Polimerik tosil hidrazon kullanarak ayrıştırma reaksiyonları
Başlık çevirisi mevcut değil.
- Tez No: 55603
- Danışmanlar: DOÇ.DR. OYA ATICI (GALİOĞLU)
- Tez Türü: Yüksek Lisans
- Konular: Kimya, Chemistry
- Anahtar Kelimeler: Belirtilmemiş.
- Yıl: 1996
- Dil: Türkçe
- Üniversite: İstanbul Teknik Üniversitesi
- Enstitü: Fen Bilimleri Enstitüsü
- Ana Bilim Dalı: Belirtilmemiş.
- Bilim Dalı: Belirtilmemiş.
- Sayfa Sayısı: 48
Özet
Özet yok.
Özet (Çeviri)
SUMMARY DECOMPOSITION OF POLYMER1C HYDRAZONE Aldehydes and ketones can be converted into corresponding alkenes ör bicyclo (n. 1.0.) ring systems by treating their tosyl hydrazone derivatives with strong base. This method has considerably been used in recent years and given rather good results. These reactions are called as Bamford-Stevens reactions. in this method, p-toluen sulfonyl hydrazones (tosyl hydrazones) of the ketones ör aldehydes are first obtained, then the diazo compound is formed by elimination of p-toluen sulphinate anion from tosyl hydrazone in a strong basic medium at high temperature ör by photochemical reaction of tosyllhydrazone. As shown in the scheme below, if the decomposition are carried out in aprotic solvents, the reaction proceeded through a carben intermediates \vhereas the decomposition under protic conditions leads to the formation of products via diazonium and /ör carbonium intermediates.Na+ /s~^\baS6“. - NaTs -C-N=N-S02-(O/ Ch^*”-C=N-N-Ts -^4* -C=N=N | ^\-/ll Protic »_C_H^ ^ + _cLH -H* » products solvent,^Nl -(Jİ-NSN:diazonium ioncarbonium ion -C=N=N l AProtic» ^ + -c:^ products solventcarben Polymeric reagents are also used in organic reactions. Polymeric reagents are more advatages than organic reagents. Öne of the advantages of using polymeric reagents, is that they are easily separatable, by simple filtration ör centrifügation from having compounds low-moleculer-weights when studied with insoluble polymers, by ultrafiltration when studied with soluble polymer. These reagents also often lack many inconvenient proporties of the corresponding low-moleculer-weighted reagent, such as lability, volatility, toxicity ör odor. in this work, thermal decomposition of tosylhydrazones and polymer bounded sulphonyl hydrazone of cyclohexyl phenyl ketone have been studied in the presence viof a strong base with aprotic and protic solvent. in order to find out ifa improvement in product yields and distribution are achieved ör not by the polymer support. Cyclohexyl phenyl ketone were readily converted to corresponding tosyl hydrazone with tosylhydrazine in acidic methanol (recrystallized from methanol, yield 83-92%, m.p.: 107-108°C). The FTIR spectral properties of cyclohexyl phenyl ketone tosyl hydrazone were, vmax = 3345, 1327,1165 cm“. ONNHTs r^^r- J-rXXs| NH2NHTs|f::^r~^~rX>Xl LS^ k^/J pH=3.5, methanol ^^ ^S Polymeric reagents, resins, consisting of cross-linked poly (styrene-co- divinylbenzene) matrics functionalized with sulfonyl hydrazine group was used in our study. Resins were readily converted, to the intermediate poly(styrene-co- divinylbenzene) sulfonylchloride by refluxing in a solution of phosphor pentachloride in dichlormethane. Then the reaction of the polymer with cyclohexyl phenyl ketone in refluxing methanol gave the corresponding hydrazone derivative. The polymeric reagents showed typical spectral vibrations, v^* = 3325, 1370, 1310, 1150 cm”. fc^-sc* pc^ffA. Q-©-aoft -ÜMÜ» A S02NHNH2 O+ Or^~O“* ©-X^-S°2NHN=f~ SO2NHNH2V-V in the subsequent decompositions N-methyl pyrrolidone and ethylene glycol were used as aprotic and protic solvents. On the other hand sodium methoxide and sodium |3-hydroxy ethoxide were prefifered as strong bases. Both bases NaOCH3 and sodium p-hydroxy ethoxide were prepared by dissolving metalic sodium in absolute methanol and ethylene glycol respectively. After decomposition, remaining the presence of unreacted tosylhydrazone has - ahvays been checked. Reaction yields were based on the starting ketone ör tosylhydrazone derivatives. Identifıcation of the reaction products have been achieved by using, GLC (gas liquid chromatography), TLC (thin-layer chromatography), GC- viiMS (gas chromatography-mass spectroscopy), FTIR (infrared spectroscopy), UV (ultraviole spectroscopy), NMR (nuclear magnetic resonans). Decomposition of tosylhydrazones derivated from cyclohexyl phenyl ketone was found to produce a mbcture of product. The results have been summarized in Table 1. As shown table l, öne of the products was benzyl cyclohexan (product 1). The product was probably formed by the effect of parent tosyl hydrazone, free sulphonic acid groups methanol ör acid side of in exchange resin. The spectral proporties of benzyl cyclohexane were, FTIR,vmax = 3080, 3060, 2926, 2853, 1599 cm'1, 'H-NMR (CDC13), 8 2.2 (2H, doublet), El, m/z = 173(38) (molecular ion), 115(5.1), 92(100), 83(45.5), 67(11.5). Reaction mechanism was shown below. -C=N-NKTs ba36> -(&N^frTs.*-*-C-N=NTs-^-GrjNNN: |l l ”“l ”" J -TsOR1^ r^VC I I I I I I l I I &£QfJ* TTT u| cx5 >n »-ı tsj â/^SStl..»o'ı-î ' ' ö ö VQ m g>>^J/Ş -ı m 3' ı^7^ §§ jö^îl?
Benzer Tezler
- Keto-siklobütan yan zincirli metakrilat monomer sentezi ve karakterizasyonu
Synthesis and characterization of methacrylate monomer bearing keto-cyclobutane side chain
MUSTAFA DEĞİRMENCİ
- Makromoleküler ağ örgülü ftalosiyanin polimerik ftalosiyanin bileşiklerinin sentezi ve karakterizasyonu
Synthesis and characterization of macromolecular network polymeric phthalocyanine compounds
SONGÜL ŞAHİN
Yüksek Lisans
Türkçe
2013
KimyaOndokuz Mayıs ÜniversitesiOrganik Kimya Ana Bilim Dalı
DOÇ. DR. ERBİL AĞAR
- Development and functionalization of novel polymeric materials from poly(oxazoline)s for potential bioapplications
Potansiyel biyouygulamalar için poli(oksazolin)lerden yeni polimerik materyallerin geliştirilmesi ve fonksiyonlandırılması
UMUT UĞUR ÖZKÖSE
Doktora
İngilizce
2020
Kimyaİstanbul Teknik ÜniversitesiKimya Ana Bilim Dalı
DR. ÖĞR. ÜYESİ ONUR ALPTÜRK
DR. ÖZGÜR YILMAZ
- Synthesis and evaluations of cyclopolymerizable and cyclopolymeric type I photoinitiators
Siklopolimerleşebilen ve I. tip fotobaşlatıcıların sentezı ve değerlendirilmesi
BURCU BALABAN
- Synthesis of poly(ethylene glycol) based liquid crystalline mesogen and investigation of liquid crystalline properties
Poli(etilen glikol) bazlı sıvı kristal mesojen sentezi ve sıvı kristal özelliklerinin incelenmesi
GÜLÇİN ALMİNA FİDANLIK
Yüksek Lisans
İngilizce
2018
Polimer Bilim ve Teknolojisiİstanbul Teknik ÜniversitesiPolimer Bilim ve Teknolojisi Ana Bilim Dalı
PROF. DR. YEŞİM GÜRSEL