Faz transfer katalizörü olabilecek kaliksaren türevlerinin sentezi ve seçilmiş reaksiyonlarda uygulamaları
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Dosyalar
Tarih
2011-01-28
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Yayıncı
Selçuk Üniversitesi Fen Bilimleri Enstitüsü
Erişim Hakkı
info:eu-repo/semantics/openAccess
Özet
Bu çalışma kaliks[4]arenin fenolik birimlerinin p-pozisyonundan ve fenolik-O üzerinden farklı gruplarla fonksiyonlandırılmış türevlerinin sentezi ve bu bileşiklerin bazı reaksiyonlarda kataliz uygulamalarını içermektedir. Sentez çalışmalarında, literatürde belirtilen metoda göre p-terbütilkaliks[4]aren (1) sentezlendikten sonra, tersiyer bütil grupları dealkilasyonla giderildi. Kaliks[4]aren (2), metil bromoasetat ile uygun koşullarda etkileştirilerek diester türevine (3) dönüştürüldü. Kaliksarenin diester türevi önce karboksilik asit türevine, daha sonra tiyonil klorür ile asitklorür türevine ve daha sonra da farklı aminlerle (N-etilpiperazin, 1,4-dioksa?8-azaspiro[4,5]dekan, 3-morfolin-1-propilamin, diallilamin, dibütilamin ve tersiyerbütilamin) etkileştirilerek amit türevleri (6, 7, 8, 9,10 ve 11) sentezlendi. Diğer bir şemada (Şekil 3.2) kaliks[4]arenin dibrom bileşiği ile N-etilpiperazin ve 1,4-dioksa?8-azaspiro[4,5]dekan ile etkileştirilerek amin bileşikleri elde edildi (13, 14). Kaliks[4]arenin fenolik birimlerinin p-pozisyonundan değişik dialkil amin türevlerini sentezlemek amacıyla seçimli dealkilleme işlemi yapıldı. Elde edilen bu bileşik (17) farklı sekonder aminler kullanarak Mannich reaksiyonuna göre dialkil amin türevli kaliksarenlere (18, 19 ve 20) dönüştürüldü. Başka bir şemada (Şekil 3.4) kaliksarenin fenolik birimlerinin p-pozisyonundan değişik tetra alkil amin türevleri sentezlendi. Bileşik 2 Mannich reaksiyonuna göre p-pozisyonundan tek basamakta değişik sekonder aminler ve formaldehit ile tepkimeye sokularak alkil amino kaliksarenler (21 ve 22) sentezlendi. Sentezlenen bu bileşikler esterleşme reaksiyonlarında faz transfer katalizörü olarak kullanıldı. Ayrıca kaliks[4]arenin diamit türevleri (6, 10 ve 11) H2SO4 ortamında sülfolanarak suda çözünebilen p-sülfonatokaliks[4]arenler (23, 24 ve 25) sentezlendi. 6 ve 9 nolu kaliksarenler CH3I ile etkileştirilerek kuaterner amonyum bileşiklerine (26, 27) dönüştürüldü. Sentezlenen 23, 24, 26 ve 27 nolu, kaliksaren bileşikleri Mannich-tipi tepkimelerde katalizör olarak kullanıldı. Sentezlenen makrosiklik bileşiklerin yapıları spektroskopik teknikler (FTIR, 1H NMR ve 13C-NMR) ile aydınlatıldı.
This study contains synthesis of calix[4]arene derivatives which functionalized from p-position and phenolic-O, and utilization of selected some catalysis reactions. In the synthetic work, the synthesis of p-ter-butylcalix[4]arene 1 and dealkyllation of this compound were made according to the literature metods. Calix[4]arene (2) was converted to diester derivative (3) with methylbromoacetate in suitable condition. Calix[4]arene diester derivative was firstly converted to carboxylic acid derivative, afterwards acid chloride derivative with thionyl chloride and then treated with various amines (N-ethylpiperazine, 1,4-dioxa?8-azaspiro[4,5]decane, 3-morpholinopropyl amine, diallylamine, dibutylamine and tertiarybutylamine) in order to synthesize amide (6,7,8,9, 10 and 11) derivatives. In another schema (Figure 3.2), calixarene dibromide derivative was treated with N-ethylpiperazine and 1,4-dioxa?8-azaspiro[4,5]decane to obtain amine (13, 14) derivatives. For synthesized different dialkyl amine derivatives on p-position of phenolic unit of calix[4]arene, selective dealkyllation. The compound 17 was treated with various secondary amine for synthesized dialkylamine derivative calixarenes (18, 19 and 20). In another work (Figure 3.4), compound 2 was treated with various secondary amine and formaldehyde in one step according to the Mannich reaction to obtain alkyl amine calixarenes (21, 22). The synthesized compounds were used in esterification reaction as the phase transfer catalyst. Calix[4]arene diamide derivatives (6, 10 and 11) were reacted with H2SO4 to obtain p-sulfonatocalix[4]arene (23, 24 and 25). Compound 6 and 9 were reacted with CH3I for synthesized quaternary onium compounds (26, 27). The synthesized compounds 23, 24, 26 and 27 were used as catalyst in Mannich-type reactions. The molecular structures of the synthesized macrocyclic compounds were characterized by spectroscopic techniques (FTIR, 1H NMR and 13C-NMR).
This study contains synthesis of calix[4]arene derivatives which functionalized from p-position and phenolic-O, and utilization of selected some catalysis reactions. In the synthetic work, the synthesis of p-ter-butylcalix[4]arene 1 and dealkyllation of this compound were made according to the literature metods. Calix[4]arene (2) was converted to diester derivative (3) with methylbromoacetate in suitable condition. Calix[4]arene diester derivative was firstly converted to carboxylic acid derivative, afterwards acid chloride derivative with thionyl chloride and then treated with various amines (N-ethylpiperazine, 1,4-dioxa?8-azaspiro[4,5]decane, 3-morpholinopropyl amine, diallylamine, dibutylamine and tertiarybutylamine) in order to synthesize amide (6,7,8,9, 10 and 11) derivatives. In another schema (Figure 3.2), calixarene dibromide derivative was treated with N-ethylpiperazine and 1,4-dioxa?8-azaspiro[4,5]decane to obtain amine (13, 14) derivatives. For synthesized different dialkyl amine derivatives on p-position of phenolic unit of calix[4]arene, selective dealkyllation. The compound 17 was treated with various secondary amine for synthesized dialkylamine derivative calixarenes (18, 19 and 20). In another work (Figure 3.4), compound 2 was treated with various secondary amine and formaldehyde in one step according to the Mannich reaction to obtain alkyl amine calixarenes (21, 22). The synthesized compounds were used in esterification reaction as the phase transfer catalyst. Calix[4]arene diamide derivatives (6, 10 and 11) were reacted with H2SO4 to obtain p-sulfonatocalix[4]arene (23, 24 and 25). Compound 6 and 9 were reacted with CH3I for synthesized quaternary onium compounds (26, 27). The synthesized compounds 23, 24, 26 and 27 were used as catalyst in Mannich-type reactions. The molecular structures of the synthesized macrocyclic compounds were characterized by spectroscopic techniques (FTIR, 1H NMR and 13C-NMR).
Açıklama
Anahtar Kelimeler
Kaliks[4]aren, Suda çözünen kaliksarenler, Faz transfer reaksiyonu, Katalizör, Mannich reaksiyonu, Calix[4]arene, Water soluble calixarenes, Phase-transfer reaction, Catalyst, Mannich reaction
Kaynak
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Scopus Q Değeri
Cilt
Sayı
Künye
Akceylan, E. (2011). Faz transfer katalizörü olabilecek kaliksaren türevlerinin sentezi ve seçilmiş reaksiyonlarda uygulamaları. Selçuk Üniversitesi, Yayımlanmış doktora tezi, Konya.
