Organic chemistry

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Resonance:
Resonance, also known as mesomerism, is a means of defining bonding in specific molecules or ions in
valence bond theory by combining many contributing structures (or forms, also known as canonical
structures or resonance structures) into the resonance hybrid (or hybrid structure). It’s especially useful
for explaining delocalized electrons within molecules or polyatomic ions where the bonding can’t be
stated by a single Lewis structure.

Even while no single Lewis structure contains two N–O bonds with the same formal bond order, the two
N–O bond lengths are equal in the NO2–nitrite anion. Its measured structure, on the other hand, is
consistent with a description as a resonance hybrid of the two major contributing structures shown
above: it has two equal N–O bonds of 125 pm, which are halfway between a typical N–O single bond
(145 pm in hydroxylamine, H2N–OH) and a N–O double bond (115 pm in nitronium ion, [O=N=O]+). Each
N–O bond is an average of a formal single and formal double bond, resulting in a true bond order of 1.5,
according to the contributing structures. The Lewis description of bonding in NO2– is reconciled with the
experimental observation that the anion possesses equivalent N–O bonds as a result of this averaging.

R&S :
1. Stereochemistry is the branch of chemistry that deals with the study of the spatial atomic
arrangement that forms the molecular structure.
2. R/S system is the nomenclature system for enantiomers.
3. In this type of nomenclature, each chiral center is assigned R or S following a system by which its
substituents are each assigned a priority based on atomic number, following the Cahn-Ingold-
Prelog rules.
4. The R means Rectus in Latin (means right) and S means Sinister in Latin (means Left).
5. Molecules that rotate the plane polarised light to right is said as R isomer.
6. Molecule that rotate the plane polarised light to left is said as S isomer.
7. Example:

E-Z :
 It is a type of stereoisomerism.
  It applies to alkene which contains C=C double bond and two different groups on both end.

Rules for E-Z system:

 The atoms or groups attached to each olefinic carbon are given priority as per the sequence
rule.
 If the higher priority groups are present on same sides across the double bond, the geometrical
isomer is said to have Z-configuration or 'cis'.
 If the higher priority groups are present on opposite sides across the double bond, the
geometrical isomer is said to have E-configuration or 'trans'.
 For example:

Sequence rule:
Sequence Rules It is the spatial arrangement of atoms within the chiral molecules that is described in
terms of absolute configuration (R) and stereochemistry (S). The Sequence Rules were developed by
Cahn, Ingold, and Prelog to assign priority orders to the atoms or groups directly attached to
stereocenters. These rules determine whether a stereocenter's absolute configuration is (R) or (S).
Rule 1 - The atom with the highest atomic number receives priority over the atom with the lowest
atomic number

For example, I > Br > Cl > F >O > N > C > H.

Rule 2 - Priority is given to isotopes with higher atomic weights.

For example, 3H (tritium) > 2H (deuterium) > 1H (hydrogen) Rule 3 - Whenever two or more atoms are
directly attached to the same stereocenter, the next atom on the chain determines the priority order.

Rule 3 - Whenever two or more atoms are directly attached to the same stereocenter, the next atom on
the chain determines the priority order.

For example, –CO2CH3 > –CO2H > CONH2 > COCH3 > CHO > CH2OH
Rule 4 - The amount of a double bond taken into account when an atom is single bonded to two atoms
is the same as if it were a single bond. In the case of a triple bond between two atoms, treat this atom as
if it were 13 bonded to a single atom. To order the priority of the unsaturated groups attached to the
stereocenter, convert the unsaturated groups into saturated groups, e.g.

Rule 5 - There may not be a difference between a smaller group and a longer one in priority.
For example, The priority of –CH2Cl is greater than that of –CH2CH2CH2CH3.

Rule 6 - Assign the lowest priority group at the front of the molecule, when it is facing the plane. S is
anticlockwise, and R is clockwise.

Rule 7 - The stereocenter of the whole molecule can be defined by using a number that identifies the
stereocenter preceding configuration (e.g., 1R, 4S) when there are multiple chiral carbons.

Conformational Analysis of n-Butane:

Rotation (of a rear cluster radially) all around the C2-C3 bond like a consequence of torsion angle yields
several conformations in n-butane, C1H3 -C2H2-C3H2 -C4H3, which have been expressed in Newman
projection formulae as regards:

One pairing of eclipsed methyls as well as two sets of eclipsed hydroxyl groups make up conformation A.
It is also achiral and also has a plane. This would be the n-butane conformation with the most energy,
which results from rotation around the C2-C3 bond. This conformation has the highest amount of
energy (18-26 kJ mol-1) in the potential power curve of n-butane.

The van der Waals gross repulsive connections, primarily here between two eclipse methyl groups
(CH3/CH3 eclipsing interaction), as well as torsion stress due to the eclipse of three sets of vicinal bonds,
contribute to the rotational energy gap.
Fischer projection:
Fischer projection formula or cross formula : The three dimensional (3-D) view of a molecule is presented
on plane of paper. A Fischer projection formula can be drawn by visualizing the main carbon chain verical
in the molecule. Each carbon on the vertical chain is represented by a cross.

Conventionally the horizontal lines of the cross represent bonds projecting up from the carbon and the
vertical lines represent the bonds going below the carbon.

What are Free Radicals?

 A free radical is termed as a molecular species which can contain an unpaired electron in its
atomic orbital and can exist independently. Free radicals are unique and rare species and are
present only under special and limited conditions. However, some free radicals are familiar to us
in our lives.
 So free radicals are very familiar to us in our lives and are very important chemicals.
 Free radicals are highly reactive and very unstable. They can donate an electron or accept an
electron from other molecules, therefore, can behave as oxidants or reductants.

Examples of Free Radicals

Consider three reactive species: a methyl anion, methyl cation and methyl radical. These radicals are
shown below.

Types of Free Radicals

Most organic radicals are quite unstable and very reactive. There are two kinds of radicals, neutral
radicals and charged radicals as shown below.
Titration Procedure:
The process of titration involves the preparation of a titrant/titrator, which is a standard solution whose
volume and concentration are predetermined. This titrant is then made to react with the analyte until
some endpoint or equivalence point is reached; at that stage, the concentration of the analyte can be
determined by measuring the amount of titrant consumed. Alternatively, titration is the concept of
stoichiometry that is applied to find the unknown concentration of a solution.

As the first step of the procedure, a very precise amount of the analyte is added to a beaker or
Erlenmeyer flask. A small amount of indicator (such as phenolphthalein) is placed underneath a
calibrated burette or chemistry pipetting syringe, which consists of the titrant.

Small volumes of the titrant are added to the analyte and indicator. This will go on until the indicator
changes colour in reaction to the titrant saturation threshold. At this point, it will represent that we
have come to the endpoint of the titration. Basically, in this case, the amount of titrant balances the
amount of analyte present during the reaction.

Termination of Free Radical:

Termination is the final step in the polymerization process. Termination occurs in different stages. If
longer chains are expected, the initiator concentration should be less; otherwise, many short chains will
form.

Conformational Isomers:
If we observe the ball and stick model of ethane and rotate one carbon atom keeping another carbon
atom stationary about the C-C axis. We will observe that the rotations will result in an infinite number of
spatial arrangements of hydrogen atoms attached to one carbon atom with respect to the hydrogen
atoms attached to the other carbon atom. These different arrangements are better known
as conformational isomers or conformers.

Predominantly, these can be broadly classified into two different cases:

Eclipse conformation:
Conformation in which hydrogen atoms are attached to two carbons stay nearest to each other as
possible is known as eclipsed

Staggered conformation:
Confirmation in which hydrogen atoms attached to two carbons are as far as possible with respect to
each other is known as staggered The staggered conformation is thus relatively more stable in
comparison to eclipse conformation as there are minimum repulsive forces, minimum energy due to
many separations between the electron clouds of C-H bonds.

What Is Hydrogen Bonding?

Hydrogen bonding refers to the formation of hydrogen bonds, which are a special class of attractive
intermolecular forces that arise due to the dipole-dipole interaction between a hydrogen atom that is
bonded to a highly electronegative atom and another highly electronegative atom which lies in the
vicinity of the hydrogen atom. For example, in water molecules (H2O), hydrogen is covalently bonded to
the more electronegative oxygen atom. Therefore, hydrogen bonding arises in water molecules due to
the dipole-dipole interactions between the hydrogen atom of one water molecule and the oxygen atom
of another H2O molecule.

Examples of Hydrogen Bonding

Hydrogen Bonding in Hydrogen Fluoride

Fluorine, having the highest value of electronegativity, forms the strongest hydrogen bond.

1. Hydrogen bonds are weak bonds.

2. Some applications of hydrogen bonds in organic molecules are because of the hydrogen bonding
that can occur between water and the alcohol molecule, lower alcohols are soluble in water.

3. A compound's melting point rises when hydrogen bonds are present.

4. A compound having a hydrogen bond is more soluble as compared to other compounds.

Carbocation:
A carbocation is a molecule in which a carbon atom has a positive charge and three bonds. We can say
that, basically, they are carbon cations. Formerly, it was known as carbonium ion. Carbocation today is
defined as any even-electron cation that possesses a significant positive charge on the carbon atom.

In carbocation, the hybridization of carbon will be sp2 and its shape is trigonal planar. There is
also a vacant p orbital which indicates its electron-deficient nature. The carbon has 6 electrons in
its valence shell. Due to this, it is an electron-deficient species, also known as an electrophile.

A carbocation is generally observed in an SN1 reaction, elimination reaction, etc.

When haloalkane or alkyl halide with a β-hydrogen atom is heated with alcoholic solution of potassium
hydroxide (alc.KOH), the OC2H5− ion acts as a base and eliminate an hydrogen from β - carbon atom
then this elimination is known as β - elimination. There is also a simultaneous elimination of halogen
atoms from α - carbon. As a result, an alkene is formed.
This reaction is also called dehydrohalogenation.

E1 Reaction:
 In the E1 mechanism which is also known as unimolecular elimination, there are usually two
steps involved – ionization and deprotonation.

 During ionization, there is a formation of carbocation as an intermediate. In deprotonation, a

proton is lost by the carbocation.
  This happens in the presence of a base which further leads to the formation of a pi-bond in the
molecule.

 In E1, the reaction rate is also proportional to the concentration of the substance to be
transformed.

 It exhibits first-order kinetics.

E2 Reaction
 In an E2 mechanism which refers to bimolecular elimination is basically a one-step mechanism.

 Here, the carbon-hydrogen and carbon-halogen bonds mostly break off to form a new double
bond.

 However, in the E2 mechanism, a base is part of the rate-determining step and it has a huge
influence on the mechanism.

 The reaction rate is mostly proportional to the concentrations of both the eliminating agent
and the substrate.

 It exhibits second-order kinetics.

The E2 mechanism can generally be represented as below. In the below-mentioned representation, B

stands for base and X stands for halogen.

The rate of the E2 reaction is

Rate = k[RX][Base]

So the reaction rate depends on both the substrate (RX) and the base involved. In the elimination
reaction, the major product formed is the most stable alkene.