32 ORGANIC CHEMISTRY:

FUNCTIONAL GROUPS
AND THE MOLECULES
OF BIOCHEMISTRY

I n Chapter 23 we had an introduction to organic chemistry in

our study of the hydrocarbons. As we pointed out there, all organic
In this chapter the most common
functional groups of the two main
compounds can be thought of as derived from hydrocarbons. Very types—groups with only covalent
small differences in structure can have remarkably great effects on the single bonds and groups that include
properties of organic compounds. One type of simple structural dif­ covalent double bonds—are discussed.
ference might be in the addition or subtraction of a few carbon atoms The nomenclature of compounds con­
of the hydrocarbon skeleton of a compound. Another might be the dif­ taining these groups is explained.
ference between two isomers of the same compound. A third difference Examples are given of some simple
might be in the location or type of groups attached to the hydrocarbon compounds and some more complex
skeleton. compounds of specific interest con­
In this chapter we discuss some of the functional groups of taining each of the groups. A few of
atoms that, when attached to hydrocarbons, impart specific properties the most common preparations and
to the molecules. A primary purpose of this chapter is to give you some reactions of the various types of com­
familiarity with the most common of these groups, which include pounds are included. The chapter (and
atoms of elements other than carbon, most often halogen, oxygen, the book) ends with a brief introduc­
nitrogen, or sulfur atoms. tion to proteins, carbohydrates, lipids,
To convey how varied organic compounds are, we include with and nucleic acids—the molecules of
the discusson of each group a few examples of interesting or practical biochemistry.
compounds that contain these groups. We have no intention that you
should memorize the structures of such compounds.
Never underestimate the power of a functional group. Urea, the
first synthetic organic chemical, a component of urine, and a
common fertilizer, differs by only one functional group, C = 0 versus
C = S , from thiourea, a compound suspected of being a cancer-
causing agent.
O
II
H 2 N—C — NH 2
H 2 N—C —NH 2
urea thiourea

1009
 The arrangement of the functional groups — N 0 2 or —NH 2 makes a
vast difference in the taste of the following three compounds.

OCH2CH2CH3 OCH2CH2CH, OCH2CH2CH3

.N0 2 ,NH2 .N0 2

NH2 N0 2 N0 2
tasteless 4100 times sweeter bitter
than suiiar
TABLE 32.1
Chemistry has come a long way in predicting the effects on
Some common functional groups
chemical and physical properties of variations in the groups at­
Compound structure tached to organic compounds. However, we do not yet know the
{functional group0 explanation for many of the subtle relationships between structure
in color) Compound name
and biochemical activity. The study of such relationships is at the
R—X Alkyl halide frontier of scientific research today.
R—OH Alcohol
Ar—OH Phenol
ROR Ether 32.1 Functional groups
R—NH2 Amine
If one of the hydrogen atoms of the water molecule is replaced by one
R—C=0 Aldehyde of the various saturated alkyl groups, the series that begins with
I CH3OH results.
n
R2C=0 Ketone HOH
R—C=0 Carboxylic acid CH3OH
I CH3CH OH
OH CH3CH2CH2OH
Amide CH.CHXHXH.OH
R—C=0 etc.
I
NH2 Acyl halide These compounds can all be represented by the general expression,
R —XC = 0 ROH, where, except for water, R is some collection of carbon and hy­
drogen atoms.
R -C- -0—C—R Acid anhydride
The chemistry of these compounds is dominated by the OH
() O group. All compounds of the formula ROH exhibit similar chemical
R—C=0 Ester behavior, no matter how long the continuous chain of carbon atoms
I may be. Saturated hydrocarbons, you will recall (Section 23.4), are
relatively unreactive, so we should not expect the hydrocarbon part
OR Nitroalkane to overshadow the waterlike part. The compounds of the family re­
R—N02 Sulfonic acid presented by the formula ROH are collectively called alcohols, and
R—S03H Nitrile the OH group is referred to as a functional group. A functional group
R—CN is an atom or group that bonds to one or more carbon atoms in an
" Ar is the abbreviation used for an aromatic organic molecule and contributes a characteristic chemical behavior
group, such as the phenyl group (C e H 5 ). to the molecule.
X represents any halogen atom.
Table 32.1 lists the most common functional groups. Large and
even not so large molecules can contain many functional groups of
[32.1J ORGANIC CHEMISTRY different types.

1010
 Functional groups with
covalent single bonds Alky l halides, RX
Aryl halides, ArX

32.2 Halogen derivatives of hydrocarbons

Fluorine, chlorine, bromine, and iodine can all be found in organic
molecules. The halides of hydrocarbons may be alkyl halides, RX, TABLE 32.2
where R is a saturated group; aryl halides, ArX, where Ar is an aro­ Halogen derivatives of
matic group, or they may contain u n s a t u r a t e d R groups; X usually hydrocarbons
represents any halogen. Some common halogen derivatives of hydro­ The common name is given first; the
carbons are listed in Table 32.2 to illustrate their nomenclature (com­ systematic name is given in parentheses.
pare with the saturated hydrocarbons, Table 23.2) and the effect of The general molecular structure of
molecular structure on boiling point. these hydrocarbon halides is R—X
Halogen atoms are more electronegative than the carbon atom,
Boiling point
so the halogen atom draws the electron pair in a halogen-carbon
(°C)
bond toward itself. The result is a polar covalent bond, as, for ex­
ample, in methyl bromide CH 3 Br 5
methyl bromide
δ+ δ- (bromomethane)
CH3- -Br
CH 3 I 42
The effect of this polarization is shown in the reactions of com­ methyl iodide
pounds containing such bonds. The halogen atom is rather easily re­ (iodomethane)
moved as a halide ion. Furthermore, the carbon atom is readily at­
tacked by anions or by molecules that possess an unshared pair of Cri 3 CH 2 Br 38
ethyl bromide
electrons (nucleophilic reagents, Section 23.8). The following equa­ (bromoethane)
tions illustrate a few reactions in which the halogen is displaced by a
nucleophilic group. CH 3 CH 2 CH 2 Br 71
propyl bromide
Na + OH- + CH3—Br - ^ CH3OH + NaBr (1 -bromopropane)
(1)
an alcohol
LH3LHCH2
Na+CN" + CH3—Br - ^ CH3CN + NaBr (2)
Br Br 141
a nit rile
propylene dibromide
H2o (/ ,2-dibromopropane)
:NH 3 + C H 3 — B r —i-> CH3NH2 + HBr (3)
an amine
CH2=CHC1 14
Halogen atoms on aromatic rings are inert to such displacement vinyl chloride
reactions. (chloroethene)
Alkyl halides can also be induced to lose HX (where X is Cl, Br, or

O
I) and form alkenes, for example,
132
CH3CH2CH2Br — — — > CH 3 CH=CH 2 + NaBr + H 2 0
1 , . , alcohol, heat , chlorobenzene
propyl bromide propylene

Many pesticides are highly chlorinated compounds. There can be

no doubt as to the value of these compounds in improving the yield of
good crops by preventing insects from destroying the crops. How- ORGANIC CHEMISTRY [32.2]

1011
 H Cl Cl

α^ί\-ί^ί~Υα
Insecticides
Cl —C—Cl
I
Cl Cl
DDT Chlordane
\1,1,1 -trichloro-2,2-his
(p-chlorophenyl)ethane |

Cl
,P /
0
Herbicides Cl—^ 7—OCH 2 C OCH 2 C
\
OH
2,4-D
[(2,4-dichlorophenoxy)acetic acid \
2,4,5-T
[(2,4,5-trichlorophenoxy)acetic acid}

Fungicide
cv ^γ xi
Cl
PCP
(pentachlorophenol)

TABLE 32.3 ever, some of the compounds listed in Table 32.3 have come under
Chlorinated hydrocarbon criticism for (1) their long persistence in the environment and/or (2)
pesticides their toxicity to both m a n and animals. Aldrin and a structurally sim­
ilar compound, dieldrin, have now been banned, and the use of DDT
and chlordane is carefully restricted. 2,4,5-T, an herbicide used as a
defoliant during the Vietnam war, has been suspected of causing
genetic defects. However, these effects seem to be due to the presence
of small amounts of a very highly toxic impurity, dioxin.

Cl O Cl

Cl o Cl
dioxin
a very toxic substance

32.3 Alcohols
In organic compounds, the OH group is usually covalently bonded
and is called the hydroxyl group. The ending ol indicates the presence
[32.2] ORGANIC CHEMISTRY of a functional —OH in an organic molecule. Alcohols have the gen-

1012
eral formula ROH. The generic n a m e for alcohols is alkanol when R
is saturated, alkenol when R is olefinic, and alkynol when R is acety-
lenic. (When R is aromatic, the compound is a phenol; next section.) Alcohols, ROH
In the common system of nomenclature, the R group is named
and the word alcohol follows, as in methyl alcohol (CH3OH) and cy-
clohexyl alcohol (C 6 H n OH). Ethyl alcohol (C2H5OH) is the common
beverage alcohol. In the IUPAC system of nomenclature, the n a m e is TABLE 32.4
derived from the longest hydrocarbon chain that includes the OH Alcohols
group by dropping the final e and adding ol, as in methanol, ethanol, The general molecular formula for an
and cyclohexanol. When necessary, a n u m b e r is used to show the po­ alcohol is ROH
sition of the OH group. Numbering starts at the end of the chain
nearest to the OH group. Table 32.4 provides a few examples. Boiling point
(°C)
Alcohols are classified as primary, secondary, or tertiary, de­
pending on whether the carbon atom to which the hydroxyl group is CH 3 OH 65
attached is primary, secondary, or tertiary. Like water the alcohols methyl alcohol
exhibit hydrogen bonding, which causes their boiling points to be {methanol)
relatively high.
Methanol, once known as wood alcohol because of its formation CH 3 CH 2 OH 78
during wood distillation, is now made synthetically from carbon ethyl alcohol
{ethanol)
monoxide and hydrogen in quantities exceeding those of most other
synthetic organic chemicals (5000 million pounds in 1975). CH 3 CH 2 CH 2 OH 97
propyl alcohol
CO(g) + 2H2(g) -±> CH3OH(g) {1-propanol)

Most of this methanol is converted to formaldehyde. Methanol is C ri 3 CH. Cri.3 82

toxic and causes blindness or death when taken internally. OH
Ethanol, in addition to being a component of many beverages, is isopropyl alcohol
a valuable solvent and a frequently used reagent in organic synthesis. {2-propanol)
Ethylene glycol is used as a permanent antifreeze in automobiles be­
cause of its relatively low volatility. Isopropyl alcohol is rubbing al­ HOCH 2 CH 2 OH 197
cohol, and large quantities are converted into acetone (Section 32.7). ethylene glycol
Glycerol has a strong attraction for water and, because of this prop­ {1,2-ethanediol)
erty, it is used in lotions and other applications where moisture re­
tention is desired. Glycerol is also used in the manufacture of paints, CHoCHCHo 290 (dec)
varnishes, explosives, and a variety of other products. II 1
OHOHOH
The formation of an alcohol from the reaction of an alkyl halide
glycerol {glycerin)
with an aqueous base was shown in Equation (1). The reaction of one {1 2,3-propanetriol)
class of organic compound often becomes a method of preparation for
another class of compound. Alcohols can also be prepared by the treat­
ment of olefins with sulfuric acid, followed by hydrolysis. ^ ^CH2CH2OH 219

ß-phenylethyl alcohol
CH 2 =CH 2 + H 2 S0 4 > CH3CH2OS03H —% CH3CH2OH + H 2 S0 4 {2-phenylethanol)

Fermentation of various grains, fruits, and other natural prod­

ucts that contain starch or sugars produces ethyl alcohol. Enzymes,
which are the catalysts in biochemical systems, first convert starch to
sugars, and the sugars are then converted to ethyl alcohol and carbon
dioxide by other enzymes.
At one time all ethyl alcohol was produced commercially by fer­
mentation. It is now more economical to make ethyl alcohol by the ORGANIC CHEMISTRY [32.3]

1013
 reaction of water with ethylene, which is readily available from
petroleum refineries.

heat, catalysts,

CH2=CH2 + H20 -> CHXHoOH

TABLE 32.5
Fermentation, however, is still the preferred method of obtaining
Alcoholic beverages ethyl alcohol for beverages, many of which retain flavors character­
istic of the material that was fermented (Table 32.5). After fermenta­
Beverage Starting material tion, a solution contains up to 14% ethyl alcohol. Except for wines
and beer, this solution is distilled to remove water and increase the
Whiskey Grains (rye, corn, wheat, oats,
barley)
alcohol content. Up to 95% ethyl alcohol by weight, which is the com­
position of a constant-boiling mixture of alcohol and water, can be
Rum Molasses
obtained by distillation. The usual 80-proof beverage is a 40% solu­
Brandy Grapes and other fruits
tion of ethyl alcohol.
Gin Grains (distilled and flavored Absolute ethyl alcohol, 100% or 200 proof, is made by removing
with juniper berry)
the remaining water from 95% ethyl alcohol by distillation with ben­
Vodka Potatoes and corn zene or by chemical means. (An azeotropic mixture of benzene, al­
Wines Grapes cohol, and water distills at 65°C and removes the last few percent of
Sake Rice water.) Ethyl alcohol for beverages is subject to a federal tax. In order
Mead Honey to render industrial ethyl alcohol unfit for drinking, various toxic or
objectionable materials (e.g., methanol) that are difficult to remove
Beer Barley and hops
from ethyl alcohol are added. This denatured alcohol is tax-free, hence
Tequila Cactus
much cheaper for industrial users.
Like water, alcohols can act as either acids or bases. As acids,
they are even weaker than water, however. In the presence of rela­
tively strong bases, alcohols donate protons. For example, reaction of
alcohols with active metals such as Li, Na, K, Mg, or Al gives a class
of compounds known as alkoxides, RO~M + . The reaction of ethyl al­
cohol with sodium

2CH,CH 2 OH + 2Na 2CH 3 CH 2 0 Na + + H 2

sodium ellioxide

is sufficiently moderate to permit the disposal of waste sodium by

converting it to sodium ethoxide, an alkaline, ionic compound com­
parable to sodium hydroxide.
In the presence of concentrated acids, alcohols act as proton ac­
ceptors in overall reactions such as

CH,OH + HBr CH 3 Br + H 2 0

Similar results are obtained with concentrated HC1, HI, H 2 S0 4 , and

H N 0 3 . The reaction of glycerol with nitric acid yields nitroglycerin,
an explosive and a component of dynamite

CH 2 OH CH 2 ON0 2
CHOH + 3 H N 0 3 CHONO, | N 2 + 3C0 2 + fH 2 0 + i 0 2
CH 2 OH CH 2 ON0 2
glycerol glyceryl trinitrate
[32.3] ORGANIC CHEMISTRY {nitroglycerin)

1014
Nitroglycerin is also useful in the treatment of heart disease because
of its action in dilating blood vessels.
Phenols, ArOH

32.4 Phenols
The attachment of a hydroxyl group to an aromatic ring gives a class TABLE 32.6
of organic compounds known as phenols, ArOH. The simplest com­ Phenols
pound in the group is phenol itself, C 6 H 5 OH (Table 32.6). The structu­ The general molecular formula of a
ral similarity of phenols to alcohols is apparent. However, the aro­ phenol is ArOH
matic ring modifies the chemical behavior of the hydroxyl group.
Melting point (°C)
Phenols are weak acids; most of them have pKa values of about 10,
which makes them much stronger acids than alcohols. The acidity of OH
phenols arises in part because the aromatic ring delocalizes the nega­
tive charge on the anion; for example,
42

/ \-OH^=^H+ +

phenol resonance structures of the

phenoxide ion 36

Furthermore, the hydroxyl group causes the aromatic ring to be

much more reactive toward substitution and oxidation. The Br, N 0 2 ,
and S0 3 H groups are readily substituted on ring carbon atoms in OH
phenols under conditions that do not cause any reaction to occur
with benzene.
Phenol itself is poisonous and will cause blisters on the skin. The 94
biggest use for phenol is in the manufacture of phenol-formaldehyde
resins (among them the product known as Bakelite). Another impor­ a-naphthol
{1-naphthol)
tant use of phenols is in bactericidal products. "Carbolic acid" is a
name given to phenol and its aqueous solutions. Joseph Lister, apply­
ing Pasteur's theories about bacteria and infection in the late 1800s, OH
did surgery under a spray of carbolic acid. Some of the more common
antiseptic phenols are hexylresorcinol (Table 32.7) and the cresols
169
TABLE 32.7 OH
Some additional phenols hydroquinone
Urushiol is a mixture of phenols that vary only in the amount ofunsaturation
in the side chain. OH
OH OH OH OH
02N N02 OH 104

OH ^IsHoi ca techoi
urushiol
N02 CH2vCH2)4CH3
picric acid hexylresorcinol
ORGANIC CHEMISTRY [32.4]

1015
 (methylphenols) (Table 32.6). Phenols are also used in the manufac­
ture of dyes, drugs, photographic developers, adhesives, and a large
Ethers, ROR variety of other products. Picric acid (Table 32.7) is a strong acid and
a high explosive. Many phenols occur naturally, for example, the ac­
tive component in poison ivy (urushiol, Table 32.7) and several essen­
tial oils (oil of cloves, oil of aniseed).
One method for the preparation of phenol itself is illustrated by
the following equations.

ci+ 2NaOH
TABLE 32.8
Ethers
C^
chlorohenzene
-> C \— ONa+ + H 2 0 + NaCl

sodium
The general molecular formula for an phenoxide
ether is ROR

Boiling point (°C)

- ^ / ^ O H + Na +
CH3OCH3 -24
diethyl ether phenol
{ethoxy ethane)
Millions of pounds of phenol are made annually by this and other
CH3CH2OCH2CH3 35 processes (1700 million pounds in 1975).
diethyl ether
{ethoxy ethane)

CH 3 OCH 2 CH 2 OCH 3 85 32.5 Ethers

ethylene dycol dimethyl
ether ("gfyrne") An ether can be viewed as derived from water by replacing both
(/ ,2-dimethoxy ethane)
hydrogen atoms with hydrocarbon groups. An ether has the general
formula ROR. If the two hydrocarbon groups are alike, the ether is a
H» H2 101
simple or symmetrical ether; if they are different, the ether is a mixed
C-
or unsymmetrical ether.
0
< /
C- CH,
H2 -c
H2
CH3CH 2 CH2CHQ
dioxane \
{1,4-d oxin) CH3
diethyl ether ethyl isopropyl ether
11 a simple ether a mixed ether
H 2 C- -CH 2
o The common system of nomenclature names the groups attached
ethylene oxide
(oxirane) to the oxygen atom followed by the word ether, as just shown. Some­
times the di is omitted when the groups are identical. Diethyl ether is
then simply named ethyl ether. RO— is an alkoxy group, and in the
154 IUPAC system of nomenclature, the ether is named as an alkoxy
derivative of the longest-chain hydrocarbon to which the alkoxy
anisole group is attached. The position of attachment is given by a number,
{m ethoxy benzene) starting at the end of the chain nearest the alkoxy group. Thus, ethyl
isopropyl ether is 2-ethoxypropane. Table 32.8 gives several ex­
amples. Note that cyclic ethers are also known.
An ether cannot form hydrogen bonds with itself. As a conse­
quence, the boiling points of ethers are near those of hydrocarbons
[32.4] ORGANIC CHEMISTRY having the same molecular weight. The effect of hydrogen bonding is

1016
 TABLE 32.9
Note that the two isomers differ in structure only in the position of one double Tetrahydrocannabinol
bond, but differ considerably in activity.
{active ingredient in marijuana)
isomeric double bond isomeric
double bond
CH, major activity CH3
from this isomer

ΟϊΗη C,H,

TABLE 32.10
dramatically exposed by a comparison of the boiling points of ethyl-
ene glycol (HOCH 2 CH 2 OH, b.p. 197°C) and 1,2-dimethoxyethane Classification of amines
(CH 3 OCH 2 CH 2 OCH 3 , b.p. 85°C). Primary amine, RNH 2
The ethers are rather unreactive and are often used as solvents in CH,NH2
carrying out reactions. However, ethers do have an unfortunate tend­ methylamine
b.p. -6°C
ency to form peroxides (compounds containing—O—O— bonds) when
exposed to the oxygen in air. These peroxides are susceptible to explo­ Secondary amine, R 2 NH
(CH,),NH
sive decomposition and for this reason special precautions must dimethylamine
always be used when working with ethers. b.p. 7°C
Diethyl ether, a volatile and flammable liquid, is often used as a Tertiary amine, R.,N
general anesthetic and is an excellent solvent. The ether linkage is (CH,),N
trimethvlamine
found in many naturally occurring compounds, among them tetrahy- b.p. 3°C
drocannabinol, which in its two isomeric forms (Table 32.9) is the
Quaternary ammonium salt, R 4 N + X _
active component in marijuana and hashish from the hemp plant.
(CH,) 4 N + I-
Ethers can be obtained from alcohols by intermolecular dehy­ tetramethylammonium iodide
dration, a method that is used industrially. m.p. 230°C (dec)

cone. H 2 S0 4
2CH3CH2OH CH 3 CH 2 OCH 2 CH 3 + H 2 0
heat
ethyl diethyl ether
alcohol TABLE 32.11
Aromatic and cyclic amines

Aromatic amines Cyclic amines

32.6 Amines NH2

Replacement of the hydrogen atoms of an a m m o n i a molecule by hy­

NT
drocarbon groups gives amines (not to be confused with ammines,
pyridine
Chapter 28). Amines are classified (Table 32.10) as primary (RNH 2 ), b.p. 116°C
aniline
secondary (R 2 NH), or tertiary (R 3 N), according to the n u m b e r of hy­ b.p. 183°C o.
drogen atoms of the a m m o n i a molecule that have been replaced by
NH2
bonds to carbon atoms. Addition of a fourth hydrocarbon group
yields a quaternary a m m o n i u m ion. The common system of nomen­ N
H
clature for amines is illustrated in Table 32.10. Aniline, pyridine, and
morpholine
morpholine (Table 32.11) are nonsystematic names. ß-naphthylamine b.p. 130°C
(2-naphthylamine)
Aromatic amines are those with the amine group attached to an m.p. fl2°C
aromatic ring, as in aniline. Such amines are usually prepared by

1017
the nitration of an aromatic compound and subsequent reduction of
the nitro group, N 0 2 , with, for example, tin and concentrated hydro­
chloric acid.

Ο^ΟΝΟ·^0-ΝΗ·+2Η·°
benzene nitrobenzene aniline

The reaction of ammonia with alkyl halides also produces amines.

CH3CH2C1 + NH3 > CH3CH2NH3C1- - ^ > CH3CH2NH2 + NH4C1

ethyl ethylammonium ethylamine
chloride chloride

In this reaction the ethylamine can react further with ethyl chloride
to form diethylamine, which can then react to form triethylamine.
The mixture from the reaction of an alkyl halide with ammonia nor­
mally contains all of the possible amines (RNH 2 , R 2 NH, R 3 N), as well
as the quarternary a m m o n i u m salt, R 4 NX. Amines with unlike
groups attached to the nitrogen atom are attainable by an extension
of this method.
,CH3
/ ^ - N H 2 + 2CH3Br > / YN
- + 2HBr
CH3
aniline N ,N-dimethylaniline
b.p. 193°C

Amines are basic. Like ammonia, they form salts with acids.

CH3NH2 + HC1 > CH3NH3+C1-

methylamine methylammonium
chloride

The aliphatic amines are comparable to ammonia in basic strength.

Aromatic amines are considerably weaker bases, because, in theory,
the unshared electron pair on the nitrogen can be delocalized around
the ring.
Most amines have fairly strong, unpleasant odors; the salts are
odorless, water-soluble solids. Amine salts are easily converted to the
amine by treating with a base.

CH3NH3C1 + NaOH > CH3NH2 + NaCl + H 2 0

Physiologically active amines (Table 32.12) found in plants are

known as alkaloids. Nicotine is present in tobacco and is used as an
insecticide. Morphine, a sedative and analgesic (pain killer), is a
major component of opium. Codeine, another popular analgesic, is
the methyl ether (at the phenolic hydroxyl group) of morphine.
Heroin is also a derivative of morphine. Coniine, a relatively simple
alkaloid, is the toxic substance in the hemlock that poisoned So­
crates. The "uppers," or stimulating drugs, amphetamine and methe-
drine are also amines. Note the structural similarity of these stimu-
lants to epinephrine, also known as adrenalin, a naturally occurring
stimulant that is released by the adrenal glands under conditions of
fear or stress.
Aliphatic primary amines react quantitatively with nitrous acid
and liberate nitrogen.

CH3NH2 + HN02 CH,OH + N 2 + H 2 0

methvlamine (HC1 + NaN0 2 )

(Nitrous acid, H N 0 2 , is not stable, so to carry out this reaction,

sodium nitrite is added to an aqueous solution of the amine salt in di­
lute hydrochloric acid. Nitrous acid is formed in solution and reacts
with the amine salt.) Aromatic p r i m a r y amines react with a chilled
nitrous acid solution to form water-soluble and fairly unstable dia-
zonium salts, ArN 2 + X~

Q^ NH *#rf^H c| - +2H >°

aniline benzenediazonium
chloride

Much of the early incentive to study organic compounds arose

from the desire to make synthetic dyes. An important class of dyes,
the azo dyes, is formed by the coupling of diazonium salts with
phenols or aromatic amines.

.OH
02N / \ N2C1 +

p-nitrobenzene- 2-naphthol
diazonium chloride

N0 2

+ HC1

para red
an azo dye

The azo group, — N = N — , is a chromophoric group, that is, a

color-producing group. Any organic molecule that possesses a chro­
mophoric group is colored. However, not all colored compounds are
good dyes. For example, a satisfactory fabric dye must adhere to the
fabric and be stable to light, heat, and soap. Para red has these qual­
ities.
A dye that is suitable as an indicator of the pH of a solution must
change color within a narrow pH range (Section 17.7). Methyl orange
is yellow in a solution having a pH above 4.4 and becomes red when
the solution is more acidic than a pH of 3.1. Obviously, some change ORGANIC CHEMISTRY L32.6J

1019
 in molecular structure must accompany the change in color. This
change is expressed in the following equation.

NaO,S N=N—</ Y-N(CH3)2

yellow

NaO:,S N(CH,)2

red

NaO,S-Xx //H~N N(CH3)2

H
TABLE 32.13 At a pH of 3.1 a nitrogen atom of the azo group adds a proton, and the
Aldehydes resulting positive charge is delocalized as shown. The azo group is
The general molecular formula for an not present in either of the resonance structures, but the structural
aldehyde, often written as RCHO, is feature

Boiling point (°C)

is also a chromophoric group, and the contribution of the resonance
HCHO -21 structure containing it accounts for the red color in the more acidic
formaldehyde solution. This new chromophoric group is referred to as a quinonoid
(methanaf)
structure, and all compounds possessing this particular arrangement
of atoms and bonds are colored.
CH,CHO 21
acetaldehyde
{ethanal)
Functional groups with
CH 3 (CH 2 ) 4 CHO
caproaldehyde
128
covalent double bonds
(hexanal)" 32.7 Aldehydes and ketones
CH2=CHCHO 52 The carbonyl group consists of a carbon atom and an oxygen atom
acrolein joined by a covalent double bond.
(propenal)

c=o
<f~VcHO 179
δ+ δ-
\ /
benzaldehyde 0:0:
/
" Note that the aldehyde group must be at a carbonyl group
the end of a chain, so it is unnecessary to
write 1-hexanal.
Like the covalent double bond between two carbon atoms, the cova­
lent double bond in a carbonyl group is a combination of a <x bond
[32.6] ORGANIC CHEMISTRY and a π bond. The carbonyl group and its two attached groups lie
1020
in the same plane and include an sp2-type carbon atom with valence
angles near 120°. The actual molecular structure of the carbonyl
group is a hybrid of the two principal resonance structures shown
above. In effect, the carbon atom is slightly positive and the oxygen
atom is slightly negative. The greater electronegativity of the oxygen
atom plays a role in establishing this bond polarity.
The carbonyl group is present in aldehydes and ketones, and in Ketones, R 2 C = 0
the rest of the functional groups discussed in this chapter.
An aldehyde, RCHO, is a compound in which a hydrogen atom
and a hydrocarbon group are bonded to a carbonyl group (Table
32.13). In the simplest possible case, R is a hydrogen atom also. The
common names of the aldehydes are derived from the names of the
carboxylic acids (next section) containing the same carbon skeleton
by replacing the final ic by aldehyde. Thus, formaldehyde, HCHO, is TABLE 32.14
the aldehyde corresponding to formic acid, HCOOH. The IUPAC Ketones
system of nomenclature for aldehydes requires only the replacement The general molecular formula for a ketone,
of the final e of the name of the longest-chain hydrocarbon including often written as R2CO or RCOR', and
the aldehyde group by al. Substitutions or branches along this main in which Rand R' may be the same or
chain are designated by n u m b e r s (the carbonyl carbon atom is num­ different, is R
bered 1) and names by prefixes. Table 32.13 gives several examples. / C = 0
Formaldehyde is used mainly in the manufacture of p h e n o l - R'
formaldehyde resins. It also finds some use as a disinfectant and a
preservative, often as formalin, a 37% aqueous solution of formalde­ Boiling point
hyde. Trichloroacetaldehyde, Cl 3 CCHO, forms a hydrate, chloral hy­ (°C)
drate Cl 3 CCH(OH) 2 , that is a sleep-inducing drug. CH3COCH3 56
Several aldehydes have been isolated from fruits, to which they dimethyl ketone {acetone)
contribute characteristic odor and taste. Citral, a terpene aldehyde, is (2-propanone)
found in the oil from citrus fruits and in oil of lemon grass. It has a
strong lemonlike odor. Vanillin is used as a vanilla flavoring agent. CH3CH2COCH2CH3 102
diethyl ketone
OH (3-pentanone)

OCH,
CH3C = CHCH2CH2C=CHCHO CH3COCH2CH2CH3 102
methyl n-propyl ketone
CH3 CH3 (2-pentanone)

CHO
citral vanillin CH3COCOCH3 88
(3,1'-dimethyl-2,6-octadienal) biacetyl" (dimethylglyoxal)
(2,3-butanedione)
A ketone, R 2 C = 0 , contains two hydrocarbon groups attached to
the carbon atom of the carbonyl group (Table 32.14). In the common
system of nomenclature, the two hydrocarbon groups are named, fol­ f Y-COCH3 200
lowed by the word ketone, as in methyl ethyl ketone, CH 3 COCH 2 CH 3 .
Dimethyl ketone is almost always referred to by its trivial name, ace­ methyl phenyl ketone
(acetophenone)
tone. In the IUPAC system of nomenclature, a ketone is designated by
the suffix one, which replaces the final e of the n a m e of the longest- a
This is one of the few colored (yellowish
chain hydrocarbon containing the carbonyl group. A number is nor­ green) organic liquids. Practically all pure
mally used to show the position of the carbonyl group, starting at the organic liquids are colorless; many pure
solids are colored, however.
end of the chain nearest the carbonyl group. Thus, methyl ethyl ke­
tone is 2-butanone in the IUPAC system. Substitutions and branches
on the main chain are treated as before (Section 23.4). Table 32.14
gives several examples.
Ketones are used extensively as solvents, especially in lacquers ORGANIC CHEMISTRY [32.7]

1021
 TOOLS OF .bsorption spectra arise when energy from incoming radiation is
CHEMISTRY absorbed, causing atoms, molecules, or ions to move into a higher en­
ergy state. Among the valuable tools of the organic chemist are infra­
red (IR) and ultraviolet (UV) absorption spectroscopy.
Infrared and The infrared region of the electromagnetic spectrum extends from
2.5 /xm to 15 μπ\ (1 μπι = 1 x 10~4 cm = 1000 nm). Infared spectra
ultraviolet originate in an increase in energy level of the motions of atoms in a
molecule relative to each other. The atoms in a molecule are never
spectroscopy motionless. They may, for example, bend or stretch (Figure A) or un­
dergo other motions known as wagging, rocking, deformation, and so
on. When the motion involves a change in dipole moment, and when
the frequency of incoming radiation matches the frequency of the
motion, absorption occurs and a "peak" appears in the infrared spec­
trum. Figure B shows the spectra of ethylene glycol and ethylene­
diamine with the origins of many of the peaks identified
(str = stretching; def = deformation; wag = wagging). Customarily
. . — ►
in infrared spectra the percent of the radiation transmitted (% trans-
mittance) is plotted versus the wavelength (in μ,πι, for example) or
wave numbers (in cm - 1 )·
The more complicated a molecule is, the more possibilities there
(a) are for relative motions of the atoms. Therefore, infrared spectra can
be quite complex, and the larger the molecule, the more peaks will
appear in the spectrum. In spectra with many peaks, identification of
the origin of all the peaks is difficult.
Infrared spectra are most useful in two ways. One depends upon
the fact that the same functional groups cause absorption at the same
or close to the same wavelength in the spectra of all the molecules in
which they occur. From the study of the spectra of thousands of com­
pounds "correlation c h a r t s " have been assembled. These charts show
the location of peaks that result from the presence of specific groups
of atoms. A small portion of a correlation chart is shown in Figure C.
This segment includes the location of the peaks of functional groups
that contain a carbon-nitrogen single bond.
(b)
In the determination of the structure of an unknown compound,
FIGURE A the infrared spectrum is used to indicate which functional groups are
present by comparison of the spectrum with such charts. This is often
not as simple and straightforward as it sounds, but with experience,
much useful information about structure can be gleaned from infra­
red spectra. For example, an experienced observer would quickly
FIGURE B know from the two spectra in Figure B that one compound contained
Infrared spectra of ethylene glycol OH groups and the other, NH 2 groups.
(1,2-ethanediol) and ethylenediamine Infrared spectra, like mass spectra, are also used as fingerprints.
(1,2-diaminoethane). It has been said that the infrared spectrum of a compound may be its

μιτι
11 12 13 14 15

ethylene glycol OH def CH 2 wag Τ^Γ^

3600 3200 2800 2400 2000 1900 1800 1700 1600 1500 1400 1300 1200 1100 1000 900 800 700

1022
 M
C-N •M Primary amine aryl-NH 2
-NH2 NH2-- -NH2 --Ü
W _NH Secondary amine aryl-NH-
aryl-N — NH2 (broad)
—-CH2-NH-CH2
Tertiary amine CH2-NH-CH2--
N(CH2)2.-N(CH3)2-- aryl-N(CH 3 ) 2 -
S
■ C -NH; Ammonium ion _NH;-—T—
Primary amine salt -NH3-.
♦ Secondary amine salt
NH
~ Tertiary amine salt
3600 3200 2800 2400 2000 1900 1800 1700 1500 1400 1100 1000 900 800 700 600

most characteristic physical property. By comparison of the spec­ FIGURE C

trum of a compound, say a reaction product that has not been identi­ Portion of an infrared correlation
fied, with the spectra of known compounds that might be products, chart. This segment shows the location
identification can often be made. For example, if a compound was of peaks for groups that contain carbon-
known to be either ethylenediamine or ethylene glycol, comparing its nitrogen single bonds. The letters S, M,
spectrum with the two known spectra in Figure B would quickly and W indicate strong, medium, and
weak bands, respectively.
show which compound had been produced.
The near-ultraviolet region of the electromagnetic spectrum ex­
tends from 200 to 400 n m . (Far-ultraviolet spectra, at longer wave­
lengths, are difficult to measure experimentally and are of less prac­
tical value.) Ultraviolet radiation is of higher energy than infared
radiation. At such energy, absorption occurs by transitions of outer π
or nonbonding electrons into higher energy levels, usually into unoc­
cupied antibonding, σ* or π* orbitals.
A simple saturated hydrocarbon does not absorb in the near-
m . ■:■;-
ultraviolet region. The presence of carbon-carbon multiple bonds or Pyridine
4.5
of functional groups containing multiple bonds, that is the presence
of 7Γ electrons, and π orbitals, is required for UV absorption. Ultravio­
let spectra are much more simple than infrared spectra. They show a
single peak or a few peaks for each isolated functional group or Solvent: 95% ethanol
carbon-carbon multiple bond present in the molecule. Ultraviolet
spectra are described in terms of Xmax, the wavelength of m a x i m u m
absorption. Usually measured in solution, ultraviolet spectra are pre­ 3.0
sented as plots of absorption versus wavelength or, as in the pyridine
spectrum shown in Figure D, as the logarithm of the molar absorptiv­
ity, log e, versus wavelength. Molar absorptivity, e, is a function of
the amount of radiation transmitted, the concentration of the sub­
«u 2.0
stance in solution, and the length of the path of the light through the O
sample. Ultraviolet absorption peaks are shifted to longer wave­ 200 220 240 260 280 300
lengths when a molecule contains conjugated systems, for example, Wavelength (nm)
— C H = C H — C H = C H — or — C H = C H — C H = 0 .
Ultraviolet spectra can be used for structure analysis and com­ FIGURE D
pound identification in the same way as infrared spectra are used. Ultraviolet spectrum of pyridine. (From
However, their application in these ways is limited because there are R. M. Silverstein et ai, Spectrometric
fewer peaks in ultraviolet spectra and the peaks are broader. Spectra Identification of Organic Compounds,
in the near-ultraviolet region are more often used in quantitative 3rd ed., John Wiley & Sons, Inc., New
York, 1974.)
analysis, as are spectra in the visible region. The spectra are measured
in solution and the intensity of the absorption varies with the concen­
tration of the absorbing species. The relationship between the ultra­
violet absorption and concentration is first determined experi­
mentally. Then an unknown concentration can be found by compari­
son with the data for known concentrations. Titrations can be followed
by spectral changes, and frequently, the concentration of a substance
in a complex mixture can be measured by its characteristic absorption.
1023
 and other coatings. They frequently serve as starting materials for
organic synthesis. Phenacyl chloride (Table 32.15), a potent lachry-
mator (tear inducer), is used in tear gas (Mace and CN). Camphor,
from the camphor tree, is a terpene ketone that has some use in medi­
cine and plastics. Methadone is an addictive analgesic and is used in
a controlled program to combat heroin addiction.
TABLE 32.15 Alcohols are often the starting materials for the preparation of al­
Some additional ketones dehydes and, especially, ketones. Sodium dichromate easily oxidizes
a primary alcohol to an aldehyde and a secondary alcohol to a ketone.
COCHoCl
H

CH3CH2OH
Na 2 Cr 2 0 7 I
H 2 SO, ► CH3C=0 + H20
ethyl alcohol acetaldehyde
phenacyl a primary alcohol
chloride
camphor Na,Ct 2 0 7
CH3CHCH3 CH 3 CCH 3 + H 2 0
H 2 S0 4

OH o
O ^ ^ CH3 i sop ropy I alcohol acetone
a secondary alcohol
CH 3 CH 2 C C—CH2CHN(CH3)2
A ketone is resistant to further oxidation under these conditions,
but an aldehyde is readily oxidized to the corresponding carboxylic
acid (next section). This method for the preparation of aldehydes re­
methadone quires the immediate removal of the aldehyde from the reaction
medium, a circumstance that limits the method to quite volatile al­
dehydes.
Commercially, the conversion of an alcohol to an aldehyde or ke­
tone is often effected by passing the alcohol vapor and air over a
heated copper catalyst in a dehydrogenation reaction—a reaction in
which H 2 is removed.

H
Cu 3Q0 C
CH3CH2OH ' ° ) CH3C=0

Cu 300 C
CH3CHCH3 ' ° > CH3CCH3
OH O

Most acetone is made in this manner.

Aldehydes, but not ketones, are easily oxidized.

H
I
CH,C=0 > CH3COH

O
acetic acid
a carboxylic acid

Even atmospheric oxygen will bring about the conversion of many al­
[32.7J ORGANIC CHEMISTRY dehydes to the corresponding acids. A very mild oxidizing agent,

1024
[Ag(NH 3 ) 2 ]OH, called Tollens' reagent, provides a diagnostic test for
aldehydes.
Carboxylic acids, RCOOH
RCHO + 2[Ag(NH3)2]OH 2Ag + RCOONH4 + H 2 0 + 3NH3

When this reaction is carried out in a clean test tube, the elemental
silver that forms deposits as a silver mirror on the walls of the test
TABLE 32.16
tube. A process for the silvering of mirrors utilizes this reaction.
Carboxylic acids
The general molecular formula for a
carboxylic acid, often written RCOOH or
RC02H, and in which R can be a
32.8 Carboxylic acids hydrogen atom, is
RC­ OH
A carboxylic acid, RCOOH, has a functional group that is a combina­ 0
tion of a carbonyl group and a hydroxyl group
Boiling point (°C)
O
HCOOH 101
II formic acid
RCOH {methanoic acid)
a carboxylic
acid
CH3COOH 118
The more familiar carboxylic acids carry common names that are as­ acetic acid
{ethanoic acid)
sociated with the sources from which they were first isolated. In the
IUPAC system of nomenclature, the ending oic replaces the final e of
the hydrocarbon n a m e that is formed from the longest continuous CH 3 CH 2 COOH 140
propionic acid
chain of carbon atoms including the carboxyl group. The word acid {propanoic acid)
follows this derived n a m e . When this chain of carbon atoms is num­
bered, the carboxylic carbon atom is numbered 1. Table 32.16 shows
CH 3 CH 2 CH 2 COOH 163
the structures and names of some of the more common carboxylic butyric acid
acids. {butanoic acid)
Simple, unsubstituted monocarboxylic acids have pKa values in
the range 4 - 5 ; they are weaker as acids than sulfonic acids (RS0 3 H) CH2=CHCOOH 140
but stronger than phenols (Section 32.4). The ionization of a carbox­ acrylic acid
{propenoic acid)
ylic acid, as shown, produces the carboxylate ion, RCOO".
Melting point (°C)

RC=0;
J3 /°"
H+ + RC' <—> RC^
COOH
I
OH
o-
a carboxylate ion
o
0^ benzoic acid
121

This ion is stabilized by the delocalization of the negative charge over

(X
the two oxygen atoms. COOH 230
All of the carboxylic acids form salts when they are treated with
bases (e.g., hydroxides, carbonates, or bicarbonates). COOH
phthalic acid
+
CHgCOOH + N a O H CH3COONa + H20
acetic acid sodium acetate
{ethanoic acid) {sodium ethanoate)

The n a m e of the salt is obtained from the n a m e of the cation, followed

by the name of the carboxylic acid with the final ic replaced by ate. ORGANIC CHEMISTRY [32.1

1025
TABLE 32.17
Some additional carboxylic acids COOH CH2COOH
COOH H —C—OH HO — C —COOH
1
— C —OH HO — C — H CH2COOH
1 1
1 1 citric acid
CH,
lactic acid COOH
tartaric
acid
HO H2
V C* H (CH2)3COOH
/ Ύ CH=C
r ^ C ^ ^C-(CH2)4CH3
HO H H1 OH
prostaglandin FUt
(one of several prostaglandins)
TABLE 32.18
Esters of carboxylic acids
The general molecular formula for a
carboxylic acid ester, often written as
RCOOR' or RC0 2 R', and in which R and Acetic acid is produced in large quantities (2000 million pounds
R' may be alike or different, is in 1975) for use in making plastics and solvents. Phthalic acid is also
R—C—O—R' widely used in the production of varnishes, paints, and plastics (4000
million pounds in 1975).
0 Many carboxylic acids occur in nature, either free or combined in
some form. The combination of hydroxyl groups and carboxylic acid
Boiling point (°C)
groups in the same molecule to give hydroxy acids is very common in
HCOOCH3 32 nature. Lactic acid (Table 32.17) is found in sour milk (racemic form)
methyl formate and in the muscles of m a n and animals (dextrorotatory isomer). Tar­
(methyl methanoate)
taric acid (dextrorotatory isomer) occurs in many fruits. Citric acid
occurs in both plants and animals; lemon juice contains 5-8% citric
CH 3 COOCH 2 CH 3 77 acid.
ethyl acetate
(ethyl ethanoate) Currently there is considerable interest in some physiologically
active substances called prostaglandins (Table 32.17). These sub­
stances are found in many body tissues and fluids, but they seem to
CH2=CHCOOCH3 85
methyl acrylate occur in greatest amounts in h u m a n and sheep seminal plasma. Be­
{methyl propenoate) cause of their broad physiological activity, high hopes are held for
their use in medicine, particularly with respect to induced abortion,
prevention of conception, and the regulation of menstruation and fer­
ζ V-COOCHg 198 tility.

methyl benz.oate
32.9 Esters
jCOOC2H5 298
A compound in which the acidic hydrogen atom of a carboxylic acid
molecule is replaced by a hydrocarbon group is an ester, RCOOR',
"COOC 2 H 5
diethyl phthalate
for example

CH 3 COCH 3
132.8] ORGANIC CHEMISTRY methyl acetate

1026
In the two-word name for an ester, the first word is the name of the
R' group in RCOOR'. This word could be methyl (CH3), ethyl (C 2 H 5 ),
phenyl (C6H5), or the like. The second word of the n a m e is the n a m e of Esters, RCOOR'
the carboxylic acid with the final ic replaced by ate, identical with the
name of the carboxylate anion. Table 32.18 illustrates the common
and IUPAC system names.
Esters of the lower carboxylic acids and lower alcohols, for ex­
ample, ethyl acetate and butyl acetate, are used extensively as sol­
vents. Most esters of carboxylic acids have quite pleasant odors, even
when derived from rather foul-smelling acids. Many fruits and flow­
ers owe their flavor and fragrance to the esters present (Table
32.19); esters are often used as artificial flavors.
Aspirin, the popular fever reducer and pain killer, is an ester
formed between acetic acid, CH 3 COOH, and salicylic acid. When the
aspirin reaches the alkaline environment of the intestines, the sali­
cylic acid is liberated. Salol (phenyl salicylate) is used to coat a pill
when it is desired that the pill pass through the stomach unchanged
and release its contents in the intestines. (Such a coating is called an
enteric coating.) The salol coating is inert to the acidic conditions in
TABLE 32.19
The natural flavoring and odor of a food arise from a combination of a large group
of substances and not from just a single compound. For example, the total
Characteristic odors of some
number of flavoring substances in the strawberry is over 250. These substances esters
are esters, alcohols, carboxylic acids, aldehydes, ketones, and several other
classes of organic compounds.

Structure and common name Characteristic odor

CH 3 COOCH 2 CH 2 CH(CH 3 ) 2 Banana

isoamyl acetate

CH 3 CH 2 CH 2 COO(CH 2 ) 4 CH 3 Apricot
amyl butyrate

(CH 3 ) 2 CHCH 2 COOCH 2 CH 2 CH(CH 3 ) 2 Apple

isoamyl isovalerate

CH 3 CH 2 CH 2 COOC 2 H 5 Pineapple
ethyl butyrate

COOCH 3 Grape

NH2
methyl anthranilate

OH Wintergreen

COOCH 3
methyl salicylate
ORGANIC CHEMISTRY [32.9]

1027
 the stomach, but it is hydrolyzed and dissolves in the alkaline intes­
tines.

o
II
OH 0CCH3 OH

COOH COOH COC ß H s

O
salicylic aspirin salol
acid (acetylsalicylic acid) (phenyl salicylate)

Inorganic acids also form esters, such as glyceryl trinitrate and

dimethyl sulfate, (CH 3 ) 2 S0 4 , as well as sulfites, phosphites, phos­
phates, nitrites, borates, and others. Malathion, an important insecti­
cide, is an ester of both an inorganic acid (H 3 P0 2 S 2 ) and a carboxylic
acid.

(C 2 H 5 0) 2 PSCHCOOC 2 H 5

S CH 2 COOC2H 5
malathion

One advantage in the use of malathion as an insecticide is that it is

not persistent and is degraded in a few weeks after application. This
behavior is in contrast to that of DDT (Section 13.11), which remains
unchanged in the environment for years. On the other hand, ma­
lathion is an enzyme poison and is highly toxic to animals, whereas
DDT is less hazardous in this respect.
A carboxylic acid and an alcohol form an ester in an esterifica-
tion reaction when they are heated together in the presence of an acid
catalyst.

O
H 2 S0 4 ||
CH3C=0 + CH 3 CH 2 OH < CH 3 C—OCH 2 CH 3 + H 2 0

OH
acetic acid ethvl alcohol ethvl acetate

The hydrogen ion from the sulfuric acid attaches to the oxygen atom
of the carbonyl group, thereby enhancing the positive character and
the reactivity of the carbonyl carbon atom.
The hydrolysis of an ester is the reversal of the reaction leading
to its formation.

O
II : CH 3 COOH + CH 3 CH 2 OH
CH 3 C—OCH 2 CH 3 + H 2 0 :
ethyl acetate acetic acid ethvl alcohol

Hot aqueous sodium hydroxide will also hydrolyze esters; the

reaction is referred to as saponification, a term that is associated with
[32.9] ORGANIC CHEMISTRY the process for making soap (Section 13.12).

1028
 H20
CH3COOCH2CH3 + NaOH CH3COONa + CH3CH2OH
ethyl acetate sodium acetate ethyl alcohol
Acyl halides, RCOX
The saponification reaction is initiated by the attachment of the hy­ Acid anhydrides, (RCO) 2 0
droxide ion, a relatively good nucleophile, to the carbonyl carbon
atom.

32.10 Acyl halides and carboxylic

acid anhydrides

The replacement of the hydroxyl group of a carboxylic acid by a halo­

gen atom gives an acyl halide, RCOX, also called an acid halide
(Table 32.20). An acyl group

Ό
RC(
an acyl group

is named by dropping the final ic from the n a m e of the corresponding

carboxylic acid, and adding yl. The complete name of the acyl halide
is then the name of the acyl group, followed by the anionic n a m e for
the halogen atom.
An acid anhydride, (RCO) 2 0—the anhydride of a carboxylic
acid—results from the loss of water between two carboxyl groups.

O O O O
II II II II
RCOH + HOCR RC—O—CR + H 2 0

The anhydrides are given the n a m e of the corresponding acid, fol­

lowed by the word anhydride. Mixed anhydrides, from two different
carboxylic acids, and cyclic anhydrides, are named similarly, for in­
stance, acetic butyric anhydride, (CH 3 CO)0(COC 3 H 7 ), or phthalic an­
hydride (Table 32.20).

TABLE 32.20
COC1

Λ
CH3C=0 Acyl halides and carboxylic acid

U
anhydrides
Cl

acetyl chloride henzoyl chloride

(ethanoyl chloride) h.p. 197°C
h.p. 55°C

Q2
CH 3 C=0
>
CH 3 C=0
ΓΛ c—o—c
^ /
o o
acetic anhydride phthalic anhydride benzoic anhydride
(ethanoic anhydride) m.p. 13J°C m.p. 42°C
h.p. 138°C
ORGANIC CHEMISTRY [32.10J

1029
 The acyl halides, usually the chlorides, are used almost exclu­
sively for the synthesis of other compounds. Acid anhydrides, partic­
Amides, RCONH 2 ularly acetic anhydride and phthalic anhydride, are valuable in the
synthesis of esters, for example,

O O
C H X O C C H , + CH,CH2OH CH,COOCH2CH, + CH,COOH
TABLE 32.21 acetic ethyl ethyl acetic
anhvdride alcohol acetate acid
Amides
The general molecular formula for an
amide, often written RCONH2, is
RC=0
32.11 Amides
NH2
The replacement of a hydrogen atom in an ammonia molecule by an
CH 3 C=0 HC=0 alkyl group gives an amine (RNH 2 ). Replacement of a hydrogen atom
I in an ammonia or an amine molecule by an acyl group gives an
NH2 N(CH 3 ) 2
acetamide N ,N-dimethyl- amide, RCONH2. The common name for an amide is derived by re­
{ethanamide) formamide placing the yl of the acyl name by amide. Thus, acetamide is the name
m.p. 82°C h.p. 153°C
for CH3CONH2. Since the acyl group is named by replacing the ic of
the carboxylic acid name by yl, one can derive the amide name from
CONH 2 CH,C=0 the corresponding acid name by dropping the ic (or oic of the IUPAC
NH name) and adding amide (Table 32.21).
If one or more of the hydrogen atoms on the amide nitrogen atom
are replaced by hydrocarbon groups, the structure is named as an
benzamide TV-substituted amide.
m.p. 128°C N-phenyla cetam ide Amide molecules form intermolecular hydrogen bonds with
(acetanilide)
m.p. 114°C themselves, or with other appropriate molecules such as water.
Practically all of the amides are solids. A^A^Dimethylformamide
(DMF), one of the few liquid amides, is an excellent solvent. Urea,
H 2 NCONH 2 , is the diamide of carbonic acid.
An amide of considerable current interest is the hallucinogenic
drug LSD (lysergic acid diethylamide) (Table 32.22), also known as
"acid" and by several other names. Lysergic acid, from which the
diethylamide is derived, is present in ergot, a fungus found on rye.
TABLE 32.22
p-Aminobenzenesulfonamide (sulfanilamide) (Table 32.22) and
Some additional amides
CON(C 2 H 5 ) 2 NH2 NH CH 3
RCNH-
CH 3
CH, O 0 ^-N- COOH

penicillin u{H is L(fi:<LIi2)

S02NH2 N(CH3)2
sulfanilamide OH

CONHo
H
sulfadiazine OH O HO | O
lysergic acid
diethylamide H
(LSD) Aureomvcin

1030
some of its ^ - s u b s t i t u t e d derivatives are known as the sulfa drugs, an
important group of drugs that combat the growth of bacteria.
The penicillins, which are amides, were the first of the antibiotics
to be discovered; they have to a great extent displaced sulfa drugs in
the treatment of infectious diseases. Many penicillins are known;
they differ only in the R group of the structure shown. Aureomycin is
a representative of a group of tetracycline antibiotics.
Compounds with two acyl groups bonded to the nitrogen atom of
an ammonia molecule are known as imides. Barbiturates are cyclic
imides that are depressants. They are the " d o w n e r s " that have a
sedative or soporific action, typified by Nembutal, Luminal, and
Seconal.

O
II H
R C—N

II H
o
Nembutal (R, C2H5; R', CH3CH2CH2CHCH3)
Luminal (phenobarbital) (R, C2H5; R', CQH5)
Seconal (R, CH,=CHCH2; R', CH:fH,CH,CHCH:i)

The molecules of biochemistry

It may be going too far to introduce a subject as broad as biochemis­
try in the last section of a book as long as this one. And yet, everyone TABLE 32.23
should know at least a little about the marvelous molecular machin­ Composition of cells
ery that keeps us alive. So, particularly for those of you who will not
have the opportunity to study the subject at another time, we give Bacterium,
E. coli Rat liver
here a brief introduction to some of the molecules of biochemistry Component (%) (%)
and what their functions are.
The four major classes of organic compounds in living cells are Water 70 69
proteins, carbohydrates, lipids, and nucleic acids. Table 32.23 shows Protein 15 21
the amounts of these substances that, together with water, inorganic Amino acids 0.4 —
ions and smaller molecules, are present in the cells of a microor­
Nucleic acids 7 1.2
ganism and an animal. The ratios vary from species to species and
among different types of cells. But the proteins, carbohydrates, Nucleotides 0.4 —
lipids, and nucleic acids perform similar functions in all plants and Carbohydrates 3 3.8
animals. Lipids 2 6
Many of the large molecules of biochemistry are polymers, in Other small
which many simple structural units are held together by similar molecules 0.2 —
types of bonds. However, while polystyrene, for example, is made up Inorganic ions 1 0.4
of thousands of identical repeating units

—CH2CH-/CH2CH-VCH2CH—
1 ( 1 ) 1
C6H5\ C6H5/ C6H5

polystyrene ORGANIC CHEMISTRY [32.11]

1031
 polymeric biochemical molecules are often made up of repeating
units that are similar but different. The subtle and highly specific
functions of many biochemical molecules are made possible by the
combination of different small molecules in an exact sequence.

TABLE 32.24 32.12 Proteins

Some functions of proteins
Amino acids are the building blocks of proteins. As the name implies,
Enzymes Catalyze biochemical
reactions
an amino acid contains both an amine group and a carboxylic acid
group. In solution and in the crystalline state, amino acids exist in an
Hormones Regulate growth and
metabolism
ionic, or inner salt, form.
Storage proteins Release amino acids H H
Ό O
when they are
needed R—C—C—OH R—C — C— 0"
Transport proteins Bind and transport
I
NH2 NH3+
other molecules in an a-amino acid ionic form of an
bloodstream a-amino acid
Structural proteins Form bone, connec­
tive tissue, cartilage The a indicates that the amino group is attached to the carbon
Contractile proteins Form muscle tissue atom next to the carboxyl group. As the general formula shows, a-
Protective proteins Act as antibodies, amino acids contain a carbon atom with four different groups at­
blood-clotting tached. Therefore, these amino acids form optically active isomers
agents (except when R = H), which are designated as either D or L forms. All
amino acids found in proteins are α-L-amino acids. (For historical
reasons, D and L in amino acid nomenclature refer to absolute config­
urations, not to the direction of rotation of polarized light.)
Amino acids combine with each other by the formation of a pep-
tide bond, which can be pictured as the loss of water between a car­
boxyl group and an amine group. Because each amino acid has both
functional groups, two amino acids can combine to form dipeptides
in two different ways:

O
H
(H) NCH2C—iOHJ + (H) NCHC OH
CH 3
glycine alanine

pep tide pep tide

O y
' linkage O
' linkage
I V
H 2 NCH 2 CNHCHCOOH or H2NCH< N11CH2COOH
CH3 CH 3
glycylalanine alanylglycine

dipeptides

Twenty α-amino acids are the major constituents of all proteins.

This is quite remarkable when we realize that proteins serve func­
tions as diverse as supporting the body and regulating metabolism
132.11] ORGANIC CHEMISTRY and growth (Table 32.24). The shapes of protein molecules vary with
1032
their size and function. Figure 32.1 shows some of the possible forms FIGURE 32.1
of a protein composed of 300 amino acids. Some shapes a protein molecule of
300 amino acids might assume. (From
D. E. Metzler, Biochemistry: The
Chemical Reactions of Living Cells,
32.13 Carbohydrates p. 76, Academic Press, New York, 1977.)

Carbohydrate molecules are either simple sugars, called monosac-

charides; or polymers of two to ten sugars, called oligosaccharides;
or polymers of more than ten sugars, called polysaccharides. The
monosaccharides are either polyhydroxy aldehydes or polyhydroxy
ketones (Table 32.25). Most monosaccharides contain several asym­ Sphere,
diameter = 4.3 nm
metrically substituted carbon atoms, and like amino acids, mono­
saccharides and their derivatives form optically active isomers.
Sugars with five or six carbon atoms are more stable in a ring
structure than in the open structures of Table 32.25. The ring is
Oblate spheroid,
formed by the reaction of a carbonyl group with a hydroxyl group to 5.4 X 2.7 nm
give what is called a hemiacetal. The general reaction is

H H OH
C = 0 + ROH > C
R' R' OR
a hemiacetal
Prolate spheroid,
For D-glucose, writing the structures as though the ring is perpendic­ 6.8 X 3.4 nm
ular to the plane of the paper, the ring forms as follows
Collagen
XH.OH ,CH,OH triple helix,
~ 29 nm long
HsC () H
I/H \l
H
' i\? M'
H O C i ^ H H i C OH
2
H OH Ί I Cube,
H OH 3.45 nm
ß-D-glucose D-glucose
aldehyde form a-D-glucose a helix,
45 nm long
1.1 nm dia.
The a and ß indicate the two different configurations possible at ~ 80 turns
carbon atom 1. Brick,
1.8 X 3 . 6 X 6.3 nm
TABLE 32.25
Some monosaccharides ΓΓΓΤΤΤΤηΤΤΤ

Aldoses (aldehyc les) Ketoses (ketones)

CHO CH,OH
CHO 1 CH2OH 1
1 HCOH
c=o β pleated sheet,
CHO HCOH 1 c=o 1 7 X 7nm
1
HCOH 1
HCOH HOCH
1
HCOH HOCH
~ 0.5 nm thick
1 1
1 2OH
CH 1
HCOH HCOH 1 HCOH
1 HCOH 1 Double helical
1 HCOH 1 HCOH rope, ~ 21 nm long
CH2OH 1 CH2OH 1
D-glxceraldehxde D-rihose D-glucose
CH2OH D-rihulose CH2OH
D-fructose 10 15 20 nm

1033
 TABLE 32.26
Some functions of carbohydrates Derivatives of monosaccharides Metabolism intermediates
Plant pigments
Blood anticoagulant (heparin)
Vitamin C
Structural polysaccharides Plant cell walls (cellulose)
Animal cell coating
Skin (keratin)
Storage polysaccharides Release monosaccharides (starch in plants; glyco-
gen in animals)
Release energy when oxidized

Monosaccharides combine with each other by the loss of water

between two OH groups to form a glycosidic linkage. For example,
sucrose, or common table sugar, is a disaccharide of glucose and fruc­
tose.
CHoOH

H, -O H

,OH H CH 2 OH
HO

H OH
°^J\„„
D- glucose O-fructose

a glycoside linkage

CHoOH

CHoOH

OH H

Cellulose and starch are both polymers of D-glucose. In cellulose,

which may contain from hundreds to thousands of glucose units,
linear molecules are organized into bundles. Cotton is 98% cellulose.
Starch, which is the major source of energy in plants, contains two
different polymers of D-glucose—amylose and amylopectin. Amy lose
is a linear polymer and amylopectin is a highly branched, treelike
polymer. The functions of carbohydrates are summarized in Table
32.26.

32.14 Lipids

There are several types of lipids—they are all nonpolar compounds

that contain large hydrocarbon segments and are insoluble in water,
but soluble in organic solvents. In contrast to proteins and carbohy­
drates, lipids are not polymeric.
[32.13] ORGANIC CHEMISTRY We have already encountered fatty acids—long, straight-chain

1034
carboxylic acids—in soaps (Section 13.12). The naturally occurring
esters of fatty acids form one class of lipids. The most common of
these are esters of glycerol (1,2,3-propanetriol) called glycerides

O
CH2OCR
O
II
CHOCR
O
. II
CH2OCR
a glyceride
Animal fats, such as lard, tallow, and butter, and vegetable oils, such
as corn oil, soybean oil, linseed oil, olive oil, and peanut oil are all
glycerides. In simple glycerides the R groups are all alike, and in
mixed glycerides the R groups are not all alike. There are monoglyc-
erides, in which only one OH group of glycerol has been esterified,
and diglycerides and triglycerides. Most fats and oils are mixtures of
mixed glycerides. In fats the hydrocarbon chains of the fatty acids
are largely saturated, and in oils they are predominantly unsatur-
ated. The fatty acids found in glycerides nearly always have an even
number of carbon atoms.
The major function of glycerides is to store energy. In animals
fats consumed in the diet are partially broken down to mono- and
diglycerides in the intestines and then pass through the intestine
walls. Triglycerides are reformed and carried to the liver and other
tissues. At these sites the triglycerides are either chemically trans­
formed to release energy or deposited as fat droplets for future con­
version to energy. Sugars can be converted to fats in the liver and
then are either used to produce energy or are stored in the body.
Several other types of compounds are included in the lipid class.
Phospholipids are generally derived from glycerol by esterification of
two OH groups by fatty acids and of one OH group by a phosphoric
acid derivative.

O
II
CH2OCR
O
II
CHOCR
I
CH 2 OP0 3 R'
a phospholipid
Phospholipids have important functions in cell m e m b r a n e s . Waxes,
which form protective coatings on, for example, leaves or feathers,
are lipids that are esters of long-chain fatty acids and long-chain
monohydroxy alcohols. Steroids all contain a four-ring hydrocarbon
unit. Cholesterol, which has been implicated in " h a r d e n i n g " of the
arteries and heart disease, is one example of a steroid. ORGANIC CHEMISTRY [32.14]

1035
 cyclopentanoperhydrophenanthrene,
basis for all steroids HO ^ — H3C -CH3
cholesterol, a steroid

Terpense, such as the unsaturated hydrocarbons that occur in

plants (Sections 23.5), are also lipids.

32.15 Nucleotides and nucleic acids

Nucleic acids are polymers of great structural complexity. The re­

peating units in a nucleic acid are nucleotides. Uncombined nucleo­
tides are also present in many cells and play major biochemical roles.
Each nucleotide has three parts: (1) a heterocyclic base that contains
either a purine or a pyrimidine ring

N
N

^N
> O N"
H
purine pyrimidine

(2) a sugar—either D-ribose (see Table 32.25) or 2-deoxy-D-ribose,

which is ribose in which the CHOH group at the second carbon atom

FIGURE 32.2
—OCH2 / ° \ t>ase
Examples of a nucleoside, a nucleotide, and the linkage of nucleo­ \ l CH
tides in a nucleic acid. In each structure, the monosaccharide is Λ H H7
shown in color. H \l 1/
c—c
H
NH2 the base NH2 O
the base
O — P — O — CH 2 A base
<■ the phosphate
I I
o- CH
O H \| 1/
II c—c
the sugar HO—P—O—CH the sugar
H
OH O
H \l |/ H . II
c—c o—p—
I
OH OH OH H o-
a nucleoside a nucleotide two nucleotide units
(adenosine) {deoxycy tidy lie acid) in a DNA molecule

1036
has been transformed to a CH 2 group; and (3) one or more phosphate
groups.
A nucleic acid consists of several thousand nucleotides joined
together by ester linkages between the third carbon atom of the sugar
of one nucleotide and the phosphate group of another. Nucleosides,
which do not play a biochemical role as free molecules but are inter­
mediates in metabolism, are nucleotides without the phosphate unit.
A nucleoside, nucleotide, and two units of a nucleic acid are shown in
Figure 32.2.
The nucleotide adenosine triphosphate, commonly referred to as
ATP, is the primary source of energy within the cell. The transfer of
one phosphate group from ATP to another molecule releases energy
for use as heat or to support some chemical process that requires
energy.

o- o- o-
—O—P—O—P—O—P—O—CHo/O base

o o o

+ HP0 4 2 - + H+

OH OH
ADP

AG° = -7.3 kcal (-31.U)

When excess energy is available to be stored, the preceding reaction

is reversed. The three phosphate groups in ATP can store or release a
total of about 16 kcal/mole of energy.
The role of nucleic acids is to store genetic information in code
form and to regulate protein synthesis. The code resides in the se­
quence of bases in the deoxyribonucleic acids (DNAs) and ribonucleic
acids (RNAs) of all the different species of living things, and the
three-dimensional molecular structure of DNA is all important in al­
lowing the transfer of genetic information. In 1953 James Watson and
Francis Crick proposed that DNA has the structure of a double helix
and explained how the sequence of nucleotides is duplicated in the
synthesis of new DNA molecules and passed along by RNA to the sites
of protein synthesis. This was one of the most exciting and funda­
mental discoveries of biochemistry.
In DNA the phosphate-sugar portions of the nucleotides form
two intertwined helical chains that are connected by successive pairs ORGANIC CHEMISTRY [32.15]

1037
 Base pairs

phate-sugar

FIGURE 32.3
The double helix of DNA. (a) Flattened view of the structure
of DNA, (b) the intertwined helices.

of bases, one from each of the adjacent nucleotides. The bases are at­
tracted to each other by hydrogen bonds. A flattened view of the
structure is given in Figure 32.3, together with a simple sketch of the
double helix connected by the base pairs.

THOUGHTS ON
CHEMISTRY

Kekule describes the ongins

KEKULE's DREAM, by August Kekule
L32.15J ORGANIC CHEMISTRY
of his theones
It is also said that genius thinks in leaps. Gentlemen, the growing in­
tellect does not think in leaps. That is not given to it.
Perhaps it will interest you, if I let you know through highly in­
discreet disclosures from my inner life, how I arrived at some of my
ideas.
During my stay in London I resided for a considerable time in
Clapham Road in the neighborhood of Clapham Common. I fre­
quently, however, spent my evenings with my friend Hugo Müller at
Islington at the opposite end of the metropolis. We talked of many
things but most often of our beloved chemistry. One fine summer eve­
ning I was returning by the last bus, "outside," as usual, through the
deserted streets of the city, which are at other times so full of life. I fell
into a reverie (Träumerei), and lo, the atoms were gamboling before

1038
my eyes! Whenever, hitherto, these diminutive beings had appeared to
me, they had always been in motion; but up to that time I had never
been able to discern the nature of their motion. Now, however, I saw
how, frequently, two smaller atoms united to form a pair; how a
larger one embraced the two smaller ones; how still larger ones kept
hold of three or even four of the smaller; whilst the whole kept
whirling in a giddy dance. I saw how the larger ones formed a chain,
dragging the smaller ones after them but only at the ends of the chain.
I saw what our past master, Kopp, my highly honored teacher and
friend, has depicted with such charm in his "Molekular-welt"; but I
saw it long before him. The cry of the conductor: "Clapham Road,"
awakened me from my dreaming; but I spent a part of the night in
putting on paper at least sketches of these dream forms. This was the
origin of the "Structural Theory."
Something similar happened with the benzene theory. During my
stay in Ghent I resided in elegant bachelor quarters in the main thor­
oughfare. My study, however, faced a narrow side-alley and no day­
light penetrated it. For the chemist who spends his day in the labora­
tory this mattered little. I was sitting writing at my textbook but the
work did not progress; my thoughts were elsewhere. I turned my chair
to the fire and dozed. Again the atoms were gamboling before my eyes.
This time the smaller groups kept modestly in the background. My
mental eye, rendered more acute by repeated visions of the kind, could
now distinguish larger structures of manifold conformation: long
rows, sometimes more closely fitted together all twining and twisting
in snake-like motion. But look! What was that? One of the snakes had
seized hold of its own tail, and the form whirled mockingly before my
eyes. As if by a flash of lightning I awoke; and this time also I
spent the rest of the night in working out the consequences of the
hypothesis.
Let us learn to dream, gentlemen, then perhaps we shall find the
truth.
KEKULE'S DREAM, by August Kekule, 1890 {Berichte der Deutschen Chemis­
chen Gesellschaft. Translated by P. Theodor Benfey; from Journal of Chemi­
cal Education, Vol. 35, p. 21, 1958)

Significant terms defined in this chapter

functional group amines carboxylate ion
alkyl halides diazonium salts ester
aryl halides chromophoric group esterification reaction
hydroxyl group carbonyl group saponification
alcohols aldehyde acyl halide
alkoxide ketone acyl group
phenols dehydrogenation reaction acid anhydride
ether carboxylic acid amide
alkoxy group ORGANIC CHEMISTRY

1039
 Exercises hyde, (i) cyclobutanone, (j) 2,2-dimethylpropanoic acid, (k)
a m m o n i u m benzoate, (1) acetic propionic anhydride, and
(m) isopropyl formate.
32.1 A student was given three bottles labeled A, B, and C.
One of these contained acetic acid, one contained acetalde-
hyde, and one contained ethyl alcohol, (a) Write a struc­ 32.7 Give a name (common or IUPAC) for each of the fol­
tural formula for each of these compounds and (b) n a m e lowing compounds:
them using the IUPAC nomenclature. The student ob­ (a) CH 3 CH 2 CH 2 CH 2 OH (i) CH 3 CH 2 CHO
served that substance A reacted with substance B to form
an ester under certain conditions and that substance B (b) CH 3 —CH—CH 3 O
formed an acidic solution when dissolved in water, (c)
NH 2 (j) <^ V-CCH 2 CH 3
Identify which compound is in each bottle and (d) write
balanced chemical equations for the reaction involving
the formation of the ester and for the ionization of the
acid. To confirm the identification, the student treated the
(c) Br /Λ Br (k) CH 3 —CH—COOH

compounds with a strong oxidizing agent and found that CH3

compound A required roughly twice as much oxidizing
O
agent as compound C. (e) Write chemical equations for the
reactions of compounds A and C with an acidic solution of
Mn0 4 ~.
<d» ( 3 - ° - 0 (1) / Vo-CCH,
(e)
32.2 Distinguish clearly among: (a) alkyl, aryl, and acyl (m) CH 3 CH 2 CNH 2
OH
halides; (b) alkanols, alkenols, alkynols, and phenols; (c)
simple and mixed ethers; (d) primary, secondary, and ter­ O
tiary amines; and (e) amines, amides, and imides. (f) CH3—C=CH2
O
Cl
32.3 Which statements are true? Rewrite any false state­ (n) <^ V-C—NHCH3
ment so that it is correct. (g) (CH3CH2)3N
(a) The covalent bond between the carbon atom and the
halogen atom in an alkyl halide is polar because of the
larger electronegativity of the carbon atom.
(b) The boiling point of ethyl alcohol is significantly (h)
greater than that of dimethyl ether because there is con­
siderable hydrogen bonding in the alcohol.
(c) Denatured alcohol contains various toxic or objection­
able materials that are difficult to remove so that it cannot
be used for internal consumption. 32.8 A laboratory procedure called for oxidizing 2-
(d) Phenols act as weak acids in many reactions, alcohols propanol to acetone using an acidic solution of K 2 Cr 2 0 7 .
as weak acids and bases, and amines as weak bases. However, an insufficient amount of K 2 Cr 2 0 7 was on hand,
(e) All alkanols can be oxidized easily to carboxylic acids. so the laboratory instructor decided to use an acidic solu­
tion of K M n 0 4 instead. How many grams of K M n 0 4 in
32.4 Alcohols can be used as starting reagents for pro­ place of 1.0 g of K 2 Cr 2 0 7 were required to carry out the
ducing many other types of compounds: (a) alkoxides, (b) same oxidation process?
ethers, (c) aldehydes and ketones, (d) acids, (e) esters, and
(f) alkyl halides. Write a chemical equation showing each 32.9 The equilibrium constant for the equation
of these reactions. CH 3 CH 2 OH + CH 3 COOH ^ = ± CH 3 CH 2 OOCCH 3 + H 2 0
32.5 Ethanol, like water, can act as a weak acid or a weak is
base. Write chemical equations showing CH 3 CH 2 OH act­
[CH3CH2OOCCH3] [H2Q]
ing (a) as a base with HCl and (b) as an acid with Na(s). K = 4
(c) Name the compounds formed. [CH 3 CH 2 OH] [CH3COOH]
(Note that in this case water is not the solvent and is not in
32.6 Draw the molecular structure for each of the follow­ large excess. Its concentration appears in the equilibrium
ing compounds: (a) p-bromotoluene, (b) cyclohexanol, (c) expression because the activity is not unity.) What fraction
o-cresol, (d) 2-methoxy-3-methylbutane, (e) diethylamine, of the alcohol reacts if the original reaction mixture con­
(f) o-chlorophenol, (g) 1,4-butanediol, (h) propionalde- tained equal concentrations of alcohol and acid?

1040
32.10 Complete the following equations: 32.11 Show by equations how you might be able to carry
out the following conversions. You may use any other
(a) CH3CH2I + NaOH -^-* organic or inorganic compounds you need. More than one
step may be necessary.

(b) H3C / V OH + NaOH

(a) CH 3 —CH—CH 3 to CH 3 —CH—CH 3

OH Br

(c) H3C / \ NO- cone HCl

(b) H 3 C—<f V - N02 to H3C—<f \-NH 2

Br
I
H20
(d) ^ ^ N H 3 + C 1 - + NaOH (c) CH 3 CH 2 CH 2 Br to CH 3 CHCH 2
Br

NH 2 (d) H03S /Λ NH 2 to
HO
NaN02
cold H03S ^\-H=HJ

/ \ Cr2072
(e) CH 3 CH 2 OH
(f) < ^ j > - O H ~ (f) CH 3 CH 2 OH
to
to (CH 3 CH 2 ) 4 N + Br-

(g) 2CH 3 COOH + Ba(OH) 2 32.12 Many of the classes of compounds discussed in this
chapter can be "derived" from the water molecule
Mn0 4 H!—O—H 2
(h) CH 3 CH 2 CHO —£-
by changing one or both of the hydrogens for various
organic groups. Name the class of compound formed when
(a) Hi is replaced by an alkyl group, (b) Η χ is replaced by
(0 l· Jl + (CH3CO)20 an aromatic group, (c) Hi and H 2 are replaced by alkyl
groups, (d) Hi is replaced by R — C = 0 group, (e) Hx is
replaced by a R — C = 0 group and H 2 is replaced by an
alkyl group, and (f) H! and H 2 are replaced by R — C = 0
O groups.
CH,CH,OH II
32.13 What is the approximate p H of a 0.10M solution
(j) <P of sodium benzoate? Ka = 6.6 x 10" 5 for benzoic acid,
C 6 H 5 COOH. Would this solution be more or less acidic
II than a 0.10M solution of sodium acetate? Ka = 1.754 x
o
K r 5 for acetic acid, CH 3 COOH.

(k) CH 3 CH 2 COOCH 3 32.14" A piece of glass 12 inches by 18 inches is to be sil­

vered using the following reaction
CH 3 CHO 4- 2[Ag(NH 3 ) 2 ]OH >
o 2Ag + CH 3 COONH 4 + H 2 0 + 3NH 3
II
(1) ^OCCH3 aq NaOH If the thickness of the silver is to be 0.0003 inch, what mass
of acetaldehyde is needed for the reaction? The density of
COOH Ag is 10.5 g/cm 3 .

1041
32.15 In aqueous solution, acetic acid exists mainly in
the molecular form (Ka = 1.745 x 10 -5 ). (a) Calculate the
freezing point depression for a 0.10 molal aqueous solu­
tion of acetic acid neglecting any ionization of the acid.K{p
= 1.86 for water. In nonpolar solvents such as benzene,
acetic acid exists mainly as dimers
/H—Ö—C—CH3
:d: - ||
II .. : p :
CH3—C—O—W
as a result of hydrogen bonding, (b) Calculate the freezing
point depression for a 0.10 molal solution of acetic acid in
benzene. K{p = 4.90 for benzene.
32.16" A "chemist" decided to make some nitroglycerin
using a home chemistry set. Without taking any precau­
tions, he heated a mixture of 25 g of glycerol with 25 ml of
12M H N 0 3 in a 100 ml flask, (a) Write the equation for the
reaction and (b) calculate the theoretical yield of nitro­
glycerin. However, the nitroglycerin underwent detona­
1042
tion and the room was filled with flying pieces of glass as a
result of the explosion, (c) Write the equation for the explo­
sion (note that no additional reactants such as 0 2 from the
air are required). Calculate the number of moles of gase­
ous products formed (d) for each mole of nitroglycerin that
reacted and (e) for the sample that exploded.
An explosion takes place so fast because the energy re­
leased cannot be dissipated to the surroundings and there­
fore the products are formed at very high temperatures
and rapidly expand. We can find the approximate temper­
ature by dividing the heat of reaction, - 3 4 2 kcal/mole of
nitroglycerin, by the heat capacity of the product gases
and adding 25°C to this value, (f) Calculate the heat capac­
ity of the product gases by adding together the number of
moles of each gas formed multiplied by the heat capacity
of that gas using the following data for heat capacity: 8.87
cal/mole °C for C0 2 , 6.961 cal/mole °C for N 2 , 8.025
cal/mole °C for H 2 0 , and 7.016 cal/mole °C for 0 2 . (g) Cal­
culate the approximate temperature of the product gases.
(h) Assuming the ideal gas law to be valid, what pressure
did the product gases exert on the inside of the flask before
the explosion?