Visualizing Chemistry -

PROBLEM Name the following amine, including $R, S$ stereochemistry, and draw the product of its reaction with
24-28 excess iodomethane followed by heating with $\mathrm{Ag}_{2} \mathrm{O}$ (Hofmann elimination). Is the stereochemistry of the alkene product $Z$ or $E$ ? Explain.
![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-0888.jpg?height=359&width=686&top_left_y=1834&top_left_x=416)


Visualizing Chemistry -

PROBLEM Which nitrogen atom in the following compound is most basic? Explain.
24-29
![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-0889.jpg?height=396&width=544&top_left_y=187&top_left_x=411)


Mechanism Problems -

PROBLEM Predict the product(s) and write the mechanism for each of the following reactions:
24-30 (a)
![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-0889.jpg?height=161&width=535&top_left_y=727&top_left_x=481)
![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-0889.jpg?height=150&width=540&top_left_y=738&top_left_x=478)
(b)
![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-0889.jpg?height=123&width=527&top_left_y=730&top_left_x=1089)

PROBLEM Predict the product(s) and write the mechanism for each of the following reactions:
24-31 (a)
![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-0889.jpg?height=196&width=753&top_left_y=978&top_left_x=480)
(b)
![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-0889.jpg?height=202&width=654&top_left_y=1189&top_left_x=481)

PROBLEM Predict the product(s) and write the mechanism for each of the following reactions:
24-32 (a)
![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-0889.jpg?height=128&width=486&top_left_y=1481&top_left_x=478)
![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-0889.jpg?height=123&width=487&top_left_y=1489&top_left_x=477)
(b)
![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-0889.jpg?height=139&width=513&top_left_y=1486&top_left_x=1061)
(c)
![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-0889.jpg?height=135&width=510&top_left_y=1635&top_left_x=482)
(d)
![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-0889.jpg?height=135&width=580&top_left_y=1640&top_left_x=1068)

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


Mechanism Problems -


Mechanism Problems -

PROBLEM The diazotization of aniline first involves the formation of $\mathrm{NO}^{+}$(nitrosonium ion) by the dehydration
24-34 of nitrous acid with sulfuric acid. The aniline nitrogen then acts as a nucleophile and eventually loses water. Propose a mechanism for the formation of the dizaonium salt of aniline using curved arrows to show all electron movement.


Mechanism Problems -

PROBLEM Substituted pyrroles are often prepared by treatment of a 1,4-diketone with ammonia. Propose a 24-35 mechanism.
![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-0890.jpg?height=171&width=733&top_left_y=191&top_left_x=414)


Mechanism Problems -

PROBLEM 3,5-Dimethylisoxazole is prepared by reaction of 2,4-pentanedione with hydroxylamine. Propose a
24-36 mechanism.
![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-0890.jpg?height=196&width=744&top_left_y=496&top_left_x=417)


Mechanism Problems -

3,5-Dimethylisoxazole
PROBLEM One problem with reductive amination as a method of amine synthesis is that by-products are
24-37 sometimes obtained. For example, reductive amination of benzaldehyde with methylamine leads to a mixture of $N$-methylbenzylamine and $N$-methyldibenzylamine. How do you suppose the tertiary amine by-product is formed? Propose a mechanism.


Mechanism Problems -

PROBLEM Chlorophyll, heme, vitamin $\mathrm{B}_{12}$, and a host of other substances are biosynthesized from
24-38 porphobilinogen (PBG), which is itself formed from condensation of two molecules of 5-aminolevulinate. The two 5-aminolevulinates are bound to lysine (Lys) amino acids in the enzyme, one in the enamine form and one in the imine form, and their condensation is thought to occur by the following steps. Use curved arrows to show the mechanism of each step.
![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-0890.jpg?height=340&width=1429&top_left_y=1212&top_left_x=467)


Mechanism Problems -

Enzyme-bound 5-aminolevulinate
![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-0890.jpg?height=407&width=1077&top_left_y=1645&top_left_x=470)


Mechanism Problems -

PROBLEM Choline, a component of the phospholipids in cell membranes, can be prepared by $\mathrm{S}_{\mathrm{N}} 2$ reaction of
24-39 trimethylamine with ethylene oxide. Show the structure of choline, and propose a mechanism for the reaction.
![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-0890.jpg?height=88&width=570&top_left_y=2230&top_left_x=428)


Mechanism Problems -

PROBLEM The antitumor antibiotic mitomycin C functions by forming cross-links in DNA chains. 24-40
![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-0891.jpg?height=359&width=1318&top_left_y=189&top_left_x=420)


Mechanism Problems -

Mitomycin C
![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-0891.jpg?height=359&width=700&top_left_y=631&top_left_x=414)
(a) The first step is loss of methoxide and formation of an iminium ion intermediate that is deprotonated to give an enamine. Show the mechanism.
(b) The second step is reaction of the enamine with DNA to open the three-membered, nitrogencontaining (aziridine) ring. Show the mechanism.
(c) The third step is loss of carbamate $\left(\mathrm{NH}_{2} \mathrm{CO}_{2}{ }^{-}\right)$and formation of an unsaturated iminium ion, followed by a conjugate addition of another part of the DNA chain. Show the mechanism.
PROBLEM $\alpha$-Amino acids can be prepared by the Strecker synthesis, a two-step process in which an aldehyde
24-41 is treated with ammonium cyanide followed by hydrolysis of the amino nitrile intermediate with aqueous acid. Propose a mechanism for the reaction.
![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-0891.jpg?height=156&width=804&top_left_y=1429&top_left_x=411)


Mechanism Problems -

An $\alpha$-amino acid
PROBLEM One of the reactions used in determining the sequence of nucleotides in a strand of DNA is reaction
24-42 with hydrazine. Propose a mechanism for the following reaction, which occurs by an initial conjugate addition followed by internal amide formation.
![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-0891.jpg?height=305&width=744&top_left_y=1810&top_left_x=414)


Mechanism Problems -

PROBLEM When an $\alpha$-hydroxy amide is treated with $\mathrm{Br}_{2}$ in aqueous NaOH under Hofmann rearrangement
24-43 conditions, loss of $\mathrm{CO}_{2}$ occurs and a chain-shortened aldehyde is formed. Propose a mechanism.
![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-0891.jpg?height=196&width=1047&top_left_y=2252&top_left_x=414)


Mechanism Problems -

PROBLEM The following transformation involves a conjugate nucleophilic addition reaction (Section 19.13)
24-44 followed by an intramolecular nucleophilic acyl substitution reaction (Section 21.2). Show the mechanism.
![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-0892.jpg?height=237&width=1075&top_left_y=348&top_left_x=414)

PROBLEM Propose a mechanism for the following reaction:
24-45
![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-0892.jpg?height=150&width=1454&top_left_y=673&top_left_x=409)


Mechanism Problems -

PROBLEM One step in the biosynthesis of morphine is the reaction of dopamine with
24-46 $p$-hydroxyphenylacetaldehyde to give ( $S$ )-norcoclaurine. Assuming that the reaction is acidcatalyzed, propose a mechanism.
![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-0892.jpg?height=435&width=1169&top_left_y=978&top_left_x=418)


Mechanism Problems -

PROBLEM Draw structures corresponding to the following IUPAC names:
24-48
(a) $N, N$-Dimethylaniline
(b) (Cyclohexylmethyl)amine
(c) $N$-Methylcyclohexylamine
(d) (2-Methylcyclohexyl)amine (e) 3-(N,N-Dimethylamino)propanoic acid


Amine Basicity -

PROBLEM Although pyrrole is a much weaker base than most other amines, it is a much stronger acid ( $\mathrm{p} K_{\mathrm{a}} \approx$
24-50 15 for the pyrrole versus 35 for diethylamine). The $\mathrm{N}-\mathrm{H}$ hydrogen is readily abstracted by base to yield the pyrrole anion, $\mathrm{C}_{4} \mathrm{H}_{4} \mathrm{~N}^{-}$. Explain.


Amine Basicity -

PROBLEM Histamine, whose release in the body triggers nasal secretions and constricted airways, has three
24-51 nitrogen atoms. List them in order of increasing basicity and explain your ordering.
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Amine Basicity -

Histamine


Amine Basicity -

PROBLEM Account for the fact that $p$-nitroaniline ( $\mathrm{p} K_{\mathrm{a}}=1.0$ ) is less basic than $m$-nitroaniline ( $\mathrm{p} K_{\mathrm{a}}=2.5$ ) by
24-52 a factor of 30 . Draw resonance structures to support your argument. (The $\mathrm{p} K_{\mathrm{a}}$ values refer to the corresponding ammonium ions.)


Synthesis of Amines -

PROBLEM How would you prepare the following substances from 1-butanol?
24-53 (a) Butylamine (b) Dibutylamine (c) Propylamine (d) Pentylamine
(e) $N, N$-Dimethylbutylamine (f) Propene

PROBLEM How would you prepare the following substances from pentanoic acid?
24-54 (a) Pentanamide (b) Butylamine (c) Pentylamine (d) 2-Bromopentanoic acid
(e) Hexanenitrile (f) Hexylamine
PROBLEM How would you prepare aniline from the following starting materials?
24-55 (a) Benzene (b) Benzamide (c) Toluene
PROBLEM How would you prepare benzylamine, $\mathrm{C}_{6} \mathrm{H}_{5} \mathrm{CH}_{2} \mathrm{NH}_{2}$, from benzene? More than one step is needed.
24-56
PROBLEM How might you prepare pentylamine from the following starting materials?
24-57 (a) Pentanamide
(b) Pentanenitrile
(c) 1-Butene
(d) Hexanamide
(e) 1-Butanol
(f) 5-Decene (g) Pentanoic acid


Synthesis of Amines -


Synthesis of Amines -

Ephedrine


Reactions of Amines -

PROBLEM How would you convert aniline into each of the following products?
24-59
(a) Benzene
(b) Benzamide
(c) Toluene


Reactions of Amines -

PROBLEM Write the structures of the major organic products you would expect from reaction of $m$-toluidine 24-60 ( $m$-methylaniline) with the following reagents:
(a) $\mathrm{Br}_{2}$ (1 equivalent)
(b) $\mathrm{CH}_{3} \mathrm{I}$ (excess)
(c) $\mathrm{CH}_{3} \mathrm{COCl}$ in pyridine
(d) The product of (c), then $\mathrm{HSO}_{3} \mathrm{Cl}$

PROBLEM Show the products from reaction of $p$-bromoaniline with the following reagents:
24-61 (a) $\mathrm{CH}_{3} \mathrm{I}$ (excess)
(b) HCl
(c) $\mathrm{HNO}_{2}, \mathrm{H}_{2} \mathrm{SO}_{4}$
(d) $\mathrm{CH}_{3} \mathrm{COCl}$
(e) $\mathrm{CH}_{3} \mathrm{MgBr}$
(f) $\mathrm{CH}_{3} \mathrm{CH}_{2} \mathrm{Cl}, \mathrm{AlCl}_{3}$ (g) Product of (c) with $\mathrm{CuCl}, \mathrm{HCl}$ (h) Product of (d) with $\mathrm{CH}_{3} \mathrm{CH}_{2} \mathrm{Cl}, \mathrm{AlCl}_{3}$


Reactions of Amines -

PROBLEM What are the major products you would expect from Hofmann elimination of the following amines?


Reactions of Amines -


Reactions of Amines -

PROBLEM Predict the product(s) of the following reactions. If more than one product is formed, tell which is 24-64 major.
(a)
![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-0894.jpg?height=204&width=971&top_left_y=1427&top_left_x=482)
(b)
![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-0894.jpg?height=150&width=809&top_left_y=1649&top_left_x=482)
(c)
![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-0894.jpg?height=228&width=917&top_left_y=1832&top_left_x=482)
(d)
![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-0894.jpg?height=87&width=790&top_left_y=2076&top_left_x=478)


Reactions of Amines -

Spectroscopy
PROBLEM Phenacetin, a substance formerly used in over-the-counter headache remedies, has the formula
24-65 $\mathrm{C}_{10} \mathrm{H}_{13} \mathrm{NO}_{2}$. Phenacetin is neutral and does not dissolve in either acid or base. When warmed with aqueous NaOH , phenacetin yields an amine, $\mathrm{C}_{8} \mathrm{H}_{11} \mathrm{NO}$, whose ${ }^{1} \mathrm{H}$ NMR spectrum is shown. When heated with HI , the amine is cleaved to an aminophenol, $\mathrm{C}_{6} \mathrm{H}_{7} \mathrm{NO}$. What is the structure of
phenacetin, and what are the structures of the amine and the aminophenol?
![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-0895.jpg?height=500&width=1397&top_left_y=257&top_left_x=418)


Reactions of Amines -

PROBLEM Propose structures for amines with the following ${ }^{1} \mathrm{H}$ NMR spectra:
24-66 (a) $\mathrm{C}_{3} \mathrm{H}_{9} \mathrm{NO}$
![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-0895.jpg?height=500&width=1402&top_left_y=886&top_left_x=475)
(b) $\mathrm{C}_{4} \mathrm{H}_{11} \mathrm{NO}_{2}$
![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-0895.jpg?height=497&width=1397&top_left_y=1448&top_left_x=478)
(c) $\mathrm{C}_{8} \mathrm{H}_{11} \mathrm{~N}$
![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-0895.jpg?height=510&width=1402&top_left_y=2000&top_left_x=475)


Reactions of Amines -

PROBLEM Draw the structure of the amine that produced the ${ }^{1} \mathrm{H}$ NMR spectrum shown in Problem 24-66(c).
24-67 This compound has a single strong peak in its IR spectrum at $3280 \mathrm{~cm}^{-1}$.


General Problems -

PROBLEM Fill in the missing reagents a-e in the following scheme:
24-68
![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-0896.jpg?height=424&width=1080&top_left_y=428&top_left_x=411)


General Problems -


General Problems -

Oxazole


General Problems -

PROBLEM Protonation of an amide using strong acid occurs on oxygen rather than on nitrogen. Suggest a 24-70 reason for this behavior, taking resonance into account.
![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-0896.jpg?height=155&width=508&top_left_y=1218&top_left_x=418)


General Problems -

PROBLEM What is the structure of the compound with formula $\mathrm{C}_{8} \mathrm{H}_{11} \mathrm{~N}$ that produced the following IR 24-71 spectrum?
![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-0896.jpg?height=524&width=1449&top_left_y=1516&top_left_x=411)


General Problems -

PROBLEM Fill in the missing reagents a-d in the following synthesis of racemic methamphetamine from 24-72 benzene.
![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-0896.jpg?height=209&width=1348&top_left_y=2167&top_left_x=410)


Cyclopentamine -

PROBLEM Tetracaine is a substance used as a spinal anesthetic.
24-74
![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-0897.jpg?height=327&width=717&top_left_y=403&top_left_x=414)
(a) How would you prepare tetracaine from the corresponding aniline derivative, $\mathrm{ArNH}_{2}$ ?
(b) How would you prepare tetracaine from $p$-nitrobenzoic acid?
(c) How would you prepare tetracaine from benzene?


Cyclopentamine -

PROBLEM Atropine, $\mathrm{C}_{17} \mathrm{H}_{23} \mathrm{NO}_{3}$, is a poisonous alkaloid isolated from the leaves and roots of Atropa
24-75 belladonna, the deadly nightshade. In small doses, atropine acts as a muscle relaxant; 0.5 ng (nanogram, $10^{-9} \mathrm{~g}$ ) is sufficient to cause pupil dilation. On basic hydrolysis, atropine yields tropic acid, $\mathrm{C}_{6} \mathrm{H}_{5} \mathrm{CH}\left(\mathrm{CH}_{2} \mathrm{OH}\right) \mathrm{CO}_{2} \mathrm{H}$, and tropine, $\mathrm{C}_{8} \mathrm{H}_{15} \mathrm{NO}$. Tropine is an optically inactive alcohol that yields tropidene on dehydration with $\mathrm{H}_{2} \mathrm{SO}_{4}$. Propose a structure for atropine.
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Cyclopentamine -

PROBLEM Tropidene (Problem 24-75) can be converted by a series of steps into tropilidene 24-76 (1,3,5-cycloheptatriene). How would you accomplish this conversion?


Cyclopentamine -

PROBLEM Propose a structure for the product with formula $\mathrm{C}_{9} \mathrm{H}_{17} \mathrm{~N}$ that results when 24-77 2-(2-cyanoethyl)cyclohexanone is reduced catalytically.
![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-0897.jpg?height=144&width=567&top_left_y=1603&top_left_x=416)


Cyclopentamine -

PROBLEM Coniine, $\mathrm{C}_{8} \mathrm{H}_{17} \mathrm{~N}$, is the toxic principle of the poison hemlock drunk by Socrates. When subjected
24-78 to Hofmann elimination, coniine yields 5 -( $N, N$-dimethylamino)-1-octene. If coniine is a secondary amine, what is its structure?


Cyclopentamine -

PROBLEM How would you synthesize coniine (Problem 24-78) from acrylonitrile ( $\mathrm{H}_{2} \mathrm{C}=\mathrm{CHCN}$ ) and ethyl
24-79 3-oxohexanoate $\left(\mathrm{CH}_{3} \mathrm{CH}_{2} \mathrm{CH}_{2} \mathrm{COCH}_{2} \mathrm{CO}_{2} \mathrm{Et}\right)$ ? (See Problem 24-77.)
PROBLEM Tyramine is an alkaloid found, among other places, in mistletoe and ripe cheese. How would you
24-80 synthesize tyramine from benzene? From toluene?
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PROBLEM Reaction of anthranilic acid (o-aminobenzoic acid) with $\mathrm{HNO}_{2}$ and $\mathrm{H}_{2} \mathrm{SO}_{4}$ yields a diazonium salt
24-81 that can be treated with base to yield a neutral diazonium carboxylate.
(a) What is the structure of the neutral diazonium carboxylate?
(b) Heating the diazonium carboxylate results in the formation of $\mathrm{CO}_{2}, \mathrm{~N}_{2}$, and an intermediate that reacts with 1,3-cyclopentadiene to yield the following product:
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Cyclopentamine -

What is the structure of the intermediate, and what kind of reaction does it undergo with cyclopentadiene?


Cyclopentamine -

PROBLEM Cyclooctatetraene was first synthesized in 1911 by a route that involved the following 24-82 transformation:
![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-0898.jpg?height=150&width=437&top_left_y=668&top_left_x=413)


Cyclopentamine -

How might you use the Hofmann elimination to accomplish this reaction? How would you finish the synthesis by converting cyclooctatriene into cyclooctatetraene?


Cyclopentamine -

PROBLEM Propose structures for compounds that show the following ${ }^{1} \mathrm{H}$ NMR spectra.
24-83 (a) $\mathrm{C}_{9} \mathrm{H}_{13} \mathrm{~N}$
![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-0898.jpg?height=503&width=1399&top_left_y=1055&top_left_x=477)
(b) $\mathrm{C}_{15} \mathrm{H}_{17} \mathrm{~N}$
![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-0898.jpg?height=505&width=1394&top_left_y=1623&top_left_x=474)


Cyclopentamine -

PROBLEM 4-Dimethylaminopyridine (DMAP) acts as a catalyst in acyl transfer reactions. DMAP's catalytic
24-84 activity stems from its nucleophilic character at the pyridine nitrogen, not the dimethylamino group. Explain this behavior, taking resonance into account.
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CHAPTER 25 <br> Biomolecules: Carbohydrates -


FIGURE 25.1 Produced by honeybees from the nectar of flowers, honey is primarily a mixture of the two simple sugars fructose and glucose. (credit: modification of work "Apis mellifera" by Thomas Bresson/Flickr, CC BY 2.0)


CHAPTER CONTENTS -

25.1 Classification of Carbohydrates
25.2 Representing Carbohydrate Stereochemistry: Fischer Projections
25.3 D,L Sugars
25.4 Configurations of the Aldoses
25.5 Cyclic Structures of Monosaccharides: Anomers
25.6 Reactions of Monosaccharides
25.7 The Eight Essential Monosaccharides
25.8 Disaccharides
25.9 Polysaccharides and Their Synthesis
25.10 Some Other Important Carbohydrates


CHAPTER CONTENTS -

WHY THIS CHAPTER? We've now seen all the common functional groups and reaction types that occur in organic and biological chemistry. In this and the next four chapters, we'll focus on the major classes of biological molecules, beginning with a look at the structures and primary biological functions of carbohydrates. Then, in Chapter 29, we'll return to the subject to see how carbohydrates are both synthesized and degraded in organisms.


CHAPTER CONTENTS -

Carbohydrates occur in every living organism. The sugar and starch in food, and the cellulose in wood, paper, and cotton are nearly pure carbohydrates. Modified carbohydrates form part of the coating around living cells, other carbohydrates are part of the nucleic acids that carry our genetic information, and still others are used as medicines.


CHAPTER CONTENTS -

The word carbohydrate derives historically from the fact that glucose, the first simple carbohydrate to be obtained in pure form, has the molecular formula $\mathrm{C}_{6} \mathrm{H}_{12} \mathrm{O}_{6}$ and was originally thought to be a "hydrate of
carbon, $\mathrm{C}_{6}\left(\mathrm{H}_{2} \mathrm{O}\right)_{6}$." This view was soon abandoned, but the name persisted. Today, the term carbohydrate is used to refer loosely to the broad class of polyhydroxylated aldehydes and ketones commonly called sugars. Glucose, also known as dextrose in medical work, is the most familiar example.
![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-0900.jpg?height=356&width=716&top_left_y=342&top_left_x=707)


CHAPTER CONTENTS -

Glucose (dextrose),
a pentahydroxyhexanal
Carbohydrates are synthesized by green plants during photosynthesis, a complex process in which sunlight provides the energy to convert $\mathrm{CO}_{2}$ and $\mathrm{H}_{2} \mathrm{O}$ into glucose plus oxygen. Many molecules of glucose are then chemically linked for storage by the plant in the form of either cellulose or starch. It has been estimated that more than $50 \%$ of the dry weight of the earth's biomass-all plants and animals-consists of glucose polymers. When eaten and metabolized, carbohydrates then provide animals with a source of readily available energy. Thus, carbohydrates act as the chemical intermediaries by which solar energy is stored and used to support life.


CHAPTER CONTENTS -

$$
6 \mathrm{CO}_{2}+6 \mathrm{H}_{2} \mathrm{O} \xrightarrow{\text { Sunlight }} 6 \mathrm{O}_{2}+\mathrm{C}_{6} \mathrm{H}_{12} \mathrm{O}_{6} \longrightarrow \text { Cellulose, starch }
$$


CHAPTER CONTENTS -

Glucose
Because humans and most other mammals lack the enzymes needed for digestion of cellulose, they require starch as their dietary source of carbohydrates. Grazing animals such as cows, however, have microorganisms in their first stomach that are able to digest cellulose. The energy stored in cellulose is thus moved up the biological food chain when these ruminant animals eat grass and are themselves used for food.


CHAPTER CONTENTS - 25.1 Classification of Carbohydrates

Carbohydrates are generally classified as either simple or complex. Simple sugars, or monosaccharides, are carbohydrates like glucose and fructose that can't be converted into smaller sugars by hydrolysis. Complex carbohydrates are made of two or more simple sugars linked together by acetal bonds (Section 19.10). Sucrose (table sugar), for instance, consists of one glucose linked to one fructose. Similarly, cellulose is made up of several thousand glucose units linked together. Enzyme-catalyzed hydrolysis of a complex carbohydrate breaks it down into its constituent monosaccharides.
![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-0900.jpg?height=250&width=1137&top_left_y=1737&top_left_x=494)


Sucrose (a disaccharide)
![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-0900.jpg?height=305&width=1058&top_left_y=2119&top_left_x=501)


Monosaccharides are further classified as either aldoses or ketoses. The -ose suffix designates a carbohydrate, and the prefixes aldo- and keto- identify the kind of carbonyl group in the molecule, whether aldehyde or ketone.

The number of carbon atoms in the monosaccharide is indicated by the appropriate numerical prefix tri-, tetr-, pent-, hex-, and so forth, in the name. Putting it all together, glucose is an aldohexose, a six-carbon aldehyde sugar; fructose is a ketohexose, a six-carbon keto sugar; ribose is an aldopentose, a five-carbon aldehyde sugar; and sedoheptulose is a ketoheptose, a seven-carbon keto sugar. Most of the common simple sugars are either pentoses or hexoses.
![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-0901.jpg?height=492&width=1094&top_left_y=426&top_left_x=510)


CHAPTER CONTENTS - 25.2 Representing Carbohydrate Stereochemistry: Fischer Projections

Because most carbohydrates have numerous chirality centers, it was recognized long ago that a quick method for representing their stereochemistry was needed. In 1891, the German chemist Emil Fischer suggested a method based on the projection of a tetrahedral carbon atom onto a flat surface. These Fischer projections were soon adopted and are still a common means of representing stereochemistry at chirality centers in carbohydrate chemistry.


A tetrahedral carbon atom is represented in a Fischer projection by two crossed lines. The horizontal lines represent bonds coming out of the page, and the vertical lines represent bonds going into the page.


For example, (R)-glyceraldehyde, the simplest monosaccharide, can be drawn as in FIGURE 25.2.
![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-0901.jpg?height=362&width=1267&top_left_y=1879&top_left_x=407)


FIGURE 25.2 A Fischer projection of (R)-glyceraldehyde.
Because a given chiral molecule can be drawn in many ways, it's sometimes necessary to compare two projections to see if they represent the same or different enantiomers. To test for identity, Fischer projections can be moved around on the paper, but only two kinds of motions are allowed; moving a Fischer projection in any other way inverts its meaning.

- A Fischer projection can be rotated on the page by $180^{\circ}$, but not by $90^{\circ}$ or $270^{\circ}$. Only a $180^{\circ}$ rotation
maintains the Fischer convention by keeping the same substituent groups going into and coming out of the plane. In the following Fischer projection of ( $R$ )-glyceraldehyde, for instance, the -H and -OH groups come out of the plane both before and after a $180^{\circ}$ rotation.
![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-0902.jpg?height=372&width=1131&top_left_y=345&top_left_x=524)