Volume 03 Issue 12-2023
49
International Journal of Pedagogics
(ISSN
–
2771-2281)
VOLUME
03
ISSUE
12
P
AGES
:
49-53
SJIF
I
MPACT
FACTOR
(2021:
5.
705
)
(2022:
5.
705
)
(2023:
6.
676
)
OCLC
–
1121105677
Publisher:
Oscar Publishing Services
Servi
ABSTRACT
In the reaction of α
-
bromoacylthiain and α
-bromoacylthiochromenes with secondary amines, that, piperidine and
morpholine, respectively, α
-amino ketones of these substances and hydrochloride compounds of these substances
were obtained by passing hydrogen chloride gas in benzene.
KEYWORDS
P
iperidine, morpholine, α
-piperidino-5-acetyl-2-methyl-1-
thiain hydrochloride, α
-morpholino-5-acetyl-2-methyl-1-thiain
hydrochloride,
α
-piperidino-6-acetyl-1-
thiochroman
hydrochloride,
α
-morpholino-6-acetyl-1-thiochroman
hydrochloride.
INTRODUCTION
It is known that most amino ketones with an organic
structure are first synthesized as biologically active
compounds and as metal corrosion inhibitors. In
particular, β
-amino ketones of 1-thiandan and 1-
thiochromenes have been identified as excellent local
anesthetics.
For
example,
1-piperidino-3,6-(1-
thiochroman)-yl-3-propane and its hydrochlorides are
3-5 times superior to novocaine in terms of local
anesthetic properties and 2-5 times in terms of
pharmacological
effects.
time
advantage
is
determined. β
-aminoalcohols and aminoketones of
these compounds have been found to be good
inhibitors of metal corrosion protection.
MATERIALS AND METODS
When the reaction of α
-
bromoacylthiandan and α
-
bromoacylthiochromenes with secondary amines, i.e.,
piperidine and morpholine, was carried out for 30
Research Article
SYNTHESIS OF BENZO[B]THIOPHENE Α
-HALOKETONE
HYDROCHLORIDES
Submission Date:
December 01, 2023,
Accepted Date:
December 05, 2023,
Published Date:
December 10, 2023
Crossref doi:
https://doi.org/10.37547/ijp/Volume03Issue12-10
Rakhmatova Guzal
Doctor Of Philosophy (Phd), Karshi Engineering Economics Institute, Karshi Uzbekistan
Journal
Website:
https://theusajournals.
com/index.php/ijp
Copyright:
Original
content from this work
may be used under the
terms of the creative
commons
attributes
4.0 licence.
Volume 03 Issue 12-2023
50
International Journal of Pedagogics
(ISSN
–
2771-2281)
VOLUME
03
ISSUE
12
P
AGES
:
49-53
SJIF
I
MPACT
FACTOR
(2021:
5.
705
)
(2022:
5.
705
)
(2023:
6.
676
)
OCLC
–
1121105677
Publisher:
Oscar Publishing Services
Servi
minutes in a benzene solution, α
-aminoketones of
these substances were formed, respectively.
S
R
BrCHCOC
R
1
R
2
H
S
R
R
2
CHCOC
R
1
R=CH
3
; R
1
=H; R
2
= piperidine. (I)
R=CH
3
; R
1
=H; R
2
= morpholine. (II)
S
RCHCOC
Br
S
RCHCOC
R
1
H
R
1
R=H; R
1
= piperidine (III)
R=H; R
1
= piperidine (IV)
According to the above reaction scheme, the following α
-amino ketones of thiaindan and thiochromans were
synthesized: α
-piperidino-5-acetyl-2-methyl-1-thiaindan (I).
REZULTS
When analyzing the IR-spectrum of 1-thiaindan and 1-
thiochroman α
-amino ketones, the absorption lines indicating
the replacement of the bromine atom in the side chain of the molecule with an amine group give valence vibrations
characteristic of the nitrogen atom in the region of 1230-1240 cm-1. Also, in this spectrum, the loss of valence
vibrations related to carbon-bromine bonds visible in the region of 655-640 cm-1 was observed.
Thiaindan and α
-amino ketones of the thiochroman series Data of IR spectr Table 1
The frequency shift.cm
-1
Compounds
I
II
III
IV
in a benzene ring C=C
1595 1600 1600
1600
in a benzene ring CN
840
830
850
840
in a benzene ring H
940
930
940
920
-C=O
1685 1680 1680
1690
-C-N
1240 1240 1230
1240
C-S-C
730
720
730
740
Volume 03 Issue 12-2023
51
International Journal of Pedagogics
(ISSN
–
2771-2281)
VOLUME
03
ISSUE
12
P
AGES
:
49-53
SJIF
I
MPACT
FACTOR
(2021:
5.
705
)
(2022:
5.
705
)
(2023:
6.
676
)
OCLC
–
1121105677
Publisher:
Oscar Publishing Services
Servi
Every nucleophilic reagent exhibits basicity to a greater
or lesser extent. This indicates that it not only reacts
with an electron-deficient carbon atom at the expense
of its unshared electron pair, but can also disconnect
the mobile hydrogen, i.e., protons, in the substrate.
Due to this, it can form compounds that are less
dissociable compared to the original substrate.
Therefore, to a greater or lesser extent, the reaction of
dehydrohalogenation (elimination of hydrogen halide)
takes place simultaneously with the reaction of
nucleophilic substitution of the halogen atom. As a
product of such reactions, alkenes are formed and it
has a quantitative effect on the yield of the main
product of the reaction.
As a result of the reaction, it was found that amino
ketones containing a thiochroman fragment have a
higher mass percentage in the reaction than amino
ketones containing a thiamine fragment. It was also
found that the nucleophilic ability of piperidine and
morpholine obtained as an active reagent in this
reaction is high in the morpholine molecule. According
to the yield of the products formed as a result of the
reaction, it was found that the nucleophilicity of the
morpholine molecule is higher than that of piperidine
on both substrates.
Table 2 below presents the physico-
chemical data of α
-amino ketones from 2-methyl-1-thiamine.
Physicochemical data of thiaindan α
-aminoketones
S
R
1
HCOC
R
R
2
R
1
= H; R
2
= piperidine and morpholine.
Table 2.
R
percentage,
%
Liquefaction
temperature,
0
S
Found,%
Calculated,%
S
N
S
C
H
S
CH
3
64
piperidine
49-50
69,92
69,86
7,94
7,78
11,74
11,69
69,77
7,68
11,64
CH
3
72
morpholine
n
20
d
=1,3751
69,21
69,03
7,60
7,39
12,49
12,33
68,92
7,32
12,26
Similarly, the physicochemical data of 1-
thiochroman α
-amino ketones are presented in Table 3 below.
Thiochromane series of α
-amino ketones
physical chemical constants
Volume 03 Issue 12-2023
52
International Journal of Pedagogics
(ISSN
–
2771-2281)
VOLUME
03
ISSUE
12
P
AGES
:
49-53
SJIF
I
MPACT
FACTOR
(2021:
5.
705
)
(2022:
5.
705
)
(2023:
6.
676
)
OCLC
–
1121105677
Publisher:
Oscar Publishing Services
Servi
R
1
= piperidine and morpholine.
HCOC
R
R
1
S
Table 3
R
percentage,
%
n
20
d
Found,%
Calculated%
S
N
S
C
H
S
H
85
piperidine
1,3653
69,92
69,86
7,94
7,78
11,74
11,69
69,77
7,68
11,64
N
88
morpholine
1,3621
69,21
69,03
7,60
7,39
12,49
12,33
68,92
7,32
12,26
Hydrochloride compounds of these substances were obtained by passing dry hydrogen chloride gas from the resulting
solution of α
-amino ketones in benzene. The general scheme for the preparation of hydrochlorides of thiaindan and
thiochroman α
-aminoketones was given through the following reaction scheme:
S
CH
2
COC
H
N
S
CH
2
COC
N
HCl
Cl
By the same route, from α
-piperidino-5-acetyl-2-methyl-1-
thiain hydrochloride in 70% yield (V), from α
-morpholino-5-
acetyl-2-methyl-1-
thiain hydrochloride in 75% yield (VI), α
-piperidino-6-acetyl-1-thiochroman hydrochloride in 77% yield
(VII) and α
-morpholino-6-acetyl-1-thiochroman hydrochloride (VIII) were formed in 81% yield.
Tables 4 and 5 below provide descriptive information on 1-thiaindan and 1-
thiochroman α
-aminoketone
hydrochlorides.
α
-Aminoketones such as 1-thiain description of hydrochlorides
S
R
1
HCOC
R
R
2
HCl*
Table 4
R
R
1
R
2
percentage
,
%
tempera
ture
0
C
Found,%
Calculated,%
C
H
S
C
H
S
CH
3
N
piperidine
70
182-183
62,04
6,91
10,68
61,59
7,05
10,28
CH
3
N
morpholine
75
184-185
57,28
6,13
10,31
57,45
6,37
10,22
Volume 03 Issue 12-2023
53
International Journal of Pedagogics
(ISSN
–
2771-2281)
VOLUME
03
ISSUE
12
P
AGES
:
49-53
SJIF
I
MPACT
FACTOR
(2021:
5.
705
)
(2022:
5.
705
)
(2023:
6.
676
)
OCLC
–
1121105677
Publisher:
Oscar Publishing Services
Servi
α
-Aminoketones of the 1st thiochromane series
description of hydrochlorides
S
R
1
CHCOC
R
Table 5
R
R
1
Per-
centa
ge,
%
temperature
0
C
Found,%
Calculated,%
Gross
formula
C
H
S
C
H
S
S
16
H
22
OSNCl
N
piperi
dine
77
183-184
62,01
6,88
10,60 61,59 7,05
10,28
N
morph
oline
81
180-181
57,28
6,11
10,28 57,45 6,37
10,22 C
15
H
20
O
2
SNCl
CONCLUSION
In the reaction of α
-
bromoacylthiain and α
-
bromoacylthiochromenes with secondary amines, i.e.,
piperidine and morpholine, α
-aminoketones of these
substances were formed, respectively. As a result of
the reaction, it was found that aminoketones
containing a thiochroman fragment had a higher mass
percentage in the reaction than aminoketones
containing a thiamine fragment. Also, it was shown
that the nucleophilic ability of piperidine and
morpholine obtained as an active reagent in this
reaction is high in the morpholine molecule.
Hydrochloride compounds of these substances were
synthesized by passing dry hydrogen chloride gas from
the resulting solution of α
-amino ketones in a
REFERENCES
1.
Рахматова.Г.Б., Курбанов. М.Ж., Рузибоев М.Т.,
Синтез
и
изучение
скорости
реакции
ацилирования 1
-
тианданов и 1
-
тиохроманов.
Universum: Химия и биология Выпуск:
12(66)Декабрь 2019 Москва 2019. 82
-
86 с.
2.
2.G. Rakhmatova Kinetic properties of bicyclic
sulfur organic inhibitors Universum: Химия и
биология выпуск: 12(90)дека
-
брь 2021 ISSN: 2311 –
5459 doi:10.32743/Unichem. 2021.90.12-2
3.
Kamol M. Dovud. Regio-and stereoselective
synthesis
of
bis-spiropyrazoline-5,3/-
spiropyrazoline(thiochroman)-4-one
derivatives
via bis-nitrilimines. Tetrahedron. Volume 61. Issue
22, 30 may, 2005, pages 5229-5233.
