Yeni vic-dioksimlerin sentezi ve reaksiyonları
Synthesis and characterisation of three new vic-dioximes and their metal complexes
- Tez No: 39665
- Danışmanlar: PROF.DR. ÖZER BEKAROĞLU
- Tez Türü: Doktora
- Konular: Kimya, Chemistry
- Anahtar Kelimeler: Belirtilmemiş.
- Yıl: 1994
- Dil: Türkçe
- Üniversite: İstanbul Teknik Üniversitesi
- Enstitü: Fen Bilimleri Enstitüsü
- Ana Bilim Dalı: Belirtilmemiş.
- Bilim Dalı: Belirtilmemiş.
- Sayfa Sayısı: 92
Özet
ÖZET Oksim bileşikleri; şelat oluşturma, biyolojik olarak parçal anabilme, oksijen tutma özelliklerinin yanısıra biyolojik ve fotokimyasal reaksiyonlardaki farklı etkileriyle tanınırlar. Tarımda, eczacılıkta ve diğer özel alanlarda kullanılan oksimlerin son yıllarda non-lineer optik, gaz sensor, antiferrom anyetik özellik, katalizör olarak kullanılma gibi farklı özellikleri tespit edildiğin den bu maddelere olan ilgi gittikçe artmaktadır. Bu çalışma üç farklı vic-dioksim ve metal komplekslerinin sentezini içermektedir. İlk bölümde, başlangıç maddesi olarak tetraaminodi benzo [18. crown. 6] hazırlanmış, bunun antimonoklorgli oksim ve antidiklorglioksimle reaksiyonu sonucu elde edilen ligandlardan azokinoksalin ve vicdioksim metal kompleksleri sentezlenmiştir. İkinci olarak, 1, 8 diaminonaftalin 'in anti-monoklorglioksimle reaksiyonundan perimidin - 2 - formaldoksim anti - dikiorglioksimle reaksiyonu sonucunda da 2, 2 ' - biperimidin elde edilmiş olup 2,2'- biperimidin ' in metal kompleksleri hazırlanmıştır. Ayrıca 2, 2 ' - azokinoksalin ve tetrametil - 2, 2 ' - azokinoksalin sentezlenilerek, paladyum ( 1 1 ) kompleksleri yapılmıştır. Elde edilen yeni maddelerin yapıları elemen- tel analiz, İR, NMR ve kütle spektrumiarı ile aydınlatılmıştır.
Özet (Çeviri)
SU MMÂR Y SYNTHESIS AMD CHARACTERISATION THREE NEW v I c - D I O X I Wl E S AND THEIR METAL COMPLEXES OF Oximes are condensation of hyd roxy I am i n e with aldehydes and ketones (carbonyl com pounds). In addition, special oximes include the compounds derived from hy rd oxy I a m i n e such as substituted hyd roxy I am i nes, oximates, oxamic acids, ect. as well as salts of hyd roxy I a m i n e. Oxime compounds are widely recognized for their unique properties such as chelation, oxygen- scavenging, biodegradability and unusual activity in biological and photochemical reactions. A new generation of pesticides (e.g. carbomates) and drugs (e.g. cephalosporins) contain hydroxy- I a m i n e/o x i m - d e r i ve d units essential part of their molecular structures. Oximes are used both as end products and as intermediates. Agricultural and pharmaceuti cal intermediates and products, anti -ox i d an ts and blocking (prepolymer) agents are among gro wing areas of oxime applications. During last decade many other applications for oxime have been developed some of which are listed below: 1 Anti, knock agent fuels. 2. Intermediates for dyes. 3. Formulation of magnetic tape binders. 4. Improvement of light fastness in colourations. 5. Scavengers for recovery of valuable metals. 6. Action as an intumescent agent for improving fire retardant properties. 7. Removal of metal ion contaminations of waste streams. VI8. Solution mining of transition metals 9. B i o c i d e s 1 0. G rowth re g ul ant 11. Sweeteners 12. Photo additives 13. UV stabilizers 14. Perfumes 15. Treatment for leather and fibrous materials to increase softness and water repellency 16. Increase octane rating in fuels 17. Anti -ski nni ng agent in paints. The name oxime may be considered to be de rived from oxy-imine, C = NOH. The oxime group is amphiprotic with a slightly basic nitrogen and a mildy acidic hydroxy! group. The most significant early discovery in the chemistry of metal oximates was the reaction between nickel (II) salts and d i m e t h y I g I y o x i m e, which is the best known example of a vicinal dioxime (abreciated as vic-dioxime). The d i cove rer Tschufaeff correctly identifed the bidentate nature of vi c- d i ox i m e s. However, the chelate ring size remained uncertain and went through the incorrect a seven and six-membered formulations before the correct f ive -m e m be re d ring was fully established. The detailed structures of fairly large num ber of metal vi c-d i oxi m ates are known from X-ray investigations. The important features, apart from N 4 planar binding, are strong (O...H...O) hyd- rogen bondings and the stacking of the planar units parallel to each other in the crystal, in the cases of Ni(ll) and Pd(ll) complexes in general. The object of this study is to synthesize three new vic-dioximes and their metal comple xes. In the first part, ( 1 8. cro wn. 6 ) b i s ( q u i nox a I i n vuoxime) (5) has been synthezised from tetraamino d i be n zo [ 1 8. cro wn. 6] (4) and anti -m o n och I o rog ly - oxime. 5 was converted to (18. crown. 6) bridged a z o q u i n oxal i n polymer (6) by reacting with C0CI2 6H2O in DMF D i b e nzo ( 1 8. crown. 6) bridged vic- dioxime has been prepared by reacting 4 with an t i -d i eh I orog lyoxi m e (7). Its Cu(ll) and Ni(II) complexes were also prepared. In the second part, pe r i m i d i n -2 -f o rm al d oxi me (10) and 2, 21 - b i pe ri m i d i n (11) have been syn thesized and metal complexes have been repor ted. In the third part, 2, 21 -azoq u i noxal i n e and t e tram e t hy I -2, 2' -azoq u i noxal i ne were prepared and their palladium complexes have been syn thesized. Starting from d i be nzo[ 1 8. cro wn. 6 ] nitration with concentrated HNO3 in acetic acid led to a mono-nitro derivative on each benzene nucleus which was reduced to an amine by hydrazinium hydroxide using Pd-C catalyst. Although these compounds are a mixture of“cis”and“trans”izomers, no isolation procedure was carried out. Further nitration, after protection of the amine groups by acetylation, gave N - s u b s t i t u t i o n on the 4, 5 - pos i t i o n s of each benzene nucleus. Deacety- lation and reduction gave b i s (o - d i a m i n o ) compo und 4. Although the same compound has been reported from the reduction of a sy m m e t r i ca 1 1 1 y substituted teîranitro derivative, the yield was rather low in our trials and the reproducibility of the reaction was doubtful. Therefore, the multi- step reaction squence, which has been proven in the case of a b e n zo [ 1 5. cro wn. 5] derivative, is preferred. [1 8.crown.6]bis(quinoxalin-2-one-oxime) was synthesized from a n îi - m 0 n o eh I o r o g I y o x i m e and the bis(diamino) compound 4 in methanol at 30- 35°C. The colour of the product was darker than the bright yellow colour of mono derivatives. In the IR spectrum of 5 characteristic absorbs i on VIIIbands due to oxime formation are present at 3360 cm-1 for NH and 3200 cm 1 for OH vibrations. Bands due to C = N and NO stretches are at 1615 cm-1 and 955 cm“1. The 1H NMR spectrum of 5 conformed with the proposed struc ture, showing two D 2O -exca n g e a b I e protons at 10.13 ppm and 9.89 ppm for the OH and NH gro ups together with a singlet at 7.67 ppm for the azomethine group. Although the reaction product was expected to contain both cis and trans izomers with respect to the position of the oxime groups in each quinoxaline moiety of the mole cule, these isomers could not be detected by cho ro m atog ra ph i c techniques while the NMR spectrum also gave no hint of them. The condensation of quinoxalin-2-one oxime groups to azoq u i noxal i n e was accomplished by both the template effect of C0Cİ2 and by treat ment with a strong base KOH. The yield of the brown reaction product 6 was higher in the for mer case. Comparision of IR spectra of the po- limeric product 6 with the b i s ( 2 - q u i 0 n ox a I i n o n e oxime) 5 confirmed the reaction by the disappe- rance of the NH and OH stretches at 3360 and 3200 cm”1, respectively, after condensation. In order to estimate the degree of polymerization of 6 qualitatively by IR, the b i s ( 2 -q u i oxa I i n o n e oxi me) 5 was used as a model compound to compare the ratio of the absorption intensities of N-O groups of oximes at 955 cm“1 with those of the Ar-O-C groups of crown ethers at 1230 cm-1, the average of several trials for iog(l-| 220/*995) was ca.0.20±0.1 for 6, while similar calculations for the model compound 5 resulted in an average value of 0.55 + 0.1. Consequently, we conclued that the ratio of crown ether to oxime is appro ximately four times higher in 6 than in monome- ric compound 5. In contrast to the case of 2,2'-azobisben- z 0 [ 1 5. c r o w n. 5 ] e n 0 ( g ) - q u i ox a I i n e, the azoquinoxa- line polymer with a b e n zo [ 1 8. cro wn. 6 j bridge 6 is only slightly soluble in d i m e t h y I s u I f o x i d e ( D M S O ) thus hindering further spectroscopic investi gation and determination of the alkali-binding properties in s o I u t i 0 n. F i g u r e 1 IXIn order to obtain dibenzo(18.crown.6) bridged vi c-d ioxim e (7), anti -d ichl o rog lyoxi m e was added to 4 in dry DMF at 25-30°C. The 1H NMR spectrum of 7 conformed with the proposed structure, showing two D20-exchangeable pro tons at 9.97 ppm and 9.08 p p m for the OH and N H groups. Figure 1 (18. crown. 6)bridged-Azoquinoxaline It is known that the dioximes according to the positions of the NOH group in space anti, amphi and syn-isomers can be isolated. Since the syn form is unable to form metal complexes should be either in anti or amphi form. A singlet at 9.97 ppm in the NMR spectrum of 7 is strong evidence for the anti structure of the dioxime. Intramolecular hydrogen bonding in one of the oxime groups of am p h i - d i oxi m e would cause two different peaks for two oxime protons. Transition metal complexes of 7 have been also isolated and their structures have been in vestigated by elemental analysis and IR spectra. It has been found that Cu(ll), Ni(li) form comp lexes with a metal:ligand ratio of 1:2. In the square planar complexes (O--H--O) bending vibrations are observed 1710 cm 1- 10 was sythesized by reaction of 1,8- d i a m i n o n a p t h a I e n e with a n ti - m o n och I o ro g I y ox i m e. In this reaction; while the easily accesible addition reaction of acid chloride to one of the NH2 group was taking place, the other group reacted with one of the oxime groups byelimination of H2N-OH. After these eiiminations either six membered perimidin or seven membe- red diazepine rings are obtained. In the mass spectrum of 10, the loss of CHNOH group at m/z 167 is strong evidence for the perimidin form the IR spectra of 10, NH and OH vibrations observed at 3380 and 3140 cm-1 C = N and bands are at 1630 cm”1and 910 cm'1. In the NMR spectrum of 10, the chemical shifts for and NH protons are observed at 11.93 and 10 In a re NO 1H OH.21 ppm respectively. Mass spectrum of 10 exhibits molecular ion m/z 211. When solution of C0CI2 6H2O in THF was added into the solution of 10 in THF, the color of solution gradually turned to brown and bright black crystals are obtained. This complex is insoluble in the common solvents. Elemental analytical results for the complex correspond to C 24 H 1 6 N 6 O 2C o. F i g u r e 2 Figure 2 Synthetic Route of Perimidin-2 formaldoksim When a n t i - d i eh i o rog i y ox i m e in absolute ethanol was added into 1,8-diamino-napthalene in absolute ethanol dark red crystals precipi tated. The scope of this reaction was to isolate the addition products of one an t i -ch I 0 ro g I y oxi m e to 1, 8 -d i am i - n ap t h aie ne in order to obtain di- oxime. However, dioxime could not be obtained, after cyclization 2, 2 ' - b i p e r i m i d i n formed. In the İR spectra of 11, NH and C = N vibrations are observed at 3040 cm'1 and 1630 cm“1. Mass spectrum didn't exhibit a molecular ion but peak at m/z 335(M + 1) was observed. On heating 11 in THF with CUCI22H2O or NİCI26H2O in ethanol, Cu(ii) and Ni(ll) complexes were obtained. The se complexes aren't soluble in commen solvents. Their structure can be poiimeric form according to elemental analysis Figure 3. XIIn order to obtain acetato bridged dinuciear Pd(ll)(16) compound, 2, 2' -azoq ui noxai i n was reacted with Pd(CH3COO)2 in acetic acid. ÎR spectra of this compound, 1750-1700 cm”1 C^O peak, 1610 cm'1 C =? H peak were observed. On heating 16 with concentrated HCI, chloro bridged dinuciear Pd(il) compound was obtained. in IR spectra, C = 0 peak was not observed. CÎ.N©H HON C! ^ Figure 3 Synthetic Route of 2 -2' -bi pe r i m i d i n Tetramethyl-2,2'-azoquinoxaline allowed to react with Pd(CH3COO)2 in acetic acid. Thus acetato bridged dinuciear Pd(ii) complex was produced, served at p e rt i e s of Figure 4. In the I R 1 740-1 660 cm these complexes spectra, 1. w C=0 peak was o b- Liquid crystal pro - iii be investigated. /x\ * NT Figure 4 Palladium Complexes XII
Benzer Tezler
- Aminooksimlerin sentezi, karakterizasyonu ve bazı metallerle komplekslerinin incelenmesi
Başlık çevirisi yok
EŞREF TAŞ
- Vic-dioksimlerin aminopiridinli türevlerinin sentezi ve geçiş metalleri ile yaptıkları komplekslerin incelenmesi
The Synthesis of vic-dioximes derivaties with amino pyridine and a study of their complexes with some transition metals
İSMAİL CANARI
- Diaza-dioxa substitue ftalosiyanin, oksim ve kompleksleri
Diaza-dioxa substitue phthalocyanine, oxime and complexes
ESİN HAMURYUDAN
- Yeni vic-dioksim ligandlar ve onların geçiş metal komplekslerinin sentezi, karakterizasyonu ve redoks özellikleri
New vic-dioximes and theirs trans metals complexes of synthesis, characterization and redox features
HATİCE KARA
- Oksimler'in renkli sıvı kristal özelliği gösteren metal komplekslerinin sentezi
Başlık çevirisi yok
GÜLAY GÜMÜŞ
