Synthesis of New Asymmetrical Pyromellitdiimide and Their Amic Acids Containing Heterocyclic Unit Jumbad H. Tomma Kadhim M. Lazim AL-Aliawi Imad T. Ali Dept. of Chemistry/College of Education for Pure Science(Ibn Al-Haitham) /University of Baghdad Received in : 10 September 2013 , Accepted in : 4 December 2013 Abstract This work involves the synthesis and characterization of asymmetrical pyromellitdiimide derivatives [VII]a-f by four sequences steps reaction . One mole of pyromellitic dianhydride was reacted with one mole of various primary aromatic amines [2- aminothiazole , 2-aminobenzothiazole , 5-(4-amino phenyl)-1,3,4-oxadiazole-2-thiol , 4-nitro aniline , 4-chloro aniline , 4-toludine] in excess of dry acetone to produce six compounds (N- substituted-pyromellitamic monoacid) [IV]a-f . These new compounds [IV]a-f were converted to the corresponding N- substituted- pyromellitmonoimide [V]a-f when heating then at (80- 90) 0C in sodium acetate-acetic anhydride system .The compounds [V]d-f were allowed to react with one mole of another primary amines (containing benzothiazole or 1,3,4-oxadiazole unit) in dry acetone to give new derivatives of amic acid [VI]a-f followed by intramolecular cyclization reaction of these compounds in sodium acetate-acetic anhydride system to yield the desired asymmetrical pyromellitdiimide derivatives [VII]a-f, the above reactions can be summarized in Scheme 1. Structures of the synthesized compounds have been ascertained by their melting points , C.H.N analysis , UV-Vis, FTIR and 1HNMR spectroscopy. Key words : Asymmetrical pyromellitdiimide, Pyromellitic dianhydride, pyromellitamic monoacid , pyromellitmonoimide. 234 | Chemistry @a@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@ÚÓ‘Ój�n€a@Î@Úœäñ€a@‚Ï‹»‹€@·rÓ:a@Âig@Ú‹©@Ü‹127@@ÖÜ»€a@I1@‚b«@H2014 Ibn Al-Haitham Jour. for Pure & Appl. Sci. Vol. 27 (1) 2014 Introduction Pyromellitdiimides are best known as segments of highly insulating polyimide dielectrics , it is though nevertheless quit surprising that no attempt has been made to fabricate transistor from pyromellitdiimide derivatives , which have the simple aromatic ring (benzene) in the center, and the tetra carboxylic diimides on both sides of the benzene ring . Thus , it is possible to screen a large number of imide side chains and investigate the impact of side chains on the mobility and environmental stability of the pyromellitdiimide derivatives [1,2 ]. N-substituted cyclic imides are heterocyclic compounds represent an important class of bioactive molecules that show a wide range of pharmacological activities [3] such as androgen receptor antagonistic [4], anti-inflammatory , anxiolytic [5] , antiviral [6], antibacterial [7], and antitumor [8] properties . Moreover , they are synthetic precursors with application in organic synthesis , supramolecular chemistry , polymer synthesis , and for the development of new materials and molecular electronic devise [9]. Aromatic polyimides that are derived from pyromellitic dianhydride are widely used in advanced technological areas because of their excellent thermal stability , chemical resistance and they are extensively used in the electronics industry as insulators in complex devices , owing to their high thermal resistance and low dielectric constant , beside the electrical properties , their optical properties have been extensively investigated due to the potential applications in the field of optical communications[10]. Also they are used in microelectronics, as well as in nanotechnology as a matrix in the production of nanocomposite layers [11]. In addition, the effect of different concentrations of some pyromellitamic diacids and pyromellitdiimides on the activity of human serum cholinesterase have been investigated in vitro , the inhibitory effect increases with the increase of the concentration of such compounds [12] . The aim of this work is the synthesis of novel asymmetrical pyromillitdiimide derivatives containing heterocyclic unit such as benzothiazole or 1,3,4-oxadiazole. 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 shimadzu (8400S) and shimadzu (IR Prestige-21).1HNMR spectra were carried out by company : Bruker , model: ultra shield 300 MHz , origin : Switzerland and are reported in ppm(S), DMSO was used as solvent with TMS as an internal standard. Measurements were made at Chemistry Department, AL-Albyat University, Elemental microanalysis (C.H.N) were carried out by a (C.H.N) company : Euro vector , model EA3000A origin : Italy . AL-Albayt University, Jordan . Uncorrected melting points were determined by using Hot-Stage, Gallen Kamp melting point apparatus .UV-Vis spectra of solution were performed on CEC1 7200 England Spectrophotometer using CHCl3 as a solvent. 235 | Chemistry @a@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@ÚÓ‘Ój�n€a@Î@Úœäñ€a@‚Ï‹»‹€@·rÓ:a@Âig@Ú‹©@Ü‹127@@ÖÜ»€a@I1@‚b«@H2014 Ibn Al-Haitham Jour. for Pure & Appl. Sci. Vol. 27 (1) 2014 Synthesis methods + CH3CO2Na , (CH3CO)2O (80-90) 0C R NH2 [VI]a-f N HO2C C R O H N O O R dry acetone RT , R = NN O SH N S Cl CH3NO2 R = NR N O O O O R [VII]a-f , NN O SH N S , N S , O CO2H CO NH R O O [IV]a-f NO O O O O R [V]a-f OO O O O O + excess of dry acetone RT CH3CO2Na , (CH3CO)2O (80-90) 0C R NH2 and and scheme (1) Ethyl-4-Amino benzoate [I]: was prepared following the procedure by Vogel [13] . 4-amino phenyl hydrazide[II]: This compound was prepared according to the let.[14]. 5-(4-amino phenyl)-1,3,4-Oxadiazole-2-thiol [III]: This compound was prepared according to the let. [15]. N-substituted -pyromellitamic monoacid[IV]a-f : To a solution of pyromellitic dianhydride (0.218g, 0.001 mole) in (30mL) acetone , a very dilute solution of amine (0.001 mole) in (90mL) acetone was added dropwise during about 18 hrs . After the solution was filtered off from any precipitate and the clear solution was evaporated under reduced pressure . The product was collected , washed by petroleum ether and recrystalized from chloroform. The physical data of N-substituted – pyromellitamic monoacid [IV]a-f are listed in Table 1. Synthesis of N- substituted- pyromellitmonoimide[V]a-f : A (0.001 mole) of N-pyromellitamic monoacid was placed in (50 mL) round bottom flask with a condenser , a mixture of sodium acetate (0.082g , 0.001 mole) and acetic anhydride (1mL ,0.001mole) was added . The mixture was maintained between (80-90) 0C by means of a water-bath and stirred for half an hour . The mixture was allowed to stirring for one hour at room temperature . Then the mixture was poured on ice-water (400mL ) and filtered off , recrystalized from acetone . The physical data of N- substituted- pyromellitmonoimide [V]a-f are listed in Table 2. Synthesis of (N- substituted pyromellitmonoimide)-N─- (substituted-pyromellitamic monoacid) [VI]a-f : These compounds were synthesized as described in procedure which is used for synthesized of monoimide[IV]a-f . The physical data of (N- substituted - pyromellitmonoimide)-N─- (substituted-pyromellitamic acid) [VI]a-f are listed in Table 3. 236 | Chemistry @a@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@ÚÓ‘Ój�n€a@Î@Úœäñ€a@‚Ï‹»‹€@·rÓ:a@Âig@Ú‹©@Ü‹127@@ÖÜ»€a@I1@‚b«@H2014 Ibn Al-Haitham Jour. for Pure & Appl. Sci. Vol. 27 (1) 2014 Synthesis of N,N--- disubstituted pyromellitdiimide [VII]a-f : These novel compounds were synthesized as described in procedure which is used for the synthesis of compounds [V]a-f .All these compounds were recrystalized from diethyl ether . The physical data of N,N--- disubstituted pyromellitdiimide [VII]a-f are listed in Table 4 . Elemental analysis of compound [VII]a : Theoretical : C% = 58.71 , H% = 2.14 , N% = 11.19 Found : C% = 57.83 , H% = 3.03 , N% = 11.98 Results and discussion The reaction sequences leading to the formation of novel compounds of asymmetrical pyromellitdiimide [VII]a-f are outlined in the following scheme 1. The amic acids [IV]a-f were synthesized by the reaction of one mole of pyromellitic dianhydride with one mole of different amines in the presence of excess of dry acetone as a solvent . The mechanism involves nucleophilic addition reaction [16] as follows , scheme 2. AcetoneOO O O O O R NH2 C C O O O O O O H N R H Scheme (2) Proton exchange C C O O O O OH N R H O [IV] The structure of these acids[IV]a-f was studied by melting points , FTIR and UV-Vis spectroscopy . The FTIR absorption-spectra showed the disappearance of absorption bands due to NH2 of the starting materials together with the appearance of new absorption stretching bands due to O-H of carboxylic moiety at (2350-3530) cm-1, C=O (carboxylic acid) at (1684-1709) cm-1 , C=O (amid) at (1632-1674) cm-1 and C=N (endocyclic) for [IV]a-c at (1609-1628) cm-1 of heterocyclic unit . And there is an appearance of two peaks in the region (1720-1838) cm-1 which could be attributed to stretching vibration of C=O (anhydride) symmetrical and asymmetrical , in addition to the appearance of absorption band around (1060) cm-1 for the C-O-C (cyclic) [17]. The UV-Vis spectroscopy of these compounds [IV]a-f exhibited the characteristic bands due to π-π* and n-π* transitions. The FTIR data of functional groups which are characteristic of the these new amic acids[IV]a-f and the UV-Vis data (λmax) are listed in Table 5. N-substituted-pyromellitmonoimides [V]a-f were obtained by the intramolecular cyclization reaction of N-substituted-pyromellitamic monoacids [IV]a-f in acetic anhydride and anhydrous sodium acetate at (80-90) 0C . The mechanism involves nucleophilic substitution reaction[18] as follows , scheme 3. 237 | Chemistry @a@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@ÚÓ‘Ój�n€a@Î@Úœäñ€a@‚Ï‹»‹€@·rÓ:a@Âig@Ú‹©@Ü‹127@@ÖÜ»€a@I1@‚b«@H2014 Ibn Al-Haitham Jour. for Pure & Appl. Sci. Vol. 27 (1) 2014 C C O O O O O OH N R H C C O O O O O O N R H H3C C O C CH3 O O CH3CO2Na C C O O O O O O N R H C CH3 O NO O O O O O R C CH3 O NO O OO O R [IV] [V] Scheme(3) (80-90)0C CH3CO2H H The structure of these compounds [V] a-f was studied by melting points , FTIR , UV-Vis and 1HNMR spectroscopy. The FTIR spectra exhibited significant two peaks in the region (1674-1765) cm-1 which could be attributed to stretching vibration of the carbonyl group (imide cyclic) and two absorption bands around 1170 cm-1 and 755cm-1 for asymmetrical and symmetrical of C-N-C (cyclic) together with the appearance of two peaks in the region (1709-1857) cm- 1 which could be attributed to stretching vibration of C=O (cyclic anhydride) symmetrical and asymmetrical , the appearance of absorption band around (1050) cm-1 for the C-O-C (cyclic) . They also shows the disappearance of absorption stretching bands of N-H , O- H and C=O (carboxylic moiety) groups of amic acid . The UV-Vis spectroscopy of these compounds [V]a-f exhibited the characteristic bands due to π-π* and n-π* transitions . The FTIR absorption bands data and the (λmax) data of these compounds [V]a-f are listed in Table (6). 1HNMR spectrum of compound [V]a ,showed the following characteristic chemical shift ( DMSO as a solvent) : A doublet band at δ (7.85-7.87) ppm due to the two protons of thiazole aromatic ring , a singlet sharp signal at δ 8.48 ppm for the two protons of centre aromatic ring . The amic acids [VI]a-f were synthesized by the reaction of one mole of N- substituted-pyromellitmonoimides [V]d-f with one mole of 2-amino benzothiazole or 5-(4- amino phenyl)-1,3,4-Oxadiazole-2-thiol in the presence of excess dry acetone as a solvent. NO O OO O R [V] R NH2 N C C O O R O O HO HNR [VI] + RT The structure of these compounds [VI]a-f was studied by melting point , FTIR , UV-Vis and 1HNMR spectroscopy. The FTIR absorption-spectra, showed the disappearance of absorption peaks characterized of cyclic anhydride of pyromellitmonoimides [V]d-f together with the appearance of new absorption stretching bands due to O-H of carboxylic moiety at (2450-3520) cm-1, C=O (carboxylic acid) at (1663-1692) cm-1 , C=O (amid) at (1635-1645) cm-1 and C=N (endocyclic) at (1609-1630) cm-1 of heterocyclic unit . Two peaks in the region (1695-1790) cm-1 which could be attributed to stretching vibration of the carbonyl group (imide cyclic) and two absorption bands around 1175cm-1 and 745cm-1 for asymmetrical and symmetrical of C-N-C (cyclic) . The UV-Vis spectrum data showed the characteristic (λ max) in the region (254-320) nm . The FTIR absorption bands data and the UV-Vis spectrum data of these compounds [VI]a-f are listed in Table 7. 238 | Chemistry @a@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@ÚÓ‘Ój�n€a@Î@Úœäñ€a@‚Ï‹»‹€@·rÓ:a@Âig@Ú‹©@Ü‹127@@ÖÜ»€a@I1@‚b«@H2014 Ibn Al-Haitham Jour. for Pure & Appl. Sci. Vol. 27 (1) 2014 1HNMR spectrum of compound [VI]e , showed the following characteristic chemical shift ( DMSO as a solvent) : A singlet sharp signal at δ 1.97 ppm could be assigned to the three protons of terminal CH3 group , a singlet signal at δ 4.78 ppm could be attributed to the one proton of NH amide group . A singlet sharp signal at δ 7.46 ppm for two protons of centre aromatic ring , four aromatic protons appeared as mulitiplet bands at δ 7.0-7.3 ppm and a doublet signal at δ 7.59-7.62 ppm due to four aromatic protons of p-disubstituted benzene ring . Finally, a proton of carboxylic moiety (O-H) appeared at δ 10.07 ppm . N,N─- disubstituted pyromellitdiimides [VII]a-f were obtained by the intramolecular cyclization reaction of amic acid [VI]a-f in acetic anhydride and sodium acetate at (80-90) 0C . N C C O O R O O HO HNR [VI] NN O OO O R [VII] R (CH3CO)2O , CH3CO2Na (80-90) 0C The structure of these compounds [VII]a-f was studied by melting points , FTIR , UV-Vis and 1HNMR spectroscopy. The FTIR spectra , exhibited significant two peaks in the region (1682-1786) cm-1 which could be attributed to stretching vibration of the carbonyl group (imide cyclic) and two absorption bands around 1175 cm-1 and 760 cm-1 for asymmetrical and symmetrical of C-N-C (cyclic) , in addition two peaks of (imide cyclic) from another side in the region (1668-1734) cm-1 and two absorption bands around 1160 cm-1 and 740 cm-1 for asymmetrical and symmetrical of C-N-C (cyclic) . They also shows the disappearance of absorption stretching bands of N-H , O-H and C=O (carboxylic moiety) groups of amic acid [VI]a-f . The UV-Vis spectroscopy of these compounds [VII]a-f exhibited the characteristic bands due to π-π* and n-π* transitions. The FTIR absorption bands data and the (λmax) data of these compounds [VII]a-f are listed in Table 8 . 1HNMR spectrum of compound [VII]f , showed the following characteristic chemical shift ( DMSO as a solvent) : A singlet signal at δ 1.93 ppm is due to the three protons of terminal CH3 group , one proton of S-H group appeared as a sharp signal at δ 2.2 ppm . A good singlet signal at δ 7.94 ppm is due to the two protons of centre aromatic ring , eight aromatic protons appeared as a pair of doublet signal at δ (7.07-7.2) ppm . Also, the 1HNMR spectrum showed a sharp signal at δ 12.3 ppm which is due to the one proton of N- H group of oxadiazole ring[19] . The elemental analysis (C.H.N) of compound [VII]a are consistent with their proposed structure . References 1. Sharma ,P.; Kukreja , P.; Choudhary,V. and Narula , A., (2005), Curing and Thermal Behaviour of Epoxy Resin in The Presence of Aromatic Imide –Amines, Ind. J. of Engin. and Mat. Sci. of Chem., 12: 259-264. 2. Lee , S.; Shin, G.; Chi, J.; Zin, W.; Jung , J.; Hahm ,S.; Ree , M. and Chang ,T., (2006), Synthesis , characterization and liquid-crystal-aligning properties of novel aromatic polypyromellitimides bearing (n-alkyloxy) biphenyloxy side chains, Polymer, 47: 6606- 6621. 3. Kankanala, K.; Reddy, V.; Mukkantia, K. and Pal, S., (2010), Lewis Acid Free High Speed Synthesis of Nimesulide-Based Novel N-Substituted Cyclic Imides, J. Braz. Chem. Soc., 21( 6):1060-1064. 4. Salvati, M. E.; Balog , A.; Shan, W.; Wei ,D. D.; Pickering, D.; Attar, R. M.; Geng, J. ; Rizzo, C. A.; Gottardis, M. M.; Weinmann, R.; Krystek, S. R.; Sack, J.; An, Y. and Kish, 239 | Chemistry @a@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@ÚÓ‘Ój�n€a@Î@Úœäñ€a@‚Ï‹»‹€@·rÓ:a@Âig@Ú‹©@Ü‹127@@ÖÜ»€a@I1@‚b«@H2014 Ibn Al-Haitham Jour. for Pure & Appl. Sci. Vol. 27 (1) 2014 K., (2005), Synthesis and study of some new N-substituted imide derivatives as potential antibacterial agents, Bioorg. Med. Chem. Lett., 15:271. 5. Shibata, Y.; Shiehita, M.; Sasaki, K.; Nishimura, I. L.; Hashimoto ,Y. and Iwasaki ,S., (1995), Synthesis and study of some new N-substituted imide derivatives as potential antibacterial agents, Chem. Pharm. Bull., 43:177. 6. Jindal, D.; Bedi ,P.; Jit,V.; Karkra, B.; Guleria, N.; Bansal ,S.; Palusczak, R. A. and Hartmann, R. W., (2005), Synthesis and study of some new N-substituted imide derivatives as potential antibacterial agents,. Farmaco. , 60:283. 7. Machado, A.; Lima, L. L. M.; Arau , j. O.; Fraga ,C. A.; Koatz, L. G. and Barreiro, V. E., (2005), Design, synthesis and anti-inflammatory activity of novel phthalimide derivatives structurally related to thalidomide, Bioorg. Med. Chem. Lett., 15:1169 - 1172. 8. Kenji, S.; Hideko, N.; Yoshihiro, U.; Yoshikazu, S.; Kazuharu, N.; Motoji, W.; Konstanty, W.; Tadafumi, T.; Tetsuji, A.; Yuji ,Y.; Kenji ,K. and Hitoshi, H. (2005) 11,12- Epoxyyeicosatrinoic acid (11,12-EET): structural determination for inhibition of TNF-a- induced VCAM-1 expression, Bioorg. Med. Chem., 13:4011-4014. 9. Diego ,G.; Natalya, V.; Herbert, H. ; Guzman, J.; Likhatchev, D. and Palou ,R. (2006) Efficient microwave-assisted synthesis of bisimides, General Papers ARKIVOC, (x): 7-20. 10. Tkachenko ,V.; Marino, A.; Vita, F.D.; Amore, F.; DeStefano, L.; Malinconico, M.; Rippa , M. and Abbate , G. (2004) Optically active and organosoluble poly(amide-imides) derived from N,N-(pyromellitoyl)bis-L-histidine, Euro. Phys. J.E–Soft Matter, 14:185. 11. Yeganeh, H.; Tamami, B. and Ghazi, I. (2005) Synthesis and Properties of Novel Optically Active, Iran. Poly. J. 14 (3):277-285. 12. Al-azzawi, M.; Atto, A.; Al-ahadami, B. and Ali, I. (1989)The synthesis of pyromellitamic diacids and pyromellitdiimide and their effect on the human serum cholinesterase activity in vitro, J. Bio. Sci. Res. 19(1): 84-93. 13. Vogel A. (1974) Practical Organic Chem. Longman Group Ltd., Londdon, 3rd Edition. 14. Atto, A.; Mohamed, M. and Hameed , A. (2000) Synthesis , Spectroscopy and study of Some New 1,3,4-Oxadiazole Derivatives, Iraqi J. Chem., 26(1): 86-93. 15. Tomma , J.; Al-Mehdawy, M.; Mubbrik , S. and Al-Dujaili , A. (2004) Synthesis Antibacterial Activity of Some New Schiff Bases containing 1,3,4-Oxadiazole Ring, Iraqi J. Sci. 45(1): 39-45. 16. Dunson, D. L., (2000), Synthesis and Characterization of Thermosetting Polyimide Oligomers for Microelectronics Packing, Ph.D. thesis ,Virginia Polytechnic Institute . 17. Sharma, Y. R. (2009) Elementary Organic Spectroscopy,4th Edition , Ramnagar , New Delhi Ind. , 122,233 . 18. Ali, I. T. (2012) Synthesis of New Asymmetrical Pyromellitdiimides Derived From Pyromellitic Dianhydride, Ibn Al-Haitham Journal for Pure and Applied Science, 25(3): 285-286. 19. Silverstein, R. M.; Bussel, C. C. and Morrill, T.C. (1981) Spectrometric identification of Organic compounds, 4 th Edition , Academic Press , New York. 240 | Chemistry @a@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@ÚÓ‘Ój�n€a@Î@Úœäñ€a@‚Ï‹»‹€@·rÓ:a@Âig@Ú‹©@Ü‹127@@ÖÜ»€a@I1@‚b«@H2014 Ibn Al-Haitham Jour. for Pure & Appl. Sci. Vol. 27 (1) 2014 Table (1): The physical properties of N-substituted-pyromellitamic monoacid[IV]a-f Com. No. Nomenclature Structural formula Molecular formula M.P ◦C Yield % Color [IV]a N-(2-thiazole)- pyromellitamic monoacid. O CO2H C NH O O O N S C13H6N2O6S >30 0 95 Pale yellow [IV]b N-(2-benzothiazole)- pyromellitamic monoacid. O CO2H C NH O O O N S C17H8N2O6S >30 0 99 White [IV]c N-[4-(2-thiol-1,3,4- oxadiazole-5-yl)- phenyl]- pyromellitamic monoacid. O CO2H C NH O O O NN O SH C18H9N3O7S 270 dec. 89 Orange [IV]d N-(4-nitro phenyl)- pyromellitamic monoacid O CO2H C NH NO2 O O O C16H8N2O8 >30 0 96 Yellow [IV]e N-(4-chlorophenyl)- pyromellitamic monoacid. C O O O CO2H O NH Cl C16H8NO6CI >30 0 95 Pale grey [IV]f N-(4-tolyl)-pyromellitamic monoacid. C O O O CO2H O NH CH3 C17H11NO6 >30 0 98 Pale yellow Table (2): The physical properties of N- substituted- pyromellitmonoimide[V]a-f Com. No. Nomenclature Structural formula Molecular formula M.P ◦C Yield % Color [V]a N-(2-thiazole)- pyromellitmonoimide. O O O N O O N S C13H4N2O5S >300 90 Yellow [V]b N-(2-benzothiazole)- pyromellitmonoimide. O O O N O O N S C17H6N2O5S >300 78 Yellow [V]c N-[4-(2-thiol-1,3,4- oxadiazole-5-yl)-phenyl]- pyromellitmonoimide. O O O N O O NN O SH C18H7N3O6S 150- 52 84 Yellow [V]d N-(4-nitro phenyl)]- pyromellitmonoimide. O O O N NO2 O O C16H6N2O7 198- 200 91 Yellow [V]e N-(4-chlorophenyl)- pyromellitmonoimide. NO O O O O CI C16H6NO5C I 174- 76 83 Dark grey [V]f N-(4-tolyl)- pyromellitmonoimide. NO O O O O CH3 C17H9NO5 >300 60 Pale yellow 241 | Chemistry @a@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@ÚÓ‘Ój�n€a@Î@Úœäñ€a@‚Ï‹»‹€@·rÓ:a@Âig@Ú‹©@Ü‹127@@ÖÜ»€a@I1@‚b«@H2014 Ibn Al-Haitham Jour. for Pure & Appl. Sci. Vol. 27 (1) 2014 Table (3): The physical properties of (N- substituted-pyromellitmonoimide)-N─- (substitutedpyromellitamic monoacid) [VI]a-f Com.No. Nomenclature Structural formula Molecular formula M.P ◦C Yield % Color [VI]a N-(4-nitro phenyl)- pyromellitmonoimide, N─- (2-benzothiozole)]- pyromellitamic monoacid. N O O HO2C NO2 S N HN O C23H12N4O7 S 164- 66 98 Yellow [VI]b N-(4-nitro phenyl)- pyromellitmonoimide ,N─- [4-(2-thiol-1,3,4- oxadiazole-5-yl)-phenyl]- pyromellitamic monoacid. N O O HO2C HN O NO2 NN O HS C24H13N5O8 S 192- 94 96 Pale yellow [VI]c N-(4-chloro phenyl)- pyromellitmonoimide , N─-(2-benzothiazole) - pyromellitamic monoacid. N O O HO2C Cl S N HN O C23H12N3O5 SCl 138- 40 96 Pale grey [VI]d N- (4-chloro phenyl)- pyromellitmonoimide , N─- [4-(2-thiol-1,3,4- oxadiazole-5-yl)-phenyl]- pyromellitamic monoacid. N O O HO2C HN O Cl NN O HS C24H13N4O6 SCl 204- 06 93 Orange [VI]e N- (4-tolyl)- pyromellitmonoimide , N─-(2-benzothiazole)- Pyromellitamic monoacid. N O O HO2C CH3 S N HN O C24H15N3O5 S 84-86 93 Pale yellow [VI]f N-(4-tolyl)- pyromellitmonoimide , N─-[4-(2-thiol-1,3,4- oxadiazole-5-yl)-phenyl]- pyromellitamic monoacid. N O O HO2C HN O CH3 NN O HS C25H16N4O6 S 182- 83 90 Orange 242 | Chemistry @a@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@ÚÓ‘Ój�n€a@Î@Úœäñ€a@‚Ï‹»‹€@·rÓ:a@Âig@Ú‹©@Ü‹127@@ÖÜ»€a@I1@‚b«@H2014 Ibn Al-Haitham Jour. for Pure & Appl. Sci. Vol. 27 (1) 2014 Table (4): The physical properties of N,N--- disubstituted pyromellitdiimide[VII]a-f Com. No. Nomenclature Structural formula Molecular formula M.P ◦C Yield % Color [VII]a N-(4-nito phenyl), N─- (2-benzothiazole)- pyromellitdiimide NO2 S N N N O O O O C23H10N4O6 S 170- 72 90 Yellow [VII]b N-(4-nitro phenyl) N─- [4-(2-thiol-1,3,4-ox- adiazole-5-yl)-phenyl]- pyromellitdiimide. NO2 NN O HS N N O O O O C24H11N5O7 S 150- 52 87 Yellow [VII]c N-(4-chloro phenyl) N─-(2-benzothiazole)- pyromellitdiimide. Cl S N N N O O O O C23H10N3O4 SCl 178- 80 90 Yellow [VII]d N-(4-chloro phenyl) N─-[4-(2-thiol-1,3,4- oxadiazole-5-yl)- phenyl]- pyromellitdiimide. Cl NN O HS N N O O O O C24H11N4O5 SCl 118- 20 90 Yellow [VII]e N-(4-tolyl) N—-(2- benzothiazole)]- pyromellitdiimide. CH3 S N N N O O O O C24H13N3O4 S 129- 31 90 Yellow [VII]f N-(4-tolyl) N─-[4-(2- thiol-1,3,4-oxadiazole- 5-yl)-phenyl]- pyromellitdiimide. CH3 NN O HS N N O O O O C25H14N4O5 S 148- 50 85 Pale yellow Table(5): Characteristic FTIR absorption bands and UV data (λmax) of compounds[IV]a-f Comp. No. λma (nm ) VN- H VO-H VC=O cyclic anhydride asym.,sym VC=O carboxylic VC=O amid VC=N endocyc. VC=C arom. VC-O-C cyclic [IV]a 274 3302 3390- 2350 1830,1720 1690 1655 1625 1580 1055 [IV]b 248 3285 3350- 2350 1815,1780 1686 1659 1628 1591 1051 [IV]c 307 3399 3530- 2380 1838,1750 1704 1674 1609 1580 1072 [IV]d 353 3217 3540- 2410 1836,1785 1705 1632 1597 1036 [IV]e 253 3220 3350- 2500 1810,1770 1709 1640 1585 1042 [IV]f 248 3277 3400- 2500 1790,1742 1684 1655 1589 1068 243 | Chemistry @a@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@ÚÓ‘Ój�n€a@Î@Úœäñ€a@‚Ï‹»‹€@·rÓ:a@Âig@Ú‹©@Ü‹127@@ÖÜ»€a@I1@‚b«@H2014 Ibn Al-Haitham Jour. for Pure & Appl. Sci. Vol. 27 (1) 2014 Table(6): Characteristic FTIR absorption bands and UV data (λmax) of compounds [V]a-f C om p. N o. λ m a ( nm ) V C -H ar om . V C =O cy cl ic an hy dr id e as ym ., sy m . V C =O Im id e as ym ., sy m . V C =N en do cy c. V C =C ar om . V C -O -C cy cl ic V C -N -C cy cl ic A sy m ., Sy m . O th er [V]a 296 3107 1857,1782 1732,168 5 1640 1605 1066 1171,736 [V] b 276 3048 1790,1710 1744,1674 1639 1597 1038 1161,768 [V]c 302 3101 1820,1730 1765,169 5 1624 1593 1083 1151,756 VN- H:3339 VC=S:13 06 VS-H: 2522 [V]d 317 3096 1780,1745 1755,168 4 1599 1035 1178,750 4-NO2: 1506,130 4 [V]e 263 3075 1847,1775 1735,167 5 1603 1040 1171,752 4-Cl:970 [V]f 259 3060 1780,1709 1740,168 0 1603 1045 1159,756 VC-H aliphatic 2954- 2831 Table(7): Characteristic FTIR absorption bands and UV data (λmax) of compounds[VI]a-f C om p. N o. λ m ax (n m ) V N -H ar om . V O -H V C =O Im id e as ym .,s y m V C =O ca rb ox yl V C =O am id e V C =N en do cy c. V C =C ar om . V C -N -C cy cl ic as ym .,s y m O th er [VI]a 320 3277 3500- 2480 1790,174 0 1682 1641 1620 1597 1182,746 4- NO2 : 1503, 1304 [VI] b 316 3279 3480- 2515 1736,170 0 1682 1635 1616 1600 1173,748 4- NO2: 1503,1304 VN-H: 3352 VC=S:133 4 [VI]c 268 3194 3500- 2500 1755,171 5 1670 1645 1609 1595 1180,745 4-Cl : 905 [VI]d 318 3352 3520- 2400 1745,172 0 1692 1665 1618 1600 1171,745 4-Cl: 935, VN-H : 3336, VC=S:130 8 [VI]e 254 3302 3400- 2500 1738,171 5 1667 1645 1630 1604 1175,743 aliphatic: 2924-2855 [VI]f 306 3292 3400- 2450 1740,169 5 1663 1640 1612 1595 1171,752 VC-H aliphatic 2953-2868, VN- H:3352 VC=S:132 1 244 | Chemistry @a@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@ÚÓ‘Ój�n€a@Î@Úœäñ€a@‚Ï‹»‹€@·rÓ:a@Âig@Ú‹©@Ü‹127@@ÖÜ»€a@I1@‚b«@H2014 Ibn Al-Haitham Jour. for Pure & Appl. Sci. Vol. 27 (1) 2014 Table(8): Characteristic FTIR absorption bands and UV data(λmax) ofcompounds[VII]a- f Comp. No λma (nm) VC-H arom VC=O Imide asym.,sym VC=N endocyc. VC=C arom. VC-N-C cyclic Asym., Sym. Other [VII] a 300 3065 1740,1682 1730,1670 1640 1599 1178,766 1155,760 4- NO2:1506, 1304 [VII] b 308 3100 1746,1695 1732,1682 1616 1599 1179,754 1163,735 4- NO2:1503, 1304, VN-H : 3337 ,VC=S:1330 [VII] c 276 3061 1786,1696 1717,1674 1640 1597 1171,760 1160,725 4-Cl : 935 [VII]d 302 3100 1750,1695 1734,1668 1618 1593 1178,752 1165,740 4-Cl : 933 , VN-H : 3337 ,VC=S:1315 [VII]e 280 3060 1740,1697 1720,1670 1635 1602 1170,768 1160,760 aliphatic: 2970-2920 [VII]f 302 3100 1745,1695 1734,1670 1622 1593 1175,755 1170,735 aliphatic: 2928-2855, VN-H : 3339 ,VC=S:1317 245 | Chemistry @a@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@ÚÓ‘Ój�n€a@Î@Úœäñ€a@‚Ï‹»‹€@·rÓ:a@Âig@Ú‹©@Ü‹127@@ÖÜ»€a@I1@‚b«@H2014 Ibn Al-Haitham Jour. for Pure & Appl. Sci. Vol. 27 (1) 2014 وحوامض االمیك لھا المتماثلة غیر میدیاال ثنائیةالبایرومیلت مركبات ضیرتح على حلقة غیر متجانسة التي تحتوي الجدیدة جمبد ھرمز توما العلیاوي الزم كاظم ماذي عماد تقي علي جامعة بغداد / )ابن الھیثم( للعلوم الصرفة كلیة التربیة / قسم الكیمیاء 2013كانون األول 4، قبل البحث في: 2013أیلول 10استلم البحث في : الخالصة انتقائي بتفاعل a-f[VII] المتماثلة غیر االیمید ثنائیة البایرومیلت مشتقات وتشخیص تحضیر البحث ھذا تضمن األمیناتمول واحد من البایرومیلیتك ثنائي االنھدرید مع مول واحد من ةبمفاعلأربع خطوات متتابعة األولى تبدأ من مكون –4، 3، 1-امینوفنیل)-4(-5-الكیل ثایو- 2امینو بنزوثایازول و-2امینو ثایازول و -2المتنوعة ( االروماتیة األولیة باستعمال a-f[IV]تولویدین) وتكوین حوامض االمیك األحادیة -4كلورو أنیلین ، -4وأنیلین و رنایت-4اوكسادایازول و a-f[V] بایرومیلیت أحادي االیمید -Nإلى a-f[IV]الجاف مذیباً. والثانیة تحویل المركبات المحضرة األسیتونوفرة من تضمنت ف. أما الخطوة الثالثة الخلیكم في مزیج من خالت الصودیوم وانھدرید ◦) 90-80وذلك بتسخینھا بدرجة حرارة ( مع مول واحد من أمینات أولیة تحتوي حلقة غیر d-f[V]تفاعل مول واحد من مركبات البایرومیلیت أحادیة االیمید باستعمال وفرة من a-f[VI]یك اوكسادایازول) لتعطي مشتقات جدیدة من حوامض االم-4، 3، 1متجانسة (بنزوثایازول و . األسیتون الجاف مذیبا لنحصل على ستة a-f[VI] وأخیراً الخطوة الرابعة تضمنت الغلق الحلقي الضمني لحوامض االمیك األحادیة بوجود مزیج من خالت الصودیوم وانھدرید الخلیك عوامل a-f[VII]مركبات من البایرومیلت ثنائي االیمید غیر المتماثل م .◦) 90-80مساعدة وبدرجة حرارة ( لعناصر ل الدقیق تحلیلالقیاس درجات انصھارھا و باستعمال المحضرة المركبات جمیع وشخصت درست وطیف الرنین النووي البروتوني ،وطیف األشعة تحت الحمراء ،بطیف األشعة فوق البنفسجیة ق الطیفیة المتمثلةائوالطر . للبعض منھا حامض البایرمیلتامیك األحادي ,بایرومیلیتیك ثنائي االنھدرید, بایرومیلیت ثنائي االیمید الغیر متماثل الكلمات المفتاحیة : . ، بایرومیلیت أحادي االیمید 246 | Chemistry @a@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@ÚÓ‘Ój�n€a@Î@Úœäñ€a@‚Ï‹»‹€@·rÓ:a@Âig@Ú‹©@Ü‹127@@ÖÜ»€a@I1@‚b«@H2014 Ibn Al-Haitham Jour. for Pure & Appl. Sci. Vol. 27 (1) 2014