nghiên cứu tổng hợp, cấu trúc và tính chất một số dẫn xuất của quinolin trên cơ sở eugenol từ tinh dầu hương nhu bản tóm tắt tiếng anh

MINISTRY OF EDUCATION AND TRAINING
HANOI NATIONAL UNIVERSITY OF EDUCATION







LE VAN CO











RESEARCH SYNTHESIS, STRUCTURE AND PROPERTIES
OF SOME QUINOLINE DERIVATIVES
ON THE BASIS OF EUGENOL FROM OCIMUM SANCTUM L. OIL



SPECIALITY : ORGANIC CHEMISTRY
Classification : 62.44.01.14

SUMMARY OF PHD THESIS



Advisor: Prof. Dr. Nguyen Huu Dinh



HA NOI, 2014

2
This thesis was completed in: Departments of Organic Chemistry –
Faculties of Chemistry – Hanoi National University of Education.




Advisor: Prof. Dr. Nguyen Huu Dinh
.




Reviewer 1: Prof.Dr.Sc. Nguyen Dinh Trieu
Hanoi University of Science – Vietnam National University.
Reviewer 2: Prof.Dr.Sc. Tran Van Sung
Vietnam Academy of Science and Technology.
Reviewer 2: Assoc.Prof.Dr. Dinh Thi Thanh Hai
Hanoi University of Pharmacy.

This thesis will be dotted to the Council to perform thesis at the:
Departments of Organic Chemistry – Faculties of Chemistry – Hanoi National
University of Education at the time hour October , 2014.




This Thesis can be found at the Library of Hanoi National University of Education
or Central Library for Science & Technology

3
INTRODUCTION
1. Reasons for selecting topic
Chemistry of heterocyclic compounds is a strong growth sector and has
created many compounds in practical applications. In that field, quinoline
heterocyclic plays an important role. Many compounds containing a quinoline
skeleton is used in various industries such as cosmetics, food, catalysts, dyes and
especially in the pharmaceutical industry. For example, quinine, cinchonine,
chloroquine, pamaquine are used as anti-malarial drugs. Several other
derivatives of quinoline were applied to cure cancer as camptothecin, antibacterial,
antifungal, anti-tuberculosis as bedaquiline
Notably, the diarylquinoline currently classified in one of ten new-generation
antibiotic alternative for antibiotic resistant bacteria have been.
Not only that, the kind of quinoline compounds also have many applications
in chemical analysis: Ferron, snazoxs, brombenzthiazo used as an indicator of
some metals analysis by photometric method. Many ligand complexes with
quinoline compounds are more substituents have very good optical properties of

interest in solar cell manufacturing.
Recently, the organic synthesis group - Hanoi National University of Education
have discovered a new reaction: synthetic quinoline ring from quinone-aci
compound prepared from eugenoxyaxetic acid. It has opened a research synthesis
of new types of quinoline polysubstituted compounds. However, this reaction is not
stable, performance is low, and the reaction mechanism has not been elucidated.
The perfect way to create a new quinoline ring and metabolic studies of the
products obtained new compounds not only theoretically significant but also the
search for promising compounds have high biological activity and the ligand for
complex research.
Therefore, we selected topeak: “Research synthesis, structure and properties
of some quinoline derivatives on the basis of eugenol from Ocimum sanctum L. Oil”.
2. The purpose and tasks of the thesis
– Complete method and study mechanism of the quinoline ring synthesis
reaction from quinone-aci compound prepared from eugenol in basil oil.

4
– Synthesis of some new quinoline polysubstituted compounds.
– Study the relationship between the structure of the synthetic compound
with their spectral properties.
– Study the possibility of fluorescence of some kind hemixianin quinoline
compounds.
– Exploration of bioactive compounds synthesized.
3. Research Methodology
● Synthesis: application of synthetic organic methods of traditional and
innovative choice to suit each new object. Focus on improving efficiency, reducing
the amount of reactants, carefully refined to be clean nature.
● Study structure: The structure of the synthetic compounds were identified
by IR,
1

H NMR,
13
C NMR,
2
D NMR and MS spectrum coordination. Some
compounds was studied further UV-Vis, fluorescence emission spectra and single-
crystal XRD. The spectrums were analyzed in detail, the spectral data and the
system were arranged to draw comment.
● Tested antibacterial activity, antifungal substance with some Gram (+) and
Gram (-), yeasts, molds under successive dilution method. Tested cytotoxicity of
compounds for four cancer cell lines differ. Tested the activity of antioxidant
compounds. In particular, tested the activity against malaria for 7-carboxymethoxy-
6-hydroxy-3-sulfoquinoline (Q).
4. New contributions of the thesis
4.1. Synthesis
– Completing a new method to synthesize quinoline ring from quinone-axi from
eugenol in basil oil led to new quinoline compound is 7-carboxymethoxy-6-
hydroxy-3-sulfoquinoline (Q); Use the single-crystal diffraction method to confirm
the structure of Q; Using dynamic
1
H NMR methods to propose the mechanism for
quinoline cyclization reaction not seen in the references.
– Detect an abnormal nucleophilic reaction of N-metylquinolinium compounds: the
replacement of the carboxymethoxy group (OCH
2
COOH) by ankylamino group (RNH).
Through extensive research this reaction, has proposed an unusual reaction
mechanism.

5

– Detect a reaction which occurs simultaneously with the replacement of the
OCH
2
COOH group by the NHNH
2
group and the replacement of Br atom by H
atom. On the basis of experimental and theoretical proposed the reaction
mechanism of this unprecedented reaction.
4.2. Study the structures and properties
– Have determined the structure of 60 new compounds type of quinoline
polysubstituted by using coordinate spectroscopeak methods IR,
1
H NMR,
13
C
NMR, HSQC, HMBC, NOESY and MS.
– Provide reliable data on the chemical shift and constant spin-spin interactions of
protons and carbons in a few series quinoline polysubstituted compounds.
– Study UV-Vis and fluorescence emission spectra of 11 compounds kinds of 7-
alkylamino-1-methylquinolinium-3-sunfonate, sorbents in the visible range and
fluorescence with λ
max
in the range of 505-674 nm.
– Identified that, Q compound exhibits activity against malaria, but not strong;
QNO
2
has very weak cytotoxic activity; HzQBr has cytotoxic activity against cell
carcinoma; A0 and Q have strong antibacterial activity; HzQBr has weak
antibacterial, V5 has average antibacterial and R1 has weak antifungal.
5. Layout of the thesis

The dissertation consists of 148 typed pages, printed on A4 paper with 26
diagrams, 59 photographs and 45 tables are distributed as follows: Introduction: 03
pages, 25 pages Overview, page 16 Experiments, Results and Discussion page 87,
page 02 Conclusion, references 14 pages. There is also 126 pages of appendix.
CONTENTS OF THE THESIS
Chapter 1. OVERVIEW
Have literature review of domestic and foreign research on the synthesis of
homocyclic and heterocyclic compounds from with eugenol, the main constituent
of Ocimum sanctum L. Oil and preliminary studies on the compounds containing a
quinoline ring. Especially noticed a ring-closed reduction reaction of quinone-aci
derivative creates a quinoline compound (detected by organic synthesis group -
Hanoi National University of Education ) is a new reaction should continued to refine
in order to open up a new direction research of polysubstituted quinoline
derivatives.

6
Chapter 2. EXPERIMENTAL
2.1. SYNTHESIS Q AND SOME DERIVATIVES FROM Q

Scheme 1. Diagram synthetic Q and some derivatives from Q
Results synthesis derivatives of Q
Table 1. Structure and data synthesis of derivatives from Q

Order
Notation
R
1
/R
2

R
3
/R
4

Yield
(%)
Spectrums measurement and analysis
IR
1
H
13
C
QC
BC
MS
1
MeQ
Me/H
H/OH
64,9
x
x
x
x
x
x
2
EsQ
H/H

H/OMe
65,2
x
x
x
-
-
x
3
HzQ
H/H
H/NHNH
2

62,3
x
x
x
-
-
x
4
QAc
H/H
COMe/OH
55,1
x
x
x
-

x
x
5
QCHO
H/CHO
H/OH
27,0
x
x
x
-
x
x
6
QCl
H/Cl
H/OH
62,3
x
x
x
-
x
x
7
QBr
H/Br
H/OH
70,1
x

x
x
-
-
x
8
EsQBr
H/Br
H/OMe
65,1
x
x
x
-
x
x
9
HzQBr
H/Br
H/NHNH
2

71,9
x
x
x
-
-
x
10

QNO
2

H/NO
2

H/OH
37,0
x
x
x
x
x
x
11
QNH
2

H/NH
2

H/OH
80,1
x
x
x
-
x
-
12

QNHAc
H/NHCOMe
H/OH
50,0
x
x
x
-
x
x
13
MeQBr
Me/Br
H/OH
66,8
x
x
x
-
x
x
14
MeQNO
2

Me/NO
2

H/OH
-

x
x
-
-
-
-
15
MeQNHNH
2

-
x
x
-
-
-
-

14
14
13
2
9
12


7
2.2. THE REACTION OF QCHO WITH AMINO COMPOUNDS
Table 2. Structure and data synthesis of R1-R7 imins

Order
Notation
Y
Yield
(%)
Spectrums measurement and analysis
IR
1
H
13
C
QC
BC
NOESY
MS
1
R1
PhNH
70,0
x
x
-
-
-
-
-
2
R2
2,4-
(NO

2
)
2
PhNH
79,8
x
x
x
-
-
-
-
3
R3
Ph
70,0
x
x

-
-
-
-
4
R4
2-MePh
60,4
x
x
x

-
x
-
x
5
R5
4-MePh
74,2
x
x
x
-
-
-
-
6
R6
Naphtyl
73,2
x
x
x
x
x
x
-
7
R7
Xyclohexyl
50,0

x
x
-
-
-
-
-

7
7
4
1
2
1
1

2.3. THE REACTION OF MeQBr WITH ANKYLAMINE
Table 3. Structure and data synthesis of S1-S8 compounds

Order
Notation
R
Yield
(%)
R
f
**

Spectrums measurement and analysis
IR

1
H
13
C
QC
BC
MS
1
S1a
Me
72
0,74
x
x
x
x
x
-
2
S1b
Me
-
0,70
x
x
x
-
x
-
3

S2a
Et
68
0,68
x
x
x
-
-
-
4
S2b
Et
-
0,65
x
x
x
-
-
-
5
S3a
Pr
72
0,67
x
x
x
-

-
-
6
S3b
Pr
-
0,65
x
x
x
-
-
-
7
S4a
PhCH
2

74
0,55
x
x
x
x
x
x
8
S4b
PhCH
2

-
0,50
x
x
x
-
-
-
9
S5a
(*)
65
0,64
x
x
x
x
x
x
10
S5b
HOCH
2
CH
2

-
0,62
x

x
x
x
x
-
11
S6a
(*)
64
0,18
x
x
x
-
x
-
12
S6b
CH
2
CH
2
NH
2
.HCl
-
0,08
x
x
x

-
-
-
13
S7a
(*)
68,4
0,12
x
x
X
-
-
-
14
S8b
Xiclo-C
6
H
11

-
0,61
x
x
x
-
-
-

14
14
14
4
6
2
(*)
: Internal salt);
(
**)
: Thin-layer chromatography in solvent MeOH/CHCl
3
(1:1))


8
2.4. THE REACTION OF MeQNO
2
WITH ANKYLAMINE
Table 4. Structure and data synthesis of T1-T8 compounds

Order
Notation
R
Yield
(%)
R
f
*
Spectrums measurement and analysis

IR
1
H
13
C
QC
BC
MS
1
T1a
-
50,6
0,8
x
x
x
-
-
x
2
T1b
H
-
0,75
x
x
x
-
-
-

3
T2
Me
70,3
0,6
x
x
x
-
x
x
4
T3
Et
50,2
0,62
x
x
x
-
x
x
5
T4
Pr
70,4
0,65
x
x
x

-
-
-
6
T5
PhCH
2

66,8
0,7
x
x
x
-
x
x
7
T6
HOCH
2
CH
2

58,5
0,55
x
x
x
-
x

x
5
T7
CH
2
CH
2
NH
2
.HCl
58,2
0,3
x
x
x
-
x
x
9
T8
Xiclo-C
6
H
11

-
0,7
x
x
x

-
x
x

9
9
9
0
6
6
(R
f
*
: Thin-layer chromatography in solvent MeOH/CHCl
3
(1:2))
2.5. THE SYNTHESIS AND REACTION OF QNHNH
2
CARBONYL COMPOUNDS

Table 5. Structure and data synthesis of V1-V13 hydrazons

Order
Notation
R
1

R
2

Yield
(%)
R
f
*

Spectrums measurement and analysis
IR
1
H
13
C
QC
BC
MS
1
V1
H
Ph
64,0
0,84
x
x
x
-
-
x
2
V2
H

3-MePh
65,2
0,78
x
x
x
-
-
x
3
V3
H
3-OHPh
61,0
0,83
-
x
x
-
x
-
4
V4
H
4-OHPh
61,0
0,83
-
x
x

-
x
x
5
V5
H
4-ClPh
71,6
0,80
x
x
x
x
x
x
6
V6
H
4-NO
2
Ph
60,4
0,77
x
x
x
-
-
x
7

V7
H
4-Me
2
NPh
67,5
0,82
x
x
x
-
-
x
8
V8
H
4-OH-3-OCH
3
Ph
68,0
0,83
x
x
x
-
-
x
9
V9
H

2,4-(OH)
2
Ph
50,0
0,81
x
x
x
-
-
-
10
V10
Me
Me
71,3
0,80
x
x
x
x
x
x
11
V11
Me
Et
66,7
0,79
x

x
x
-
x
-
12
V12
Me
Ph
65,0
0,76
x
x
x
-
-
x
13
V13
Me
4-NH
2
Ph
63,7
0,82
-
x
x
-
-

-

10
13
13
2
5
9
(R
f
*
: Thin-layer chromatography in solvent MeOH/CHCl
3
(1:1))


9
Chapter 3. RESULTS and DISCUSSION
3.1. Q: 7-CARRBOXYMETHOXY-6-HYDROXY-3-SULFOQUINOLINE
3.1.1. Complete the synthesis method of Q
By changing the molar ratio of the reactants, temperature, time of reaction
stages and acidulating agent in stage 2, we have found conditions for synthesis
reaction Q with high and stability yield. Compound Q was checked by IR, NMR
and MS spectroscopy, the results consistent with those previously published.
Result analyzed single-crystal diffraction (Figure 1) also shows that Q has
structured in accordance with the expected formula.

Figure 1. structure of Q determined by single-crystal XRD method
3.1.2. Study mechanisms reaction synthesis Q from A0
Through monitoring reaction progress by

1
H NMR method, we propose a
mechanism for the transformation from A0 to Q as Scheme 2.

Scheme 2. Reaction mechanism to form Q from A0

10
3.2. SYNTHESIS, STRUCTURE AND PROPERTIES OF SOME DERIVATIVES
OF Q
From the Q-key, by the methylation reaction, halogenated, nitrated, acyl-
esterified, hydrazide and condensation, have synthesized 14 new quinoline
polysubstituted compounds.
– IR spectra of derivatives of Q contains peaks characterize the main functional
groups: OH, NH, CH, C=O, … accordance with structure are listed in tables 3.5 –
3.17 of the thesis.
–
1
H NMR,
13
C NMR HSQC, HMBC and MS spectrum are shown in tables 3.5 -
3.17 of the thesis. Spectral data showed that synthetic compounds have been
structure accordance with the expected formula.
- The results analyzed single-crystal diffraction EsQBr compound is shown in figure
2.

Figure 2. Structure of EsQBr determined by single-crystal XRD diffraction
3.3. SPECTRA PROPERTIES AND STRUCTURE OF R1-R7 IMINES
3.3.1. Infrared spectrum (IR)
Some main absorbtion peak in the IR spectra of the imine R1-R7 are shown
in table 3:19 of the thesis.

3.3.2. NMR and MS spectrum of R1-R7

11
Based on the chemical shift, constant spin-spin interaction and combined
with 2D NMR spectral analysis, we have determined exactly the signal of the
proton resonances of the imines R1-R7,
1
H NMR spectral data are listed in table 6.
Table 6. Signals on the
1
H NMR spectrum of R1-R7,  (ppm), J (Hz)

Y
H2
H4
H8
H7a
H5a
H12
H16
H13
H15
H14
Others
R1

8,79
s;1H
9,15
s;1H

7,42
s;1H
5,05
s;2H
9,92
s;1H
7,11
d;1H
J=8
7,11
d;1H
J=8
7,28
t;1H
J = 8
7,28
t;1H
J = 8
6,84
t;1H
J=7,5
OH:11,74
NH: 0,80
R2

9,55
s;1H
9,05
d;1H
J=1,5

7,47
s;1H
5,04
s;2H
9,93
s;1H
-
8,09
d;1H
J = 10
8,89
d;1H
J=2,5
8,28
dd;1H
J1=2,5
J2=9,5
-
NH: 1,97
R3

8,90
s;1H
9,50
s;1H
7,30
s;1H
4,9
s;2H
9,8

s;1H
7,9 d;1H
J = 8
7,5 t;3H
J = 8
7,4
t;1H

OH: 15,7
R4

8,71
d;1H
J=1.5
8,82
d;1H
J=1.5
7,17
s;1H
4,85
s;2H
9,58
s;1H
-
8,09
d;1H
J = 8
7,37 d;1H
J = 7.5
7,24

t;1H

H12a: 2,46
R5

8,87
s;1H
9,34
s;1H
7,25
s;1H
4,94
s;2H
9,72
d;1H
J=9,5
7,74 d;2H
J = 8,5
7,35 d;2H
J = 8
-
OH: 15,82
H14a: 2,36
R7

8,64
d;1H
J = 2
8,52
d;1H

J =
1,5
7,15
s;1H
4,23
s;2H
9,26
d;1H
J =
11
H11: 3,9 s;1H; H12e/H16e: 1,97 s; 2H
H12a/H13a/H15a/H16a:1,4 m;4H;
H13e/H15e: 1,72 d; 2H; H14a: 1,25 d;1H
H14e: 1,57 t;1H

The analysis NOESY spectrum of imine R6 not only helps to attribute all the
proton signals of R6 but also determined that the C=N double bond of R6 in E
configuration (structure A in Figure 5). If R6 in E configuration - structure B (Figure
3), the H5a and H4 are away from each other should not be so strong signal
interaction.

Figure 3. A number possible structures of R6

12
3.4. SPECTRA PROPERTIES AND STRUCTURE OF S1-S8
3.4.1. The reaction of MeQBr with ankylamines
When performing the reaction of QBr with ankylamines at room
temperature as well as heating reflux we have not carried out this reaction
substitution Br atom in position 5. Transforming QBr into MeQBr we hope that
the presence N

+
in quinoline core will make it easy for nucleophilic substitution
reaction with Br to form 5-ankylamino derivatives (5-RNH-Q). But Br atom had
not been replaced so that the OCH
2
COOH group was replaced by RNH groups
forming 7-ankylamino derivatives S1-S8.

In the reaction on the left side above Scheme, OR groups linked to aromatic
was replaced by amine creating NHR group. It is an unprecedented nucleophilic
substitution reaction on the quinoline heterocyclic in particular and on general
aromatic compounds.
In the literature review mentioned, the nucleophile substitution on the 7
th

position of quinoline ring is difficult. Although there are also a number of studies
have been done a number of nucleophilic reactions with halogenated in 7
th
position
of quinoline ring, but have not found substitute reaction -OR group (ether) linked to
the quinoline ring particular and general aromatic. The fact that the alkyl aryl ether
RO-Ar is inert with nucleophilic agents such as Cl
-
, OH
-
, amine, Because in -O-
Ar, the effect of -p conjugated, R-O group sustainable linked with aromatic should
be so difficult to replace.
When cleavage linked RO-Ar with HI, the OR group is not replaced (not
leave), the group OAr is leaving group as HO-Ar. We have the following scheme

illustrates.

13

The reaction (3) is essentially S
N
2 reaction at saturated carbon atom (


)
not nucleophilic reaction of aromatic compounds (S
N
Ar). Such the replacement
reaction OCH
2
COOH group with ankylamine as presented above is a clearly
abnormal response unprecedented.
To explain this unusual reaction we propose a mechanism similar to the
S
N
Ar mechanism (or addition-elimination mechanism) as described in scheme 3.

Scheme 3. Mechanism of reaction replacement OCH
2
COOH group by amine
3.4.2. Infrared spectrum (IR) of S1-S8
IR spectra of MeQBr have characteristic absorption peaks of C=O bond at
1754 cm
-1
, also on the spectra of S1-S8 only remaining absorption peaks of C=C,

C=N bond of quinoline ring at 1540-1610 cm
-1
; in the 3000-3500 cm-1, absorption
peaks on IR spectra of MeQBr blended to form absorption band, but on the
spectrum of S1-S8, there is a clear separation of the two amino fluctuated with
medium intensity. Some absorption peaks on the IR spectra of the series S1-S8 are
listed in Table 3.24 of the thesis.
3.4.3. NMR spectrum of S1-S8

14
Based on the chemical shift, constant spin-spin interaction and combined
with 2D NMR spectral analysis, we have determined exactly the signal of the
proton resonances of S1-S8 compounds,
1
H NMR spectral data are listed in table 7.
Table 7. Signals on the
1
H NMR spectrum of S1-S8,  (ppm), J (Hz)

H1
H2

H4

H8
H11
H12
H13
H11’
(**)

H12’
(**)

H13’
(**)

Others
S1a
4,23
s;3H
8,35
s;1H
8,36
s;1H
6,39
s;1H
2,99
d;3H
J = 5
-
-
2,39
s;3H
-
-
NH:7,56;
NH
3
+
: 7,56

S1b
4,37
s;3H
9,09
s;1H
8,75
s;1H
6,71
s;1H
3,01
d;3H
J = 5
-
-
-
-
-
NH: 7.86
S2a
4,23
s;3H
8,35
d;1H
J = 1
8,26
d;1H
J = 1
6,46
s;1H
2,83

q;2H
J = 7
1,14
t;3H
J = 7
-
3,42
m;2H
J = 7
1,26
t;3H
J = 7
-
NH: 7,25
S2b
4,37
s;3H
9,08
d;1H
J = 1
8,75
s;1H
6,78
s;1H
3,49
1,27
t;3H
J = 7,5
-
-

-
-
NH: 7,71
S3a
4,22
s;3H
8,33
s;1H
8,25
s;1H
6,4
s;1H
2,74
t;2H
J = 7,5
1,56
m;2H
J = 7,5
0,90
t;3H
J = 7,5
Bị
che
lấp
1,70
m;2H
J = 7,5
0,96
t;3H
J = 7,5

NH:7,27
S3b
4,36
s;3H
9,07
s;1H
8,74
s;1H
6,77
s;1H
3,40
d;2H
J = 6
1,70
q;2H
J = 7,5
0,96
t;3H
J = 7,5
-
-
-
NH: 7,68
S4a
4,12
s;3H
8,34
d;1H
J = 1
8,28

s;1H
6,53
s;1H
4,63
d;2H
J = 6
H12/H16/H13’/H17’
(**)
: 7,43 t; 4H; J = 7,5
H13/H14/H15: 7,35 t, 3H; J = 7,5
H14’/H16’
(**)
: 7,39 t; 2H; J = 7,5;
H5’
(**)
: 7,26 t; 1H; J = 7,5
NH: 7,79
S4b
4,23
s;3H
9,05
d;1H
J = 1
8,75
s;1H
6,81
s;1H
4,70
d;2H
J = 6

H12/H16: 7,47 d; 2H; J = 7,5
H13/H15: 7,36 dd; 2H; J1 = 8;J2 = 2
H14: 7,27 t; 1H; J = 7,5
NH: 8,37
S5a
4,22
s;3H
8,34
d;1H
J = 1
8,27
s;1H
6,51
s;1H
3,45
q;2H
J = 5,5
3,69
t;2H
J = 5,5
-
-
-
-
NH: 7,34
S5b
4,36
s;3H
9,09
d;1H

J = 1
8,75
s;1H
6,88
s;1H
3,52
q;2H
J = 5,5
3,71
t;2H
J = 5,5
-
-
-
-
NH: 7,50
S6a

4,27
s;3H
8,46
d;1H
J = 2
8,36
s;1H
6,59
s;1H
3,71
q;2H
J = 6

3,19
t;2H
J = 6
-
-
-
-
NH:7,87;
NH
3
+
: 8,13
S6b
4,44
s;3H
9,13
d;1H
J = 2
8,78
s;1H
7,01
s;1H
3,79 q
J = 6,5
3,10
dd;2H
J1 = 5,5
J2 = 6,5
-
-

-
-
NH: 7,85
NH
3
+
: 8,19
S7a
(*)

3,94
s;3H
8,34
s, 1H
8,25
s, 1H
5,90
s, 1H
2,58
d;2H
J = 7
1,35
s;2H
1,63
s;2H
H14:
3,11
s; 2H
-
-

-
S8b
4,37
s;3H
9,06
s, 1H
8,76
s, 1H
6,84
s, 1H
3,79
m,1H
H12e/H16e: 1,97 m;2H;
H14e: 1,64d;1H; H14a:1,21 m;1H
H13e/H15e: 1,77 m;2H;
NH: 7,13

15

H1
H2

H4

H8
H11
H12
H13
H11’
(**)

H12’
(**)

H13’
(**)

Others
H12a/H13a/ H15a/ H16a: 1,47 m;4H

(*)
measured in D
2
O);
(**)
H11’ – H17’ the amino protons in salt.
Table 7 shows,
1
H NMR spectrum of the S1a-S7a compounds are similar and
different from the spectrum of MeQBr the signal losing at  = 5.21 ppm of 2 proton
H7a, the resonance signals of H2, H4, H8 shift in the downfield than the spectrum
of MeQBr because of the effect +C of RNH group (replaced OCH
2
COOH group).
Also, in the 7-7.9 ppm appears a triplet with 1H of intensity attributed to NH proton
(RCH
2
NH group).
For S1a-S4a compounds, beside of the resonance signal of 7-ankylamino
molecule (denoted Q-NHR), there appears signals of amino RNH
3

+
ion with Q-
NHR/RNH
3
+
intensity ratio is equal to 1:1. Therefore, we believe that these
compounds exist in the form of amino salt [RNH-Q-O]
-
[H
3
N-R]
+
.
For S6a and S7a, two amino function amine is used, on the spectrum have
not appeared resonance signal of an amine molecule to create salt, but an NH
2

group remaining molecules will create internal salt.
On the
13
C NMR spectra of each compounds in the S1-S8 series, we found
enough resonance signals of the carbon atoms not equivalent, in accordance with
their structural formula. The difference from
13
C NMR spectrum of MeQBr is not
appearing the resonance signal in 160-180 ppm of C7b (COOH group); not appears
the signal in 60-70ppm of C7a (OCH
2
group). On the HMBC spectrum of each
compounds have still interaction peak between C7 and H11, interaction peak

between C6 and C8 (j and i example in Figure 4) that confirmed the amino group R-
NH replaced OCH
2
COOH group in 7
th
position.

16

Figure 4. Part of HMBC spectrum of S6b
Combined results analysis HSQC, HMBC spectrum, the signals on the
13
C
NMR spectrum of S1-S8 has been attributed as in table 8.
Table 8. The chemical shift on the spectrum
13
C NMR of S1-S8

S1a
S1b
S2a
S2b
S3a
S3b
S4a
S4b
S5a
S5b
S6a

S6b
S7a
(*)

S8b
C1
45,6
44,4
43,8
44,5
43,8
44,4
43,8
44,4
43,80
44,5
44,0
45,1
44,4
44,5
C2
131,3
141,3
131,4
141,4
131,6
141,4
131,8
141,7
131,3

141,5
-
141,6
130,6
141,5
C3
135,1
136,3
135,0
136,2
135,0
136,2
135,1
136,5
135,1
136,3
135,7
136,7
134,2
136,2
C4
128,0
136,4
128,1
136,5
128,2
136,5

136,6
128,0

136,5
128,9
136,5
130,0
136,5
C5
97,1
105,0
97,2
105,4
97,3
105,5
97,5
105,6
97,1
105,4
98,1
105,4
100,8
105,8
C6
157,5
145,9
157,5
145,8
157,4
145,8
157,5
145,9
157,7

145,8
-
146,1
156,1
145,7
C7
152,6
148,5
151,4
147,5
151,5
147,7
151,3
147,4
151,8
147,9
151,3
147,5

146,5
C8
86,2
90,2
86,26
90,3
86,4
90,4
87,2
91,1
86,5

90,77
87,0
91,1
87,2
90,6
C9
135,5
138,6
135,5
138,6
135,5
138,6
135,3
138,2
135,4
138,5
135,7
138,3
134,2
138,6
C10
125,7
121,6
125,6
121,6
125,5
121,6

121,7
125,7

121,6
125,6
121,8
125,1
121,5
C11
29,1
29,7
36,7
37,3
43,6
44,1
45,6
45,7
44,7
45,2
72,5
45,1
42,4
50,99
C12
-
-
13,7
13,2
21,4
20,8
127,2
128,5
59,1

58,9
37,7
37,1
29,6
31,3
C16
-
-
-
-
-
-
-
-
-
-
-
C14
-
-
-
-
-

127,3
-
-
-
-
40,5

25,1
C13
-
-
-
-
11,5
11,4
128,5
127,6
-
-
-
-
25,2
24,5
C15
-
-
-
-
-
-
-
-
-
-

Ci
-

-
-
-
-

138,3
137,5
-
-
-
-
-
-
C11’
(**)

24,5

34,2
-
40,5

42,4
-
-
-
-
-
-
-

C12’
(**)

-

12,6
-
20,4

134,0
-
-
-
-
-
-
-


17

S1a
S1b
S2a
S2b
S3a
S3b
S4a
S4b
S5a

S5b
S6a

S6b
S7a
(*)

S8b
C13’
(**)

-
-
-
-
10,8

128,8
-
-
-
-
-
-
-
C17’
(**)

-
-

-
-
-
-
-
-
-
-
-
-
-
C14’
(**)

-
-
-
-
-
-
128,5
-
-
-
-
-
-
-
C16’
(**)

-
-
-
-
-
-
-
-
-
-
-
-
-
C15’
(**)

-
-
-
-
-
-
127,2
-
-
-
-
-
-

-

(*)
measured in D
2
O;
(**)
C11’ – C17’: carbon atoms in the amino salt.
The difference spectrum of S1b-S8b compounds compared to
13
C NMR
spectrum of S1a-S8a are: losing signals of the carbon atoms in the ankylamino ion
(RNH
3
+
); signals of C6 of the S1a-S8a series appear in the 156-158 ppm proved
C6 linked with O
-
group, remaining S1b-S8b series, those signals appear at 145,5 –
146,1 ppm proved the C6 linked with OH group.
For S6 and S7, two amino functions amine is used, on the 13C NMR
spectrum of S6a and S6b have 11 signals corresponding to 11 carbon atoms; S7a
has 13 signals. However, in the spectrum of S7a and S6a the signals of C6
resonance at 156,1 ppm (similar to S1a-S5a), while spectrum of S6b has signal of
C6 at 146,1 ppm (similar to S1b-S5b and S8b). Thus it can be stated, S7a and S6a
form internal salt between the OH group at position 6
th
and 2
nd
NH

2
function group
of ankyldiamine molecule, and whereas S6b form internal salt with a molecule of
acid (there hydrochloric acid is in solvent crystallization).
3.4.4. MS spectrum of a number of S series
We have recorded mass spectrum of the S5b and S4b compounds. The results
of the spectral analysis of compounds are received the molecular weight is equal to
molecular weight calculated by the assuming formula with the molecular ion peak
has high intensity (Table 9).
Table 9. The results analysis MS spectrum of S4b and S5b

Molecular Formular /M
Main peaks, m:z / intensity (%)
S4b
C
17
H
15
BrN
2
O
4
S
422/424
445/100, 447/98: [M+Na
+
]; 423/47, 425/46: [M+H
+
]
421/94, 423/100: M-H

+
]
S5b
C
12
H
13
BrN
2
O
5
S
376/378
399/95, 401/100: [M+Na
+
]; 377/28, 379/32: [M+H
+
]
375/92, 377/100: [M-H
+
]
3.4.5. UV-Vis spectrum and fluorescence spectroscopy of a number of S series
The UV-Vis spectrum of MeQBr different from the spectrum of the S1-S3
and S5, it has 4 separate peaks so popular and separated from the spectra of other

18
compounds, while in the spectrum of the remaining compounds, 2 absorption peaks
in the visible range mixed together but still filling enough to realize two distinct
spectral peak tips, in addition have some shoulder spectral. The value λ
max

and
intensity of the absorption peaks are listed in table 10. In this table, we add value
λ
max
in UV-Vis spectrum of S2a and S2b measured in the solid state for comparison
purposes.
Table 10. Absorption peaks on UV-Vis spectrum of S1-S3 and S5, λ
max
(nm)/ logε
Notation
Peak I
Peak II
Peak III
Peak IV
MeQBr
241/ 0.9975
294/ 0.8363
366/ 0.2855
420/ 0.1659
S1a
254/ 1.0411
284/ 0.7198
413/ 0,6573
430/ 0.6641
S1b
254/ 1.0386
284/ 0.7189
414/ 0,6593
429/ 0.6667
S2a

253/ 0.8539

*
245
286/ 0.6673
*
305
414/ 0,5406

*
385
430/ 0.5510
*
450
S2b
254/ 1.0464
*
240/
284/ 0.7541

*
305/
415/ 0,6965

*
370/
430/ 0.7077

*
440/

S3a
255/ 0.9447
284/ 0.6756
417/ 0,6370
430/ 0.6435
S3b
255/ 1.1373
284/ 0.8160
415/ 0,7651
431/ 0.7773
S5a
254/ 0.9277
284/ 0.6677
414/ 0,6221
429/ 0.6182
S5b
255/ 0.6208
283/ 0.4524
413/ 0,4167
427/ 0.4261
(*)
measured in the solid state.
The results shows, the first, S1-S3 and S5 compounds are strong absorption
in the visible region rather than MeQBr only absorbs in the ultraviolet region; the
second, λ
max
values of peak III and peak IV of S1A-S3a and S5a are similar to
corresponding S1b-S3b and S5b.
λ
max

values, fluorescence intensity I and width of absorption peaks of a
number of a number of S series are listed in Table 11
Table 11. Fluorescence maxima of research compounds
Compounds
λ
max
(nm)
I (au)
Compounds
λ
max
(nm)
I (au)
width (nm)
MeQBr
644; 685
878; 1033
S4a
543
43872
78,1
S1a
594; 674
6574; 3014
S1b
514
30880
91,4
S2a
600; 674

3508; 2023
S2b
522
13356
56,8
S3a
589; 674
7194; 3508
S3b
505
5053
71,6
S5a
587; 674
4748; 2178
S5b
516
20397
62,1
S6a
596; 674
2550; 1343
S6b
532
2529
70,8

19
From the data of table 11, we drawn following comments: the fluorescence
of the S1a, S2a; S3a; S5a and S6a compounds are similar; the fluorescence of

S1b-S6b are similar too, but also different from MeQBr and S4a. That MeQBr is
not the type of hemixianine and S4a has addition benzene core. Coloring matters
Xianin used in biotechnology CY2, Cy3, Cy3B, Cy3.5 and Cy5 have λ
max
of
fluorescence respectively 506; 570; 572; 594 and 670 nm. The S4a, S1b, S2b and
S5b compounds have λ
max
of fluorescence similar to the foregoing, there are strong
fluorescence intensities and spectral widths so small would certainly be useful for
the purpose of using them in the classification area.
3.5. SPECTRA PROPERTIES AND STRUCTURE OF T1-T8
3.5.1. Infrared spectra of T1-T8
IR spectrum of T1-T8 compounds are similarities: not appear absorption
peak so characteristic vibrations of C=O bond in 1700 -1750 cm
-1
, and in 3000-
3500 cm
-1
appear two amino absorption peak of the average intensity (Table 3.33
of the thesis).
3.5.2. NMR spectrum of T1-T8
1
H NMR spectrum of the T1-T8 compounds are similarities, they differ only
in part amine (RNH) and different from the spectrum of MeQNO
2
: appears only
true signals with the expected structural formula, this means lost the signal at  =
5,1 ppm with equal intensity 2H (H7a) of precursor MeQNO
2

, resonance signals
of H2, H4, H8 shift upfield than MeQNO
2
because of the effect +C of RNH group
(replaced OCH
2
COOH group, Table 12).
Table 12. Resonance Signals on
1
H NMR of T1-T8,  (ppm), J (Hz)


H1
H2

H4

H8
H11
H12
H16
H13
H15
H14
Others
T1a
4,17
s;3H
8,52
s;1H

8,48
d;1H
J =1,5
6,76
s;1H
-
-
-
-
-
-
NH
4
+
:
7,10 s
T1b
4,34
s;3H
9,03
s;1H
8,42
s;1H
7,07
s;1H
-
-
-
-
-

-
-
T2
4,34
s;3H
8,91
s;1H
8,43
s;1H
6,65
s;1H
3,02
s;3H
-
-
-
-
-
NH: 7,9

20
T3
4,32
s;3H
8,86
s;1H
8,42
s;1H
6,69
s;1H

3,46
q; 2H
J = 7,5
1,26
t; 3H
J = 7,5
-
-
-
-
NH: 7,75
T4
4,32
s; 3H
8,85
d; 1H
J = 1
8,42
s;1H
6,69
s;1H
3,40
t; 2H
J = 7,5
1,70
m; 2H
J = 7,5
-
-
-

-
NH: 7,75
T5
4,19
s;3H
8,79
s;1H
8,44
s;1H
6,70
s;1H
3,67
s; 2H
7,54 d; 2H
J = 7,5
7,34 t; 2H
J = 7,5
7,27
t; 1H
J = 7,5
NH: 8,32
T6
4,32
s;3H
8,90
d;1H
J = 1
8,43
s;1H
6,81

s;1H
3,51
t; 2H
J = 6
3,70
t; 2H
J = 6
-
-
-
-
NH: 7,65
T8
4,33
s;3H
8,86
s;1H
8,40
s;1H
6,75
s;1H
3,77
m;1H
H12e, H16e: 1,96 m; 2H
H12a/H13a/H15a/H16a:1,46m;4H
H13e/H15e: 1,75 m; 2H
H14e: 1,64 d;1H; H14a:1,22 m; 1H
NH: 7,30
On the
13

C NMR spectra of T1-T8, we found enough resonance signals of
the carbon atoms are not equivalent in accordance with the formula. Difference
spectrum of QNO
2
: Not appear the resonance signal at 160-180 ppm of C7b and
signal at 60-70ppm of C7a (OCH
2
COOH group). Other hand, the HMBC spectrum
of each compounds have interaction peak between C7 and H11. This proves that
OCH
2
COOH group was replaced by RNH group at 7
th
position. Combining analysis
and 13C NMR HMBC spectrum have attributed the chemical shift of the carbon
atoms in the T1-T8 molecule (Table 13).
Table 13. The chemical shift of C in
13
C NMR spectrum of T1-T8, δ (ppm)

T1a
T1b
T2
T3
T4
T5
T6
T8
C1
44,0

44,3
44,62
44,56
44,62
44,56
44,64
44,60
C2
136,0
139,9
138,67
138,11
138,16
138,00
138,59
138,18
C3
134,1
136,8
136,59
136,56
136,52
137,56
136,67
136,56
C4
125,4
129,7
128,97
128,44

128,48
128,56
128,79
128,35
C5
126,5
130,9
129,50
129,24
129,78
129,13
129,48
129,38
C6
157,94
146,62
148,45
149,39
149,30
149,71
148,71
149,21
C7
154,41
150,9
150,34
149,49
149,73
150,20
149,75

148,38
C8
90,6
94,5
90,24
89,92
90,02
90,65
90,63
90,11
C9
133,4
135,2
135,59
135,38
135,40
134,94
135,37
135,31
C10
121,4
116,9
117,59
117,87
117,86
118,28
117,66
117,73
C11
-

-
29,64
40,09
44,09
45,76
45,16
50,63
C12
-
-
-
13,33
20,91
127,70
58,88
31,24
C16
-
-
-
-
-
-
C13
-
-
-
-
11,43
128,56

-
25,03
C15
-
-
-
-
-
-
C14
-
-
-
-
-
127,33
-
24,32

21

T1a
T1b
T2
T3
T4
T5
T6
T8
Ci

-
-
-
-
-
136,78
-
-

3.4.3. MS spectrum of T1-T8
We have recorded ESI MS spectrum of T1, T2 and T4 compounds. The main
peaks in the spectrum show that their molecular weight equal to the molecular
weight by calculated as expected (Table 14).
Table 14. Kết quả phân tích phổ MS của T1, T2 và T4

NHR
Molecular formula /M
Main peaks, m/z / (%)
T1
NH
2
C
10
H
9
N
3
O
6
S

299
298/100: [M-H
+
]; 299/11:
13
C; 300/5,7:
34
S;
282/10: [M-H
+
-O]
-
T2
NHCH
3
C
11
H
11
N
3
O
6
S
313
312/100: [M-H
+
]; 313/13:
13
C; 314/6:

34
S;
297/10: [M-H
+
-CH
3
]
-

T4
NHC
3
H
7
C
13
H
15
N
3
O
6
S
341
340/100: [M-H
+
]; 331/15:
13
C; 342/7:
34

S;
325/10: [M-H
+
-CH
3
]
-


3.5. QNHNH
2
HYDRAZINE and V1-V13 HYDRAZONES
3.5.1. MeQNHNH
2
: 7-hydrazinyl-6-hydroxy-1-methylquinolinium-3-sunfonate
When heating a mixture of MeQBr and hydrazine excess in 3 hours, we
obtained a yellow solid brown, dark gradually when exposed in air. On Thin-layer
chromatography of the products have 2 different spots close together. We denote
this product is Qhh.
IR and NMR spectrum of Qhh proved OCH
2
COOH group linked to the
aromatic group that has been replaced by NHNH
2
group. Simultaneously Br atom
in position 5 is replaced by H atom as scheme 4.

Scheme 4. Replacement reaction mechanism OCH
2
COOH group lead to NHNH

2
group

22
On Scheme above, the first reaction is similar with the replacement reaction
OCH
2
COOH group by ankylamine according to mechanism such as in the section
3.4.1, mechanism of the second reaction is suggested such as scheme following

Scheme 5. Replacement reaction mechanism Br by H when MeQBr reacts with
hydrazine
3.5.2. Structure and spectrum properties of the V1-V13 hydrazones
a. Infrared spectrum of V1-V13 hydrazones
The IR spectrum of V1-V13 are similar to each other: no absorption peak
characteristic C=O bond in 1700 -1750 cm
-1
which appear absorbtion peaks in
1625-1630 cm
-1
attributed to C=N quinoline ring (Table 3.39 of the thesis).
b. NMR spectrum of V1-V13 hydrazones
The
1
H NMR and
13
C NMR spectrum of the studied hydrazones have signals
of many groups of protons and carbon atoms. Combined with analysis of HMBC
spectrum, we have attributed the exact signals on
1

H NMR spectrum of the
hydrazones as in Table 15.

Table 15. Signals on the
1
H NMR spectrum of V1-V13


Structure
H1
H2

H4

H5
H8
Hi;
H11
H12
H16
H13
H15
H14
Others
V1

4,48
s;1H
9,13
d;1H

J=1,5
8,91
s;1H
7,56
s;1H
7,75
s;1H
8,57
s;1H
7,84 dd;2H
J1 = 7
J2 = 2
7,47 m;3H
NH: 11,22
OH6:11,91


23
V2

4,49
s;1H
9,13
d;1H
J = 1
8,92
s;1H
7,56
s;1H
7,73

s;1H
8,54
s;1H
7,60
s;1H
7,64
d;1H
J = 7,5
-
7,37
t;1H
J = 7,5
7,25
d;1H
J = 7,5
NH: 11,20
OH6: 11,89
H13a: 2,38
V3

4,47
s;1H
9,13
s;1H
8,91
s;1H
7,55
s;1H
7,69
s;1H

8,47
s;1H
7,21 d;2H
J = 2
-
7,27
t;1H
J = 8
6,84
dd,1H
J1= 7,5
J2= 1,5
NH: 11,17
OH6: 11,91
OH13:9,7
V4

4,44
s;1H
9,08
s;1H
8,86
s;1H
7,51 s
7,65
s;1H
8,46
s;1H
7,66 d;2H
J = 8,5

6,86 d
J = 8,5
-
NH: 11,04
OH6: 11,85
OH14: 9,90
V5

4,49
s;1H
9,14
d;1H
J = 1
8,93
s;1H
7,57
s;1H
7,75
s;1H
8,55
s;1H
7,85 d;2H
J = 8,5
7,53 d
J = 8,5
-
NH: 11,26
OH6: 11,89
V6

4,52
s;1H
9,17
s;1H
8,96
s;1H
7,59
s;1H
7,84
s;1H
8,63
s;1H
8,29 d;2H
J = 8,5
8,07 d
J = 8,5
-
NH: 11,50
OH6:11,96
V7

4,43
s;1H
9,07
s;1H
8,83
s;1H
7,52
s;1H
7,63

s;1H
8,46
s;1H
7,67 d;2H
J = 9
6,88 d
J = 6
-
NH: 11,03
OH6: 11,85
H14a: 3,01
V8

4,46
s;1H
9,08
s;1H
8,85
s;1H
7,51
s;1H
7,70
s;1H
8,45
s;1H
7,43
d;1H
J = 2
7,18
dd;1H

J1 =
8,5
J2 = 2
-
6,86
d;1H
J = 8,5
-
NH: 9,60
OH6: 11,1
H13a: 3,89
OH14: 9,55
V9

4,44
s;1H
9,06
s;1H
8,84
s;1H
7,51
s;1H
7,65
s;1H
8,75
s;1H
-
7,67
d;J=8
6,36

s;1H
6,37
s;1H
-
NH: 11,04
OH6: 11,85
OH12:11,1
OH14:11,8
V10

4,39
s;1H
9,12
s;1H
8,90
s;1H
7,53
s;1H
7,47
s;1H
2,12
s;3H
-
-
-
-
-
NH: 9,1
Hk:2,06 s;3H
V11

4,38
s;1H
9,11
s;1H
8,88
s;1H
7,52
s;1H
7,47
s;1H
2,40
q,2H
J=7,5
1,15
t;3H
J=7,5
-
-
-
-
NH: 9,11
OH6: 11,91
Hk:2,04 s;3H
V12

4,49
s;1H
9,16
d;1H

J = 1
8,96
s;1H
7,60
s;1H
7,74
s;1H
-
7,98 dd;2H
J1 = 8,5
J2 = 2
7,48 m;3H
NH: 9,42
OH6: 12,0
Hk:2,46 s;3H
V13

4,44
s;1H
9,10
s;1H
8,89
s;1H
7,59
s;1H
7,53
s;1H
-
7,70 d;2H
J = 8,5

6,61 d
J = 8,5
-
NH: 9,30
OH6: 11,95
NH
2
: 5,68
Hk:2,35 s;3H

On
13
C NMR spectrum of V1-V13, we have found enough resonance signals
of the carbon atoms are not equivalent in accordance with the expected formula.
Combined with HMBC spectrum identified the chemical shift of the carbon atoms
of V1-V13 as in Table 16.
Table 16. The chemical shift of C on
13
C NMR spectrum of V1-V13, δ (ppm)

V1
V2
V3
V4
V5
V6
V7
V8
V9
V10

V11
V12
V13
C1
44,1
44,1
44,1
44,1
44,2
44,3
43,9
43,9
43,9
44,0
44,1
44,1
44,0
C2
141,3
141,3
141,3
141,0
141,4
141,8
140,8
141,0
140,8
141,1
141,2
141,6

141,0
C3
137,3
137,3
137,2
136,9
137,4
138,2
136,9
136,9
136,9
137,2
137,1
137,7
137,0
C4
137,8
137,8
137,8
137,5
137,8
140,8
137,3
137,5
137,3
137,7
137,8
138,1
137,6

24
C5
109,3
109,3
109,3
109,0
109,3
109,7
108,9
109,0
108,1
109,0
109,1
109,3
108,8
C6
147,0
147,0
147,0
146,9
147,1
147,5
147,2
147,0
147,0
146,9
146,9
147,1
147,1
C7

143,2
143,3
143,3
143,4
143,1
142,7
143,4
143,4
143,2
143,6
143,7
143,1
143,3
C8
94,3
94,2
94,1
93,5
94,5
95,4
93,3
93,7
93,0
93,5
93,1
94,9
93,7
C9
136,6
136,6

136,6
136,8
136,5
137,8
136,7
136,8
136,8
136,6
136,7
136,4
136,7
C10
124,6
124,2
124,6
124,4
124,7
125,0
124,4
124,4
124,4
124,3
124,3
124,7
124,6
C11
134,4
134,3
135,6
125,4

133,3
136,2

125,9
128,7
-
-
137,6
124,5
C12
127,1
128,8
118,4
128,9
128,7
124,1
128,5
109,6
160,7
25,3
31,7
126,3
127,7
C16
130,6
113,1


121,7
112,0

-
-
C14
127,2
124,6
117,2
159,4
134,2
147,1
147,0
149,0
158,3
-
-
129,4
150,5
C13
128,9
138,1
157,7
115,8
128,9
127,8

148,1
102,4
-
9,44
129,4
113,3

C15
127,7
129,9


115,6
108,9
-
-
Ci
146,3
146,5
146,5
146,9
144,8
143,2

146,8
145,6
156,1
159,6
151,9
153,1
Others
-
C13a:
20,9
-
-
-

-
C14a
C13a:
55,6
-
Ck:
17,0
Ck:
15,7
Ck:
13,4
Ck:
13,0
c. MS spectrum of V1-V13 hydrazones
We have record mass spectrometry of some hydrazones, spectral analysis of
the compounds received the molecular weight equal to molecular weight calculated
by the expected formula (Table 17).
Table 17. Results of the MS spectral analysis of hydrazones

Formula / M
Main peaks, m:z / intensity (%)
V1
C
17
H
15
N
3
O
4

S
357
380/100: [M+Na
+
]; 358/48: [M+H
+
]; 381/20:
13
C; 737/18: [2M+Na
+
]
356/100: [M-H
+
]; 357/20:
13
C; 713/17: [2M-H
+
]
V2
C
18
H
17
N
3
O
4
S
371
394/93: [M+Na

+
];372/31: [M+H
+
]; 357/18: [M+Na
+
–CH
3
];
370/100: [M-H
+
]; 371/23:
13
C; 356/25: [M+H
+
–CH
3
]
V4
C
17
H
15
N
3
O
5
S
373
396/100: [M+Na
+

]; 374/34: [M+H
+
]; 769/23: [2M+Na
+
]
372/100: [M-H
+
]; 373/22:
13
C; 745/8: [2M-H
+
]
V5
C
17
H
14
N
3
O
4
SCl
391/393
414/74: [M+Na
+
]; 392/45: [M+H
+
]; 805/15: [2M+Na
+
]

V6
C
17
H
14
N
4
O
6
S
402
401/100: [M-H
+
]; 402/21:
13
C; 385/36: [M-H
+
–O]
V7
C
19
H
20
N
4
O
4
S
400
401/100: [M+H

+
]; 402/28:
13
C; 423/27: [M+Na
+
]
399/100: [M-H
+
]; 400/24; 401/20; 799/9: [2M-H
+
]
V8
C
18
H
17
N
3
O
6
S
403
426/70: [M+Na
+
]; 427/18;
13
C
402/100: [M-H
+
]; 403/22:

13
C; 805/8: [2M-H
+
];
V10
C
13
H
15
N
3
O
4
S
309
332/100: [M+Na
+
]; 310/47: [M+H
+
]; 333/16:
13
C
308/100: [M-H
+
]; 309/16:
13
C; 252/7: [M+Na
+
–SO
3

]
V12
C
18
H
17
N
3
O
4
S
371
394/38: [M+Na
+
]; 372/13: [M+H
+
];
370/100: [M-H
+
]; 371/25:
13
C
3.6. BIOLOGICAL ACTIVITY TESTS
– Of the 32 polysubstituted quinoline compounds, A0 and Q have strong
antibacterial activity; HzQBr has weak antibacterial; V5 has average antibacterial
and R1 has antifungal likely weak.

25
– The results testing antioxidant activity of 08 samples hydrazone showed that they
have not antioxidant activity.

– Of the 04 sample testing cell toxicity, QNO
2
has cytotoxic activity against four
cancer cell lines at weak; HzQBr has cytotoxic activity against cell carcinoma.
– We only test activity against malaria for 7-carboxymethoxy-6-hydroxy-3-
sulfoquinoline (Q). The results show that Q has activity against the malaria
parasite but not strong.