Dinaftofuranofuran ve türevi bileşiklerin sentezi
Shynthesis of naphthofurano-naphthofuran and derivatives
- Tez No: 22012
- Danışmanlar: DOÇ. DR. NACİYE TALINLI
- Tez Türü: Yüksek Lisans
- Konular: Kimya, Chemistry
- Anahtar Kelimeler: Belirtilmemiş.
- Yıl: 1992
- Dil: Türkçe
- Üniversite: İstanbul Teknik Üniversitesi
- Enstitü: Fen Bilimleri Enstitüsü
- Ana Bilim Dalı: Belirtilmemiş.
- Bilim Dalı: Belirtilmemiş.
- Sayfa Sayısı: 77
Özet
QZET p-naftol ile bir a-dikarbonil bileşiği alan gliok- salin susuz ortamda kondenzasyon reaksiyonundan dinaf- tof uranof uran bileşiği 1940 ' lı yıllarda sentezlenmiştir. Bu çalışma dakondenzasyon reaksiyanundaki başlangıç bile şiği olan (3-naftol bileşiği, p-naf tol-6-sülf onik asit bileşiği ile değiştirilip dinafto furanofuran bileşiği nin disülfonik asit türevi ve bu grup üzerinden birkaç türev daha yapılmaya çalışılmıştır. Ancak disülf odinaf- tof uranof uran bileşiğinin -S03H grubundan dolayı sudaki çözünürlüğünün çok yüksek alması nedeniyle bileşiğin su lu çözeltiden izolasyonu mümkün olamamıştır. Reaksiyon lar polar ve apolar çözücülerde gerçekleştirilmiş fakat olumlu sonuçlar alınamamıştır. Daha önceki çalışmalarda sentezlenmiş olan dinafto- furanafuran bileşiğinin önce nitrolanması, sonra nitro grubunun indirgenmesiyle aminodinaf tof uranof uran bile şiği sentezlenmiştir. Amino grubu taşıyan dinaftofu- ranofuran bileşiği diazolanarak türev sayısı artırılmış- tir. Amino türevinden yararlanarak acil türevleri, klor, iyot ve -GH türevleri ile diazo bileşiğinin Ş-naf- tal ile kenetleme reaksiyonu sonucu kırmızı-bordo renkli aza bileşiği ele geçmiştir.
Özet (Çeviri)
SHYNTHESIS OF NAPHTHQFURANO-NAPHTHQFURAN AND DERIVATIVES SUMMARY The reaction af two males of 2-naphthol with glyaxal or glyoxalbisulphite yield a compound called nap h t ha f ur ana-nap h t ho f uran. H \ C = 0 I,£. = a If naphthal derivatives are used in place of the 2-naphthol (e.g 4~methoxy-1 -naphthoic naphthof urano- naphthofuran derivatives are obtained. \ / C I c qch. (B) Generally, aromatic nitro and sulphonic acid compounds and derivatives are used as antiseptic and disinfectans This study had as its goal the preparation of the sulpho and nitro derivatives of naphthofurano-naphthof uran compounds. vxThere have been no reports of the reaction of naphfchbl sulphonic acid with glyoxal in recent literature. Hence, glyoxal bisulphite and 2-hydroxy- naphthalene-6- sulphonic acid have been reacted by using sulfuric acid as catalyt in formic acid solution. The structure of the expected product of the reaction which was studied, is shown below. ?\ C = 0 + C = 0 / cm) A new product was observed in the analysis by Thin Layer Chromotograms, after the reaction mixture was neutralized. Since the solubility of the product in water was considerably high, it could not be isolated from the reaction mixture and could not be transferred into any organic solvent. The same product was tried to obtain using strong acid cation exchanger resins in nanpolar solvents (e.g. toluene), but no product was. observed in the analysis by T.L.C. Since 2-hydroxy-naphthalene-S-sulphonic acid and the product which we obtained in formic acid solution dissolve a great deal in water. 2-naphthol -6- sulphonic acid was converted to the sulphonylchloride derivative by using phosphorus pentachloride. Then the product and ammonia were reacted and the compound 2- naphthol -6-sulphoamide was obtained. ClO^S NH. NH202S Since -SD3H group of product was converted to -S0“1\IH”group, the solubility of the product in water was minimized. VllThe compound 2-naphthol -6-sul phoamide and glyaxalbisulphite were reacted but no product mas obtained. \ H2MD2S C I c a o H2N02S H + V) Since 2-naphthal -6- sulphaamid and glyaxalbi sulphite were no reaction, naphthof urano'-naphthaf uran was reacted with concentrated sulfuric acid to obtain sulphonic acid derivative but, again this product could not be isolated from reaction mixture. Nitro compound are readily prepared by direct nitration hence, naphthof urano - naphthofuran was reacted with a mixture of nitric and sulfuric acids in anacetic acid solution. At the end of the reaction a yellow nitro compound precipitated. It was determined from the 1 H-NMR spectrum of new compound that it contains only one nitro group. HN03/H2S0^ (33) Primary aromatic amines are obtained by reduction of the nitrocompounds. Nitro compounds can be reduced in two general ways (a) by catalytic hydrogenation using molecular hydrogen or (b) by chemical reduction usually by using metal and acid or a metal and metal salts. Since catalytic hydrogenation is more difficult than chemical reduction in the laboratory, the nitro compound was reduced with zinc dust and calciumchloride in alcohol. At the end of the reaction the alcohol was poured into a large amount of water, amine compound precipitatied. vmZn/CaCl, If aminocompaunds are reacted with acid chloride or acid anhydrides, amides farm. The benzoyl derivative of the compound was obtained by the reaction of the amino compound and benzoyl chloride, ^ (2m y and the acetyl derivative of the compound was obtained by the same way. + 0 tl CH3-C-C1 The primary aromatic amines obtained by reduction of the nitro compounds are readily converted into diazonium salts; the diazonium group in turn, can be replaced by a large number of other groups. In most cases this sequence is the best method of introducing these other groups (e.g.-NH2, -OH, -CN, -Cl-I, etc. ) into the aromatic ring, in addition, diazonium salts can be used to prepare the azo-dyes. IXArH ArMD, -* ArNH, ArN, ?* ArX -* ArOH ?* ArCH -> Azodyes (30 The amine compound was dissolved in an aqueous solution gf the hydrochloric acid. The mixture of the amino compound and the acid was cooled in ice-salt mixture. Then, a cooled aqueous solution of sodium nitrite was added very slowly. Since diazonium salts slowly decompose even at ice-bath temperature, the solution was used immediately after preparation. ^ cr^n\i+= n ]ci The replacement of the diazonium group by -I reguires the use of potassium iodide in place of thecupraushalide ; hence, the diazonium salt and potassium iodide mere simply mixed together and allouied to react, The iodo derivatives which is brown, precipitated. T~toT H-, -
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