Assignment:- Advance Organic Chemistry (B-2)

Paper :- B-2(1st/A-2014) Name:-Muhammad Shahzad Ayyaz Roll No :-16

Submitted to:- Dr. Saifullah Jami
Explain the followings with short answers.
Q :-(1) Why a polar solvent usually shifts the π-π̽ transition to a longer wavelength?
Ans: In case of π-π̽ transition, the excited states are more polar than the ground state and the dipole-
dipole interactions with the solvent molecules lower the energy of the excited state more than that of
the ground state .Therefore a polar solvent decreases the energy of π-π̽ transition and absoption
maximum appears nearly 10-20 nm red shifted in going from hexane to ethanol solvent.
Thus less energy and more wavelength is required for such transition and in this π-π̽ , transition is
shifted towads longer wavelength.
Q:- (2) Explain the difference between frequency and wavenumber?
Ans: Frequency : The number of waves which can pass through a fixed point in one second is called
frequency. It is denoted by Ѵ (nu). It’s unit is hertz or cycle per second (1Hz=1cps). It’s mathematical
formula is given below Ѵ=Ϲ/λ where C is velocity of electromagnetic radiation and λ is a wavelength
of radiation.
Wave Number: The reciprocal of wavelength is called wave number. OR The total number of waves
which can pass through a space of one cm or one meter. It is denoted by Ѵ̅. It’s unit is per centimeter or
per meter. It’s mathematical formula is given below Ѵ̅ =1/λ
Q:- (3) Describe the role of overtones in IR Spectroscopy?
Ans: When a molecule absorb infrared radiation of appropriate energy besides fundamental
vibrations, other bands also occur corresponding to the excitation to the 2 nd, 3rd or 4th excited
states.These bands also known as overtones.

They are weak but are important in characterization of certain classes of compounds particularly
benzene derivative.
Aliphatic and aromatic aldehydes may be distinguished from the presence of overtone band in range of
2000-1665cm-1.
Q:- (4) How you can differentiate between acetone and acetaldehyde using IR Spectroscopy?
Ans: Both acetaldehyde and acetone show a very prominent C=O stretching around 1700cm-1.

But in acetaldehyde additional peak around 2820 and 2720 is also present.They often look like a doublet
and sometime refered to as a fermi-doublet. These are C-H stretches between aldeydic proton and
carbonyl carbon. The presence of these peaks along with the carboyl peak is a good indication of an
acetaldehyde.
Q:- (5) How cis-cinnamic acid can be distinguished from trans-cinnamic acid by NMR Spectroscopy?
Ans:
Q:- (6) How benzoic acid can be differentiated from benzyl alcohol by Mass Spectrometry?
Ans: Benzyl alcohol: Benzyl alcohol is a representative member of group alcohol. It exhibits intense
and strong peak due to loss of CO (M-28) and loss of CHO (M-29).

Benzoic Acid:-

Through fragmentation pattern both benzoic acid and benzyl alcohol can be distinguished by mass
spectrometry.
Q:-(7) Differntiate the term molecular ion peak and base peak?
Ans: Molecular ion peak: A peak is called molecular ion peak if it fulfill following conditions
(1) It is always at higher m/e value along x-axis in mass spectrum except isotopic peaks.
(2) It will form by losing one electron of low ionization potential.
(3) It is the peak of original compound.
(4) It is represented by M⁺ or M·⁺.
(5) Sometime molecular ion form undergo a collision with the neutral portion of the molecules.The part
of neutural portion may get detach and attach to the molecular ion forming ions having masses more
than the parent molecule. The peak due to these ions in mass spectrum is called Quasi moleular ion
peak.
(6) Absence of molecular ion peak means that the compound is highly unsatable.
(7) Stable compunds show intense peak.
Base Peak: The most intense peak of mass spectrum is called base peak. It is assigned a relative
intensity of 100% and the intensities of other peaks are expressed as %age of base peak. It is the peak
due to the most stable uni-positive ion which may be due to parent molecule or fragment ion.
Q:-(8) How the ̶ NH2 group can be protected by converting it into amide and then deprotected?Quote
an example?
Ans: This can be prepared by the reaction of amine and formic acid or formyl chloride in the presence
of acetic anhydride. For example

It can also be prepared by the reaction of an amine with HCl /H ₂O in dioxane in refluxing condition. For
example

A formamide is stable to sponification of an ester group.

Cleavage:- There are several method for the cleavage of this group. i-e
Q :-(9) Summarize the " isoprene rule" executed in the biosynthesis of terpene molecule?
Ans: This rule was first pointed out by WALLACH (1887) which states that The thermal decomposition
of almost all terpenoids give isoprene as one of the product.This suggested that the skeleton(structure)
of all natural occuring terpenoids is built up of isoprene units.

Isprene = C₂H₈

Thus the divisibility of terpenoids into isoprene units may be regarded as a necessary condition to be
satisfied by the structure of any plant synthesized terpenoids.
Q:-(10) How the term "secondary metabolites" can be defined?Quote two examples of well known
secondary metabolotes?
Ans: Secondary metabolites are organic compound that are not directly involved in the normal
growth,development,reproduction of an organism unlike primary metabolites.

Absence of secondary metabolites does not result in immediate death but rather in long term
impairment of the organisms survival or aesthetics.Secondary metabolites are often restricted to a
narrow set of species within a phylogenetic group.It plays important role in plant defence against
herbivory.Human use secondary metabolites as 1- Medicine 2- Flavouring 3- Drugs

Metabolites are the substances produced during metabolism .They are of two types which are given as
1- Primary metabolite 2- Secondary metabolite