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 = log 10 (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

Chapter - III: Spectral Studies 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. 128

Chapter - III: Spectral Studies

(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 CN 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

Chapter - III: Spectral Studies 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.

130

Chapter - III: Spectral Studies

TABLE-10 1-(4-chlorophenyl)-3-(4'-fluorophenyl)-2-propen-1-one [A-1]

Cl

C

C H

C H

F

O

Sr. No.

Functional group (vibration mode)

Frequency (cm-1)

1 2 3 4 5 6

C-H str aromatic -C=O str C=C str. aromatic -CH=CH- str C-F str C-Cl str

3022 1667 1611, 1508 1599 1158 817

TABLE-11 3-(3'-bromophenyl)-1-(2,4-dichloro-5-fluorophenyl)-2-propen-1-one [A-7] F

Cl

C

C H

C H

O Cl

Br

Sr. No.

Functional group (vibration mode)

Frequency (cm-1)

1 2 3 4 5 6 7

C-H str aromatic -C=O str -CH=CH- str C=C str. aromatic C-F str C-Br str C-Cl str

3094 1693 1594 1567, 1469 1170 1096 819

TABLE-12 131

Chapter - III: Spectral Studies

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

H 3 CO

C

C H

C H

O NO2

Sr. No.

Functional group (vibration mode)

Frequency (cm-1)

1 2 3 4 5 6

C-H str aromatic -OCH3 str -C=O str C=C str. aromatic -CH=CH- str -NO2 str

3012 2825 1663 1610, 1527 1571 1527

TABLE-13

132

Chapter - III: Spectral Studies

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

Cl

F

N

N

NH2

Sr. No.

Functional group (vibration mode)

Frequency (cm-1)

1 2 3 4 5 6 7

NH2 str C-H str aromatic C=N str C=C str. aromatic C-N str C-F str C-Cl str

3494 3012 1606 1599, 1492 1365 1158 808

TABLE-14 4-(3'-bromophenyl)-6-(2,4-dichloro-5-fluorophenyl)-2pyrimidinamine [A-23] F

Cl N

N

Cl

Br NH2

Sr. No.

Functional group (vibration mode)

Frequency (cm-1)

133

Chapter - III: Spectral Studies 1 2 3 4 5 6 7 8

NH2 str C-H str aromatic C=N str C=C str. aromatic C-N str C-F str C-Br str C-Cl str

3427 3085 1610 1565, 1471 1376 1254 1093 784

TABLE-15 4-(4-methoxyphenyl)-6-(3'-nitrophenyl)-2-pyrimidinamine [A-28]

H3 CO N

N NO 2 NH2

Sr. No.

Functional group (vibration mode)

Frequency (cm-1)

1 2 3 4 5 6 7

NH2 str C-H str aromatic -OCH3 str C=C str. aromatic C=N str -NO2 str C-N str

3433 3002 2816 1615, 1481 1602 1526 1347

TABLE-16 4-chloro-2,6-dimethylquinoline [A-33]

134

Chapter - III: Spectral Studies Cl H 3C

N

CH3

Sr. No.

Functional group (vibration mode)

Frequency (cm-1)

1 2 3 4 5

C-H str aromatic -CH3 str C=C str. aromatic C-N str C-Cl str

2997 2978 1592, 1495 1310 818

TABLE-17 4,7-Dichloroquinoline [A-36] Cl

Cl

N

Sr. No.

Functional group (vibration mode)

Frequency (cm-1)

1 2 3 4

C-H str aromatic C=C str. aromatic C-N str C-Cl str

3011 1608, 1487 1345 815

TABLE-18

135

Chapter - III: Spectral Studies

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

R' N

N HN

Cl

N

N4-[4-(4-chlorophenyl)-6-(4'-fluorophenyl)-2-pyrimidinyl]-7-chloro4-quinolinamine [A-37]

where R= -Cl, R’=F

Sr. No.

Functional group (vibration mode)

Frequency (cm-1)

1 2 3 4 5 6 7

NH str C-H str aromatic C=C str. aromatic C=N str C-N str C-F str C-Cl str

3332 3208 1636, 1492 1600 1365 1159 808

N4-[4-(4'-fluorophenyl)-6-(4-methylphenyl)-2-pyrimidinyl]-7-chloro4-quinolinamine [A-40] where R= -CH3, R’=F

Sr. No.

Functional group (vibration mode)

Frequency (cm-1)

1 2 3 4 5 6 7 8

NH str C-H str aromatic CH3 str C=C str. aromatic C=N str C-N str C-F str C-Cl str

3326 3056 2930 1654, 1487 1608 1344 1185 815

136

Chapter - III: Spectral Studies

N4-[4-(4'-chlorophenyl)-6-(4-methylphenyl)-2-pyrimidinyl]-7-chloro4-quinolinamine [A-49] where R= -CH3, R ‫=׳‬ -Cl

Sr. No.

Functional group (vibration mode)

Frequency (cm-1)

1 2 3 4 5 6 7

NH str C-H str aromatic CH3 str C=C str. aromatic C=N str C-N str C-Cl str

3310 3056 2937 1638, 1487 1609 1345 815

TABLE-19 137

Chapter - III: Spectral Studies

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

phenyl)-2-pyrimidinyl]-

R N

R'

N NH

H3C N

CH3

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

Sr. No.

Functional group (vibration mode)

Frequency (cm-1)

1 2 3 4 5 6 7

NH str C-H str aromatic CH3 str C=N str C=C str. aromatic C-N str C-F str

3330 3207 2923 1637 1596, 1492 1364 1159

N4-[4-(4-methoxyphenyl)-6-(3'-nitrophenyl)-2-pyrimidinyl]-2,6dimethyl-4-quinolinamine [A-64] where R= -OCH3, R’=3’-NO2 Sr. No.

Functional group (vibration mode)

Frequency (cm-1)

1 2 3 4 5 6 7 8

NH str C-H str aromatic CH3 str O-CH3 str C=N str C=C str. aromatic NO2 str C-N str

3373 3073 2921 2820 1607 1591, 1438 1524 1309

TABLE-20

138

Chapter - III: Spectral Studies

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

R

N

R'

N NH

Cl N

CH3

N4-[4-(3'-bromophenyl)-6-(2,4-dichloro-5-fluorophenyl)-2pyrimidinyl]-6-chloro-2-methyl-4-quinolinamine [A-75] where R= 2,4-(Cl)2-5-F, R’=3’-Br Sr. No.

Functional group (vibration mode)

Frequency (cm-1)

1 2 3 4 5 6 7 8 9

NH str C-H str aromatic CH3 str C=N str C=C str. aromatic C-N str C-F str C-Br str C-Cl str

3326 3033 2925 1616 1584, 1480 1307 1168 1082 806

139

Chapter - III: Spectral Studies

N4-[4-(4'-chlorophenyl)-6-(4-methoxyphenyl)-2-pyrimidinyl]-6chloro-2-methyl-4-quinolinamine [A-83] where R= 4-OCH3, R’=4’-Cl Sr. No.

Functional group (vibration mode)

Frequency (cm-1)

1 2 3 4 5 6 7 8 9

NH str C-H str aromatic CH3 str O-CH3 str C=N str C=C str. aromatic NO2 str C-N str C-Cl str

3385 3196 2921 2853 1608 1568, 1443 1531 1307 814

TABLE-21

140

Chapter - III: Spectral Studies

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

R' R

N

N NH

H3CO N

CH3

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

Sr. No.

Functional group (vibration mode)

Frequency (cm-1)

1 2 3 4 5 6 7 8 9

NH str C-H str aromatic CH3 str O-CH3 str C=C str. aromatic C=N str C-N str C-F str C-Cl str

3333 3009 2975 2835 1638, 1492 1601 1365 1159 808

141

Chapter - III: Spectral Studies

N4-[4-(4'-chlorophenyl)-6-(2,4-dichloro-5-fluorophenyl)-2pyrimidinyl]-6-methoxy-2-methyl-4-quinolinamine [A-98] where R= 2,4-(Cl)2-5-F, R’=-Cl Sr. No.

Functional group (vibration mode)

Frequency (cm-1)

1 2 3 4 5 6 7 8 9

NH str C-H str aromatic CH3 str O-CH3 str C=N str C=C str. aromatic C-N str C-F str C-Cl str

3384 3091 2923 2841 1653 1588, 1476 1346 1092 805

TABLE-22

142

Chapter - III: Spectral Studies

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

H3 CO N

N Br NH

N HN

N N Cl

COONa

N N

NH

SO 3Na N

O SO3 Na

Sr. No.

Functional group (vibration mode)

Frequency (cm-1)

2 3 4 5 6 7 8 9 10 11 12

NH str C-H str aromatic O-CH3 str -C=O str -N=N- str C=C str. aromatic -COO- str C-N str -SO3- str C-Br str C-Cl str

3306 2931 2854 1629 1550 1462 1450 1377 1176 1031 846

143

Chapter - III: Spectral Studies

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

N NH

N

N N

NH

OH

N N

Cl NaO3 S

N

OCH3

SO3 Na

OCH3

Sr. No.

Functional group (vibration mode)

Frequency (cm-1)

1 2 3 4 5 6 7 8 9 10 11

-OH str NH str C-H str aromatic O-CH3 str -C=O str -N=N- str C=C str. aromatic C-N str -SO3- str C-Br str C-Cl str

3431 3363 2955 2854 1604 1537 1508, 1462 1375 1174 1045 788

144

Chapter - III: Spectral Studies

145

Chapter - III: Spectral Studies

146

Chapter - III: Spectral Studies

147

Chapter - III: Spectral Studies

148

Chapter - III: Spectral Studies

149

Chapter - III: Spectral Studies

150

Chapter - III: Spectral Studies

151

Chapter - III: Spectral Studies

152

Chapter - III: Spectral Studies

153

Chapter - III: Spectral Studies

154

Chapter - III: Spectral Studies

155

Chapter - III: Spectral Studies

156

Chapter - III: Spectral Studies

157

Chapter - III: Spectral Studies

158

Chapter - III: Spectral Studies

159

Chapter - III: Spectral Studies

160

Chapter - III: Spectral Studies

161

Chapter - III: Spectral Studies

162

Chapter - III: Spectral Studies

163

Chapter - III: Spectral Studies

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

Chapter - III: Spectral Studies 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 h υ (∆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

Chapter - III: Spectral Studies 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,

13

C, and

29

Si 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

Chapter - III: Spectral Studies 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. 1

H-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

Chapter - III: Spectral Studies

TABLE-23 1-(4-chlorophenyl)-3-(4'-fluorophenyl)-2-propen-1-one [A-1]

Cl

C

C H

C H

F

O

Sr. No. 1 2 3

Signal position δ ( ppm )

Relative No. of Protons 1H 1H 8H

7.26 7.28 7.30-8.16

Multiplicity

Ass ig n men t

d d m

=CH-CO -CH Ar-H

TABLE-24 3-(3'-bromophenyl)-1-(2,4-dichloro-5-fluorophenyl)-2-propen-1-one [A-7] F

Cl

C

C H

C H

O Br

Cl

Sr. No. 1 2 3

Signal position δ ( ppm ) 7.16 7.19 7.21-7.92

Relative No. of Protons 1H 1H 6H

Multiplicity

Ass ig n men t

d d m

=CH-CO -CH Ar-H

168

Chapter - III: Spectral Studies

TABLE-25 1-(4-methoxyphenyl)-3-(3'-nitrophenyl)-2-propen-1-one [A-12]

H3 CO

C

C H

C H

O NO2

Sr. No. 1 2 3 4

Signal position δ ( ppm ) 3.31 7.36 7.38 7.70-8.75

Relative No. of Protons 3H 1H 1H 8H

Multiplicity

Ass ig n men t

s d d m

-OCH3 =CH-CO -CH Ar-H

169

Chapter - III: Spectral Studies

TABLE-26 4-(4-chlorophenyl)-6-(4'-fluorophenyl)-2-pyrimidinamine [A-17]

Cl

F

N

N

NH2

Sr. No. 1 2

Signal position δ ( ppm )

Relative No. of Protons 2H 9H

5.40 7.33-8.29

Multiplicity

Ass ig n men t

s m

-NH Ar-H

TABLE-27 4-(3'-bromophenyl)-6-(2,4-dichloro-5-fluorophenyl)-2pyrimidinamine [A-23] F

Cl N

N

Cl

Br NH2

Sr. No. 1 2

Signal position δ ( ppm ) 5.40 7.00-8.32

Relative No. of Protons 2H 7H

Multiplicity

Ass ig n men t

s m

-NH Ar-H

170

Chapter - III: Spectral Studies

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

H3 CO N

N NO 2 NH2

Sr. No. 1 2 3

Signal position δ ( ppm ) 3.33 5.40 7.31-9.02

Relative No. of Protons 3H 2H 7H

Multiplicity

Ass ig n men t

s s m

-OCH3 -NH Ar-H

171

Chapter - III: Spectral Studies

TABLE-29 4-chloro-2,6-dimethylquinoline [A-33] Cl H 3C

N

Sr. No. 1 2 3

Signal position δ ( ppm ) 2.50 2.89 7.59-7.86

Relative No. of Protons 3H 3H 4H

CH3

Multiplicity

Ass ig n men t

s s m

-CH3 -CH3 Ar-H

TABLE-30 4,6-dichloro-2-methylquinoline [A-34] Cl Cl

N

Sr. No. 1 2

Signal position δ ( ppm ) 2.69 7.47-7.81

Relative No. of Protons 3H 4H

CH 3

Multiplicity

Ass ig n men t

s m

-CH3 Ar-H

TABLE-31

172

Chapter - III: Spectral Studies

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

R' N

N HN

Cl

N

N4-[4-(4-chlorophenyl)-6-(4'-fluorophenyl)-2-pyrimidinyl]-7-chloro4-quinolinamine [A-37] where R= -Cl, R’=F

Signal position δ ( ppm )

Sr. No. 1 2

6.77 7.28-8.84

Relative No. of Protons 1H 14H

Multiplicity

Ass ig n men t

s m

-NH Ar-H

N4-[4-(4'-fluorophenyl)-6-(4-methylphenyl)-2-pyrimidinyl]-7-chloro4-quinolinamine [A-40] where R= -CH3, R’=F Signal position δ ( ppm )

Sr. No. 1 2 3

2.38 6.82 7.21-8.77

Relative No. of Protons 3H 1H 14H

Multiplicity

Ass ig n men t

s s m

-CH3 -NH Ar-H

N4-[4-(4'-chlorophenyl)-6-(4-methylphenyl)-2-pyrimidinyl]-7-chloro4-quinolinamine [A-49] where R= -CH3, R ‫ =׳‬-Cl

Sr. No. 1 2 3

Signal position δ ( ppm ) 2.39 6.89 7.26-8.77

Relative No. of Protons 3H 1H 14H

Multiplicity

Ass ig n men t

s s m

-CH3 -NH Ar-H

TABLE-32

173

Chapter - III: Spectral Studies

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

phenyl)-2-pyrimidinyl]-

R N

R'

N NH

H3C N

CH3

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

Sr. No. 1 2 3 4

Signal position δ ( ppm ) 2.56 2.69 6.91 7.15-8.07

Relative No. of Protons 3H 3H 1H 13H

Multiplicity

Ass ig n men t

s s s m

-CH3 -CH3 -NH Ar-H

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

Sr. No. 1 2 3 4 5

Signal position δ ( ppm ) 2.55 2.69 3.88 6.88 7.00-8.91

Relative No. of Protons 3H 3H 3H 1H 13H

Multiplicity

Ass ig n men t

s s s s m

-CH3 -CH3 -OCH3 -NH Ar-H

TABLE-33 174

Chapter - III: Spectral Studies

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

R

N

N

R'

NH Cl N

CH3

N4-[4-(3'-bromophenyl)-6-(2,4-dichloro-5-fluorophenyl)-2pyrimidinyl]-6-chloro-2-methyl-4-quinolinamine [A-75] where R= 2,4-(Cl)2-5-F, R’=3’-Br Sr. No. 1 2 3

Signal position δ ( ppm ) 2.70 6.99 7.26-8.15

Relative No. of Protons 3H 1H 11H

Multiplicity

Ass ig n men t

s s m

-CH3 -NH Ar-H

N4-[4-(4'-chlorophenyl)-6-(4-methoxyphenyl)-2-pyrimidinyl]-6-chloro2-methyl-4-quinolinamine [A-83] Sr. No. 1 2 3 4

Signal position δ ( ppm ) 2.34 3.33 6.86 7.29-9.00

Relative No. of Protons 3H 3H 1H 13H

where R= -OCH3, R’=4’-Cl Multiplicity

Ass ig n men t

s s s m

-CH3 -OCH3 -NH Ar-H

TABLE-34

175

Chapter - III: Spectral Studies

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

R' R

N

N NH

H3CO N

CH3

N4-[4-(4'-chlorophenyl)-6-(2,4-dichloro-5-fluorophenyl)-2pyrimidinyl]-6-methoxy-2-methyl-4-quinolinamine [A-98] where R=2,4-(Cl)2-5-F, R’= -Cl Sr. No. 1 2 3 4

Signal position δ ( ppm ) 2.46 3.80 6.87 7.41-8.06

Relative No. of Protons 3H 3H 1H 11H

Multiplicity

Ass ig n men t

s s s m

-CH3 -OCH3 -NH Ar-H

176

Chapter - III: Spectral Studies

TABLE-35 4-((5-(4-(4-(3-bromophenyl)-6-(4-methoxyphenyl)-pyrimidin-2ylamino)-6-chloro-1,3,5-triazin-2-ylamino)-2sulfophenyl)diazenyl)-5-oxo-1-(4-sulfophenyl)pyrazolidine-3carboxylic acid [A-101]

H3 CO N

N Br NH

N HN

N N Cl

COONa

N N

NH

SO 3Na N

O SO3 Na

Sr. No. 1 2 3 4

Signal position δ ( ppm ) 3.81 6.82 6.08 6.94-8.31

Relative No. of Protons 3H 1H 2H 16H

Multiplicity

Ass ig n men t

s s s m

-OCH3 -NH Pyrazolidine ring proton Ar-H

177

Chapter - III: Spectral Studies

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

N NH

N

N N

NH

OH

N N

Cl NaO3 S

N

OCH3

SO3 Na

OCH3

Sr. No. 1 2 3 4 5

Signal position δ ( ppm ) 3.75 3.78 6.81 6.54-8.10 9.87

Relative No. of Protons 3H 3H 1H 16H 1H

Multiplicity

Ass ig n men t

s s s m s

-OCH3 -OCH3 -NH Ar-H -OH

178

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182

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183

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184

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185

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186

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187

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188

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189

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190

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191

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192

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193

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194

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196