Synthesis and Characterization of New Heterocyclic Derived from Pyromellitic Dianhydride Sahar F. Abbas Emad T. Ali Jumbad H. Tomma Dept. of Chemistry/College of Education for Pure Science (Ibn Al-Haitham)/ University of Baghdad Received in : 28 May 2013 , Accepted in :26 August 2013 Abstract In this work two moles of 2-amino benzothiazole were allowed to react with one mole of pyromellitic dianhydride to produce N,N‾-Bis-(benzathiazol-2-yl) pyromellitamic diacid [I] which was submitted to esterification via the reaction with dimethyl sulphate in sodium carbonate in acetone as a solvent to synthesize N,N‾-bis-(benzothiazol-2-yl) pyromellitam diacetate [II] .This ester was used to produce novel compounds through two paths :- Path one:- Reaction of ester [II] with hydrazine in ethanol as a solvent to form the corresebonding N,N‾-bis (benzothiazole-2-yl) –pyromellitamic acid hydrazide [III] which react with acetyl acetone in ethanol or with phthalic anhydride in dioxane to yield new pyrazole, N,N‾-bis[(2-amidobenzothiazol) 3,5-dimethyl pyrazole] pyromellitic [IV] . and new imide; N,N‾-bis-[(2-amidobenzothiazol)-amido phthalimide] pyromellit [V] respectively. Path two:- Reaction of ester [II] with thiosemicarbazide to form bis [N,N‾(2- amidobenzothiazole) thiosemicarbazide] pyromellitic acid [VI] ,which is converted to triazole. bis[N,N‾ (2-amido benzothiazol) 1,2,4-triazole -3-yl] pyromellit [VII] under basic condition treatment of the last product with different alkyl halides to give new series of thio- alkyl triazoles; bis [N,N-(2-amido benzothiazole)-5-thio alkyl 1,2,4-triazole-3-yl] pyromellit[VIII]n All the above compoundes were characterized by their melting points, elemental analysis and by their spectral data,FTIR and 1HNMR for (some of them). Key word : pyromellitic dianhydride , pyrazol , imide ,1,2,4- triazole , hydrazide. 268 | Chemistry @@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@ÚÓ‘Ój�n€a@Î@Úœäñ€a@‚Ï‹»‹€@·rÓ:a@Âig@Ú‹©@Ü‹1a26@@ÖÜ»€a@I3@‚b«@H2013 Ibn Al-Haitham Jour. for Pure & Appl. Sci. Vol. 26 (3) 2013 Introduction The wide spread applications of pyromellitic dianhydride (PMDA) in several fields,such as synthesis of an important monomer in the preparation of a variety of thermoplastic polymers such as polyimides, epoxy resins and metal carboxylate complexes. Moreover, it is also useful in the preparation of high performance coatings that have been widely employed in many fields in our daily life because of its excellent thermal , oxidative stability and excellent mechanical properties [1] . Pyrazoles played a crucial part in the development of theoretical studies and also useful building blocks in organic synthesis , with wide applications as dyestuff, analytical reagents and agrochemicals . The pyrazole ring system is a useful structural moiety found in numerous biologically active compounds. and in the field of the medicinal chemistry . They display various biological activities such as, analgesic , anti-inflammatory , anti anxiety , antibacterial , antifungal , antitumour , antitubercular , and antiparasitic [2] . Imides possess excellent mechanical properties , thermal stability and important class of bioactive molecules that show a wide range of pharmacological activities such as androgen receptor antagonistic, anti-inflammatory , anxiolytic, antiviral, antibacterial, and antitumor properties. Moreover , they are synthetic precursors with application in organic synthesis , polymer synthesis , and for the development of new materials and molecular electronic devise [3]. A large number of 1,2,4-triazole-containing ring system have been incorporated into a wide variety of therapeutically interesting drug candidates including Anti-septic, analgesic, anti-convulsant, anti-biotic, anti-allergic, anti-inflammatory, diuretic, fungicidal , insecticidal, herbicidal, anti-bacterial, anti-viral, anti-depressant, anti-microbial, anti-tumor, and antihypertensive [4 ]. The aim of this work is the synthesis of a novel pyrazole ,imides , 1,2,4- triazole derivatives from pyromellitic anhydride by many reaction steps which are given in scheme 1 Experimental Materials: All the chemicals were supplied from Merck , Fluka ,GCC and Aldrich chemicals Co. and used as received. Techniques :FTIR spectra were recorded using potassium bromide discs on a Shimadzo (Ir prestige-21) FTIR spectroscopy. Uncorrected melting points were determined by using Hot- Stage, Gallen Kamp melting point apparatus, 1HNMR spectra were carried out by company : Ultra Shield 300 MHz, Bruker, Switzerland, at University of Al-albayt , Jordan, and are reported in ppm(δ), DMSO was used as a solvent with TMS as an internal standard . Elemental analyses of some compounds were performed on a (C.H.N.S) Company: Euro vector, model EA 3000A origin: Italy. University of Al-albayt, Jordan 269 | Chemistry @@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@ÚÓ‘Ój�n€a@Î@Úœäñ€a@‚Ï‹»‹€@·rÓ:a@Âig@Ú‹©@Ü‹1a26@@ÖÜ»€a@I3@‚b«@H2013 Ibn Al-Haitham Jour. for Pure & Appl. Sci. Vol. 26 (3) 2013 [I] C C C C OO OO OH HO HN NH S NS N C O C O NH S N C O H2N C HN HN C O NH S N S [VI] C O NH S N C O NH S N NN N NN N SH HS [VII] C O NH S N C O NH S N NN N H NN N H SR RS [VIII] C O NH C O NH S N C C O NH S N NH N O O N O O O [V] C O C O NH S NC O C O NH S N NN NN CH3H3C CH3H3C [IV] [III] C O NH C O NH S N C O HN C O NH S N NH2 H2N OO O O O O S N NH2 [II] C O OCH3 C O NH S N C O H3CO CHN S N O acetone Na2CO3(CH3)2SO4 NH2NH2 ethanol phthalic anhydrid dioxane KOH R=CnH2n+1 , n=1-5 x=Br or I aq. NaOH ethanol R X Path one Path two ethanol CH3 -C-CH2-C-CH3 O O NH NH C NH2 S NH2 NH C NH2 S Scheme 1 H H Synthesis of asymmetrical diamic acid N,N‾-Bis-(benzothiazol-2-yl) pyromellitamic diacid [I] To a solution of pyromellitic dianhydride (0.218g , 0.001mole) in (15mL) acetone , a solution of the 2-amino benzothiazol ( 0.3 g ,0.002 mole) in (15mL) acetone was added dropwise during one hour, the mixture was then left at room temperature with continuous stirring for 24 hrs , the white product was then filtered off and recrystallized from acetone to give the a corresponding N,N‾-Bis-(benzothiazol-2-yl) pyromellitamic diacid [I] [5] , yield 90% ,mp >300 ⁰C. 270 | Chemistry @@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@ÚÓ‘Ój�n€a@Î@Úœäñ€a@‚Ï‹»‹€@·rÓ:a@Âig@Ú‹©@Ü‹1a26@@ÖÜ»€a@I3@‚b«@H2013 Ibn Al-Haitham Jour. for Pure & Appl. Sci. Vol. 26 (3) 2013 Synthesis of N,N‾-bis-(benzothiazol-2-yl) pyromellitam diacetate [II] A mixture of compound [I]. (6.73g,0.013mol) and anhydrous sodium carbonate (2.7 g,0.026 mol) was dissolved in 25mL of acetone , to this solution ( 0.026 mol ) of dimethyl sulphate was added then 20 min after, the resulting mixture was heated under reflux for 4 hrs. The reaction mixture was allowed to cool down at room temperature, extraction with chloroform. The product was collected by evaporating the chloroform to give a white compound[II] [6], yield 90% ,mp(174-176)⁰C. Elemental analysis of compound [II] : Theoretical : C% =57.14 , H% = 3.29 , N% =10.25 S%=11.72 Found : C% = 57.30 , H% = 3.42 , N% =9.16 S%=11.61 Path one: Synthesis of N,N‾-bis (benzothiazol-2-yl)-pyromellitamic acid hydrazide [III] A A solution of N,N‾-bis-(benzothiazol-2-yl) pyromellitam diacetate [II] (32.76 g,0.06 mol ) and hydrazine hydrate (15mL) in 25 mL of ethanol was heated under reflex for 2 hrs . The mixture was then cooled at room temperature, and the obtained pale orange solid was filtered and recrystallized from ethanol .yield 86% ,mp135-137⁰C . Synthesis of N,N‾-bis[(2-amido benzothiazol) 3,5 dimethyl pyrazole ] pyromellitic [IV] A mixture of acid hydrazide [III] ( 1.09 g,0.002mol ) and acetyl acetone (0.002mol) in absolute ethanol 4mL was heated under reflux for 4 hrs. The reaction mixture was cooled and the formed precipitate was filtered off and recrystallized to give yellow compound [IV], yield 71%, mp162-164⁰C . Synthesis of N,N‾-bis-[(2-amidobenzothiazol)-amido phthalimide] pyromellit[V] A mixture of acid hydrazide [III] (1.09g , 0.002mol) and phthalic anhydride (0.59 g,0.002mol) was refluxed in dry dioxane (20) mL for 5 hrs .The reaction mixture was left overnight for slow evaporation . The browen product was recystallized from dioxane to give new imide [V] , yield 60 % , mp >300⁰C . Path two: Synthesis of symmetrical bis [N,N‾- (2-benzothiazol) thiosemicarbazide] pyromellitamic acid [VI] To a solution of compound [II] ( 0.54 g, 0.01mol) in absolute ethanol (20mL) was added thiosemicabazide (0.18 g ,0.01mole), the mixture was refluxed for 4 hrs .And after cooling the white precipitate was filtered and recrstallized from ethanol [7] , yield 93% ,mp 150-152⁰C. Synthesis of symmetrical bis[ N,N‾-(2- benzothiazol) -1,2,4 -triazole-3-yl ] pyromellit amide [VII] A stirring solution of compound [VI] (6.64 g, 0.01 mol) and 10 mL 4% aqueous sodium hydroxide solution was refluxed for 4 hrs. After that, the mixture was filtered and the filtered was acidified with dilute hydrochloric acid. The pale browen precipitate was filtered and washed several times with water , yield 58% , mp (100-101) oC. Synthesis of a new series of symmetrical bis [N,N‾-(2-benzothiazole) -5-thio alkyl - 1,2,4 –triazole -3-yl] pyromellit amide [VIII]1-5 Potassium hydroxide (6.72 g, 0.12mole) dissolved in minimum volume of water,was added dropwise to a stirred solution of triazole (5.74 g , 0.01 mole) in (10mL) of dioxane at 250⁰C. After heating, the mixture for (15min.) and cooling , n-alkyl halide ((methyl 271 | Chemistry @@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@ÚÓ‘Ój�n€a@Î@Úœäñ€a@‚Ï‹»‹€@·rÓ:a@Âig@Ú‹©@Ü‹1a26@@ÖÜ»€a@I3@‚b«@H2013 Ibn Al-Haitham Jour. for Pure & Appl. Sci. Vol. 26 (3) 2013 iodide,ethyl bromide ,propyl bromide ,butyl bromide or bentyl bromide) (0.01mole) was added dropwise . The solution was refluxed for (3 hrs) . Afterwards the solvent was evaporated on a rotator evaporator, ice-water (100 mL) was added, the resulting precipitate was collected , and recrystallized .The physical properties data of a new series [VIII]1-5.are given in table 1. Result and Discussion N,N‾-Bis-(benzothiazol-2-yl) pyromellitamic diacid [I] was synthesized by the reaction of one mole of pyromellitic dianhydride with two moles of 2-amino benzothiazole in acetone as a solvent. The mechanism involves nucleophilic addition reaction , as follows scheme 2 .[5] [I] OO O O O O S N NH2 aceton C C C C OO OO O O NH S N H S N HN H proton exchange C C C C OO OO OH HO HN NH S NS N Scheme 2 S N NH2 The structure of amic acid was studied by it′s melting point and FTIR, FTIR spectrum which shows the disappearance of absorption bands of NH2 group and other peaks characterized of cyclic anhydride of the starting materials together with the appearance of new absorption stretching bands due to O-H of carboxylic moiety at (3284-2450)cm-1, C=O (carboxylic acid) stretching at (1685)cm-1 , C=O (amid) stretching at (1654) cm-1 and C=N (endocyclic) stretching at (1627)of hetrocyclic unite .The FTIR data support the proposed structure. N,N‾-Bis-(benzothiazol-2-yl) pyromellitamic diacid [I] was converted to ester by the common esterifiction process using dimethyl sulphate in the presence of anhydrous sodium carbonate in dry acetone . N,N‾-bis-(benzothiazol-2-yl) pyromellitam diacetate [II] was charecteized by melting point, C.H.N.S and FTIR sprcetrum . the FTIR spectrum shows absorption band at 1734 cm-1 due to stretching vibration of the (C=O) for ester , also appearance band at 1188 cm-1 was due to ( C-O) bending of ester ,besides to disappearance two bands of O-H and C=O of carboxylic moiety . the (C.H.N.S) analysis is consistent with their proposed structure . The new N,N‾-bis-(benzothiazol-2-yl) pyromellitam diacetate [II] was used to synthesize new compounds by using two paths as follows : 272 | Chemistry @@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@ÚÓ‘Ój�n€a@Î@Úœäñ€a@‚Ï‹»‹€@·rÓ:a@Âig@Ú‹©@Ü‹1a26@@ÖÜ»€a@I3@‚b«@H2013 Ibn Al-Haitham Jour. for Pure & Appl. Sci. Vol. 26 (3) 2013 Path one:- The acid hydrazide [III] was synthesized by the reaction of compound [II] with hydrazine hydrate and refluxing in ethanol to form compound [III] which was characterized by melting point, FTIR and 1HNMR spectram . FTIR spectrum shows absorption bands at (3278-3170) cm-1 due to the asymmetric and symmetric stretching vibration of the (-NH-NH2) group and stretching vibration band at 1680 cm-1 due to (C=O) for amide . 1HNMR spectrum (in DMSO as asolvent) of acid hydrazid [III] showed abroad signals at δ2.77 ppm for two protons of CONH group , many signals at δ(7.17-7.66) ppm that could be attributed to the ten aromatic protons The spectrum also showed a douplet signal at δ1.2 ppm for protons of NH2 group and a triplet signal at δ(3.43-3.72) ppm due to of NH protons of hydrazide moiety . The pair of electrons on nitrogen atoms in compound [ІІІ] facilitate the reaction of this compound in two ways: A ) acetyl acetone as shown in the following mechanism (scheme 3) to produce the pyrazol derivatives ,which was identified by it′s melting point,FTIR, 1HNMR spectroscopy .FTIR spectrum of pyrazole compound showed the following the disappearance a stretching bands at (1680 ) cmˉ¹due to C=O amide groups of hydrazide moity . Appearance of new absorption bands of NH at (3419) cmˉ¹ and C=N group endocyclic of pyrazole at (1618 ) cmˉ¹ was shown. 1HNMR of pyrazole compound [IV] showed two sharp signals at δ 1.74ppm and δ 1.79ppm due to two CH3 groups of pyrazole ring [8] , a singlet signal at δ 3.15 ppm could be attributed to two protons of NH group and many signals in the region δ (6.76-7.28) ppm for aromatic protons . C O NH C O NH S N C O HN C O NH S N NH2 H2N [III] [IV] O O CH3 -C-CH2-C-CH3 C O NH C O NH S N C O HN C O NH S N NH HN C CH2C CH3 O HO CH3 C H3C OH H2CCH3C O C O NH C O NH S N C OHN C O NH S N N N C CH2C CH3 OCH3 C CH3 H2CCH3C O C O C O NH S N C O C O NH S N NN CH3 HO CH3 NN CH3CH3 OH C O C O NH S N C O C O NH S N N N CH3H3C NN CH3CH3 O O CH3 -C-CH2-C-CH3 -2H2O -2H2O Scheme 3 B) phthalic anhydride to form the imide as afinal product as shown in (scheme 4) was studied by melting point , FTIR spectrum . The FTIR spectrum exhibited significant two peaks at 1735cm-1 and1720cm-1 which could be attributed to asymmetry and symmetry 273 | Chemistry @@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@ÚÓ‘Ój�n€a@Î@Úœäñ€a@‚Ï‹»‹€@·rÓ:a@Âig@Ú‹©@Ü‹1a26@@ÖÜ»€a@I3@‚b«@H2013 Ibn Al-Haitham Jour. for Pure & Appl. Sci. Vol. 26 (3) 2013 stretching vibration of the carbonyl group (imide cyclic) [9] and two absorption bands around 1186 cm-1 and 750 cm-1 for asymmetrical and symmetrical of C-N-C (cyclic) .[10-12] C O NH C O NH S N C O HN C O NH S N NH2 H2N O O O O O O C O NH C O NH S NC C O NH S N NH N O O N O O O proton exching heat -2H2O [III] [V] C C O NH S N C C O NH S N H2N HN O O O O O O HN H2N O O C C O NH S N C C O NH S N HNHN O O O O O HO HNHN OH O Scheme 4 Path two:- bis [N,N‾- (2-benzothiazol) thiosemicarbazide] pyromellitamic acid [VI] ,was obtained by treatment compound [ІІ] with thiosemicarbazide under reflux in ethanol, the structural assignments of [VI] are based on melting points, and their spectral data (FTIR and 1HNMR spectroscopy) . The FTIR absorption-spectrum of this compound [VI] showed (C=O) amid absorption band at 1690 cm-1 , the spectrum showed many peaks in the region 3367-3178cm-1 which could be attributed to asymmetric and symmetric stretching vibration of NH and NH2 groups besides to 1310cm-1 and 2652 cm-1 due to C=S groups and S-H group , respectively . The 1HNMR spectrum of this compound showed a good signal at δ3.70 ppm due to two protons of NH2 group .Abroad signal at δ 4.48 ppm for two protons of amide group (CO-NH- Ph) , two signals doublet and singlet at δ 7.45-7.58ppm and δ7.98ppm for aromatic protons of para substitution benzene rings and central benzene ring , respectively .The spectrum showed two signals due to protons of two NH group of (CO-NH-NH-CS) moiety at δ8.62ppm and δ9.80 ppm 274 | Chemistry @@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@ÚÓ‘Ój�n€a@Î@Úœäñ€a@‚Ï‹»‹€@·rÓ:a@Âig@Ú‹©@Ü‹1a26@@ÖÜ»€a@I3@‚b«@H2013 Ibn Al-Haitham Jour. for Pure & Appl. Sci. Vol. 26 (3) 2013 C O C O NH S N C O C O NH S N C O OCH3 C O NH S N C O H3CO CHN S N O C C O NH S N C O CHN S N O O OCH3H3CO NH2 NH C S NH2 -2CH3OH [II] [VI] NH2 NH C NH2 S NH2 C NH NH S NH NH C NH2 S C C O C OH CHN S N O OH OCH3H3CO NH NH C S NH2 Scheme 5 p.t NH2 C NH NH S NH2 C NH NH2 S NH S N NH2 NH C NH2 S The triazole compound [VII] was synthesized by oxidative cyclization of carboxylic thiosemicarbazide derivatives[VI] in the presence of (4%) aqiueous NaOH. The mechanism of the reaction may be outlined as follows in scheme (6) C O NH S N C O NH S N C O NH S N C O NH S N NN N NN N SH HS 2H [VII] C O C O NH S NC O NH C O NH S N S [VI] NH NH C NH2 NH C NH2 S NNHN N S NHN N S H H C O NH S N C O NH S N NHHN N S NHHN N S H H O O C O NH S N C O NH S N NHN N S NHN N S H H HO OH H H -2H2O Scheme 6 H H 2OH C O C O NH S NC O NH C O NH S N SH NH NH C HN NH C NH HS C O C O NH S NC O NH C O NH S N S NH NH C HN NH C NH S This compound was characterized by melting point and FTIR ,1HNMR spectroscopy . The FTIR spectrum showed disappearance of absorption bands due to υC=O 275 | Chemistry @@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@ÚÓ‘Ój�n€a@Î@Úœäñ€a@‚Ï‹»‹€@·rÓ:a@Âig@Ú‹©@Ü‹1a26@@ÖÜ»€a@I3@‚b«@H2013 Ibn Al-Haitham Jour. for Pure & Appl. Sci. Vol. 26 (3) 2013 (amide) and NH2 group of compound [VI] together with the appearance of three characteristic stretching bands at 3248cm-1 ,1645cm-1 and 1205cm-1, which are assigned to υN-H ,υC=N and υC=S groups ,respectively . 1HNMR spectrum of triazole compound [VII] showed the following characteristic chmical shefts (in DMSO as a solvent) showed two singlet signals at δ8.63 ppm and δ8.16 ppm that could be attributed to protons of two NH groups of triazole (tautomerism stat between thion and thiol forms SH+NH) , many signals (triplet, doublet and singlet ) in the region δ6.94-8.54 ppm due to ten aromatic protons. The spectrum also showed a good sharp singlet signal SH group and a weak peak at δ 4.05ppm due to protons of amide group (NHCO). Thio alkyl derivatives [VІІІ]1-5 of triazole was obtained by the treatment of compound [VІІ] with selective alkyl halides and potassium hydroxide in dry dioxane as a solvent. These compounds were identified by melting points and FTIR ,1HNMR. C O NH S N C O HN S N NN N H NN N H SH HS C O NH S N C O HN S N NN N H NN N SR RS 2KOH C O NH S N C O S N NN N H NN N H S K K S R X [VII] [VIII]1-5 NH R X H Scheme 7 K X The FTIR spectra show disappearance bands of S-H ,C=S and NH together with the appearance of new bends at 2966-2854cm-1 due to υC-H aliphatic and 869-855 cm-1for C-S stretching group [13] the spectral data of new series [VIII]1-5 are listed in table 2. 1HNMR spectrum of 5-thio methyl triazole compound [VIII]1 showed the following signals (in DMSO as a solvent ) : asinglet signal at δ3.07 ppm for two protons of NH (amide) group ,a good signal at δ8.17 ppm for two protons of NH(triazol) group . The spectrum also showed three doublet signals which could be assigned to the eight aromatic protons of pare substation benzene ring in the region δ6.97-7.67 ppm and a singlet signal at δ7.50 ppm due to two aromatic protons of central benzene ring and a singlet for six aliphatic protons at δ1.29 ppm of SCH3 group. References 1.Abo-bakr,A.; Hassan ,M .; Temirek, H. and Mosallam ,A .(2012) "Synthesis of Some New Heterocyclic Nitrogen Compounds Starting from Pyromellitic Dianhydride", Oriental journal of chemistry , 28 (4) : 1567-1578 2. Awadi, S.; Jyotil, Yadav. M. and Pathak , D.(2011) " Synthesis and characterization of some substituted pyrazoles asanalgesics and anti inflammatory agents" , Scholars Research Library , 3(1): 215-222 276 | Chemistry @@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@ÚÓ‘Ój�n€a@Î@Úœäñ€a@‚Ï‹»‹€@·rÓ:a@Âig@Ú‹©@Ü‹1a26@@ÖÜ»€a@I3@‚b«@H2013 Ibn Al-Haitham Jour. for Pure & Appl. Sci. Vol. 26 (3) 2013 3.Hussein, Sh. ; Ali, E. and Tomma, J. (2012 ) "Evidence supports the formation of isoimide derived from pyromellitic di anhydride", Ibn Al-Haitham Jour. For Pure &AppI .Sci , 2(1772) , 1-14 4. El Rayes ,S .(2009) "Convenient synthesis of some novel amino acid coupled triazoles". 13rd international Electronic conferenceone synthetic chemistry (ECSOC-13), 1-7 5. Ali, E.; AL-Aliawy, K. and Tomma ,J. (2011) "Synthesis and Characterization of New Symmetrical Pyromellitdiimide Derivatives and Their Amic Acids", IBN AL- HAITHAM J. FOR PURE & APPL. SCI ,24 (3):1-11 6. Al-Rwbaiy, Z .(1998) "synthesis and characterization of some new Derivatives 1,2,4 – triazole and 1,3,4 –thiadiazole " M.Sc thesis ,College of Education –Ibn –Al Haitham , Baghdad university . 7.Askar, F .; Hassan, H. and Janzeei ,N . (2010) " synthesis of some hetrocyclic compound derived from 2-mercapto pyrimedene ", Baghdad time J. , 7(2):1014-1022 8. El-masry, A.; Fahmy, H. and Abd wahed ,A. (2000) "synthesis and Antimicrobiad Activity of some new Benzimidazole Derivatives " , Molecules J. ,5(12):1429 -1438. 9 Garg ,M. and Quamara,.J .(2007) "Atomic and Molecular Physics FTIR analysis of high energy heavy ion irradiated kapton-H polyimide" ,Ind. J. Pure Appli. Phys.,45:563-568. 10. Weilin ,S.; Xuesong, G. and Fengcai ,L.(1997) "study on synthesis and properties of some novel polyimides containing bisthiazole rings", Chinese Journal of Polymer Science , 15 (4) : 325-331 11. Al Arbash, A.; Ahmad ,Z.; Al-Sagheer ,F. and Ali, A .(2006) "Microstructure and Thermomechanical Properties of Polyimide-Silica Nanocomposites", Journal of Nanomaterials" ,1- 9 12. Zahmatkesh ,S. and Vakili, M .(2010) "Synthesis and Characterization of New Optically Active Poly (ethyl L-lysinamide)s and Poly (ethyl L-lysinimide) ", J. Amino Acids , 1-6 13. Al-Rawi, M .; Tomma, J .; Muklus,.A. and Al-Dujaili, A. (2013) "synthesis and characterization of new Schiff Bases Hetrocyclic compounds and their N-Acyl ,Thiourea and Imidazol Derived from D-Erthroascorbic Acid ",American Journal of organic chemistry ,3(1) ,1-8 277 | Chemistry @@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@ÚÓ‘Ój�n€a@Î@Úœäñ€a@‚Ï‹»‹€@·rÓ:a@Âig@Ú‹©@Ü‹1a26@@ÖÜ»€a@I3@‚b«@H2013 Ibn Al-Haitham Jour. for Pure & Appl. Sci. Vol. 26 (3) 2013 Table No. (1):The physical properties of compounds [VІІІ] 1-5 Comp. No. Nomenclature Structural formula Molecuar formula M. P 0C Yied% Color [VІІІ]1 bis[N,N′-(2- benzothiazole)- 5-thio methyl - 1,2,4- triazol- 3yl] pyromellit amide C O NH S N C O NH S N NN N NN N SCH3 H3CS C27H17O2N10S4 158-160 67 Pale orange [VІІІ]2 bis[N,N′-(2- benzothiazole)- 5-thio ethyl - 1,2,4- triazol- 3yl] pyromellit amide C O NH S N C O NH S N NN N NN N SC2H5 C2H5S C28H19O2N10S4 130-132 92 Pale Brown [VІІІ]3 bis[N,N′-(2- benzothiazole)- 5-thio propyl- 1,2,4- triazol- 3yl] pyromellit amide C O NH S N C O NH S N NN N NN N SC3H7 C3H7S C29 H21O2 N10S4 94-95 93 Pale yellow [VІІІ]4 bis[N,N′-(2- benzothiazole)- 5-thio butyl- 1,2,4- triazol- 3yl] pyromellit amide C O NH S N C O NH S N NN N NN N SC4H9 C4H9S C30H23O2N10S4 108-109 83 Pale Brown [VІІІ]5 bis[N,N′-(2- benzothiazole)- 5-thio pentyl - 1,2,4- triazol- 3yl] pyromellit amide C O NH S N C O NH S N NN N NN N SC5H11 C5H9S C31H25O2N10S4 118-120 95 Pale Brown 278 | Chemistry @@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@ÚÓ‘Ój�n€a@Î@Úœäñ€a@‚Ï‹»‹€@·rÓ:a@Âig@Ú‹©@Ü‹1a26@@ÖÜ»€a@I3@‚b«@H2013 Ibn Al-Haitham Jour. for Pure & Appl. Sci. Vol. 26 (3) 2013 Table No.(2):Characteristic FTIR absorption band of compound[VIII]1-5 Comp. No. √NH of triazole √C-H Aliph. √C=O amid √C=N Of triazole √C=C arom. √C-S [VIII]1 3248 2954-2854 1645 1636 1598 869 [VIII]2 3246 2926-2854 1653 1642 1597 858 [VIII]3 3248 2966-2864 1656 1645 1597 856 [VIII]4 3248 2962-2856 1658 1645 1597 855 [VIII]5 3248 2945-2854 1655 1640 1599 865 279 | Chemistry @@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@ÚÓ‘Ój�n€a@Î@Úœäñ€a@‚Ï‹»‹€@·rÓ:a@Âig@Ú‹©@Ü‹1a26@@ÖÜ»€a@I3@‚b«@H2013 Ibn Al-Haitham Jour. for Pure & Appl. Sci. Vol. 26 (3) 2013 تحضیر مركبات حلقیة غیر متجانسة مشتقة من انھدرید البایروملتیك ودراستھا سحر فاضل عباس عماد تقي علي جمبد ھرمز توما / جامعة بغداد )ابن الھیثم(قسم الكیمیاء / كلیة التربیة للعلوم الصرفة 2013آب 26، قبل البحث في : 2013آیار 28استلم البحث في: الخالصة ( انھدرید البایروملتیك) للحصول على امینو بنزوثایزول ) مع مول واحد -2تم في ھذا البحث مفاعلة مولین من ( ]. Іیل) بایرومالتامیك داي اسید [-2-(بنزوثایزول , N,N -بس-′ -مثیل سلفیت وبوجود كاربونات الصودیوم واستعمل االستون مذیبآ للحصول على بس المقابل من خالل مفاعلة مع داي ]ІІیل)بایرومالتام داي اسیتیت[-2-(بنزوثایزول - ′N,N استعمل ھذا اال ستر النتاج وتحضیر مركبات جدیدة من خالل عملیتین: -: العملیة االولى-1 ول مذیبآ للحصول على تفاعل االستر مع الھیدرازین في االیثان ] ІІІیل)بایرومالتامیك اسید ھیدرازاید [-2 -( بنزوثایزول-بس -′N,N الذي بدوره تم مفاعلتھ مع االستیل اسیتون في اال یثانول مذیبآ او مع انھدرید الفثالك في الدایوكسان للحصول على مركبات حلقیة غیر متجانسة جدیدة (البایروزالت ) ] ᴠІداي میثیل بایرزول ] بایروملتیك [ 5,3امیدو بنزوثایزول)-2[(-بس -′N,N واالیمیدات المقابلة على التوالي ]ᴠامیدوفثالماید] بایروملیت [–امیدو بنزوثایزول) -2[(-بس -′N,N :العملیة الثانیة-2 تفاعل االستر مع ثایوسیمي كاربازاید لمحاولة الحصول على ]Іᴠبنزوثایزول ) ثایوسیمي كاربازاید ] بایروملتیامیك اسید [ -N¸N′ - )2[ -بس الذي تم تحویلھ الى التراییوزول المقابل ] ІІᴠیل ] بایروملیت امید [-3-ترایزول -4,2,1بنزوثایزول) -N¸N ′ - )2بس [ لى مجموعة من مشتقات باستعمال محیط قاعدي مناسب .استعمل المركب االخیر مع ھالیدات الكیل متنوعة للحصول ع الكیل تراییوزول-الثایو ]ІІІᴠ[ nیل ]بایروملیت امید -3-ترایزول -4,2,1ثایو الكیل -5-بنزوثایزول ) -N¸N′ - )2بس [ شخصت جمیع المركبات المحضرة اعاله ودرست من خالل ایجاد درجة اال نصھار، وتحلیل العناصر، واطیاف االشعة ین النووي المغناطیسي للبعض منھا، اذ حیث وجد تطابق النتائج النظریة والعملیة للمركبات تحت الحمراء، وطیف الرن المحضرة ترایزول ،ھیدرزاید - 4,2,1انھدرید البایروملتیك ،البایروزول ،االیمیدات ، -الكلمات المفتاحیة : 280 | Chemistry @@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@ÚÓ‘Ój�n€a@Î@Úœäñ€a@‚Ï‹»‹€@·rÓ:a@Âig@Ú‹©@Ü‹1a26@@ÖÜ»€a@I3@‚b«@H2013 Ibn Al-Haitham Jour. for Pure & Appl. Sci. Vol. 26 (3) 2013