Aliphatic Hydrocarbons
Classification of Organic Compounds
Alkanes
Sources of Alkanes: Petroleum
The primary source of alkanes is petroleum. Petroleum is a complex mixture
of organic compounds, most of which are alkanes and aromatic hydrocarbons. It also
contains small amounts of oxygen-, nitrogen-, and sulfur-containing compounds.
Some of the molecules in petroleum are clearly of biological origin. The natural
origin of petroleum is still under debate, however. Many scientists believe petroleum
originated with decay of primordial biological matter. Recent theories suggest,
however, that organic molecules may have been included as Earth formed by
accretion of interstellar materials.
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Shapes of Alkanes
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IUPAC Nomenclature of Alkanes
Nomenclature of Unbranched Alkyl Groups
If we remove one hydrogen atom from an alkane, we obtain what is called an
alkyl group. These alkyl groups have names that end in -yl. When the alkane is
unbranched, and the hydrogen atom that is removed is a terminal hydrogen atom,
the names are straightforward:
Nomenclature of Branched-Chain Alkanes
Branched-chain alkanes are named according to the following rules:
1. Locate the longest continuous chain of carbon atoms; this chain determines
the parent name for the alkane. We designate the following compound, for
example, as a hexane because the longest continuous chain contains six carbon
atoms:
The longest continuous chain may not always be obvious from the way the formula is
written. Notice, for example, that the following alkane is designated as a heptane
because the longest chain contains seven carbon atoms:
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2. Number the longest chain beginning with the end of the chain nearer the
substituent. Applying this rule, we number the two alkanes that we illustrated
previously in the following way:
3. Use the numbers obtained by application of rule 2 to designate the location of
the substituent group. The parent name is placed last, and the substituent group,
preceded by the number designating its location on the chain, is placed first.
Numbers are separated from words by a hyphen. Our two examples are 2-
methylhexane and 3-methylheptane, respectively:
4. When two or more substituents are present, give each substituent a number
corresponding to its location on the longest chain. For example, we designate the
following compound as 4-ethyl-2-methylhexane:
5. When two substituents are present on the same carbon atom, use that number
twice:
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6. When two or more substituents are identical, indicate this by the use of the
prefixes di-, tri-, tetra-, and so on. Then make certain that each and every
substituent has a number. Commas are used to separate numbers from each other:
Application of these six rules allows us to name most of the alkanes that we shall
encounter. Two other rules, however, may be required occasionally:
7. When two chains of equal length compete for selection as the parent chain,
choose the chain with the greater number of substituents:
8. When branching first occurs at an equal distance from either end of the
longest chain, choose the name that gives the lower number at the first point of
difference:
Preparation of Alkanes
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Conformation of Alkanes
Different arrangements of aton1s that can be converted into one another by
rotation about single bonds are called conformations. I is called the eclipsed
conformation; II is called the staggered conformation. (The infinity of intermediate
conformations are called skew conformations.)
(a) The staggered conformation of ethane. (b) The Newman projection formula for the staggered
conformation. (c) The dihedral angle between these hydrogen atoms is 60°.
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Physical Properties of Alkanes
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Reactions of Alkanes
Decomposition of a compound by the action of heat alone is known as
pyrolysis. This word is taken from the Greek pyr, fire, and lysis, a loosing, and hence
to chemists means “cleavage by heat”.
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Bromination gives the corresponding bromides but in different proportions:
Mechanism of halogenation
Halogenation of alkanes proceeds by the same mechanism as halogenation of
methane:
A halogen atom abstracts hydrogen from the alkane (RH) to form an alkyl
radical (R#). The radical in turn abstracts a halogen atom from a halogen molecule to
yield the alkyl halide (RX).
Which alkyl halide is obtained depends upon which alkyl radical is formed.
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Study of the chlorination of a great many alkanes has shown that these are
typical results. After allowance is made for differences in the probability factor, the
rate of abstraction of hydrogen atoms is always found to follow the sequence 3° > 2°
> 1°.
At room temperature, for example, the relative rates per hydrogen atom are
5.0 : 3.8 : 1.0. Using these values we can predict quite well the ratio of isomeric
chlorination products from a given alkane. For example:
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Alkenes
Nomenclature of Alkenes and Cycloalkenes:
Many older names for alkenes are still in common use. Propene is often called
propylene, and 2-methylpropene frequently bears the name isobutylene:
The IUPAC rules for naming alkenes are similar in many respects to those for
naming alkanes:
1. Determine the parent name by selecting the longest chain that contains the
double bond and change the ending of the name of the alkane of identical length
from –ane to -ene. Thus, if the longest chain contains five carbon atoms, the parent
name for the alkene is pentene; if it contains six carbon atoms, the parent name is
hexene, and so on.
2. Number the chain so as to include both carbon atoms of the double bond, and
begin numbering at the end of the chain nearer the double bond. Designate the
location of the double bond by using the number of the first atom of the double
bond as a prefix. The locant for the alkene suffix may precede the parent name
or be placed immediately before the suffix. We will show examples of both styles:
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3. Indicate the locations of the substituent groups by the numbers of the carbon
atoms to which they are attached:
4. Number substituted cycloalkenes in the way that gives the carbon atoms of
the double bond the 1 and 2 positions and that also gives the substituent groups
the lower numbers at the first point of difference. With substituted cycloalkenes it
is not necessary to specify the position of the double bond since it will always begin
with C1 and C2. The two examples shown here illustrate the application of these
rules:
5. Name compounds containing a double bond and an alcohol group as alkenols
(or cycloalkenols) and give the alcohol carbon the lower number:
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6. Two frequently encountered alkenyl groups are the vinyl group and the allyl
group:
Using substitutive nomenclature, the vinyl and allyl groups are called ethenyl and
prop-2-en-1-yl, respectively. The following examples illustrate how these names are
employed:
7. If two identical or substantial groups are on the same side of the double bond,
the compound can be designated cis; if they are on opposite sides it can be
designated trans:
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Industrial source
Alkenes are obtained in industrial quantities chiefly by the cracking of
petroleum. The smaller alkenes can be obtained in pure form by fractional distillation
and are thus available for conversion into a large number of important aliphatic
compounds. Higher alkenes, which cannot be separated from the complicated
cracking mixture, remain as valuable components of gasoline.
1-Alkenes of even carbon number, consumed in large quantities in the
manufacture of detergents, are available through controlled ionic polymerization of
ethylene by the Ziegler-Natta method.
General methods for the preparation of Alkenes
Mechanism of dehydrohalogenation:
The function of hydroxide ion is to pull a hydrogen ion away from carbon;
simultaneously a halide ion separates and the double bond forms. We should notice
that, in contrast to free radical reactions, the breaking of the C−H and C−X bonds
occurs in an unsymmetrical fashion: hydrogen relinquishes both electrons to carbon,
and halogen retains both electrons. The electrons left behind by hydrogen are now
available for formation of the second bond (the π bond) between the carbon atoms.
What supplies the energy for the breaking of the C−H and C−X bonds?
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(a) First, there is formation of the bond between the hydrogen ion and the very
strong base, hydroxide ion.
(b) Next, there is formation of the π bond which, although weak, does supply
about 70 kcal/mole of energy.
Orientation and reactivity in dehydrohalogenation
In cases where a mixture of isomeric alkenes can be formed, which isomer, if
any, will predominate? Study of many dehydrohalogenation reactions has shown that
one isomer generally does predominate, and that it is possible to predict which
isomer this will be − that is, to predict the orientation of elimination on the basis of
molecular structure.
Ease of formation of alkenes:
R 2 C=CR 2 > R 2 C=CHR > R 2 C=CH 2 , RCH=CHR > RCH=CH 2
Stability of alkenes
R 2 C=CR 2 > R 2 C=CHR > R 2 C=CH 2 , RCH=CHR > RCH=CH 2 > CH 2 =CH2
In dehydrohalogenation, the more stable the alkene the more easily it is formed.
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Mechanism of dehydration of alcohols
The generally accepted mechanism for the dehydration of alcohols is
summarized in the following equations. The alcohol unites (step 1) with a hydrogen
ion to form the protonated alcohol, which dissociates (step 2) into water and a
carbonium ion; the carbonium ion then loses (step 3) a hydrogen ion to form the
alkene.
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Rearrangement of carbonium ions:
Very often, dehydration gives alkenes that do not fit the mechanism as we
have so far seen it. The double bond appears in unexpected places; sometimes the
carbon skeleton is even changed. For example:
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Physical properties
As a class, the alkenes possess physical properties that are essentially the same
as those of the alkanes. They are insoluble in water, but quite soluble in nonpolar
solvents like benzene, ether, chloroform, or ligroin. They are Jess dense than water.
The boiling point rises with increasing carbon number; as with the alkanes, the
boiling point rise is 20-30° for each added carbon, except for the very small
homologs. As before, branching lowers the boiling point.
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Like alkanes, alkenes are at most only weakly polar. Since the loosely held π
electrons of the double bond arc easily pulled or pushed, dipole moments are larger
than for alkanes.
Reactions of the carbon -carbon double bond: addition
Alkene chemistry is the chemistry of the carbon−carbon double bond.
What kind of reaction may we expect of the double bond? The double bond
consists of a strong a bond and a weak π bond; we might expect, therefore, that
reaction would involve the breaking of this weaker bond. This expectation is correct;
the typical reactions of the double bond are of the sort,
where the π bond is broken and two strong σ bonds are formed in its place.
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A reaction in which two molecules combine to yield a single molecule of
product is called an addition reaction.
Hydrogenation is exothermic: the two σ bonds (C−H) being formed are,
together, stronger than the σ bond (H−H) and π bond being broken. The quantity of
heat evolved when one mole of an unsaturated compound is hydrogenated is called
the heat of hydrogenation.
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A possible mechanism for the addition of a bromine or chlorine to an alkene is
one that involves the formation of a carbocation.
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Examination of a large number of such additions showed the Russian chemist
Vladimir Markovnikov (of the University of Kazan) that where two isomeric
products are possible, one product usually predominates. He pointed out in 1869 that
the orientation of addition follows a pattern which we can summarize as: In the ionic
addition of an acid to the carbon-carbon double bond of an alkene, the hydrogen of
the acid attaches itself to the carbon atom that already holds the greater number of
hydrogens. This statement is generally known as Markovnikov's rule.
Using Markovnikov's rule, we can correctly predict the principal product of
many reactions. For example:
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Mechanism:
Addition of the acidic reagent, HZ, is believed to proceed by two steps:
Step (1) involves transfer of hydrogen ion from : Z to the alkene to form a carbonium
ion; this is a transfer of a proton from one base to another.
Step (2) is the union of the carbonium ion with the base :Z.
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Electrophilic addition: orientation and reactivity
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Geometrical Isomerism
Earlier we learned to use the terms cis and trans to designate the
stereochemistry of alkene diastereomers. These terms are unambiguous, however,
only when applied to disubstituted alkenes. If the alkene is trisubstituted or
tetrasubstituted, the terms cis and trans are either ambiguous or do not apply at all.
Consider the following alkene as an example:
It is impossible to decide whether A is cis or trans since no two groups are the
same. A system that works in all cases is based on the priorities of groups in the
Cahn–Ingold–Prelog convention (Section 5.7). This system, called the (E)–(Z)
system, applies to alkene diastereomers of all types. In the (E)–(Z) system, we
examine the two groups attached to one carbon atom of the double bond and decide
which has higher priority. Then we repeat that operation at the other carbon atom:
We take the group of higher priority on one carbon atom and compare it with
the group of higher priority on the other carbon atom. If the two groups of higher
priority are on the same side of the double bond, the alkene is designated (Z) (from
the German word zusammen, meaning together). If the two groups of higher priority
are on opposite sides of the double bond, the alkene is designated (E) (from the
German word entgegen, meaning opposite).
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The following example illustrates this:
The two stereoisomers of 1-bromo-1,2-dichloroethene cannot be designated as
cis and trans in the normal way because the double bond is trisubstituted. They can,
however, be given (E) and (Z) designations. Write a structural formula for each
isomer and give each the proper designation.
Strategy and answer: We write the structures (below), then note that chlorine
has a higher priority than hydrogen, and bromine has a higher priority than chlorine.
The group with higher priority on C1 is bromine and the group with higher priority at
C2 is chlorine. In the first structure the higher priority chlorine and bromine atoms
are on opposite sides of the double bond, and therefore this isomer is (E). In the
second structure those chlorine and bromine atoms are on the same side, so the latter
isomer is (Z).
Uses of Alkenes:
Alkenes are used as starting materials in the synthesis of alcohols, plastics,
detergents, and fuels. The most important alkenes for the chemical industry are
ethene, propene, and 1,3-butadiene. Ethene is the most important organic feedstock
in the chemical industry.
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Dienes
Alkadienes and Polyunsaturated Hydrocarbons
Many hydrocarbons are known that contain more than one double or triple
bond. A hydrocarbon that contains two double bonds is called an alkadiene; one that
contains three double bonds is called an alkatriene, and so on. Colloquially, these
compounds are often referred to simply as dienes or trienes. A hydrocarbon with two
triple bonds is called an alkadiyne, and a hydrocarbon with a double and triple bond
is called an alkenyne.
The following examples of polyunsaturated hydrocarbons illustrate how
specific compounds are named. Recall from IUPAC rules that the numerical locants
for double and triple bonds can be placed at the beginning of the name or
immediately preceding the respective suffix. We provide examples of both styles.
The multiple bonds of polyunsaturated compounds are classified as being
cumulated, conjugated, or isolated.
The double bonds of a 1,2-diene (such as 1,2-propadiene, also called allene)
are said to be cumulated because one carbon (the central carbon) participates in two
double bonds.
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Hydrocarbons whose molecules have cumulated double bonds are called
cumulenes. The name allene (Section 5.18) is also used as a class name for
molecules with two cumulated double bonds:
An example of a conjugated diene is 1,3-butadiene.
In conjugated polyenes the double and single bonds alternate along the chain:
If one or more saturated carbon atoms intervene between the double bonds of
an alkadiene, the double bonds are said to be isolated.
An example of an isolated diene is 1,4-pentadiene:
The Diels–Alder Reaction: A 1,4-Cycloaddition Reaction of Dienes
In 1928 two German chemists, Otto Diels and Kurt Alder, developed a 1,4-
cycloaddition reaction of dienes that has since come to bear their names. The
reaction proved to be one of such great versatility and synthetic utility that Diels and
Alder were awarded the Nobel Prize in Chemistry in 1950.
An example of the Diels–Alder reaction is the reaction that takes place when
1,3-butadiene and maleic anhydride are heated together at 100 °C. The product is
obtained in quantitative yield:
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In general terms, the Diels–Alder reaction is one between a conjugated diene
(a 4π-electron system) and a compound containing a double bond (a 2π-electron
system) called a dienophile (diene+philein, Greek: to love). The product of a Diels–
Alder reaction is often called an adduct.
In the Diels–Alder reaction, two new σ bonds are formed at the expense of two
p bonds of the diene and dienophile. The adduct contains a new six-membered ring
with a double bond. Since s bonds are usually stronger than π bonds, formation of the
adduct is usually favored energetically, but most Diels–Alder reactions are
reversible.
We can account for all of the bond changes in a Diels–Alder reaction by using
curved arrows in the following way:
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Free-radical polymerization of alkenes
When ethylene is heated under pressure with oxygen, there is obtained a
compound of high molecular weight (about 20 000), which is essentially an alkane
with a very long chain. This compound is made up of many ethylene units and hence
is called polyethylene. It is familiar to most of us as the plastic material of packaging
films.
The formation of polyethylene is a simple example of the process called
polymerization: the joining together of many small molecules to form very large
molecules. The compound composed of these very large molecules is called a
polymer (Greek: poly + meros, many parts).The simple compounds from which
polymers are made are called monomers (mono, one).
Polymerization of substituted ethylenes yields compounds whose structures
contain the long chain of polyethylene, with substituents attached at more or less
regular intervals. For example, vinyl chloride yields poly(vinyl chloride), used to
make phonograph records, plastic pipe, and—when plasticized with highboiling
esters—raincoats, shower curtains, and coatings for metals and upholstery fabrics.
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Many other groups (e.g., −COOCH 3 , −CH 3 , −C 6 H 5 ) may be attached to the
doubly bonded carbons. These substituted ethylenes polymerize more or less readily,
and yield plastics of widely differing physical properties and uses, but the
polymerization process and the structure of the polymer are basically the same as for
ethylene or vinyl chloride.
Polymerization requires the presence of a small amount of an initiator.
Among the commonest of these initiators are peroxides, which function by breaking
down to form a free radical. This radical adds to a molecule of alkene, and in doing
so generates another free radical. This radical adds to another molecule of alkene to
generate a still larger radical, which in turn adds to another molecule of alkene, and
so on. Eventually the chain is terminated by steps, such as union of two radicals that
consume but do not generate radicals.
This kind of polymerization, each step of which consumes a reactive particle
and produces another, similar particle, is an example of chain-reaction
polymerization.
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Alkynes
IUPAC naming of alkynes
The rules are exactly the same as for the naming of alkenes, except that the
ending -yne replaces -ene. The parent structure is the longest continuous chain that
contains the triple bond, the positions both of substituents, and of the triple bond are
indicated by numbers. The triple bond is given the number of the first triply-bonded
carbon encountered, starting from the end of the chain nearest the triple bond.
Physical properties of alkynes
Being compounds of low polarity, the alkynes have physical properties that are
essentially the same as those of the alkanes and alkenes. They are insoluble in water
but quite soluble in the usual organic solvents of low polarity: ligroin, ether, benzene,
carbon tetrachloride. They are less dense than water. Their boiling points show the
usual increase with increasing carbon number, and the usual effects of chain-
branching; they are very nearly the same as the boiling points of alkanes or alkenes
with the same carbon skeletons.
Industrial source of acetylene
The alkyne of chief industrial importance is the simplest member of the
family, acetylene. It is made by the controlled, high-temperature partial oxidation of
methane.
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Preparation of alkynes
Reactions of alkynes
Addition reactions
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A triply-bonded carbon acts as though it were an entirely different element − a
more electronegative one − from a carbon having only single or double bonds. As a
result, hydrogen attached to triply-bonded carbon, as in acetylene or any alkyne with
the triple bond at the end of the chain (RC≡C−H), shows appreciable acidity. For
example, sodium reacts with acetylene to liberate hydrogen gas and form the
compound sodium acetylide.
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