Monometilal aldehitlerin hidroksiaromatik bileşikleri ile reaksiyonları
Reaction of monomethylol aldehydes with hydroxy aromatic compounds
- Tez No: 46403
- Danışmanlar: PROF.DR. AHMET AKAR
- Tez Türü: Doktora
- Konular: Kimya, Chemistry
- Anahtar Kelimeler: Aldehitler, Bileşikler, Aldehydes, Compounds
- Yıl: 1995
- Dil: Türkçe
- Üniversite: İstanbul Teknik Üniversitesi
- Enstitü: Fen Bilimleri Enstitüsü
- Ana Bilim Dalı: Belirtilmemiş.
- Bilim Dalı: Belirtilmemiş.
- Sayfa Sayısı: Belirtilmemiş.
Özet
ÖZET Bu çalışmada, aldehit ve hidroksi aldehitlerin çeşitli mono ve dihidroksi aromatik bileşikleri ile asitli ortamda kondenzasyon reaksiyonları incelenmiştir. Daha önce gerçekleştirilen çalışmalarda, dimetilol ketonların ve dialdehitlerin 2-naftol arasındaki kondenzasyon reaksiyonları incelenmiş ve bu reaksiyonlarda elde edilen ürünlerin piranopiran ve furanofûran tipi bileşikler olduğu saptanmıştır. Bu çalışmayı genişletmek amacı ile aldehit monometilol türevlerinin, metilol ketonlar ve dialdehitlerde gerçekleştirildiği gibi, naftollerle kondenzasyon reaksiyonu verip vermediğini ortaya çıkarmak ve reaksiyon mekanizmasını aydınlatmak için bu çalışma gerçekleştirilmiştir. Reaksiyonlarda düz zincirli ve dallanmış aldehitlerden, asetaldehit, propanal, butanal, pentanal, benzaldehit, isobütiraldehit, 2-metilbütanal, 2-metilpentanal, 2-etil- bütiraldehit ve 2-fenilpropanal kullanılmıştır. Hidroksi aldehitler, 2-alkil aldehitlerin formaldehit ile çapraz aldol kondenzasyonu sonunda sentezlenmiştir. Düz zincirli aldehitlerle 2-naftolün kondenzasyon reaksiyonu sonunda 9-alkil [1,2; 7, 8] dibenzoksantenler elde edilmiştir. Dallanmış aldehitlerden, isobütiraldehit 9- isopropil [1,2; 7, 8] dibenzoksanten, 2-metil bütiraldehit ile bisfenol tipi bileşik vermiştir. İsobütiraldehitin, 2,7-, 2,3- ve 1,6-dihidroksinaftalen arasındaki reaksiyonları sonucunda polimerler oluşmuştur. İsobütiraldehit ile 2-tiyonaftolün reaksiyonunda ise 1,1-di (2-naftiltiyo)-2-metilpropan elde edilmiştir. Aldehit monometilolleri ile 2-naftol arasındaki reaksiyonlarda ise değişik ürünler elde edilmiştir. İsobütiraldehit monometilol ile 2-naftol'ün reaksiyon ürünü 3,3-dimetil-4-(2-hidroksi-l-naftil)benzo[d]kromandır. Diğer aldehitlerin monometilol türevleri ve DL-gliseraldehit ile 2-naftol arasındaki reaksiyonlar sonunda 9-alkil [1,2; 7, 8] dibenzoksanten tipi ürünler elde edilmiştir. İsobütiraldehit monometilolü ile 2,3- ve 2,7-dihidroksi naftalenler arasındaki reaksiyon ürünlerinin 9-alkil [1,2;7,8] dibenzoksanten türü bileşikler olduğu saptanmış fakat 1,6- ve 1,5- dihidroksinaftalenlerle polimer ürünleri vermiştir. vu
Özet (Çeviri)
SUMMARY REACTION OF MONOMETHYLOL ALDEHYDES WITH HYDROXY AROMATIC COMPOUNDS In this study, 2-alkyl aldehydes and their monomethylol derivatives were reacted with hydroxy aromatic compounds and linear aldehydes. The reaction mechanism was also investigated in order to compare with those obtained from the reactions between 2-naphthol with hydroxy ketone and dicarbonyl compounds, such as glyoxal and glutardialdehyde. The reactions of 2-naphthol with hydroxy ketone and dicarbonyl compounds, were studied previously in our department. It was found that the products of these reactions were naphthopiranopiran, naphthofiiranofuran and naphthodioxosin type compounds. The reactions are as follows: OH o ChUOH K VCHjOH OH CHO I CHO H+ OH (CH^' / CHO H* V CHO Furthermore, similar condensation reaction was carried out by dihydroxynaph- thalenes with dicarbonyl and hydroxycarbonyl compounds and corresponding fiiranofiiran type compounds or polymers were produced. viaIn order to extend this work, 2-alkylaldehyde were reacted with formaldehyde such that aldol condensation to produce monomethylol aldehyde for condensation reaction with mono or dihydroxynaphthalenes. Two methods were used for the preparation of monomethylol derivatives of 2-alkylaldehydes. In the first method, excess of formaldehyde was reacted with 2-alkylaldehyde in the presence of K2CO3 resulting low yield. As a second method, equivalent amount of formaldehyde was allowed to react with 2-alkylaldehyde in the presence of Et3N catalyst yielding higher than first method. R CHO + CH20 2 V ^'“-N CHO +Acetals «y or Rf HOH,C B3N 2 R= methyl, ethyl, phenyl., Ri= methyl, ethyl. Preliminary studies showed that condensation reaction between monomethy lol aldehyde with 2-naphthol proceeded via condensation of aldehyde groups with two moles of naphthol in order to give bisphenol type compound. Thus, the reaction of aldehydes with 2-naphthol was first studied in order to elucidate the reaction mechanism. Isobutyraldehyde, 2-metylbutyraldehyde, 2-ethylbutyraldehyde, 2-phenylpro- panal, acetaldehyde, propanal, butyraldehyde, pentanal and benzaldehyde were reacted with 2-naphthol in the presence of strong acid catalyst such as H2S04, HC1 and CH3SO3H. Three different experimental conditions were used for these reac tions. Except acetaldehyde and 2-methylbutyraldehyde, the reaction products of aldehydes were 9-alkyl-[l,2:7,8]dibenzoxanthenes (Table 1). Reaction of 2-naphthol with acetaldehyde gave either 9-methyl-[l,2:7,8]dibenzoxanthene or 2-methyl-4-(2- hydroxy-l-naphtyl)benzo[d]chroman compounds depending on the reaction conditions such as mol ratio, temperature, kind of catalyst and solvent. However, the reaction of 2-naphthol with 2-methylbutyraldehyde gave bisphenol type compound i.e. 1, l-Bis(2-hydroxy-l-naphthyl)-2-methylbutane. -CHO + OH40 IXTwo moles of 2-naphthol were reacted with aldehydes to give phenolic type product followed by condensation of two hydroxyl groups to produce 9-alkyl- [ 1,2;7,8]dibenzoxanthene. The reaction of isobutyraldehyde monomethylol with 2-naphthol gave chroman type compound i.e.3,3-dimethyl-4-(2-hydroxy-l-naphtyl)benzo[d]-chroman.. However, the reaction products of monomethylol derivatives of other alde-hydes were 9-alkyl-[l,2:7,8]dibenzoxanthene type compounds(Table 2). The condensation reaction of aldehydes with 2-naphthol, depending on the type of aldehyde monomethylol, proceeded to give either chroman or 9-alkyl- [l,2:7,8]dibenzoxanthene. Chroman type compounds were produced by condensation of one of naphtholic hydroxyl groups and hydroxyl group of monomethylol. On the other hand, 9-alkyl-[l,2:7,8]dibenzoxanthenes formed if two naphtholic hydroxyl groups condenced. Ru,\ c| HOI^C HO + OH ¦ÜU HOH2C R^CH* C2H5, CqH5 R=CH3lC2H5 Similarly, aldehydes and hydroxyaldehydes were reacted with 2-hydroxydi- benzofuran, 2,3-dihydroxynaphthalene, 2,7-dihydroxynaphthalene, 1,6-dihydroxy- naphthalene, 1,5-dihydroxynaphthalene, 6-bromo-2-naphthol, 2-thionaphthol and 2- hydroxy-3 -naphthoic acid. The reaction condition and identified products were summarized in the table 1 and 2.Table 1: The reaction products of aldehydes with naphthols. Carbonyl Compound Naphthol Compound Products Acetaldehyde 2-Naphthoi ¦<T ”i Acetaldehyde Propanal Benzaldehyde Isobutyraldehyde Butanal Pentanal 2- Naphthol 2-Naphthol 2-Naphthol 2-Naphthol 2-Naphthol 2-Naphthol XITable 1: The reaction products of aldehydes with naphthols(Continue). Carbonyl Compound Naphthol Compound Products 2-Methylbutanal 2-Phenylpropanal 2-Phenylpropanal 2-Phenylpropanal 2-Ethyfbutanai 2-Naphthol <V*' 2-Naphthol 2,3-Dihydroxynaphthalene 2,7-Dihydroxynaphthalene 2-Naphthol Polymer Isobutyraldehyde 2,3-Dihydroxynaphthalene Isobutyraldehyde 2,7-Dihydroxynaphthalene Polymer Isobutyraldehyde 2-Methylpentanal 2-Thionaphthol 2-Naphthol XIITable 2 : The reaction products of hydroxyaldehydes with hydroxyaromatic compounds Carbonyl compounds Naphthol compounds CI-^OH ¦) - CHO 2-Naphthol Products 6- Bramo-2- naphthol 2- Hydroxy- 3- naphthoicacid 2,3-Dihydroxynaphthalene 2,7-Dihydroxy naphthalene COOH COOH CHjOH XJllTable 2 : The reaction products of hydroxyaldehydes with hydroxyaromatic compounds(Continue). Carbonyl Compound Naphthol Compound Products CHjOH h..m) - cho 2-hydroxydibenzofuran 2-Thionaphthol ; asetikasit-3,3-di(2-naftiltiyo)-2,2-dimetilpropilesteri CHjOH 2-Naphthol 2,3-Dihydroxynaphthalene POLYMER CHjOH.>....;> CHO »4 CHC ¦l/ CHjOH } CHO ch/ CH2OH ; - ci HO Orf 2,7-Dihydroxynaphthalene POLYMER CHjOH O 2-Naphthol 2-Naphthol 2-Naphthol XIV
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