CC BY
19
Table 5. - Yields of vinyl esters of investigated
carbonic acids in the presence of elaborated catalysts (mole ratio of carbonic acid : acetylene — 1 : 4-5, temperature 300 °C)
Catalysts Yields of products, %
I II III
AW trace - -
Zn (CH3COO)2/activated coal 43.4 33.2 31.4
Zn (CH3COO)2/Al2O3 61.8 51.3 48.5
Cd (CH3COO)2/Al2O3 52.7 37.4 35.2
Zn (C6H13C°°)2/A12°3 63.4 - -
Zn (C8H17COO)2/Al2O3 - 55.4 -
Zn (C6H11COO)2/Al2O3 - - 53.0
In table 5 — I, II and III vinyl esters of enantic, pel-argonic and cyclohexancarbonic acids.
This is caused by fact that with increasing of molecular mass of carbonic acids their acidity has decreased what is carried out to decreasing of yields of their vinyl esters. Results have shown that investigated acids by of their ratio to vinylation by acetylene can be presented by following raw:
c,h cooh < chcooh < c h cooh.
6 11 8 17 6 13
Maximal yields of their vinyl esters were 53.0 and 63.4 %. At investigation of nature of catalysts at vinyl-ation above mentioned acids by acetylene it was determined that zink salt of every acid is active catalyst for vinylation namely of this acid.
References:
1. Лебедев Н. Н. Химия и технология основного органического и нефтехимического синтеза. - М.,1988. - 245 с.
2. Раднаева Л. Д. Полимеры на основе ненасышенных карбоновых кислот и их производных. - Улан-Удэ, 2005. - 354 c//[Electronic resource]. - Available from: http://bankrabot.com
3. Плате Н. А., Сливинский Е. В. Основы химии и технологии мономеров. - М.: Наука, 2002. - 415 с.
4. Нарметова Г. Р., Хамидов Б. Н., Рябова Н. Д., Арипов Э. А. Очистка, идентификация и применение нефте-новых кислот. - Ташкент, 1983. - 144 с.
5. Муратова С. Х., Нурманов С., Нарметова Г. Р., Сирлибаев Т. С. Винилирование карбоновых (нефтяных) кислот//Узб. хим. журн. - Ташкент, 2003. - № 6. - С. 13-17.
6. Бродская Е. С. Нефтяные и синтетическые нефтеновые кислоты, их свойств и применение//Журн. орг. хим. -1999. - Т. 35, Вып. 2. - С. 221-226.
7. Наметкин Н. С., Егорова Г. М., Хамаева В. Х. Нафтеновые кислоты и продукты их химической переработка/Химия. - 1982. - С. 182-186.
D OI: http://dx.doi.org/10.20534/AJT-17-1.2-132-134
Smanova Zulaykho, National University of Uzbekistan E-mail: smanova. chem @mail.ru
Yangibayev Azim,
Yakhshieva Khurniso E-mail: yaxshiyeva67@mail.ru
Raximov Samariddin, National University of Uzbekistan named after Mirzo Ulugbek
Chemism of complex formation of pyridine and anabasine dyes
Abstract: Between problems standing befor investigators working in field of synthesis of organic reagents one of the important is finding of general principls of selection analytical reagents with help of which it is possible to determine content of different ions of metals with high sensibility. Decision of this problem is connected with investigation of particulities of spacial and electronical structure of reagents, ions of different metals, their complexes and also changing carring ont at their interaction.
Chemism of complex formation of pyridine and anabasine dyes
Knowing all particulities has allowed to outline the base directions of synthesis and physico-chemical investigations for obtain newq important analytical reagents.
Keywords: immobilization, nitrozonaftolov derivatives, heavy and toxic metals.
It was determined that new synthesized pyridine and anabasine dyes namely: N-methylanabazine a -azo-chro-motropical acid; N-methylanabazine a-azo-1,8 aminon-aphtol-4,6 disulfoacid; 6-methylpyridil -2-azo-n-amin-ophenol; 1- (5-methylpyridilazo)-5-diaminophenol; 1- (2-pyridilazo)-2-oxynaphtaline-6-sulfoacid-sodium have formed strong and coloured complexes with ions of different metals [1; 2; 5].
Formation of their complexes has carried out basically in acid and moderate acid mediums. Owingr mul-tydentatntion and multybasicality of compounds on the base of anabasine and pyridine at examination of chemical structure of their complexes it is necessary to take into account state of azodyes in conditions of carring out of reaction. On the base of spectral data [3; 4] it is possible to make conclusion that in different by nature mediums different protinozation has carried out at: pH 2 atom of nitrogen of pyridine and pyperidine nucleuses is protenized in molecules of all dyes: pH 4.5 only atom of nitrogen of tertiary amino-group of pyperidine nucleus is protonized but ionization of OH-group didn't carried out; pH = 10 tertiary atom of nitrogen is unde-gone to protenization but also it is possible ionization of OH-group; pH higher 12 tertiary atom of nitrogen of pyperidine nucleuse is deprotinozed and also full dissociation of OH-group has carried out. Ability to formation to complexes can be examine in general aspect from the point of view their donoral ability to formation of coor-dational bonds by oxygen atom owing to displacement of hydrogen atom. Degree of strong of complexes is depended on position of OH-group in aromatical nucleus.
Ability of phenoxylical anions to coordination is depended on strong of acceptation by ion of metal of n-electrons of anion of oxygen. From literature data [6] and obtain our data it is show that metals have displaced hudrogen atom from compounds also in acid medium; increasing of stronge ofbond Me-O in composision with H-O can be explain by transition of n-electrons of oxygen atom on free orbitals cenral o ion of metal. Strong of compexes is depended on degree of filling of d-orbitales (Ti 3+, Fe 3+, Co 3+).
The second coordinating group in molecules of azodyes is azo-group which has accepted hydrid-ions. Therefore if in metal iones there are fulled d- orbitals then they are able to form coordinated bond which azo-group. In article [7] properties of PAA complexes have
been compared with complexes with a-o-hydroxophen ylaminoethylpyridine; saliciliden-2-aminopyridine and some others ligands in which azo- group is substituted on pyridilazomethinal or phenoxymethinal groups such comparison has carried out to conclustion that complexes with ligands having azo-group are stronger and their spectral characteristics have allowed to conclude that in chelated complexes of such type azo-group has entered in reaction of complex-formation. It is important that this ability is determined by energy of free n-orbitale of azo-group and by presence of fulled d-orbitales at complexoformator (that is at iones of metals).
Owing to fact that oxygen atom of OH group has performed as n- donor and azo-group as n-acceptor than combination of theres two groups in orto-position of phenolical and naphtilical radicals has promoted to increasing of strong of obtained complex compounds.
To interaction of nitrogen atom of pyridine is devoted a great number of early investigated complexes of this reagent with great number of ions of different metals. But complex formation with pyridine it is impossible to explain by only using of undivided pair of electrons of nitrogen atom. More essential is interaction between free or fulled d- or f- orbitals of the central ion. Owing to these complexes with pyridine can exist in weak-acid mediums but at the same time it is impossible correlation between constants of basecality of different nitrogen-containing aliphatic and aromatical bases with constant of unsta-bility of complexes of these ligands. Position of pyridil radical in melecules, of azodye such that in mort cases it is possible it's interaction by tertiary coordinate of ion of given metal at presence ofbond with -OH- or azo-groups.
Essential pecullarity of azodyes synthesised and investigated in our laboratory is presence in their olecules N-methylpyperidine uncleus. As far as ternary N-methyl group is a strong basical and nitrogen atom of aliphatical amines didn't able to formation ofn-bond with ions ofmet-als and correspondenly it is impossible to wait of formation of strong coordinational bond by this nitrogen atom of azo-dye, Owing to coplasity of molecules of dyes important role is devoted to spherical factors at formation of complexes. In this plane N-methylpyperidine system can manifast double role: to create difficulties to interaction of pyridine nucleus by third coordinate of six and more coordinating ion creating conditions for introduction of second or third molecule of dye in coordinational sphere
or contrary this grouping can to prevent introduction of second molecular of azodye in coordinational sphere. Obviously this effect must to became apparent for ions forming 3, 4 and 5 coordinating bonds.
Presence ofthis group in molecule of organical reagent has allowed as is shown from experimental date to carried out reactions in more acid mediums. increazing of acidility of medium is connected with possibility of protonization N-methylpyperidine, owing to this fact using of azodyes as analytical reagents is more comfortable. At this also it is necessary to take into account fact, that many ions of investigated metals in weak-base and neutral mediums able to formation of forms uncomfortable for interaction with
ligands (owing to such reactions as hydrolysis, polymerization and so on) and by this reason increasing of acidity has carried out to increasing ofprecision and sensibility of determination. Also it is important increasing ofmolecular mass of reagents leconrse at this sensibility of analytical methods of determination of metal ions and their affinity to used organical reagents.have leen increazd.
Owing to purpose ful changing of structure of azodyes not only by effect of additional coordinating groups by also of their immobilization it is possible essential changing of properties of complexes and also theoretical and practical preconditions to selection of specifical analytical reagents are created.
References:
1. Smanova Z. A., Manzurhojaev V. M. Extraction - photometrical determination ofNi by azoreagent 2- (5-meth-ylpyridilazo) - 2-hydroxy - 5-methoxybenzole//Vestnik of NUUz. - Tashkent, 2005. - № 4. - P. 124-126.
2. Smanova Z. A. Reagent 1- (4-antipyrilazo)-2-naphtol-6 - sulphoacidal sodium for determination of some heavy and toxical metals//Usb. chem. journal. - Tashkent, 2008. - № 2. - P. 52-55.
3. Ivanov V. M. Geterocyclical nitrogen - containing azocompounds. - M.: Zeience, 1982. - P. 129-136.
4. Smanova Z. A. Immobilized organical reagents and their analytical application at determination of heavy toxical metals. Avtoreferat of doctor dis. On the competition of d. ch. s. - Tashkent, 2015. - 88 p.
5. Smanova Z. A. Elaboration of sorptionno - spektroskopical methods of analysis with using of immobilized organical reagents (review)//Vestnic NUUz. - Tashkent, 2010. - № 4. - P. 67-71.
D OI: http://dx.doi.org/10.20534/AJT-17-1.2-134-138
Shomurotov Shavkat Abduganievich, PhD, Senior Researcher, Department of Chemistry of Polysaccharides,
Institute of Bioorganic chemistry UzAS E-mail: shsha@mail.ru Akhmedov Oliy Ravshanovich, Institute of Bioorganic chemistry UzAS, Researcher
E-mail: oliy86@bk.ru Mamatmusaeva Nilufar Erkinovna, PhD, Researcher Department of Chemistry of Polysaccharides
E-mail: erkinova81@mail.ru Sagdullaev Bakhodir Takhirovich, DSc, Senior Researcher, Department of Chemistry of Polysaccharides
E-mail: bsagdullaev29@gmail.com Turaev Abbaskhan Sabirkhanovich, DSc, professor, Institute of Bioorganic chemistry UzAS
E-mail: abbaskhan@mail.ru
Modified derivatives of polysaccharides having anti tuberculosis activity
Abstract: The research on the synthesis of polymeric complexes of polygalacturonic acid with anti-TB preparations having antituberculosis activity was conducted. The structures were ascertained and studied
