IV INTERNATIONAL SCIENTIFIC CONFERENCE OF YOUNG RESEARCHERS
176
Qafqaz University 29-30 April 2016, Baku, Azerbaijan
химического взаимодействия в системе Bi
2
Se
3
-Nd
3
Se
4
. Растворимость со стороны Bi
2
Se
3
при
комнатной температуре составляет 5 моль % Nd
3
Se
4
. Изучение электрофизических свойств
полученных твердых растворов в широком интервале температур. Все сплавы из области
твердых растворов имеют р- тип проводимости. Более подробное обсуждение результатов
изучения электрофизических параметров можно провести с помощью исследования других
кинетических коэффициентов, но близость составов и родственный характер температурных
термоэлектрических параметров, свидетельствует об аналогичности механизма явлений
переноса в настоящих веществах с ранее изученными твердыми растворами на основе Bi
2
Se
3
.
СИНТЕЗ N-АЛКИЛАМИНОCПИРТОВ НА ОСНОВЕ
ГАЛОГЕНГИДРИНОВ НОРБОРНЕНОВОГО РЯДА
О.А.САДЫГОВ
Институт нефтехимических
процессов им. Ю.Г.Мамедалиева
НАНA
omar.sadiqov@gmail.com
AЗЕРБАЙДЖАН
Ш.И.ИСМАЙЫЛОВА
Институт нефтехимических
процессов им. Ю.Г.Мамедалиева
НАНA
AЗЕРБАЙДЖАН
Х.М.АЛИМАРДАНОВ
Институт нефтехимических
процессов им. Ю.Г.Мамедалиева
НАНA
AЗЕРБАЙДЖАН
Возросший интерес к бициклическим соединениям с азот- и кислородными функциями
обусловлен их устойчивостью и высокой биологической активностью .Эти вещества
представляют самостоятельный интерес, а так же являются удобными синтонами для
получения полифункциональных соединений применяемых в качестве лекарственных
препаратов различного назначения . Структурные фрагменты бициклических аминоспиртов
входят в состав молекул природных соединений и их синтетических аналогов. Среди N-
алкиламиноcпиртов наиболее известны их вицинальные производные, получаемые
непосредственно аминолизом эпоксидов непредельных соединений различной структуры.
Установлено ,что такие соединения участвуют в метаболизме ненасыщенных
канцерогенов ,трансформирующихся под действием ферментов в оксираны. Последние при
взаимодействии с азот- и серосодержащими фрагментами белковых молекул подвергаются
раскрытию цикла.
В настоящем сообщении предлагается новый альтернативный вариант получения
бициклических вицинальных аминоспиртов, путем электрофильного присоединения
галогеноватистых кислот
4, в условиях их “in situ” образования к молекулам норборнена и
его алкилпроизводных, с последующим замещением атомов гологена соответствующими
вторичными аминами, при мягких условиях:
Где: X=Cl (I), Br (II); III, Q=N(CH
3
)
2
(a); N(C
2
H
5
)
2
(b); NC
5
H
10
(c); N(CH
2
)
4
O(d); HNC
6
H
5
(e)
Установлено, что выход транс – вицинальных гидроксигалогенидов в первой стадии
реакции зависит, главным образом от температуры и концентрации галогеноводородных
кислот. Наиболее высокий выход хлоргидринов ( до 81% ) и бромгидринов ( до 78% )
обеспечиваются при температуре 30 – 40 °С в случае применения 6 – 10 % - ного водного
раствора галогеноводородных кислот. При одновременной загрузке реактора исходными
компонентами образование ди брома(дихлора) производного по сравнению с реакцией
индуцированного бром(хлор) гидроксилированого норборненов протекает с более высокой
IV INTERNATIONAL SCIENTIFIC CONFERENCE OF YOUNG RESEARCHERS
177
Qafqaz University 29-30 April 2016, Baku, Azerbaijan
скоростью. Выход продуктов индуцированного бром(хлор) гидроксилирования циклоолефинов
можно регулировать изменением скорости подачи окислителя, в частности,пероксида
водорода. Выход аминоспиртов в стадии аминирования , в основном, зависеть от молярного
отношения вторичных аминов и синтезированных гидроксигалогенидов. Двукратный избыток
первого обеспечивает более высокий выход соответствующих транс – вицинальных
аминоспиртов в интервале 78 – 86,5 %.
Структура полученных галогенгидринов и соответствующих N,N- диметил,- N,N- диэтил-
, пиперидино- и морфолиногидроксинорборнанов подтверждена данными ИК -, ЯМР
1
Н и
13
С
спектральных анализов. В ИК спектрах синтезированных соединений I и II обнаруженные
полосы поглощения в области 745,780 см
-1
(для связи С-Сl), 623,640 см
-1
(для связи С-Br) и
1100-1170, 3615 см
-1
(для группы ОН) являются общими, а полосы при 1378, 1420, 1443 см
-1
соответствуют деформационным колебаниям группы СН
2
цикла. В спектрах ЯМР
1
Н
соединений I и II присутствуют дублеты при δ 1,53-1,75 м.д. с J 5 Гц соответствующим двум
протонам, расположенным в голове мостика С
1
и С
4
. Сигнал одного из них расщеплен в дублет
с J 5 Гц и перекрывает сигнал другого. Протоны при С
1
и С
4 У
соединении II также проявляется
в виде дублета в области δ 1,53-1,85 м.д. Сигналы при δ 3,46 - 3,48 м.д., и δ 3,3 6 - 3,5 8 м.д., в
виде дублета к протонам у С
2
и С
3
соединений I и II. Сигналы протонов гидроксильной
группы соединений I и II наблюдаются в области δ 4,81 м.д. в виде уширенного синглета.
Таким образом, использование принципа индуцирования электрофильных
реагентов - галогеноватистых HOХ (где Х=Cl, Br) кислот в сильнокислотной среде
позволяет синтезировать с высокой селективностью N-алкиламинобицикло[ 2,2,1 ]гептан-2-
олов через соответствующие галогенгидринных интермедиатов при мягких условиях.
PHASE PROPERTIES OF THE SYSTEMS As
2
Se
3
-TmSe AND As
2
Se
3
-
Tm
2
Se
3
T.M.ILYASLY
Baku State University
AZERBAİJAN
F.M.SADIQOV
Baku State University
AZERBAİJAN
Z.I.ISMAYILOV
Baku State University
zakir-51@mail.ru
AZERBAİJAN
G.H.QAXRAMANOVA
Baku State University
AZERBAİJAN
The synthesis of the system alloys was carried out by direct melting in a rotating furnace.The
components were encapsulated in quartz ampoules evacuated to 10
-4
Too r.The synthesis temperatures
varied from 650 to 1300 K.The Syntheses were terminated after 16-20 h,followed by a slow cooling at
a rate of 3-4 K min
-1
.Immediately after the synthesis,the alloys containing up to 12 mol% of TmSe as
well as those with up to 10 mol% of Tm
2
Se
3
were in a glassy state.In order to reach the equilibrium
state,all alloys were annealed at 553 K for 600 h.After annealing,the physico-chemicial
analyses(differential thermal analysis,microstructural analysis,and X-ray diffraction analysis as well as
IR spectroscopy)were repeated.
The system As
2
Se
3
-TmSe is a quasi-binary section of the ternary system Tm-As-Se.Three
ternary compounds of composition TmAs
4
Se
7
,TmAs
2
Se
4
and Tm
3
As
4
Se
9
are formed in it.The liquidus
of the system consists of five branches of primary crystallization of phases: α-solid solution based on
As
2
Se
3
,TmAs
4
Se
7
,TmAs
2
Se
4
,Tm
3
As
4
Se
9
,TmAsSe
3
and TmSe.
The compound TmAs
4
Se
7
melts congruently at 875 K,whereas TmAs
2
Se
4
and Tm
3
As
4
Se
9
are
formed according to the following peritectic reactions:
IV INTERNATIONAL SCIENTIFIC CONFERENCE OF YOUNG RESEARCHERS
178
Qafqaz University 29-30 April 2016, Baku, Azerbaijan
1035K
L+TmSe ⇆ Tm
3
As
4
Se
9
865K
L+ TmSe ⇆ TmAs
2
Se
4
The region of solid solutions based on As
2
Se
3
reaches 1 mol % of TmSe.On the TmSe side of the
phase diagram we were unable to detect any region of solid solubility.
The T-x state diagram of the system As
2
Se
3
- Tm
2
Se
3
,as constructed according to our experimental
data. The liquidus of this section consists of three branches of primary crystallization of phases: α-
solid solution based on As
2
Se
3
,TmAsSe
3
and Tm
2
Se
3
.The existence of SmAsSe
3
is reported for the
first time.This ternary compound is formed according to the following peritectic reaction:
845K
L+Tm
2
Se
3
⇆ TmAsSe
3
The limit of the region of solid solutions based on the glass-forming compound As
2
Se
3
was
determined as 0.8 mol % of Tm
2
Se
3
.
As a result of the analysis of the phase diagrams of the studied systems,the structural units in the
glass phases have been determined,and it has been established that the predominant structural unit is
As
2
Se
3
.
I. The formation of ternary compounds of the type LnBX
3
,where B=As,Sb and X= S,Se is possible
only with the participation of arsenic and divalent rare earth elements,the exception being the system
EuS-Sb
2
S
3
2 where Eu
3
Sb
4
S
9
is formed.In telluride systems the corresponding compounds are not
formed.
II.The character of the compounds Ln
3
As
4
X
9
(X=S,Se) changes in the sequence Ln=Eu,Tb,Sm,Tm
from congruently melting in the case of Eu,Yb and Sm to incongruently melting in the case of
Tm.This appears to be connected with the decreasing stability of the divalent state of rare earth
elements.
III. The eutectic alloys and the solid solutions based on As
2
Se
3
are responsible for the glass formation
in these systems.
IV.The temperature of melting and formation of the compounds LnB
4
X
7
,LnB
2
X
4
and Ln
3
B
4
X
9
increases in the sequence Eu,Yb,Sm,Tm and from tellurium to selenium and sulphur.
The compound TmAs
4
Se
7
melts congruently at 875 K,whereas TmAs
2
Se
4
and Tm
3
As
4
Se
9
are
formed according to the following peritectic reactions:
865K
L+ TmSe⇆ TmAs
2
Se
4
1035K
L+TmSe⇆ Tm
3
As
4
Se
9
IV INTERNATIONAL SCIENTIFIC CONFERENCE OF YOUNG RESEARCHERS
179
Qafqaz University 29-30 April 2016, Baku, Azerbaijan
SYNTHESIS AND STUDY PROPERTIES OF N,N –BIS P –
(DIMETHYLAMINO BENZYLIDENE) DIAMINOPROPAN AND ITS
METAL COMPLEXES
T.M.ILYASLY
Baku State University
AZERBAİJAN
A.R.RAHIMOVA
Baku State University
rahimova_aysel@mail.ru
AZERBAİJAN
Z.I.ISMAYILOV
Baku State University
AZERBAİJAN
M.N.ALIYEVA
Baku State University
AZERBAİJAN
The synthesis of complexes of Cu(II) and Ni(II) with N,N-bis-(p-dimethylaminobenzylidene)
diaminopropan obtained by condensation of N,N-(p-dimethylaminobenzaldehyde with diaminopropan
has been realized. All obtained compounds were characterized by their spectra (IR, NMR).
Antimicrobial properties of initial azomethine and its complexes with Cu and Ni were analyzed. It was
established that they showed high bactericidal and fungicidal activity in M-8 oil.
One of the main methods for forming machine parts is machining. The most important element of
the process of metal cutting is using cutting fluids.As CFfor metal cutting there are proposed various
compositions of organic and inorganic compounds, most of which are oil-based liquids. Oil-based CFs
meet a series of requirements: in particular, they must not cause a pronounced biological effect on the
skin and respiratory system of employee, must have a minimal irritating effect when exposing to the
mucous membranes, have low oil mist, not contain 3,4-benzpyrene and certain other hazardous
substances. It is important to know the molecular composition of the oil-based CF to identify
individual compounds of potential environmental pollutants.
Prospective N-containing compounds are wide class of organic chelate forming compounds
containing hetero atoms. Such compounds are able to coordinate with metals, and complexes obtained
on their basis often have an effective biological activity [6,7].
As is known from literature, ligands and their metal complexes are considerably active against
Baccilus megaterium and Candida tropicalis, but the effect of metal complexes is stronger than
influence of ligands. It was also reported that ligands and their metal complexes are active against
Fuherica Coli, Barilum sp and Pseudomanan acurtuginan. Morever, Cu complexes of ligands were
reported to be inhibiting active against bacteria and fungi. It was also determined that ligands could
produce an inhibiting effect on the development of Aspergillus niger, Penisilum rubium and
Augergillus ferreus. Furthermore, it was also established that ligands had an antibacterial and
antifungal effect.
There was developed method for obtaining N,N-bis-(p-dimethylaminobenzylidene)
diaminopropan. Its structure was proved by methods of IR and NMR-spectroscopy.
Functional properties of the compounds were studied in M-8 oil by use of standard laboratory
methods. Results of studying antimicrobial and antiwear properties of the synthesized compounds are
indicated in the table. As follows from the table in condition of friction regime synthesized Schiff base
and its complexes at 1% concentration have high antimicrobial properties (0,47-0,40 mm) and
improve lubricating properties of the oil. Studied additives are better than known additive
(tricresilphosphate).
Antimicrobial efficiency of studied compounds in M-8 oil was evaluated by diameters of the
degradation zone around the cavity both with additive and without it: increasing diameters leads to
improving antimicrobial efficiency. M-8 oil itself doesn’t have biostability. Results of the study are
indicated in the table. As follows from the table synthesized azomethine and its metal complexes have
antimicrobial properties. They overbalance known additive - Sodium pentachlorophenolate (etalon) by
efficiency (at the same concentrations).
IV INTERNATIONAL SCIENTIFIC CONFERENCE OF YOUNG RESEARCHERS
180
Qafqaz University 29-30 April 2016, Baku, Azerbaijan
THE CHARACTER OF PHASE FORMATION OF THE TM-SB-TE
TERNARY SYSTEM
T.M.ILYASLY
Baku State University
AZERBAİJAN
F.M.SADIQOV
Baku State University
AZERBAİJAN
Z.I.ISMAYILOV
Baku State University
zakir-51@mail.ru
AZERBAİJAN
G.H.QAXRAMANOVA
Baku State University
AZERBAİJAN
The investigation of phase interaction in the Tm-Sb-Te system is of interest in connection with
the application of rare-earth metals for the commutation of thermal elements based on antimony
telluride Phase diagrams of boundary binary systems of the ternary system under investigation are
taken from.
In this work, the ternary Tm-Sb-Te system is investigated over the entire concentration range
using the methods of physicochemical analysis.
Starting reactants for the alloy synthesis were thullium Tul-O, antimony Sb-B4, and tellurium Te-
A2.
The components were directly alloyed in evacuated silica ampules at 1000-1200 K (depending on
the composition) with subsequent cooling in a switched-off furnace. In order to equilibrate the alloys,
they were subjected to homogenizing anneal in evacuated silica ampules for 500 h at temperatures
50-100 K below the solidus temperature.
The samples were investigated using the methods of physicochemical analysis according to the
procedure described earlier .
In the Sb
2
Te
3
-TmTesystem , two compounds are formed, TmSb
4
Te
7
(S
1
), TmSb
2
Te
4
(S
2
).
.
The
former compound melts congruently at 875 K, and the latter melts incongruently at 1050 K. Eutectic
coordinates are 15 mol % TmTe at 850 K and 42 mol % TmTe at 835 K. In the Sb
2
Te
3
-Tm
2
Te
3
system, for the 1:1 composition, the ternary TmSbTe
3
(S
3
) compound is formed by a peritectic reaction
at 1335 K. Eutectic coordinates are 15 mol % Tm
2
Te
3
and 750 K. For both systems, solid solubility in
Sb
2
Te
3
is up to
-
5 mol % at room temperature.
Here, we report experimental data on the joins Sb
2
Te
3
-Tm
3
Te
4
, TmSb-TmTe, TmSb
4
Te
7
(S
1
)-
Tm
3
Te
4
, TmSb
4
Te
7
(S
1
)- Sb, TmTe-Sb, Sb
2
Te
3
-Tm, and TmSb
4
Te
7
(S
1
)- Te.
Investigations demonstrated that the joins Sb
2
Te
3
-
Tm
3
Te
4
,TmTe-Sb, TmSb-TmTe,TmSb
4
Te
7
(S
1
)-
Sb and TmSb
4
Te
7
(S
1
)- Tm
3
Te
4
are pseudobinary of a simple eutectic type. Selected data on these joins
are listed in Table 1.
Table 1. Character of interaction along the eutectic-type joins in the Tm-Sb-Te system.
Join Sb
2
Te
3
-Tmis nonpseudo-binary and intersects four subordinate (secondary) ternary systems:
Sb
2
Te
3
-Sb- TmSb
4
Te
7
( I ), Sb- TmSb
4
Te
7
-TmTe (II), Sb- TmSb-TmTe (III), and TmSb-Tm-TmTe(
IV) (Fig. 1). The part of the join within subordinate system I is characterized by the formation of
γ,β
1
and β phases at 800, 750 and 700 K respectively, and by a three-phase nonvariant equilibrium at
550 K. The reactions proceeding at these points are listed in Table 2.
Join Eutectic
coordinates
Composition of Sb
2
Te
3
-based and TmSb
4
Te
7
based solid solution, mol %
Composition, mol
%
T, K
Sb
2
Te
3
-Tm
3
Te
4
85
Sb
2
Te
3
800 3
Tm
3
Te
4
TmSb-TmTe 50
TmSb
1700
-
TmTe-Sb 10
TmTe
810
-
TmSb
4
Te
7
-Sb
90 Sb
750
2 Sb
TmSb
4
Te
7
- Tm
3
Te
4
13
Tm
3
Te
4
790 3
Tm
3
Te
4
|