284 مجلة إبن الهيثم للعلوم الصرفة و التطبيقية 2012 السنة 25 المجلد 3 العدد Ibn Al-Haitham Journal for Pure and Applied Science No. 3 Vol. 25 Year 2012 Synthesis Of New Asymmetrical Pyromellitdiimides Derived From Pyromellitic Dianhydride E. T. Ali Department of Chemistry, College of Education, Ibn Al- Haitham, University of Baghdad Abstract This work involves the synthesis and characterization of asymmetrical pyromellitdiimide derivatives [IV]a-f by four sequence steps selective reaction . One mole of pyromellitic dianhydride was reacted with one mole of various primary aromatic amines [ 4-nitro aniline , 4-chloro aniline , 4- toludine and 4-anisidine] in excess of dry acetone to produce six compounds (N-substituted- pyromellitamic monoacid) [I]a-f . These new compounds [I]a-d were converted to the corresponding N- substituted- pyromellitmonoimide [II]a-d via their heating at (80-90) 0C in sodium acetate-acetic anhydride mixture . The compounds [II]a-f were allowed to react with one mole of another primary amines in excess of dry acetone to give new derivatives of amic acid [II]a-d followed by intramolecular cyclization reaction of these compounds [IV]a-f in sodium acetate-acetic anhydride system to yield the desired asymmetrical pyromellitdiimide derivatives [IV]a-f , the above reactions can be summarized in Scheme 1. All the synthesized compounds have been studied and charachterized by their melting points , FTIR , and 1HNMR spectroscopy (for some of them). Key words: pyromellitic dianhydride, pyromellitidiimides, pyromellitidiisoimides. 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 tetracarboxylic 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 . Morover , 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 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 [10,11]. Also they are used in microelectronics , as well as in nanotechnology as a matrix in the production of nanocomposite layers [12]. 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 [13] . The aim of this work is the synthesis of a new asymmetrical pyromillitdiimide derivatives and proved the truth of the pathway which is used for synthesis of these compounds by using opposite pathway to give the same product. 285 مجلة إبن الهيثم للعلوم الصرفة و التطبيقية 2012 السنة 25 المجلد 3 العدد Ibn Al-Haitham Journal for Pure and Applied Science No. 3 Vol. 25 Year 2012 Synthesis of Asymmetrical Pyromellitimide : Synthesis of N-substituted -pyromellitamic monoacid[I]a-d O CO2H CO NH R O O [I]a-d CH3ClNO2 ,,R = OCH3or To a solution of pyromellitic dianhydride (0.218g, 0.001 mol) in (30mL) acetone , a very dilute solution of amine (0.001 mole) in (90mL) acetone was added dropwise during about 18 hrs . After all the amine has been added the solution was filtered off from any precipitate and the clear solution was evaporated under reduced pressure and the product filtered [14], washed and recrystalized from chloroform . The physical data of N-substituted –pyromellitamic monoacid [I]a-d are listed in Table 1 . Synthesis of N- substituted- pyromellitmonoimide[II]a-d NO O O O O R [II]a-d CH3ClNO2 ,,R = OCH3or A (0.001 mole) of N-pyromellitamic monoacid was placed in (50 mL) round bottom flask fitted , 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 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 [II]a-d are listed in Table 1 . Synthesis of (N- substituted-pyromellitmonoimide)-N─- (substituted-pyromellitamic monoacid) [III]a-f [III]a-f ClNO2 CH3 N HO2C C R O H N O O R ,,, R = OCH3 OCH3 CH3 ClNO2 R= , , , To a solution of N- substituted- pyromellitmonoimide [II]d-f (0.001mol) in (30mL) acetone , A very dilute solution of amine (0.001 mole) in (90mL) acetone was added dropwise during about 18 hrs. After all the amine has been added the solution was filtered off from any precipitate and the clear solution was evaporated under reduced pressure and the residue recrystalized from acetone . The physical data of (N- substituted - pyromellitmonoimide)-N─- (substituted-pyromellitamic acid) [III]a-f are listed in Table 1 . Synthesis of N,N--- disubstituted pyromellitdiimide [IV]a-f 286 مجلة إبن الهيثم للعلوم الصرفة و التطبيقية 2012 السنة 25 المجلد 3 العدد Ibn Al-Haitham Journal for Pure and Applied Science No. 3 Vol. 25 Year 2012 NR N O O O O R [IV]a-f ClNO2 CH3 , ,, R = OCH3 OCH3 CH3 ClNO2 R= , , , These novel compounds were prepared as described in procedure which is used for the synthesis of compounds [II]. All these compounds were recrystalized from diethylether . The physical data of N,N--- disubstituted pyromellitdiimide [IV] are listed in table 1. Results and Discussion The reaction sequences leading to the formation of novel compounds of asymmetrical pyromellitdiimide [IV]a-f are outlined in the following scheme 1. [III]a-f N HO2C C R O H N O O R [IV]a-f CH3CO2Na , (CH3CO)2O R NH2 RT O CO2H CO NH R O O [I]a-d NO O O O O R [II]a-d OO O O O O RT CH3CO2Na , (CH3CO)2O R NH2 NR N O O O O R + (80-90) 0C excess of dry acetone + excess of dry acetone (80-90) 0C Scheme 1 The amic acids [I]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 [15] as follows , in scheme 2. O C C O O O O OH N R H O O O O O O R NH2 C O O O O O C O H N R H RT Acetone Scheme 2 Proton exchange The structure of these acids[I]a-f was studied by melting point , FTIR 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 (2410-3530) cm-1, C=O (carboxylic acid) at (1680-1709) cm-1 and C=O (amid) at (1630-1655) cm-1 and NH group at (3217-3277) cm-1 . And appearance of two peaks in the region (1715-1840) cm [16] which could be attributed to stretching vibration of C=O (anhydride) 287 مجلة إبن الهيثم للعلوم الصرفة و التطبيقية 2012 السنة 25 المجلد 3 العدد Ibn Al-Haitham Journal for Pure and Applied Science No. 3 Vol. 25 Year 2012 symmetry and asymmetry , in addition to the appearance of absorption band around at (1040) cm-1 for the C-O-C (cyclic) [17] . The FTIR absorption bands data of these compounds [I]a-f are listed in Table 3. N-substituted-pyromellitmonoimide [II]a-f were obtained by the intramolecular cyclization reaction of N-substituted-pyromellitamic monoacid [II]a-f in acetic anhydride and sodium acetate at (80-90) 0C . The mechanism involves nucleophilic substitution reaction [18] as follows , in scheme 3. C O O O C O O O N R H C O C CH3 H3C O O CH3CO2Na C C O O O O O O N R H C CH3 O NHO O O O O O R C CH3 O NO O OO O R [X] 850C C C O O O O O OH N R H CH3CO2H Scheme 3 The structure of these compounds [II] a-f was studied by melting point , FTIR , and 1HNMR spectroscopy. The FTIR spectra exhibited significant two peaks in the region (1675-1710) 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) [19] together with the appearance of two peaks in the region (1709-1800) cm-1 which could be attributed to stretching vibration of C=O (cyclic anhydride) symmetry and asymmetry , also the appearance of absorption band around (1040) cm-1 due to C-O-C (cyclic) . They also show the disappearance of stretching absorption bands of N-H , O-H and C=O (carboxylic moiety) groups of amic acid . The FTIR absorption bands data of these compounds [II]a-f are listed in Table 3. 1HNMR spectrum of compound [II]c showed the following characteristic chemical shift ( DMSO as a solvent) : a pair of doublet band appear at δ (7.06-7.46) ppm due to the four aromatic protons , a singlet sharp signal at δ 8.73 ppm for the two protons of centre aromatic ring . A singlet sharp signal at δ 2.23 ppm could assigned to the three protons of termenal CH3 group . The amic acids [III]a-f were synthesized by the reaction of one mole of N-substituted- pyromellitmonoimide [III]a-f with one mole of another primary aromatic amine in the presence excess of dry acetone as a solvent. R NH2 N C C O O R O O HO HNR NO O OO O R RT + The structure of these compounds [III]a-f was studied by melting point , FTIR and 1HNMR spectroscopy . The FTIR absorption-spectra showed the disappearance of absorption peaks characterized of cyclic anhydride of pyromellitmonoimides [III]a-f together with the appearance of new absorption stretching bands due to O-H of carboxylic moiety at (2420-3504) cm-1, NH amide in the region (3273-3304) cm-1 , C=O (carboxylic acid) at (1663-1692) cm-1 , and C=O (amid) at (1632-1650) cm-1. Two peaks in the region (1720-1780) cm-1 which could be attributed to 288 مجلة إبن الهيثم للعلوم الصرفة و التطبيقية 2012 السنة 25 المجلد 3 العدد Ibn Al-Haitham Journal for Pure and Applied Science No. 3 Vol. 25 Year 2012 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 FTIR absorption bands data of these compounds [III]a-f are listed in Table 4. 1HNMR spectrum of compound [III]c showed the following characteristic chemical shift ( DMSO as a solvent) : a singlet signal at δ 2.04 ppm due to the three protons of terminal CH3 group , ten aromatic protons appeared at δ (7.34-7.94) ppm . Also showed a singlet signal at δ 4.34 ppm could be attributed to the one proton of NH amide group and a good signal at δ 10.05 ppm could be attributed to the one proton of carboxylic moiety (O-H) . 1HNMR spectrum of compound [III]e showed the following characteristic chemical shift ( DMSO as a solvent) : A singlet signal at δ 3.61 ppm could assigned to the three protons of termenal OCH3 group , a singlet signal at δ 4.30 ppm could be attributed to the one proton of NH amide group . A singlet sharp signale at δ 8.19 ppm for two protons of centre aromatic ring , eight aromatic protons appeared as in the region at δ 6.57-8.60 ppm . Finally, a proton of carboxylic moiety (O-H) appeared at δ 10.54 ppm . N,N─- disubstituted pyromellitdiimide [IV]a-f were obtained by the intramolecular cyclization reaction of amic acid [III]a-f in acetic anhydride and sodium acetate at (80-90) 0C . NN O OO O RRN C C O O R O O HO HNR (CH3CO)2O , CH3CO2Na (80-90) 0C The structure of these compounds [IV]a-f was studied by melting point , FTIR and 1HNMR spectroscopy. The FTIR spectra exhibited significant two peaks in the region (1670-1786) 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 to 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 [III]a-f . The FTIR absorption bands data of these compounds [IV]a-f are listed in Table 5 . 1HNMR spectrum of compound [IV]f showed the following characteristic chemical shift ( DMSO as a solvent) : a singlet signal at δ 2.20 ppm due to the three protons of terminal CH3 group , three protons of OCH3 group appeared as a singlet signal at δ 4.77 ppm . A signal at δ 9.79 ppm due to the two protons of central aromatic ring , eight aromatic protons appeared as many signals at δ (6.85-7.71) ppm . For comparision purpose the compound [IV]c2 was also synthesized by as follows : [I]c N HO2C C O O O N O O N O O HN N O O O CH3 O O CH3 CH3Cl Cl H2NPhCl CH3COONa (CH3CO)2O 80-90 0C [V] Scheme 4 [IV]c2 The physical and spectral data of compound [IV]c1,2 which is synthesized by two ways in Scheme 1 and Scheme 4 are the same in the two cases . These data give a good evidence for the 289 مجلة إبن الهيثم للعلوم الصرفة و التطبيقية 2012 السنة 25 المجلد 3 العدد Ibn Al-Haitham Journal for Pure and Applied Science No. 3 Vol. 25 Year 2012 formation of these compounds and a prove the truth of the pathway which is used to synthesis the compounds by using opposite pathway to give the same product. References 1- Yang, R. D.; Gredig, T.; Colesniuc, C. N.; Park, J.; Schuller, I. K. ; Trogler, W. C. and Kummel, A. C. ( 2007) "Pyromellitic Diimide:Minimal cores for high Mobility n-channel transistor semiconductors" Appl. Phys. Lett. 90:263506. 2- Huang, J.; Miragliotta, J.;Becknell,A.; Katz, H. E. and Amar, J. (2007) "Pyromellitic Diimideorganic semiconductors and devices" Chem. Soc., 129: 9366. 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, K. (2005) Synthesis and study of some new N-subsitituted 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-subsitituted 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-subsitituted 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), 2006(x), 7-20. 10- Tkachenko ,V. ;Marino, A. ; Vita, F. ;DAmore, F. ;De Stefano, 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 OpticallyActive", Iran. Poly. J., 14 (3):277-285. 12- Breeze, J.;Salomone, A. ; Ginley, D. S.; Gregg, B. A. and Tillman, N. (2002) Appl. Phys. Lett. , 81 :3085 . 13- Vogel,A.I. Practical (1974) OrganicChem.,Longman Group Ltd,London 3rd Edition . 14- Al-azzawi, M. Atto; Al-ahadami, A. B. and Ali, I. (1989) The synthesis of pyromellitamic diacids and pyromellitdi-imide and their effect on the human serum cholinesterase activity in vitro", J. Biol. Sci. Res., 19(1): 84-93. 15- Dunson, D. L. (2000) Synthesis and Characterization of Thermosetting Polyimde Oligomers for Microelectronics Packing. Ph. D . thesis , Virginia Polytechnic Institute . 16- Danev ,G. and spassova, E. (2005) vacuum deposited polyimide – a perfect matrix for nanocomposite materials", J. Assa . 7(3):1179-1190. 290 مجلة إبن الهيثم للعلوم الصرفة و التطبيقية 2012 السنة 25 المجلد 3 العدد Ibn Al-Haitham Journal for Pure and Applied Science No. 3 Vol. 25 Year 2012 17- Sharma ,Y. R. (2009) Elementary Organic Spectroscopy,4th Eddition ,Ramnagar , New Delhi Ind. , 122:233. 18- Anthamatten, M. ; Stephan, A. L. ;Katherine, D. ;Robert ,C. C.;Anthony, P. G. ;Tracy , P. H. and William, K. N . (2004) "Soild – state amidization and imidization reaction in vapor- deposited poly(amic acid) J. Polym. Sci. , A 42:5999-6010 . 19- Zahmatkesh, S. and Vakili, M. R. (2010) Synthsis and characterization of new optically active poly(ethyl L- lysinamide)sSynthsis and characterization of new optically active poly(ethyl L- lysinamide)s and poly (ethyl L-lysinimide)s, Journal of Amino Acids,2010 1-6. Table (1) : Physical properties of new synthesized compounds [I]a-d - [IV]a-f Com .No. Nomenclature Structural formula Molecular formula M.P ◦C Yield % Color [I]a N-(4-nitro phenyl)- pyromellitamic monoacid O CO2H C NH NO2 O O O C16H8N2O8 >300 96 Yellow [I]b N-(4-chlorophenyl)- pyromellitamic monoacid. C O O O CO2H O NH Cl C16H8NO6C l >300 95 Pale grey [I]c N-(4-tolyl)-pyromellitamic monoacid. C O O O CO2H O NH CH3 C17H11NO6 >300 98 Pale yellow [I]d N-(4-methoxy phenyl)- pyromellitamic monoacid. C O O O CO2H O NH OCH3 C17H11NO7 >300 93 Pale Brown [II]a N-(4-nitro phenyl)]- pyromellitmonoimide. O O O N NO2 O O C16H6N2O7 198- 200 91 Yellow [II]b N-(4-chlorophenyl)- pyromellitmonoimide. NO O O O O CI C16H6NO5C l 174- 176 83 Dark grey [II]c N-(4-tolyl)- pyromellitmonoimide. NO O O O O CH3 C17H9NO5 >300 60 Pale yellow [II]d N-(4-methoxy phenyl)- pyromellitmonoimide NO O O O O OCH3 C17H9NO6 210- 212 82 Brown [III]a N-(4-chloro phenyl)- pyro mellitmonoimide, N─-(4- nitroph enyl)pyromellitamicmonoacid. N O O HO2C HN O Cl O2N C22H12N3O7 Cl 140- 142 92 Grey [III]b N-(4-tolyl)- pyromellitmonoimide ,N─- (4- nitro phenyl) -pyromellitamic monoacid. N O O HO2C CH3 HN O O2N C23H15N3O7 200- 202 90 Pale yellow [III]c N-(4-chloro phenyl)- pyromellitmonoimide , N─- (4- tolyl)-pyromellitamic monoacid. H3C N O O HO2C HN O Cl C23H15N2O5 Cl 158- 160 88 Pale grey [III]d N-(4-chloro phenyl)- pyromellitmonoimide , N─- (4- methoxy phenyl)- pyromellitamic monoacid. N O O HO2C HN O H3CO C22H15N2O6 Cl 154- 156 87 Brown [III]e N-(4-nitro phenyl)- pyromellitmonoimide , N─-(4- methoxy phenyl)- Pyromellitamic monoacid. N O O HO2C N HN O H3CO C22H12N3O8 198- 200 85 Pale brown 291 مجلة إبن الهيثم للعلوم الصرفة و التطبيقية 2012 السنة 25 المجلد 3 العدد Ibn Al-Haitham Journal for Pure and Applied Science No. 3 Vol. 25 Year 2012 Table (2): Characteristic FTIR absorption bands of compounds [I]a-d Comp. No Characteristic bands FTIR spectra (cm-1) VN-H amide VO-H VC=O cyclic anhyd. (asym, sym VC=O carboxylic VC=O amide VC=C arom. VC-O-C cyclic [I]a 3217 3540-2410 1836,1785 1705 1632 1597 1036 [I]b 3220 3350-2500 1810,1770 1709 1640 1585 1042 [I]c 3277 3400-2500 1790,1742 1684 1655 1589 1068 [I]d 3433 3480-2550 1840, 1715 1630 1590 1031 [III]f N-(4-tolyl)- pyromellitmonoimide , N─-(4- methoxy phenyl)- pyromellitamic monoacid. N O O HO2C HN O H3CO C C23H15N2O6 >300 90 Pale Brown [IV]a N-(4-chloro phenyl),N─-(4- nitro phenyl) - pyromellitdiimide. N O O N O O O2N C22H10N3O6 Cl 168- 170 88 Brown [IV]b N-(4-nitro phenyl), N─- (4-nitro phenyl) - pyromellitdiimide. N O O CHN O O O2N C23H13N3O6 220- 222 87 Yellow [IV]c 1 N-(4-chloro phenyl) , N─- (4- tolyl)-pyromellitdiimide. N O O ClN O O H3C C23H13N2O4 Cl 198- 200 81 Grey [IV]c 2 N-(4-tolyl) , N─- (4- chlorophenyl)- pyromellitdiimide. N O O N O O CH3Cl C23H13N2O4 Cl 198- 200 81 Grey [IV]d N-(4-chloro phenyl), N─-(4- meth oxy phenyl)- pyromellitdiimide. N O O ClN O O H3CO C22H13N2O5 Cl 141- 143 76 Dark brown [IV]e N-(4-nito phenyl),N—(4- methoxy phenyl)- pyromellitdiimide. N O O NO2N O O H3CO C22H10N3O7 178- 180 77 Brown [IV]f N-(4-tolyl), N─(4-methoxy phenyl)-pyromellitdiimide. N O O CH3N O O H3CO C23H13N2O5 >300 68 Brown 292 مجلة إبن الهيثم للعلوم الصرفة و التطبيقية 2012 السنة 25 المجلد 3 العدد Ibn Al-Haitham Journal for Pure and Applied Science No. 3 Vol. 25 Year 2012 Table (3): Characteristic FTIR absorption bands of compounds [II]a-d Comp. No. Characteristic bands FTIR spectra (cm-1) VC-H arom. VC=O cyclic anhydride asym.,sym. VC=O Imide, asym.,sym. VC=C arom. VC-O-C cyclic VC-N-C cyclic asym., sym. Other [II]a 3096 1780,1745 1755,1684 1599 1035 1178,750 4-NO2: 1506,1304 [II]b 3075 1847,1775 1735,1675 1603 1040 1171,752 4-Cl : 970 [II]c 3060 1780,1709 1740,1680 1603 1045 1159,756 VC-H aliphatic 2954-2831 [II]d 3067 1861,1796 1784,1726 1606 1032 1180,767 VC-H aliphatic 2980-2837 Table (4): Characteristic FTIR absorption bands of compounds [III]a-f Comp. No. Characteristic bands FTIR spectra (cm-1) VN-H amide VO-H VC=O Imide asym.,sym VC=O carboxyli c VC=O amide VC=C arom. VC-N-C cyclic asym.,sym Other [III]a 3304 3485-2650 1760,1720 1665 1632 1597 1182,754 4-NO2 : 1506,1304 [III]b 3279 3320,2700 1780,1735 1682 1650 1599 1179,751 VC-H aliphatic 2824 4-NO2:1505,1304 [III]c 3279 3310-2420 1775,1735 1682 1650 1599 1179,750 4-Cl : 968 [III]d 3304 3500-2780 1780,1740 1667 1645 1595 1170,754 4-Cl : 970 [III]e 3278 3320-2450 1765,1735 1682 1645 1599 1179,750 VC-H aliphatic 2924-2855 [III]f 3273 3504-2550 1775,1738 1680 1647 1600 1175,756 VC-H aliphatic 2953-2868 ,VN-H: 3352,VC=S:1321 Table (5): Characteristic FTIR absorption bands of compounds [IV]a-f Comp.N o. Characteristic bands FTIR spectra (cm-1) VC-H arom. VC=O Imide asym., sym. VC=C aroma. VC-N-C cyclic asym., sym Other [IV]a 3065 1740,1682 1730,1670 1599 1178,766 1155,760 4-NO2 :1506 , 1304 [IV]b 3100 1746,1695 1732,1682 1599 1179,754 1163,735 4-NO2 :1506,1304, VN-H : 3337, VC=S:1330 [IV]c 3061 1786,1696 1717,1674 1597 1171,760 1160,725 4-Cl: 935 [IV]d 3100 1750,1695 1734,1668 1593 1178,752 1165,740 4-Cl:933, VN-H: 3337, VC=S:1315 [IV]e 3060 1740,1697 1720,1670 1602 1170,768 1160,760 VC-H aliphatic 2970-2920 [IV]f 3100 1745,1695 1734,1670 1593 1175,755 1170,735 VC-H aliphatic 2928-2855 ,VN-H at 3339,VC=S:1317 293 مجلة إبن الهيثم للعلوم الصرفة و التطبيقية 2012 السنة 25 المجلد 3 العدد Ibn Al-Haitham Journal for Pure and Applied Science No. 3 Vol. 25 Year 2012 تحضير البيروميليت ثنائية االميد غير المتماثلة الجديدة المشتقة من البايروميليت ثنائي االنهيدريد عماد تقي علي جامعة بغداد،ابن الهيثم للعلوم الصرفة -كلية التربية ،قسم الكيمياء 2012تشرين األول 22قبل البحث في : 2012أيار 27استلم البحث في : الخالصة بتفاعل انتقائي مكون من a-f[VI]تضمن هذا البحث تحضير وتشخيص مشتقات البايروميلت ثنائية االيميد غير المتماثلة اربع خطوات متتابعة االولى تبدأ بمفاعلة مول واحد من البايروميليتك ثنائي االنهدريد مع مول واحد من االمينات االروماتية االولية باستعمال وفرة من a-d[I] انيسيدين وتكوين حوامض االميك االحادية-4تولودين ،و-4كلورو انلين ،و -4انلين ،وونيتر-4المتنوعة a-d[II] بايروميليت احادي االيميد -Nاالسيتون الجاف مذيبا" وبدرجة حرارة الغرفة . والثانية تحويل المركبات المحضرة الى م في مزيج من خالت الصوديوم وانهدريد الخليك . أما الخطوة الثالثة فتضمنت تفاعل ◦) 90-80وذلك بتسخينها بدرجة حرارة ( مع مول واحد من امينات اروماتية اولية متنوعة لتعطي مشتقات جديدة من a-d[II]مول واحد من مركبات البايروميليت احادية االيميد لجاف مذيبا" وبدرجة حرارة الغرفة . واخيرا" الخطوة الرابعة تضمنت باستعمال وفرة من االسيتون ا a-f[III]حوامض االميك لنحصل على ستة مركبات من البايروميلت ثنائي االيميد غير المتماثل a-f[III]الغلق الحلقي الضمني لحوامض االميك االحادية [IV]a-f م . ◦) 90-80حرارة (بوجود مزيج من خالت الصوديوم وانهدريد الخليك عوامل مساعدة وبدرجة درست وشخصت جميع المركبات المحضرة باستعمال قياس درجات انصهارها والطرائق الطيفية المتمثلة بطيف االشعة تحت الحمراء وطيف الرنين النووي المغناطيسي البروتوني (لبعض منها) . . ثنائي االميد ،بايرومليت ثنائي االيزو اميد انهدريد البايروميليمتاميك ،بايرومليت: مفتاحيةالكلمات ال