linecap:round;stroke-dasharray:none;stroke-width:1.26" stroke="url('#line-m6sn3p3lgih5vd7m2t-37')"></line><line x1="189.8125699718535" y1="76.48881221030466" x2="191.11656968052912" y2="76.13940591417672" style="stroke-linecap:round;stroke-dasharray:none;stroke-width:1.26" stroke="url('#line-m6sn3p3lgih5vd7m2t-37')"></line><line x1="188.37231465062638" y1="71.98304761262791" x2="190.11098092886058" y2="71.51717255112399" style="stroke-linecap:round;stroke-dasharray:none;stroke-width:1.26" stroke="url('#line-m6sn3p3lgih5vd7m2t-37')"></line><line x1="186.93205932939932" y1="67.47728301495117" x2="189.10539217719207" y2="66.89493918807126" style="stroke-linecap:round;stroke-dasharray:none;stroke-width:1.26" stroke="url('#line-m6sn3p3lgih5vd7m2t-37')"></line><line x1="185.49180400817227" y1="62.97151841727444" x2="188.09980342552353" y2="62.27270582501855" style="stroke-linecap:round;stroke-dasharray:none;stroke-width:1.26" stroke="url('#line-m6sn3p3lgih5vd7m2t-37')"></line><line x1="155.55385517210908" y1="51.426659869098216" x2="185.98052235921602" y2="59.57944613423666" style="stroke-linecap:round;stroke-dasharray:none;stroke-width:1.26" stroke="url('#line-m6sn3p3lgih5vd7m2t-39')"></line><line x1="150.13944098400918" y1="20.26624677813132" x2="158.29225456032793" y2="50.692906647229535" style="stroke-linecap:round;stroke-dasharray:none;stroke-width:1.26" stroke="url('#line-m6sn3p3lgih5vd7m2t-41')"></line><line x1="144.66264220757154" y1="21.73375322186868" x2="152.81545578389023" y2="52.1604130909669" style="stroke-linecap:round;stroke-dasharray:none;stroke-width:1.26" stroke="url('#line-m6sn3p3lgih5vd7m2t-43')"></line><line x1="133.28000156132083" y1="73.70053347305799" x2="155.55385517210908" y2="51.426659869098216" style="stroke-linecap:round;stroke-dasharray:none;stroke-width:1.26" stroke="url('#line-m6sn3p3lgih5vd7m2t-45')"></line><line x1="133.28000156132083" y1="73.70053347305799" x2="141.43281513763955" y2="104.12719334215623" style="stroke-linecap:round;stroke-dasharray:none;stroke-width:1.26" stroke="url('#line-m6sn3p3lgih5vd7m2t-47')"></line><line x1="102.85333437421392" y1="65.54774720791954" x2="133.28000156132083" y2="73.70053347305799" style="stroke-linecap:round;stroke-dasharray:none;stroke-width:1.26" stroke="url('#line-m6sn3p3lgih5vd7m2t-49')"></line><line x1="78.79756887579174" y1="81.58493980154148" x2="96.61665176442233" y2="63.76584091837364" style="stroke-linecap:round;stroke-dasharray:none;stroke-width:1.26" stroke="url('#line-m6sn3p3lgih5vd7m2t-51')"></line><line x1="80.57948076342569" y1="87.82162081187934" x2="102.85333437421392" y2="65.54774720791954" style="stroke-linecap:round;stroke-dasharray:none;stroke-width:1.26" stroke="url('#line-m6sn3p3lgih5vd7m2t-53')"></line><line x1="94.70052079789515" y1="35.12108733882128" x2="102.85333437421392" y2="65.54774720791954" style="stroke-linecap:round;stroke-dasharray:none;stroke-width:1.26" stroke="url('#line-m6sn3p3lgih5vd7m2t-55')"></line><line x1="50.15281357631875" y1="79.6688345467409" x2="80.57948076342569" y2="87.82162081187934" style="stroke-linecap:round;stroke-dasharray:none;stroke-width:1.26" stroke="url('#line-m6sn3p3lgih5vd7m2t-57')"></line><line x1="65.84901880177401" y1="33.26037979387597" x2="90.19035255145954" y2="39.78260880598668" style="stroke-linecap:round;stroke-dasharray:none;stroke-width:1.26" stroke="url('#line-m6sn3p3lgih5vd7m2t-59')"></line><line x1="64.27385361078822" y1="26.96830107368288" x2="94.70052079789515" y2="35.12108733882128" style="stroke-linecap:round;stroke-dasharray:none;stroke-width:1.26" stroke="url('#line-m6sn3p3lgih5vd7m2t-61')"></line><line x1="48.29208013406955" y1="50.81733422081514" x2="54.81433099512456" y2="75.1586621160937" style="stroke-linecap:round;stroke-dasharray:none;stroke-width:1.26" stroke="url('#line-m6sn3p3lgih5vd7m2t-63')"></line><line x1="42" y1="49.242174677642694" x2="50.15281357631875" y2="79.6688345467409" style="stroke-linecap:round;stroke-dasharray:none;stroke-width:1.26" stroke="url('#line-m6sn3p3lgih5vd7m2t-65')"></line><line x1="42" y1="49.242174677642694" x2="64.27385361078822" y2="26.96830107368288" style="stroke-linecap:round;stroke-dasharray:none;stroke-width:1.26" stroke="url('#line-m6sn3p3lgih5vd7m2t-67')"></line></g><g><text x="269.1077703237328" y="187.2543267047978" class="debug" fill="#ff0000" style="
                font: 5px Droid Sans, sans-serif;
            "></text><text x="246.833896719773" y="164.9804730940096" class="debug" fill="#ff0000" style="
                font: 5px Droid Sans, sans-serif;
            "></text><text x="254.98668298491145" y="134.55380590690265" class="debug" fill="#ff0000" style="
                font: 5px Droid Sans, sans-serif;
            "></text><text x="285.41334285400967" y="126.40099233058392" class="debug" fill="#ff0000" style="
                font: 5px Droid Sans, sans-serif;
            "></text><text x="288.31605461019757" y="101.22430517899751" class="element-m6sn3p3lgih5vd7m2t" fill="currentColor" style="
                text-anchor: start;
                writing-mode: horizontal-tb;
                text-orientation: mixed;
                letter-spacing: normal;
                direction: ltr;
            "><tspan>O</tspan></text><text x="293.56605461019757" y="95.97430517899751" class="debug" fill="#ff0000" style="
                font: 5px Droid Sans, sans-serif;
            "></text><text x="302.4371619136142" y="153.92490048564284" class="element-m6sn3p3lgih5vd7m2t" fill="currentColor" style="
                text-anchor: start;
                writing-mode: horizontal-tb;
                text-orientation: mixed;
                letter-spacing: normal;
                direction: ltr;
            "><tspan>O</tspan><tspan style="unicode-bidi: plaintext;">H</tspan></text><text x="307.6871619136142" y="148.67490048564284" class="debug" fill="#ff0000" style="
                font: 5px Droid Sans, sans-serif;
            "></text><text x="228.77530938095165" y="117.52995229611442" class="element-m6sn3p3lgih5vd7m2t" fill="currentColor" style="
                text-anchor: start;
                writing-mode: horizontal-tb;
                text-orientation: mixed;
                letter-spacing: normal;
                direction: ltr;
            "><tspan>N</tspan></text><text x="232.71280938095165" y="112.27995229611442" class="debug" fill="#ff0000" style="
                font: 5px Droid Sans, sans-serif;
            "></text><text x="224.55999580463296" y="81.85329242701619" class="debug" fill="#ff0000" style="
                font: 5px Droid Sans, sans-serif;
            "></text><text x="235.05998356136422" y="59.82348513915554" class="element-m6sn3p3lgih5vd7m2t" fill="currentColor" style="
                text-anchor: start;
                writing-mode: horizontal-tb;
                text-orientation: mixed;
                letter-spacing: normal;
                direction: ltr;
            "><tspan>O</tspan></text><text x="240.30998356136422" y="54.57348513915554" class="debug" fill="#ff0000" style="
                font: 5px Droid Sans, sans-serif;
            "></text><text x="194.13333593553472" y="90.0061060033349" class="debug" fill="#ff0000" style="
                font: 5px Droid Sans, sans-serif;
            ">S</text><text x="168.95667606643647" y="103.40891957965363" class="element-m6sn3p3lgih5vd7m2t" fill="currentColor" style="
                text-anchor: start;
                writing-mode: horizontal-tb;
                text-orientation: mixed;
                letter-spacing: normal;
                direction: rtl; unicode-bidi: bidi-override;
            "><tspan>H</tspan></text><text x="163.70667606643647" y="98.15891957965363" class="debug" fill="#ff0000" style="
                font: 5px Droid Sans, sans-serif;
            "></text><text x="185.98052235921602" y="67.45444613423666" class="element-m6sn3p3lgih5vd7m2t" fill="currentColor" style="
                text-anchor: start;
                writing-mode: vertical-rl;
                text-orientation: upright;
                letter-spacing: -1px;
                direction: rtl; unicode-bidi: bidi-override;
            "><tspan>N</tspan><tspan style="unicode-bidi: plaintext;">H</tspan></text><text x="185.98052235921602" y="59.57944613423666" class="debug" fill="#ff0000" style="
                font: 5px Droid Sans, sans-serif;
            "></text><text x="155.55385517210908" y="51.426659869098216" class="debug" fill="#ff0000" style="
                font: 5px Droid Sans, sans-serif;
            "></text><text x="142.15104159579036" y="26.25" class="element-m6sn3p3lgih5vd7m2t" fill="currentColor" style="
                text-anchor: start;
                writing-mode: horizontal-tb;
                text-orientation: mixed;
                letter-spacing: normal;
                direction: ltr;
            "><tspan>O</tspan></text><text x="147.40104159579036" y="21" class="debug" fill="#ff0000" style="
                font: 5px Droid Sans, sans-serif;
            "></text><text x="133.28000156132083" y="73.70053347305799" class="debug" fill="#ff0000" style="
                font: 5px Droid Sans, sans-serif;
            "></text><text x="136.18281513763955" y="109.37719334215623" class="element-m6sn3p3lgih5vd7m2t" fill="currentColor" style="
                text-anchor: start;
                writing-mode: horizontal-tb;
                text-orientation: mixed;
                letter-spacing: normal;
                direction: ltr;
            "><tspan>N</tspan><tspan style="unicode-bidi: plaintext;">H<tspan baseline-shift="sub" class="sub-m6sn3p3lgih5vd7m2t">2</tspan></tspan></text><text x="141.43281513763955" y="104.12719334215623" class="debug" fill="#ff0000" style="
                font: 5px Droid Sans, sans-serif;
            "></text><text x="102.85333437421392" y="65.54774720791954" class="debug" fill="#ff0000" style="
                font: 5px Droid Sans, sans-serif;
            "></text><text x="80.57948076342569" y="87.82162081187934" class="debug" fill="#ff0000" style="
                font: 5px Droid Sans, sans-serif;
            "></text><text x="50.15281357631875" y="79.6688345467409" class="debug" fill="#ff0000" style="
                font: 5px Droid Sans, sans-serif;
            "></text><text x="42" y="49.242174677642694" class="debug" fill="#ff0000" style="
                font: 5px Droid Sans, sans-serif;
            "></text><text x="64.27385361078822" y="26.96830107368288" class="debug" fill="#ff0000" style="
                font: 5px Droid Sans, sans-serif;
            "></text><text x="94.70052079789515" y="35.12108733882128" class="debug" fill="#ff0000" style="
                font: 5px Droid Sans, sans-serif;
            "></text><text x="202.28614951185344" y="120.43276587243315" class="debug" fill="#ff0000" style="
                font: 5px Droid Sans, sans-serif;
            "></text><text x="199.383363246715" y="156.1094330595401" class="element-m6sn3p3lgih5vd7m2t" fill="currentColor" style="
                text-anchor: start;
                writing-mode: horizontal-tb;
                text-orientation: mixed;
                letter-spacing: normal;
                direction: rtl; unicode-bidi: bidi-override;
            "><tspan>S</tspan></text><text x="194.133363246715" y="150.8594330595401" class="debug" fill="#ff0000" style="
                font: 5px Droid Sans, sans-serif;
            "></text><text x="216.40723685067476" y="173.1332866703283" class="debug" fill="#ff0000" style="
                font: 5px Droid Sans, sans-serif;
            "></text></g></svg>"/>


Cephalexin (a cephalosporin)


The biological activity of penicillins and cephalosporins is due to the presence of the strained $\beta$-lactam ring, which reacts with and deactivates the transpeptidase enzyme needed to synthesize and repair bacterial cell walls. With the wall either incomplete or weakened, the bacterial cell ruptures and dies.
![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-0768.jpg?height=435&width=1223&top_left_y=338&top_left_x=451)
![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-0768.jpg?height=281&width=530&top_left_y=819&top_left_x=456)
(inactive enzyme)


Key Terms -

- acid anhydride
- acid halide
- acyl phosphate
- amide
- carboxylic acid derivative
- chain-growth polymer
- ester
- Fischer esterification reaction
- lactam
- lactone
- nucleophilic acyl substitution reaction
- saponification
- step-growth polymer
- thioester


Key Terms -


Summary -

Carboxylic acid derivatives-compounds in which the -OH group of a carboxylic acid has been replaced by another substituent-are among the most widely occurring of all molecules and are involved in almost all biological pathways. In this chapter, we covered the chemistry necessary for understanding them and thus also necessary for understanding living organisms. Acid halides, acid anhydrides, esters, and amides are the most common such derivatives in the laboratory; thioesters and acyl phosphates are common in biological molecules.


Summary -

The chemistry of carboxylic acid derivatives is dominated by the nucleophilic acyl substitution reaction. Mechanistically, these substitutions take place by addition of a nucleophile to the polar carbonyl group of the acid derivative to give a tetrahedral intermediate, followed by expulsion of a leaving group.
![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-0768.jpg?height=185&width=1018&top_left_y=2119&top_left_x=548)


Summary -

The reactivity of an acid derivative toward substitution depends both on the steric environment near the carbonyl group and on the electronic nature of the substituent, Y. The reactivity order is acid halide >acid anhydride $>$ thioester $>$ ester $>$ amide.


Summary -

The most common reactions of carboxylic acid derivatives are substitution by water to yield an acid (hydrolysis), by an alcohol to yield an ester (alcoholysis), by an amine to yield an amide (aminolysis), by hydride ion to yield
an alcohol (reduction), and by an organomagnesium halide to yield an alcohol (Grignard reaction).
Step-growth polymers, such as polyamides and polyesters, are prepared by reactions between difunctional molecules. Polyamides (nylons) are formed by reaction between a diacid and a diamine; polyesters are formed from a diacid and a diol.


Summary -

IR spectroscopy is a valuable tool for the structural analysis of acid derivatives. Acid chlorides, anhydrides, esters, and amides all show characteristic IR absorptions that can be used to identify these functional groups.


Summary of Reactions -

1. Reactions of carboxylic acids (Section 21.3)
a. Conversion into acid chlorides
![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-0769.jpg?height=131&width=749&top_left_y=672&top_left_x=734)
b. Conversion into esters
![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-0769.jpg?height=281&width=811&top_left_y=838&top_left_x=706)
c. Conversion into amides
![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-0769.jpg?height=131&width=633&top_left_y=1162&top_left_x=795)
d. Reduction to yield primary alcohols
![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-0769.jpg?height=120&width=616&top_left_y=1336&top_left_x=803)
2. Reactions of acid chlorides (Section 21.4)
a. Hydrolysis to yield acids
![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-0769.jpg?height=128&width=711&top_left_y=1562&top_left_x=756)
b. Reaction with carboxylates to yield anhydrides
![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-0769.jpg?height=131&width=819&top_left_y=1729&top_left_x=702)
c. Alcoholysis to yield esters
![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-0769.jpg?height=129&width=793&top_left_y=1898&top_left_x=715)
d. Aminolysis to yield amides
![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-0769.jpg?height=137&width=790&top_left_y=2073&top_left_x=716)
e. Reduction to yield primary alcohols
![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-0769.jpg?height=120&width=562&top_left_y=2255&top_left_x=830)
f. Grignard reaction to yield tertiary alcohols
![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-0769.jpg?height=118&width=589&top_left_y=2424&top_left_x=817)
g. Diorganocopper reaction to yield ketones
![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-0770.jpg?height=134&width=457&top_left_y=231&top_left_x=883)
3. Reactions of acid anhydrides (Section 21.5)
a. Hydrolysis to yield acids
![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-0770.jpg?height=137&width=714&top_left_y=471&top_left_x=754)
b. Alcoholysis to yield esters
![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-0770.jpg?height=128&width=920&top_left_y=641&top_left_x=651)
c. Aminolysis to yield amides
![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-0770.jpg?height=131&width=1006&top_left_y=818&top_left_x=603)
4. Reactions of esters (Section 21.6)
a. Hydrolysis to yield acids
![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-0770.jpg?height=139&width=733&top_left_y=1047&top_left_x=745)
b. Reduction to yield primary alcohols
![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-0770.jpg?height=129&width=754&top_left_y=1231&top_left_x=737)
c. Partial reduction to yield aldehydes
![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-0770.jpg?height=131&width=754&top_left_y=1404&top_left_x=737)
d. Grignard reaction to yield tertiary alcohols
![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-0770.jpg?height=137&width=779&top_left_y=1577&top_left_x=722)
5. Reactions of amides (Section 21.7)
a. Hydrolysis to yield acids
![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-0770.jpg?height=129&width=725&top_left_y=1822&top_left_x=749)
b. Reduction to yield amines
![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-0770.jpg?height=125&width=611&top_left_y=2000&top_left_x=806)


Additional Problems -


Visualizing Chemistry -

PROBLEM Name the following compounds:
21-27
(a)
![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-0771.jpg?height=321&width=465&top_left_y=208&top_left_x=483)
(b)
![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-0771.jpg?height=327&width=646&top_left_y=216&top_left_x=1024)


Visualizing Chemistry -

PROBLEM How would you prepare the following compounds starting with an appropriate carboxylic acid and
21-28 any other reagents needed? (reddish brown $=\mathrm{Br}$.)
(a)
![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-0771.jpg?height=291&width=586&top_left_y=678&top_left_x=485)
(b)
![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-0771.jpg?height=283&width=500&top_left_y=672&top_left_x=1146)


Visualizing Chemistry -

PROBLEM The following structure represents a tetrahedral alkoxide-ion intermediate formed by addition of a
21-29 nucleophile to a carboxylic acid derivative. Identify the nucleophile, the leaving group, the starting acid derivative, and the ultimate product (green $=\mathrm{Cl}$ ).
![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-0771.jpg?height=324&width=443&top_left_y=1150&top_left_x=429)


Visualizing Chemistry -

PROBLEM Electrostatic potential maps of a typical amide (acetamide) and an acyl azide (acetyl azide) are
21-30 shown. Which of the two do you think is more reactive in nucleophilic acyl substitution reactions? Explain.
![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-0771.jpg?height=345&width=868&top_left_y=1665&top_left_x=547)
Acetamide
<img class="imgSvg" id = "m6sn3p3opus52f8s4h" src="data:image/svg+xml;base64,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"/>


Visualizing Chemistry -


Acetyl azide -


Mechanism Problems -

PROBLEM Predict the product(s) and write the mechanism for the following reactions:
21-31 (a)
![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-0771.jpg?height=128&width=763&top_left_y=2381&top_left_x=486)
(b)
![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-0772.jpg?height=237&width=578&top_left_y=207&top_left_x=481)

PROBLEM Predict the product(s) and write the mechanism for the following reactions:


21-32 (a) -


21-32 (a) -

PROBLEM Predict the product(s) and write the mechanism for each of the following reactions:
21-33 (a)
![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-0772.jpg?height=134&width=597&top_left_y=768&top_left_x=482)
![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-0772.jpg?height=137&width=597&top_left_y=769&top_left_x=482)

PROBLEM Predict the product(s) and write the mechanism for the following reactions:
21-34 (a)
![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-0772.jpg?height=134&width=793&top_left_y=985&top_left_x=479)
(b)
![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-0772.jpg?height=126&width=657&top_left_y=1132&top_left_x=485)


21-32 (a) -

PROBLEM Pivalic mixed anhydrides are often used to form amide bonds between amino acids. Unlike with a
21-35 symmetrical anhydride, this reaction is highly regioselective, with the nucleophile adding only to the amino-acid carbonyl. Provide the complete mechanism for the following reaction and explain the regioselectivity.
![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-0772.jpg?height=275&width=1489&top_left_y=1481&top_left_x=413)


21-32 (a) -

PROBLEM When 4-dimethylaminopyridine (DMAP) is added in catalytic amounts to acetic anhydride and an
21-36 alcohol, it significantly increases the rate of ester formation. The process begins with a reaction between acetic anhydride and DMAP to form a highly reactive acetylpyridinium intermediate that is more reactive than acetic anhydride itself. Propose a mechanism for this process that includes the formation and reaction of the acetylpyridinium intermediate.


21-32 (a) -

PROBLEM Fats are biosynthesized from glycerol 3-phosphate and fatty-acyl CoA's by a reaction sequence that
21-37 begins with the following step. Show the mechanism of the reaction.
![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-0772.jpg?height=313&width=936&top_left_y=2120&top_left_x=410)


21-32 (a) -

PROBLEM Treatment of an $\alpha$-amino acid with DCC yields a 2,5-diketopiperazine. Propose a mechanism. 21-38
![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-0773.jpg?height=326&width=657&top_left_y=192&top_left_x=411)


21-32 (a) -

PROBLEM Succinic anhydride yields the cyclic imide succinimide when heated with ammonium chloride
21-39 at $200^{\circ} \mathrm{C}$. Propose a mechanism for this reaction. Why do you suppose such a high reaction temperature is required?
![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-0773.jpg?height=239&width=752&top_left_y=688&top_left_x=407)


21-32 (a) -

PROBLEM The hydrolysis of a biological thioester to the corresponding carboxylate is often more complex
21-40 than the overall result might suggest. The conversion of succinyl CoA to succinate in the citric acid cycle, for instance, occurs by initial formation of an acyl phosphate, followed by reaction with guanosine diphosphate (GDP, a relative of adenosine diphosphate [ADP]) to give succinate and guanosine triphosphate (GTP, a relative of ATP). Suggest mechanisms for both steps.
![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-0773.jpg?height=137&width=533&top_left_y=1189&top_left_x=403)


21-32 (a) -

GTP


21-32 (a) -

PROBLEM One step in the gluconeogenesis pathway for the biosynthesis of glucose is the partial reduction
21-41 of 3-phosphoglycerate to give glyceraldehyde 3-phosphate. The process occurs by phosphorylation with ATP to give 1,3-bisphosphoglycerate, reaction with a thiol group on the enzyme to give an enzyme-bound thioester, and reduction with NADH. Suggest mechanisms for all three reactions.
![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-0774.jpg?height=199&width=243&top_left_y=193&top_left_x=426)


21-32 (a) -

3-Phosphoglycerate
![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-0774.jpg?height=188&width=435&top_left_y=204&top_left_x=688)


21-32 (a) -

Glyceraldehyde 3-phosphate
![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-0774.jpg?height=188&width=220&top_left_y=670&top_left_x=1424)


21-32 (a) -

PROBLEM Bacteria typically develop a resistance to penicillins and other $\beta$-lactam antibiotics (see Chemistry
21-42 Matters at the end of this chapter) due to bacterial synthesis of $\beta$-lactamase enzymes. Tazobactam, however, is able to inhibit the activity of the $\beta$-lactamase by trapping it, thereby preventing a resistance from developing.
![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-0774.jpg?height=374&width=1189&top_left_y=1068&top_left_x=422)
(a) The first step in trapping is reaction of a hydroxyl group on the $\beta$-lactamase to open the $\beta$-lactam ring of tazobactam. Show the mechanism.
(b) The second step is opening the sulfur-containing ring in tazobactam to give an acyclic imine intermediate. Show the mechanism.
(c) Cyclization of the imine intermediate gives the trapped $\beta$-lactamase product. Show the mechanism.


21-32 (a) -

PROBLEM The following reaction, called the benzilic acid rearrangement, takes place by typical carbonyl-
21-43 group reactions. Propose a mechanism ( $\mathrm{Ph}=$ phenyl).
![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-0774.jpg?height=212&width=605&top_left_y=1824&top_left_x=413)


21-32 (a) -

PROBLEM In the iodoform reaction, a triiodomethyl ketone reacts with aqueous NaOH to yield a carboxylate
21-44 ion and iodoform (triiodomethane). Propose a mechanism for this reaction.
![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-0774.jpg?height=133&width=614&top_left_y=2167&top_left_x=411)


Naming Carboxylic Acid Derivatives -


Naming Carboxylic Acid Derivatives -

PROBLEM Draw structures corresponding to the following names:
21-46 (a) $p$-Bromophenylacetamide (b) $m$-Benzoylbenzamide (c) 2,2-Dimethylhexanamide
(d) Cyclohexyl cyclohexanecarboxylate (e) Ethyl 2-cyclobutenecarboxylate
(f) Succinic anhydride


Naming Carboxylic Acid Derivatives -

PROBLEM Draw and name compounds that meet the following descriptions:
21-47 (a) Three acid chlorides having the formula $\mathrm{C}_{6} \mathrm{H}_{9} \mathrm{ClO}$
(b) Three amides having the formula $\mathrm{C}_{7} \mathrm{H}_{11} \mathrm{NO}$


Naming Carboxylic Acid Derivatives -

Nucleophilic Acyl Substitution Reactions
PROBLEM Predict the product, if any, of reaction between propanoyl chloride and the following reagents:
21-48
(a) $\mathrm{Li}(\mathrm{Ph})_{2} \mathrm{Cu}$ in ether
(b) $\mathrm{LiAlH}_{4}$, then $\mathrm{H}_{3} \mathrm{O}^{+}$
(c) $\mathrm{CH}_{3} \mathrm{MgBr}$, then $\mathrm{H}_{3} \mathrm{O}^{+}$
(d) $\mathrm{H}_{3} \mathrm{O}^{+}$
(e) Cyclohexanol (f) Aniline (g) $\mathrm{CH}_{3} \mathrm{CO}_{2}^{-} \mathrm{Na}^{+}$


Naming Carboxylic Acid Derivatives -

PROBLEM Answer Problem 21-48 for reaction of the listed reagents with methyl propanoate.
21-49
PROBLEM Answer Problem 21-48 for reaction of the listed reagents with propanamide.
21-50
PROBLEM What product would you expect to obtain from Grignard reaction of an excess of phenylmagnesium
21-51 bromide with dimethyl carbonate, $\mathrm{CH}_{3} \mathrm{OCO}_{2} \mathrm{CH}_{3}$ ?
PROBLEM How might you prepare the following compounds from butanoic acid?
21-52 (a) 1-Butanol (b) Butanal (c) 1-Bromobutane (d) Pentanenitrile (e) 1-Butene
(f) $N$-Methylpentanamide (g) 2-Hexanone (h) Butylbenzene (i) Butanenitrile


Naming Carboxylic Acid Derivatives -

PROBLEM Predict the product(s) of the following reactions:


Naming Carboxylic Acid Derivatives -

21-53 (a)
![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-0775.jpg?height=147&width=307&top_left_y=2019&top_left_x=481)
![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-0775.jpg?height=153&width=313&top_left_y=2016&top_left_x=472)
(b)
$\xrightarrow[\text { 2. } \mathrm{H}_{3} \mathrm{O}^{+}]{\text {1. } \mathrm{CH}_{3} \mathrm{CH}_{2} \mathrm{MgBr}}$ ?
![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-0775.jpg?height=123&width=551&top_left_y=2020&top_left_x=1183)
(d)
![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-0775.jpg?height=205&width=421&top_left_y=2185&top_left_x=982)
![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-0776.jpg?height=352&width=1222&top_left_y=187&top_left_x=408)
(e)
![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-0776.jpg?height=101&width=532&top_left_y=215&top_left_x=490)
(h)
![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-0776.jpg?height=129&width=448&top_left_y=391&top_left_x=1039)
![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-0776.jpg?height=136&width=467&top_left_y=382&top_left_x=1038)


Naming Carboxylic Acid Derivatives -

PROBLEM The following reactivity order has been found for the saponification of alkyl acetates by aqueous
21-54 NaOH. Explain.
$\mathrm{CH}_{3} \mathrm{CO}_{2} \mathrm{CH}_{3}>\mathrm{CH}_{3} \mathrm{CO}_{2} \mathrm{CH}_{2} \mathrm{CH}_{3}>\mathrm{CH}_{3} \mathrm{CO}_{2} \mathrm{CH}\left(\mathrm{CH}_{3}\right)_{2}>\mathrm{CH}_{3} \mathrm{CO}_{2} \mathrm{C}\left(\mathrm{CH}_{3}\right)_{3}$


Naming Carboxylic Acid Derivatives -

PROBLEM Explain the observation that attempted Fischer esterification of 2,4,6-trimethylbenzoic acid with
21-55 methanol and HCl is unsuccessful. No ester is obtained, and the acid is recovered unchanged. What alternative method of esterification might be successful?


Naming Carboxylic Acid Derivatives -

PROBLEM Outline methods for the preparation of acetophenone (phenyl methyl ketone) starting from the 21-56 following:
(a) Benzene
(b) Bromobenzene
(c) Methyl benzoate
(d) Benzonitrile
(e) Styrene


Naming Carboxylic Acid Derivatives -

PROBLEM Treatment of 5 -aminopentanoic acid with DCC (dicyclohexylcarbodiimide) yields a lactam. Show 21-57 the structure of the product and the mechanism of the reaction.


Naming Carboxylic Acid Derivatives -

PROBLEM When ethyl benzoate is heated in methanol containing a small amount of HCl , methyl benzoate is 21-58 formed. Propose a mechanism for the reaction.


Naming Carboxylic Acid Derivatives -

PROBLEM tert-Butoxycarbonyl azide, a reagent used in protein synthesis, is prepared by treating 21-59 tert-butoxycarbonyl chloride with sodium azide. Propose a mechanism for this reaction.
![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-0776.jpg?height=128&width=993&top_left_y=1389&top_left_x=414)


Step-Growth Polymers -

PROBLEM The step-growth polymer nylon 6 is prepared from caprolactam. The reaction involves initial
21-60 reaction of caprolactam with water to give an intermediate open-chain amino acid, followed by heating to form the polymer. Propose mechanisms for both steps, and show the structure of nylon 6.
<img class="imgSvg" id = "m6sn3p4d3jwze9zgv8v" src="data:image/svg+xml;base64,<svg id="smiles-m6sn3p4d3jwze9zgv8v" xmlns="http://www.w3.org/2000/svg" viewBox="0 0 185 112.7798575170717" style="width: 184.50527285094014px; height: 112.7798575170717px; overflow: visible;"><defs><linearGradient id="line-m6sn3p4d3jwze9zgv8v-1" gradientUnits="userSpaceOnUse" x1="111.00527539566815" y1="53.554968592143126" x2="142.50527539565545" y2="53.554996866757506"><stop stop-color="currentColor" offset="20%"></stop><stop stop-color="currentColor" offset="100%"></stop></linearGradient><linearGradient id="line-m6sn3p4d3jwze9zgv8v-3" gradientUnits="userSpaceOnUse" x1="111.00527030623755" y1="59.22496859214084" x2="142.50527030622484" y2="59.22499686675522"><stop stop-color="currentColor" offset="20%"></stop><stop stop-color="currentColor" offset="100%"></stop></linearGradient><linearGradient id="line-m6sn3p4d3jwze9zgv8v-5" gradientUnits="userSpaceOnUse" x1="97.33790959420799" y1="84.77047566316135" x2="111.00527285095285" y2="56.38996859214198"><stop stop-color="currentColor" offset="20%"></stop><stop stop-color="currentColor" offset="100%"></stop></linearGradient><linearGradient id="line-m6sn3p4d3jwze9zgv8v-7" gradientUnits="userSpaceOnUse" x1="97.33796054330253" y1="28.009436985331803" x2="111.00527285095285" y2="56.38996859214198"><stop stop-color="currentColor" offset="20%"></stop><stop stop-color="currentColor" offset="100%"></stop></linearGradient><linearGradient id="line-m6sn3p4d3jwze9zgv8v-9" gradientUnits="userSpaceOnUse" x1="66.62767406879934" y1="91.7798575170717" x2="97.33790959420799" y2="84.77047566316135"><stop stop-color="currentColor" offset="20%"></stop><stop stop-color="currentColor" offset="100%"></stop></linearGradient><linearGradient id="line-m6sn3p4d3jwze9zgv8v-11" gradientUnits="userSpaceOnUse" x1="66.62773760128104" y1="21" x2="97.33796054330253" y2="28.009436985331803"><stop stop-color="currentColor" offset="20%"></stop><stop stop-color="currentColor" offset="100%"></stop></linearGradient><linearGradient id="line-m6sn3p4d3jwze9zgv8v-13" gradientUnits="userSpaceOnUse" x1="42" y1="72.13990665254586" x2="66.62767406879934" y2="91.7798575170717"><stop stop-color="currentColor" offset="20%"></stop><stop stop-color="currentColor" offset="100%"></stop></linearGradient><linearGradient id="line-m6sn3p4d3jwze9zgv8v-15" gradientUnits="userSpaceOnUse" x1="42.00002827461434" y1="40.63990665255855" x2="66.62773760128104" y2="21"><stop stop-color="currentColor" offset="20%"></stop><stop stop-color="currentColor" offset="100%"></stop></linearGradient><linearGradient id="line-m6sn3p4d3jwze9zgv8v-17" gradientUnits="userSpaceOnUse" x1="42" y1="72.13990665254586" x2="42.00002827461434" y2="40.63990665255855"><stop stop-color="currentColor" offset="20%"></stop><stop stop-color="currentColor" offset="100%"></stop></linearGradient></defs><mask id="text-mask-m6sn3p4d3jwze9zgv8v"><rect x="0" y="0" width="100%" height="100%" fill="white"></rect><circle cx="142.50527285094014" cy="56.38999686675636" r="7.875" fill="black"></circle><circle cx="97.33796054330253" cy="28.009436985331803" r="7.875" fill="black"></circle></mask><style>
                .element-m6sn3p4d3jwze9zgv8v {
                    font: 14px Helvetica, Arial, sans-serif;
                    alignment-baseline: 'middle';
                }
                .sub-m6sn3p4d3jwze9zgv8v {
                    font: 8.4px Helvetica, Arial, sans-serif;
                }
            </style><g mask="url(#text-mask-m6sn3p4d3jwze9zgv8v)"><line x1="111.00527539566815" y1="53.554968592143126" x2="142.50527539565545" y2="53.554996866757506" style="stroke-linecap:round;stroke-dasharray:none;stroke-width:1.26" stroke="url('#line-m6sn3p4d3jwze9zgv8v-1')"></line><line x1="111.00527030623755" y1="59.22496859214084" x2="142.50527030622484" y2="59.22499686675522" style="stroke-linecap:round;stroke-dasharray:none;stroke-width:1.26" stroke="url('#line-m6sn3p4d3jwze9zgv8v-3')"></line><line x1="97.33790959420799" y1="84.77047566316135" x2="111.00527285095285" y2="56.38996859214198" style="stroke-linecap:round;stroke-dasharray:none;stroke-width:1.26" stroke="url('#line-m6sn3p4d3jwze9zgv8v-5')"></line><line x1="97.33796054330253" y1="28.009436985331803" x2="111.00527285095285" y2="56.38996859214198" style="stroke-linecap:round;stroke-dasharray:none;stroke-width:1.26" stroke="url('#line-m6sn3p4d3jwze9zgv8v-7')"></line><line x1="66.62767406879934" y1="91.7798575170717" x2="97.33790959420799" y2="84.77047566316135" style="stroke-linecap:round;stroke-dasharray:none;stroke-width:1.26" stroke="url('#line-m6sn3p4d3jwze9zgv8v-9')"></line><line x1="66.62773760128104" y1="21" x2="97.33796054330253" y2="28.009436985331803" style="stroke-linecap:round;stroke-dasharray:none;stroke-width:1.26" stroke="url('#line-m6sn3p4d3jwze9zgv8v-11')"></line><line x1="42" y1="72.13990665254586" x2="66.62767406879934" y2="91.7798575170717" style="stroke-linecap:round;stroke-dasharray:none;stroke-width:1.26" stroke="url('#line-m6sn3p4d3jwze9zgv8v-13')"></line><line x1="42.00002827461434" y1="40.63990665255855" x2="66.62773760128104" y2="21" style="stroke-linecap:round;stroke-dasharray:none;stroke-width:1.26" stroke="url('#line-m6sn3p4d3jwze9zgv8v-15')"></line><line x1="42" y1="72.13990665254586" x2="42.00002827461434" y2="40.63990665255855" style="stroke-linecap:round;stroke-dasharray:none;stroke-width:1.26" stroke="url('#line-m6sn3p4d3jwze9zgv8v-17')"></line></g><g><text x="138.56777285094014" y="61.63999686675636" class="element-m6sn3p4d3jwze9zgv8v" fill="currentColor" style="
                text-anchor: start;
                writing-mode: horizontal-tb;
                text-orientation: mixed;
                letter-spacing: normal;
                direction: ltr;
            "><tspan>O</tspan></text><text x="142.50527285094014" y="56.38999686675636" class="debug" fill="#ff0000" style="
                font: 5px Droid Sans, sans-serif;
            "></text><text x="111.00527285095285" y="56.38996859214198" class="debug" fill="#ff0000" style="
                font: 5px Droid Sans, sans-serif;
            "></text><text x="97.33790959420799" y="84.77047566316135" class="debug" fill="#ff0000" style="
                font: 5px Droid Sans, sans-serif;
            "></text><text x="66.62767406879934" y="91.7798575170717" class="debug" fill="#ff0000" style="
                font: 5px Droid Sans, sans-serif;
            "></text><text x="42" y="72.13990665254586" class="debug" fill="#ff0000" style="
                font: 5px Droid Sans, sans-serif;
            "></text><text x="42.00002827461434" y="40.63990665255855" class="debug" fill="#ff0000" style="
                font: 5px Droid Sans, sans-serif;
            "></text><text x="66.62773760128104" y="21" class="debug" fill="#ff0000" style="
                font: 5px Droid Sans, sans-serif;
            "></text><text x="97.33796054330253" y="35.8844369853318" class="element-m6sn3p4d3jwze9zgv8v" fill="currentColor" style="
                text-anchor: start;
                writing-mode: vertical-rl;
                text-orientation: upright;
                letter-spacing: -1px;
                direction: rtl; unicode-bidi: bidi-override;
            "><tspan>N</tspan><tspan style="unicode-bidi: plaintext;">H</tspan></text><text x="97.33796054330253" y="28.009436985331803" class="debug" fill="#ff0000" style="
                font: 5px Droid Sans, sans-serif;
            "></text></g></svg>"/>


Step-Growth Polymers -

Caprolactam


Step-Growth Polymers -


Step-Growth Polymers -

Qiana


A polyimide -

Spectroscopy
PROBLEM How would you distinguish spectroscopically between the following isomer pairs? Tell what 21-64 differences you would expect to see.
(a) N -Methylpropanamide and $\mathrm{N}, \mathrm{N}$-dimethylacetamide
(b) 5-Hydroxypentanenitrile and cyclobutanecarboxamide
(c) 4-Chlorobutanoic acid and 3-methoxypropanoyl chloride
(d) Ethyl propanoate and propyl acetate


A polyimide -

PROBLEM Propose a structure for a compound, $\mathrm{C}_{4} \mathrm{H}_{7} \mathrm{ClO}_{2}$, that has the following IR and ${ }^{1} \mathrm{H}$ NMR spectra:
21-65
![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-0777.jpg?height=492&width=1383&top_left_y=968&top_left_x=417)
![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-0777.jpg?height=494&width=1402&top_left_y=1515&top_left_x=421)

PROBLEM Assign structures to compounds with the following ${ }^{1} \mathrm{H}$ NMR spectra:
21-66
(a) $\mathrm{C}_{4} \mathrm{H}_{7} \mathrm{ClO}$


A polyimide -

IR: $1810 \mathrm{~cm}^{-1}$
![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-0778.jpg?height=500&width=1402&top_left_y=322&top_left_x=475)
(b) $\mathrm{C}_{5} \mathrm{H}_{7} \mathrm{NO}_{2}$


A polyimide -

IR: 2250, $1735 \mathrm{~cm}^{-1}$
![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-0778.jpg?height=494&width=1394&top_left_y=951&top_left_x=482)


General Problems -

PROBLEM The following reactivity order has been found for the basic hydrolysis of $p$-substituted methyl
21-67 benzoates:
$\mathrm{Y}=\mathrm{NO}_{2}>\mathrm{Br}>\mathrm{H}>\mathrm{CH}_{3}>\mathrm{OCH}_{3}$
How can you explain this reactivity order? Where would you expect $\mathrm{Y}=\mathrm{C} \equiv \mathrm{N}, \mathrm{Y}=\mathrm{CHO}$, and $\mathrm{Y}=\mathrm{NH}_{2}$ to be in the reactivity list?
![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-0778.jpg?height=153&width=934&top_left_y=1821&top_left_x=417)


General Problems -

PROBLEM When a carboxylic acid is dissolved in isotopically labeled water, the label rapidly becomes
21-68 incorporated into both oxygen atoms of the carboxylic acid. Explain.
![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-0778.jpg?height=125&width=445&top_left_y=2106&top_left_x=417)


General Problems -

PROBLEM We said in Section 21.6 that mechanistic studies on ester hydrolysis have been carried out using
21-69 ethyl propanoate labeled with ${ }^{18} \mathrm{O}$ in the ether-like oxygen. Assume that ${ }^{18} \mathrm{O}$-labeled acetic acid is your only source of isotopic oxygen, and then propose a synthesis of the labeled ethyl propanoate.


General Problems -

PROBLEM Treatment of a carboxylic acid with trifluoroacetic anhydride leads to an unsymmetrical anhydride
21-70 that rapidly reacts with alcohol to give an ester.
![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-0779.jpg?height=134&width=1153&top_left_y=188&top_left_x=413)
(a) Propose a mechanism for formation of the unsymmetrical anhydride.
(b) Why is the unsymmetrical anhydride unusually reactive?
(c) Why does the unsymmetrical anhydride react as indicated rather than giving a trifluoroacetate ester plus carboxylic acid?


General Problems -


General Problems -

Butacetin


General Problems -

PROBLEM Phenyl 4-aminosalicylate is a drug used in the treatment of tuberculosis. Propose a synthesis of this
21-72 compound starting from 4-nitrosalicylic acid.
![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-0779.jpg?height=302&width=909&top_left_y=906&top_left_x=407)


General Problems -

PROBLEM Tranexamic acid, a drug useful against blood clotting, is prepared commercially from
21-74 p-methylbenzonitrile. Formulate the steps likely to be used in the synthesis. (Don't worry about cis-trans isomers; heating to $300^{\circ} \mathrm{C}$ interconverts the isomers.)
![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-0779.jpg?height=207&width=635&top_left_y=1699&top_left_x=420)


General Problems -

PROBLEM One frequently used method for preparing methyl esters is by reaction of carboxylic acids with
21-75 diazomethane, $\mathrm{CH}_{2} \mathrm{~N}_{2}$.
![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-0779.jpg?height=310&width=971&top_left_y=2030&top_left_x=406)


General Problems -

The reaction occurs in two steps: (1) protonation of diazomethane by the carboxylic acid to yield methyldiazonium ion, $\mathrm{CH}_{3} \mathrm{~N}_{2}{ }^{+}$, plus a carboxylate ion; and (2) reaction of the carboxylate ion with $\mathrm{CH}_{3} \mathrm{~N}_{2}{ }^{+}$.
(a) Draw two resonance structures of diazomethane, and account for step 1.
(b) What kind of reaction occurs in step 2?


General Problems -

PROBLEM Draw the structure of the polymer you would expect to obtain from reaction of dimethyl 21-76 terephthalate with a triol such as glycerol. What structural feature would this new polymer have that was not present in Dacron (Table 21.2)? How do you think this new feature might affect the properties of the polymer?


General Problems -

PROBLEM Assign structures to compounds with the following ${ }^{1} \mathrm{H}$ NMR spectra:
21-77 (a) $\mathrm{C}_{5} \mathrm{H}_{10} \mathrm{O}_{2}$
IR: $1735 \mathrm{~cm}^{-1}$
![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-0780.jpg?height=502&width=1397&top_left_y=627&top_left_x=478)
(b) $\mathrm{C}_{11} \mathrm{H}_{12} \mathrm{O}_{2}$


General Problems -

IR: $1710 \mathrm{~cm}^{-1}$
![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-0780.jpg?height=500&width=1394&top_left_y=1257&top_left_x=479)


General Problems -

PROBLEM Propose structures for compounds with the following ${ }^{1} \mathrm{H}$ NMR spectra:
21-78 (a) $\mathrm{C}_{5} \mathrm{H}_{9} \mathrm{ClO}_{2}$
IR: $1735 \mathrm{~cm}^{-1}$
![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-0780.jpg?height=519&width=1402&top_left_y=1947&top_left_x=470)
(b) $\mathrm{C}_{7} \mathrm{H}_{12} \mathrm{O}_{4}$


General Problems -

IR: $1735 \mathrm{~cm}^{-1}$
![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-0781.jpg?height=503&width=1399&top_left_y=323&top_left_x=474)


General Problems -

PROBLEM Propose a structure for the compound with the formula $\mathrm{C}_{19} \mathrm{H}_{9} \mathrm{NO}_{2}$ and the following IR and NMR 21-79 spectra
![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-0781.jpg?height=527&width=1449&top_left_y=967&top_left_x=414)
![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-0781.jpg?height=500&width=1372&top_left_y=1490&top_left_x=420)
![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-0781.jpg?height=527&width=1375&top_left_y=1992&top_left_x=418)


General Problems -

PROBLEM Draw the structure of the compound that produced the following spectra. The infrared spectrum has 21-80 strong bands at 1720 and $1738 \mathrm{~cm}^{-1}$.
![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-0782.jpg?height=693&width=1470&top_left_y=304&top_left_x=422)


General Problems -

PROBLEM When an amide is formed from an acid chloride or an anhydride, two equivalents of base are
21-81 required. However, when an ester is used as the starting material, only one equivalent of base is needed. Explain this reactivity in terms of basicity of the leaving groups.


General Problems -

PROBLEM Epoxy adhesives are prepared in two steps. $\mathrm{S}_{\mathrm{N}} 2$ reaction of the disodium salt of bisphenol A with
21-82 epichlorohydrin forms a "prepolymer," which is then "cured" by treatment with a triamine such as $\mathrm{H}_{2} \mathrm{NCH}_{2} \mathrm{CH}_{2} \mathrm{NHCH}_{2} \mathrm{CH}_{2} \mathrm{NH}_{2}$.
![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-0782.jpg?height=202&width=782&top_left_y=1333&top_left_x=647)
![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-0782.jpg?height=356&width=1494&top_left_y=1557&top_left_x=413)


General Problems -

Draw structures to show how addition of the triamine results in a strengthening of the polymer.


CHAPTER 22 -

Carbonyl Alpha-Substitution Reactions
![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-0783.jpg?height=912&width=1890&top_left_y=349&top_left_x=231)


CHAPTER 22 -

FIGURE 22.1 Tear gas is a controversial riot-control device used by some military and police forces. It is a simple chloroketone made by a carbonyl $\alpha$-substitution reaction. (credit: modification of work "Tear Gas in CWB Hennessy Road View" by The Stand News/Wikimedia Commons, Public Domain)


CHAPTER CONTENTS -


CHAPTER CONTENTS - 22.1 Keto-Enol Tautomerism

22.2 Reactivity of Enols: $\alpha$-Substitution Reactions
22.3 Alpha Halogenation of Aldehydes and Ketones
22.4 Alpha Bromination of Carboxylic Acids
22.5 Acidity of Alpha Hydrogen Atoms: Enolate Ion Formation
22.6 Reactivity of Enolate Ions
22.7 Alkylation of Enolate Ions