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 NMR
Ø INTRODUCTION
• NMR is absorption spectrometry.
• Permits identification of atomic configuration.
• Radiofrequency waves are used in NMR.RF waves have long wavelength so less
energy.
• Range of RF is from 30 KHZ TO 30 MHZ.
• Felix Bloch and Edward Purcell received Nobel Prize for NMR discovery.
• NMR mechanism includes change in spin orientation on exposure to magnetic
field.
• Spin quantum number(I) describes angular momentum.
• Total spin quantum number depends on the number of nucleons and symmetry of
charge distribution.
• Precessional frequency-No. of spin carried out by the nucleus in the presence of
magnetic field per second.
Thus when magnetic field applied the nucleus spins with precessional frequency.
Before application of magnetic field it was moving with random frequency.
• When no magnetic field, only one energy level. but in presence of magnetic field
2 energy levels with aligned and opposite orientations of the nuclear spins.
• Precessional frequency is directly proportional to field strength(ν)
ν ά Bo
• Remember-
When mag.field=1.4 tesla,ν=60MHZ.
When mag.field=2.3 tesla,ν=100MHZ.
When mag.field=7.0tesla,ν=300MHZ.
When mag.field=14.1Tesla,ν=600MHZ.

1 Tesla=104 Gauss.so 1.4 Tesla=14000 Gauss.

Imp-Tesla is measure of magnetic flux density not field strength.

• Resonance occurs when,
Applied frequency from RF oscillator=precissional frequency of spinning nucleus.

• VARIOUS NUCLEUS
• When mass no. is odd,atomic no.odd/even spin quantum number(SQN) is in
fraction e:g 1H=1/2,11B=3/2.,13C=19F=31P=1/2.
• When mass no. is even,atomic no.odd spin quantum number(SQN) is in integer;
E;g 10B=3,14N=1.2D=1.
rem = they exhibit quadrapole moment.
• When mass no. is even,atomic no.even spin quantum number(SQN) is 0.
E:g 12C=0,16O=0.

IMPORTANT POINTS (continued)…

• No of possible orientations= 2I+1,so 1H will have 2 and 2D & 14N will have 3 orientations.
 • Imp.formula
ω = Ho
ω=larmor frequency.
But ω=2πν,so ultimate equation,

ν= Bo/2π

= µ/I

=gyro magnetic ratio

µ=nuclear magnetic moment
I=nuclear angular momentum.
• Remember = gyro magnetic ratio of 1H=268,while of 13C NMR is 67.so 13 C NMR is 4
times less sensitive than 1H NMR. so if the resonance frequency of particular nucleus
in1HNMR is 300 MHZ, in 13CNMR it is 300/4 = 75MHZ.
Gyro magnetic ratio of 2H is 1/3 of 1H.
• There are some more nuclei in lower energy state which are responsible
for absorption of RF. so NMR phenomenon occurs. This distribution is
according to Boltzmann’s law.

frequency Excess nuclei frequency Excess nuclei

20 3 100 16
40 6 200 32
60 9 300 48
80 12 600 96

Relaxation process of nucleus

• Spin-lattice or longitudinal relaxation-gives energy to lattice so system
gets heated.
• Spin-spin or transverse relaxation-give energy to nearby nuclei so no net
change in energy of system.
REMEMBER:spin-lattice relaxation time (T1)determines the rate at which
absorption of RF can occur.
Rememeber : relaxation process follow first order process and T1 is the
reciprocal of first order rate constant.
T2 is spin-spin relaxation time.
Remember-if T1 and T2 small,broad absorption lines,if they r large sharp
abs. lines.
FOR non-viscous solids T1 is large so sharp lines in NMR spectrum.
FOR 14N nucleus T1 is small due to quadrapole so broad signals in 14N NMR.
REMEMBER
• Solids are difficult to analyze by NMR so MAGIC ANGLE is used for solid
samples which is 54.6 degree. Thus solid samples are oriented at this angle
and observed.thus solids can be analyzed.
INSTRUMENTATION
• Magnet
• RF oscillator
• Sweep generator
• RF receiver
• Recorder

Internal standards
• TMS(tetramethyl silane)(0.01-1%) – universally accepted,used only in organic
solvents.TMS is used in 1H and 13C NMR.
• Sodium salt of 3-(trimethylsilyl)-propane sulfonic acid and DDS is used in
aqueous solvents.
• CFCl3 for 19F NMR.
• H3PO4 for 31P NMR.
• NH3(absolute standard) and nitromathane(mostly used) for 14N NMR.
• Water for 17O NMR.

CHEMICAL SHIFT
• Expressed in ppm (delta or tau) units.
=10-δ
High delta value=downfield
Low delta value=upfield
For tau it is reverse.
Rem - δ is dimensionless number and it is field independent.
• Chemical shift values depend on shielding and deshielding.
TMS has 12 protons to shielding of nucleus by protons so less δ i:e=0.
If electronegative element, like Cl than removal of electrons near nucleus
so deshielding so large δ.
• Chemical shift values range from 1-20.

FACTORS AFFECTING CHEMICAL SHIFT

• Hybridization effect
• Electronegativity- Protons which are attatched to the most electronegative
atoms are considered to be highly deshielded. It results in increase in chemical
shift value.
• Van der walls deshielding-observed in rigid molecules.effect less than 1 ppm.
• Anisotropic effect-called space effect also.anisotopic means effects are not
same in all directions (in some direction effect is paramagnetic,in some directions
it is diamagnetic).(TABLETS are anisotropic in nature).
Due to this effect δ value of proton is higher in ethane,lower than expected in
ethyne,higher in aldehyde and acids.(for more refer pavia).
• Hydrogen bonding-increases δ.
Solvents for NMR
• CDCl3 mostly used.
• Should not contain hydrogen (aprotic solvents)
• For polar solutes-D2O,DMSO-d6,CCl2,CS2 ,CF3.
• Compound solubility should be atleast 10%.

TWO METHODS OF RECORDING NMR

1. CONTINUOUS WAVE METHOD

• RF remains constant and mag. Field is varied. This is called
sweeping.
2. Fourier transform methods.
• In this, the sample is irradiated with strong pulse of
radiofrequency energy containing all frequency of 1H range.
• It gives spectrum in frequency domain.
• Pulse duration is 10 microsecond and then pulse is switched off
so nuclei get relaxed.
• Process of transfer of magnetization from RF to nuclei is called
free induction decay.
• Higher sensitivity, can work in low concentrations.
• Used for sparingly soluble substances.

GOLAY COILS/SHIMMING COILS

• These are used to increase the accuracy of the instrument.
• They are electromagnetic coils which induce small electromagnetic
fields in order to improve the inhomogenity of the field.(sample can
also be spun to remove inhomogenity)
IMP-ringing phenomenon is produced in CW mode and not in FTNMR mode.

REMEMBER
• Sensitivity is ratio of signal to noise. For 1HNMR,quartet of ethyl
benzene spectrum is used for calculating S/N ratio and for
13CNMR,largest aromatic peak in ethyl benzene spectrum is used as
standard.

A VERY VERY IMPORTANT POINT

• Superconducting magnets are used for higher fields. A metal
becomes a super conductor when it is cooled in liquid helium at
4K(Kelvin).
• Niobium and Titanium alloy is used as superconductor.
• For higher fields like 10 T, Nb3Sn can be used.

Chemical shift table (only imp)(for more refer pavia-but these are
enough)
structure Chem..shift structure Chemical shift
alkane 0.5-1.5 Aliphatic ketone 2-2.7
 alkene 1.5-3.0 OCH3(methoxy) 3.82
alkyne 1.7-2.7 Benzylic proton 2.3-2.7
Benzene and 6-9 Aliphatic ester 3.5-5
aromatics
aldehyde 8-10 Phenolic proton 4-7
acid 11-12 amide 5-9

Imp-CDCl3 solvent gives peak at 7-7.5, which is a solvent peak.

IMPORTANT POINTS
• If protons are magnetically and chemically equivalent as in CH3, only
one signal for that proton.
• Two protons are chemically equivalent if they are in same chemical
environment and have same chemical shift value.
• Two protons are magnetically equivalent if each couples equally to
neighboring proton.
• Chemical eq. means chemical shift equivalency.
• Magnetic eq. means coupling equivalency.
• Accidental equivalence- It is observed in 2,5-dichloro nitrobenzene.

SPIN-SPIN COUPLING
• The signal splits according to the n+1 rule. This is due to coupling
interaction between neighboring protons.
• E;g CH3CH2OH
Singlet for OH (bcoz proton is not directly attached with carbon).
Quartet for CH2 (bcoz in neighbor 3 protons so n+1=3+1=4).
Triplet for CH3 (bcoz in neighbor 2 protons so n+1=2+1=3).
• It is also field independent.

COUPLING COSTANT(J)
• Measure of interaction between nuclei.
• It is separation between the peaks in the multiplets.
• It is independent of magnetic field.
• Unit is HZ
• Cis form in alkenes J value is 4-12.
• Trans form in alkenes J value is 12-18.
TYPES OF COUPING
• Germinal-10-18 Hz,strong and on same carbon.
• Vicinal-0-12 Hz in rigid systems,and 8 Hz in freely rotating carbons.it is
between neighbouring protons.
• Long range-in alkanes,small coupling.
• Aromatic: ortho-7-10Hz,meta- 2-3 Hz,para 0-1 Hz.
• Allylic-in allyl chloride,four bond coupling and it is small(0-2 Hz)
RESTRICTED ROTATION
• Observed in N,N dimethyl formamide.
• Two signals for methyl proton instead of one at room temp.
• This is due to restricted rotation due to resonance.
• At 130 deg. C it gives one signal.
REMEMBER
• Karpluss equation is related with vicinal coupling which explains
variation in vicinal coupling constant with dihedral angle( )
• Largest vicinal C.C when protons are in trans position ( =180 deg.)
• Smallest vicinal C.C when ( =90 dg.).
• For cis form ( =0 dg.) and C.C is large.
Ø Dueteriation technique is used to detect the presence of OH groups.
Ø Virtual coupling is observed in long alkyl chains as a result spectra gets
distorted.

THERE ARE 3 WAYS TO SIMPLIFY COMPLEX NMR SPECTRA.

Ø By increasing field strength
Ø By double irradiation – one proton is irradiated with high energy so speedy
transitions so no coupling with neighboring proton so no complex spectra.
For this technique chemical shift positions for the coupling multiplets
should be no closer than 1 ppm.
Ø By using shift reagents – praseodymium (gives low shifts), europium,
ytterbium, holmium, erbium are used (all give higher shifts).
Ø Lanthanide elements are used.
Ø All shift reagents are mild lewis acids.
Ø Shift reagents are paramagnetic.
Ø They are used in non-polar solvents.

NUCLEAR OVERHAUSER EFFECT

Ø Space effect
Ø One proton irradiated and other neighbouring proton in space gives
enhanced signal. Effect is upto shorter distance (3.5 angstrom).It
tells about whether two protons are near to each other are not.
Ø Range for this effect is 2-4 angstrom.
Ø Isovanillin shows this effect. Many other compounds can also show
this effect.

13
C NMR
3
§ Gyromagnetic ratio of 1 C NMR is 4 times less than that of proton NMR so 4
times less sensitive.
§ Spin quantum no. is ½ for 13C.
§ Relative abundance of 13C is 1.1 %.
§ Generally spectra is recorded by pulsed FTNMR mode.
§ Chemical shift values range from 1-200.
§ Heteronuclear coupling occurs because SQN for H and 13C is same (i:e ½)
so decoupler is to be used in order to prevent coupling between 13C and 1H.
§ To increase the line intensity in spectrum paramagnetic species like
chromium acetylacetonate and shift reagents are added.

OTHER IMPORTANT POINTS

DEPT (Distortionless Enhancement by Polarization Transfer) SPECTRA

Ø It increases sensitivity by a factor of for 13C.
In DEPT technique,sample is irradiated with a complex sequence of
pulses in both 13C and 1H channels.The result of these pulse sequences
is that 13C signal in the carbon atom will exhibit different phases
depending on number of hydrogen atoms attached to it. Each type of
carbon behaves slight differently, depending on duration of complex
pulses.

COSY (Correlation Spectroscopy)

Ø It is a 2D-NMR.
Ø It can be homonuclear or heteronuclear.
Ø This techniques enables correlation to be made between protons which
are coupled to each other

HMQC (Heteronuclear Multiple Quantum Coherence) and HMBC (Heteronuclear

Multiple Bond Coherence)
2D inverse correlation techniques that allow for the determination of
connectivity between two different nuclear species.

MRI (Magnetic Resonance Imaging)

Ø Diagnostic technique which uses NMR principle.
Ø MAXIMUM OF 1.5 TESLA MAGNETIC FIELD CAN BE USED.
Ø CARDIAC PATIENTS NOT ELIGIBLE FOR MRI.

CIDNP (Chemically Induced Dynamic Nuclear Polarization)

Ø A technique which induces polarization by chemical reaction.
 GPAT AND NIPER ASKED QUESTIONS FROM
THE CHAPTER
(Answers find yourself)
1. Chemical shift is expressed in?
2. Magic angle in NMR is?
3. MRI uses which technique?
4. Difference between 13C NMR and 1H NMR in terms of sensitivity (GPAT-2010)-4
options were given and u have to find wrong answer.
5. Splitting related question i:e a compound was given and we have to find out the
no of splits for that.
6. Standard in NMR?
7. Hydrogen bond can be detected by?(IR can also detect, bur most widely used is
Raman so if RAMAN is given you tick that)
8. Methyl chloride cause ( shielding or deshielding)?
9. No. of peaks in 1,3 dichloropropane?
10. RF range?
11. 1 Tesla is equal to how many gauss?
12. Radio frequency oscillator is used in?
13. Unit of coupling constant?
14. NMR can give information about?
15. Shimming coils are used in which technique?
16. Solvent for NMR? Choose appropriate from options.
17. No of peaks in 1,4 dioxane?

EXTRA QUESTIONS
1. Nuclear Overhauser Effect is upto how much angstrom?
2. COSY is?
3. If applied frequency for 1H NMR is 600 MHZ, then what will be the applied
frequency in 13C NMR?
4. Relative abundance of 13C?
5. Which moeity will give inverse peak in DEPT?
6. Full form of DEPT?
7. Karpluss equation is related with?
8. Unit of delta?(don’t say ppm, it is dimensionless)
9. Cis form and trans form J value?
10. CDCl3 will give peak at?
11. Which spectroscopy will result in quadrapole?
12. In 60 MHZ instrument, no. of excess nuclei will be?
13. Aldehyde chemical shift?
14. Which effect is responsible of low delta value in alkyne although it is more
electronegative than alkene and alkane?
15. Gyro magnetic ratio is the ratio of?

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