Académique Documents
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of Carbon
Introduction
The many organic compounds found in living organisms-proteins and amino
acids, sugars, organic acids and bases, fats, and hormones-are possible only
because of the many different kinds of atoms and groups of atoms that can be
attached to carbon backbones. In the next chapter we shall see what several of
these compounds are like.
In the previous chapter we mentioned that life occupies the midranges of size
and temperature in the universe.
Carbon occupies the midposition in Row 2 of the periodic table, and has
exactly half as many electrons as are needed to fill. its outer shell. It neither
loses nor gains electrons in chemical reactions, so its compounds are not ionic.
This is critical for its role, since the nondirectional electrostatic forces between
ions are inadequate for building elaborate molecules (right).
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Introduction
The ultimate in carbon tetrahedra is the crystal lattice of diamond,
shown below, in which the tetrahedral array of carbon atoms goes
on forever, and there are no hydrogen atoms present at all.
Hydrocarbons that have only single bonds between carbon atoms
can be thought of as fragments of this three-dimensional diamond
lattice. Organic compounds in general are in a reduced state, and
therefore are storehouses of energy for the reasons discussed in
Chapter 12.
Carbon shares its four electrons in four covalent bonds with other
electron-sharing atoms. Because these four bonding electron
pairs still are bound to the atoms from which they came, they hold
the atoms together in a molecule.
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Hydrocarbons
Hydrocarbons are the most reduced compounds of all,
with nothing but C and H atoms. Hydrocarbons with
single C-C bonds, known as saturated hydrocarbons or
alkanes, can be thought of as being built by the
snapping together of carbon tetrahedra, with unused
carbon bonding positions filled by hydrogen atoms.
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Hydrocarbons
Hydrocarbons are the most reduced compounds of all,
with nothing but C and H atoms. Hydrocarbons with
single C-C bonds, known as saturated hydrocarbons or
alkanes, can be thought of as being built by the
snapping together of carbon tetrahedra, with unused
carbon bonding positions filled by hydrogen atoms.
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Hydrocarbons
Hydrocarbons are the most reduced compounds of all,
with nothing but C and H atoms. Hydrocarbons with
single C-C bonds, known as saturated hydrocarbons or
alkanes, can be thought of as being built by the
snapping together of carbon tetrahedra, with unused
carbon bonding positions filled by hydrogen atoms.
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Hydrocarbons
Hydrocarbons are the most reduced compounds of all,
with nothing but C and H atoms. Hydrocarbons with
single C-C bonds, known as saturated hydrocarbons or
alkanes, can be thought of as being built by the
snapping together of carbon tetrahedra, with unused
carbon bonding positions filled by hydrogen atoms.
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Hydrocarbons
Another possible structure is isooctane, right. These two are structural isomers
of octane, because they have the same number of each kind of atom, but are
arranged in different ways. Isooctane is familiar from the "octane rating" of
gasoline.
Pentane has three structural isomers, all of which are shown in the right
margin. Their common names are n-pentane, isopentane, and neopentane, but
these molecules can be used to illustrate the systematic way of naming
organic compounds. "Normal," "iso" (meaning an isomer), and "neo" (meaning
new) may suffice for a pentane, but for the 75 different structural isomers of
decane a more orderly method of choosing names is required.
The carbon atoms along the backbone are numbered from one end.
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Hydrocarbons
Another possible structure is isooctane, right. These two are structural isomers
of octane, because they have the same number of each kind of atom, but are
arranged in different ways. Isooctane is familiar from the "octane rating" of
gasoline.
Pentane has three structural isomers, all of which are shown in the right
margin. Their common names are n-pentane, isopentane, and neopentane, but
these molecules can be used to illustrate the systematic way of naming
organic compounds. "Normal," "iso" (meaning an isomer), and "neo" (meaning
new) may suffice for a pentane, but for the 75 different structural isomers of
decane a more orderly method of choosing names is required.
The carbon atoms along the backbone are numbered from one end.
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Hydrocarbons
Another possible structure is isooctane, right. These two are structural isomers
of octane, because they have the same number of each kind of atom, but are
arranged in different ways. Isooctane is familiar from the "octane rating" of
gasoline.
Pentane has three structural isomers, all of which are shown in the right
margin. Their common names are n-pentane, isopentane, and neopentane, but
these molecules can be used to illustrate the systematic way of naming
organic compounds. "Normal," "iso" (meaning an isomer), and "neo" (meaning
new) may suffice for a pentane, but for the 75 different structural isomers of
decane a more orderly method of choosing names is required.
The carbon atoms along the backbone are numbered from one end.
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Hydrocarbons
Another possible structure is isooctane, right. These two are structural isomers
of octane, because they have the same number of each kind of atom, but are
arranged in different ways. Isooctane is familiar from the "octane rating" of
gasoline.
Pentane has three structural isomers, all of which are shown in the right
margin. Their common names are n-pentane, isopentane, and neopentane, but
these molecules can be used to illustrate the systematic way of naming
organic compounds. "Normal," "iso" (meaning an isomer), and "neo" (meaning
new) may suffice for a pentane, but for the 75 different structural isomers of
decane a more orderly method of choosing names is required.
The carbon atoms along the backbone are numbered from one end.
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Hydrocarbons
As an example, the longest chain that can be traced through the isopentane
molecule contains four carbon atoms, so in systematic nomenclature this
molecule is a butane.
A methyl group (CH3-) branches off from the second carbon along the chain,
so isopentane is called 2-methylbutane. One also could call it 3-methylbutane
by beginning the backbone numbering from the other end, but there is no
logical reason for using this name.
The numbering is begun at the end that leads to the simplest name with the
smallest numbers. Notice that there is no 1-methylbutane or 4-methylbutane;
these molecules simply would be the straight-chain pentane.
Example: What is the systematic name for isooctane, shown at the top of the
preceding page?
Solution: With five carbons as the longest continuous carbon chain, the
molecule is called 2,2-dimethyl-4-methylpentane. In this example the
systematic name clearly is clumsier than the name isooctane, which is why the
latter name ordinarily is used.
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Hydrocarbons
For more complex compounds a common name frequently will not exist, and
the systematic nomenclature is the only solution.
The three isomers of pentane differ somewhat in chemical and physical
properties, as the melting and boiling points in the margin of the preceding
page indicate.
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Hydrocarbons
For more complex compounds a common name frequently will not exist, and
the systematic nomenclature is the only solution.
The three isomers of pentane differ somewhat in chemical and physical
properties, as the melting and boiling points in the margin of the preceding
page indicate.
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Hydrocarbons
For more complex compounds a common name frequently will not exist, and
the systematic nomenclature is the only solution.
The three isomers of pentane differ somewhat in chemical and physical
properties, as the melting and boiling points in the margin of the preceding
page indicate.
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Hydrocarbons
For more complex compounds a common name frequently will not exist, and
the systematic nomenclature is the only solution.
The three isomers of pentane differ somewhat in chemical and physical
properties, as the melting and boiling points in the margin of the preceding
page indicate.
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Hydrocarbons
For more complex compounds a common name frequently will not exist, and
the systematic nomenclature is the only solution.
The three isomers of pentane differ somewhat in chemical and physical
properties, as the melting and boiling points in the margin of the preceding
page indicate.
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Properties of Hydrocarbons
The smallest of the hydrocarbons, methane (CH4) through butane Polyethylene is tough because the long molecules are entwined
(C4H10), are gases, which are familiar as industrial, cooking, and around one another and are difficult to unwind and separate.
heating fuels.
We use vast quantities of simple hydrocarbons as fuels and
Methane also is known as marsh gas because some bacteria in lubricants. Natural gas is 85% methane.
swamps can oxidize hydrogen (produced from decomposing
matter by other bacteria), using C02 rather than 02, to yield Crude petroleum is a mixture of hydrocarbons, which usually are
methane and water - 4H2 + CO2 ---> CH4 + 2H20 separated by distillation. The fraction with 5 to 10 carbons is sold
as gasoline, and kerosene has 10 to 18 carbons.
The flickering fire of ignited marsh gas in a swamp has been the
origin of any number of good tales of ghosts and the supernatural. Fuel oils typically have 18 to 22 carbons per molecule, and
paraffin waxes have 20 or more. Crude oil contains all of these
The larger the hydrocarbon molecule, the stronger are the van der compounds, plus various ring hydrocarbons.
Waals forces between molecules, and the higher the temperature
needed to melt the solid or vaporize the liquid. Pentane (C5H12) Much of the natural petroleum originally came from the
through heptadecane (C17H36) are liquids at room temperature, decomposition of organic matter from once-living organisms,
and octadecane (C18H38) and larger molecules are waxy solids under conditions of high temperature and pressure beneath the
(facing page.) surface of the Earth.
Polyethylene plastic, which is familiar as a tough, inert but flexible Petroleum thus is a "fossil fuel" like coal is, and the prospect of
material for laboratory and kitchenware, is a straight-chain soon running out of the supply of fossil fuels is currently a
hydrocarbon with 5000 to 50,000 carbon atoms per chain. distressing one for our energy-devouring economy. What has
taken hundreds of millions of years to deposit, we are in danger of
depleting in less than two centuries.
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Cyclic Hydrocarbons
Saturated hydrocarbons, or alkanes, can form rings as well as straight and
branched chains (right). Open-chain alkanes, straight or branched, have the
general formula CnH2n + 2 , in which n is the number of carbon atoms.
In ring alkanes the chain bends back to connect with itself again, and the
overall formula is CnH2n.
3
The overlap of sp orbitals on adjacent carbon atoms is poor, hence the bonds
are weak. Cyclobutane (C4H8) and cyclopentane (C5H10) are less strained,
and the cyclohexane ring (C6H12) has no strain at all.
Cyclohexane can adopt either the "chair" or the "boat" configurations shown
above, with the "chair" being favored because it keeps the ends of the
molecule farther apart.
The chair form of cyclohexane is the prototype of the six-membered ring found
in glucose and similar sugar molecules, which we shall see in Chapter 21.
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Unsaturated Hydrocarbons
Hydrocarbons that have double or triple bonds between carbon atoms are
called unsaturated hydrocarbons; they are unsaturated in the sense that more
hydrogen atoms can be added when H2 reacts across the double or triple
bonds ( right ).
Virtually free rotation exists about a carbon-carbon single bond. A methyl group
(CH3-) can spin like a top about the single bond joining it to another atom.
Unsaturated hydrocarbons, which have double bonds, are called alkenes and
have similar names ending with the suffix "-ene", as in ethene (C2H4), propene
(C3H6), butene, pentene, and hexene. Ethene, propene, and butene are
commonly known as ethylene, propylene, and butylene.
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Unsaturated Hydrocarbons
Hydrocarbons that have double or triple bonds between carbon atoms are
called unsaturated hydrocarbons; they are unsaturated in the sense that more
hydrogen atoms can be added when H2 reacts across the double or triple
bonds ( right ).
Virtually free rotation exists about a carbon-carbon single bond. A methyl group
(CH3-) can spin like a top about the single bond joining it to another atom.
Unsaturated hydrocarbons, which have double bonds, are called alkenes and
have similar names ending with the suffix "-ene", as in ethene (C2H4), propene
(C3H6), butene, pentene, and hexene. Ethene, propene, and butene are
commonly known as ethylene, propylene, and butylene.
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Unsaturated Hydrocarbons
Unsaturated hydrocarbons with triple bonds are called alkynes. In systematic
nomenclature, C2H2 would be ethyne, although a more common name for it is
acetylene.The simplest alkenes and alkynes are shown in the margin, on the
previous page, with the geometry that results from their carbon-carbon bonds.
A new kind of isomerism appears with butene, C4H8. Butene has three
different structural isomers, depending on whether the four carbons are in a
straight or branched chain, and where the double bond is located.
These structural isomers are 1-butene, 2-butene (with the number describing
the position of the double bond), and isobutylene. (The systematic name for
isobutylene is 1-methylpropene.) 1-Butene, 2-butene, and isobutylene are
genuine structural isomers because their atoms are connected to one another
in different ways.
2-Butene has one methyl group on each double-bonded carbon, but these
methyl groups can be placed in two different ways relative to the double bond:
on the same side of the molecule, or diagonally across the bond. These two
possibilities result in two geometrical isomers, cis2-butene and trans-2-butene,
which are shown on the next page ( page 11 ). These are geometrical rather
than structural isomers because they have the same connections between
atoms.
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Unsaturated Hydrocarbons
All that would be needed to change cis-2-butene to trans-2-butene is to break
the double bond momentarily, twist the molecule around, then reconnect the
same bond. One cannot go from 2-butene to either of the other structural
isomers by breaking, twisting, and then re-forming the same bond. Cis-trans
isomerism is possible whenever two different groups are connected to each
end of a double bond ("cis-" means "on the same side," and "trans-" means
"across from").
All of the isomers of butene have similar chemical and physical properties, and
the distinction between geometrical and structural isomers is less significant to
their properties than is the actual shape of the molecule.
1-Butene has a "swivel' about the bond from the CH3CH2- to the C=C, and is a
flexible molecule. It therefore packs clumsily into a solid crystalline lattice, and
0
melts at a low -185 C. All of the other three isomers are rigid.
Trans-2-butene is a lumpy rod that packs well with its neighbors in the solid
0
and hence does not melt until -106 C. The other two isomers are more
irregular, but are similar in shape and melt at an intermediate temperature
0
within 1 C of each other.
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Unsaturated Hydrocarbons
All that would be needed to change cis-2-butene to trans-2-butene is to break
the double bond momentarily, twist the molecule around, then reconnect the
same bond. One cannot go from 2-butene to either of the other structural
isomers by breaking, twisting, and then re-forming the same bond. Cis-trans
isomerism is possible whenever two different groups are connected to each
end of a double bond ("cis-" means "on the same side," and "trans-" means
"across from").
All of the isomers of butene have similar chemical and physical properties, and
the distinction between geometrical and structural isomers is less significant to
their properties than is the actual shape of the molecule.
1-Butene has a "swivel' about the bond from the CH3CH2- to the C=C, and is a
flexible molecule. It therefore packs clumsily into a solid crystalline lattice, and
0
melts at a low -185 C. All of the other three isomers are rigid.
Trans-2-butene is a lumpy rod that packs well with its neighbors in the solid
0
and hence does not melt until -106 C. The other two isomers are more
irregular, but are similar in shape and melt at an intermediate temperature
0
within 1 C of each other.
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Reactions of Hydrocarbons
Many oxidations and other useful chemical reactions are spontaneous
(accompanied by a decrease in free energy) and exothermic (accompanied by
a decrease in enthalpy) and hence are useful as energy sources; yet the
reactions often are extremely slow.
If an initial heat supply is provided to start the process, then the heat given off
by oxidation is enough to keep the reaction going.
Alkanes are relatively unreactive; the term "paraffins" often applied to them
means "little affinity." Why should reactions of saturated hydrocarbons have
such high activation energies? What is the barrier to reaction?
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Reactions of Hydrocarbons
The answer is that a carbon atom is well-shielded from any attacking group by
the four atoms tetrahedrally placed around it. There are no "open sides"
exposed to attack (see movie, right).
This property, plus the tetrahedral shielding around the carbon atom, means
thatalthough saturated hydrocarbons may be thermodynamically able to react,
they have no convenient mechanism for doing so, and will react only slowly.
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Reactions of Hydrocarbons
The main reactions that saturated hydrocarbons do undergo are
dehydrogenation and cracking, combustion (with F2 or 02), and halogenation
(especially with Cl and Br).
The selection of the right catalyst (often finely divided metals or metal oxides)
and right temperature and pressure to maximize the yield of the desired
product is one of the black arts of the petroleum chemist.
Combustion or oxidation by 02 or F2 is a destructive attack by very
electronegative atoms, which results in the complete fragmentation of the
molecule (see page 15).
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Reactions of Hydrocarbons
Although these reactions (right) are slow at room temperature, they are
selfsustaining once triggered because of the large amount of heat they give off.
With a less electronegative element such as chlorine, the reaction that occurs
is a simple displacement of one or more hydrogens, instead of destruction of
the chain (right).
The "monster" (bottom button) has the perfectly good systematic name of 1-
bromo-2-chloro-2-methylpropane.
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Reactions of Unsaturated Hydrocarbons
Saturated hydrocarbons undergo few other reactions. The halogen derivatives
are not important for their own sake, but because they are a bridge to other,
more useful compounds. Once formed, halogen compounds can react to form
alcohols, acids, amine bases, and other types of molecules to be discussed in
Chapter 20.
The Achilles' heel of alkanes is the double bond, and the main alkene reaction
is the addition across this bond of a variety of reagents.
Notice that only one product is formed when an asymmetric reagent such as
HCl or H20 is used. 2-Chloropropane is formed to the exclusion of 1-
chloropropane.
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Alkene Polymerisation
Alkenes also link together or polymerize into long chains -a reaction that is of
great importance in plastics and rubbers. When ethylene polymerizes, the
double bond opens up to join monomer units into a continuous, saturated
hydrocarbon chain, as shown to the right.
Most plastics must have at least 1000 repeating monomer units in each chain
before they begin to show familiar "plastic" properties.
Chain lengths usually are not uniform, but the range of lengths can be
controlled by the conditions of polymerization. Polyethylene for use in
laboratory ware has 5000 to 50,000 carbons per chain.
Polyvinyl chloride chains, which have as many as 25,000 units, are used for
phonograph records and plastic pipe, and with the addition of a plasticiser, as
artificial leather.
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Alkene Polymerisation
If all of the hydrogens of polyethylene are replaced by fluorines, the result is
Teflon, a tough and unreactive material widely used for laboratory tubing.
Orlon is a well-known artificial fiber, and polystyrene is a hard and clear plastic
that even can be used for furniture and walls.
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Alkene Polymerisation
Alkenes with two double bonds per molecule are termed dienes, and the
smallest, butadiene, has two structural isomers, as shown at the left. 1,2-
Butadiene is a rigid molecule of relatively little use.
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Polymers and Rubber
In this "vulcanization" process, the sulfur atoms cross-link between adjacent
polyisoprene chains and hold them more nearly stationary, opposing any
outside stretch or deformation.
Soft rubbers contain 1-2% sulfur; hard rubbers may have as much as 35%.
Cross-linking of polymer chains is a standard method today of producing a
hard, mechanically strong plastic or resin.
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Conjugation, Aromaticity, and Colour
As we saw first in Chapter 9, 1,3-butadiene is a planar molecule because its
double bonds are delocalized along the entire four-carbon chain (right).
Just as three electron pairs are delocalized around six carbon atoms in a
benzene ring, so two electron pairs are delocalized along the four-carbon chain
of butadiene.
Delocalization can occur whenever single and double bonds alternate along a
chain of atoms, so that after all single bonds are formed, each atom along the
chain has an unused p orbital and one unused electron. Such molecules are
termed conjugated.s
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Conjugation, Aromaticity, and Colour
The polybutadiene chains of natural and synthetic rubbers on The electronic structure of butadiene also can be explained in
page 20 are not conjugated, because more than one single bond terms of delocalization of electrons in molecular orbitals that extend
intervenes between double bonds. over the entire carbon skeleton, as in benzene. This is termed
conjugation. The butadiene molecule is more stable than would be
The carbon atoms that are surrounded on both sides by single expected if delocalisation did not occur ( below - all carbon-carbon
bonds have all of their electrons and orbitals tied up in sigma bonds equivalent s).
bonds, and act as "insulators," thereby preventing the double-
bond electrons from combining into one delocalized pool.
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Photosynthesis
These molecules are useful in photosynthesis because they help the plant or
bacterium to absorb and harvest light energy.
The three molecules absorb in the blue-violet, the green, and the purple-red
regions of the visible spectrum, respectively, so the molecules are coloured
yellow-orange, purple, and green by the unabsorbed wavelengths (click on
'Properties table' button).
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Aromatic Compounds
As we shall see in Chapter 23, the carotenes are assistants to chlorophyll in
photosynthesis. They absorb light of wavelengths that chlorophyll does not,
and transfer the energy in the form of excited electronic states to chlorophyll
molecules.
They are called antenna molecules, and the different numbers of electrons in
their delocalized systems represent a "tuning" of the antenna.
In all of these molecules, the doublebond electrons are delocalized over the
entire set of carbon atoms (over the entire sheet for graphite). Delocalization
sometimes is represented by dotted circles within the rings, as shown right for
benzene and naphthalene.
The Kekule'-like structures with localized double bonds are easier to draw,
however, and cause no confusion as long as one remembers that the double-
bond electrons really are delocalized.
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Aromatic Compounds
As we shall see in Chapter 23, the carotenes are assistants to chlorophyll in
photosynthesis. They absorb light of wavelengths that chlorophyll does not,
and transfer the energy in the form of excited electronic states to chlorophyll
molecules.
They are called antenna molecules, and the different numbers of electrons in
their delocalized systems represent a "tuning" of the antenna.
In all of these molecules, the doublebond electrons are delocalized over the
entire set of carbon atoms (over the entire sheet for graphite). Delocalization
sometimes is represented by dotted circles within the rings, as shown right for
benzene and naphthalene.
The Kekule'-like structures with localized double bonds are easier to draw,
however, and cause no confusion as long as one remembers that the double-
bond electrons really are delocalized.
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Aromatic Compounds
We shall meet many of the derivatives of these aromatic compounds in later
chapters, but a few of the more common ones are shown right.
Toluene, phenol, aniline, and benzoic acid are derivatives in which different
chemical groups are substituted onto the benzene ring.
Pyridine is a variant in which a nitrogen atom replaces a C-H in the ring without
destroying delocalization.
As we saw in Chapter 10, pyridine is a base because it can use its nitrogen
lone pair to bind a proton. Ring compounds with more extensive nitrogen
substitution are important components of DNA and other nucleic acids.
The large porphyrin ring at the far right is the parent compound of chlorophyll
and heme. The entire 24-atom ring is one large delocalized system, which
makes the molecule a good absorber of light energy.
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Aromatic Compounds
We shall meet many of the derivatives of these aromatic compounds in later
chapters, but a few of the more common ones are shown right.
Toluene, phenol, aniline, and benzoic acid are derivatives in which different
chemical groups are substituted onto the benzene ring.
Pyridine is a variant in which a nitrogen atom replaces a C-H in the ring without
destroying delocalization.
As we saw in Chapter 10, pyridine is a base because it can use its nitrogen
lone pair to bind a proton. Ring compounds with more extensive nitrogen
substitution are important components of DNA and other nucleic acids.
The large porphyrin ring at the far right is the parent compound of chlorophyll
and heme. The entire 24-atom ring is one large delocalized system, which
makes the molecule a good absorber of light energy.
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Aromatic Compounds
We shall meet many of the derivatives of these aromatic compounds in later
chapters, but a few of the more common ones are shown right.
Toluene, phenol, aniline, and benzoic acid are derivatives in which different
chemical groups are substituted onto the benzene ring.
Pyridine is a variant in which a nitrogen atom replaces a C-H in the ring without
destroying delocalization.
As we saw in Chapter 10, pyridine is a base because it can use its nitrogen
lone pair to bind a proton. Ring compounds with more extensive nitrogen
substitution are important components of DNA and other nucleic acids.
The large porphyrin ring at the far right is the parent compound of chlorophyll
and heme. The entire 24-atom ring is one large delocalized system, which
makes the molecule a good absorber of light energy.
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Aromatic Compounds
Ring compounds with delocalized electrons originally were called aromatic
molecules because many of them have a pronounced odour.
The term long since has been stretched beyond its original meaning, and now
includes all ring molecules similar to benzene that have delocalized electrons
and low chemical reactivity.
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Aromatic Compounds
Ring compounds with delocalized electrons originally were called aromatic
molecules because many of them have a pronounced odour.
The term long since has been stretched beyond its original meaning, and now
includes all ring molecules similar to benzene that have delocalized electrons
and low chemical reactivity.
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Reactions of Aromatic Compounds
Simple aliphatic molecules with unconjugated double bonds react quickly with
bromine or chlorine to form saturated, dihalogenated molecules:
If the Kekule' structure for benzene were correct, one would expect the same
rapid halogenation reaction:
This is not what happens at all. The reaction is slow, and only results in the
substitution of first one and then two bromine atoms for hydrogens around the
ring, with the delocalized ring structure remaining intact. (Ortho-, meta-, and
para-dibromobenzene, with the substituted bromine atoms adjacent, separated
by one carbon, and diametrically across the ring, are structural isomers of one
another.)
The reason why the ring delocalization is not affected, of course, is that
-1
delocalization confers 40 kcal mole of extra stability on the molecule. Part or
-1
all of this 40 kcal mole would have to be supplied from an outside source to
eliminate some of the delocalization in a chemical reaction. Hence aromatic
molecules have a slowness to react that is more like the behaviour of alkanes
than alkenes.
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Questions
1. Why are ionic bonds not suitable for the construction of complex molecules?
Why are covalent bonds better for this purpose?
2. What are alkanes? What is the fundamental geometry around carbon atoms
in alkane molecules?
4. How are derivatives of normal alkanes named? How is the framework for
naming a branched-chain alkane selected? How is the
5. Show with diagrams that there are only nine structural isomers of heptane.
6. What is the most common use for alkanes? What makes alkanes relatively
unreactive? In the use that you just described, how is this unreactivity
overcome?
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Questions
8. Why are cyclopropane and cyclobutane termed strained molecules? Sketch
the molecular-orbital picture of cyclopropane and account for the strain.
9. Why is the chair conformation of cyclohexane more stable than the boat
form?
11. How are alkene molecules constrained, in a way that alkanes are not?
12. What is the systematic name for isobutylene? What do the numbers in 1-
butene and 2-butene signify? Why is there no 3-butene?
13. What is the distinction between- structural and geometric isomers? Are 1-
butene and 2-butene structural, or geometric, isomers?
14. Draw the structures of cis- and trans-2-butene. Are they structural, or
geometric, isomers?
15. How do the structures of the isomers of C,H10 affect their physical
properties?
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Questions
8. Why are cyclopropane and cyclobutane termed strained molecules? Sketch
the molecular-orbital picture of cyclopropane and account for the strain.
9. Why is the chair conformation of cyclohexane more stable than the boat
form?
11. How are alkene molecules constrained, in a way that alkanes are not?
12. What is the systematic name for isobutylene? What do the numbers in 1-
butene and 2-butene signify? Why is there no 3-butene?
13. What is the distinction between- structural and geometric isomers? Are 1-
butene and 2-butene structural, or geometric, isomers?
14. Draw the structures of cis- and trans-2-butene. Are they structural, or
geometric, isomers?
15. How do the structures of the isomers of C,H10 affect their physical
properties?
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Questions
16. What types of chemical reaction do alkanes most commonly 23. How does entropy contribute to the elasticity of rubber?
undergo? What are the principal reactions of alkenes?
24. What is conjugation in molecules? What does it do to
17. Why is the E,, for alkane reactions inherently higher than for electronic energy levels?
alkenes?
25. What is aromaticity and how is it related to conjugation? What
18. What are electrophiles and nucleophiles? In the base- is the most common small aromatic molecule?
catalyzed hydrolysis of ethyl acetate, is the attacking group an
electrophile, or a nucleophile? What determines which end of the 26. Why does the extent of delocalization in conjugated and
carbonyl C~O bond this group attacks? aromatic molecules affect the light-absorbing properties of the
molecule? How is this property put to use in living organisms?
19. What is Markovnikov's rule, and what does it tell us about the Name a linear conjugated molecule and a ring compound that are
products formed in alkene reactions? used as lightgathering molecules by green plants.
20. How is ethylene the basis for a large family of plastics? What 27. How does a change in the size of the delocalized system
is the corresponding parent molecule for rubbers? change the wavelength of light absorbed in green and purple
bacteria? How does this absorption contribute to the names of
21. What effect does cross-linking have on the physical properties these classes of bacteria?
of plastics and rubbers?
28. Why is addition of a molecule across a double bond of the ring
22. What are the cis and trans isomers of polybutadiene called? an unfavorable reaction for benzene, compared with substitution
How does their molecular structure account for their differences in around the edge of the ring?
physical properties?
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Problem 1
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Problem 2
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Problems 3-6
3. Draw all the possible structures for the compounds having the 6. What is the systematic name of each of the following
following formulas. Give their systematic names. compounds?
(a)C3H8
(b)C3H4
(c)C4H8
(d)C3H5Cl
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Problems 7-10
7. Draw the structural formula for each of the following 10. Write the structural formulas of
compounds: (a) five different, simple alkanes;
(a) trans-2-hexene (b)five different, simple alkenes (only one double bond);
(b) cis-2,3-dichloro-2-butene (c) five different, simple alkynes (only one triple bond);
(c) 1-methylcyclopentene (d) five different, simple cycloalkanes (only one ring).
(d) trans-1,2-dibromocyclohexane
(e) 4-ethyl-1-octene Show that they conform to the general formulas
(f) 3-hexyne CnH2n+2,CnH2n,CnH2n-2,and CnH2n, respectively.
(g) cis-diiodoethylene
(h)2-methyl-2-butene 11. A compound, A, has the formula C5H8.
(i)2-bromo-1,3-butadiene (a) What is the maximum number of rings it could contain?
(b) What is the maximum number of double bonds it could
contain?
8. Draw all the possible structural isomers of C5H1o. Give the
(c) What is the maximum number of triple bonds it could contain?
systematic name for each isomer.
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Problems 12-14
12. A hydrocarbon has a molecular weight of approximately 60
and contains 17.2% hydrogen. What is the molecular formula of
the hydrocarbon? Write all of the structural isomers that have this
formula.
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Problems 12-14
12. A hydrocarbon has a molecular weight of approximately 60
and contains 17.2% hydrogen. What is the molecular formula of
the hydrocarbon? Write all of the structural isomers that have this
formula.
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