ORGANIC CHEMISTRY

INTRODUCTION
Organic chemistry = the chemistry of carbon compounds

Carbon
is not an abundant element in the universe
is an essential element of life
living organisms:
carbon, hydrogen, nitrogen, oxygen
trace elements: sulphur, phosphorous, sodium, potassium calcium, iron

the unique properties of carbon permits the immense diversity of
compounds associated with life.
1828, a German chemist Friedrich Whler :




Organic chemistry object refers to:
Isolation and purification of natural organic compounds, or those obtained in
laboratories.
Finding their structure, using different chemical and physical methods.
Physico-chemical characterization of organic compounds.
All organic compounds contain:
without exception, carbon
frequently hydrogen.
can contain oxygen, nitrogen, halogens, sulfur, phosphorus, and rarely metals.

organogenetic elements or organogens (C, H, O, N, S, P, Cl, F, Br, I,
metals, etc) - the totality of chemical elements which form the composition
of organic compounds

hydrocarbons - compounds, formed only of carbon and hydrogen
derivatives of hydrocarbons - substituting one or more hydrogen atoms
with other type of atoms or groups of atoms

K. Schorlemmer has defined organic chemistry as hydrocarbons
chemistry and their derivatives.
Classification of organic compounds
Organic substances are classified according to the functional group
they contain.

A functional group is the atom or the group of atoms which confers
specific physical and chemical properties to the molecules.

According to the composition, the functional groups can be:
homogenous: multiple bonds (double, triple) carbon carbon
heterogeneous: contains or not carbon, and other types of atoms, -X, -
OH, C=O, -COOH, etc

Structure - the organizational pattern or arrangement of parts that
characterizes a thing.
Chemists - the manner in which the atoms that compose a
molecule of a specific compound are attached (bonded) to one
another and oriented in space.
This information is usually provided by a structural formula
Homogenous functional groups
C C
C C
Functional
Group
Formula
Class
Denomi
nation
Specific
Example
IUPAC
Denomination
Common
Denomi
nation
Alkenes H
2
C=CH
2
Ethene Ethylene
Alkynes HCCH Ethyne Acetylene
Arenes C
6
H
6
Benzene Benzene
Functional groups containing heteroatoms,
bounded with simple bonds
Functional
Group
Formula
Class
Denomi-
nation
Specific Example
IUPAC
Denomination
Common
Denomination
halogenated
derivatives
H
3
C-I Iodomethane Methyl iodide
Alcohols CH
3
CH
2
OH Ethanol Ethyl alcohol
Ether CH
3
CH
2
OCH
2
CH
3
Diethyl ether Ether
Amines H
3
C-NH
2
Aminomethane Methyl amine
Nitro
derivatives
H
3
C-NO
2
Nitromethane
Thiol H
3
C-SH Methanethiol
Methyl
mercaptane
Sulfides H
3
C-S-CH
3
Dimethyl sulfide
Functional groups with heteroatoms
having multiple bonds
Functional
Group
Formula
Class
Denomi-
nation
Specific Example
IUPAC
Denomination
Common
Denomination
Nitrils H
3
C-CN Ethanenitril Acetonitril
Aldehydes H
3
CCHO Ethanal Acetaldehyde
ketones H
3
CCOCH
3
Propanone Acetone
Carboxylic
acids
H
3
CCOOH Ethanoic acid Acetic acid
Esters H
3
CCO
2
CH
2
CH
3
Ethyl Ethanoate Ethyl acetate
Functional
Group
Formula
Class
Denomi-
nation
Specific Example
IUPAC
Denomination
Common
Denomination
Acidic
halides
H
3
CCOCl Ethanoil chloride Acetyl chloride
Amide H
3
CCON(CH
3
)
2

N,N-Dimethyl-
ethane-amide
N,N-Dimethylacet-
amide
Acidic
anhydrides
(H
3
CCO)
2
O
Ethanoic
anhydride
Acetic anhydride
Important aspects of structural formulas:
Composition: types and numbers of atoms that compose a molecule of a
compound.
Constitution: manner in which the component atoms of a molecule are bonded
to each other. Different compounds having the same composition but different
constitutions are called isomers.
Configuration: shape of a molecule in three-dimensional space. Isomers
differing only in configuration are called stereoisomers.

Analytic steps to find the structure of a pure organic compound:
Elementary analysis can be:
Qualitative: finds the atoms forming the substance;
Quantitative: finds the substance composition.
Percent formula indicates the mass of each element from 100 grams of
substance. It is determined using calculation and the elementary analysis
data. If the percent sum is less than 100%, the difference represents the
oxygen.
Brute formula represents the smallest ratio of whole numbers (integer)
between the component atoms of a substance.
To find the number of component atoms in 100 grams of substance, the
percent of each element is divided with its atomic mass, than the obtained
numbers are divided to the smallest value, obtained during the previous
operation. Example of brute formula: CH
2
.
Molecular formula indicates the number and type of atoms
forming the molecule, and is an integral multiple of brute formula.
Example: (CH
2
)n.
Structural formula indicates the atoms arrangement in the
molecule; is determined using different physico-chemical
methods. A specific molecular formula can represent many
structural formulas (see isomerism). An appreciation of the
organic compound nature can be done calculating the equivalent
unstauration (EU). EU can be calculated for any compound,
using the following formula:



where: n
i
represents the atom number of type i (C, H, O, N, X, etc.)
v represents the atom valence
EU value of a real compound must be an integral, positive
number, including zero.
Each double bond or saturated cycle reduces with 2 the hydrogen
atoms in a molecule, therefore the EU value will increase with one
unit.
Verifying the molecular formula can be done also by calculating
the sum of all covalences of the chemical components in that
compound. This number must be an even number.
2
) 2 ( 2

+
=
i i
v n
EU
Example of calculation in elementary analysis

Percentage formula: 64.6% C, 10.8% H and 24.6% O
C: 64.4 g/ 12.001 g/mol = 5.38 atom-gram C : 1.54 = 3.49
H: 10.8 g/ 1.008 g/mol = 10.7 atom-gram H : 1.54 = 6.95
O: 24.6 g/ 16.00 g/mol = 1.54 atom-gram O : 1.54 = 1.00

brute formula : C
3.49
H
6.95
O
1.00
Since the elements combine only in ratio of integral numbers, the
brute formula must be multiplied by 2
Real brute formula : C
7
H
14
O
2

molecular formula (C
7
H
14
O
2
)
x
.
Molecular Weight = 130 x = 1
molecular formula: C
7
H
14
O
2
The great number of carbon in compounds is possible
because carbon has:
the ability to form strong covalent bonds with other
carbon atoms,
also holds strongly the atoms of other nonmetals.
Carbon atoms have the special property to form chains,
rings, spheres, and tubes.
Chains of carbon atoms can be thousands of atoms
long, as in polyethylene
Chemical bonds in organic chemistry

high number of organic compounds > 9 millions
carbon is present in all these compounds.
carbon has unique properties, determined by the electronic structure:
It has 4 electrons on the last layer, being in the middle of the second
period, group 14 (IV< A)
the most marked tendency in the period to form stabile octet
configuration by sharing electrons - forms covalences.
It can form 4 covalent bonds to each other (with itself) or to other
organogenic elements.
It is the only chemical element that forms, practically, an infinite
number of covalent bonds to each other, generating carbon atom
chains.
It can form different chain arrangements, linear, branched, and cyclic.
It can form:
- sigma, simple covalent bonds;
- double covalent bonds (containing a sigma and a pi bond);
- triple covalent bonds (containing a sigma and two pi bonds).
In some organic compounds, covalent-coordinative
bonds can appear.
These are formed by sharing of the two electrons in the
bond, given only by one atom.


C
H
H
H
N
H
H
H Cl
C
H
H
H
N
H
H
H : +
+
Cl
-
Carbon atoms chains
Chains are classified function of their structure, as:
Saturated chains:
linear, carbon atoms are bounded consecutively, in line:

CH
3
-CH
2
-CH
3

branched, carbon atoms are bounded as branches of the base
chain (the longest one):
CH
3
-CH-CH
3

CH
3
cyclic, carbon atoms are bounded by simple covalent bonds,
forming a closed chain (a cycle):
CH
2
-CH
2

CH
2
-CH
2
Unsaturated chains:
linear, carbon atoms are bounded consecutively, in line:

CH
2
=CH
2
-CH
3
, CHCH

branched, carbon atoms are bounded also as branches of the
base chain (the longest one):

CH
3
-CH-CH=CH
2

CH
3

cyclic, carbon atoms are bounded by simple or double,
covalent bonds, forming a closed chain (a cycle):

CH
2
-CH
2

CH=CH
Aromatic chains:
mononuclear
polynuclear
Types of carbon atoms

When discussing structural formula, it is often useful to distinguish
different groups of carbon atoms by their structural characteristics.
A nular carbon (o) is one that is not bonded to any other carbon
atom.
H
2
C=O, H
3
C-NH
2
, HCOOH, etc.

A primary carbon (1
0
, p) is one that is bonded to no more than one
other carbon atom, with a single, sigma, covalent bond.

H
3
C
p
-C
p
H
3

A secondary carbon (2
0
, s) is bonded to two other carbon atoms by
sigma covalent bonds, or to one carbon atom with a double (sigma +
pi) covalent bond.

H
3
C-C
s
H
2
-CH
3
, H
2
C
s
=C
s
H
2

A tertiary carbon (3
0
, t) is bonded to three other carbon atoms by
sigma covalent bonds, or to one carbon atom with a double (sigma +
pi) covalent bond and to another carbon atom with a single bond; or
is bonded to a single carbon atom with a triple covalent bond (one
sigma and two pi).

H
3
C-C
t
H-CH
3
, HC
t
C
t
H, CH
2
=C
t
H-CH
3

CH
3


A quaternary carbon (4
0
, q) is bonded to four other carbon atoms
by sigma covalent bonds; or to other two carbon atoms with double
bonds; or to three carbon atoms, with a double covalent bond and
two single covalent bonds; or with a triple covalent to one carbon
atom and with one single bond to another carbon atom.

CH
3

H
3
C-C
q
-CH
3
, HCC
q
-CH
3
, CH
2
=C
q
=CH
2

CH
3
Isomerism

In most cases a molecular formula does not uniquely represent a single
compound.
Different compounds having the same molecular formula, but a different
spatial arrangement are called isomers
There are two main classes of isomers: constitutional isomers and
stereoisomers.
Constitutional isomers have the same number and type of atoms but
which are sequentially connected differently. This isomerism type
excludes any rearrangement that is due to the molecule rotation as a
whole, or of a single peculiar bond.

Example: molecular formula C
2
H
6
O
ethanol CH
3
CH
2
OH
dimethylether CH
3
OCH
3



But the following a and b structures are not isomers, they
represents one and the same substance - butane - with a practically
infinite representation ways of free rotation around a single bond.
C H
3
C
H
2
C
H
2
CH
3
C H
3
C
H
2
C
H
2
CH
3
a b
Structural (constitutional) isomerism types
1. Chain (skeleton) isomerism - appears doe to the branching
possibilities of carbon chains. There are 2 isomers of butane with
the formula C
4
H
10
: butane and isobutane.




Pentane C
5
H
12
presents 3 chain isomers: n-pentane, 2-methyl-
butane (isopentane) and 2,2-dimethyl-propane (neopentane).
C H
3
C
H
2
C
H
2
CH
3
C H
3
C
H
CH
3
CH
3
C H
3
C
H
2
C
H
2
C
H
2
CH
2
C H
3
C CH
3
CH
3
CH
3
C H
3
C
H
2
C
H
CH
3
CH
3
2. Position isomerism - the carbon skeleton of the compound remains
unmodified, but the functional groups change their bond position to
the carbon skeleton.
For example, the molecular formula C
3
H
7
Br has 2 position
isomers: 1-bromo-propane and 2-bromo-propane.



Butanol, with the molecular formula C
4
H
9
OH, has 2 position
isomers: 1-butanol and 2-butanol, but also 2 chain isomers, so
that the total isomers number is 4.

C H
3
C
H
2
C
H
2
Br C H
3
C
H
CH
3
Br
C H
3
C
H
2
C
H
2
C
H
2
OH
C H
3
C
H
C
H
2
CH
3
OH
C H
3
C
H
2
C
H
CH
3
OH
C H
3
C CH
3
CH
3
OH
Position isomers are found, also in the benzene case. For
example, the molecular formula C
7
H
8
Cl presents 4 isomers of
benzene nucleus:





3. Functional isomerism - is found to the compounds, which contain different
functional groups, so they belong to different classes of compounds.
For example, the molecular formula C
3
H
6
O corresponds to propanal (an
aldehyde), propanone (a ketone) or 2- propenol (a monounsaturated
alcohol of propene)
CH
2
Cl CH
3
Cl
CH
3
Cl
CH
3
Cl
C H
3
C
H
2
C
O
H
C H
3
C
O
CH
3
C H
2
C
H
C
H
2
OH
4. Tautomerism - constitutional type of isomerism - a rapid
and facile interconvertion of one form into the other -
tautomerides
isomers differ in the position of one hydrogen atom.
cyclic form linear form at glucose - due to the
possibility of the aldehyde group in the molecule to react
with a hydroxyl group in the same molecule, forming a
cycle.
In solution, a chemical equilibrium is established
between the tautomeric forms.
The concentration ration at equilibrium depends of
factors as temperature, solvent nature, pH, etc.
The tautomeric reaction is catalyzed by bases (by
deprotonation reactions with delocalized anions
formation), or acids (by protonation reactions or
delocalized cation formation).

Keto-enol tautomerism (a compound that contains a ketone group C=O is
in equilibrium with the enol form that has a hydroxyl group attached to a
carbon atom implied in a double bond C=C)
Keto-enol tautomerism is important in biochemistry to explain the high
transfer capacity of the phosphate group of phosphoelolpyruvate, the enol,
instable form, which passes by dephosphorylation in the keto, stable form.
C
O
C
H
C C
OH
ketone enol
C H
3
C
O
COOH C H
2
C
OH
COOH
pyruvic acid enolpyruvic acid
Amide-imide tautomerism



amide imide



acetamide acetimide
Lactam-lactim tautomerism appears in heterocycles, ie in the nitrogen
bases guanine, thymine and cytosine
C
O
N
H
C N
OH
C H
3
C
O
NH
2
C H
3
C
OH
NH
N
H
N
NH
2
O
N
N
NH
2
OH
Cytosine - lactam form cytosine - lactim form
5. Stereoisomerism type
Carbon atoms are secventionally connected in the same way but their
spatial arrangement differs.
Stereoisomers are divided in:
conformational isomers, which are interconvert by the rotation around a
single bond, and
configurational isomers to which the simple interconvertion is not possible







Configurational isomerism contains
enantiomers and
diastereoisomers

H
CH
3
CH
3
H
conformational isomers
H
CH
3
CH
2
CH
3
Br
H
CH
3
Br
CH
3
CH
2
configurational izomers
asymmetric carbon : a carbon atom that is bonded to four different atoms
or groups and which loses all symmetry
chiral configuration
This type of configurational stereoisomerism is termed enantiomorphism,
and
the non-identical, mirror-image pair of stereoisomers that result are called
enantiomers pairs of enantiomers
their physical and chemical properties are largely identical


H
CH
3
CH
3
CH
2
Br
H
Br
CH
2
CH
3
C H
3
*
*
chiral compound perturb plane-polarized light in opposite ways.
This perturbation is unique to chiral molecules, and has been termed
optical activity.
The instrument called a polarimeter, shown in the diagram below, can
determine the plane of polarization












One enantiomer will rotate polarized light in a clockwise direction, termed
dextrorotatory or (+), and its mirror-image partner in a counter-clockwise
manner, termed levorotatory or ().

Specific Rotation


where l = cell length in dm,
c = concentration in g/ml
D is the 589 nm light from a sodium lamp

Compounds that rotate the plane of polarized light are termed optically
active.
A 50:50 mixture of enantiomers has no observable optical activity.
Such mixtures are called racemates or racemic mixtures, and are
designated ().
1. resolution separation of racemate into its component enantiomers.
2. racemization transformation of a pure enantiomer into its racemate.
The existence of a symmetry plan cancels the optical isomerism, for
example the presence of two identical substituents bonded to the
same carbon atom.


mezo - form



Configurational stereoisomers which are not found in an
enantiomeric relationship (optical isomers) are called
diastereoisomers
Diastereoisomers which are not chiral and do not contain
stereogenic centers are called geometric isomers (cys/trans).
These isomers appear doe to a restriction of the free rotation around
of a bond.

C
CH
3
O H Br
C O H Br
CH
3
Free rotation alt the level of a single bond






The presence of a double bond block the free rotation around that bond,
and two position isomers appear: one cys (the identical substituents are on
the same part of the double bond) and trans (identical substituents are on
one side and the other side of the double bond).
C C
O H
O H
Br
Br
OH
OH
C C
O H
O H
Br
OH
Br
OH
C C
Cl
Br
Br
Cl
C C
Cl
Br
Cl
Br
trans
cis
Izomers
Constitutional
Izomers
Stereoizomers
Conformational
Izomers
Configurational
Izomers
Diastereoizomers Enatiomers
cis-trans Izomers
Diastereoizomers with
stereogenic center
Reaction mechanisms in organic
chemistry
Reaction mechanism - pathway followed by a chemical
process with the intermediary chemical species (which
cannot be isolated) that appear during the
transformation of reactants into products.
Classification:
Electrophilic addition
Electrophilic substitution
Nucleophilic addition
Nucleophilic substitution
Radicalic substitution
Radicalic addition
Elimination
Electrophilic addition
Electrophile - the chemical specie that presents affinity for negative
charges (molecular regions with electron excess). Electrophile species
realize chemical bonds by accepting a pair of electrons.
Examples: H
+
, CH
3+
, Cl
+
etc.
Alkenes give electrophilic addition with halogens, halogen hydride, water,
etc. Example: the addition of hydrobromic acid to ethene, which has the
following steps:
1st Step. Braking of the H-Br bond ions H
+
and Br
-
:


2nd Step. The ion H
+
(an electrophile) is attracted by the t electronic cloud of
the double bond in the ethene accepts a pair of electrons.



3rd Step. The hydrogen ion binds to ethene and a carbocation results:




4th Step. The already formed carbocation has the tendency to attract the
bromide ion, formed in the first step; finally the addition product results:
bromoethane.


CH
2
= CH
2
+ H-Br CH
3
- CH
2
- Br
Electrophilic substitution
Substitution reaction presumes the replacing of an atom or a group of
atoms in a molecule with another atom or group.
The electrophilic substitution reactions are characteristic to the systems that
contain benzene nuclei.
Examples of that type of substitution are halogenation, alkylation,
acylation, nitration, sulfonation of benzene.
Example: the nitration mechanism of benzene
1st Step. The reaction between sulfuric acid and nitric acid, at 50C, forms the
electrophilic ion NO
2
+
:
H
2
SO
4
+ HNO
3
HSO
4
-
+ NO
2
+
+ H
2
O
2nd Step. Two of the delocalized electrons of benzene are attracted to the
electrophilic specie, forming a bond. The resulting specie has a complete
positive charge and a delocalization of the t electrons.
3rd Step. The resulted system formed in step 3 has the tendency to accept a
pair of electrons from the negative ion, resulted during step 1. Nitrobenzene
is formed:




Nucleophilic addition
It is an addition reaction, characteristic to aldehydes and ketones;
it presumes an initial attack of a nucleophilic specie.
A nucleophilic specie - negative charged ion, which has affinity
for a molecular region with electron deficit (positive charge).
Examples: HO
-
, CN
-
etc.

Example: acetaldehyde reaction with hydrocyanic acid is a typical example
of nucleophilic addition:
1st Step. Heterolytic braking of the bond H-CN to form the nucleophile CN
-
:

HCN H
+
+ CN
-

2nd Step. Cyanide ion attacks the carbon atom of the aldehyde group, which is
positive due to the vicinity of the electronegative oxygen atom. The double
bond C=O is transformed in a single one by the movement of the electron
pair to the oxygen atom.









3rd Step. The chemical specie, formed as a result of the nucleophilic attack and
rearrangement of electrons that form the double bond, is an anion:


4th Step. The negatively charged oxygen atom attracts the hydrogen positive
ion, which forms a bond with the oxygen, by accepting the pair of electrons.






5th. Step. Finally, a new molecule results that has two functional groups: nitrile
and hydroxyl.


Nucleophilic substitution
Nucleophilic substitution mechanism: Halogen derivatives of alkanes hydrolyze
in an alkaline medium (sodium hydroxide solution) to form an alcohol.
Example is the hydrolysis of ethyl chloride.

1st Step. The hydroxyl ion attacks the carbon atom situated in the closed
vicinity of chlorine. (Carbon atom has a partially positive charge due to the
electron attracting effect of chlorine atom





2nd Step. An intermediary, with double function, is formed:
3rd Step. The bond C-Cl is broken and ethanol is formed.

+ Cl
-

Cl
-
+ Na
+
NaCl
Radicalic substitution
implies the attack of free radicals, formed in a hemolytic braking.
A simple example is the alkanes reaction with halogens in the presence of
UV radiation.
Example: radicalic chlorination of methane
1st Step. The initiating step the Cl-Cl bond is broken due to the UV radiation
to form two chlorine free radicals:
Cl + Cl

2nd Step. Propagation step a free radical reacts with a molecule to form a
new radical and a new molecule.



3rd Step. Termination step Two free radicals react to form a molecule.



Radicalic addition
It is an addition reaction that implies radicalic species.
For example: polymerization of ethene (ethylene) to form polyethylene:

nCH
2
=CH
2
[-CH
2
-CH
2
-]n

The reaction takes place at 200C and 2000 atm, in the presence of
small quantities of initiators, capable to form free radicals in the
given conditions.



1st Step. Initiating step free radical species (RCH
2
-CH
2
) are
formed in the reaction between an ethene molecule and the free
radical R, formed from the initiator.

2nd Step. Propagation step corresponds to the following reaction:

RCH
2
-CH
2
+ CH
2
=CH
2
RCH
2
-CH
2
-CH
2
-CH
2


3rd Step. Termination step - Two radical species react to form a
non-radicalic compound. For example:
RCH
2
-CH
2
-CH
2
-CH
2
+ CH
2
-CH
2
-CH
2
-CH
2
R

RCH
2
-CH
2
-CH
2
-CH
2
-CH
2
-CH
2
-CH
2
-CH
2
R
HYDROCARBONS
combinations of carbon with hydrogen.
all organic compounds can deriver from hydrocarbons by replacing
of hydrogen atoms with other elements or groups of atoms.
Besides, carbon monoxide and carbon dioxide are inorganic
substances, even if they can be considered as derivatives of
methane.
Carbon has the almost unique property to combine with itself,
forming linear, branched and cyclic chains.
Hydrocarbons formulas are obtained by saturation the rest of the
valences with hydrogen atoms.
Example:

CH
4
CH
3
CH
3
CH
3
CH
2
CH
3
Methane Ethane Propane
The hydrocarbons with > 3 carbon atoms structural (chain)
isomers
- linear (straight)
- branched chains;
The higher the number of carbon in the molecule the higher is the
number of chain isomers that are possible to exist.
The maximum number of hydrogen atoms that can be bonded to n
carbon atoms is 2n + 2.
saturated hydrocarbons have the general formula C
n
H
2n+2

Alkanes all carbon atoms are sp
3
hybridized
Cycloalkanes that have the chain closed in a ring or circle C
n
H
2n
.
unsaturated hydrocarbons - carbons bound by
double bonds and they have a hybridization sp
2
alkenes
triple bonds hybridization sp alkynes
aromatic hydrocarbons - benzene.
homologue series - the series of organic compounds that have the same
general formula and form of the chain, and the consecutive terms differ
by a methylene group (-CH
2
-)
Two consecutive compounds in a homologue series are called homologue
terms.
Saturated non-cyclic hydrocarbons alkanes
general formula C
n
H
2n+2
.
contain only simple, sigma bonds (C-C C-H)
are also called paraffines (from Latin: parum affinis = low affinity).
natural gases contain hydrocarbons with C1 C4 atoms and crude
oil (petroleum) contains a mixture of liquid hydrocarbons (alkanes,
cycloalkanes and aromatic compounds) and other organic
compounds with sulfur, nitrogen, oxygen.
Petrol (gasoline) is a mixture of alkanes and isoalkanes, especially
with 8 carbon atoms.
Nomenclature
The first four terms of the homologue series of alkanes have specific
names: methane (CH
4
), ethane (C
2
H
6
), propane (C
3
H
8
) and butane
(C
4
H
10
).
superior terms suffix ane is added to the Greek name of the
number of carbon atoms in the molecule (see next table).
normal alkanes have straight chain
isoalkanes have branched chain
No of C
atoms
Denomination
Molecular
formula
Structural
formula
1 Methane CH
4
CH
4

2 Ethane C
2
H
6
CH
3
CH
3

3 Propane C
3
H
8
CH
3
CH
2
CH
3

4 Butane C
4
H
10
CH
3
CH
2
CH
2
CH
3

5 Pentane C
5
H
12
CH
3
CH
2
CH
2
CH
2
CH
3

6 Hexane C
6
H
14
CH
3
(CH
2
)
4
CH
3

7 Heptane C
7
H
16
CH
3
(CH
2
)
5
CH
3

8 Octane C
8
H
18
CH
3
(CH
2
)
6
CH
3

9 Nonane C
9
H
20
CH
3
(CH
2
)
7
CH
3

10 Decane C
10
H
22
CH
3
(CH
2
)
8
CH
3

12 Dodecane C
12
H
26
CH
3
(CH
2
)
10
CH
3

20 Eicosane C
20
H
42
CH
3
(CH
2
)
18
CH
3

A radical is obtained by the removing of one or more hydrogen atoms from
the alkane molecule.
The radical has an unpaired electron at the carbon atom that has lost the
hydrogen.
The symbol of the radical is obtained by adding a dot (CH
3
), but usually
the valence line is used (CH
3
).
The name of the radical depends on the number of lost hydrogen atoms
from one - or two -carbon atoms.
The monovalence radicals: suffix ane yl (alkyl).
The divalence radicals:
suffix ane ene if the two hydrogen atoms are removed from two
different carbon atoms;
suffix ane yliden when the two hydrogen atoms are removed from
the same carbon atom
The trivalence radicals: ane ine.
CH
3
CH
3
CH
2
CH
2
CH
2
CH
2
CH
methyl ethyl methyliden ethandiyl methylydine
(methylene) (ethylene) (methine)
The denomination of the isoalkane is done indicating the position of the substituents
and the name of the respective radical, in the alphabetic order.









Physical properties
the bonds C-C and C-H are non-polar molecules are hydrophobic.
Only weak attraction forces, van der Waals, manifest between molecules.
Function of their molecular masses, and due to the weak attraction forces:
the inferior alkanes (C1-C4) are gaseous,
the alkanes having 5 to 17 carbon atoms are liquids, and
the ones having more than 18 carbon atoms are solid at room temperature.
The melting and boiling points increase in the homologue series with the increase
in the number of carbon atoms in the molecule,
and are greater at the normal (straight) alkanes than the isoalkanes with the same
number of carbons

6 5 4 3 2 1 1 2 3 4 5 6 7
CH
3
-CH-CH
2
-CH-CH-CH
3
CH
3
-CH-CH
2
-CH-CH
2
-CH-CH
3
I I I I I I
CH
2
CH
3
CH
3
CH
3
CH
3
CH
3
C
2
H
5

2,3,5-trimethylhexane 6-ethyl-2,4-dimethylheptane
Example: The boiling point of:
pentane CH
3
-CH
2
-CH
2
-CH
2
-CH
3
-b.p. 36.1C
neopentane - b.p. 9.4C
CH
3
I
CH
3
C CH
3
I
CH
3

Alkanes can be dissolved in:
hydrocarbons from other classes and in halogenated compounds,
but are insoluble in water and in the inferior alcohols.
The alkanes density is lower, comparing with water (they float on
water).
Chemical properties
low chemical reactivity, especially toward the ionic reagents
(bases, weak mineral acids) due to the absence of the functional
groups in their molecules.
The chemical reactions of alkanes are:
Substitution reactions: dehydrogenation or oxidation: CH bonds
are broken.
Isomerisation reactions,
thermal decomposition CC bonds are broken
burning
Different derivatives can be obtained from alkanes, as alkenes,
alkynes, alcohols, aldehydes, halogenated derivatives, hydrogen
cyanide, etc.

Isomerisation reactions - alkanes isoalkanes.
Example: normal hexane 3-methylpentane.




Oxidation reactions - function of conditions alcohols, aldehydes (ketones) or
carboxylic acids.
a. Methane oxidation to methanol; p = 130 200 atm and t = 300-400C.



b. Methane oxidation to formaldehyde; t = 600C and catalysts nitrogen
oxides.



CH
3
- (CH
2
)
4
- CH
3

50-100
AlCl
3
, AlBr
3
o
C
CH
3
- CH
2
- CH - CH
2
-CH
3

I
CH
3
methanol
OH CH O 1/2 CH
3
C 400 - 300 atm, 200 - 130
2 4
+

de formaldehy
O H O CH O CH
2 2
C 600 - 400 NO,
2 4
+ +

c. Isoalkanes oxidation is easier than the alkanes one. Isobutane
is oxidized even with potassium permanganate (oxidation of the
tertiary carbon).






d. Alkanes combustion (burning) can be done with oxygen or air,
at high temperature. Carbon dioxide and water result. The
reaction is highly exothermic.


CH
3
C
CH
3
H
CH
3
+ [O]
KMnO
4
CH
3
CH
3
CH
3
OH
C
isobuthanol
Q O 2H CO 2O CH
2 2 2 4
+ + +
Thermal decomposition of alkanes t > 300C; C-C and C-H bonds are
broken.
- cracking - when CC bonds are broken an alkane and an alkene




- dehydrogenation - braking of the CH bonds alkenes




Substitution reactions replacement of one or more hydrogen atoms with
atoms or groups from the reactant.
- halogenation - hydrogen replacement with a halogen atom (Cl, Br),
- Alkane chlorination takes place in the light (radiation) presence or at high
temperatures (t > 500C).
CH
4
+ Cl
2
CH
3
Cl + HCl
Chloromethane

Chlorinated derivatives, used in medicine as anesthetics, are
trichloromethane (chloroform CHCl
3
) ethyl chloride (CH
3
CH
2
Cl).
ethene ethane
CH CH CH - CH CH - CH - CH - CH
2 2 3 3 3 2 2 3
= +
butene
CH - CH CH - CH CH - CH - CH - CH
3 3 3 2 2 3 2
H + =
Alkenes
Definition. Nomenclature
Alkenes = olefins - are acyclic hydrocarbons that contain simple bonds CC and
CH and only one double bond between two carbon atoms.
general formula - C
n
H
2n
.
The double bond (unsaturation) determines the chemical properties. It is formed
of an type bond (very stable) and a type bond, with a much lower
stability.
Alkenes denomination - suffix ane in the alkane name ene
(ethane ethene, propane propene, butane butene, etc.)
An older denomination replaces suffix ene with ylene (ethene ethylene,
propene propylene).
In the case of a branched chain, the denomination follows the same rules as for
alkanes.
The longest chain chosen for the root name must include both carbon atoms of
the double bond.
If more than one double bond is present the compound is named as a diene,
triene or equivalent prefix indicating the number of double bonds and each double
bond is assigned a locator number.

CH
2
= CH
2
CH
2
= CH CH
3
H
2
C = CH CH
2
CH
3
H
3
C CH = CH CH
3
ethene propene 1-butene 2-butene
Physical properties
similar physical properties as alkanes.
lower boiling points than the corresponding alkanes and higher densities.
First terms of the alkenes series are gaseous, the middle terms are liquids
and the superior ones are solids.
water insoluble, but soluble in organic solvents.
Chemical properties
addition, oxidation, polymerization and substitution at the carbon atom in the
allyl position
Alkenes have a chemical reactivity higher than the alkanes.
The alkenes characteristic reactions are:
Addition to the double bond C C
Substitution of hydrogen atoms in the allyl position.


C C
CH
2
addition
substitution
Addition reactions the bond is broken
aturated compound are synthesized.
a. Halogen addition to alkenes forms dihalogenated saturated compounds. It
is an easy reaction for chlorine and bromine, in a gaseous or liquid medium.
For iodine, the reaction takes place only in the presence of light.
CH
3
CH
2
CH CH
2
+ Cl
2
CH
2
CH CH
2
CH
3
1-butene I I
Cl Cl
1,2-dichlorbutane
b. Hydrogen addition gives alkanes.




c. Hydracids addition forms monohalogenated derivatives
(monohalogeno alkanes):
CH
2
= CH
2
+ HCl CH
3
CH
2
Cl
Ethene ethyl chloride
Addition takes place differently:
unoriented for symmetric alkenes and
oriented for the asymmetric ones: The Markovnikov : during the
hydracids addition to the asymmetric alkenes, the halogen atom
binds to the hydrogen poorer carbon atom implied in the double
bond
propane propene
CH - CH - CH H CH CH - CH
3 2 3
atm 200 C, 200 - 80 divizate, fin Pd Pt, Ni,
2 2 3
+ =

d. Water addition to alkenes forms alcohols. The real reactant is
hydronium ion H
3
O
+
, formed during the reaction between the acidic
catalyst and water:
CH
3
CH = CH
2
+ H OSO
3
H CH
3
CH CH
3
,
O SO
3
H
isopropyl sulfate
CH
3
CH CH
3
+ H OH CH
3
CH CH
3
+ H
2
SO
4
, ,
O SO3H OH
isopropylic alcohol
Oxidation reaction to alkenes can be different, according to the
oxidant.
a. mild oxidation (oxidizing agent is potassium permanganate, in a weak
basic medium), the double bond is broken. A diol results:



b. strong oxidation (example with potassium permanganate in sulfuric
acid medium), acids or ketones are formed, function of the alkenes
structure. The reaction can be used to find the double bond position in
the carbon chain.
ol etylenglyc (glycol) ethandiol ethene
(OH) CH - (OH) CH O H [O] CH CH
2 2
CO Na , KMnO
2 2 2
3 2 4
+ + =
CH
3
CH
3
C CH CH
3
3[O] CH
3
CH
3
C
O
CH
3
COOH + +
2-methyl-2-butene
acetone acetic acid
CH
3
CH
CH CH
3
+ 4[O] 2 CH
3
COOH
2-butene acetic acid





CH
3
CH
3
CH
3
CH
3
C
+ 2[O]
CH
3
CH
3
C
O 2 C
2,3-dimethylbutene acetone
Polymerization reaction
represents the chemical process in which a high number of unsaturated
compound are bond to each other, forming a macromolecule.
- The initial compound is denominated monomer, and the final product, polymer.
- Monomers can be alkenes or their derivatives, generally denominated vinyl
monomers.
- Polymers are solid substances, with plastic properties (plastomers) or
elastic (elastomers).

n CH
2
= CH ( CH2 CH )n
I I
CH
3
CH
3

polypropylene
Alkynes

- acyclic hydrocarbons that contain a triple bond between 2 C
- General formula is: C
n
H
2n-2
.
- contain in their molecule carbon atoms in two hybridization states: sp (carbon
atoms of the triple bond one bond is and the other two are ) and sp
3
(the
rest of them).

No. of
C
Denomination
Molecular
Formula
Structural Formula
2
Acetylene
(ethyne)
C
2
H
2
HC CH
3
Propyne
(methylacetylene)
C
3
H
4
CH
3
C CH
4
1-butyne
(ethylacetylene)
C
4
H
6
CH
3
CH
2
C CH
5 1-pentyne C
5
H
8
CH
3
CH
2
CH
2
C CH
6 1-hexyne C
6
H
10
CH
3
CH
2
CH
2
CH
2
C CH
Denomination : suffix ane yne
(ethane ethyne, propane propyne, butane butyne, etc.)
The most important alkyne is acetylene.
Physical Properties
aggregation state depends on the carbon atom number, the first
three terms of this homologous series being gaseous.
water solubility is much higher than the alkanes and alkenes, due
to the polarization of the bond CH.
Alkynes solubility increases a lot with pressure.
Chemical Properties
unsaturated hydrocarbons, containing a triple bond
stronger unsaturated character than that given by the double
bond.
Acetylene participates to:
addition reactions,
dimerisation (to form vinylacetylene),
trimerisation (forming aromatic compounds),
oxidation (to form acids oxalic acid) and
substitution.
Addition reaction
a. Hydrogen addition alkanes or alkynes.
Pb poisoned Pt
HC CH + H
2
-----------------------> CH
2
= CH
2
acetylene ethene
Ni
HC CH + 2 H
2
-----------------------> CH
3
CH
3
acetylene ethane

b. Halogens addition. Bromine and chlorine give an easy addition
to acetylene.
methane tetrabromo - 1,1,2,2 hene dibromomet - 2 1, acetylene
CHBr - HC Br CHBr BrHC Br CH HC
2 2
Br
2
2
= +
+
c. Acids addition (inorganic or organic) to acetylene is easily realized
lower unsaturation grade (triple bond becomes double bond, the
type being vinyl monomers.
- Hydrochloric acid addition:


- Acetic acid addition:


- Hydrogen cyanide addition
chloride vinyl
CHCl CH HCl CH CH
2
170 , HgCl
2
= +
C

acetate vinyl
CH - CO - O - CH CH COOH - CH CH CH
3 2
C 200 , COO) Zn(CH
3
2 3
= +

il acrylonitr
CHCN CH HCN CH CH
2
80 Cl, NH Cl Cu
4 2 2
= +
+ C

d. Water addition to acetylene (Kucerov reaction) acetaldehyde Vinyl

alcohol (instable intermediary compound) tautomerizes to form
acetaldehyde.



Substitution reactions
Hydrogen atoms, bounded to a carbon atom that belongs to a triple bond, has a
weak acidic character.
acetylene is more acidic than ethene or ethane.
The hydrogen atom can be easily given to a strong base.
A class of substances is formed, denominated acetylides.




de acetaldehy alcohol vinyl
O CH - CH OH] - CH [CH O H CH HC
3 2 2
= = +
acetylide disodium
H Na C C Na 2Na CH HC
acetylide monosodium
H 1/2 Na C HC Na CH HC
2
- - C 200
2
- C 150
+ +
+ +
+ +
+

Dimerization reaction.
One acetylene molecule is added to another one and an enyne
compound is formed (vinylacetylene).




HCl can be added to vinylacetylene to form chloroprene (monomer in
the synthetic rubber synthesis)
CH
2
=CH-CCH + HCl CH
2
=CH-C=CH
2

Cl
Trimerisation reaction.
Acetylene trimerisation forms a benzene ring. The reaction can take place
thermically or catalytically (with complexes of transition metal as
catalyzers).
acetylene vinyl
CH C - CH C H CH HC CH HC
2
C 100 - 80 Cl, NH , CuCl
4 2
= +

CH
HC
600-800
o
C
benzene
3
Aromatic hydrocarbons (arene)
Definition. Classification
aromatic hydrocarbons or arene - hydrocarbons, which have as basic
structurally unit the benzene ring, ArH.
Aromatic hydrocarbon radicals are denominated aryl radicals Ar-.
The characteristic compound of this series is benzene C
6
H
6
.
Classification (following the benzene ring numbers in the molecule):
Mononucleus, example: benzene, toluene, xylene:




CH
3
CH
3
CH
3
benzen
toluene xylene
e
- Polynucleus
- with isolated nucleus (difenyl)
- with condensed nucleus (naphthalene, anthracene, phenanthrene)







Physical properties
The aggregation state of aromatic hydrocarbons is liquid for the
mononucleus ones and solid for the polynucleus ones.
water insoluble but soluble in different organic solvents.
Their density is lower than waters but higher than the other
hydrocarbons.
Benzene and toluene are used as solvents.
Naphthalene sublimates.

Difenyl
Naphthalene
Anthracene
Phenanthrene
Chemical properties
Aromatic hydrocarbons give substitution reactions, additions and oxidations to
the nucleus or to the side chains.
Even benzene looks like an unsaturated compound, the electrons form a common
cloud which belongs equally to the 6 carbon atoms, which become equivalents as
chemical reactivity.
benzene gives easier substitution reactions than addition ones, having an
aromatic character.
Reactions of the aromatic nucleus
a. Substitution reactions, characteristic to benzene
a. Friedel-Crafts alkylation b. Friedel-Crafts acylation






+ CH
3
CH
2
Cl
AlCl
3
+ HCl
CH
2
CH
3
ethylbenzene
ethyl chloride
+ CH
3
- CO - Cl
AlCl
3
C
O
CH
3
acetyl chloride
fenyl-methyl-ketone
+ HCl
+ HONO
2
H
2
SO
4
+ H
2
O
NO
2
nitric acid nitrobenzene
+ Cl
2
FeCl
3
Cl
+ HCl
monochlorbenzene
+ HOSO
3
H
SO
3
H
+ H
2
O
benzene-sulphonic acid
c. Nitration reaction

d. Halogenationreaction

e. Sulfonation reaction

- Substituent orientation on the benzene nucleus.
The first substituent of benzene nucleus enters randomly in any position of the
benzene ring.
If a benzene ring has already a substituent, the substitution reaction is oriented,
the position of the second substituent being determined by the preexisting
substituent, which can be:
First order substituent orients the new substituent on the positions
ortho (2) and para (4): halogens, -OH, -NH
2
, -CH
3
, -C
2
H
5
, -N(CH
3
)
2




Second order substituent -NO
2
, -COOH, -CHO, -SO
3
H, -CN, which
orients the new substituent in the meta (3) position:



2 + 2 H
2
O
+ 2HONO
2
CH
3
CH3
CH
3
NO
2
NO
2
toluene o-nitrotoluene p-nitrotoluene
+
NO
2
+Cl
2
AlCl
3
NO
2
Cl
+ HCl
nitrobenzene m-chloro-nitrobenzene




Naphthalene substitution takes place similarly to the benzene one. First
substituent will prefer the more reactive position.

+ HONO
2
H
2
SO
4
-H
2
O
+HONO
2
-H
2
O
nitrobenzene m-dinitro-benzene 1,3,5-trinitrobenzene
NO
2
NO
2
NO
2
NO
2
NO
2
O
2
N
o
o
o o
|
|
|
|
+ HONO
2

H
2
SO
4
NO2
+ H
2
O
o nitronaphthalene
b. Addition reactions. Benzene can add: hydrogen (at 250C in the
platinum presence, forming cyclohexane), chlorine (at light, forming
hexachlorcyclohexane). Polynucleus arenes give easier addition
reactions.
Hydrogen addition







Chlorine addition

C H
2
C H
2
C
H
2
CH
2
CH
2
C
H
2
+ 3H
2

cyclohexane
t
+ 3Cl
2
Cl
H
H
Cl
H
Cl
H
Cl
H
Cl
H
Cl
hexachlorcyclohexane
hv
c. Oxidation reactions. The aromatic ring is relatively stable to oxidation
Benzene can be oxidized with air in the presence of vanadium
pentoxide, at 450C, forming maleic anhydride.




Naphthalene (with an aromatic character weaker than benzenes) is
oxidized in milder conditions (at 360C, with air and vanadium
pentoxide), forming phthalic anhydride.


HC - COOH
HC - COOH
9/2 O
2
-2CO
2 -H
2
O
-H
2
O
HC
HC
C
O
O
O
C
maleic acid maleic anhydride
+ 9/2 O
2
Vn
2
O
5
, 360
o
C
-2CO
2
-H
2
O
COOH
COOH
-H
2
O
C
C
O
O
O
phthalic anhydride phthalic acid
Anthracene is oxidized with oxidizing agents or air ant catalysts, only the
middle air being affected.







Side chain reactions. The saturated alkyl side chain gives saturated
hydrocarbon characteristic reactions. Hydrogen atoms, found at the carbon
atom bounded directly to the benzene ring (benzyl position) are more
reactive than the chain.
Halogenation (Cl
2
, Br
2
) in the light presence or at high temperature.
+ 3 [O]
C
C
+ H
2
O
O
O
anthraquinone
+ Cl
2
+ HCl
CH
3
CH
2
- Cl
benzyl chloride
Oxidation (in strong conditions, with oxidizing agents like potassium
permanganate or potassium dichromate at warm).

CH
3
COOH
toluene
acid benzoic
3[O]
benzoic acid
FUNCTIONAL DERIVATIVES
Halogenated compounds
Definition. Nomenclature
contain in molecule one or more halogen atoms as functional group.
are derivatives of hydrocarbons by replacing hydrogen atoms with halogen
atoms. (F, Cl, Br, I).
According to the halogen atom number, they are mono- and
polyhalogenated.
Denomination
- adding the halogen name as prefix to the hydrocarbon name :
- halide of the hydrocarbon residue:
CH
3
Cl monochloro-methane, methyl-chloride
CH
2
=CH-Cl monochloro-ethene, vinyl-chloride
CH
3
-CH
2
-CH
2
-Cl 1-chloropropane, propyl-chloride


CH
3
CH CH
3
2-chloropropane (isopropyl chloride)
|
Cl
If two halogen atoms are found at the same carbon atom, they are called
geminals, those found in the positions 1, 2 are called vicinals.
Br
|
CH
3
C CH
3
Br CH
2
CH
2
Br
|
Br
2,2-dibromopropane 1,2-dibromoethane
geminal vicinal

Physical Properties
The saturated halogenated compounds, having a low carbon number, are
gaseous at room temperature, the other are liquid or solid.
are water insoluble, but soluble in majority of organic solvents.
Their density is higher than water density.


Chemical Properties
According to the substitution reaction:
normal reactive compounds (derivatives of alkanes),
increase reactivity compounds (with an alyl or benzyl halogen) and
low reactivity compounds (halogen bounded to a vinyl or aromatic
carbon).
Substitution Reaction
Hydrolysis Reaction forms, function of the halogenated derivative type,
different classes of compounds:
alcohols, in the monohalogenated comp.




carbonyl compounds, in the case of geminal dihalogenated comp.




organic acids, in the case of geminal trihalogenated comp.
ethanol e chlorethan
NaCl OH - CH - CH Cl - CH - CH
2 3
HOH NaOH,
2 3
+
+
aldehyde benzoic chloride benzyliden
2NaCl O CH - H C CHCl - H C
5 6
HOH 2NaOH,
2 5 6
+ =
+
ion acetate thane trichloroe
3NaCl COO - CH CCl - CH
-
3
HOH NaOH, 3
3 3
+
+
Reaction with alkaline cyanides (sodium or potassium)
nitriles, permitting to form a new carbon-carbon bond (reaction to
increase the chain)



Reaction with magnesium takes place in anhydrous ether medium
organomagnesium compounds (Grignard reagents).



Reaction with ammonia aliphatic halogenated compounds react with
ammonia at high pressure to form amines.

le acetonitri
NaI CN - CH NaCN I CH
3

3
+ +
bromide magnesium fenyl
MgBr - H C Mg Br - H C
5 6 5 6
+
e methylamin
Cl NH NH - CH 2NH Cl - CH
4 2 3 3 3
+ +
Friedel-Crafts Reaction it is based on the aliphatic halogenated
compounds property to react with arenes in the presence of anhydrous
aluminum chloride.




Hydracids elimination reaction Halogenated derivatives are treated with
strong bases in alcoholic medium
alkenes are formed.



toluen
HCl CH - H C Cl CH H C
3 5 6
AlCl
3 6 6
3
+ +
ethene
HCl CH CH Cl - CH - CH
2 2
alcoolic KOH
2 3
+ =
Hydroxylic compounds
Alcohols
Definition
have the functional group hydroxyl (-OH).
can be considered as water derivatives in which one hydrogen
atom has been replaced with an organic radical (R OH).
Nomenclature
Prefix hydroxy or suffix ol is added to the basic hydrocarbon
denomination (hydrocarbon radical name + alcohol)
CH
3
OH methanol, methyl alcohol, hydroxymethane
CH
3
CH
2
OH ethanol, ethyl alcohol, hydroxyethane
Classification - following three criteria:
the nature of the organic radical to which the OH is bounded:
saturated alcohols (alcohols):
CH
3
CH
2
OH (ethyl alcohol)
unsaturated alcohols (enols):
CH
2
= CH OH (vinyl alcohol)
aromatic alcohols:
C
6
H
5
CH
2
OH (benzyl alcohol)
the number of the functional groups:
monohydric alcohols:
CH
3
CH
2
OH (ethyl alcohol)
di (poly)hydric alcohols:
CH
2
CH
2
I I
OH OH 1,2-ethanediol (glycol)

CH
2
CH
2
CH
I I I
OH OH OH glycerol

carbon atom nature to which the functional group is bounded:
primary alcohols: CH
3
OH

secondary alcohols: - isopropyl alcohol

tertiary alcohols: - tertbutyl alcohol
CH
3
CH
3
OH C
H
3
C
CH
3
CH
3
CH
OH
Physical Properties
Inferior alcohols are liquid substances with very high boiling points,
considering their molecular weight. Superior terms are solid.
Alcohols have lower densities than waters, but superior than the
corresponding hydrocarbons.
The inferior alcohols are very soluble in water. Solubility increases
with the hydroxyl group number.
Chemical Properties
specific to the hydroxyl group, which has a higher reactivity to the
inferior terms of the series.
1. Reaction with alkaline metals
alkoxides or alcoholates (alkaline hydroxyls):




Alcohols have a weak acid character, their reaction with metals
being used as a reducing system.
ethoxide sodium
H 1/2 Na O - CH - CH Na OH - CH - CH
2
-
2 3 2 3
+ +
+
2. Esterification reaction
inorganic esters (reaction with mineral acids):
CH
3
OH + HOPO
3
H
2
CH
3
OPO
3
H
2
+ H
2
O
methanol methyl phosphate

organic esters (reaction with carboxylic acids) :
CH
3
COOH + HO CH
2
CH
3
CH
3
COO CH
2
CH
3
+ H
2
O
acetic acid ethanol ethyl acetate

3. Water elimination from alcohols takes place in two modalities,
function of working conditions:
Intramolecular elimination of water (at warm, in the presence
of sulfuric acid) forms alkenes:
CH
3
CH CH
3
CH
3
CH = CH
2
+ H
2
O
I propene
OH
isopropanol

Intermolecular elimination of water, forming an ether,
(sulfuric acid is in low quantities):
CH
3
CH
2
OH + HOCH
2
CH
3
CH
3
CH
2
OCH
2
CH
3
+ H
2
O
diethyl ether
4. Alcohol oxidation reaction
primary alcohols aldehydes,
secondary alcohols ketones.
Tertiary alcohols are resistant to a mild oxidation, but a strong
one forms many acids, with the chain braking.
a. Mild oxidation of a primary alcohol:




b. Strong oxidation (with potassium permanganate + sulfuric acid
solution):

CH
3
CH
2
CH
2
OH
K
2
Cr
2
O
7
H
2
SO
4
CH
3
CH
2
C
O
H
propanol
propanal
CH
3
CH
2
CH
2
OH CH
3
CH
2
C
O
OH
propionic acid
c. Mild oxidation of a secondary alcohol






d. Strong oxidation of a secondary alcohol
C
2
H
5
C
2
H
5
CH
OH
C
2
H
5
C
2
H
5
C
O
3-pentanol
diethylketone
C
2
H
5
C
2
H
5
CH OH
CH
3
CH
2
COOH CH
3
COOH
propionic acid
acetic acid
+
Thiols (mercaptans)

monosubstituted organic derivatives of hydrogen sulfide H
2
S,
formula RSH for thiols and ArSH for thiophenols.
Comparing with alcohols, they have lower boiling points (sulfur does
not form hydrogen bonds), but have a stronger acid character,
reacting with bases.
The group SH, called thiol is found in biochemistry in
homocysteine or cysteine.
It can form sulfur bridges by oxidation, a very important process
for the conformational organization of proteins, or for realization of
reducing systems as cysteine cystine.

SH
CH
2
H
2
N
CH
COOH
SH
CH
2
H
2
N CH COOH
S S
- 2H
H
2
N
CH
2
CH COOH
CH
2
H
2
N CH COOH
+
cysteine
cystine
SH groups can be oxidized to form important derivatives as
sulfine or sulfate.

SH SO
2
-
SO
3
2-
SO
4
2-
oxidation oxidation oxidation
thiol
sulfinate
derivative
sulfine sulfate
derivative derivative

sulfate
Phenols
Definition
contain in molecule one or more hydroxyl groups (-OH) bound
directly to a carbon atom, which belongs to the aromatic nucleus.
Classification
According the OH group numbers, phenols are:
a. Monohydric phenols (monophenols)





b. Polyhydric phenols (polyphenols)




OH
CH
3
OH
OH
phenol
cresol o-naphtol
OH
HO
OH
OH
OH
OH
OH
resorcinol hydroquinone
pyrogallol
Physical properties
Phenols are solid substances, with low water solubility (the
monohydric ones), easily soluble in alcohol, benzene, etc.
Chemical properties
Phenol chemical properties are a consequence of the reciprocal
interactions between the functional group OH and the aryl radical:
the acid character of OH group is increased (liberation of H ion);
the substitution reactions, specific to the aromatic hydrocarbons.
1. Reaction with alkaline bases it puts in evidence the weak acid
character of phenols.
Salts phenoxides (phenolates).



Phenols (being weak acids) can be liberated from their salts if a
carboxylic acid is added to the salt solution.

C
6
H
5
- OH + NaOH
C
6
H
5
- ONa + H
2
O
sodium phenolate
2. Substitution reaction to the aromatic nucleus takes place on the
ortho and para position, the OH group being a first order
substituent.
Phenol halogenation






Phenol nitration
2
2 Br
2
-2HBr
OH
OH
Br
Br
o-Br-phenol p-Br-phenol
+
+
OH
2
OH
+ 2HONO
2
- 2H
2
O
OH
OH
NO
2
NO
2
+
o-nitro-phenol
p-nitro-phenol
2,4,6-Trinitrophenol (picric acid) is obtained when concentrated nitric
acid is used, at high temperatures.





Phenol sulfonation forms, at room temperature, o-phenol-
sulfonic acid, but at 100C p-phenolsulfonic acid is obtained.

OH
NO
2
NO
2
O
2
N
OH
+ H
2
SO
4
25
o
C
OH
SO
3
H
+ H
2
O
OH
+ H
2
SO
4
100
o
C
OH
SO
3
H
+ H
2
O
3. Hydrogen addition reaction is catalytically realized (Ni) at high
pressure and temperature. Cyclohexanol is formed.

C
6
H
5
OH + 3H
2
C
6
H
11
-OH
cyclohexanol
Amines
Definition. Nomenclature
organic substances which contain in their molecule one or more amino
functional groups: NH
2
, -NH, or N<, bound to an aliphatic or
aromatic radical.
Denomination: the radical name, bound to the nitrogen + amine. If
more identical radicals are bound, their number is indicated as prefix.
Amine classification
Amines: products resulted by replacing of one, two, or even three
hydrogen atoms in NH
3
.
Amines can be classified in primary, secondary and tertiary amines.
CH
3
- NH NH
CH
3
CH
3
CH
3
CH
3
CH
3
N
methylamine
primary amine
dimethylamine
secondary amine
trimethylamine
tertiary amine
According to the hydrocarbon radical nature:
Aliphatic or aromatic (the primary ones): CH
3
-NH
2
(methylamine)
Aliphatic, aromatic or mixed (the secondary and tertiary ones): C
6
H
5

NH
2
(phenylamine, aniline)
According to the number of functional groups:
mono-, di-, tri- and polyamines:





Physical properties
Amines are found in all three aggregation states: gaseous, liquid
and solid, function of the carbon atoms number.
The gaseous ones and most of the liquid ones are totally or partially
water-soluble;
the rest of amines are soluble in organic solvents.

CH
3
CH
2
NH2
CH
2
CH
2
NH
2
NH
2
NH
2
NH
2
monoamine
(ethylamine)
diamine
(ethylendiamine)
diamine
(orthophenylendiamine)
Chemical properties
1. Amine basicity
- Due to the lone electrons of nitrogen, is manifested toward water, acids,
which function as proton donors.
- In water, soluble amines form alkyl ammonium hydroxides.
- Basicity increases from the primary amines to the tertiary ones and is
lower to the aromatic ones, comparing to the aliphatic amines.
CH
3
CH
2
NH
2
+ HOH CH
3
CH
2
NH
3
+
+ HO
-
ethylamine ethylammonium hydroxide

2. Amine alkylation - with halogenated derivatives:
amines increase their substitution grade
primary amines secondary,
secondary amines tertiary,
tertiary amines ionized quaternary ammonium salts.
CH
3 NH
2
CH
3
Cl CH
3
NH
2
CH
3
]
+
Cl
-
methylamine
primary amine
dimethyl-ammonium chloride
+
CH
3
NH
2
CH
3
]
+
Cl
-
+ NH
3
CH
3
NH
CH
3
NH
4
Cl
ammonium chloride dimethylamine
(secondary amine)
+
CH
3
NH
CH
3
+ CH
3
Cl CH
3
NH
CH
3
CH
3
]
+
Cl
-
+ NH
3
CH
3
N
CH
3
CH
3
+NH
4
Cl
secondary amine
trimethyl-ammonium
chloride
trimethylamine
CH
3
N CH
3
CH
3
+ CH
3
Cl
CH
3
CH
3
N CH
3
CH
3
]
+
Cl
-
tetramethyl-ammonium
chloride
3. Primary and secondary amines acylation
replacing of hydrogen atom in the functional group with the acyl
group RCO
+
amide
The acyl donor can be halides of acids, acid anhydrides or even
acids.






Acylamines have no longer basic character (being that possible to
separate tertiary amines from the secondary and primary ones).


e benzanilid
HCl H C - CO - NH - H C COCl - H C NH - H C
e acetanilid
O H CH - CO - NH - H C COOH - CH NH - H C
5 6 5 6 5 6 2 5 6
2 3 5 6 3 2 5 6
+ +
+ +
Aldehydes and ketones
Definition and nomenclature
contain the carbonyl group (>C=O),
bound to an organic radical and a H atom
aldehydes (R-CH=O),
bound to two organic radicals ketones
(R
2
C=O).
The name of aldehydes is formed:
By adding the suffix al to the name of
the saturated hydrocarbon, having the
same number of carbon atoms;
By adding the name aldehyde before the
name of the corresponding acid;
By adding the suffix aldehyde to the root
of the name of the corresponding acid.
O
C H
3
H
- Ethanal
- acetic aldehyde,
- acetaldehyde
The names of ketones are formed:
- By adding the suffix one to the name of the
saturated hydrocarbon, having the same
number of carbon atoms;
- By the name of the two radicals bound to
the carbonyl group, followed by the name
ketone.
- Some time the trivial names are still used.
O
C H
3
C H
3
- Propanone,
- dimethylketone,
- acetone
Physical properties
- The first term of the aldehyde series (formaldehyde) is gaseous.
- The rest of the terms and the ketones are liquid or solid substances, in
normal conditions.
- The inferior terms of both series are water soluble,
- the solubility decreases with the increase of the molecular weight.
Chemical properties
The characteristic reactions of the carbonyl compounds are:
the reactions of the carbonyl group and
the reactions of the o-position (carbon 2)
1. Nucleophilic addition:
- the carbonyl group is polarized; the electrons of the double bond
are more attracted by the oxygen atom (more electronegative than
the carbon atom).
carbon atom has a partially positive charge and is a center for the
attack of a nucleophilic agent.
a. The addition of water hydrates (twin - geminal diols),
which are instable and spontaneously eliminate water to regenerate
the carbonyl compound:
O
C H
3
C H
3
C H
3
C H
3
OH
OH
+ H
2
O
acetone propane-2,2-diol
b. The addition of alcohols, acetals (from aldehydes) or
ketals (from ketones).




acetaldehyde + ethanol diethyl acetal of acetaldehyde
c. Addition of hydrogen cyanide cyanohydrins
(hydroxynitriles)


O
C H
3
H
C H
3
H
OC
2
H
5
OC
2
H
5
O H C
2
H
5
+ 2
O
C H
3
C H
3
OH C H
3
C H
3
CN
+ HCN
acetone acetone cyanohydrin
2. Aldol and croton condensation:
- The condensation of the carbonyl group with the C-H group of
a molecule having an active methylene.
- That kind of group (with active methylene) is present in
compounds with an acidifying group (>C=O, -COOR, -NO
2
)
in the o-position of the C-H group.

C
1
O C
5
CO
H
H C
18
CH
OH
CO
C
26
C
27
CO
+
aldol condensation
-H
2
O
croton condensation
(carbonylic compound, o,| unsaturated)
C O
C H
3
C H
3
C
H
H
H
CHO C
H
CH
OH
C H
3
CHO
C
H
C
H
C H
3
CHO
+
aldol
-H
2
O
aldehida crotonica
crotonaldehyde
3. Condensation with amines
Carbonyl compounds react with ammonia or amines resulting imines
or substituted imines (Schiff bases)




amine aldehyde substituted imine
4. Reactions of oxidation and reduction:
a. Oxidation with the formation of carboxylic acids, in the
presence of KMnO
4
, CrO
3
:
R-CH=O + [O] R-COOH

b. Autooxidation with the formation of peracids:




c. Reduction of carbonyl group to form primary alcohols
(from aldehydes) or secondary alcohols (from ketones):
R C
H
O
R C
O
O O H
+ O
2
R C
H
O
CH
2
OH
+ [H] 2
R
R
2
C O
R
2
CHOH
+ [H] 2
Carboxylic acids
Definition. General formula
found in a large variety and quantity in nature.
contain the functional group carboxyl (COOH)
general formula: R-COOH
Under the influence of the carbonyl group, the hydrogen in the
hydroxyl group is weakly bound to the oxygen atom.
Therefore, carboxylic acids have a higher tendency to release
protons (H
+
) than the corresponding alcohols, manifesting a
stronger acidity.
Under the influence of the hydroxyl group, carboxylic acids do not
manifest the aldehyde or ketone character, determined by the
presence of the carbonyl group.
Nomenclature
The scientific denomination o carboxylic acids is realized adding the
suffix oic to the name of the hydrocarbon having the same carbon
atoms number.
H-COOH metanoic acid - formic acid
CH
3
COOH ethanoic acid - acetic acid
CH
3
CH
2
COOH propanoic acid - propionic acid
CH
3
CH
2
CH
2
COOH butanoic acid - butyric acid
CH
2
= CH COOH propenoic acid acrilic acid
CH
3
CH
2
CH
2
CH
2
COOH pentanoic acid - valeric acid

In the case of carboxylic acids having more than one carboxyl group,
their number is indicated with the prefix di-; tri-; etc.

HOOC - COOH ethanedioic (oxalic) acid

The position of the COOH groups is indicated using Arab numbers.
HOOC CH
2
COOH 1,3-propanedioic (malonic acid)
HOOC(CH
2
)
2
COOH 1,4-butanedioic acid (succinic acid)
HOOC(CH
2
)
3
COOH 1,5-pentanedioic (glutaric acid)
HOOC(CH
2
)
4
COOH 1,6-hexanedioic (adipic acid)
Classification
according to the radical nature:
saturated acids CH
3
CH
2
COOH propanoic acid
unsaturated acids CH
2
= CH COOH acrylic acid
aromatic acids C
6
H
5
COOH benzoic acid
according to the COOH groups number:
monocarboxylic acids CH
3
COOH acetic acid
- polycarboxylic acids HOOC COOH oxalic acid
COOH
COOH
COOH
COOH
ortho-phtalic acid terephtalic acid
Fatty acids (FA)
- are components of lipids.
> 70 FA (most majority having an even carbon atoms number, linear
chain; there are, also, fatty acids with an odd carbon atoms number,
with a branched chain, cyclic, etc.
FA classification:
saturated fatty acids
unsaturated fatty acids (mono- and polyunsaturated)
hydroxylated fatty acids
cyclic fatty acids
A. Saturated fatty acids:
- linear chain
- general formula: CH
3
-(CH
2
)
n
-COOH, n = 2 30
- the most frequently found: stearic acid (18C), palmitic acid
(16C), miristic acid (14C)


Fatty acid denomination
Carbon
atom
number
Structure
Melting
point C
Usual Systematic
Butyric n-butaneoic 4 CH
3
(CH
2
)
2
- COOH - 8,0
Capronic n-hexaneoic 6 CH
3
(CH
2
)
4
- COOH - 1.5
Caprilic n-octaneoic 8 CH
3
(CH
2
)
6
- COOH +16,5
Caprinic n-decaneoic 10 CH
3
(CH
2
)
8
- COOH +31,0
Lauric n-dodecaneoic 12 CH
3
(CH
2
)
10
- COOH +44,0
Miristic n-tetradecaneoic 14 CH
3
(CH
2
)
12
- COOH +53,8
Palmitic n-hexadecaneoic 16 CH
3
(CH
2
)
14
- COOH +62,5
Stearic n-octadecaneoic 18 CH
3
(CH
2
)
16
- COOH +69,6
Arahidic n-eicosaneoic 20 CH
3
(CH
2
)
18
- COOH +71,6
Behenic n-docosaneoic 22 CH
3
(CH
2
)
20
- COOH +80,3
Lignoceric n-tetracosaneoic 24 CH
3
(CH
2
)
22
- COOH +84,5
B. Unsaturated fatty acids
monounsaturated (with a single double bond) Cn:m
example: oleic acid (C18:9) found mostly in vegetals; the cis
form is liquid, the trans form is denominated elaidic acid (solid;
synthetic product); palmitoleic acid (C16:9)
C
C
(CH
2
)
7
CH
3
(CH
2
)
7
COOH
H
H
C
C
(CH
2
)
7
CH
3
(CH
2
)
7
COOH
H
H
oleic acid elaidic acid
polyunsaturated (with many, isolated double bonds)
Example: linoleic acid (C18:9,12); linolenic acid
(C18:9,12,15); arahidonic acid (C20:5,8,11,14)
they cannot be synthesized by human organisms, their intake
being indispensable (ESSENTIAL FATTY ACIDS)
Their deficiency produces retarded development, hair loosing,
reproduction troubles.
They are basic components of cellular and mitochondria
membranes.
They are prostaglandins precursors.
18 13 12 11 10 9 1
CH
3
- (CH
2
)
4
CH = CH CH
2
CH= CH (CH
2
)
7
COOH e6
linoleic acid

CH
3
CH
2
CH = CH - CH
2
- CH=CH - CH
2
- CH=CH - (CH
2
)
7
COOH
e3 linolenic acid

CH
3
(CH
2
)
4
(CH=CH CH
2
)
3
CH = CH (CH
2
)
3
COOH e6

arahidonic acid
C. Hydroxylated fatty acids
They are rare and contain a functional secondary hydroxyl group (- OH) in
the saturated or unsaturated chain.
Example: cerebronic acid (24C), hydroxynervonic acid (24C + a double-
bond) are found in cerebrozides





Physical properties
Saturated, acyclic, monocarboxylic acids - liquid (the inferior terms) and
solid (superior terms).
The inferior terms are water soluble, but solubility decreases as the
molecular weight increases. The superior terms are soluble only in organic
solvents.
Polycarboxylic acids are solid.
Their water solubility is much higher to the odd carbons number terms
comparing with even carbon numbers terms, and decreases with the
molecular weight.
CH
3

(CH
2
)
21
CH
COOH
OH
CH
3
(CH
2
)
7
CH COOH
OH
CH CH
(CH
2
)
12
cerebronic acid
hydroxynervonic acid
Chemical properties
Organic acids are the final products of many oxidizing reactions and
have some chemical stability.
1. Common properties with inorganic acids (ionization in water
solution, reaction with active metals, with basic oxides, with bases,
etc.).
a. Carboxylic acids are weak acids



b. Synthesis of carboxylic acid salts:
With hydroxides
CH
3
COOH + NaOH CH
3
COO
-
Na
+
+ H
2
O
sodium acetate
with basic oxides
2CH
3
COOH + K
2
O 2CH
3
COO
-
K
+
+ H
2
O
with active metals
2CH
3
COOH + 2Na 2CH
3
COO
-
Na
+
+ H
2

CH
3
- COOH + H
2
O
CH
3
- COO
-
+ H
3
O
+
acetic acid
acetate ion
2. Characteristic reactions of carboxylic acids
anhydrides, esters, amides, nitriles, halides.
a. Reaction with ammonia
Ammonium salts, which dehydrate partially, at warm, forming
amides. Total dehydration, in phosphorus pentaoxide presence,
forms nitriles.
acetate ammonium acid acetic
COONH - CH NH COOH - CH
4 3 3 3
+
CH
3
- COONH
4
partial dehydration
t
o
C, -H
2
O
CH
3
- CO - NH
2
acetamide
CH
3
- COONH
4
total dehydration
P
2
O
5
, -H
2
O
CH
3
- CN
acetonitrile
b. Reaction with amines forms an amidic bond:
CH
3
COOH + CH
3
NH
2
CH
3
CO NH CH
3
+ H
2
O
N-methyl-acetamide
These types of bonds are found in complex lipids (sphingolipids).
c. Reaction with alcohols (esterification) takes place in acid
catalysis esters.


d. Obtaining of carboxylic acid anhydrides
CH
3
- COOH + C
2
H
5
- OH CH
3
- CO - OC
2
H
5
+ H
2
O
ethyl acetate
CH
3
- COOH + HOOC - CH
3
CH
3
-CO
CH
3
- CO
O
acetic anhydride
CH
3
- COOH + HOOC - C
6
H
5
CH
3
-CO
C
6
H
5
- CO
O
mixt anyidride
acetic - benzoic
Carboxylic acid derivatives have a common property: they
regenerate by hydrolysis the carboxyl group
1. Ester hydrolysis in acidic medium:


2. Acid anhydride hydrolysis:



3. Amide hydrolysis:



4. Nitrile hydrolysis
CH
3
-CN + 2H
2
O CH
3
-COOH + NH
3
CH
3
- CO - OC
2
H
5
+ H
2
O
H
+
CH
3
- COOH + C
2
H
5
- OH
acetic acid ethanol ethyl acetatel
CH
3
- CO
CH
3
- CO
O
+ H
2
O
2 CH
3
- COOH
acetic anhydride acetic acid
C
6
H
5
- CO - NH
2
+ H
2
O
t
o
C
C
6
H
5
- COOH + NH
3
benzamide benzoic acid
Organic derivatives of phosphorus
The most spread phosphorus combinations are: esters of
phosphoric, diphosphoric and triphosphoric acids.
Phosphoric acid H
3
PO
4
- weak acid
- It has three ionization steps, the first one being the easiest one.

- The main phosphoric acid combinations are phosphates,
(esters) obtained from the combination with an alcohol.


P
O
OH
OH HO
O
O
CH
2
OH
OH
OH
OH
OH
OH
OH
OH
CH
2
OH
O P
O
OH
OH
+H
2
O
+ H
3
PO
4
glucose glucose-1-phosphate
Polyphosphoric acids are obtained by condensation of phosphoric
acid molecules.
2H
3
PO
4
H
4
P
2
O
7
+ H
2
O






Three phosphoric acid molecules form triphosphoric acid
HO - P - O - P - OH
O O
OH OH
pyrophosphoric acid
HO - P - O - P - O - P - OH
O O
OH OH
O
OH
Polyphosphoric acids are parts of molecules rich in energy, type
XTP, where X represents a purine or pyrimidine nucleozide






These molecules are macroergic, which means they store a high
quantity of energy as phosphate anhydride bonds. This energy can
be easily liberated when the bond is hydrolyzed.

N
O
N
N
N
NH
2
OH OH
CH
2
HO - P ~ O - P ~ O - P ~ O
OH OH OH
O O O
Adenosine triphosphate
ATP
Heterocycles

A. Contain one or more heteroatoms in their cycles. For example:
cyclic esters of glycine, cyclic anhydrides of dicarboxylic acids,
cyclic secondary amines, monosaccharides.
These compounds do not behave chemically very differently from
the acyclic compounds with a similar structure.
B. Heterocyclic combinations, poor in hydrogen, which are more
similar to benzene, having an aromatic character.
The main heteroatoms found in heterocyclic combinations with an
aromatic character are nitrogen, oxygen, sulfur.

N
C H
C H
C
H
CH
CH
O
C H
C
H
C
H
CH
S
C H
C
H
C
H
CH
N
H
C H
C
H
C
H
CH
N
H
C H
N C
H
CH
N
H
CH
C
H
C
H
C H
C H
C
H
O
C H
C H
C
H
CH
CH
2
N
C H
N
C
H
CH
CH N
N
N
N
N
O
pyridine
furan thiofen
pyrol
imidasol
indol pyran
phenoxasine
pyrimidine
purine