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Yeni bir sübstitüe vicdiaminoglioksim ve komplekslerinin sentez ve özelliklerinin incelenmesi

Synthesis and properties of a new substite vic-diaminoglyoxime and complexes

  1. Tez No: 39164
  2. Yazar: ŞEBNUR MEREY
  3. Danışmanlar: PROF.DR. ÖZER BEKAROĞLU
  4. Tez Türü: Yüksek Lisans
  5. Konular: Kimya, Chemistry
  6. Anahtar Kelimeler: Belirtilmemiş.
  7. Yıl: 1993
  8. Dil: Türkçe
  9. Üniversite: İstanbul Teknik Üniversitesi
  10. Enstitü: Fen Bilimleri Enstitüsü
  11. Ana Bilim Dalı: Belirtilmemiş.
  12. Bilim Dalı: Belirtilmemiş.
  13. Sayfa Sayısı: 67

Özet

DZET Yeni vic-dioksimlerin sentezi, stereoizomerlerinin ayrılması ve oluşturuldukları komplekslerin incelenmesi grubumuz tarafından yapılan çalışmaların büyük bir bölümünü oluşturmaktadır. Diaminoglioksimin Co(II) ve Co (III) komp leksleri, bilinen vic-dioksim komplekslerinden farklılık lar göstermiş ve bu komplekslerin yapıları X-ışınları difraksiyonu ile kesin olarak belirlenmiştir. Anti ve amfi izomerleri izole edilip, farklı kompleksleri elde edilen 1,4-difenil-2, 3 bis (hidroksiimino ) piperazin ve 1,3-dife- nil-2-tiokso-4, 5-bis (hidroksiimino) imidazolin ' in sentezi disiyan-di-N-oksit ile yapılmıştır. Çeşitli kobalt kompleksleri hazırlanan asenaftilen 1, 2-diondioksim, B,2 model bileşiği olarak dimetilglioksim kompleksleri ile karşılaş-* tırılmıştır. Ayrıca anti-monokloroglioksimden çeşitli sübstitüe mono ve diaminoglioksimler elde edilmiş ve kompleksleri incelenmiştir. Bu çalışmada; salisilaldehitten çıkılarak sırasıyla; 1, 2~dibromo-4,5-bis (salisilaldoksimetil ) benzen [lj, enzen [lj, idro- [c-4 ' 1,6- dioksa-10,14-diaza-2,5,ll,12,13-pentahidro- [c-4'51- DibrobenzoJ- [g, p-dibenzol-siklopehtadesin \zj, propan- 1,3- bis (salisilidenimin) [3j, 3,3-diaza- 1,5-bis (o-hidroksi- fenil) pentan [V}, 2,3-bis (hidroksiimino) -1,4-bis (21- hidroksibenzil)- 1, 4-diaza-sikloheptan [5] elde edilmiştir. £2_] ile tetrametilüre ve piridin'de yapılan ftalosiyanin denemelerinden olumlu bir sonuç alınamamıştır. ]~5İ ' in etanollü ortamda NiCİ, 6H“ü ve CuClp, 6H”0 ile reaksiyonun dan manonükleer Ni(Il7 ve Cu(II) kompleksleri sentezlenmiş- tir. Cu(II) kompleksi THF'de CuN0,,Ö ve 1, 10-f enantrolin ile muamele edilerek trinükleer komplekse geçilmiştir. Elde edilen yeni maddelerin yapısı Elernentel analiz, I.R. ve NMR'la aydınlatılmıştır. -v-

Özet (Çeviri)

SUMMARY SYNTHESIS AND PROPERTIES OF A NEW SUBSTITE vie- DIAMINOELYOXIME AND ITS COMPLEXES Dximes are condensation of hydroxylamine with aldehydes and ketones (carbonyl compounds). In addition, specialty oximes include the compounds derived from hydroxylamine such as substituted hydroxylamines, oximates, oxamic acids, etc., as well as salts of hydroxylamine. Oxime compounds are widely recognized for their unique properties such as che lation, oxygen-scavenging, biodegradability and unusual activity in biological and photochemical reactions. A new generation of pesticides (e.g., carbamates) and drugs (e.g., cephalosporins) contain hydroxylamine/oxime-derived units as an essential part of their molecular structures. Dximes are used both as end products and as intermedi ates. Agricultural and pharmaceutical intermediates and products, anti-oxidants and blocking (prepolymer) agents are among the growing areas of oxime applications. During the last few years many other applications for oximes have been developed, some of which are listed below: 1- Anti-knock agents in fuels 2- Intermediate far dyes 3- Formulation of magnetic tape binders k- Improvement, of light fastness in colorations 5- Scavengers for recovery of valuable metals 6- Action as an intumescent agent for improving fire retardant properties 7- Removal of metal ion contaminations from waste streams B- Solution mining of transition metals 9- Biocides 10- Growht regulants 11- Sweeteners 12- Photo additives 13- LIV stabilizers I^f- Perfumes -vi-15- Treatment for leather and fibrous material to increase softness and water repellency. 16- Increase octane ratings in fuels. 17- Anti-skinnig agents in paints. The name oxime may be considered to be derived from oxy-imine, C = I\IDH. The oxime group is amphiprotic with a slightly basic nitrogen and a mildly acidic hydroxyl group. The most significant early discovery in the chemistry of metal oximates was the reaction between nickel (II) salts and dimethylglyoxime, which is the best known example of a vicinal dioxime (abreviated as vic-dioxime ). The discoverer Tschufaeff correctly identified the bidentate nature of vic-dioximes. However, the chelate ring size remained uncertain and went through the incorrect seven-and six-membered formulations before the correct f ive-membered ring was fully established. The detailed structures of fairly large number of metal vic-dioximates are known from X-ray investigations. The important features, apart from N, planar binding, are the strong D H...D hydrogen bondings and the stacking of the planar units parallel to each other in the crystal, in the cases of Ni(ll) and Pd(II) complexes in general. The synthesis and complex formation of the stereoisomers of various vie - dioximes have been the essential topics of researches carried out in this laboratory. X-ray structural analysis of Co(II) and Co(III) complexes of diaminoglyoxime has shown interesting structures. The amphi - and an t i - stereoisomers and complexes of two new vie - dioximes, namely 1,4-diphenyl- 2, 3-bis (hydroxyimino) piperazine and 1, 3-diphenyl-2- thioxo-4, 5-bis (hydroxyimino) imidazoline have been isolated and interconversion of an t i - and amphi complexes has been studied. Co(lfîl complexes of 1,2- acenaphthylenedionedioxime have been prepared and they are compared with dimethylglyoxime complexes as B,“ model compounds. Transition metal complexes of some new substituted mono-and di-aminoglyoximes have been investigated. In the present work; we have synthesized the following new compounds starting from salicylaldehyde : 1,2-dibromo- 4,5-bis(salicylaldoxymethyl) benzene; 1,6-dioxa -10,14- diaza-2,5,ll,12,13-pentahydro- [c-4 ', 5 ' -riibromobenzq}- rg,p-dibenzo][-cycloheptadecine; propane-1. 3-bis (salicylideneimine) ; 2, 3-diaza-l, 5- bis (o-hydroxyphenyl ) -vii-pentane; 2,3-bis (hydroxyimino)- hydraxybenzyl] -1,4-diaza-cycloheptane. 1,4-bis [2-- The preliminary experiments to prepare new phthalociyanine from the newly synthesized 1,6-dioxa- 10,14-diaza-2,5,ll,12,13-pentahydro- Lc-£f'» 5'”dibromobenzo]- £g,p-dibenzoJ -cycloheptadecine with CuCN in pyridine and tetramethylurea, unfortunately gave no positive result. 1,2-dibromo-4,5-bis (salicylaldoxymethyl ) benzene (1_) was obtained by Williamson condensation of salicylaldehyde with 1,2-dibromo- 4,5-bis (bromomethyl ) benzene in ethanol. In the I.R. spectrum; characteristic absprbstion band due to ether formation are present at 1190cm~ L, (CO) and (CH) vibrations of aldehyde group are at 1675cm and 2760 cm“. The streching and bending vibrations of phenolic (OH) groups have been disappeared. In the H-NMR spectrum; aldehyde and etheral protons are observed at 10.42 ppm and 5.23 ppm, respectively. The condensation of 1, 3-diaminopropan with (JO gave 1,6-dioxa- 10, 14-diaza-2, 5, 11, 12, 13-pentahydro- fc-41, 5'- dibromobenzoj - [g,p-dibenzoJ -cycloheptadecine (jf) as a macrocyclic ligand with N”0_ donor sites. In the IR spectrum of (2); the band at. 1675cm-1 disappears and a new at, 1635cm“!1- which is assigned to the streching vibration of (C = N) comes out. Thelow solubility of the macrocyclic compound in suitable solvents hindered H-NMR spectral investigation. H-NMR spectra in CF,C00H showed aromatic peaks between 7-10 ppm and etheral fCH”) protons were observed at 5.0 ppm. The most definite way of verifying the macrocycle formation is by way of mass spectra which show the molecular ion at M/j* 5^2. As expected from the almost equal percentage abundance of 79gr and B^Br isotopes, in addition to M+ ion peak, the related molecular ions of mass between 541 to 547 have been also observed. In situ procedure, in the presence of nickel salt, have been used to obtain the cyclic ligand (2) as its nickel complex. The attampted synthesis of nickel complex from free macrocycle did not yield a single product. Although the major product isolated was the required one, it was contaminated with an impurity which appeared to be polymeric. However the crude product can be successfully recrystallized from chloroform as orange needles. -Vlll-In the I.R. spectrum; (C = N)« streching vibrations have been shifted to lower field after complex formation. Ni(II) complex ofmacrocyclic ring.is paramagnetic aa depicted from the broad peaks in the H-NMR spectrum. The high soulibility of the complex in -chloroform can be used to reach a conclusion that the complex is not ionic. Therefore, nickel (II) ion is an octahedral environment with two chloride ions as axial ligands. Propan -1,3-bis (salicylideneimine ) (3) was obtained by the reaction of salicylaldehyde with 1, 3-diaminopropan in ethanol and precipitated from this medium by addition of water. In the I.R. spectrum; the vibration at 1635cm“ is not observed as expected for, (OH) streching vibrations but a broad band around 25D0cm comes out. This exhibits that a hydrogen bridge can be 1 formed between (DH) and azomethine groups. In the H-NMR spectrum; (0-H) peak which disappear by deuterium exchange has shifted to lower field (13.44 ppm). Azomethine protons are observed as a singlet at B.56ppm; CH”protons near the aza groups of propylene appear as a triplet around 3,6B ppm; the other two protons appear as a pentate at 2.03 ppm. 2, 3-diaza -1,5-bis (o-hydroxyphenyl) pentane (40 was prepared by reduction of (_3) with sodium borahydride in methanol. In the. I.R. spectrum; the (C=N) band at 1635cm“1 disappears; (N-H) bending and (N~H-)~ stretrhlhg vibrations are observed around 1600cm-1 and 3280 cm-1. respectively. A broad band appear at 2500-3000cm”1 region. (OH) streching vibration was not observed as expected for (0-H) group. An inner salt formation can be proposed with an hydrogen bridge between phenolic (OH) and secondary amine functions. In the NMR spectrum; the broad band which di sappeared after deuterium exchange was observed at 6.0ppm. (Ar-CH^-N) protons appear as a singlet at 3.80ppm. Protons near nitrogens at propylene group appear as a triplet at 2.56ppm, others appear as a pentate at 1.64 ppm. 2, 3-bis (hydroxyimino)-l,4-bis (2 ' -hydroxybenzyl) - 1,4-diaza-cycloheptane (5i) was synthesized from the reaction of (_4) with dichloro anti-glyoxime. Since the order of relative reactivity for the groups on reaction with dichloro anti-glyoxime was NH“^ SH >0H, in this work DCGD has reacted with (NH) instead of (DH) functions. Excess of NoHC03 was added into the reaction mixture in order to neutralize HC1 formed during the reaction. DCG0/(j4) ration is 1:1 according to the results of elemental analysis. -ix-In the I.R. spectrum; characteristic (OH) streching absorptions of oxime groups were observed as a broad band at 3300cm and (C = NX stretches at 1630cm. The broad band at 2500-3000 cm”has been disappeared and it can be understood as disappearence of inner salt formation. In the H-NMR spectrum; two protons which disappear by deuterium exehange appear around 9.72 and 9.0ppm, the latter corresponding to phenolic (OH) groups. No chemical shifts attributable to secondary amine groups have been present. The conformations of the N=C-C=N moiety of the dioxime groups permit NN-chelation with Ni(II) and Cu(II). As in the cases of most anti-dioximes, (5) forms complexes with Cu(II) and Ni(II) with a metal/ligand ratio of 1:2. xes ; rved fted re - g to (ID has (OH) not In the I.R. spectrum of nickel and copper comple intramolecular hydrogen-bridged (OH) protons were obse at 1700crrfr (C = N) vibration at0 1630cm has been shi to 1590cm~. As expected for d configuration in aqua planar field, Ni (II) complex is diamagnetic accordin the NMR spectrum. In the H-NMR spectrum of Ni complex, intramolecular hydrogen bridged (OH) protons been shifted to lower field (16.28ppm). Phenolic protons which disappear. by deuterium exchange have been affected considerably after complex formation. O-H-0 l I NVNX /NyN I I 0-H---0 FİG: 1. Mononuclear Ni(II) And Cu(II) Complexes Of 2,3- Bis ( Hydroxy imino)-l,^-Bis (2' -Hydroxybenzyl) -1,4- Diazacycloheptane. M=Ni(II), Cu(II). Transition metal complexes of vie- dioximes recently get importance to prepare ferromagnetic, antif erromagnetic and; cryomagnetic heteronuclear complexes. The oximate group ( = N-0~) can function as a bridge between two metal ions through the imino nitrogen and the deprotonated oxygen, to afford bi-and tri-nuclear complexes. -x-In this work, homo-and he'tero-trinuclear complexes. But in these complexes; the second and third metal ions have been coordinated to phenolic (OH) groups instead of hydrogen bridges. 0---H-0 O-H-0 Y/-V FIG: 2. Homo-And Hetero. Trinuclear Complexes. M=Ni(II), Cu(II). -xi-

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