Yeni dibenzo (3n+2) crown-n eterlerin sentezleri ve bazı makrohalkalı eterlerin reaksiyon hızına etkilerinin incelenmesi
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- Tez No: 75084
- Danışmanlar: PROF. DR. ÇAKIL ERK
- Tez Türü: Doktora
- Konular: Kimya, Chemistry
- Anahtar Kelimeler: Belirtilmemiş.
- Yıl: 1998
- Dil: Türkçe
- Üniversite: İstanbul Teknik Üniversitesi
- Enstitü: Fen Bilimleri Enstitüsü
- Ana Bilim Dalı: Organik Kimya Ana Bilim Dalı
- Bilim Dalı: Belirtilmemiş.
- Sayfa Sayısı: 121
Özet
ÖZET Doktora tezi kapsamında yapılan deneysel çalışmaların birinci bölümünde, farklı iki başlangıç maddesi kullanılarak bazı yeni tip podand sentezleri üzerinde çalışmalar yapılmıştır. Bunların sentezleri için, o-vanilin ve p-vanilin ile o- ve p- hidroksi asetofenonlar, 1,2-dibromoetan ve p\Ş'-diklorodietil eter ile alkali karbonatların varlığında DMF/DMSO ortamında reaksiyona sokulmuştur. Bu şartlarda istenilen zincir uzunluğundaki ürünler iyi verimlerle elde edilmiştir. Daha sonra bu podandlardan çıkılarak Dairin reaksiyonları ile bis(o,p- hidroksifenoksi) aromatik uç grubu içeren podandlrın sentezleri üzerinde çalışmalar yapılmıştır. Bu reaksiyonlar, asidik ve bazik ortamda hidrojen peroksit kullanılarak gerçekleştirilmiştir. Sentetik çalışmaların ikinci bölümünü, supramoleküller olarak son yıllarda ortaya çıkan ve makrohalkalı eterlerin yeni bir sınıfı olan 1,3-konumundaki dioksi grupları üzerinden kondanse oksietilen halkasından oluşan yapıların sentezlerini içermektedir. Bu bileşikler bine yakın türevi yapılan makrohalkalı eterler arasında daha az tanınan 1,3-dihdroksibenzen yani resorsin türevleridir. Çalışmalarımıza esas oluşturan sentezlerin amacı, bu grubun oluşabilen en küçük yapıdaki makro halkalarını elde etmekdir. Daha önce bu konuda yapılan çalışmalarda elde edilen ürünler n=m=4'den başlamaktadır. Bu çalışmada ise özellikle bu güne kadar yapılmamış olan n^m
Özet (Çeviri)
THE SYNTHESIS OF NOVEL MACROCYCLIC ETHERS AND INVESTIGATION OF EFECTS OF SOME MACROCYCLIC ETHERS ON REACTION RATES SUMMARY 1. Introduction to Macrocyclic Ethers Cyclic polyethers are consisted from the ethylene or propyleneoxy units which could be derived with different aliphatic or aromatic moieties forming a macrocycle. Such structures behave as a hydrophobic exterior of hydrocarbon skeleton linked with hydrophilic oxygene donors. This type of macromolecular structures could be examplified with Figure La, b. Figure 1. a. [18]crown-6 b. [15]crown-5 The finder of such compounds, Dr. Pedersen, however, obtained the series of this molecules just accidentally. In fact at least 1000 different types of similar molecules have been synthesised and their molecular recognition were conducted since 1967. Such molecules are capable to rearrange their macrocylic backbones changing their conformations during the complex formation to orient the s elec trons to almost centered strong electropositive alkali or alkaline-earth cation to bind. The process of the cation binding is thermodynamically controlled and therefore could be used to estimate the binding role of a macrocycle quantitatively. Such estimations give preferential roles to macrocycles and their functional groups which is called the molecular recognition. The binding power is of course governed by the mother solvent in the solution. However, in solid state there are plenty of stable cation-ligand complexes of very high melting points and such solid structures exhibited the preferred conformation of the macrocycle which could be identified by X-ray methods. xraStudies with novel and classical physical and chemical methods caused excellent application of the common theories and aspects of ion-ligand interactions. 2. The Macrocyclic Benzo Crown Ethers The plenty of macrocyclic oligo ethers have been synthesised and characterised since the discovery of such macromolecules by Pedersen designed with oxygen donors. The most popular series of such compounds are known as benzocrowns which are the oligocyclic derivatives of 1,2-dihydroxybenzene so called cathecol. Because of the low solubilities of this series of macromolecules they have been extensively synthesised and recognized so far. Figure 2.a, b, c, show the typical examples of such macrocycles. Figure 2.a. Benzo[12]crown-4 b. Benzo[15]crown-5 c. Dibenzo[18]crown-6 Such molecules are ensembled with two aromatic rings as described in Figure 2c. However, this molecules are the most well known crown ether family of the macrocycles. Macrocyclic oligo ethers are the most well known alkali and alkaline earth cation recepters so far known. They mostly attract the cations with the Coulombig forces. Their interactions are involved among the highly electropositive alkali or alkaline-earth cations and the 2s electrons of the macrocycle oxygens, see Figure 3. Such systems have been reviwed by Weber. However, such way of doing infra structures should be depended on the macromolecular stereochemistry. This field is full of synthesis, stereochemistry, spectroscopy and the molecular recognition chemistry. Figure 3. The views of the K+ cation complexed [18]crown-6 macrocycle molecule. XIVThe complex formation roles of the macrocyclics have been survived with different analytical methods. This is shown form the work Inoue and Gokel at Table 1. for 1:1 ratio complexes with the complexing free energies, AG, and LnK» of cations with the macrocyclic ether and the solvent, see Equations. 1, 2. The mother solvent and polar organics could interact with macrocyclics like cations forming some HOST-GUEST complexes, Table 1. nC'+mLo C+nLm Ka = [C+nLm]/[L]m[CT (1) (2) Table 1. The thermodynamic data for the complexation of some crown ethers at 25 °C. XV3. Experimental Section 3. A Some Novel Synthesis of Bis-(o,p-carbonylphenoxy) Polyglycoles and Their Hydroxylations with Hydrogen Peroxide We are used different compounds as starting materials for the obtaining a new type of podands. The synthesis of the such podands are conducted starting from the o-vanilin, p-vanilin, o- and p-hydroxyacetophenones reacting with dibromo- or dichloro- polyglycols in the presence of K2CO3/DMF. In such conditions the yields are good and the products are stable. We therefore tried the substituted the -OH group into the carbonyls in podands to obtain the o,o'-dihydroxy phenoxy polyglycols. Reactions were carried out in acetic acid at fixed temperature (40 °C) with hydrogene peroxide (H202, 30 %) or reacted with dilueted NaOH at cold temperature (< 0 °C) with hydrogene peroxide (H202, 30 %). Some of this reactions, but not all, gave poor results and oxidation products. Reactions are presented in Scheme 1 and spectral data and yields are given in Table 2. ^"+ U-o-V^3 R 2a-d n=0,X=Br n=1,X=CI DMF r-f^o^ H2OJ NaOH OfiC CH3COOH 40 °C r^o^ Of* ^O Scheme 1. The reaction route of bis-(o,p-carbonylphenoxy) polyglycoles and those of Dakin reactions. XVI
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