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M O D U L E
5
ORGANIC CHEMISTRY:
FUNCTIONAL GROUPS
O2.1 Functional Groups
O2.2 OxidationReduction Reactions
O2.3 Alkyl Halides
O2.4 Alcohols and Ethers
O2.5 Aldehydes and Ketones
O2.6 Reactions at the Carbonyl Group
O2.7 Carboxylic Acids and Carboxylate Ions
O2.8 Esters
O2.9 Amines, Alkaloids, and Amides
O2.10 Grignard Reagents
Chemistry in the World Around Us: The Chemistry of Garlic
Br
A
CH3 CHP CHCH3 Br2 CH3CHCHCH3
A
Br
CH3 Br CH3
A A A
CH3 CHPCCH2CH3 Br2 CH3CHCCH2CH3
A
Br
Instead of trying to memorize both equations, we can build a general rule that bromine re-
acts with compounds that contain a CPC double bond to give the product expected from
addition across the double bond. This approach to understanding the chemistry of organic
compounds presumes that certain atoms or groups of atoms known as functional groups
give these compounds their characteristic properties.
1
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Functional groups focus attention on the important aspects of the structure of a mol-
ecule. We dont have to worry about the differences between the structures of 1-butene
and 2-methyl-2-hexene, for example, when the compounds react with hydrogen bromide.
We can focus on the fact that both compounds are alkenes that add HBr across the CPC
double bond in the direction predicted by Markovnikovs rule, introduced in Section O1.8.
The CPO group plays a particularly important role in organic chemistry. This group
is called a carbonyl, and some of the functional groups based on a carbonyl are shown in
Table O2.2.
O
B
O COH Aldehyde CH3 CHO (acetaldehyde)
O
B
O CO Ketone CH3COCH3 (acetone)
O
B
O CO Cl Acyl chloride CH3COCl (acetyl chloride)
O
B
O COOH Carboxylic acid CH3CO2H (acetic acid)
O
B
O COOO Ester CH3CO2CH3 (methyl acetate)
O
B
O CONH2 Amide CH3CONH2 (acetamide)
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Exercise O2.1
Root beer hasnt tasted the same since the use of sassafras oil as a food additive was out-
lawed because sassafras oil is 80% safrole, which has been shown to cause cancer in rats
and mice. Identify the functional groups in the structure of safrole.
OOCH2
i
O
Safrole
CH2
G
CHPCH2
Solution
Safrole is an aromatic compound because it contains a benzene ring. It is also an alkene
because it contains a CPC double bond. The most difficult functional group to recognize
in the molecule might be the two ether linkages (OOO).
Exercise O2.2
The following compounds are the active ingredients in over-the-counter drugs used as anal-
gesics (to relieve pain without decreasing sensibility or consciousness), antipyretics (to re-
duce the body temperature when it is elevated), and/or anti-inflammatory agents (to coun-
teract swelling or inflammation of the joints, skin, and eyes). Identify the functional groups
in each molecule.
O
B
OH CH3 C
G D G
O OH CH OH
M D O
C B
OOCOCH3
Aspirin
CH3 NH
G D
(acetylsalicylic acid) C CH3 CH
B
Tylenol
G D 2
O (acetaminophen) CH
A
Advil
CH3 (ibuprofen)
Solution
All three compounds are aromatic. Aspirin is also a carboxylic acid (OCO2H) and an es-
ter (OCO2CH3). Tylenol is also an alcohol (OOH) and an amide (OCONHO). Ibupro-
fen contains alkane substituents and a carboxylic acid functional group.
Exercise O2.3
The discovery of penicillin in 1928 marked the beginning of what has been called the
golden age of chemotherapy, in which previously life-threatening bacterial infections
1012T_mod05_1-36 1/22/05 11:32 Page 4
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were transformed into little more than a source of discomfort. For those who are allergic
to penicillin, a variety of antibiotics, including tetracycline, are available. Identify the nu-
merous functional groups in the tetracycline molecule.
HO CH3 N(CH3)2
/ H
OH
Tetracycline
B CPO
OHB f
OH O OH O NH2
Solution
The compound contains an aromatic ring fused to three six-membered rings. It is also an
alcohol (with five OOH groups), a ketone (with CPO groups at the bottom of the second
and fourth rings), an amine [the ON(CH3)2 substituent at the top of the fourth ring], and
an amide (the OCONH2 group at the bottom right-hand corner of the fourth ring.)
We can divide the reaction into two half-reactions. One involves the oxidation of sodium
metal to form sodium ions.
Oxidation Na Na e
The other involves the reduction of an H ion in water to form a neutral hydrogen atom
that combines with another hydrogen atom to form an H2 molecule.
S
O
O
D G
Reduction 2H H 2 H 2 SO
O OH
Q
2 H 2 e 2 HT H2
Once we recognize that water contains an OOH functional group, we can predict what
might happen when sodium metal reacts with an alcohol that contains the same functional
group. Sodium metal should react with methanol (CH3OH), for example, to give H2 gas
and a solution of the Na and CH3O ions dissolved in the alcohol.
Because they involve the transfer of electrons, the reactions between sodium metal and
either water or an alcohol are examples of oxidationreduction reactions. But what about
the following reaction, in which hydrogen gas reacts with an alkene in the presence of a
transition metal catalyst to form an alkane?
H H H H
G D Ni
C PC H2 H C C H
D G
H H H H
There is no change in the number of valence electrons on any of the atoms in the reaction.
Both before and after the reaction, each carbon atom shares a total of eight valence elec-
trons and each hydrogen atom shares two electrons. Instead of electrons, the reaction
involves the transfer of atomsin this case, hydrogen atoms. There are so many atom-
transfer reactions that chemists developed the concept of oxidation number (see Chapter 5)
to extend the idea of oxidation and reduction to reactions in which electrons arent neces-
sarily gained or lost.
During the transformation of ethene into ethane, there is a decrease in the oxidation num-
ber of the carbon atom. The reaction therefore involves the reduction of ethene to ethane.
2
H H H H
G D Ni
C PC H2 H C C H
D G
H H H H
3
Reactions in which none of the atoms undergo a change in oxidation number are called
metathesis reactions. Consider the reaction between a carboxylic acid and an amine, for
example,
These are metathesis reactions because there is no change in the oxidation number of any
atom in either reaction.
The oxidation numbers of the carbon atoms in a variety of compounds are given in
Table O2.3. The oxidation numbers can be used to classify organic reactions as either
oxidationreduction reactions or metathesis reactions.
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Alkane CH4 4
Alkyllithium CH3Li 4
Alkene H2CPCH2 2
Alcohol CH3OH 2
Ether CH3OCH3 2
Alkyl halide CH3Cl 2
Amine CH3NH2 2
Alkyne HCqCH 1
Aldehyde H2CO 0
Carboxylic acid HCO2H 2
CO2 4
Exercise O2.4
Solution
(a) This is a metathesis reaction because there is no change in the oxidation number of
the carbon atoms when an alcohol is converted to an ether.
(b) This is a metathesis reaction because there is no change in the oxidation number of any
of the carbon atoms when a carboxylic acid reacts with an alcohol to form an ester.
(c) This is an oxidationreduction reaction because the carbon atom is reduced from the
2 to the 2 oxidation state when CO combines with H2 to form methanol.
CO 2 H2 88n CH3OH
2 2
(d) This is an oxidationreduction reaction because the carbon atom is reduced from the
2 to the 4 oxidation state when CH3Br reacts with lithium metal to form CH3Li.
Because electrons are neither created nor destroyed, oxidation cant occur in the absence
of reduction, and vice versa. It is often useful, however, to focus attention on one compo-
nent of the reaction and ask, is that substance oxidized or reduced?
Exercise O2.5
Determine whether the following transformations involve the oxidation or the reduction
of the carbon atom.
H O
B
H C OH H C H
H
O O
B B
H C H H C OH
O
B
H C OH OPC PO
Solution
Each of the transformations involves the oxidation of the carbon atom. The first reaction
involves oxidation of the carbon atom from the 2 to the 0 oxidation state. In the second
reaction the carbon atom is oxidized to the 2 state, and the third reaction involves oxi-
dation of the carbon atom to the 4 oxidation state.
2 H O 0
B
H C OH H C H
H
0 O O 2
B B
H C H H C OH
2 O 4
B
H C OH OPCPO
Oxidation occurs when hydrogen atoms are removed from a carbon atom or when
an oxygen atom is added to a carbon atom.
Reduction occurs when hydrogen atoms are added to a carbon atom or when an
oxygen atom is removed from a carbon atom.
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The first reaction in Exercise O2.5 involves oxidation of the carbon atom because
a hydrogen atom is removed from that atom when the alcohol is oxidized to an
aldehyde.
O
B
CH3OH 8n HCH
The second reaction in the exercise is an example of oxidation because an oxygen atom is
added to the carbon atom when an aldehyde is oxidized to a carboxylic acid.
O O
B B
HC H HCOH
Reduction, on the other hand, occurs when hydrogen atoms are added to a carbon atom
or when an oxygen atom is removed from a carbon atom. An alkene is reduced, for ex-
ample, when it reacts with H2 to form the corresponding alkane.
Ni
CH2PCHCH3 H2 88n CH3CH2CH3
O O
B B
CH4 CH3OH HCH HCOH CO2 FIGURE O2.1 The stepwise oxidation
4 2 0 +2 +4 of carbon.
The characteristic red-orange color of bromine disappears the instant this reagent is
added to the alkene in the upper left corner as the Br2 molecules add across the CPC dou-
ble bond in the alkene.
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Br
A
CH2PCH(CH2)3CH3 Br2 88n BrCH2CH(CH2)3CH3
The other crystallizing dish picks up the characteristic color of a dilute solution of bromine
because the reagent doesnt react with alkanes under normal conditions.
If the crystallizing dish in the upper right corner is moved into the center of the pro-
jector, however, the color of the bromine slowly disappears. This can be explained by not-
ing that alkanes react with halogens at high temperatures or in the presence of light to
form alkyl halides, as noted in Section O1.8.
Br
A
Light
CH3(CH2)4CH3 Br2 88n CH3CH(CH2)3CH3 HBr
The light source in an overhead projector is intense enough to initiate the reaction, al-
though the reaction is still much slower than the addition of Br2 to an alkene.
The reaction between an alkane and one of the halogens (F2, Cl2, Br2, or I2) can be
understood by turning to a simpler example.
Chain Initiation
A Cl2 molecule can dissociate into a pair of chlorine atoms by absorbing energy in the form
of either ultraviolet light or heat.
The chlorine atom produced in the reaction is an example of a free radicalan atom or
molecule that contains one or more unpaired electrons.
Chain Propagation
Free radicals, such as the Cl atom, are extremely reactive. When a chlorine atom collides
with a methane molecule, it can remove a hydrogen atom to form HCl and a CH3
radical.
If the CH3 radical then collides with a Cl2 molecule, it can remove a chlorine atom to form
CH3Cl and a new Cl radical.
Because a Cl atom is generated in the second reaction for every Cl atom consumed in
the first, the reaction continues in a chainlike fashion until the radicals involved in the chain
propagation steps are destroyed.
Chain Termination
If a pair of the radicals that keep the chain reaction going collide, they combine in a chain
terminating step. Chain termination can occur in three ways.
Because the concentration of the radicals is relatively small, the chain termination reac-
tions are relatively infrequent.
The chain reaction mechanism for free radical reactions explains the observations listed
for the reaction between CH4 and Cl2.
The reaction doesnt occur in the dark or at low temperatures because energy must
be absorbed to generate the free radicals that carry the reaction.
The reaction occurs in the presence of ultraviolet light because a UV photon has
enough energy to dissociate a Cl2 molecule to a pair of Cl atoms. The reaction oc-
curs at high temperatures because Cl2 molecules can dissociate to form Cl atoms
by absorbing thermal energy.
The reaction continues after the light has been turned off because light is needed
only to generate the Cl atoms that start the reaction. The chain reaction then con-
verts CH4 into CH3Cl without consuming the Cl atoms.
The reaction doesnt stop at CH3Cl because the Cl atoms can abstract additional
hydrogen atoms to form CH2Cl2, CHCl3, and eventually CCl4.
The formation of C2H6 is a clear indication that the reaction proceeds through a
free radical mechanism. When two CH3 radicals collide, they combine to form an
ethane molecule.
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Free radical halogenation of alkanes provides us with another example of the role of
atom transfer reactions in organic chemistry. The net effect of the reaction is to oxidize a
carbon atom by removing a hydrogen from the atom.
The reaction, however, doesnt involve the gain or loss of electrons. It occurs by the trans-
fer of a hydrogen atom in one direction and a chlorine atom in the other.
The systematic nomenclature for alcohols adds the ending -ol to the name of the parent
alkane and uses a number to identify the carbon that carries the OOH group. The sys-
tematic name for isopropyl alcohol, for example, is 2-propanol.
CH3OH Methanol
CH3CH2OH Ethanol
CH3CHOHCH3 2-Propanol
Exercise O2.6
More than 50 organic compounds have been isolated from the oil that gives rise to the
characteristic odor of a rose. One of the most abundant of the compounds is known by the
common name citronellol. Use the systematic nomenclature to name this alcohol, which
has the following structure.
CH3
A
CH
D G
H2C CH2
A A
H2C CH2O OH
G
CH
B
C
D G
CH3 CH3
Solution
The longest chain of carbon atoms in the compound contains eight atoms.
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CH3
3A
CH 2
4 D G
H2C CH2
A A
H2C 5 CH2O OH
G 1
6 CH
B
C
D7 G
CH3 CH3
8
The longest chain contains the OOH group, which means the compound is named as a de-
rivative of octane. Because it is an alcohol, it would be tempting to name it as an octanol.
But it contains a CPC double bond, which means it must be an octenol. We now have to
indicate that the OOH group is on one end of the chain and the CPC double bond oc-
curs between the sixth and seventh carbon atoms of the chain, which can be done by con-
sidering the compound to be a derivative of 6-octen-1-ol. Finally, we have to indicate the
presence of a pair of CH3 groups on the third and seventh carbon atoms. The compound
is therefore given the systematic name 3,7-dimethyl-6-octen-1-ol.
Methanol, or methyl alcohol, is also known as wood alcohol because it was originally
made by heating wood until a liquid distilled. Methanol is highly toxic, and many people
have become blind or have died from drinking it. Ethanol, or ethyl alcohol, is the alcohol
associated with alcoholic beverages. It has been made for at least 6000 years by adding
yeast to solutions that are rich in either sugars or starches. The yeast cells obtain energy
from enzyme-catalyzed reactions that convert sugar or starch to ethanol and CO2.
When the alcohol reaches a concentration of 10% to 12% by volume, the yeast cells die.
Brandy, rum, gin, and the various whiskeys that have a higher concentration of alcohol are
prepared by distilling the alcohol produced by the fermentation reaction. Ethanol isnt as
toxic as methanol, but it is still dangerous. Most people are intoxicated at blood-alcohol
levels of about 0.1 gram per 100 mL. An increase in the level of alcohol in the blood to
between 0.4 and 0.6 g/100 mL can lead to coma or death.
The method of choice for determining whether an individual is DUIdriving under
the influenceor DWIdriving while intoxicatedis the Breathalyzer, for which a patent
was issued to R. F. Borkenstein in 1958. The chemistry behind the Breathalyzer is based
on the reaction between alcohol in the breath and the chromate or dichromate ion.
The instrument contains two ampules that hold small samples of potassium dichromate dis-
solved in sulfuric acid. One of the ampules is used as a reference. The other is opened and
the breath sample to be analyzed is added. If alcohol is present in the breath, it reduces
the yellow-orange Cr2O72 ion to the green Cr3 ion. The extent to which the color bal-
ance between the two ampules is disturbed is a direct measure of the amount of alcohol
in the breath sample. Measurements of the alcohol on the breath are then converted into
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estimates of the concentration of the alcohol in the blood by assuming that 2100 mL of air
exhaled from the lungs contains the same amount of alcohol as 1 mL of blood.
Measurements taken with the Breathalyzer are reported in units of percent blood-
alcohol concentration (BAC). In most states, a BAC of 0.10% is sufficient for a DUI or
DWI conviction. (This corresponds to a blood-alcohol concentration of 0.10 gram of alco-
hol per 100 mL of blood.)
Ethanol is oxidized to CO2 and H2O by the alcohol dehydrogenase enzymes in the
body. This reaction gives off 30 kilojoules per gram, which makes ethanol a better source
of energy than carbohydrates (17 kJ/g), and almost as good a source of energy as fat
(38 kJ/g). An ounce of 80-proof liquor can provide as much as 3% of the average daily
caloric intake, and drinking alcohol can contribute to obesity. Many alcoholics are mal-
nourished, however, because of the absence of vitamins in the calories they obtain from
alcoholic beverages.
As a general rule, polar or ionic substances dissolve in polar solvents; nonpolar sub-
stances dissolve in nonpolar solvents. As a result, hydrocarbons dont dissolve in water.
They are often said to be immiscible (literally, not mixable) in water. Alcohols, as might
be expected, have properties between the extremes of hydrocarbons and water. When the
hydrocarbon chain is short, the alcohol is soluble in water. There is no limit on the amount
of methanol (CH3OH) and ethanol (CH3CH2OH), for example, that can dissolve in a given
quantity of water. As the hydrocarbon chain becomes longer, the alcohol becomes less sol-
uble in water, as shown in Table O2.4. One end of the alcohol molecules has so much non-
polar character it is said to be hydrophobic (literally, water-hating). The other end con-
tains an OOH group that can form hydrogen bonds to neighboring water molecules and
is therefore said to be hydrophilic (literally, water-loving). As the hydrocarbon chain be-
comes longer, the hydrophobic character of the molecule increases, and the solubility of
the alcohol in water gradually decreases until it becomes essentially insoluble in water.
Alcohols are classified as either primary (1), secondary (2), or tertiary (3) on the
basis of their structures.
OH OH
A A
CH3CH2OH CH3CHCH3 CH3CCH3
A
CH3
1 2 3
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Ethanol is a primary alcohol because there is only one alkyl group attached to the carbon
that carries the OOH substituent. The structure of a primary alcohol can be abbreviated
as RCH2OH, where R stands for an alkyl group. The isopropyl alcohol found in rubbing
alcohol is a secondary alcohol, which has two alkyl groups on the carbon atom with the
OOH substituent (R2CHOH). An example of a tertiary alcohol (R3COH) is tert-butyl (or
t-butyl) alcohol or 2-methyl-2-propanol.
Another class of alcohols are the phenols, in which an OOH group is attached to an
aromatic ring, as shown in Figure O2.3. Phenols are potent disinfectants. When antiseptic
techniques were first introduced in the 1860s by Joseph Lister, it was phenol (or carbolic
acid, as it was then known) that was used. Phenol derivatives, such as o-phenylphenol, are
still used in commercial disinfectants such as Lysol.
OH
OH
FIGURE O2.3 The structures of phenol and
Phenol o-Phenylphenol o-phenylphenol.
Water has an unusually high boiling point because of the hydrogen bonds between the
H2O molecules. Alcohols can form similar hydrogen bonds, as shown in Figure O2.4.
CH3 O H
H ,, O
CH3 FIGURE O2.4 A hydrogen bond between a pair of methanol molecules.
As a result, alcohols have boiling points that are much higher than alkanes with similar
molecular weights. The boiling point of ethanol, for example, is 78.5C, whereas propane,
with about the same molecular weight, boils at 42.1C.
Alcohols are Brnsted acids in aqueous solution.
Alcohols therefore react with sodium metal to produce sodium salts of the corresponding
conjugate base, as noted in Section O2.2.
[Na][CH3O] [Na][CH3CH2O]
Sodium methoxide Sodium ethoxide
OH
H2SO4
A
CH3CHP CHCH3 H2O CH3CHCH2CH3
Less substituted 1 alcohols can be prepared by substitution reactions that occur when a
primary alkyl halide is allowed to react with the OH ion.
Alcohols (ROH) can be thought of as derivatives of water in which one of the hydro-
gen atoms has been replaced by an alkyl group. If both of the hydrogen atoms are replaced
by alkyl groups, we get an ether (ROR). These compounds are named by adding the word
ether to the names of the alkyl groups.
Diethyl ether, often known by the generic name ether, was once used extensively as an
anesthetic. Because mixtures of diethyl ether and air explode in the presence of a spark,
ether has been replaced by safer anesthetics.
There are important differences between both the physical and chemical properties of
alcohols and ethers. Consider diethyl ether and 1-butanol, for example, which are consti-
tutional isomers with the formula C4H10O.
CH3CH2OCH2CH3 CH3CH2CH2CH2OH
BP 34.5C BP 117.2C
density 0.7138 g/mL density 0.8098 g/mL
Insoluble in water Soluble in water
The shapes of the molecules are remarkably similar, as shown in Figure O2.5.
O OH
FIGURE O2.5 The structures of diethyl ether and 1-butanol.
The fundamental difference between the compounds is the presence of OOH groups in
the alcohol that are missing in the ether. Because hydrogen bonds cant form between the
molecules in the ether, the boiling point of the compound is more than 80C lower than
that of the corresponding alcohol. Because there are no hydrogen bonds to organize the
structure of the liquid, the ether is significantly less dense than the corresponding alcohol.
Ethers can act as a hydrogen bond acceptor, as shown in Figure O2.6, but they cant
act as hydrogen bond donors. As a result, ethers are less soluble in water than alcohols
with the same molecular weight.
H O CH3
H O
CH3 FIGURE O2.6 Water acting as a hydrogen bond donor toward an ether.
The absence of an OOH group in an ether also has important consequences for its
chemical properties. Unlike alcohols, ethers are essentially inert to chemical reactions. They
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dont react with most oxidizing or reducing agents, and they are stable to most acids and
bases, except at high temperatures. They are therefore frequently used as solvents for chem-
ical reactions.
Compounds that are potential sources of an H ion, or proton, are often described as
being protic. Ethanol, for example, is a protic solvent.
Substances that cant act as a source of a proton are said to be aprotic. Because they dont
contain an OOH group, ethers are aprotic solvents.
Ethers can be synthesized by splitting out a molecule of water between two alcohols
in the presence of heat and concentrated sulfuric acid.
H
2 CH3CH2OH CH3CH2OCH2CH3
They can also be formed by reacting a primary alkyl halide with an alkoxide ion.
H H H H
G D Ni
C PC H2 H C C H
D G
H H H H
The driving force behind the reaction is the difference between the strengths of the bonds
that must be broken and the bonds that form in the reaction. In the course of the hydro-
genation reaction, a relatively strong HOH bond (435 kJ/mol) and a moderately strong
carboncarbon bond (~270 kJ/mol) are broken, but two strong COH bonds (439 kJ/mol)
are formed. The reduction of an alkene to an alkane is therefore an exothermic reaction.
What about the addition of an H2 molecule across a CPO double bond?
H O H OH
B Pt
H C C H H2 H C C H
H H H
Once again, a significant amount of energy has to be invested in the reaction to break the
HOH bond (435 kJ/mol) and the carbonoxygen bond (~375 kJ/mol). The overall re-
action is still exothermic, however, because of the strength of the COH bond (439 kJ/mol)
and the OOH bond (498 kJ/mol) that are formed.
The addition of hydrogen across a CPO double bond raises several important points.
First, and perhaps foremost, it shows the connection between the chemistry of primary al-
cohols and aldehydes. But it also helps us understand the origin of the term aldehyde. If a
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O
[O] B
CH3CH2OH CH3CH
The reaction also illustrates the importance of differentiating between primary, sec-
ondary, and tertiary alcohols. Consider the oxidation of isopropyl alcohol, or 2-propanol,
for example.
OH O
A [O] B
CH3CHCH3 CH3CCH3
The product of this particular reaction was originally called aketone, although the name
was eventually softened to azetone and finally acetone. Thus, it is not surprising that any
substance that exhibited chemistry that resembled aketone became known as a ketone.
Aldehydes can be formed by oxidizing a primary alcohol; oxidation of a secondary al-
cohol gives a ketone. What happens when we try to oxidize a tertiary alcohol? The an-
swer is simple: Nothing happens.
OH
A [O]
CH3CCH3
A
CH3
There arent any hydrogen atoms that can be removed from the carbon atom carrying the
OOH group in a 3 alcohol. And any oxidizing agent strong enough to insert an oxygen
atom into a COC bond would oxidize the alcohol all the way to CO2 and H2O.
A variety of oxidizing agents can be used to transform a secondary alcohol to a ketone.
A common reagent for the reaction is some form of chromium(VI)chromium in the 6
oxidation statein acidic solution. The reagent can be prepared by adding a salt of the
chromate (CrO42) or dichromate (Cr2O72) ion to sulfuric acid. Or it can be made by
adding chromium trioxide (CrO3) to sulfuric acid. Regardless of how it is prepared, the ox-
idizing agent in the reactions is chromic acid, H2CrO4.
OH O
A H2CrO4
B
CH3CHCH2CH3 CH3CCH2CH3
O O
H2CrO4 B B
CH3CH2OH CH3CH CH3COH
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A weaker oxidizing agent, which is just strong enough to prepare the aldehyde from the
primary alcohol, can be obtained by dissolving the complex that forms between CrO3 and
pyridine, C6H5N, in a solvent such as dichloromethane that doesnt contain any water.
O
CrO3 /pyridine B
CH3CH2OH CH2Cl2
CH3CH
O O
B B
HCOH HCH
Formic acid Formaldehyde
O O
B B
CH3COH CH3CH
Acetic acid Acetaldehyde
The systematic names for aldehydes are obtained by adding -al to the name of the parent
alkane.
O O
B B
HCH CH3CH
Methanal Ethanal
The presence of substituents is indicated by numbering the parent alkane chain from the
end of the molecule that carries the OCHO functional group. For example,
O
B
BrCH2CH2CH 3-Bromopropanal
The common name for a ketone is constructed by adding ketone to the names of the
two alkyl groups on the carbon of the CPO double bond, listed in alphabetical order.
O
B
CH3CCH2CH3 Ethyl methyl ketone
The systematic name is obtained by adding -one to the name of the parent alkane and us-
ing numbers to indicate the location of the CPO group.
O
B
CH3CCH2CH3 2-Butanone
odor of almonds, vanillin is responsible for the flavor of vanilla, and cinnamaldehyde makes
an important contribution to the flavor of cinnamon.
O O
B B
CH HO CH O
B FIGURE O2.7 Aromatic alde-
CH hydes with characteristic
Benzaldehyde CH3O Vanillin Cinnamaldehyde odors.
OS
S
O SO
O
B A
C C
D G D G
We can represent the polar nature of the hybrid by indicating the presence of a slight neg-
ative charge on the oxygen () and a slight positive charge () on the carbon of the
CPO double bond.
O
O
O
B
C
D G
Reagents that attack the electron-rich end of the CPO bond are called electrophiles
(literally, lovers of electrons). Electrophiles include ions (such as H and Fe3) and neu-
tral molecules (such as AlCl3 and BF3) that are Lewis acids, or electron pair acceptors.
Reagents that attack the electron-poor end of the bond are nucleophiles (literally,
lovers of nuclei). Nucleophiles are Lewis bases (such as NH3 or the OHion).
S
O Electrophiles
O
The polarity of the CPO double bond can be used to explain the reactions of carbonyl
compounds. Aldehydes and ketones react with a source of the hydride ion (H) because
the H ion is a Lewis base, or nucleophile, that attacks the end of the CPO bond.
When this happens, the two valence electrons on the H ion form a covalent bond to the
carbon atom. Since carbon is tetravalent, one pair of electrons in the CPO bond is dis-
placed onto the oxygen to form an intermediate with a negative charge on the oxygen atom.
1012T_mod05_1-36 1/22/05 11:32 Page 20
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OS
S
O SO
O
B A
C CH3OC OCH3
D G A
CH3 CH3 H
HS
The alkoxide ion can then remove an H ion from water to form an alcohol.
OS
SO O OH
SO
A A
CH3OC OCH3 H2O CH3OC OCH3 OH
A A
H H
Common sources of the H ion include lithium aluminum hydride (LiAlH4) and sodium
borohydride (NaBH4). Both compounds are ionic.
LiAlH4: [Li][AlH4]
NaBH4: [Na][BH4]
The aluminum hydride (AlH4) and borohydride (BH4) ions act as if they were com-
plexes between an H ion, acting as a Lewis base, and neutral AlH3 or BH3 molecules,
acting as a Lewis acid.
H H
A A
HOAlOH HS AlOH
A A
H H
LiAlH4 is such a good source of the H ion that it reacts with the H ions in water or
other protic solvents to form H2 gas. The first step in the reduction of a carbonyl with
LiAlH4 is therefore carried out using an ether as the solvent. The product of the hydride
reduction reaction is then allowed to react with water in a second step to form the corre-
sponding alcohol.
O 1. LiAlH4
B in ether
CH3CH2CH 2. H2O
CH3CH2CH2OH
NaBH4 is less reactive toward protic solvents, which means that borohydride reductions
are usually done in a single step, using an alcohol as the solvent.
O OH
B NaBH4
A
CH3CH2CCH3 CH CH OH CH3CH2CHCH3
3 2
O O
J J
O
CH3 C O
CH3 C H
G G
OH O
The carboxylate ion formed in the reaction is a hybrid of two resonance structures.
O O
J D
CH3O C CH3O C
G M
O O
Resonance delocalizes the negative charge in the carboxylate ion, which makes the ion
more stable than the alkoxide ion formed when an alcohol loses an H ion. By increasing
the stability of the conjugate base, resonance increases the acidity of the acid that forms
the base. Carboxylic acids are therefore much stronger acids than the analogous alcohols.
The Ka value for a typical carboxylic acid is about 105, whereas alcohols have Ka values
only 1016.
O O
J J
CH3C CH3C H Ka 1.8 105
G G
OH O
Carboxylic acids were among the first organic compounds to be discovered. As a re-
sult, they have well-established common names that are often derived from the Latin stems
of their sources in nature. Formic acid (Latin formica, an ant) and acetic acid (Latin ace-
tum, vinegar) were first obtained by distilling ants and vinegar, respectively. Butyric acid
(Latin butyrum, butter) is found in rancid butter, and caproic, caprylic, and capric acids
(Latin caper, goat) are all obtained from goat fat. A list of common carboxylic acids is
given in Table O2.5.
The systematic nomenclature of carboxylic acids is easy to understand. The ending
-oic acid is added to the name of the parent alkane to indicate the presence of the OCO2H
functional group.
Unfortunately, because of the long history of carboxylic acids and their importance in bi-
ology and biochemistry, you are more likely to encounter these compounds by their com-
mon names.
Formic acid and acetic acid have sharp, pungent odors. As the length of the alkyl chain
increases, the odor of carboxylic acids becomes more unpleasant. Butyric acid, for exam-
ple, is found in sweat, and the odor of rancid meat is due to carboxylic acids released as
the meat spoils.
The solubility data in Table O2.5 show that carboxylic acids also become less soluble
in water as the length of the alkyl chain increases. The OCO2H end of the molecule is po-
lar and therefore soluble in water. As the alkyl chain gets longer, the molecule becomes
more nonpolar and less soluble in water.
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Solubility in H2O
Common Name Formula (g/100 mL)
Compounds that contain two OCO2H functional groups are known as dicarboxylic
acids. A number of dicarboxylic acids (see Table O2.6) can be isolated from natural sources.
Tartaric acid, for example, is a by-product of the fermentation of wine, and succinic, fu-
maric, malic, and oxaloacetic acids are intermediates in the metabolic pathway used to ox-
idize sugars to CO2 and H2O.
Several tricarboxylic acids also play an important role in the metabolism of sugar. The
most important example of this class of compounds is the citric acid that gives so many
fruit juices their characteristic acidity.
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CH2CO2H
A
HOC OCO2H Citric acid
A
CH2CO2H
O2.8 ESTERS
Carboxylic acids (OCO2H) can react with alcohols (ROH) in the presence of either acid
or base to form esters (OCO2R). Acetic acid, for example, reacts with ethanol to form
ethyl acetate.
O O
B H
B
CH3COH CH3CH2OH CH3COCH2CH3 H2O
This isnt an efficient way of preparing an ester, however, because the equilibrium constant
for the reaction is relatively small (Kc 3). Chemists therefore tend to synthesize esters
from carboxylic acids in a two-step process. They start by reacting the acid with a chlori-
nating agent such as thionyl chloride (SOCl2) to form the corresponding acyl chloride.
O O
B B
CH3COH SOCl2 CH3CCl SO2 HCl
They then react the acyl chloride with an alcohol in the presence of base to form the ester.
O O
B B
B
CH3CCl CH3CH2OH CH3COCH2CH3 BHCl
The base absorbs the HCl given off in the reaction, thereby driving it to completion.
As might be expected, esters are named as if they were derivatives of a carboxylic acid
and an alcohol. The ending -ate or -oate is added to the name of the parent carboxylic acid,
and the alcohol is identified using the alkyl alcohol convention. The following ester, for
example, can be named as a derivative of acetic acid (CH3CO2H) and ethyl alcohol
(CH3CH2OH).
O
B
CH3COCH2CH3 Ethyl acetate
O
B
CH3COCH2CH3 Ethyl ethanoate
The term ester is commonly used to describe the product of the reaction of any strong
acid with an alcohol. Sulfuric acid, for example, reacts with methanol to form a diester
known as dimethyl sulfate.
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O O
A A
HO S OH 2 CH3OH CH3O S OCH3 2 H2O
A A
O O
Phosphoric acid reacts with alcohols to form triesters such as trimethyl phosphate.
O O
A A
HO P OH 3 CH3OH CH3O P OCH3 3 H2O
A A
OH OCH3
Compounds that contain the OCO2R functional group might therefore best be called car-
boxylic acid esters, to indicate the acid from which they are formed.
Carboxylic acid esters with low molecular weights are colorless, volatile liquids that of-
ten have a pleasant odor. They are important components of both natural and synthetic
flavors (see Figure O2.8).
CH3O O
B
C
OH O CH2 CH3
E
CH2 C CH2 CH
B
CH3 CH2 O CH3
Methyl salicylate Isoamyl butyrate
(oil of wintergreen) (chocolate)
CH3 CH3
A A
(CH3)2CHNH2 CH3CH2NH CH3 NCH3
Isopropylamine Ethylmethylamine Trimethylamine
The systematic names of primary amines are derived from the name of the parent alkane
by adding the prefix amino- and a number specifying the carbon that carries the ONH2
group.
CHP CH NH2
D G D
CH3 CH2O CH 5-Amino-2-hexene
G
CH3
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The chemistry of amines mirrors the chemistry of ammonia. Amines are weak bases
that pick up a proton to form ammonium salts. Trimethylamine, for example, reacts with
acid to form the trimethylammonium ion.
CH3 CH3
A A
CH3ONS H CH3ONOH
A A
CH3 CH3
The salts are more soluble in water than the corresponding amines, and the reaction can
be used to dissolve otherwise insoluble amines in aqueous solution.
The difference between amines and their ammonium salts plays an important role in
both over-the-counter and illicit drugs. Cocaine, for example, is commonly sold as the hy-
drochloride salt, which is a white, crystalline solid. By extracting the solid into ether, it is
possible to obtain the free base. A glance at the side panel of almost any over-the-
counter medicine will provide examples of ammonium salts of amines that are used to en-
sure that the drug dissolves in water (see Figure O2.9).
CH3
CH3O CH3 NH2Cl
CH
Dextromethorphan
hydrobromide HO CH
(cough suppressant)
H
Pseudoephedrine
N Br hydrochloride
(decongestant)
CH3
Amines that are isolated from natural sources, especially from plants, are known as al-
kaloids. They include poisons such as nicotine, coniine, and strychnine (shown in Figure
O2.10). Nicotine has a pleasant, invigorating effect when taken in minuscule quantities but
is extremely toxic in larger amounts. Coniine is the active ingredient in hemlock, a poison
that has been used since the time of Socrates. Strychnine is another toxic alkaloid that has
been a popular poison in murder mysteries.
N
N
CH3
N H
Nicotine Coniine
N O
Strychnine
The alkaloids also include a number of drugs, such as morphine, quinine, and cocaine.
Morphine is obtained from poppies; quinine can be found in the bark of the chinchona
tree; and cocaine is isolated from coca leaves. This family of compounds also includes syn-
thetic analogs of naturally occurring alkaloids, such as heroin and LSD (see Figure O2.11).
To illustrate the importance of minor changes in the structure of a molecule, three
amines with similar structures are shown in Figure O2.12. One of the compounds is caf-
feine, which is the pleasantly addictive substance that makes a cup of coffee an important
part of the day for so many people. Another is theobromine, which is the pleasantly ad-
dictive substance that draws so many people to chocolate. The third compound is theo-
phylline, which is a prescription drug used as a bronchodilator for people with asthma.
O
B
HOH CH3COO
Morphine Heroin
O O
ECH3
NOCH3 N
E E
HO CH3CO
B
CH3H O
N CHPCH2
O
Cocaine
CO2CH3
O
HO N
H H E
OC O CH
A
P
CH3OH
O Quinine
O
CH3CH2H B
NOCO
E Lysergic acid
CH3CH2 NH diethylamide
(LSD)
N
A
CH3
FIGURE O2.11 The structures of some alkaloids used as drugs.
O CH3 O CH3 O H
CH3H f HH f CH3H i
N N N N N N
O N N O N N O N N
A A A
CH3 CH3 CH3
Caffeine Theobromine Theophylline
FIGURE O2.12 The caffeine in coffee, the theobromine in chocolate, and the active in-
gredient in a common bronchodilator are central nervous system stimulants with very
similar structures.
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It is tempting to assume that carboxylic acids will react with amines to form the class
of compounds known as amides. In practice, when aqueous solutions of carboxylic acids
and amines are mixed all we get is an acidbase reaction.
O O
B B
CH3COH CH3NH2 CH3COCH3NH3
The best way to prepare an amide is to react the appropriate acyl chloride with an amine.
O O
B B
CH3CCl 2 CH3NH2 CH3CNHCH3 CH3NH3Cl
Excess amine is used to drive the reaction to completion by absorbing the HCl given off
in the reaction.
Et O
CH3Br Mg 88n
2
CH3MgBr
H
A
HO CS
A
H
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CH3 CH3
G A
CH3S CPO CH3O C O O
D A
CH3 CH3
If we treat the product of the reaction with water, we get a tertiary alcohol.
CH3 CH3
A A
CH3OC OO H2O CH3OC OOH OH
A A
CH3 CH3
If we wanted to make a secondary alcohol, we could add the Grignard reagent to an alde-
hyde, instead of a ketone.
O OH
B 1. CH 3MgBr A
CH3CH 2. H2O
CH3CHCH3
By reacting a Grignard reagent with formaldehyde we can add a single carbon atom to
form a primary alcohol.
CH3 CH3 O
A CrO3 /pyridine
A B
CH3CCH2CH2OH CH2Cl2
CH3CCH2CH
A A
CH3 CH3
The Grignard reagent therefore provides us with a way of performing the following over-
all transformation.
CH3 1. H2CO CH3 O
A 2. H2O
A B
CH3CCH2MgBr 3. CrO3 /pyridine
CH3CCH2CH
A A
in CH2Cl2
CH3 CH3
A single carbon atom can also be added if the Grignard reagent is allowed to react
with CO2 to form a carboxylic acid.
Perhaps the most important aspect of the chemistry of Grignard reagents is the ease
with which the reaction allows us to couple alkyl chains. Isopropylmagnesium bromide, for
1012T_mod05_1-36 1/22/05 11:32 Page 29
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example, can be used to graft an isopropyl group onto the hydrocarbon chain of an ap-
propriate ketone, as shown in Figure O2.13.
CH3
H
B A A
O
G H2O
E CHMgBr CH 3 CH 2 CCH 3 CH3CH2CCH3 CH3CH2CCH3
CH3 A A
CH CH
D G D G
CH3 CH3 CH3 CH3
FIGURE O2.13 Grignard reagents provide a powerful way to introduce alkyl groups onto a
hydrocarbon chain.
CH2OH
CH2OH CPO
A
H
Garlic, onions, and mustard seed differ from most other sources of essential oils.
In each case, the fragrance producing part of the plant must be crushed before the
volatile components are released. For more than 100 years, chemists have known
that the principal component of the oil that distills from garlic is diallyl disulfide
[F. W. Semmler, Archiv der Pharmazie, 230, 434448 (1892)].
Only recently, however, have chemists explained how the compound is produced when a
clove of garlic is crushed [E. Block, Angewandte Chemie, International Edition in Eng-
lish, 31, 11011264 (1992)].
Before garlic is crushed, the intact cell contains S2-propenyl-L-cysteine S-oxideor
alliinwhich can be found in the cell cytoplasm.
O NH3
B A
CH2PCHCH2SCH2CHCO2 Alliin
Within the cell there are vacuoles that contain an enzyme known as alliinase. When the
cell is crushed, the enzyme is released. The enzyme transforms the natural product alliin
into an intermediate that reacts with itself to form a compound known as allicin.
O
B
CH2PCHCH2SSCH2CHPCH2 Allicin
Allicin has been described as an odoriferous, unstable antibacterial substance that poly-
merizes easily and must be stored at low temperatures. When heated, it breaks down to
give a variety of compounds, including the diallyl disulfide obtained when oil of garlic is
distilled from the raw material.
An alliinase enzyme can also be found in onions, where it converts an isomer of al-
liin known as S-(E)-1-propenyl-L-cysteine S-oxide into propanethial S-oxide.
The product of the reaction is known as the lacrimator factor of onion because it is the
substance primarily responsible for the tears generated when onions are cut.
A great deal of progress has been made in recent years in identifying the various
organosulfur compounds formed when garlic and onion are cut and in understanding the
process by which the compounds are formed. The structures of some of the principal
organosulfur compounds associated with garlic are shown in Figure O2.15. In spite of
the progress made so far, much still has to be learned about the compounds that can be
isolated from extracts of the genus Allium, which includes both garlic and onion.
O
S
S
SOH H
O
S
S S
S
S O S
O
S
S
S
S
S
S S S
S S S
S
S S S
S
S
S
S S FIGURE O2.15 Some of the organosulfur
S S S
S compounds associated with garlic.
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KEY TERMS
Acyl chloride Carboxylate ion Ether
Alcohol Carboxylic acid Free radical
Aldehyde Carboxylic acid ester Functional group
Alkaloid Chain initiation Grignard reagent
Alkoxide Chain propagation Hydrophilic
Amide Chain reaction Hydrophobic
Amine Chain termination Ketone
Aprotic Dicarboxylic acid Nucleophile
Carbanion Electrophile Oxidation number
Carbonyl Ester Protic
PROBLEMS
Functional Groups
1. Give examples of compounds that contain each of the following functional groups.
(a) an alcohol (b) an aldehyde (c) an amine (d) an amide (e) an alkyl halide
(f) an alkene (g) an alkyne
2. Describe the difference between the members of each of the following pairs of func-
tional groups.
(a) an alcohol and an alkoxide ion
(b) an alcohol and an aldehyde
(c) an amine and an amide
(d) an ether and an ester
(e) an aldehyde and a ketone
3. Classify the following compounds as an alcohol, an aldehyde, an ether, or a ketone.
O O
B B
(a) CH3CH2CH (b) CH3CH2OH (c) CH3CH2OCH2CH3 (d) CH3CH2CCH3
4. Classify the following compounds as primary, secondary, or tertiary alcohols.
CH3 CH3 OH
A A A
(a) CH3CH2OH (b) CH3CH2CHOH (c) CH3CH2COH (d) CH3CH2CHCH2CH3
A
CH3
5. Cortisone is an adrenocortical steroid that is used as an anti-inflammatory agent.
Use the fact that carbon is tetravalent to determine the molecular formula of the com-
pound from the following stick structure. Identify the functional groups present in the
molecule.
CH2OH
A
CPO
O CH3A
M A O OH
CH3
A
J
O
1012T_mod05_1-36 1/22/05 11:32 Page 32
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N
O B
O
O
CO2H
OH
OH
OXIDATIONREDUCTION REACTIONS
10. Arrange the following substances in order of increasing oxidation number of the car-
bon atom.
(a) C (b) HCHO (c) HCO2H (d) CO (e) CO2 (f) CH4 (g) CH3OH
11. Classify the following reactions as examples of either metathesis or oxidationreduction
reactions.
(a) CH4 Cl2 n CH3Cl HCl
(b) CH3OH n HCHO
(c) HCHO n HCO2H
(d) CH3OH HBr n CH3Br H2O
(e) (CH3)2CO n (CH3)2CHOH
12. Classify the following transformations as examples of either oxidation or reduction.
(a) CH3CH2OH n CH3CHO
(b) CH3CHO n CH3CO2H
(c) (CH3)2CPO n (CH3)2CHOH
(d) CH3CHPCHCH3 n CH3CH2CH2CH3
(e) (CH3)2CHCqCH n (CH3)2CHCH2CH3
1012T_mod05_1-36 1/22/05 11:32 Page 33
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Alkyl Halides
19. Use Lewis structures to describe the free radical chain reaction mechanism involved
in the bromination of methane to form methyl bromide. Clearly label the chain initi-
ation, chain propagation, and chain termination steps.
20. Use Lewis structures to describe the difference between a CH3 ion, a CH3 radical,
and a CH3 ion. Which of these Lewis structures describes a carbanion? Which describes
a carbocation?
21. How many different products could be formed by the free radical chlorination of pen-
tane? If attack at the different hydrogen atoms in the compound were more or less
random, what would be the relative abundance of the different isomers of chloropen-
tane formed in the reaction?
22. Consider the reaction between a Cl atom and a pentane molecule. Classify the dif-
ferent intermediates that could be produced in the reaction as either primary, secondary,
or tertiary free radicals.
OH
OH
A B
33. Assign a systematic name to the compound known by the common name menthol.
OH
O O
P
A B
38. Assign a systematic name to the compound known by the common name geranial.
42. Explain the difference between CH3CH2OH and CH3CO2H that makes one of the
COOH bonds in the compounds more than 10 orders of magnitude more acidic than
the other when values of Ka for the compounds are compared.
43. Use the structures shown in Figure O2.11 to propose a series of reactions that could
be used to convert morphine into heroin.
Grignard Reagents
47. Use Lewis structures to decide whether the organic component of a Grignard reagent
is a nucleophile (Lewis base) or an electrophile (Lewis acid). Predict which end of a
CPO bond this portion of the Grignard reagent will attack.
48. If CH3CH2MgBr can be thought of as containing the CH3CH2, Mg2, and Br ions,
what would be the product of the reaction between the Grignard reagent and dilute
hydrochloric acid?
49. Explain why Grignard reagents are prepared in an aprotic solvent, such as an ether,
rather than a protic solvent such as an alcohol.
50. Write a step-by-step mechanism for the reaction between CH3MgBr and H2CPO to
form CH3CH2OH.
51. Predict the product of the reaction between (CH3)2CHMgBr and 2-pentanone.
O
B
52. If CH3CH2CCH3 is used as the starting material, show how a tertiary alcohol can be
synthesized by a Grignard reaction.
53. Select from the reagents given below to design a sequence of reactions that would lead
to the following compound.
OH
A
CH3CHCHCH3
A
CH3
Integrated Problems
62. Identify the Brnsted acids and the Brnsted bases in the following reaction.
63. Succinic acid plays an important role in the Krebs cycle, malic acid (apple acid) is found
in apples, and tartaric acid ( fruit acid) is found in many fruits. Which of these dicar-
boxylic acids is chiral? See Table O2.6.