Z. Abood, H. D. Hanoon, R. T. Haiwal
2012
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journal of kerbala university
Abstract
This work included synthesis of some new 1,3-oxazepine derivatives starting from 4Amino-1,5-dimethyl-2-phenyl-1H-pyrazol-3(2H)-one [1]. Firstly, compound [1] was converted to the corresponding imine derivatives [2] and [3] through condensation reaction with each 4Hydroxy-3-methoxybenzaldehyde and 2-Hydroxy-3-methoxybenzaldehyde, respectively, in presence of glacial acetic acid in absolute ethanol. Imine derivatives [2] and [3] were then introduced in [2+5] cycloaddition reaction with each Phethalic anhydride, 3-Nitrophthalic anhydride and Maleic anhydride, respectively, in dry benzene to give 1,3-oxazepine derivatives [4-9]. These new derivatives might have some biological activity. The structures of all prepared compounds were confirmed by C.H.N. elementary analysis and FT-IR spectra. Also 1 H-NMR spectroscopy was used to identify structure of one new compound. <ةصلاخلا مم سٍممضشت رمم ت ع عرمما ه ممضت 1 ، 3 ممكس ع همم دممٌدي هٍنش ممسكوع 4 ممىٍ أ 1،5 رممٍل ً ممىث 7 رممٍىف 1 H لوشعسٌ ن 3 ( 7 H ) [ نو 1 [ كس ع رٌ شت مت ،ةٌعدب ع ًف .] 1 [ هٍلن ع هٍ ٌلأع ً ى ع ] 7 [و ] 3 ث مات رمع فت للاخ ه ] هم رمك كم 4 ًممسكوزدٍا 3 و دمٌ يٌد عصىن ًممسك لٍ 7 ًممسكوزدٍا 3 م مي ن ،ً ع م ع ىمملع ،دمٌ يٌد عصىن ًممسك لٍ لل ع كٍلخ ع [ سضش ع هٍ ٌلاع ل خ ع مت ك ذ دتن .قلط ع ل و لٌلاع ًف دع س ر تك ًج 7 [و ] 3 ةف مفلاع رمع فت ًمف ] [ ةٍ لش ع 7 + 5 و كٍ لف ع دٌزديوع ه رك ك ] 3 م مف مج ع هٌصمىب ع ًمف ،ً ع م ع ىملع ،كمٍٍ ع دمٌزديوع و كمٍ لف ع دٌزديوعوس و ىلع ل صش ع 1،3 [ هٍنش سكوع 4 9 .ةٍي ٌ ن ةٍ تف كل ت دق دٌدج ع ع يرا نع .] ( سم ىتل قٍقدم ع ًم ا ع رمٍلش ع ةل مي ن سمضش ع مبكس ع كمٍ ي مٍكعست تمصخش C.H.N. ةتمشلاع مٍلأو ) دٌدج ع بكس ع ه د عو كس صٍخ ت ًف ن توسبل ًسٍل ىغ ع يو ى ع هٍوس ع ةٍف ٍط ل ت يع مت ك .ءعس ش ع تشت . Introduction: [2+5] Cycloaddition reaction is recently used for the synthesis of 1,3-oxazepine ring (1-4) . This reaction differs from the classical methods that were used to synthesis oxazepines, since it is not limited and produces various 1,3-oxazepine ring derivatives (5,6) . This reaction passes through cyclic transition state involves imine group as two-membered component and cyclic anhydrides as five-membered component (7,8) . Oxazepine derivatives showed various biological activities such as antibacterial (9) and inhibitors for some enzymes action (10) . Some of oxazepine derivatives are used in another applied fields (11) . Pyrazole derivatives play a vital role in many biological processes and synthetic drugs (12) . Pyrazolones are the most important derivatives of pyrazole (13) . Pyrazolone derivatives exhibit a wide variety of potentially useful applications including biological, clinical and pharmacological (14,15) . Journal of kerbala university , vol. 10 no.3 scientific . 2012 768 Experimental: 1. Materials All materials have been used as provided from commertial supplier (BDH) except benzene which was purified:{4-Amino-1,5-dimethyl-2-phenyl-1H-pyrazol-3(2H)-one}, 4-Hydroxy-3methoxybenzaldehyde, 2-hydroxy-3-methoxybenzaldehyde, Absolute ethanol, Glacial acetic acid, Phthalic anhydride, 3-Nitrophthalic anhydride, Maleic anhydride, Benzene and Ethyl acetate. 2. Apparatus 1. Melting points were determined by stuart melting point apparatus. 2. Elemental analysis measured on E.A.300, Euro, Italy, 2003-AL-albayt University (Jordan). 3. FT-IR spectra were recorded on FT-IR 8400s, schimadzuspectrophotometer and using KBr discs-Kerbala University. 4. H-NMR spectra were recorded on J 10631 C:\ Burker \ TOPSPIN 500 MHZ using tetramethyl silane as internal standard and DMSO as solvent. Measurements were made at Tahran University (Iran). 3. Preparation Methods Synthesis of 4-(4-Hydroxy-3-methoxybenzylideneamino)-1,5-dimethyl-2phenyl -1H-pyrazol-3(2H)-one [2] 4-Amino-1,5-dimethyl-2-phenyl-1H-pyrazol-3(2H)-one [1] (0.203g, 0.001mol) was dissolved in absolute ethanol (10mL), then 4-Hydroxy-3-methoxybenzaldehyde (0.152g, 0.001mol) was dissolved in absolute ethanol (10mL). Then, a drop glacial acetic acid was added to the aldehyde solution which was then added drop wise to the amine solution under reflux with stirring on water bath at 70oC for 2hrs. Then, the mixture was allowed to cool down to room temperature. The coloured precipitate was filtered and recrystallized from ethanol, Yield 79%, M.p. 176-178oC. Synthesis of 4-(2-Hydroxy-3-methoxybenzylideneamino)-1,5-dimethyl-2-phenyl1H-pyrazol-3(2H)-one [3] Imine derivative [3] was prepared by using the same procedure which was used for the prepare of compound [2] with the following modifications: 2-Hydroxy-3methoxybenzaldehyde (0.203g, 0.001mol) instead of 4-Hydroxy-3-methoxybenzaldehyde, Yield 74%, M.p. 172-174oC. Synthesis of 4-(1,5-Dimethyl-3-oxo-2-phenyl-2,3-dihydro-1H-pyrazol-4-yl)-3-(4hydroxy-3-methoxyphenyl)-3,4-dihydrobenzo[e][1,3]oxazepine-1,5-ione [4] Imine derivative [2] (0.337g, 0.001mol) and Phthalic anhydride (0.148g, 0.001mol) were dissolved in dry benzene (20mL). The reaction mixture was refluxed with stirring on water bath at 75oC for 5hrs, the mixture was then allowed to cool down to room temperature, the coloured precipitate was filtered and recrystallization from ethyl acetate, Yield 69%, M.p. 142-144oC. Synthesis of 4-(1,5-Dimethyl-3-oxo-2-phenyl-2,3-dihydro-1H-pyrazol-4-yl)-3-(4hydroxy-3-methoxyphenyl)-6-nitro-3,4-dihydrobenzo[e][1,3]oxazepine-1,5-dione [5] Oxazepine derivative [5] was prepared by using the same procedure which was used for the prepare of compound [4] with the following modifications: 3-Nitrophthalic anhydride (0.193g, 0.001mol) instead phthalic anhydride, Yield 72%, M.p. 151-153oC. Synthesis of 3-(1,5-Dimethyl-3-oxo-2-phenyl-2,3-dihydro-1H-pyrazol-4-yl)-2-(4hydroxy-3-methoxyphenyl)-2,3-dihydro-1,3-oxazepine-4,7-dione [6] Oxazepine derivative [6] was prepared by using the same procedure which was used for the prepare of compound [4] with the following modifications: Maleic anhydride (0.980g, 0.001mol) instead phthalic anhydride, Yield 65%, M.p. 134-136oC. Journal of kerbala university , vol. 10 no.3 scientific . 2012 769 Synthesis of 4-(1,5-dimethyl-3-oxo-2-phenyl-2,3-dihydro-1H-pyrazol-4-yl)-3-(2hydroxy-3-methoxyphenyl)-3,4-dihydrobenzo[e][1,3]oxazepine-1,5-ione [7] Imine derivative [3] (0.337g, 0.001mol) and phthalic anhydride (0.148g, 0.001mol) were dissolved in dry benzene (20mL). The reaction mixture was refluxed with stirring on water bath at 75oC for 5hrs, the mixture was then allowed to cool down to room temperature, the coloured precipitate was filtered and recrystallized from ethyl acetate, Yield 62%, M.p. 128-130oC. Synthesis of 4-(1,5-Dimethyl-3-oxo-2-phenyl-2,3-dihydro-1H-pyrazol-4-yl)-3-(2hydroxy-3-methoxyphenyl)-6-nitro-3,4-dihydrobenzo[e][1,3]oxazepine-1,5-dione [8] Oxazepine derivative [8] was prepared by using the same procedure which was used for the prepare of compound [7] with the following modifications: 3-Nitrophthalic anhydride (0.193g, 0.001mol) instead of phthalic anhydride, Yield 71%, M.p. 139141oC. Synthesis of 3-(1,5-Dimethyl-3-oxo-2-phenyl-2,3-dihydro-1H-pyrazol-4-yl)-2-(2hydroxy-3-methoxyphenyl)-2,3-dihydro-1,3-oxazepine-4,7-dione [9] Oxazepine derivative [9] was prepared by using the same procedure which was used for the prepare of compound [7] with the following modifications: Maleic anhydride (0.980g, 0.001mol) instead of Phthalic anhydride, Yield 60%, M.p. 119-121oC. Table (1): Melting points, percent yields and (C.H.N.) analysis of the prepared compounds (2-9) Comp. No. Formula M.Wt. (M.P.)oC Yield% C.H.N. analysis Calculated Found C% H% N% C% H% N% [2] C19H19N3O3 337 176-178 79 67.65 7685 64668 89655 76:4 64688 [3] C19H19N3O3 337 172-174 96 89687 7685 64668 89666 7694 6467; [4] C27H23N3O6 485 142-144 8; 886:6 6696 :687 89665 665; ;666 [5] C27H22N4O8 756 151-153 94 86665 6667 66678 866:: 6666 666:6 [6] C23H21N3O6 657 134136 87 85666 66:4 ;687 85656 7665 ;65: [7] C27H23N3O6 485 128130 84 886:6 6696 :687 886;9 6676 :6;: [8] C27H22N4O8 756 139 -141 96 86665 6667 66678 86666 664; 66697 [9] C23H21N3O6 657 119 -121 86 85666 66:4 ;687 85647 6696 ;666 Results and Discussion: The following scheme shows the synthetic plane of this work: Journal of kerbala university , vol. 10 no.3 scientific . 2012