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Unit
Natural Compounds
2.2 Hydrocarbons
organic compounds containing only the elements carbon and hydrogen are called
hydrocarbons. The hcs are broadly divided into aliphaic hcs and aromatic hcs.
We use hydrocarbons every day, mainly as fuels, such as natural gas, acetylene,
propane, butane, and the principal components of gasoline, diesel fuel, and heating
oil. The familiar plastics polyethylene, polypropylene, and polystyrene are also
hydrocarbons.
Classification of hydrocarbons
Hydrocarbons are further broadly classified into aliphatic and aromatic hydrocarbons
constitutional isomers are also commonly used). Constitutional isomers have the
same molecular formula but different spatial arrangements of the atoms in their
molecules.
We use the term normal, or the prefix n, to refer to a chain of carbon atoms
carbon atom in the center of the Lewis structure is bonded to three other carbon
atoms)
The Basics of Organic Nomenclature: Naming Alkanes
The International Union of Pure and Applied Chemistry (IUPAC) has devised a
system of nomenclature that begins with the names of the alkanes and can be
adjusted from there to account for more complicated structures.
The nomenclature for alkanes is based on rules:
IUPAC Rules for Alkane Nomenclature
1.Find and name the longest continuous carbon chain.
2. Identify and name groups attached to this chain.
3. Number the chain consecutively, starting at the end nearest a substituent group.
4. Designate the location of each substituent group by an appropriate number and
name.
5. Assemble the name, listing groups in alphabetical order.
6. The prefixes di, tri, tetra etc., are used to designate several groups of the same
kind.
Alkyl Groups
An alkyl group is formed by removing one hydrogen from the alkane chain and is
described by the formula CnH2n+1. The removal of this hydrogen results in a stem
change from -ane to -yl. Take a look at the following examples. R stands for any
alkyl group
The names and formulas for various alkyl groups formed by the removal of hydrogen
atoms from different locations are given below.
Give the IUPAC name of the following structure
5,7-diethyl-3,4,7-trimethyl-5-propyldecane
The identical substituents are grouped by first specifying the number of their
positions, and then by adding a prefix to denote the number of groups: di for two,
tri for three, tetra for four, penta for five, etc. The compound below is correctly
named by IUPAC rules as 2,2,4-trimethylhexane. The numbers must be separated
by commas and followed by a hyphen.
1.
2.
Chemical reactions of alkanes
a) Combustion
CH4(g)+2O2(g)⟶CO2(g)+2H2O(g)
Alkenes
Carbon atoms linked by a double bond are bound together by two bonds, one σ
bond and one π bond.
Ethene, C2H4, is the simplest alkene. Each carbon atom in ethene, commonly
called ethylene, has a trigonal planar structure. The second member of the series
is propene (propylene) .
1. Combustion Reactions
CnH2n + 1.5nO2 ---> n CO2 + n H2O
Hydrogenation generally requires a catalyst such as Pt, Pd and may also require
heat and / or pressure.
The double bond reacts rapidly at room temp with either Cl2 or Br2. No catalyst is
needed. F>> Cl > Br >>> I (iodine hardly reacts, fluorine reacts explosively).
Halogenation can be used as a qualitative test for alkenes
Suspect compound + dilute solution of Br2. If red color disappears then the
compound is probably an alkene.
c. Addition of water = Hydration
In the presence of acid, water adds to an alkene double bond.
The IUPAC nomenclature for alkynes is similar to that for alkenes except that the
suffix -yne is used to indicate a triple bond in the chain.
For example, CH3CH2C≡CH is called 1-butyne.
Chemical reactions of alkynes
Chemically, the alkynes are similar to the alkenes.
1. Addition Reactions
The principal reaction of the alkynes is addition across the triple bond to form
alkanes. These addition reactions are analogous to those of the alkenes.
Since the C≡C functional group has two π bonds, alkynes typically react even
more readily, and react with twice as much reagent in addition reactions. The
reaction of acetylene with bromine is a typical example:
a) Hydrogenation. Alkynes undergo catalytic hydrogenation with the same
catalysts used in alkene hydrogenation: platinum, palladium, nickel, and
rhodium.
Hydrogenation proceeds in a stepwise fashion, forming an alkene first, which
undergoes further hydrogenation to an alkane.
b) Halogenation.
The addition of halogens to an alkyne proceeds in the same manner as halogen
addition to alkenes. The halogen atoms add to an alkyne molecule in a stepwise
fashion, leading to the formation of the corresponding alkene, which undergoes
further reaction to a tetrahaloalkane.
c) Hydrohalogenation.
Hydrogen halides react with alkynes in the same manner as they do with alkenes.
Both steps in the above addition follow the Markovnikov rule. Thus, the addition
of hydrogen bromide to 1‐butyne gives 2‐bromo‐1‐butene as the major product
of the first step.
d) Hydration.
The addition of the elements of water across the triple bond of an alkyne leads to
the formation of aldehydes and ketones.
Water addition to terminal alkynes leads to the generation of aldehydes, while
nonterminal alkynes and water generate ketones.
Water adds across the triple bond of an alkyne via a carbocation mechanism.
Dilute mineral acid and mercury(II) ions are needed for the reaction to occur.
2.Oxidation.
Alkynes are oxidized by the same reagents that oxidize alkenes.
Disubstituted alkynes react with potassium permanganate to yield vicinal diketones
(Vic‐diketones or 1,2‐diketones) or, under more vigorous conditions, carboxylic
acids.
3. Combustion .
Alkynes, like other hydrocarbons, undergo combustion, producing carbon
dioxide and water (with complete combustion) or mixtures of carbon dioxide,
carbon monoxide, carbon, and water (with incomplete combustion).
4. Polymerization.
Alkynes can be polymerized by both cationic and free‐radical methods. The
reactions and mechanisms are identical with those of the alkenes.
2.2.3 Aromatic Hydrocarbons
Benzene, C6H6, is the simplest member of a large family of hydrocarbons, called
aromatic hydrocarbons.
drawn as a ring of six carbon atoms, with alternating double bonds and single bonds:
Carbon-carbon single bonds are longer than carbon-carbon double bonds, so if there were
"real" single and double bonds in the molecule, the shape of the benzene molecule would be a
distorted hexagon:
What is actually found is that all of the bond lengths in the benzene rings are
1.397A , which is roughly intermediate between the typical lengths of single bonds
(~1.5A) and double bonds (~1.3 A) .
All of the carbon atoms in the benzene rings are sp2-hybridized: the overlap of
the sp2 orbitals around the ring produces a framework of six sigma bonds, while the
unhybridized p-orbitals which are perpendicular to this plane overlap in a side-to-
side fashion to form three pi-bonds.
These pi-bonds are delocalized around the ring, leading to an unusual stability for
the benzene ring compared to other alkenes.
Thus benzene contain ring structures and exhibit bonding that must be described
using the resonance hybrid concept of valence bond theory or the delocalization
concept of molecular orbital theory. The resonance structures for benzene, C6H6 ,
are:
There are many derivatives of benzene. The hydrogen atoms can be replaced by
many different substituents.
Aromatic compounds more readily undergo substitution reactions than addition
reactions; replacement of one of the hydrogen atoms with another substituent will
leave the delocalized double bonds intact.
The following are typical examples of substituted benzene derivatives:
Toluene and xylene are important solvents and raw materials in the chemical
industry. Styrene is used to produce the polymer polystyrene.
A few another derivatives of benzene
Reactions of Benzene and Its Derivatives
Ethanol is the alcohol produced by some species of yeast that is found in wine, beer,
and distilled drinks. It has long been prepared by humans harnessing the metabolic
efforts of yeasts in fermenting various sugars.
Large quantities of ethanol are synthesized from the addition reaction of
water with ethylene using an acid as a catalyst
ethylene
ethanol
Alcohols containing two or more hydroxyl groups can be made. Examples
include 1,2-ethanediol (ethylene glycol, used in antifreeze) and 1,2,3-
propanetriol (glycerine, used as a solvent for cosmetics and medicines):
Classification of Alcohols
• Alcohols are classified as primary (1°), secondary (2°), or tertiary (3°) according to
how many carbon groups are attached to the carbon bearing the OH group:
• The number of hydrogens on the carbon bearing the OH group does affect some
chemical properties.
Numenclature of alcohols
The following is list of some common alcohols based on the IUPAC naming
system
In the body, oxidation of ethanol to acetaldehyde takes place in the liver; the
acetaldehyde is further oxidized to acetyl coenzyme A, which can be used to
synthesize fat or eventually be oxidized to water and carbon dioxide.
Oxidation of 2° Alcohols
• Secondary alcohols are oxidized to ketones, which cannot be oxidized any further:
Oxidation of 3° Alcohols
• Tertiary alcohols, because there is by definition no hydrogen on the alcoholic
carbon, cannot be oxidized:
b) Ethers
Ethers are compounds that contain the functional group –O–. Ethers do
not have a designated suffix like the other types of molecules we have
named so far.
In the IUPAC system, the oxygen atom and the smaller carbon branch
are named as an alkoxy substituent and the remainder of the molecule
as the base chain, as in alkanes. As shown in the following compound,
the red symbols represent the smaller alkyl group and the oxygen atom,
which would be named “methoxy.” The larger carbon branch would be
ethane, making the molecule methoxyethane.
Many ethers are referred to with common names instead of the IUPAC
system names. For common names, the two branches connected to the
oxygen atom are named separately and followed by “ether.”
Naming Ethers
Provide the IUPAC and common name for the ether shown here:
Solution
IUPAC: The molecule is made up of an ethoxy group attached to an ethane chain,
so the IUPAC name would be ethoxyethane.
Common: The groups attached to the oxygen atom are both ethyl groups, so the
common name would be diethyl ether.
Ethers can be obtained from alcohols by the elimination of a molecule of water from
two molecules of the alcohol. For example, when ethanol is treated with a limited
amount of sulfuric acid and heated to 140 °C, diethyl ether and water are formed:
In the general formula for ethers, R—O—R, the hydrocarbon groups (R) may be
the same or different. Diethyl ether, the most widely used compound of this
class, is a colorless, volatile liquid that is highly flammable. It was first used in
1846 as an anesthetic, but better anesthetics have now largely taken its place.
Diethyl ether and other ethers are presently used primarily as solvents for
gums, fats, waxes, and resins.
2.4 Aldehydes and Ketones
Both aldehydes and ketones contain a carbonyl group, a functional group with a
carbon-oxygen double bond.
The names for aldehyde and ketone compounds are derived using similar
nomenclature rules as for alkanes and alcohols, and include the class-identifying
suffixes -al and -one, respectively:
In an aldehyde, the carbonyl group is bonded to at least one hydrogen atom.
Aldehydes are commonly prepared by the oxidation of alcohols whose –OH functional
group is located on the carbon atom at the end of the chain of carbon atoms in the
alcohol
Alcohols that have their –OH groups in the middle of the chain are necessary to
synthesize a ketone, which requires the carbonyl group to be bonded to two other
carbon atoms:
Formaldehyde
It is an aldehyde with the formula HCHO. It is a colorless gas with a pungent and
proteins, so it kills bacteria (and any other living organism) and stops many of
propanol.
Acetone is a colorless liquid. Among its many uses are as a solvent for lacquer
plastics, and varnishes; as a paint and varnish remover; and as a solvent in the
carboxylic acid dissolved in water are ionized at any given time. The remaining
functional group is located on the carbon atom at the end of the chain of carbon
7. Decarboxylation
Decarboxylation reaction occurs when soda lime (NaOH + CaO) is distilled with
sodium salts of carboxylic acids, resulting in alkanes.
8. Formation of Anhydrides
Acid anhydrides are formed when two molecules of carboxylic acid are heated with
a dehydrating agent such as phosphorus pentoxide.
2RCOOH ⇢ RCO-O-RCO + H2O
Esters are produced by the reaction of acids with alcohols. For example, the ester
ethyl acetate, CH3CO2CH2CH3, is formed when acetic acid reacts with ethanol:
The simplest carboxylic acid is formic acid, HCO2H, known since 1670. Its name
comes from the Latin word formicus, which means “ant”; it was first isolated by
the distillation of red ants.
It is partially responsible for the pain and irritation of ant and wasp stings, and is
responsible for a characteristic odor of ants that can be sometimes detected in
their nests.
Acetic acid, CH3CO2H, constitutes 3–6% vinegar. Cider vinegar is produced by
allowing apple juice to ferment without oxygen present. Yeast cells present in
the juice carry out the fermentation reactions.
The fermentation reactions change the sugar present in the juice to ethanol, then
to acetic acid. Pure acetic acid has a penetrating odor and produces painful burns.
It is an excellent solvent for many organic and some inorganic compounds, and it is
essential in the production of cellulose acetate, a component of many synthetic
fibers such as rayon.
Esters
Esters are present in a many biologically important molecules, which have a wide
range of effects.
Esters include compounds such as fats, waxes, Vitamin C, Cocaine, Novacaine, oil
of wintergreen, and aspirin.
Esters are compounds often the sources of the pleasant aromas of many fruits.
Mthylethanoate Ethylbutanoate
The distinctive and attractive odors and flavors of many flowers, perfumes,
and ripe fruits are due to the presence of one or more esters.
Among the most important of the natural esters are fats (such as lard,
tallow, and butter) and oils (such as linseed, cottonseed, and olive oils),
which are esters of the trihydroxyl alcohol glycerine, C3H5(OH)3, with large
Palmitic and stearic acids are saturated acids that contain no double or triple
bonds.
Reactions of Esters
1. Conversion of Esters to Carboxylic Acids:
Hydrolysis
Esters can be cleaved back into a carboxylic acid and an alcohol through reaction
with water and a catalytic amount of strong acid. This reaction represents the
reverse of the acid catalyzed esterification of a carboxylic acid and an alcohol
Conversion of Esters to Carboxylic Acids: Saponification
Esters can also be cleaved into a carboxylate and an alcohol through reaction
with water and a base. The reaction is commonly called a saponification from
the Latin sapo which means soap. This name comes from the fact that soap
used to me made by the ester hydrolysis of fats.
Saponification reaction utilize a better nucleophile (hydroxide) and are typically
faster than an acid catalyzed hydrolysis. The carboxylation ions produced by
saponification are negatively charged and very unreactive toward further
nucleophilic substitution which makes the reaction irreversible.
Conversion of Ester to Amides: Aminolysis
It is possible to convert esters to amides through direct reaction with ammonia or
amines. However, these reactions are not commonly used because the formation of an
amide using an acid chloride is a much simpler reaction.
2.6 Amines and Amides
a) Amines
Amines are molecules that contain carbon-nitrogen bonds. The nitrogen atom
in an amine has a lone pair of electrons and three bonds to other atoms, either
carbon or hydrogen. Various nomenclatures are used to derive names for
amines, but all involve the class-identifying suffix –ine as illustrated here for a
few simple examples:
In some amines, the nitrogen atom replaces a carbon atom in an aromatic
hydrocarbon.
Pyridine is one such heterocyclic amine. A heterocyclic compound contains
atoms of two or more different elements in its ring structure.
Like ammonia, amines are weak bases due to the lone pair of electrons on their
nitrogen atoms:
The basicity of an amine’s nitrogen atom plays an important role in much of the
compound’s chemistry.
natural and synthetic dyes, polymers, vitamins, and medications such as penicillin
and codeine.
They are also found in many molecules essential to life, such as amino acids,
A water molecule is eliminated from the reaction, and the amide is formed from
the remaining pieces of the carboxylic acid and the amine (note the similarity to
previous section)
:
The reaction between amines and carboxylic acids to form amides is biologically
important.
It is through this reaction that amino acids (molecules containing both amine and