Dimetilol aldehitlerin fenol ve naftollerle reaksiyonu
Reaction of alfa, alfa-dimethylol aldehydes with 2-naphthols
- Tez No: 14407
- Danışmanlar: PROF.DR. AHMET AKAR
- Tez Türü: Yüksek Lisans
- Konular: Kimya, Chemistry
- Anahtar Kelimeler: Dimetilol aldehitler, Fenoller, Naftol, Dimethylol aldehydes, Phenols, Naphthol
- Yıl: 1991
- Dil: Türkçe
- Üniversite: İstanbul Teknik Üniversitesi
- Enstitü: Fen Bilimleri Enstitüsü
- Ana Bilim Dalı: Belirtilmemiş.
- Bilim Dalı: Belirtilmemiş.
- Sayfa Sayısı: Belirtilmemiş.
Özet
ÖZET Birimimizde daha önce yapılan çalışmalarda, dimetilal ketonlar ile 2-naftal arasında yapılan reaksiyonlar sonucunda naftopirananaftopiran türevleri sentez edilmiştir. Bu çalışmada ise «<,.<. -dimetilal aldehitlerin 2- naftal ile reaksiyonları incelenmiştir. Bunun için butiraldehitin formaldehitle reaksiyonu sonucunda -c,.<- dimetilal aldehit türevleri hazırlanmış ve daha sonra 2-naftol ile reaksiyona sokulmuştur. Deneyler sonucunda, dinaf toksanten bileşiği ele geçmiştir. Dinaf toksanten bileşiği reaksiyon koşullarında for maldehit ile 2-naftolün reaksiyon ürünüdür. Burdan hareketle -c, ^c -dimetilal bileşiklerinin reaksiyon ortamında bozunarak farmaldehit verip vermediği, bu bileşiklerin hidrazonlarının TLC ile inceleyerek araştırılmış ve formaldehit tespit edilememiştir, -t, «^<c - Dimetilal bileşeğinin, bir metilalünün, 2-naftal ile kandenzasyona girdik ten sonra molekül içi göçmeler ve çevrilmeler sonunda dinaftoksanten bileşiğine dönüştüğü ileri sürülmüştür. I. aşamada meydana gelen bileşik molekül içi bir yarı asetal yapıya kalayca dönüşmesi bu molekül içi çevrilme nin meydana gelişi, dinaftoksanten oluşumunun en önemli nedenidir. Diğer yandan butiraldehit ve valeraldehitin 2-naftal ile reaksiyon ürünü Bis-fenol türünde, sırasıyla 1,1-Bls (2-Hidraksinaftil) Bütan ve 1, 1, -Bis(2-Hidroksinaf til) pentan bileşiklerini verdiği ortaya çıkmıştır.
Özet (Çeviri)
REACTION DF 2- NAPHTHDLS -DIMETHYLQL ALDEHYDES WITH SUMMARY Naphthopyranopyran type compounds uere recently produced by the reaction of -* - -* -dimethylal ketones with 2-naphthal in organic chemistry department. Reac tion of «-c, -^ -dimethylol aldehydes with 2-naphthol under similar condition was studied in order to produce corresponding naphthopyranopyrans. R- CH“DH I 2 C- Cv- CH, I V 3 VD CH2QH + 2 %cbc? CH. ^, <*£ - Dimethylolketone Naphthapyranopyran «- C,-4-DimethyİDİ butyraldehyde and o-d,.<? - dimethylol valeraldehyde were synthesized by cross-aldol condensation of formaldehyde with corresponding aldehyde under mild basic condition. R - CH2- C = Q + 2CH2D CH20H D H CH2QH «xl, <^ -dimethylal aldehyde R = -G2H5, -C3H? vxRaw dimethylal aldehydes contained very little higher number af methylols and manomethylol derivatives. This uias shown by TLC examination of hydrazanes af dimethylols as well as hydrazanes of formaldehyde and corresponding aldehydes, ^t «< -Dimethylal aldehydes are not very stable under strong conditions. They polymerize to give resin type products at higher temperature and also strong acids such as H^SO, decomposes <<, «< -dimethylol aldehydes. The reaction of dimethylol aldehydes with 2-naphthol oo was carried out at 65 C - 7G C under the effect of acid catalysts, such as HC1, H-SD,, HCDDH and CH,COGH, recovered product was dinaphtha.-xanthene. The CH2DH a R- G- C S K CH OH + 2 [1,2;7,8-]Dibenzaxanthene This was an unexpected product since dinaphtho- xanthene was the reaction praduct af 2-naphthol. and formaldehyde. The formation of dinaphthaxanthene was further examined and the results were summarized in the fallowing table. Table: The reaction praduct af 2-naphthal with formal dehyde and dimethylol aldehydes and the yield. Catalyst Temp.( C) SDD-G5°C 60D-65DC 75a-78°C 75°-78DC 75a-78DC 75 -78aC 75D_7QaC DMBA= -4, U. -Dimethylal butyraldehyde. DMVA= <4, ”c -Dimethylal vaieraldehyde. Xanthene = [l, 2 ; 7, a}-Dibenzaxanthene VllFormation of dinaphthoxanthene from the reaction of 2-naphthiL with dimethylol aldehyde suggests that the dimethylol aldehyde decomposes into formaldehyde which reacts with 2-naphthol to give xanthene compounds. H+ 2-naphthol ^, o^ -dimethylol aldehyde > CH“0 > Xanthene derivatives (fl, 2 ; 7, aJ-Dibenzoxanthene) However, «<£, *£. -dimethylol aldehyde did not produce any formaldehyde when it was reacted with H”S0, under the similar condition. It was then concluded that «<, «*c -dimethylol aldehyde reacted with 2-naphthol to form intermediate which rearrangement to give dinaphthoxanthene. The purposed reaction mechanisms were as follows : Scheme I, Acid pratones attached one hydroxyl of dimethylol following, one mole of water elimination a carbocations forms then reaets with 2-naphthol to give intermediate (I) which -is basicly in the form of semi-acetal (2). Protonation and water elimination (2) gives carbacation intermediate (3) that rearranges to more sTable carba cation (4). This carbacation (k) acts as an electrophile to reacts with another 2-naphthol molecule and produces the product (5) which is a vinyl ether. This vinyl ether type intermediate product (5) is easily converted by the action of catalyst, to a mixture of dinaphthoxanthene and ~< -manomethylol aldehyde. vmCH20H CH20H Î-C-C ^ + \KJ OH,,+ CH20H CH2DH CHo0H CH OH CH,QH (5) 0-CH=C - R CH"DH I 2 +R-CH-CH0 «c-monamethylol aldehyde [1,2;7,a]öibenzaxanthene Scheme I IXIn order to find aut the reaction of aldehydes with 2-naphthol, hutyraldehyde and valeraldehyde mere reacted with 2-naphthol. Corresponding Bis-phenol type products, i.e., 1,1, -Bis (2-Hidroxynaphthyl)butane and 1,1 -Bis ( 2-Hidroxynaphthyl) pentane and were recovered as well as, small amount of acetal type com pounds. R -CHG + GH R - C- H R= -C2H5> -CH. R - C - H Q Bis- phenol type product. D Acetal type product.
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