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`

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`ORGANIC
`CHEMISTRY,:
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`·paula·Yurkanis BfUjd~
`_University of California, Santa B:arbara ·,·,
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`PRENTICE HAiL · : ')
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`Upper Saddle River, New'JerStiY 074$8' -,· ,
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`

`Librmy of Congress Cataloging-in-Publication Data
`Bruice, Paula Yurkanis
`Organic chemistry I Paula Yurkanis Bruice.-2nd ed.
`p.
`em.
`Includes index.
`ISBN 0-13-841925-6
`I. Chemistry, Organic
`QD251.2.B784 1998
`547-dc21
`
`I. Title.
`
`97-29107
`CIP
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`Senior Editor: John Challice
`Editor in Chief: Paul F. Corey
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`© 1998, 1995 by Prentice-Hall, Inc.
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`All rights reserved. No part of this book may be
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`

`CARBOHYDRATES
`
`u-o-glucose, ~-o-glu cose
`
`Carbohydrates are the first group .of bioorganic compounds we will stud.
`
`Bioorganic compounds are organic compounds that are found in biological
`systems. The structures of most bioorganic compounds are more comph·
`cated than the structures of many of the organic compounds you are used to seeing.
`but do not let the complicated-looking structures fool you into thinking their chelll
`istry is equally complicated. Bioorganic compounds follow the same principles P
`structure and reactivity as the organic molecules we have discussed so far. On
`reason bioorganic compounds have complicated structures is because the com
`pounds must be able to recognize each other, and much of their structure is for tlu
`purpose-a concept known as molecular recognition.
`Carbohydrates are the most abundant class of compounds in the biologiL· 1
`world, making up more than 50%" of the dry weight of Earth's biom~1'
`Carbohydrates are important constituents of all living organisms, and have a vant:l.
`of different functions. Some are impqrtant structural components of cells, and 5011
`act as recognition sites on cell surfaces. Others serve as a major source of roetaboh
`energy. For example, the leaves, stems, and roots of plants contain carbohydnll ·
`that plants use both for their own metabolic needs and for the metabolic need~
`the animals that eat them.
`-
`The first carbohydrates investigated had molecular formulas that n1ade th~
`appear to be hydrates · of carbon, C,iH20)n; hence the name. Later stru.ctu~l
`studies revealed that these compouncis were not hydrates because they .dtd d l
`contain intact water molecules. However, the term "carbohydrate" perstste ·
`now refers either to polyhydroxy aldehydes such as D-glucose and polyhydrtt ·
`ketones such as D-fructose, or to compounds such ·o as sucrose that can . .
`heillll
`Th
`tru
`hydrolyzed to polyhydroxy aldehydes or polyhydroxy ketones.
`e c
`structures of ~arbohydr~tes_ are co~only represented by wedge-and-dash sha'
`tures or by Fischer proJections. NotJce that both D-glucose and D-fructose t 0
`f ar,ll
`molecular formulas [C6(H20)6] that make them appear to be hydrates o c
`
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`Section 19.1 Classification of Carbohydrates
`
`871
`
`HC=O
`g ...-C- OH
`I
`ao--c - H
`I
`g ...-C- OH
`I
`B- <;- OH
`CH20H
`wedge-and-dash
`struct ure
`
`HC=O
`H
`HO
`H
`H
`
`OH
`H
`OH
`OH
`CH20H
`Fischer projection
`
`CH20H
`I
`C=O
`I
`Ho- c - H
`I.
`H - C- OH
`I
`H - C- OH
`CH20H
`wedge-and-dash
`structure
`
`CH20H
`I
`C=O
`H
`OH
`OH
`CH20H
`Fischer projection
`
`HO
`H
`H
`
`(
`
`o-glucose
`
`o-glucose
`a polyhydroxy aldehyde
`
`o-fructose
`a polyhydroxy ketone
`
`o-fructose
`
`The most abundant carbohydrate is D-glucose. Cells of organisms oxidize
`o-glucose in the first of a series of process'es that provide energy to the cells.
`When animals have more D-glucose than they need for energy, they convert the
`excess D-glucose into a polymer called glycogen. When an animal needs energy,
`glycogen is broken down into individual D-glucose molecules. Plants convert
`excess D-glucose into a polymer known as starch. Cellulose is another polymer of
`o-glucose. It is the major structural component of plants. Chitin, a carbohydrate
`similar to cellulose, makes up the exoskeletons of crustaceans, insects and other
`arthropods, and the structural material of fungi.
`Animals obtain glucose by eating plants or by eating food containing glucose.
`Plants obtain glucose by a process known as photosynthesis. During photosyn-
`thesis, plants take up water through their roots and use carbon dioxide from the air
`to synthesize glucose and oxygen. Because photosynthesis is the opposite of the
`process used by organisms to obtain energy, plants require energy to carry out the
`process of photosynthesis. They acquire this energy from sunlight. Chlorophyll
`molecules in green plants capture the light energy used in photosynthesis. Notice
`that photosynthesis uses the C02 that animals exhale as waste and generates the 0 2
`that animals inhale. Nearly all the oxygen in Earth's atmosphere has been released
`by photosynthetic processes.
`
`C6H 1206 + 6 02
`glucose
`
`oxidation
`photosynthesis
`
`The terms "carbohydrate," "saccharide," and "sugar" are often used interchange-
`ably. Saccharide comes from the word for "sugar" in several early languages
`(sarkara in Sanskrit, sakcharon in Greek, and saccharum in Latin).
`There are two classes of carbohydrates-simple carbohydrates and complex car-
`bohydrates. Simple carbohydrates are monosaccharides (single sugars).
`Complex carbohydrates contain two or more sugar subunits linked together:
`disaccharides have two linked sugar subunits; oligosaccharides have three to ten
`sugar subunits (oligos is Greek for "few"); and polysaccharides have more than
`ten sugar subunits linked together. Disaccharides, oligosaccharides, and polysac-
`charides can be broken down to monosaccharide subunits by hydrolysis.
`
`19.1
`CLASSIFICATION OF
`CARBOHYDRATES
`
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`872
`
`CHAPTER 19 Carbohydrates
`
`-M-M-M-M~M-M-M-M-M­
`polysaccharide
`
`hydrolysis
`
`M
`monosaccharide
`
`A monosaccharide can be a polyhydroxy aldehyde or a polyhydroxy ketone.
`Polyhydroxy aldehydes are lmown as aldoses ("ald" is for aldehyde; "ose" is the
`suffix for a sugar), while polyhydroxy ketones are called ketoses. Monosaccharides
`are also classified according to the number of carbons they contain: monosaccha-
`rides with three carbons are trioses; those with four carbons are tetroses; those with
`five carbons are pentoses; and those with six and seven carbons are hexoses and
`heptoses, respectively. A six -carbon polyhydroxy aldehyde such as n-glucose is an
`aldohexose; a six -carbon polyhydroxy ketone such as D-fructose is a ketohexose.
`
`PROBLEM 1+
`Classify the following monosaccha1ides.
`
`CH20H
`I
`C=O
`H
`OH
`OH
`OH
`CH20H
`o-sedoheptulose
`
`HO
`H
`H
`H
`
`HO
`HO
`H
`H
`
`HC=O
`H
`H
`OH
`OH
`CH20H
`o-man nose
`
`H
`H
`H
`
`HC=O
`OH
`OH
`OH
`CH20H
`o-ribose
`
`19.2
`THE D AND L
`NOTATION
`
`The smallest aldose and the only one whose name does not end in "ose" is an
`aldotriose. Chemists and biochemists -invariably refer to this compound by it
`common name, glyceraldehyde.
`
`0
`II
`HOCH2CHCH
`I
`OH
`glyceraldehyde
`
`Recall that in Fischer pro-
`jections, horizontal bonds
`point toward the viewer
`while vertical bonds point
`away from the viewer
`(Section 4.4).
`
`Because glyceraldehyd~ has a chirality center, it can exist as a pair of enantiomer
`The Fischer projections of the enantiomers of glyceraldehyde are shown below.
`
`HC=O
`H+OH
`CH20H
`(R)-(+)-glyceraldehyde
`
`HC=O
`HO+H
`CH20H
`(5)-(-)-glyceraldehyde
`
`h " "
`Emil Fischer and his colleagues studied carbohydrates in the late nineteent Ll
`tury, when t~chniques for determining the configurations of compounds weref;1~
`available. Fischer arbitrarily assigned the configuration shown above on the Ie
`
`/
`
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