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EQA
M O D U L E
4
ORGANIC CHEMISTRY:
STRUCTURE AND
NOMENCLATURE OF
HYDROCARBONS
O1.1
What Is an Organic Compound?
O1.2
The Saturated Hydrocarbons, or Alkanes
O1.3
The Cycloalkanes
O1.4
Rotation around CC Bonds
O1.5
The Nomenclature of Alkanes
O1.6
The Unsaturated Hydrocarbons: Alkenes and Alkynes
O1.7
Alkene Stereoisomers
O1.8
The Reactions of Alkanes, Alkenes, and Alkynes
O1.9
Naturally Occurring Hydrocarbons and Their Derivatives
O1.10 Aromatic Hydrocarbons and Their Derivatives
O1.11 The Chemistry of Petroleum Products
O1.12 The Chemistry of Coal
O1.13 Chiral Stereoisomers
O1.14 Optical Activity
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OH
O
B
CH3 H EC H
OH
CH
OP
EOH
C
O
B
OOC O CH3
Aspirin
(acetylsalicylic acid)
CH3 H E NH
C
B
Tylenol
O (acetaminophen)
CH3 H ECH2
CH
CH3
Advil
(ibuprofen)
FIGURE O1.1 The structures of the active ingredients in three common painkillers.
You then drive to campus, where you sit in a plastic chair to eat a sandwich that has
been wrapped in plastic, without worrying about why one of the plastics is flexibile while
the other is rigid. While youre eating, a friend stops by and starts to tease you about the
effect of your diet on the level of cholesterol in your blood, which brings up the questions,
What is cholesterol? and Why do so many people worry about it?
Answers to each of these questions fall within the realm of a field known as organic
chemistry. For more than 200 years, chemists have divided materials into two categories.
Those isolated from plants and animals were classified as organic, while those that trace
back to minerals were inorganic. At one time, chemists believed that organic compounds
were fundamentally different from those that were inorganic because organic compounds
contained a vital force that was only found in living systems.
The first step in the decline of the vital force theory occurred in 1828, when Friederich
Whler synthesized urea from inorganic starting materials. Whler was trying to make ammonium cyanate (NH4OCN) from silver cyanate (AgOCN) and ammonium chloride
(NH4Cl). What he expected is described by the following equation.
AgOCN(aq) NH4Cl(aq) 88n AgCl(s) NH4OCN(aq)
The product he isolated from the reaction, however, had none of the properties of cyanate
compounds. It was a white, crystalline material that was identical to urea, H2NCONH2,
which could be isolated from urine.
Expected Product
H
A
HONOH
A
H
Ammonium cyanate
OOCqN
Observed Product
O
H
H
B
G
D
NOCON
D
G
H
H
Urea
Neither Whler nor his contemporaries claimed that his results disproved the vital force
theory. But his results set in motion a series of experiments that led to the synthesis of a
variety of organic compounds from inorganic starting materials. This inevitably led to the
disappearance of vital force from the list of theories that had any relevance to chemistry,
although it did not lead to the death of the theory, which still had proponents more than
90 years later.
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If the difference between organic and inorganic compounds isnt the presence of some
mysterious vital force required for their synthesis, what is the basis for distinguishing between these classes of compounds? Most compounds extracted from living organisms contain carbon. It is therefore tempting to identify organic chemistry as the chemistry of carbon. But that definition would include compounds such as calcium carbonate (CaCO3) as
well as the elemental forms of carbondiamond and graphitethat are clearly inorganic.
We will therefore define organic chemistry as the chemistry of compounds that contain both
carbon and hydrogen.
Even though organic chemistry focuses on compounds that contain carbon and hydrogen, more than 95% of the compounds that have been isolated from natural sources or
synthesized in the laboratory are organic. The special role of carbon in the chemistry of
the elements is the result of a combination of factors, including the number of valence electrons on a neutral carbon atom, the electronegativity of carbon, and the atomic radius of
carbon atoms (see Table O1.1).
TABLE O1.1 Physical Properties
of Carbon
Electronic configuration
Electronegativity
Covalent radius
Carbon has four valence electrons (2s2 2p2), and it must either gain four electrons or
lose four electrons to reach a rare gas configuration. The electronegativity of carbon is too
small for carbon to gain electrons from most elements to form C4 ions, and too large for
carbon to lose electrons to form C4 ions. Carbon therefore forms covalent bonds with a
large number of other elements, including the hydrogen, nitrogen, oxygen, phosphorus,
and sulfur found in living systems.
Because they are relatively small, carbon atoms can come close enough together to
form strong CPC double bonds or even CqC triple bonds. Carbon also forms strong double and triple bonds to nitrogen and oxygen. It can even form double bonds to elements
such as phosphorus and sulfur that do not form double bonds to themselves.
When the unmanned Viking spacecraft carried out experiments designed to search for
evidence of life on Mars, the experiments were based on the assumption that living systems
contain carbon, and the absence of any evidence for carbon-based life on that planet was
presumed to mean that no life existed. Several factors make carbon essential to life.
These factors provide an almost infinite variety of potential structures for organic compounds, such as vitamin C shown in Figure O1.2. No other element can provide the variety of combinations and permutations necessary for life to exist.
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O
HO
C
C
HO
C
O
CH
CH O CH2OH
OH
The simplest alkane is methane: CH4. The Lewis structure of methane can be generated by combining the four electrons in the valence shell of a neutral carbon atom with
four hydrogen atoms to form a compound in which the carbon atom shares a total of eight
valence electrons with the four hydrogen atoms.
HT
H
HT
TP
CT
R
TH
H C
H
P
H
Methane is an example of a general rule that carbon is tetravalent; it forms a total of four
bonds in almost all of its compounds. To minimize the repulsion between pairs of electrons
in the four COH bonds, the geometry around the carbon atom is tetrahedral, as shown in
Figure O1.3.
Exercise O1.1
Use the fact that carbon is usually tetravalent to predict the formula of ethane, the alkane
that contains two carbon atoms.
Solution
As a rule, compounds that contain more than one carbon atom are held together by COC
bonds. If we assume that carbon is tetravalent, the formula of the compound must be C2H6.
H H
A A
HOCOCOH
A A
H H
Ethane
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The alkane that contains three carbon atoms is known as propane, which has the formula C3H8 and the following skeleton structure.
H H H
A A A
HOCOCOCOH
A A A
H H H
Propane
Butane
The names, formulas, and physical properties for a variety of alkanes with the generic formula CnH2n2 are given in Table O1.2. The boiling points of the alkanes gradually increase
with the molecular weight of the compounds. At room temperature, the lighter alkanes are
gases; the midweight alkanes are liquids; and the heavier alkanes are solids, or tars.
TABLE O1.2
Name
Molecular
Formula
Melting
Point (oC)
Boiling
Point (oC)
State
at 25oC
Methane
Ethane
Propane
Butane
Pentane
Hexane
Heptane
Octane
Nonane
Decane
Undecane
Dodecane
Eicosane
Triacontane
CH4
C2H6
C3H8
C4H10
C5H12
C6H14
C7H16
C8H18
C9H20
C10H22
C11H24
C12H26
C20H42
C30H62
182.5
183.3
189.7
138.4
129.7
95
90.6
56.8
51
29.7
24.6
9.6
36.8
65.8
164
88.6
42.1
0.5
36.1
68.9
98.4
124.7
150.8
174.1
195.9
216.3
343
449.7
Gas
Gas
Gas
Gas
Liquid
Liquid
Liquid
Liquid
Liquid
Liquid
Liquid
Liquid
Solid
Solid
The alkanes in Table O1.2 are all examples of straight-chain hydrocarbons, in which
the carbon atoms form a chain that runs from one end of the molecule to the other. The
generic formula for the compounds can be understood by assuming that they contain chains
of CH2 groups with an additional hydrogen atom capping either end of the chain. Thus,
for every n carbon atoms there must be 2n 2 hydrogen atoms: CnH2n2.
Because two points define a line, the carbon skeleton of the ethane molecule is linear,
as shown in Figure O1.4.
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Because the bond angle in a tetrahedron is 109.5, alkane molecules that contain three or
carbon atoms can no longer be thought of as linear, as shown in Figure O1.5.
Propane
Butane
In addition to the straight-chain examples considered so far, alkanes also form branched
structures. The smallest hydrocarbon in which a branch can occur has four carbon atoms.
The compound has the same formula as butane (C4H10), but a different structure. Compounds with the same formula and different structures are known as isomers (from the
Greek words isos, equal, and meros, parts). When it was first discovered, the branched
isomer with the formula C4H10 was therefore given the name isobutane.
CH3
A
CH3OCHOCH3
Isobutane
The best way to understand the difference between the structures of butane and isobutane
is to compare the ball-and-stick models of the compounds shown in Figure O1.6.
Butane
Isobutane
Butane and isobutane are called constitutional isomers because they literally differ in their
constitution. One contains two CH3 groups and two CH2 groups; the other contains three
CH3 groups and one CH group.
There are three constitutional isomers of pentane, C5H12. The first is normal pentane, or n-pentane.
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CH3OCH2OCH2OCH2OCH3
n-Pentane
A branched isomer is also possible, which was originally named isopentane. When a more
highly branched isomer was discovered, it was named neopentane (the new isomer of pentane).
CH3
A
CH3OCHOCH2OCH3
CH3
A
CH3OC OCH3
A
CH3
Isopentane
Neopentane
Ball-and-stick models of the three isomers with the formula C5H12 are shown in Figure O1.7.
n-Pentane
Isopentane
Neopentane
Exercise O1.2
The following structures all have the same molecular formula: C6H14. Which of the structures represent the same molecule?
EQA
CH3
CH3
G
CHOCH2
D
G
CH3
A CH2OCH3
CH3
G D
CH
A
CH2
G
CH2
B
A
CH3
CH3
A
CH3OCOCH3
A
C CH2
G
CH3
Solution
There is no difference between compounds A and B; they both contain a five-carbon chain
with a branch on the second carbon. Compound C, on the other hand, contains a fourcarbon chain with two branches on the second carbon atom.
Exercise O1.3
Determine the number of constitutional isomers of hexane, C6H14.
Solution
There are five constitutional isomers of hexane. There is a straight-chain, or normal, isomer.
CH3OCH2OCH2OCH2OCH2OCH3
There are two isomers with a single carbon branch.
CH3
A
CH3OCHOCH2OCH2OCH3
CH3
A
CH3OCH2OCHOCH2OCH3
CH3
A
CH3OCOCH2OCH3
A
CH3
Checkpoint
Use a set of molecular models to confirm that the following compounds are isomers,
CH3 CH3
A
A
CH3OCHOCHOCH3
CH3
A
CH3OCOCH2OCH3
A
CH3
whereas the following are different ways of writing the structure of the same compound.
CH3 CH3
A
A
CH3OCHOCHOCH3
CH3
A
CH3OCHOCHOCH3
A
CH3
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As we have seen, there are two constitutional isomers with the formula C4H10, three
isomers of C5H12, and five isomers of C6H14. The number of isomers of a compound increases rapidly with additional carbon atoms. There are over 4 billion isomers for C30H62,
for example.
Any attempt to force the four carbons that form a cyclobutane ring into a plane of
atoms would produce the structure shown in Figure O1.9, in which the angle between adjacent COC bonds would be 90. One of the four carbon atoms in the cyclobutane ring is
therefore displaced from the plane of the other three to form a puckered structure that
is vaguely reminiscent of the wings of a butterfly.
The angle between adjacent COC bonds in a planar cyclopentane molecule would be
108, which is close to the ideal angle around a tetrahedral carbon atom. Cyclopentane is
not a planar molecule, as shown in Figure O1.10, because displacing two of the carbon
atoms from the plane of the other three produces a puckered structure that relieves some
of the repulsion between the hydrogen atoms on adjacent carbon atoms in the ring.
10
EQA
By the time we get to the six-membered ring in cyclohexane, a puckered structure can
be formed by displacing a pair of carbon atoms at either end of the ring from the plane of
the other four members of the ring. One of the carbon atoms is tilted up, out of the ring,
whereas the other is tilted down to form the chair structure shown in Figure O1.11.
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11
The lowest energy conformation is a structure in which the hydrogen atoms are staggered, as shown in Figure O1.13.
The difference between the eclipsed and staggered conformations of ethane are best illustrated by viewing these molecules along the COC bond, as shown in Figure O1.14.
Staggered
Eclipsed
FIGURE O1.14 The eclipsed and staggered conformations of ethane viewed along the COC bond.
The difference between the energies of these conformations is relatively small, only about
12 kJ/mol. But it is large enough that rotation around the COC bond isnt smooth. Although the frequency of the rotation is on the order of 1010 revolutions per second, the
ethane molecule spends a slightly larger percentage of the time in the staggered conformation.
The different conformations of a molecule are often described in terms of Newman
projections. These line drawings show the six substituents on the COC bond as if the structure of the molecule were projected onto a piece of paper by shining a bright light along
the COC bond in a ball-and-stick model of the molecule. Newman projections for the different staggered conformations of butane are shown in Figure O1.15.
CH3
H
H
CH3
CH3
H
H
CH3
CH3
H3C
H
Because of the ease of rotation around COC bonds, there are several conformations
of some of the cycloalkanes described in the previous section. Cyclohexane, for example,
forms both the chair and boat conformations shown in Figure O1.16. The difference
between the energies of the chair conformation, in which the hydrogen atoms are staggered, and the boat conformation, in which they are eclipsed, is about 30 kJ/mol. As a result, even though the rate at which the two conformations interchange is about 1 105 s1,
we can assume that most cyclohexane molecules at any moment in time are in the chair
conformation.
12
EQA
Boat
Chair
Find the longest continuous chain of carbon atoms in the skeleton structure. Name
the compound as a derivative of the alkane with that number of carbon atoms. The
following compound, for example, is a derivative of pentane because the longest
chain contains five carbon atoms.
H
A
HOCOH
A
H A H H H
A A A A A
HOCOCOCOCOCOH
A A A A A
H H H H H
Name the substituents on the chain. Substituents derived from alkanes are named
by replacing the -ane ending with -yl. This compound contains a methyl (OCH3)
substituent.
H
A
HOCOH
A
H A H H H
A A A A A
HOCOCOCOCOCOH
A A A A A
H H H H H
Number the chain starting at the end nearest the first substituent and specify the
carbon atoms on which the substituents are located. Use the lowest possible numbers. This compound, for example, is 2-methylpentane, not 4-methylpentane.
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13
H
A
HOCOH
A
H A H H H
A
A
A
A A
HOC1OC2OC3OC4OC5OH
A
A
A
A A
H H H H H
Use the prefixes di-, tri-, and tetra- to describe substituents that are found two, three,
or four times on the same chain of carbon atoms.
Arrange the names of the substituents in alphabetical order.
Exercise O1.4
Use the IUPAC system to name the following compound.
CH3
CH3
A
A
CH3OCOCH2OCHOCH3
A
CH3
Solution
The compound is a derivative of pentane because the longest chain contains five carbon
atoms. There are three identical CH3 substituents on the backbone. Two of the methyl
groups are on the second carbon, and one is on the fourth. The compound is therefore
2,2,4-trimethylpentane. Since it contains a total of eight carbon atoms, it is also known by
the common name isooctane. This compound is the octane used as a standard against
which to measure octane numbers.
Exercise O1.5
Use the IUPAC system to name the following compound.
CH3
A
CH3OCHOCH2OCHOCH2OCH3
A
CH2
A
CH2
A
CH3
Solution
The longest continuous chain in the skeleton structure of the compound contains seven
carbon atoms. It is therefore named as a derivative of heptane.
1
CH3
A
4
CH3OCHOCH2OCHOCH2OCH3
2
3
A
5
CH2
A
6
CH2
A
7
CH3
14
EQA
The heptane chain contains two substituents: a methyl group on the second carbon atom
and an ethyl group on the fourth carbon atom.
CH3
A
CH3OCHOCH2OCHOCH2OCH3
A
Methyl
Ethyl
CH2
A
CH2
A
CH3
Because the substituents are listed in alphabetical order, the systematic name for the compound is 4-ethyl-2-methylheptane.
HT HT
POC
POH
HOC
A A
H H
H H
A A
HOCOCOH
A A
H H
Thus, in theory, we can transform an alkene into the parent alkane by adding an H2 molecule across a CPC double bond. In practice, the reaction occurs only at high pressures
in the presence of a suitable catalyst, such as piece of nickel metal.
H
H
CPC
H
H
H2
Ni
H H
A A
HOC OCOH
A A
H H
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15
Because an alkene can be thought of as a derivative of an alkane from which an H2 molecule has been removed, the generic formula for an alkene with one CPC double bond is
CnH2n.
Alkenes are examples of unsaturated hydrocarbons because they have fewer hydrogen
atoms than the corresponding alkanes. They were once named by adding the suffix -ene to
the name of the substituent that carried the same number of carbon atoms.
CH2PCH2
CH2PCH2OCH3
Ethylene
Propylene
The IUPAC nomenclature for alkenes names the compounds as derivatives of the parent
alkanes. The presence of the CPC double bond is indicated by changing the -ane ending
on the name of the parent alkane to -ene.
CH3OCH3
CH2PCH2
Ethane
Ethene
CH3OCH2OCH3
CH3OCHPCH2
Propane
Propene
The location of the CPC double bond in the skeleton structure of the compound is indicated by specifying the number of the carbon atom at which the CPC bond starts.
CH2PCHOCH2OCH3
CH3OCHPCHOCH3
1-Butene
2-Butene
The names of substituents are then added as prefixes to the name of the alkene.
Exercise O1.6
Use the IUPAC system to name the following compound.
CH3
A
CH3OCHPCOCH2OCHOCH3
A
CH3
Solution
The compound is a derivative of hexane because the longest carbon chain contains six carbon atoms. It contains a CPC double bond, which means it is a hexene. Because the double bond links the second and third carbon atoms, it is a 2-hexene. Because the CH3 substituents are on the third and fifth carbon atoms, the compound is 3,5-dimethyl-2-hexene.
Compounds that contain CqC triple bonds are called alkynes. These compounds have
four less hydrogen atoms than the parent alkanes, so the generic formula for an alkyne
with a single CqC triple bond is CnH2n2. The simplest alkyne has the formula C2H2 and
is known by the common name acetylene.
HOCqCOH
Acetylene
16
EQA
The IUPAC nomenclature for alkynes names the compounds as derivatives of the parent
alkane, with the ending -yne replacing -ane.
CCH2CH3
CCH2CH3
CH3
A
CCH2CHCH2CH3
CH3C
HC
CH3C
2-Pentyne
1-Butyne
5-Methyl-2-heptyne
In addition to compounds that contain one double bond (alkenes) or one triple bond
(alkynes), we can also envision compounds with two double bonds (dienes), three double
bonds (trienes), or a combination of double and triple bonds.
CH3CHPCHCH2C CH
CH2 PCHCH PCH2
4-Hexen-1-yne
1,3-Butadiene
The sigma () bond skeleton in the molecule is formed by the overlap of sp2 hybridized
orbitals on each carbon atom with either a 1s orbital on a hydrogen atom or the sp2 hybridized orbital on the other carbon atom. This leaves one unpaired electron in an empty
2p orbital on each carbon atom. The orbitals that hold these electrons interact to form a
pi () bond.1
pi bond
The geometry around a CPC double bond is therefore different from the geometry around
a COC single bond. Because of the double bond, the six atoms in a C2H4 molecule must
all lie in the same plane, as shown in Figure O1.17. The presence of the bond restricts
rotation around a CPC double bond. There is no way to rotate one end of the bond relative to the other without breaking the bond. Because the bond is relatively strong
(~270 kJ/mol), rotation around the CPC double bond cannot occur at room temperature.
Alkenes therefore form stereoisomers that differ in the way substituents are arranged
around the CPC double bond. The isomer with similar substituents on the same side of
1
Students sometimes ask, Why are there three lines between the carbon atoms in this drawing if there are
only two bonds? The answer is: Both of the curved lines are needed to represent a single bond.
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17
C
H
H
C
H
the double bond is called the cis isomer, from a Latin stem meaning on this side. The isomer in which similar substituents are across from each other, is called the trans isomer, from
a Latin stem meaning across. Consider, for example, the terms transcontinental, or transAtlantic. The cis isomer of 2-butene, for example, has both CH3 groups on the same side of
the double bond. In the trans isomer the CH3 groups are on opposite sides of the double bond.
CH3
CH3
D
G
CPC
D
G
H
H
cis-2-Butene
H
D
G
CPC
D
G
H
CH3
CH3
trans-2-Butene
Cis/trans isomers have similar chemical properties but different physical properties. cis-2Butene, for example, freezes at 138.9C, whereas trans-2-butene freezes at 105.6C.
Exercise O1.7
Name the straight-chain constitutional and stereoisomers of pentene (C5H10).
Solution
There are two constitutional isomers of pentene in which all the carbon atoms lie in the
same chain.
CH2 PCHCH2CH2CH3
CH3CH PCHCH2CH3
1-Pentene
2-Pentene
There are no cis/trans isomers of 1-pentene because there is only one way of arranging the
substituents around the double bond.
H
CH CH2CH3
D 2
G
CPC
D
G
H
H
CH3
cis-2-Pentene
H
D
G
CPC
D
G
H
CH2CH3
CH3
trans-2-Pentene
18
EQA
Br
A
CH3CHCHCH3
A
Br
2,3-Dibromobutane
This reaction provides a way to test for alkenes or alkynes. Solutions of bromine in CCl4
have an intense red-orange color. When Br2 in CCl4 is mixed with a sample of an alkane,
EQA
19
no change is initially observed. When it is mixed with an alkene or alkyne, the color of Br2
rapidly disappears.
The reaction between 2-butene and bromine to form 2,3-dibromobutane is just one example of the addition reactions of alkenes and alkynes. Hydrogen bromide (HBr) adds
across a CPC double bond to form the corresponding alkyl bromide, in which the hydrogen ends up on the carbon atom that had more hydrogen atoms to begin with. Addition
of HBr to 2-butene, for example, gives 2-bromobutane.
Br
A
CH3CHCH2CH3
2-Bromobutane
As noted in Section O1.6, H2 adds across double (or triple) bonds in the presence of a suitable catalyst to convert an alkene (or alkyne) to the corresponding alkane.
CH3CH P CHCH3 H2
Pt
CH3CH2CH2CH3
In the presence of an acid catalyst, it is even possible to add a molecule of water across a
CPC double bond.
OH
A
CH3CHCH2CH3
H2SO4
Addition reactions provide a way to add new substituents to a hydrocarbon chain and
thereby produce new derivatives of the parent alkanes.
In theory, two products can form when an unsymmetric reagent such as HBr is added
to an unsymmetric CPC double bond. In practice, only one product is obtained. When
HBr is added to 2-methylpropene, for example, the product is 2-bromo-2-methylpropane,
not 1-bromo-2-methylpropane.
CH3
G
C PCH2 HBr
D
CH3
CH3
A
CH3 O C O CH3
A
Br
CH3
A
(not CH3 O CH O CH2Br)
In 1870, after careful study of many examples of addition reactions, the Russian chemist
Vladimir Markovnikov formulated a rule for predicting the product of the reactions.
Markovnikovs rule states that the hydrogen atom adds to the carbon atom that already has
the larger number of hydrogen atoms when HX adds to an alkene. Thus, water (HOH)
adds to propene to form the product in which the OH group is on the middle carbon
atom.
OH
CH3CH PCH2 HOH
H
CH3CHCH2
H
Carbon in the
double bond with
the most H atoms
20
EQA
CH3
CH2
B
CH3
CH3
-Pinene
CH3
-Pinene
CH3
OH
CH3
Camphor
O
Menthol
EQA
21
Both of the compounds have a fragrant, penetrating odor and taste cool. Camphor is
used as a moth repellent. Menthol is a mild anesthetic that is added to some brands of
cigarettes.
Although the terpenes and terpenoids discussed so far have very different structures,
they have one important property in common: They all contain 10 carbon atoms, neither
more nor less. Each of the compounds can be traced back to a reaction in which a pair of
five-carbon molecules are fused. Thus, it isnt surprising that we can also find sesquiterpenes (15 carbon atoms), diterpenes (20 carbons), triterpenes (30 carbons), and so on. Important examples of these compounds include vitamin A and the -carotene that gives carrots their characteristic color.
CH3
CH3
CH3
OH
CH3
CH3
Vitamin A
CH3
CH3
CH3
CH3
CH3
CH3
CH3
CH3
CH3
CH3
-Carotene
Steroids arent terpenes or terpenoids in the literal sense because they dont contain
the characteristic number of carbon atoms. Consider cholesterol, for example, which is one
of the most important steroids.
CH3
CH3
Cholesterol
HO
Analysis of the structure suggests the formula C27H46O, which doesnt fit the pattern expected of a terpenoid. The biosynthetic precursor of the molecule, however, is a 30-carbon
triterpene that is converted into cholesterol by a series of enzyme-catalyzed reactions.
By definition, the steroids are compounds that have the basic structure formed by fusing three six-membered rings and a five-membered ring. The most important property of
the molecule is the fact that, with the exception of the OOH group on the lower left-hand
corner of the molecule, there is nothing about the structure of the compound that would
make it soluble in water.
In this day of cholesterol-free products, it is useful to question the label on certain products such as peanut butter that are advertised as cholesterol-free. That is like saying that
the Sahara desert is rain-free. Peanut butter is made from peanuts and cholesterol isnt a
characteristic ingredient in plants; it is synthesized by animals, particularly mammals. It is
22
EQA
also useful to note that placing someone on a cholesterol-free diet wont reduce their cholesterol level to zero. Even on a low-cholesterol diet, the individual will synthesize about 0.80
gram of cholesterol per day. The key question is, Is there an excess of cholesterol in the
bloodstream? If there is, a diet that reduces the intake of cholesterol might be important.
H
H
H
Kekuls explanation of
the structure of benzene
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23
Kekuls structure explained the formula of benzene, but it did not explain why benzene failed to behave like an alkene. The unusual stability of benzene wasnt understood
until the development of the theory of resonance. This theory states that molecules for
which two or more satisfactory Lewis structures can be drawn are an average, or hybrid,
of the structures. Benzene, for example, is a resonance hybrid of the two Kekul structures.
H
H
The resonance structures
for benzene
The difference between the equilibrium and resonance descriptions of benzene is subtle,
but important. In the equilibrium approach, a pair of arrows is used to describe a reversible
reaction, in which the molecule on the left is converted into the one on the right, and vice
versa. In the resonance approach, a double-headed arrow is used to suggest that a benzene
molecule does not shift back and forth between two different structures; it is a hybrid mixture of the structures.
One way to probe the difference between Kekuls idea of an equilibrium between two
structures and the resonance theory in which benzene is a hybrid mixture of the structures
would be to study the lengths of the carboncarbon bonds in benzene. If Kekuls idea
was correct, we would expect to find a molecule in which the bonds alternate between
relatively long COC single bonds (0.154 nm) and significantly shorter CPC double
bonds (0.133 nm). When benzene is cooled until it crystallizes, and the structure of the
molecule is studied by X-ray diffraction, we find that the six carboncarbon bonds in
the molecule are the same length (0.1395 nm). The crystal structure of benzene is therefore more consistent with the resonance model of bonding in benzene than the original
Kekul structures.
The resonance theory does more than explain the structure of benzeneit also explains why benzene is less reactive than an alkene. The resonance theory assumes that molecules that are hybrids of two or more Lewis structures are more stable than those that
arent. It is the extra stability that makes benzene and other aromatic derivatives less reactive than normal alkenes. To emphasize the difference between benzene and a simple alkene,
many chemists replace the Kekul structures for benzene and its derivatives with an aromatic ring in which the circle in the center of the ring indicates that the electrons in the
ring are delocalized; they are free to move around the ring.
H
H
H
H
It is the delocalization of electrons around the aromatic ring that makes benzene less reactive than a simple alkene.
Aromatic compounds were being extracted from coal tar as early as the 1830s. As a
result, many of the compounds were given common names that are still in use today. A
24
EQA
OH
OCH3
Phenol
Toluene
CO2H
NH2
Anisole
Aniline
Benzoic acid
There are three ways in which a pair of substituents can be placed on an aromatic ring.
In the ortho (o) isomer, the substituents are in adjacent positions on the ring. In the meta
(m) isomer, they are separated by one carbon atom. In the para (p) isomer, they are on
opposite ends of the ring. The three isomers of dimethylbenzene, or xylene, are shown
below.
CH3
CH3
CH3
CH3
CH3
Ortho
Meta
CH3
Para
Exercise O1.8
Predict the structure of para-dichlorobenzene, one of the active ingredients in mothballs.
Solution
Para isomers of benzene contain two substituents at opposite positions in the sixmembered ring. para-Dichlorobenzene therefore has the following structure.
Cl
Cl
p-Dichlorobenzene
Aromatic compounds can contain more than one six-membered ring. Naphthalene, anthracene, and phenanthrene are examples of aromatic compounds that contain two or more
fused benzene rings.
H
Naphthalene (C10H8)
Anthracene (C14H10)
H
H
H
H
H
H
Phenanthrene (C14H10)
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25
Modern cars run at compression ratios of about 91, which means the gasolineair mixture in the cylinder is
compressed by a factor of nine before it is ignited.
26
EQA
TABLE O1.3
Petroleum Fractions
Fraction
Natural gas
Petroleum ether
Gasoline
Kerosene
Fuel oils
Lubricants
Asphalt or coke
20
2060
40200
150260
260
400
Residue
C1 to C4
C5 to C6
C5 to C12, but mostly C6 to C8
Mostly C12 to C13
C14 and higher
C20 and above
Polycyclic
The relationship between knocking and the structure of the hydrocarbons in gasoline
is summarized in the following general rules.
Branched alkanes and cycloalkanes burn more evenly than straight-chain alkanes.
Short alkanes (C4H10) burn more evenly than long alkanes (C7H16).
Alkenes burn more evenly than alkanes.
Aromatic hydrocarbons burn more evenly than cycloalkanes.
The most commonly used measure of a gasolines ability to burn without knocking is its
octane number. Octane numbers compare a gasolines tendency to knock against the tendency of a blend of two hydrocarbonsheptane and 2,2,4-trimethylpentane, or isooctane
to knock. Heptane (C7H16) is a long, straight-chain alkane, which burns unevenly and produces a great deal of knocking. Highly branched alkanes such as 2,2,4-trimethylpentane
are more resistant to knocking. Gasolines that match a blend of 87% isooctane and 13%
heptane are given an octane number of 87.
There are three ways of reporting octane numbers. Measurements made at high speed
and high temperature are reported as motor octane numbers. Measurements taken under
relatively mild engine conditions are known as research octane numbers. The road index
octane numbers reported on gasoline pumps are an average of the two. Road index octane
numbers for a few pure hydrocarbons are given in Table O1.4.
TABLE O1.4
Hydrocarbon
Heptane
2-Methylheptane
Hexane
2-Methylhexane
1-Heptene
Pentane
1-Pentene
Butane
Cyclohexane
2,2,4-Trimethylpentane (isooctane)
Benzene
Toluene
0
23
25
44
60
62
84
91
97
100
101
112
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27
By 1922 a number of compounds had been discovered that could increase the octane
number of gasoline. Adding as little as 6 mL of tetraethyllead (shown in Figure O1.19) to
a gallon of gasoline, for example, can increase the octane number by 15 to 20 units. This
discovery gave rise to the first ethyl gasoline, and it enabled the petroleum industry to
produce aviation gasolines with octane numbers greater than 100.
CH3
G
CH2
CH Pb CH2
D 2
CH3
CH2
G
CH3
CH3
D
FIGURE O1.19 Structure of the tetraethyllead used to make leaded
gasoline.
Another way to increase the octane number is thermal reforming. At high temperatures (500600C) and high pressures (2550 atm), straight-chain alkanes isomerize to form
branched alkanes and cycloalkanes, thereby increasing the octane number of the gasoline.
Running the reaction in the presence of hydrogen and a catalyst such as a mixture of silica (SiO2) and alumina (Al2O3) results in catalytic reforming, which can produce a gasoline with even higher octane numbers. Thermal or catalytic reforming and gasoline additives such as tetraethyllead increase the octane number of the straight-run gasoline obtained
from the distillation of crude oil, but neither process increases the yield of gasoline from
a barrel of oil.
The data in Table O1.3 suggest that we could increase the yield of gasoline by cracking the hydrocarbons that end up in the kerosene or fuel oil fractions into smaller pieces.
Thermal cracking was discovered as early as the 1860s. At high temperatures (500C) and
high pressures (25 atm), long-chain hydrocarbons break into smaller pieces. A saturated
C12 hydrocarbon in kerosene, for example, might break into two C6 fragments. Because
the total number of carbon and hydrogen atoms remains constant, one of the products of
the reaction must contain a CPC double bond.
CH3(CH2)10CH3 888n CH3(CH2)4CH3 CH2PCH(CH2)3CH3
The presence of alkenes in thermally cracked gasolines increases the octane number (70)
relative to that of straight-run gasoline (60), but it also makes thermally cracked gasoline
less stable for long-term storage. Thermal cracking has therefore been replaced by catalytic
cracking, which uses catalysts instead of high temperatures and pressures to crack longchain hydrocarbons into smaller fragments for use in gasoline.
About 87% of the crude oil refined in 1980 went into the production of fuels such as
gasoline, kerosene, and fuel oil. The remainder went for nonfuel uses, such as petroleum
solvents, industrial greases and waxes, or starting materials for the synthesis of petrochemicals. Petroleum products are used to produce synthetic fibers such as nylon, Orlon,
and Dacron, and other polymers such as polystyrene, polyethylene, and synthetic rubber.
They also serve as raw materials in the production of refrigerants, aerosols, antifreeze, detergents, dyes, adhesives, alcohols, explosives, weed killers, insecticides, and insect repellents. The H2 given off when alkanes are converted to alkenes or when cycloalkanes are
converted to aromatic hydrocarbons can be used to produce a number of inorganic petrochemicals, such as ammonia, ammonium nitrate, and nitric acid. As a result, most fertilizers as well as other agricultural chemicals are also petrochemicals.
28
EQA
H
H
NH2
H
HOCOH H
H H
H2
HH
S
HOCOH
H H
H
H
C
f
H
H
H2
fi
HO H
H
O
H
i
C
C
f i
H H
H
O
H
S
H
i
H H
H
H
H
H2
O
H
H O
f
HOCOH
H2
H2
H
H
H2
H
H
O
S
CH3
HOCOH
H
O SO
H2
H
H
HOCOH
COC
i
H
H
HOCOH
O
H
H
H
HOCOH
H HH
C PO
MO
H2
H
i
C
H H
COC
S
H2
H
HH
O
C
H
CH2CH3
O
H
C
f
H
H
HH
f
H H
O
H
H H
H2
Anthracite coal is a dense, hard rock with a jet-black color and a metallic luster. It contains between 86% and 98% carbon by weight, and it burns slowly, with a pale blue flame
and very little smoke. Bituminous coal, or soft coal, contains between 69% and 86% carbon by weight and is the most abundant form of coal. Subbituminous coal contains less
carbon and more water, and it is therefore a less efficient source of heat. Lignite coal, or
brown coal, is a very soft coal that contains up to 70% water by weight.
The total energy consumption in the United States for 1990 was 86 1015 kJ. Of that
total, 41% came from oil, 24% from natural gas, and 23% from coal. Coal is unique as a
source of energy in the United States, however, because none of the 2118 billion pounds
used in 1990 was imported. Furthermore, the proven reserves are so large we can continue
using coal at that level of consumption for at least 2000 years.
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29
At the time this text was written, coal was the most cost-efficient fuel for heating. The
cost of coal delivered to the Purdue University physical plant was $1.41 per million kilojoules of heating energy. The equivalent cost for natural gas would have been $5.22, and
#2 fuel oil would have cost $7.34. Although coal is less expensive than natural gas and oil,
it is more difficult to handle. As a result, there has been a long history of efforts to turn
coal into either a gaseous or a liquid fuel.
Coal Gasification
As early as 1800, coal gas was made by heating coal in the absence of air. Coal gas is rich
in CH4 and gives off up to 20.5 kJ per liter of gas burned. Coal gasor town gas, as it was
also knownbecame so popular that most major cities and many small towns had a local
gas house in which it was generated, and gas burners were adjusted to burn a fuel that produced 20.5 kJ/L. Gas lanterns, of course, were eventually replaced by electric lights. But
coal gas was still used for cooking and heating until the more efficient natural gas (38.3
kJ/L) became readily available.
A slightly less efficient fuel known as water gas can be made by reacting the carbon in
coal with steam.
C(s) H2O(g) 88n CO(g) H2(g)
Water gas burns to give CO2 and H2O, releasing roughly 11.2 kJ per liter of gas consumed.
Note that the enthalpy of reaction for the preparation of water gas is positive, which means
that the reaction is endothermic. As a result, the preparation of water gas typically involves
alternating blasts of steam and either air or oxygen through a bed of white-hot coal. The
exothermic reactions between coal and oxygen to produce CO and CO2 provide enough
energy to drive the reaction between steam and coal.
Water gas formed by the reaction of coal with oxygen and steam is a mixture of CO,
CO2, and H2. The ratio of H2 to CO can be increased by adding water to the mixture, to
take advantage of a reaction known as the water-gas shift reaction.
CO(g) H2O(g) 88n CO2(g) H2(g)
The concentration of CO2 can be decreased by reacting the CO2 with coal at high temperatures to form CO.
C(s) CO2(g) 88n 2 CO(g)
Water gas from which the CO2 has been removed is called synthesis gas because it can
be used as a starting material for a variety of organic and inorganic compounds. It can be
used as the source of H2 for the synthesis of ammonia, for example.
N2(g) 3 H2(g) 88n 2 NH3(g)
It can also be used to make methyl alcohol, or methanol.
CO(g) 2 H2(g) 88n CH3OH(l)
Methanol can then be used as a starting material for the synthesis of alkenes, aromatic
compounds, acetic acid, formaldehyde, and ethyl alcohol (ethanol). Synthesis gas can also
be used to produce methane, or synthetic natural gas (SNG).
30
EQA
Coal Liquefaction
The first step toward making liquid fuels from coal involves the manufacture of synthesis
gas (CO and H2) from coal. In 1925, Franz Fischer and Hans Tropsch developed a catalyst that converted CO and H2 at 1 atm and 250300C into liquid hydrocarbons. By 1941,
FischerTropsch plants produced 740,000 tons of petroleum products per year in Germany.
FischerTropsch technology is based on a complex series of reactions that use H2 to
reduce CO to CH2 groups linked to form long-chain hydrocarbons.
CO(g) 2 H2(g) 88n (CH2)n(l) H2O(g)
The water produced in the reaction combines with CO in the water-gas shift reaction to
form H2 and CO2.
CO(g) H2O(g) 88n CO2(g) H2(g)
At the end of World War II, FischerTropsch technology was under study in most industrial nations. The low cost and high availability of crude oil, however, led to a decline in
interest in liquid fuels made from coal. The only commercial plants using this technology
today are in the Sasol complex in South Africa, which uses 30.3 million tons of coal per
year.
Another approach to liquid fuels is based on the reaction between CO and H2 to form
methanol, CH3OH.
CO(g) 2 H2(g) 88n CH3OH(l)
Methanol can be used directly as a fuel, or it can be converted into gasoline with catalysts
such as the ZSM-5 zeolite catalyst developed by Mobil Oil Company.
As the supply of petroleum becomes smaller and its cost continues to rise, a gradual
shift may be observed toward liquid fuels made from coal. Whether this takes the form of
a return to a modified FischerTropsch technology, the conversion of methanol to gasoline, or other alternatives, only time will tell.
EQA
31
FIGURE O1.21 Each hand is the mirror image of the other, but
neither hand is superimposable on the other.
Objects that possess a similar handedness are said to be chiral (literally, handed). Those
that do not are said to be achiral. Gloves are chiral. (It is difficult, if not impossible, to
place a right-hand glove on your left hand or a left-hand glove on your right hand.) Mittens, however, are often achiral. (Either mitten can fit on either hand.) Feet and shoes are
both chiral, but socks are not.
In 1874 Jacobus vant Hoff and Joseph Le Bel recognized that a compound that contains a single tetrahedral carbon atom with four different substituents could exist in two
forms that were mirror images of each other. Consider the CHFClBr molecule, for example, which contains four different substituents on a tetrahedral carbon atom. Figure O1.22
shows one possible arrangement of the substituents and the mirror image of the structure.
By convention, solid lines are used to represent bonds that lie in the plane of the paper.
Wedges are used for bonds that come out of the plane of the paper toward the viewer;
dashed lines describe bonds that go behind the paper.
H
A
C
Br ( E
F
Cl
H
A
C
E ( Br
F
Cl
FIGURE O1.22 One form of the CHFClBr molecule and its mirror
image.
If we rotate the molecule on the right by 180 around the COH bond we get the structures shown in Figure O1.23. Chiral molecules are said to be optically active because they
are capable of rotating a plane of polarized light.
H
A
C
E ( Cl
F
Br
H
A
C
E ( Br
F
Cl
32
EQA
These structures are different because they cannot be superimposed on one another, as
shown in Figure O1.24.
H
HA
AC
EC
Cl
FE
Br
F
Br
Cl
FIGURE O1.24 The compound CHFClBr is chiral because the structures are not superimposable.
CHFClBr is therefore a chiral molecule that exists in the form of a pair of stereoisomers
that are mirror images of each other. As a rule, any tetrahedral atom that carries four different substituents is a stereocenter, or a stereogenic atom. Compounds that contain a single stereocenter are always chiral. Some compounds that contain two or more stereocenters are achiral because of the symmetry of the relationship between the stereocenters.
The prefix en- often means to make, or cause to be, as in endanger. It is also
used to strengthen a term, to make it even more forceful, as in enliven. Thus, it isnt
surprising that a pair of stereoisomers that are mirror images of each other are called enantiomers. They are literally compounds that contain parts that are forced to be across from
each other. Stereoisomers that arent mirror images of each other are called diastereomers.3
The cis/trans isomers of 2-butene, for example, are stereoisomers, but they are not mirror
images of each other. As a result, they are diastereomers.
Exercise O1.9
Which of the following compounds would form enantiomers because the molecule is
chiral?
CH3
A
CH3O COCH2CH3
A
Br
CH3
A
BrCH2OC OCH2CH3
A
H
2-Bromo-2-methylbutane
1-Bromo-2-methylbutane
Solution
The second carbon atom in 2-bromo-2-methylbutane contains two identical CH3 substituents. As a result, the compound is achiral and does not form enantiomers.
CH2CH3
A
C
E ( CH3
Br
CH3
2-Bromo-2-methylbutane
The prefix dia- is often used to indicate opposite directions, or across, as in diagonal.
EQA
33
and
CH2CH3
A
EC ( H
BrCH2
CH3
Enantiomers of 1-bromo-2-methylbutane
Note: Every objectwith the possible exception of the vampires found on late-night TV
has a mirror image. The relevant question is whether the mirror image can be superimposed on the source of the image. If it can, the object is not chiral (achiral). If it cannot,
the object is chiral and it can exist as a pair of stereoisomers.
You might remember that dextro means right by noting that the predominantly right-handed world in
which we live uses words such as dextrous to mean unusually skilled at the use of ones handsin particular,
the right hand.
34
EQA
The instrument with which optically active compounds are studied is a polarimeter,
shown in Figure O1.25. Imagine a horizontal line that passes through the zero of a coordinate system. By convention, negative numbers are placed on the left and positive numbers on the right of zero. Thus levorotatory compounds are indicated with a negative sign
() and dextrorotatory compounds with a positive sign ().
Emergent light
with rotated
plane of
polarization
Nicol
prism
polarizer
Unpolarized
light
Nicol
prism
analyzer
Incident
plane-polarized
light
The magnitude of the angle through which an enantiomer rotates plane-polarized light
depends on four quantities: (1) the wavelength of the light, (2) the length of the cell through
which the light passes, (3) the concentration of the optically active compound in the solution through which the light passes, and (4) the specific rotation of the compound, which
reflects the relative ability of the compound to rotate plane-polarized light. The specific
rotation of the dextrorotatory isomer of glucose is written as follows:
[] 20
D 3.12
When the spectrum of sunlight was first analyzed by Joseph von Fraunhofer in 1814, he
observed a limited number of dark bands in the spectrum, which he labeled AH. We now
know that the D band in the spectrum is the result of the absorption by sodium atoms of
light that has a wavelength of 589.6 nm. The D in the symbol for specific rotation indicates that it is light of this wavelength that was studied. The 20 indicates that the experiment was done at 20C. The sign indicates that the compound is dextrorotatory;
it rotates light clockwise. Finally, the magnitude of the measurement indicates that when
a solution of the compound with a concentration of 1.00 g/mL was studied in a 10-cm cell,
it rotated the light by 3.12.
The magnitude of the rotations observed for a pair of enantiomers is always the same.
The only difference between the compounds is the direction in which they rotate planepolarized light. The specific rotation of the levorotatory isomer of the compound would
therefore be 3.12.
Arrange the four substituents in order of decreasing atomic number of the atoms
attached to the stereocenter. (The substituent with the highest atomic number gets
EQA
35
Br
A
CH3OCOCH2CH3
A
H
2nd priority
2nd priority
3rd priority
When two or more substituents have the same prioritysuch as the CH3 and
CH2CH3 groups in 2-bromobutanecontinue working down the substituent chain
until you find a difference. In 2-bromobutane, we would give the CH2CH3 group a
higher priority than the CH3 group because the next point down the chain is a CH3
group in the CH2CH3 substituent and an H atom in the CH3 group. Thus, the four
substituents on 2-bromobutane would be listed in the order: Br CH2CH3
CH3 H.
1st priority
Br
A
CH3OCO CH2CH3
A
H
3rd priority
2nd priority
4th priority
View the enantiomer from the direction that places the substituent with the lowest
priority as far from the eye as possible. In the following example, this involves rotating the molecule counterclockwise around the CCH2CH3 bond and tilting it
slightly around an axis that lies in the plane of the paper. When this is done, the
substituent that has the lowest priority is hidden from the eye.
CH2CH3
A
C
E ( H
CH3
Br
CH2CH3
%
C
; '
CH3
Br
Trace a path that links the substituents in decreasing order of priority. If the path
curves to the rightclockwisethe molecule is the rectus or R enantiomer. If it
curves to the leftcounterclockwiseit is the sinister or S enantiomer.
2nd priority
CH2CH3
%
C
; '
CH3
Br
3rd priority
1st priority
(S)-2-Bromobutane
36
EQA
In this example, the path curves to the left, so the enantiomer is the (S)-2-bromobutane
stereoisomer.
It is important to recognize that the (R)/(S) system is based on the structure of an individual molecule and the ()/() system is based on the macroscopic behavior of a large
collection of molecules. The most complete description of an enantiomer combines aspects
of both systems. The enantiomer analyzed in this section is best described as (S)-()-2bromobutane. It is the (S) enantiomer because of its structure and the () enantiomer because samples of the enantiomer with this structure are levorotatory; they rotate planepolarized light clockwise.
KEY TERMS
Achiral
Addition reaction
Alkane
Alkene
Alkyl bromide
Alkyl chloride
Alkyl halide
Alkyne
Branched hydrocarbon
Catalytic cracking
Catalytic reforming
Chiral
Cis/trans isomer
Coal
Coal gas
Conformation
Constitutional isomer
Crude oil
Cycloalkane
Dextrorotatory
Diastereomer
Enantiomer
Essential oil
Hydrocarbon
Isomer
Levorotatory
Markovnikovs rule
Natural gas
Newman projection
Octane number
Optical activity
Organic chemistry
Specific rotation
Stereocenter
Stereogenic atom
Steroid
Stereoisomer
Straight-chain
hydrocarbon
Straight-run gasoline
Synthesis gas
Terpene
Terpenoid
Tetravalent
Thermal cracking
Thermal reforming
Town gas
Unsaturated
hydrocarbon
Vital force
Water gas
Water-gas shift reaction
PROBLEMS
The Special Role of Carbon
1. Explain why carbon forms covalent bonds, not ionic bonds, with so many other elements.
2. Carbon forms relatively strong double bonds, not only with itself, but with other nonmetals such as nitrogen, oxygen, phosphorus, and sulfur. Why is this important in terms
of the great diversity of carbon compounds?
3. In The Life Puzzle, Graham Cairns-Smith proposed three rules for speculating on the
origin of life: (1) take a good look at atoms and see what they can do, (2) take a good
look at organisms and see how they work, and then (3) put an organism together in
the easiest way you can think of. He reports two hypotheses to explain the striking
fundamental biochemical similarity between life in all its forms. That the first organisms on Earth had a similar composition to modern forms. Or that modern biochemical
EQA
37
CH3
CH3
H
A
CH3
H
H
CH3
B
13. Provide the systematic (IUPAC approved) name for the following compound.
CH3
A
CH3CH2CHCHCH2CHCH3
A
A
CH3
CH2CH3
38
EQA
H
CH3
17. One way to decide whether a pair of structures represent different compounds is to assign a systematic name to each structure. Use this approach to decide whether the following are isomers or different descriptions of the same compound.
CH3
G
CHOCH2
D
i
CH3
CHOCH3
f
CH3
CH3
CH3
A
A
CH3CHCH2CHCH3
EQA
39
30.
31.
32.
33.
34.
40
Optical Activity
55. Describe the difference between constitutional isomers and stereoisomers. What characteristic feature of a molecule could be used to distinguish between the two forms of
isomers?
56. Objects that cannot be superimposed on their mirror images are said to be chiral, and
chiral molecules are optically active. Which of the following molecules are optically
active?
(a) CH4 (b) CH3Cl (c) CHCl3 (d) CHFCl2 (e) CHFClBr
57. Which of the following compounds are optically active?
CH3
A
(a) C2H4 (b) C6H6 (c) C6H4Cl2 (d) CH3CH2CHCH3
58. Coniine is the active ingredient in the poison known as hemlock that was given to
EQA
EQA
41
Socrates in 399 B.C. Use the following diagram of the structure of coniine to predict
whether the compound is optically active.
N
A
H
59. Use the structure of caffeine shown below to predict whether the compound is optically active.
CH3
O
CH3
N
O
N
N
CH3
60. Determine the number of centers of chirality in the structure of vitamin C shown in
Figure O1.2.
61. Predict whether the following compound is chiral.
CH2CH2CH2CH3
A
CH3ONOCH2CH3
A
CH(CH3)2
62. Which of the following compounds, which play an important role in the chemistry of
biological systems, is chiral?
CO2H
A
CH2
A
HOOCOCO2H
A
CH2
A
CO2H
Citric acid
CO2H
A
CH2
A
HOCOCO2H
A
HOOCH
A
CO2H
CO2H
A
CH2
A
CH2
A
HOOCOCO2H
A
CH2
A
CO2H
Isocitric acid
Homocitric acid
63. Which (if any) of the carbon atoms in 2-bromo-3-methylbutane are stereocenters?
64. Determine whether the following isomers are enantiomers or diastereomers. What
characteristic feature of the molecule can be used to make the decision?
CH2CH3
A
C
D ( CH3
H
Br
CH2CH3
A
C
D ( Br
H
CH3
42
EQA
65. Determine whether the following isomers are enantiomers or diastereomers. What
characteristic feature of the molecule can be used to make the decision?