Organic Chemistry Sources, Composition and Number of Organic Compounds

Major source – life related materials:

Definition Plants, animals, microorganisms, coal, and petroleum
• Study of carbon and carbon compounds. Many organic compounds are synthetically prepared from inorganic
o Not too accurate since many chemists consider some sources.
compounds that contain carbon as inorganic. Some of organic compounds derived from these sources are:
Ex. CO, CO2, Na2CO3, CaCO3 1. Plants - starch, cellulose
2. Animals - fats, proteins
3. Coal - coal tar, drugs, benzene, phenol
• Study of hydrocarbons (compounds made up exclusively of 4. Wood - wood alcohol, acetone, acetic acid
carbon and hydrogen) and their derivatives (as compounds 5. Petroleum - gasoline, kerosine, fuel oils
derived from hydrocarbon) 6. Natural Gas - methane
7. Fermentation processes - ethyl alcohol, acetone
Original Concept of Organic Chemistry: “The Vital Force Theory” 8. Laboratory synthesis
• The Vital Force Theory held that organic substances could • The elements that make up most organic compounds:
originate only from living material, that is, organic compounds o Carbon, hydrogen, oxygen, phosphorus, sulfur, the
were exclusively of plant and animal origin and that artificial halogens (Cl, Br, I)
preparation of these compounds was considered impossible.
• No organic compounds could be formed or produced without
the aid of a “vital force” supplied by living cells.
Importance of Organic Chemistry
o Vital force is a special energy or force belonging only
to the plant and animal cells • composition of organisms and other materials that we use
• This vital force theory was overthrown when several organic daily
substances were produced from non-living sources. It was • It has contributed much to the advances in medical science.
contradicted when a scientist named Wohler made urea by
heating ammonium cyanate (NH4OCN) which is an inorganic Comparison of Organic and Inorganic Compounds
compound.
o NH4OCN NH2CONH2 Organic Inorganic
Ammonium cyanide urea low boiling point high boiling point
o Urea is an authentic organic substance because it is low melting point high melting point
a product of metabolism which had been isolated from low solubility in water high solubility in water
urine. high solubility in nonpolar low solubility in nonpolar
o Inorganic as well as organic substances could be solvents solvents
used as raw materials. Out of this development has flammable non flammable
come synthetic organic compounds hence, organic covalent bonding ionic bonding
chemistry attains ever-increasing importance solutions are nonconductors of solutions are conductors of
electricity electricity
exhibit isomerism isomerism is limited
less stable towards heat stable towards heat
rarely ionize ionize readily
less reactive more reactive
 o The convention followed in the systematic | Secondary propyl or sec-
nomenclature of organic compounds was set up by CH3 propyl or isopropyl
the IUPAC (International Union of Pure and Applied CH3CH2CH2CH3 CH3CH2CH2CH2-- N-butyl
Chemistry) and is called the IUPAC system. Normal butane CH3CHCH2CH3 Sec-butyl
o Alkanes are named according to the number of |
carbon atoms contained in each molecule. Each CH3CH-CH2-- Isobutyl
name consists of a root that tells the number of |
carbon atoms, followed by the suffix -ane. CH3
• Homologous series - only differ in a CH2 (methylene group) CH3CHCH3 |
| CH3CCH3
t-butyl
CH3 |
Isobutane CH3

• The IUPAC rules for naming alkanes are:

1. Select the longest continuous chain of carbon atoms as
the parent compounds and consider all alkyl groups
attached

2. Number the chain from either end such that the

substituents are attached at the lower numbers.

3. Substituent groups are assigned the number of the

• Alkyl Groups carbon to which they are attached.
- General Formula: CnH2n+1
- One less hydrogen atom than the corresponding
alkane
-
R=CnH2n+1 (any alkyl group) 4. The name of the compound is now composed of the
ALKANE ALKYL GROUP NAME name of the parent compound preceded by the names
CH4 of the substituents in alphabetical order.
CH3 -- Methyl
Methane
CH3CH3
CH3CH2 -- Ethyl
Ethane
CH3CH2CH3 CH3CH2CH3-- Normal propyl or n-propyl
Propane CH3CH--
 5. If the substituent occurs more than once in the
molecule, the prefixes di-, tri-, tetra- and so on are used
to indicate how many it occurs. If the substituent occurs
twice on the same carbon, the number is repeated.
6. Separate numbers from names by a dash, from each
other by a comma.
7. The IUPAC name is written as one word.
• To write a structural formula from a systematic name, the
naming process is reversed.
|
CH3
• Cycloalkanes
o Cyclic aliphatic hydrocarbons or alicyclic compounds
are merely alkane chains that exist in the form of a
ring.
o Cyclic or closed-chain alkanes exist and called
cycloalkanes, cycloparaffins or naphtenes (with
general formula of CnH2n)
o Alicyclic compounds are named in the same way as
the aliphatic hydrocarbons except that the parent
name which indicates the number of carbon atoms I
the ring is preceded by the prefix cyclo-.

• Common or Trivial Names of Alkanes • Alkyl Halides

n-butane CH3CH2CH2CH3 o The letter X is commonly used to indicate a halogen
isobutane CH3CHCH3 atom attached to an alkyl group and represents the
| class of compounds known as the alkyl halides. When
CH3 R=CH3, CH3X can be CH3F, CH3Cl, CH3Br, or CH3I
n-pentane CH3CH2CH2CH2CH3 o Halogen atoms are identified as fluoro-, chloro-,
isopentane CH3CHCH2CH3 bromo-, or iodo- and are named as substituents like
| side-chain alkyl groups.
CH3
neopentane CH3
|
CH3 – C – CH3
 RCOONa + NaOH CaO Na2CO3 + RH
• Kinds of Carbon Atoms Salt of an acid alkane
1. Primary carbon atom (1) – a carbon atom that is attached
to only one carbon atom.
2. Secondary carbon atom (2) – a carbon atom that is
attached to two other carbon atoms.
3. Tertiary carbon atom (3) – a carbon atom that is attached
to two other carbon atoms
4. Quaternary carbon atoms (4) – a carbon atom that is
attached to four other carbon atoms.
2. Wurtz Synthesis
- A reaction between metallic sodium and an alkyl
halide (RX) in dry ether (ether that is free of water
and alcohol). This has limitations in the
preparations of hydrocarbons containing an odd
• Sources of Alkanes number of carbon atoms.
o Two principal large – scale sources of alkanes: 2RX + 2Na dry ether 2NaX + RR
natural gas and petroleum. Most often found in the alkane
underground deposits, frequently in the presence of
one another.
§ Petroleum and natural gas are the products
of the decomposition of prehistorical animal
and vegetable deposits.
o Methane, the principal component of natural gas is a
frequent product of biologic processes and is even
found in small amounts in human breath.
o Petroleum is an oily, viscous liquid which varies in
appearance from dark yellow to brown to greenish
black. 3. Grignard Reaction
• Preparation of Alkanes a. Preparation of Grignard reagent
1. Soda-lime Process - Grignard reagent is prepared by the reaction
- A decarboxylation method where the alkane between an alkyl halide and magnesium in dry
prepared has one carbon atom less than the ether.
carboxylate.
- Soda-lime is an intimate mixture of sodium hydroxide RX + Mg dry ether RMgX
and calcium oxide. Calcium oxide does not take part Grignard reagent
in the reaction. It only prevents etching of glass. (alkyl magnesium halide)
- This is done by heating soda-lime with sodium salt of b. Hydrolysis of Grignard reagent
an organic acid. This method is used to prepare
methane in the laboratory. The methane gas is RMgX + HOH Mg(OH)X + RH
collected by water displacement because it is Magnesium alkane
insoluble in water. Hydroxy halide
 (basic salt) RH + HONO2 RNO2 + HOH
Over-all Reaction:
RX + Mg dry ether RMgX HOH. RH + Mg(OH)X

5. Halogenation (substitution of halogens for hydrogen)

- Useful industrial process. The reaction is initiated
by heat or ultraviolet (uv) light and results in the
substitution of a halogen atom for a hydrogen atom
with the generation of 1 mole of the corresponding
hydrohalic acid.
- The order of halogen reactivity being F2>Cl2>Br2> I2
- Fluorine is too reactive and Iodine is too unreactive,
• Chemical Properties thus, only Chlorine and Bromine is normally used.
1. Oxidation or Combustion
- Undergo combustion with oxygen with the evolution RH + X2 heat or uv light RX + HX
of large amounts of heat energy.
CH4 + 2O2 CO2 + 2H2O + 191.8 kcal
2. Alkanes are relatively inert
- inactive with aqueous reagents like water solution of
acids, bases, oxidizing agents, reducing agents, etc.
- only react with powerful reagents or under conditions
of high temperature and pressure or in the presence
of catalysts
Baeyer’s Test for Unsaturation
- test used to differentiate unsaturated hydrocarbons
from saturated. Reagent used is KMnO4.
- Saturated hydrocarbons do not react while
unsaturated hydrocarbons give a brown
precipitate, MnO2.
• Substitution Reactions 6. Pyrolysis or Cracking
3. Sulfonation (at an elevated temperature) - Heating to high temp. (400-700°C) in the absence
- Reaction of organic compounds with sulfuric acid to of air to avoid combustion.
form alkyl sulfonic acid. CH3CH2CH3 400-700°C CH3CH=CH2 + CH4 + H2
7. Alkanes being saturated hydrocarbons do not undergo
RH + HOSO3H RSO3H + HOH addition reactions.

• Physical Properties
1. C1 to C4 are gases; C5 to C15 are liquids, and higher
4. Vapor phase Nitration (Temp. 400°C) members are solids
- Formation of nitroalkane in the reaction between an 2. Insoluble in water but soluble in organic liquids
alkane and nitric acid. 3. Density is less than one, hence they float in water
 4. Boiling, melting points, viscosity, specific gravity CH3CH=CHCH3 2 – butene
increases with increasing molecular weight
5. Lower members are colorless, some higher members CH3–CH–CH=CH2 3 – methyl – 1 butene
have faint characteristics odors. |
CH3
• Uses of Alkanes
1. Gaseous alkanes are used as fuels CH3–CH2–CH2–CH–CH=CH2 3 – ethyl – 1 – hexene
2. Liquids alkanes are used as solvent, motor fuel, and |
illuminating fuel CH2–CH3
3. Solids alkanes are used in the manufacture of candles a. Trivial nomenclature is not extensive. Only
4. as insecticides ethylene, propylene and isobutylene are
5. used in the preparation of ointments commonly given nonsystematic names.
CH2=CH2 Ethylene

Alkenes, also known as olefins (oil-making) because oily liquids are CH3CH=CH2 Propylene
often obtained by combination of these hydrocarbons with reagents
such as halogens and halogen acids. CH3C=CH2 Isobutylene
• General Formula: CnH2n |
• Nomenclature CH3
o characterized by the presence of a double bond b. Occasionally, the ethylene group is named as a
between two carbon atoms which is indicated in the substituent when it is attached to a complicated
nomenclature of these hydrocarbons by the ending structure. It is known as the vinyl group.
-ene. CH2=CH – Vinyl group
• The IUPAC rules for naming alkenes are: CH2=CH – CH2 – Allyl Group
1. Select the longest carbon-carbon chain that contains 5. To write a structural formula from a systematic name,
the double bond. the naming process is reversed.
2. Name this parent compound as you would an alkane
but change the -ane ending to -ene.
3. Number the carbon chain of the parent compound
starting with the end nearer to the double bond. Use the
smaller of the two numbers on the double-bonded • Preparation of Alkenes
carbon atoms to indicate the position of the double o The most common methods of synthesizing alkene in
bond. Place this number in front of the alkene name. the laboratory involve elimination reactions. In this
4. Side chains and other groups are treated as in naming reaction a suitably substituted molecule is treated in
alkanes, by numbering and assigning them to the such a way that two adjacent groups are split out and
carbon atom to which they are bonded. a carbon-carbon double bond forms.
CH2=CH2 Ethene | |
–C–C– à C=C + A–B
CH3CH=CH2 Propene | |
CH3CH2CH=CH2 1 – butene 1. Dehydration of Alcohols (acid – catalyzed dehydration)
 - Alcohols when heated with acid catalyst readily X H
lose a molecule of water to give the corresponding
alkene. The most commonly employed catalysts
are sulfuric acid and phosphoric acid. The reaction
is carried out at 165 - 175°C.
| |
acid catalyst
–C–C– C=C + H2O
165 - 175°C
| |
OH H

3. Debromination of Dibromides
- Dibromoalkanes react with zinc to give alkenes
and a molecules of zinc bromide. Zinc is the metal
catalyst.
| |
– C – C – metal catalyst C=C + ZnBr2
- The dehydration of some alcohols can results in
| |
the formation of more than one alkene.
Br Br
o When two alkenes can form from a single
alcohol, the alkene that predominates is the one
with more alkyl substituents on the double bond.
This generalization is known as the Saytzeff
rule.

• Chemical Properties
2. Dehydrohalogenation of Alkyl Halides
- When alkyl halides are treated with potassium
hydroxide dissolved in ethanol KOH/C2H5OH, a
molecule of H – X is eliminated and the
corresponding alkene forms. Other basic reagents,
such as sodium hydroxide, will also initiate the
reaction but potassium hydroxide is most often
employed because of its relatively high solubility in
ethanol. The Saytzeff rule also applies here.
| |
– C – C – basic reagent C=C + HX
| |
4. Cracking of Paraffins
- At an elevated temperature, alkanes break into
smaller molecules.
C8H18 high T C4H8 + C3H6 + CH4
1. Combustion
- Burns in air with a luminous flame forming carbon
dioxide and water as products of combustion.
CH2 = CH2 + 3O2 2O2 + 2CO2
2. Oxidation (Baeyer’s test for unsaturation)
- A dilute solution of KMnO4 will oxidize an alkene. As
the unsaturated hydrocarbon is oxidized the
permanganate ion is reduced with the loss of the
purple color, and the appearance of a brown
precipitate MnO2.
 - There is a formation of a diol. This test is used to | |
differentiate saturated & unsaturated hydrocarbons.

3. Addition Reactions
a. Hydrogenation of Alkenes
- Mixing alkene with a metal catalyst – usually
platinum, palladium or nickel – and introducing
hydrogen gas.
| |
C=C + A–B -C–C- • Physical Properties
| | 1. C1 to C4 gases, C5 to C15 liquids, higher members are
A B solids.
2. Alkenes are colorless and lower members have sweet
odor.
3. Alkenes are slightly soluble in water.
4. They are less dense than water.

b. Halogenation of Alkenes • Uses of Alkanes

X 1. lower members are used as fuel
| | 2. ethylene is used in artificial ripening fruits
C=C + X2 -C–C- 3. butenes are used as fuels and rubber
| | 4. polyethylene mixtures – electrical insulators, hospital
X equipment, and household articles
5. ethylene dichloride – solvent and insecticide
6. ethylene oxide is used as fumigant

• Dienes
c. Addition of hydrogen halides or halogen acids (HX) o Alkenes that contain two double bonds.
- Alkenes react with HCl, HBr or HI to produce o General Formula: CnH2n-2
alkyl halides. o Nomenclature
- Markownikoff’s rule: when and - Parallel to that of alkenes except that two
unsymmetrical molecule such as HX adds to numbers are needed to indicate the positions in
a carbon-carbon double bond, the hydrogen the chain of the double bonds and -ene suffix of
from HX goes to the carbon atom that has the alkenes is replaced by the suffix -adiene.
the greater number of hydrogen atoms. - If the double bonds of a diene are separated by
H more than one single bond, the diene is called a
| | nonconjugated diene.
C = C + HX -C–C-
 3. Dehalogenation of Tetrahalides
X X
- If separated by only one single bond, the diene | |
is called a conjugated diene. R – C – C – R 2Zn R – C ≡ C – R + 2ZnBr2
| |
X X

• Polyenes
o Alkenes containing several double bonds.
o One of the most interesting and commercially
significant polyenes is rubber. Rubber, is an example
of a polymer, that consists of long-chain molecules
made up of repeating, small chemical units
(monomers) joined by chemical bonds. • Chemical Properties
1. Combustion
Alkynes, contain a carbon-carbon triple bond and are often referred - Acetylene burns with air to give intensely hot flame
to as acetylenes – comes from the common name of the first (oxyacetylene) used for cutting metals and for
member of this series, acetylene for H – C ≡ C – H. welding.
• General Formula: CnH2n-2 2CH2 ≡ CH + O2 4CO2 + H2O
• Nomenclature
o The same general rules are followed as with
alkenes, except that the ending in all cases is -yne.

• Preparation of Alkynes 2. Baeyer’s Test

1. Laboratory Preparation of Acetylene 3H–C≡C–H + 10KMnO4 + 2H2O 10KMnO2 + 6O2 + 10KOH
- Calcium carbide is reacted with water to form
acetylene. The gas is collected by water
displacement.
CaCH2 + 2H2O HC ≡ HC + Ca(OH)2

2. Dehydrohalogenation of Alkyl Dihalides 3. Addition Reactions

- Dihaloalkanes yield alkynes on treatment with an a. Addition of Hydrogen
Pt, Pd or Ni
alcoholic base, KOH in ethyl alcohol. R – C ≡ C – R + 2H2 R – CH2CH2 – R
alc.
R–CH–CH–R + 2KOH R–C≡C–R + 2KX + 2H2O - If we wish to convert an alkyne to an alkene, we
| | must use a slightly deactivated or poisoned
Br Br catalyst, which is prepared by adding lead
acetate to palladium
R – C ≡ C – R + H2 Poisoned Pd R – CH = CH – R
 X
|
HX HX
R – C ≡ CH R - C ≡ CH2 R – C – CH3
| |
X H

b. Addition of Halogen
X X
| |
R – C ≡ C – R + X2 R-C–C-R
| |
X X 4. Substitution Reaction
- Acetylenic hydrogen (H aMached to a C bearing a
triple bond) are somewhat acidic, can be
replaced by metals forming salts.
HC≡CH + Cu2Cl2 + 2NH4OH CuC≡CCu + 2NH4Cl2 + 2H2O

• Physical Properties
1. Similar to alkenes. Ethyne, propyne, and 1- butyne are
gases, 2-butyne and higher members are liquids

• Uses of Alkanes
1. Acetylene is mainly used as fuel in oxyacetylene cuNng
& welding torches and as an intermediate in the
manufacturing of other substances.

Aromatic Hydrocarbons
c. Addition of Hydrogen Halide
- HCl, HBr, or HI add to alkynes in two steps. The Benzene, first isolated in 1825 by Michael Faraday, is the simplest
reac9on may be stopped a<er the first step, and member of the class of compounds known as aromatic
the haloalkene can be obtained, or a second hydrocarbons, or arenes.
molecule of HX may be allowed to react to give a o C6H6
gem-dihalide (the prefix “gem-“ from the La9n
geminus, twin, signifies that both halogens are
on the same carbon atom). The addi9on of HX to
alkynes with terminal triple bond follows
Markownikoff’s rule.
 OH

- The double-headed arrow does not indicate an

CH(CH3)2
equilibrium process. It is a device used to show
electron – delocalized structures as written with
3
CH3
localized electrons. A convenient way to represent the
two Kekulé structures resonance forms of benzene is
by inscribing a circle inside a hexagon.

CCl3
|
Cl– – Cl
|
H

• Nomenclature of Substituted Derivatives of Benzene

• Structure of Benzene - A benzene ring that has one of its hydrogens replaced
- One of the earliest structural formulas for benzene by some other group is named as substituted
was proposed by August Kekulé in 1866. Kekulé derivative of benzene. For example,
suggested a structure having alternating single and
double bonds in a ring of six carbons, each carbon
having one hydrogen attached.

- But Kekulé structures does not explain all the

observations regarding benzene’s structure and
reactivity. All six carbon – carbon bonds of benzene
are the same length, intermediate between sp2-sp2
single bonds and double bonds. The fact that all the
bond lengths are equal is not explained by the
alternating double and single bonds of Kekulé
structure. The structure of benzene is better
represented as a hybrid of the two equivalent
resonance forms shown.