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Chapter - III: Spectral Studies

INFRARED SPECTROSCOPY

INTRODUCTION

Infrared (IR) radiation refers broadly to that part of the electromagnetic

spectrum between the visible and microwave regions of greatest practical use to

the organic chemist is the limited portion between 4000 and 400 cm-1. There has

been some interest in the near IR (14290 - 4000 cm-1) and the far IR regions (700

- 200 cm-1).

Infrared radiation of frequencies less than about 100 cm-1 is absorbed and

converted by an organic molecule into energy of molecular rotation. This

absorption is quantized; thus a molecular rotation spectrum consists of discrete

lines. Infrared radiation in the range from about 10000 - 100 cm-1 is absorbed and

converted by an organic molecule into energy of molecular vibration. This

absorption is also quantized, but vibrational spectra appear as bands rather than

as lines because a single vibrational energy change is accompanied by a number

of rotational energy changes. The frequency or wavelength of absorption depends

on the relative masses of the atoms, the force constants of the bonds and

geometry of the atoms.

Band positions in IR spectra are presented here as wave numbers (ΰ)

whose unit is the reciprocal centimeter (cm-1); this unit is proportional to the

energy of vibration and modern instruments are linear in reciprocal centimeters.

Band intensities can be expressed either as transmittance (T) or absorbance (A).

Transmittance is the ratio of the radiant power transmitted by a Sample to the

radiant power incident on the Sample. Absorbance is the logarithm, to the base

10, of the reciprocal of the transmittance; A = log10 (1/T). Organic chemists

usually report intensity in semiquantitative terms (s = strong, m = medium, w =

weak).

There are two types of molecular vibrations; stretching and bending. A

stretching vibration is a rhythmical movement along the bond axis such that the

127


inter-atomic distance is increasing or decreasing. A bending vibration may consist

of a change in bond angle between bonds with a common atom or the movement

of a group of atoms with respect to the remainder of the molecule without

movement of the atoms in the group with respect to one another. For example

twisting, rocking and torsional vibrations involve a change in bond angles with

reference to a set of coordinates arbitrarily set up within the molecule.

Study of IR Spectral Characteristics

The IR spectra were obtained on a Perkin–Elmer BX series FT-IR-5000

spectrophotometer using KBr pellets at Centre of excellence, Vapi.

Interpretation of the spectra

(1) N-H stretching vibrations (secondary amine)

Secondary amines show a single weak band in the 3350 - 3310 cm-1

region. These bands are shifted to longer wavelengths than primary amines due

to hydrogen bonding.

(2) C-H stretching vibrations (Aromatic / Aliphatic)

Aromatic C-H stretching bands occur between 3100 and 3000 cm-1. Weak

combination and overtone bands appear in the 2000 - 1650 cm-1 region.

Absorption arising from C-H stretching in the alkanes occurs in the general

region of 3000 - 2840 cm-1.

(3) Ring stretching vibrations (C=C & C=N stretching

vibrations)

Ring stretching vibrations occur in the general region between 1600 and

1300 cm-1. The absorption involves stretching and contraction of all of the bonds

in the ring and interaction between these stretching modes. The band pattern and

the relative intensities depend on the substitution pattern and the nature of the

substituent.

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(4) C-N stretching vibrations (secondary amines)

Aromatic amines display strong C-N stretching absorption in the 1342 -

1266 cm-1 region. The absorption appears at higher frequencies than the

corresponding absorption of aliphatic amines because the force constant of the C-

N bond is increased by resonance with the ring.

(5) C-X (halogen group) stretching vibrations

The strong absorption of halogenated hydrocarbons arises from the

stretching vibrations of the carbon-halogen bond. C-Cl absorption is observed in

the broad region between 850 and 700 cm-1. C-Br absorption is observed in the

broad region between 1080 and 1000 cm-1. C-F absorption is observed in the

broad region between 1250 and 1100 cm-1.

(6) C-S stretching vibrations

The stretching vibrations assigned to the C-S linkage occur in the region of

800 - 600 cm-1. The weakness of absorption and variability of position make this

band of little value in structural determination.

(7) N=N stretching vibrations

The N=N stretching vibration of a symmetrical trans azo compound is

forbidden in the IR but absorbs in the 1576 cm-1 region of Raman spectrum.

Unsymmetrical para-substituted azobenzenes in which the substituent is an

electron donating group absorb near 1429 cm-1. The bands are weak because of

the non-polar nature of the bond.

(8) O-H stretching vibrations ( phenol )

The un-bonded or “free” hydroxyl group of phenols absorbs strongly in the

3650 - 3584 cm-1 region. Intermolecular hydrogen bonding increases as the

concentration of the solution increases and additional bands start to appear at

lower frequencies, 3550 - 3200 cm-1, at the expense of the “free” hydroxyl band.

129


It is observed in most of the spectra that the vibrations arose from N-H

stretching vibrations and O-H stretching vibrations got merged and showed a

single and broad curve in this region.

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TABLE-10

1-(4-chlorophenyl)-3-(4'-fluorophenyl)-2-propen-1-one [A-1]

C

O

CH

CH

Cl F

Sr. No.Functional group(vibration mode)

Frequency (cm-1)

1 C-H str aromatic 30222 -C=O str 16673 C=C str. aromatic 1611, 15084 -CH=CH- str 15995 C-F str 11586 C-Cl str 817

TABLE-11

3-(3'-bromophenyl)-1-(2,4-dichloro-5-fluorophenyl)-2-propen-1-one

[A-7]

C

O

CH

CH

Cl

Br

F

Cl


Frequency (cm-1)

1 C-H str aromatic 30942 -C=O str 16933 -CH=CH- str 15944 C=C str. aromatic 1567, 14695 C-F str 11706 C-Br str 10967 C-Cl str 819

TABLE-12

131


1-(4-methoxyphenyl)-3-(3'-nitrophenyl)-2-propen-1-one [A-12]

C

O

CH

CH

H3CO

NO2


Frequency (cm-1)

1 C-H str aromatic 30122 -OCH3 str 28253 -C=O str 16634 C=C str. aromatic 1610, 15275 -CH=CH- str 15716 -NO2 str 1527

TABLE-13

132


4-(4-chlorophenyl)-6-(4'-fluorophenyl)-2-pyrimidinamine [A-17]

Cl

N N

NH2

F


Frequency (cm-1)

1 NH2 str 34942 C-H str aromatic 30123 C=N str 16064 C=C str. aromatic 1599, 14925 C-N str 13656 C-F str 11587 C-Cl str 808

TABLE-14

4-(3'-bromophenyl)-6-(2,4-dichloro-5-fluorophenyl)-2-pyrimidinamine [A-23]

Cl

N N

NH2

Cl

F

Br


Frequency (cm-1)

133


1 NH2 str 34272 C-H str aromatic 30853 C=N str 16104 C=C str. aromatic 1565, 14715 C-N str 13766 C-F str 12547 C-Br str 10938 C-Cl str 784

TABLE-15

4-(4-methoxyphenyl)-6-(3'-nitrophenyl)-2-pyrimidinamine [A-28]

H3CO

N N

NH2

NO2


Frequency (cm-1)

1 NH2 str 34332 C-H str aromatic 30023 -OCH3 str 28164 C=C str. aromatic 1615, 14815 C=N str 16026 -NO2 str 15267 C-N str 1347

TABLE-16

4-chloro-2,6-dimethylquinoline [A-33]

134


N CH3

H3C

Cl


Frequency (cm-1)

1 C-H str aromatic 29972 -CH3 str 29783 C=C str. aromatic 1592, 14954 C-N str 13105 C-Cl str 818

TABLE-17

4,7-Dichloroquinoline [A-36]

N

Cl

Cl


Frequency (cm-1)

1 C-H str aromatic 30112 C=C str. aromatic 1608, 14873 C-N str 13454 C-Cl str 815

TABLE-18

135


N4-[4-(substituted phenyl)-6-(substituted phenyl)-2-pyrimidinyl]-7-chloro-4-quinolinamine

N N

N

HN

R R'

Cl

N4-[4-(4-chlorophenyl)-6-(4'-fluorophenyl)-2-pyrimidinyl]-7-chloro-

4-quinolinamine [A-37] where R= -Cl, R’=F


Frequency (cm-1)

1 NH str 33322 C-H str aromatic 32083 C=C str. aromatic 1636, 14924 C=N str 16005 C-N str 13656 C-F str 11597 C-Cl str 808

N4-[4-(4'-fluorophenyl)-6-(4-methylphenyl)-2-pyrimidinyl]-7-chloro-4-quinolinamine [A-40] where R= -CH3,

R’=F


Frequency (cm-1)

1 NH str 33262 C-H str aromatic 30563 CH3 str 29304 C=C str. aromatic 1654, 14875 C=N str 16086 C-N str 13447 C-F str 11858 C-Cl str 815

136


N4-[4-(4'-chlorophenyl)-6-(4-methylphenyl)-2-pyrimidinyl]-7-chloro-4-quinolinamine [A-49] where R= -CH3, R =׳-Cl


Frequency (cm-1)

1 NH str 33102 C-H str aromatic 30563 CH3 str 29374 C=C str. aromatic 1638, 14875 C=N str 16096 C-N str 13457 C-Cl str 815

TABLE-19

137


N4-[4-(substituted phenyl)-6-(substituted phenyl)-2-pyrimidinyl]- 2,6-dimethyl-4-quinolinamine

N

N N

R

NH

CH3

H3C

R'

N4-[4-(4-chlorophenyl)-6-(4'-fluorophenyl)-2-pyrimidinyl]-2,6-dimethyl-4-quinolinamine [A-53] where R= -Cl, R’=4’-F


Frequency (cm-1)

1 NH str 33302 C-H str aromatic 32073 CH3 str 29234 C=N str 16375 C=C str. aromatic 1596, 14926 C-N str 13647 C-F str 1159

N4-[4-(4-methoxyphenyl)-6-(3'-nitrophenyl)-2-pyrimidinyl]-2,6-dimethyl-4-quinolinamine [A-64] where R= -OCH3, R’=3’-NO2


Frequency (cm-1)

1 NH str 33732 C-H str aromatic 30733 CH3 str 29214 O-CH3 str 28205 C=N str 16076 C=C str. aromatic 1591, 14387 NO2 str 15248 C-N str 1309

TABLE-20

138


N4-[4-(substituted phenyl)-6-(substituted phenyl)-2-pyrimidinyl]- 6-chloro-2-methyl-4-quinolinamine

N

N N

NH

CH3

Cl

R R'

N4-[4-(3'-bromophenyl)-6-(2,4-dichloro-5-fluorophenyl)-2-pyrimidinyl]-6-chloro-2-methyl-4-quinolinamine [A-75]

where R= 2,4-(Cl)2-5-F, R’=3’-Br


Frequency (cm-1)

1 NH str 33262 C-H str aromatic 30333 CH3 str 29254 C=N str 16165 C=C str. aromatic 1584, 14806 C-N str 13077 C-F str 11688 C-Br str 10829 C-Cl str 806

139


N4-[4-(4'-chlorophenyl)-6-(4-methoxyphenyl)-2-pyrimidinyl]-6-

chloro-2-methyl-4-quinolinamine [A-83] where R= 4-OCH3, R’=4’-Cl


Frequency (cm-1)

1 NH str 33852 C-H str aromatic 31963 CH3 str 29214 O-CH3 str 28535 C=N str 16086 C=C str. aromatic 1568, 14437 NO2 str 15318 C-N str 13079 C-Cl str 814

TABLE-21

140


N4-[4-(substituted phenyl)-6-(substituted phenyl)-2-pyrimidinyl]-6-methoxy-2-methyl-4-quinolinamine

N

N N

NH

CH3

H3CO

R

R'

N4-[4-(4-chlorophenyl)-6-(4'-fluorophenyl)-2-pyrimidinyl]-6-methoxy-2-methyl-4-quinolinamine [A-85] where R= 4-Cl, R’=F


Frequency (cm-1)

1 NH str 33332 C-H str aromatic 30093 CH3 str 29754 O-CH3 str 28355 C=C str. aromatic 1638, 14926 C=N str 16017 C-N str 13658 C-F str 11599 C-Cl str 808

141


N4-[4-(4'-chlorophenyl)-6-(2,4-dichloro-5-fluorophenyl)-2-pyrimidinyl]-6-methoxy-2-methyl-4-quinolinamine [A-98]

where R= 2,4-(Cl)2-5-F, R’=-Cl


Frequency (cm-1)

1 NH str 33842 C-H str aromatic 30913 CH3 str 29234 O-CH3 str 28415 C=N str 16536 C=C str. aromatic 1588, 14767 C-N str 13468 C-F str 10929 C-Cl str 805

TABLE-22

142


Sodium-4-((5-(4-(4-(3'-bromophenyl)-6-(4-methoxyphenyl)-pyrimidin-2-yl-amino)-6-chloro-1,3,5-triazin-2-ylamino)-2-sulfonatophenyl)-diazenyl)-5-oxo-1-(4-sulfonatophenyl)-pyrazolidine-3-carboxylate [A-101]

N

N

N

N

NH

HN

N

SO3Na

Cl

N

O

COONa

SO3Na

N N

H3CO

Br

NH


Frequency (cm-1)

2 NH str 33063 C-H str aromatic 29314 O-CH3 str 28545 -C=O str 16296 -N=N- str 15507 C=C str. aromatic 14628 -COO- str 14509 C-N str 137710 -SO3

- str 117611 C-Br str 103112 C-Cl str 846

143


Sodium-5-(4-(4-(3'-bromophenyl)-6-(4-methoxyphenyl)-pyrimidin-2-ylamino)-6-chloro-1,3,5-triazin-2-ylamino)-4-hydroxy-3-((4-methoxyphenyl)-diazenyl)-naphthalene-2,7-disulfonate [A-112]

N

N

OCH3

Br

N

N

N

Cl

NH

NaO3S

N N

SO3Na

OH

OCH3

NH


Frequency (cm-1)

1 -OH str 34312 NH str 33633 C-H str aromatic 29554 O-CH3 str 28545 -C=O str 16046 -N=N- str 15377 C=C str. aromatic 1508, 14628 C-N str 13759 -SO3

- str 117410 C-Br str 104511 C-Cl str 788

144


145


146


147


148


149


150


151


152


153


154


155


156


157


158


159


160


161


162


163


PROTON NUCLEAR MAGNETIC RESONANCE

INTRODUCTION

Nuclear magnetic resonance (NMR) spectroscopy is supplementary

technique to IR spectroscopy to get detailed information about the structure of

organic compounds. Most widely studied nucleus is proton and then the technique

is called PMR spectroscopy.

IR spectra give information about the functional group while NMR spectra

provide information about the exact nature of proton and its environment. Thus

this technique is more useful in the elucidation of an organic compound. IR

spectra of isomers may appear same but their NMR spectra will markedly differ.

The phenomenon of nuclear magnetic resonance was first reported

independently in 1964 by two groups of physicists: Block, Hansen and Packard at

Stanford University detected a signal from the protons from water, and Purcell,

Torrey and Pound at Harvard University observed a signal from the protons in

paraffin wax. Block and Purcell were jointly awarded the Noble Prize for physics in

1952 for this discovery. Since that time, the advances in NMR techniques leading

to wide spread applications in various branches of science resulted in the Noble

Prize in chemistry in 1991.The applications of NMR in clinical, solid state and

biophysical sciences are really marvelous.

The proton magnetic resonance (PMR) spectroscopy is the most important

technique used for the characterization of organic compounds. It gives

information about the different kinds of protons in the molecule. In other words it

tells one about different kinds of environments of the hydrogen atoms in the

molecule. PMR also gives information about the number of protons of each type

and the ratio of different types of protons in the molecule.

It is well known that all nuclei carry a positive charge. In some nuclei this

charge ‘spins’ on the nuclear axis, and this circulation of nuclear charge generates

a magnetic dipole along the axis. Thus, the nucleus behaves like a tiny bar

164


magnet. The angular momentum of the spinning charge is described in terms of

nuclear magnetic moment (µ).

The spinning nucleus of a hydrogen atom (1H or proton) is the simplest

and is commonly encountered in organic compounds. The hydrogen nucleus has a

magnetic moment, µ =1/2.Hence, in an applied external magnetic field, its

magnetic moment may have two possible orientations.

The orientations in which the magnetic moment is aligned with the applied

magnetic field is more stable (lower energy).The energy required for flipping the

proton from its lower energy alignment to the higher energy alignment depends

upon the difference in energy (∆E) between the two states and is equal to hυ (∆E

= hυ).

In principle, the substance could be placed in a magnetic field of constant

strength, and then the spectrum can be obtained in the same way as an infrared

or an ultraviolet spectrum by passing radiation of steadily changing frequency

through the substance and observing the frequency at which radiation is

absorbed. In practice, however, it has been found to be more convenient to keep

the radiation frequency constant and vary the strength of the magnetic field. At

some value of the field strength the energy required to flip the proton matches

the energy of the radiation, absorption occurs and a signal is obtained. Such a

spectrum is called a nuclear magnetic resonance (NMR) spectrum.

Two types of NMR spectrometers are commonly encountered. They are:

a) Continuous wave (CW) NMR spectrometer

b) Fourier transforms (FT) NMR spectrometer

The CW-NMR spectrometer detects the resonance frequencies of nuclei in

a sample placed in a magnetic field by sweeping the frequency of RF radiation

through a given range and directly recording the intensity of absorption as a

function of frequency. The spectrum is usually recorded and plotted

simultaneously with recorder synchronized to the frequency of the RF source.

In FT-NMR spectroscopy, the sample is subjected to a high power short

duration pulse of RF radiation contains a broad band of frequencies and causes all

165


the spin-active nuclei to resonate all at once at their Larmor frequencies.

Immediately following the pulse, the sample radiates a signal called free induction

decay (FID), which is modulated by all the frequencies of the nuclei return to

equilibrium (intensity as a function of time) is recorded, digitized and stored as an

array of numbers in a computer. Fourier transformation of the data affords a

conventional (intensity as a function of frequency) representation of the

spectrum.

The first step in running NMR spectrum is the complete dissociation of a

requisite amount of the sample in the appropriate volume of a suitable NMR

solvent. Commonly used solvents are: CCl4, deuteron chloroform, deuteron DMSO,

deuteron methanol, deuteron water, deuteron benzene, trifluroacetic acid.

TMS is generally employed as internal standard for measuring the position

of 1H, 13C, and 29Si in the NMR spectrum because it gives a signal sharp peak, is

chemically inert miscible with a large range of solvents, being a highly volatile,

can easily be removed if the sample has to be recovered, does not involve in

intramolecular association with the sample.

Interpretation of the PMR Spectra

It is not possible to prescribe a set of rules which is applicable on all

occasions. The amount of additional information available will most probably

determine the amount of information it is necessary to obtain from the PMR

spectrum. However, the following general procedure will form a useful initial

approach to the interpretation of most spectra.

• By making table of the chemical shifts of all the groups of

absorptions in the spectrum. In some cases it will not be possible to decide

whether a particular group of absorptions arises from separate sets of nuclei, or

from a part of one complex multiplet. In such cases it is probably best initially to

include them under one group and to note the spread of chemical shift values.

• By measuring and recording the heights of the integration steps

corresponding to each group of absorptions. With overlapping groups of protons it

166


may not be possible to measure these exactly, in which case a range should be

noted. Work out possible proton ratios for the range of heights measured, by

dividing by the lowest height and multiplying as appropriate to give internal

values.

• By noting any obvious splitting of the absorptions in the table

(e.g., doublet, triplet, etc.). For spectra which appear to show first-order splitting,

the coupling constants of each multiplets should be determined by measuring the

separation between adjacent peaks in the multiplet. Any other recognizable

patterns which are not first should be noted.

• By noting any additional information such as the effect of shaking

with D2O, use of shift reagent, etc.

• By considering both the relative intensities and the multiplicities of

the absorptions attempt to determine which groups of proton s are coupled

together. The magnitude of the coupling constant may give indication of the

nature of the proton involved.

• By relating the information obtained other information available on

the compound under considerations.

1H-NMR spectra were recorded on Varian Gemini 400 MHz NMR instrument

using CDCl3 or DMSO-d6 as solvent and TMS as internal reference (Chemical shifts

in δ, ppm) at Centre of excellence, Vapi.

167


TABLE-23

1-(4-chlorophenyl)-3-(4'-fluorophenyl)-2-propen-1-one [A-1]

C

O

CH

CH

Cl F

Sr. No.

Signal position

δ ( ppm )Relative No.of Protons

Multiplicity Assignment

1 7.26 1H d =CH-CO2 7.28 1H d -CH3 7.30-8.16 8H m Ar-H

TABLE-24

3-(3'-bromophenyl)-1-(2,4-dichloro-5-fluorophenyl)-2-propen-1-one

[A-7]

C

O

CH

CH

Cl

Br

F

Cl

Sr. No.

Signal position




168


TABLE-25

1-(4-methoxyphenyl)-3-(3'-nitrophenyl)-2-propen-1-one [A-12]

C

O

CH

CH

H3CO

NO2

Sr. No.

Signal position



1 3.31 3H s -OCH3


169


TABLE-26

4-(4-chlorophenyl)-6-(4'-fluorophenyl)-2-pyrimidinamine [A-17]

Cl

N N

NH2

F

Sr. No.

Signal position



1 5.40 2H s -NH2 7.33-8.29 9H m Ar-H

TABLE-27

4-(3'-bromophenyl)-6-(2,4-dichloro-5-fluorophenyl)-2-pyrimidinamine [A-23]

Cl

N N

NH2

Cl

F

Br

Sr. No.

Signal position



1 5.40 2H s -NH2 7.00-8.32 7H m Ar-H

170


TABLE-28

4-(4-methoxyphenyl)-6-(3'-nitrophenyl)-2-pyrimidinamine [A-28]

H3CO

N N

NH2

NO2

Sr. No.

Signal position



1 3.33 3H s -OCH3

2 5.40 2H s -NH3 7.31-9.02 7H m Ar-H

171


TABLE-29

4-chloro-2,6-dimethylquinoline [A-33]

N CH3

H3C

Cl

Sr. No.

Signal position



1 2.50 3H s -CH3

2 2.89 3H s -CH3

3 7.59-7.86 4H m Ar-H

TABLE-30

4,6-dichloro-2-methylquinoline [A-34]

N CH3

Cl

Cl

Sr. No.

Signal position



1 2.69 3H s -CH3

2 7.47-7.81 4H m Ar-H

TABLE-31

172


N4-[4-(substituted phenyl)-6-(substituted phenyl)-2-pyrimidinyl]-7-chloro-4-quinolinamine

N N

N

HN

R R'

Cl

N4-[4-(4-chlorophenyl)-6-(4'-fluorophenyl)-2-pyrimidinyl]-7-chloro-4-quinolinamine [A-37] where R= -Cl, R’=F

Sr. No.

Signal position



1 6.77 1H s -NH2 7.28-8.84 14H m Ar-H

N4-[4-(4'-fluorophenyl)-6-(4-methylphenyl)-2-pyrimidinyl]-7-chloro-4-quinolinamine [A-40] where R= -CH3, R’=F

Sr. No.

Signal position



1 2.38 3H s -CH3

2 6.82 1H s -NH3 7.21-8.77 14H m Ar-H

N4-[4-(4'-chlorophenyl)-6-(4-methylphenyl)-2-pyrimidinyl]-7-chloro-4-quinolinamine [A-49] where R= -CH3, RCl- =׳

Sr. No.

Signal position



1 2.39 3H s -CH3

2 6.89 1H s -NH3 7.26-8.77 14H m Ar-H

TABLE-32

173


N4-[4-(substituted phenyl)-6-(substituted phenyl)-2-pyrimidinyl]- 2,6-dimethyl-4-quinolinamine

N

N N

R

NH

CH3

H3C

R'

N4-[4-(4-chlorophenyl)-6-(4'-fluorophenyl)-2-pyrimidinyl]-2,6-dimethyl-4-quinolinamine [A-53] where R= -Cl, R’=4’-F

Sr. No.

Signal position



1 2.56 3H s -CH3

2 2.69 3H s -CH3

3 6.91 1H s -NH4 7.15-8.07 13H m Ar-H

N4-[4-(4-methoxyphenyl)-6-(3'-nitrophenyl)-2-pyrimidinyl]-2,6-dimethyl-4-quinolinamine [A-64] where R= -OCH3, R’=3’-NO2

Sr. No.

Signal position



1 2.55 3H s -CH3

2 2.69 3H s -CH3

3 3.88 3H s -OCH3

4 6.88 1H s -NH5 7.00-8.91 13H m Ar-H

TABLE-33

174


N4-[4-(substituted phenyl)-6-(substituted phenyl)-2-pyrimidinyl]- 6-chloro-2-methyl-4-quinolinamine

N

N N

NH

CH3

Cl

R R'

N4-[4-(3'-bromophenyl)-6-(2,4-dichloro-5-fluorophenyl)-2-pyrimidinyl]-6-chloro-2-methyl-4-quinolinamine [A-75]

where R= 2,4-(Cl)2-5-F, R’=3’-Br

Sr. No.

Signal position



1 2.70 3H s -CH3

2 6.99 1H s -NH3 7.26-8.15 11H m Ar-H

N4-[4-(4'-chlorophenyl)-6-(4-methoxyphenyl)-2-pyrimidinyl]-6-chloro-

2-methyl-4-quinolinamine [A-83] where R= -OCH3, R’=4’-Cl

Sr. No.

Signal position



1 2.34 3H s -CH3

2 3.33 3H s -OCH3

3 6.86 1H s -NH4 7.29-9.00 13H m Ar-H

TABLE-34

175


N4-[4-(substituted phenyl)-6-(substituted phenyl)-2-pyrimidinyl]- 6-methoxy-2-methyl-4-quinolinamine

N

N N

NH

CH3

H3CO

R

R'

N4-[4-(4'-chlorophenyl)-6-(2,4-dichloro-5-fluorophenyl)-2-pyrimidinyl]-6-methoxy-2-methyl-4-quinolinamine [A-98]

where R=2,4-(Cl)2-5-F, R’= -Cl

Sr. No.

Signal position



1 2.46 3H s -CH3

2 3.80 3H s -OCH3

3 6.87 1H s -NH4 7.41-8.06 11H m Ar-H

176


TABLE-35

4-((5-(4-(4-(3-bromophenyl)-6-(4-methoxyphenyl)-pyrimidin-2-ylamino)-6-chloro-1,3,5-triazin-2-ylamino)-2-sulfophenyl)diazenyl)-5-oxo-1-(4-sulfophenyl)pyrazolidine-3-carboxylic acid [A-101]

N

N

N

N

NH

HN

N

SO3Na

Cl

N

O

COONa

SO3Na

N N

H3CO

Br

NH

Sr. No.

Signal position



1 3.81 3H s -OCH3

2 6.82 1H s -NH3 6.08 2H s Pyrazolidine ring proton4 6.94-8.31 16H m Ar-H

177


Sodium-5-(4-(4-(3'-bromophenyl)-6-(4-methoxyphenyl)-pyrimidin-2-ylamino)-6-chloro-1,3,5-triazin-2-ylamino)-4-hydroxy-3-((4-methoxyphenyl)-diazenyl)-naphthalene-2,7-disulfonate [A-112]

N

N

OCH3

Br

N

N

N

Cl

NH

NaO3S

N N

SO3Na

OH

OCH3

NH

Sr. No.

Signal position



1 3.75 3H s -OCH3

2 3.78 3H s -OCH3

3 6.81 1H s -NH4 6.54-8.10 16H m Ar-H5 9.87 1H s -OH

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infrared spectroscopy - shodhgangashodhganga.inflibnet.ac.in/bitstream/10603/2520/10/10_chapter...

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