Using of Intramolecular Condensation Reaction In Synthesis of Heterocyclics of (Se,S,N,O)- atoms
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| المجلة العراقية الوطنية لعلوم الكيمياء-2012 العدد الثامن والاربعون Iraqi National Journal of Chemistry,2012,volume 48, 504-510 Using of Intramolecular Condensation Reaction In Synthesis of Heterocyclics of (Se ,S,N,O)- Atoms Nagham .Mahmood .Al-Jamali Chem. Dept., Collg . Education, Univ .Kufa (NJC) (Recevied on 3/5 /2012 ) (Accepted for publication 23/10/2012) Abstract In this paper ,synthesis of five and seven-membered ring which containing hetroatom (Se ,S ,N, O) via several steps, the first step in this reaction, 2,2-methylene-bis(4-nitro phenol) reacts with (selenium ,sulphur ,nitrogen ,oxygen)-compounds to yield cyclic derivatives of (Se ,S ,N,O) which cyclized via intramolecular condensation reaction in the second step. The formated compounds [1-9] have been investigated by using various chemical techniques ,such as:(H-NMR–Spectra,(C.H.N)-analysis ,FT.IR-spectra) & Melting points .
تم في هذا البحث , تحضير مركبات حلقية خماسية وسباعية غير متجانسة محتوية ضمن تركيبها ذرات ( السلينيوم, الكبريت , النتروجين , الاوكسجين ) بعدة خطوات,تضمنت الخطوة الأولى تفاعل المركب 2,2- مثيلين-ثنائي(5-نايترو فينول) مع مركبات(سلينيوم,كبريت,أوكسجين,نايتروجين) ليعطي مشتقات حلقية لل-((Se,S,O,N والتي تتحولق عن طريق تفاعل التكاثف الضمني للجزيئة في الخطوة الثانية للتفاعل .المركبات المحضرة [9-1] شخصت باستخدام تقنيات متنوعة منها (التحليل الكمي الدقيق للعناصر , طيف الرنين النووي المغناطيسي , طيف الأشعه تحت الحمراء) و درجات الإنصهار . كلمات مفتاحية:السلينيوم ,التكاثف الضمني ,حلقية غير متجانسة
About one century ago selenium was incorporated in the table, selenium shares with sulphur and tellurium some phesical and chemical properties.Selenium ,sulphur and nitrogen-compounds act as active nucleophiles which able to react with electrophiles( alkyl halides ,carbonyl compounds such as aldehydes, carboxylic acids) to yield intermediats ,which give variouse heterocyclic compounds from(Se,S,N,O) ,this compounds have biological activity(1,2). Heterocycles are found as construction units through several biological molecules ,since these compounds have (Selenium , sulphur, nitrogen, oxygen) , atoms in their contents which make it has many pharmaceutical interest (3,4) ,dyestuffs industry(5) ,& other applications such as anticancer(6,7) ,antioxidant(8,9) ,physiology importance(10,11) , in synthesis of organic compounds(12) ,in toxicological studies(13-18) for this reasons many methods (19-20) for preparation of different heterocyclic compounds have been developed .
*All chemicals used where supplied from Merck & BDH-chemical company. *All measurement where carried out by : - Melting points :Electro thermal 9300 , melting point Engineering LTD ,U.K. - FT.IR-spectra: fourrier transform infrared shimadzu (8300) , (FT.IR) , KBr-disc was performed by CO.S.Q. Iraq . - H.NMR-Spectra &( C.H.N)-Analysis:in centre lab-Institute of earth & environmental science,Al-Bayt University ,Jordan . Synthesis of Compound [1]: Amixture of (0.02 mole , 2.7 g) of 4-nitrophenol with formaldehyde(0.01 mole) were reacted in presence of (4ml) of sulphuric acid ( 98% ) & (50ml) distilled water, the precipitate formed ,filtered off to give(3.4g) 82% of compound[1] . Synthesis of compounds [2-5]: Amixture of compound[1] (0.01mole ,2.9g) and(0.02mole) of mercaptobutoyl chloride or sodium selenobutoyl chloride or aminobutoyl chloride or alanine ) respectively were heated for (3 hrs ) in presence of ethanol , the precipitate was filtered off & recrystallized to give (80-84)% of compounds[2-5] respectively . Synthesis of compounds [6-9]: Amixture of salicyldehyde (0.02mole) and (0.01mole) of compound [1] or compound[2] or compound[3] or compound[4] or compound[5]respectively were heated under reflux for six hours in presence of ethanol ,the precipitate as filtered off & recrystallized from abs.ethanol to give(82-87)% of compounds [6-9]respectively. Reaction Scheme : 
Results and Discussion Most of the reactions employed in this work are intramolecular condensation reactions which involve several steps to give finally products of compounds [6-9]. Indeed ,seleno compounds is stronger nuleophile than sulphur compounds. All synthesized compounds [1-9] have been characterized by their melting points and spectroscopic methods(FT.IR- spectra, (C.H.N)-analysis H.NMR-spectra). FT.IR-Spectra: I H1.NMR- Spectrum : Appearance of peaks and disappearance of other peaks is evidence of formatted compounds such as disappearance of (O-H)band in compound[1] and appearance other peak(O-CO-)band of ester due to formation of compounds[2-5]. H1.NMR- Spectrum of compounds [1-9] showed : singlet signal at £(s, 10.7)ppm for proton of hydroxyl group (-OH) ,of phenol in compound [1] , while this signal disappears &other signals appear : - Signals at £(m,3.9),( t,3.4 )ppm for protons of ( -CH2CH2CH2-S) & signal at £ (s,4.25 )ppm for proton of (SH) in compound[2]. -Signals at £ (m,4.2) ,(t,3.95)ppm for proton(-CH2CH2CH2-Se)in compound [3] . - Signals at £ (m,3.5),(t,3.2)ppm for protons of (-CH2CH2CH2-N) & signal at £ (3.85) for protons of (-CH-NH2) in compound [4] . - Signal at £ (d,3.80),(m,3.40)ppm for protons of (-CH-CH3) & signal at £(3.98) for protons of (-CH-NH2) in compound [5] . - Signal at £ (t ,4.5),(t ,3.98 )ppm for protons of ( - Signal at ʆ (t,4.07),(t,3.72) for protons of ( - Signal at £ (t,3.88),(t,2.97) for protons of ( - Signal at £ (s ,8.72) for protons of (CH=N)azomethine in benzoxazepine cycle , signal at £ (s ,2.63) for protons of methyl group (-CH3) in compound [9] & signal at £ (s,5.03) for proton of (C-OH) hydroxyl group in compound [9]
& other peaks . (C.H.N) – Analysis : (C.H.N) – analysis , it was found from compared the calculated data with found data of these compounds , the results were compactable , the data of analysis , M.F, names and melting points are listed in table (2) . All these results are strong evidence for synthesized compounds[1-9] . Acknowledgement: I would like to express my thanks to ((United Arabic Company )) and ((Zaidan Company of Chemical )) in Jordan for supplied some materials. And express thank to MrMuhannad-Abu-Alsaod in Centre –Lab-Institute of Earth and Environmental Science Al-bayt University H.J.K in Jordan for providing (C.H.N)-element analytical ,H.NMR-spectra and Melting points. Table (1):FT.IR data (cm-1) of compounds[1-9].
Table(2): Melting points, M.F, Nams and (C.H.N)-Analysis of compounds[1-9]
References
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n FT.IR spectra ,the reaction is followed by appearance of hydroxyl group (-OH) absorption band of phenol at (3500)cm-1 in compound [1] ,while this band disappears & other band appears at (1705-1690)cm-1 due to carbonyl group of ester ( ) in compounds [2-5] ,which also disappear so that another band appear at (1230-1271)cm-1 due to (C-O-C) of ether in compound [6-9], other data of functional groups shown in the following table (1).
) endocyclic in compound [6].
) endocyclic in compound [7].
( 
