Aromatik sübstitüe fenol sentezi

Abstract

Bu çalışmada para yerinde antrasen, naftalin, tetralin içeren fenollerin sentezi çalışılmıştır. Bu nedenle birinci aşamada antrasen ve tetralinin p-anisoil klorürle, naftalinin anisolle Friedel Crafts reaksiyonu yapılarak ketonlar elde edilmiş, bu ketonlar hidrazin hidrat ile Wolf- Kischner senteziyle indirgenmiş, daha sonra eterik yapılar parçalanarak, 4- Hidroksi Fenil 9-Antranil Metan, 4- Hidroksi Fenil 2-Naftil Metan, 2-(4- Hidroksi Fenil) Metil Tetralin elde edilmiştir. Yapılar spektroskopik yöntemlerle aydınlatılmış, fenolle karıştırılarak fenol- formaldehit ko-polimerleri sentezlenmiştir.

The chemical and physical complexity of coal has meant that model compounds have had to be used to gain and understanding of the fundamental chemistry involved in carbonisation and liquefaction. Compounds which contain aliphatic C-C linkages known to be present in coals have used to probe the free radical chemistry of coal pyrolysis and liquefaction. An alternative dass of materials for modelling pyrolysis phenomena are cured phenol-formaldehyde resins. For this reason model compounds are incorporated into the phenolic resin structure. The aim of this study is the synthesis of aryl alkyl substituted phenols. Preparation of the substituted were carried out in three steps. The first step was Friedel Crafts acylation reaction. 0.3 mole of anthracene reacted with 0.1 mole of p-anisoyl chloride in the presence of AICI3 catalyst. The yield was higher when the reaction temperature increased to 80-100° C. 0 0 I 0 I 0 I * Jj _^T)-0CH3 Cl-C -/~o\-0-CH3__^ f^To (1) The product 1 was optained and the structure was eluducated by spectroscopic methods. The reaction of 0.05 mole of 2- naftoyl chloride reacted with 0.5 mole of anysole in the precence of AICI3 gave the product 2. o och3 o (2) The Friedel Crafts reaction between 0.3 mole of tetralen and 0.1 mole of p- anisoyl chloride in the presence of AICI3 at 100- 110 °C resulted the compound 3. 0 ° r-\ (3) The second step was the reduction of ketones. To a solution of 0.133 mole of ketone in 250 ml of diethylene glycol were added 0.4 mole of %80 hydrazine - hydrate and 0.66 mole of NaOH. 0 {J_^-0CH3 CH2\0JMCH H2NNH2 NaOH ' (4) 00. 1L0-OCH3 _ 00^{^> 0CH: (5) VI i c/*ÖVoCH3 Q^c^y0cH3 (6) The reaction time and temperature played an important role on product yields. At reflux temperature, 1 1 h was enough for the reduction of 1 and 2. Somehow only 30% of 3 was reduced to 6 at about 16 h at reflux temperature. The last step was etheric cleavage. To 0.5 mole of product was added 0.2 mole of pyridine hydrochloride and the mixture was stirred for 4 h at 200°C. CK,£> OCH, o I. ^"K^"3 OSr0*. OH (75 (8) Q0^Ki> °_^_ Viii (9) The reaction completed almost 100%. The resulting products were recrystallized and used for the preparation of phenol- formaldehyde resin. The mixture of phenol / substituted phenols (7,8 and 9 ) were reacted with formaldehyde in the presence of NaOH to produce phenol- formaldehyde resin containing naphtyl methane, antranyl methane and tetranyl methane moities. The pyrolysis of these resins were studied. CH2-<'0 >-0H 033 4 - Hydroxy Phenyl 9 - Anthranyl Methane 0^CH2< 0 >"°H 4 - Hydroxy Phenyl 2 - Naphtyl Methane o i CHr(o)-OH 2 - (4 - Hydroxy Phenyl) Methyl Tetralen Table 1 : Synthesized Compounds