IBN AL- HAITHAM J. FOR PURE & APPL. SCI. VOL.24 (2) 2011 Synthesis and Characterization of Novel Schiff Bases Containing Isoxazoline or Pyrazoline Unit M. S. Khazaal and J. H. Tomma Department of Chemistry , College of Education Ibn Al- Haitham University of Baghdad Received in : 27 February 2011 Accepted in : 12 April 2011 Abstract This work involves synthesis of novel Schiff bases derivatives contining isoxazoline or pyrazoline units starting with chalcons . 4-Aminoacetophenone was react with p- nitrobenzaldehyde or p-chlorobenzaldehyde in basic medium giving chalcones [I]a,b by claisen- schemidt reactions. The chalcones [I]a,b were reacted with hydroxylamine hydrochloride giving isoxazolines [II]a,b in basic medium. The chalcone [I]a could also reacted with hydrazine hydrate to give pyrazolines [III]a . The novel Schiff bases with structural formula [VIII]n , [IX]n , [X]m and [XI]m were prepared by the reaction of amino compounds ; isoxazoline [II]a,b and pyrazolines [III]a with monoaldehydes [VI]n and dialdehydes [VII]m , respectively in dry benzene using drops of glacial acetic acid as a catalyst with reflux . All the synthesized compounds have been characterized by melting points , FTIR , UV-Vis and 1HMNR (of some of theme) spectroscopy. Key word : isoxazoline , pyrazoline , Schiff bases. Introduction Isoxazolines are heterocyclic organic compounds that contain oxygen and nitrogen atoms at position 1 and 2 . N O 4 5 3 2 1 The classical synthesis of the isoxazolines involves the base-catalyzed condensation of substituted aromatic ketone and substituted aldehydes to give α,β-unsaturated ketones (chalcone), which on cyclization with hydroxylamine hydrochloride in alkaline medium give the corresponding isoxazoline derivatives. (1-3). Desai et .al (4) synthesized of isoxazoline derivatives [2] from substituted chalcones [1] using hydroxylamine hydrochloride in NaOH medium using microwave . IBN AL- HAITHAM J. FOR PURE & APPL. SCI. VOL.24 (2) 2011 O N S O O N S O N O NHNH C CH O CH NaOH R R NH2OH.H Cl [1] [2] R= 4-OH , 3-OCH3 , 4-CH3 , 2-Cl Microwave pyrazolines are heterocyclic compound of five membered unsaturated ring structure composed of three carbon atoms and two nitrogen atoms at position 1 and 2 . N N H 4 3 2 1 5 Synthesis and characterization of pyrazoline(5,6) derivatives has been a developing field within the realm of heterocyclic chemistry, because of their diverse properties, fairly assessable path of synthesis, wide range of therapeutic activities and variety of industrial application, the pyrazoline and ring became a center of attraction for organic chemists. Various methods were used for the preparation of pyrazolines , treatment of α,β- unsaturated ketones with hydrazines seems to be the most popular procedure for this purpose , this reaction has been conducted under various conditions (7-12). Pyrazoline derivatives are important electron rich nitrogen heterocycles which play an important role in the diverse biological activities. These nitrogen heterocycles widely occur in nature in the form of alkaloids, vitamins, p igments and as constituents of plant and animal cells. Isoxazoline and pyrazoline derivatives remain a main focus of medicinal chemist, due to their diverse pharmacological activity. Isoxazoline and pyrazolines derivatives have been reported to possess antibacterial(11), antifungal(4,13), and antimicrobial(14,15) activity . In addition, isoxazoline derivatives have played a crucial role as intermediates in the organic synthesis of number of heterocyclic pharmacological active compounds(16). Schiff bases attract much interest both for synthetic and biological point of view (17) . Through literature survey revals that Schiff bases derived from various heterocyclic possess cytotoxic (18) , anticonvulsant , antimicrobial (19, 20) , antiproliferative (17) , anticancer (21) , and antifungal (22) activities . Depending on the above finding , we decided to synthesize novel Schiff bases containing isoxazoline or pyrazoline units. Experimental Materials : All the chemicals were supplied from Merck , GCC and Aldrich Chemicals Co. and used as received . Techniques : FTIR spectra were recorded using potassium bromide discs on a 8400s Shimadzu spectrophotometer and FTIR spectrophotometer , Shimadzo (Ir prestige-21) . 1 HNMR spectra were carried out by company : Bruker , model: ultra shield 300 MHz , origin : Switzerland and are reported in ppm(S), DMSO was used as a solvent with TMS as an internal standard . Measurements were made at chemistry depart ment, Al-albyat university , Uncorrected IBN AL- HAITHAM J. FOR PURE & APPL. SCI. VOL.24 (2) 2011 melting points were determined by using Hot-Stage, Gallen Kamp melting point apparatus. UV spectra of solutions were performed on CECL 7200 Ingland Spectrophotometer using CHCl3 as a solvent . Gene ral proce du res Compounds [VIII]n , [IX]n , [X]m and [XI]m were synthesized according to Scheme 1. x C H O NH2CCH3 x CH NH2CCH O HN N NH2O2N O N NH2X NH 2 OH . H Cl NH 2NH 2EtOH N O N NH CO2RO CH=N A X O(CH2)mON=HC A XX A CH=N O [I]a,b [III]a [VIII]n - [IX]n [X]m - [XI]m X= NO2 ,Cl A(Heterocyclic unit)= , R=CnH2n+1 , n= 1 , 3 and 4 m= 3 , 12 Dry benzene G.AA OH [II]a,b CO 2 RO CHO O (C H 2 ) m O C H O C H O Base Scheme 1 Preparation of (chalcone) 4-[3-(4`-substituted phenyl)-2-propene- 1-one]-aniline [I]a,b Equimolar quantities of 4-amino acetophenone (1.35gm , 0.01 mol) and 4-chloro benzaldehyde or 4- nitro benzaldehyde (0.01 mol) were dissolved in minimum amount of alcohol. Sodium IBN AL- HAITHAM J. FOR PURE & APPL. SCI. VOL.24 (2) 2011 hydroxide solution (0.02 mol) was added slowly and the mixture becomes cold. Then the mixture was poured slowly into 400mL of ice water with constant stirring and kept in refrigerator for 24 hrs (23) .The precipitate obtained was f iltered ,washed and recrystallized from chloroform . The physical properties are given in table 1. Preparation of 4[5-(4`-substituted phenyl)-4,5-dihydroisoxazol-3-yl ] aniline [II]a,b A mixture of chalk one [I]a or[I]b (0.02 mol), hydroxylamine hydrochloride (1.39gm , 0.02 mol) and sodium hydroxide solution (0.5 gm NaOH in 25 mL of water) in ethanol (60mL) was refluxed for 6hrs. The mixture was concentrated under vaccum and poured into ice water . The precipitate obtained was filtered , washed and recrystallized from ethanol (24) physical data are listed in Table (2.1). Preparation of 4[5-(4̀ -nitro phenyl )-4,5-dihydro-1H-pyrazol -3-yl]-aniline [III]a A mixture of chalcone [I]a , (0.01 mol) and hydrazine hydrate (05g , 0.01 mol ) in ethanol (15 mL) was heated under reflux for 6hrs . m After cooling the separated solid was filtered off ,dried and crystallized from ethanol(24) physical properties listed in Table (2.1). preparation of n-alkoxy benzoic acid [IV]n : This compound was prepared according to references (25) . n-alkoxybenzoyl Chloride [V]n : General procedure for preparation of carboxylic acid chlorides was described by A. vogel (26). Preparation of 4(4`-n-alkoxy benzoyloxy) benzaldehyde [VI]n Acid chloride [V]n (10 mmol) was added to a stirred solution of 4-hydroxy benzaldehyde (10 mmol)and dry pyridine (1mL) in dry dimethyl formamide (DM F) (10 mL) at (5-10°C). Stirring was continued for 3hrs at the same temperature . The resulting mixture was poured into 100 mL of 10% HCl . The precipitate was filtered and washed with solution of 10% NaHCO3 and water for several times (27) ,dried and recrystalized from ethanol . Preparation of polymethylene-α,ω-bis-4-oxybenzaldehydes [VII]m . These compounds were prepared following the procedure described by A. Griffin et al. (28). Synthesis of Shiff bases. Mono Shiff bases [VIII]n – [IX]n A mixture of new amino compounds [II]a,b or [III]a,b (0.01 mol) ,aldehyde [VI]n (0.012 mol) ,dry benzene (15 mL) and 2drops of glacial acetic acid was refluxed for 3hrs . The solvent was evaporated under vaccum and the residue crystallized from chloroform . The physical data of these Schiff bases are listed in Table (1) . Bis Schiff bases [X]m – [XI]m These compounds [X]m – [XI]m were obtained by using the same procedure given for the synthesis of 4chiff bases [VIII]n –[IX]n except the dialdehyde [VII]m was used instead of monoaldehyde [VI]n .The physical properties of all these bis 4chiff bases are given in Table (1). IBN AL- HAITHAM J. FOR PURE & APPL. SCI. VOL.24 (2) 2011 Results and Discussion Chalcone was chosen as the starting material for the synthesis of different heterocyclic compounds , such as : isoxazolines ,pyrazolines derivatives by using approperative reagents for that purpose . The chalcones [I]a,b are synthesized by claisen-schmidt condensation of 4-amino acetophenone and p-substituted benzaldehyde by base catalyzed followed by dehydration to yield the desire chalcones. The structural assignments of the chalcones [I]a,b based on melting points and their spectral data of FTIR,UV and ¹HNMR spectroscopy. The FTIR spectra indicated the appearance two bands in the region (3273-3483)cmˉ¹ which could be attributed to asymmetric and symmetric stretching vibration of NH2 group,a week band at 3105-3119 cm ˉ¹ due to stretching vibration of (=C-H) group, Two peaks at 1650 cmˉ¹ and 1635 cmˉ¹ due to of C=O and C=C (CH=CH) stretching vibrations,respectively. The UV-VIS spectroscopy of two chalcones [I]a and [I]b exhibited λmax at 306 nm and 341.5 nm ,respectively. The 1HNMR of chalcone [I]a shows the folloing features: two pairs of doublet of doublets in the region δ7.6-8.2 ppm which can be attributed to eight proton of two p-substituted benzene rings having different substituents at positions I,4 . A doublet band at δ 6.6 ppm due to two proton of COCH= moiety and a doublet band at δ 8.3 ppm for proton of =CHAr (1). The two protons of amine group appear as a singlet band at δ 6.24 ppm. This compound [II]a,b was synthesized from the reaction of chalcones [I]a,b with hydroxylamine hydrochloride in alkaline medium.scheme , the mechanism of this reaction (29) may be outlined as follows Scheme 2. O H N N NH2O2N H HN H O2N NH2 NH2NH2 O2N O NH2 NH2 O2N O NH2 OH NH2 O2N NH2 NHHN CH 2 O2N NH2 OHCH2 N H -H2O HN [F] [D][C] [B][A] CH CH C CH CH C H N CH C Proton Transfer CH CCH CH2 C P.T Scheme 3 O2N NH2 OHCH2 NHHN CH C [E] IBN AL- HAITHAM J. FOR PURE & APPL. SCI. VOL.24 (2) 2011 The reaction proceeds via nucleophilic attak of the hydroxyl (OH) group of hydroxyl amine upon the carbon-carbon double bond in the basic medium (NaOH) to give the carbonion intermediate [A]. Proton transfer yielded [B],followed by intramolecular addition of the amino group on carbonyl carbon of [B] whole yield the intermediate [D]. Loss of H2O gives the isoxazoline compounds [E]. The structure of the isoxazolines [II]a,b have been characterized by melting point , FTIR,UV and 1 HNMR spectroscopy. The FTIR spectra of isoxazolines [II]a,b showed the disappearance of two absorption bands of the CH=CH and C=O group in the starting material [I]a,b together with appearance of new absorption bands for C=N and C-O (cyclic ether) groups around 1628 cmˉ¹ and 1180 cmˉ¹, respectively. The UV-VIS spectroscopy of isoxazolines [II]a and [II]b exhibited λmax at 301.5 nm and 293.5 nm ,respectively. The 1HNMR spectrum of compound [II]b shows the following singals : eight aromatic proton appeared as multiplate at δ7.2-7.9 ppm , a singlet at δ 5.76 ppm due to the two protons of amino group. One proton of CH-(isoxazoline) appeared as doublet at δ 6.0-6.3 ppm. While the two protons of CH2 (isoxazoline) appears as doublet of doublet at δ 2.5 ppm (29). The chalcone [I]a was further reacted with hydrazine hydrate in ethanol absolute to yield the corresponding pyrazoline derivatives by the following reaction mechanism (30) , scheme 3. O H N N NH2O2N H HN H O2N NH2 NH2NH2 O2N O NH2 NH2 O2N O NH2 O NH2 O2N NH2 NHHN CH2 O2N NH2 OH CH2 N H -H2O HN [F] [D][C] [B][A] CH CH C CH CH C H N CH C [E] Proton Transfer CH CCH CH2 C P.T Scheme 3 O2N NH2 OH CH2 N H HN CH C [E] Condensation of chalcone with hydrazine hydrate in abs.ethanol under reflux affored the addition product [C] which followed by closure reaction led to formation new pyrazoline [F] . The structure of the pyrazoline [III]a was identified by melting point , FTIR,UV and ¹HNMR spectroscopy. The FTIR spectrum of this compound showed the disappearce of two absorption bands of the CH=CH and C=O group ,in the chalcone [I]a ,and appearance of new absorption bands of NH and C=N group at 3379 cm ˉ¹ and 1620 cm ˉ¹ ,respectively. The UV-VIS spectroscopy of pyrazoline [III]a exhibited λmax at 302.5 nm . IBN AL- HAITHAM J. FOR PURE & APPL. SCI. VOL.24 (2) 2011 The 1 HNMR spectrum of compound [III]a shows the following signals : eight aromatic protons appeared as doublets at δ 7.3-8.2 ppm,a doublet at δ 6.5-6.6 ppm that could be attributed to the one proton of NH (pyrazoline). Sharp singlet at δ 5.3 ppm due to the two protons of amino group. One proton Hx of CH-(pyrazoline) appeared as triplet (24) at δ 4.8-4.95 ppm, while the protons of CH-(pyrazoline) appears as one pair doublet of doublets at δ 3.4-3.5 ppm and δ 2.5-2.8 ppm due to two protons of Ha and Hb,respectively . The new Schiff bases [VIII]n-[XI]m were synthesized by refluxing aromatic primary amine [II]a,b or [III]a and mono-aldehyde [VI]n or di-aldehyde [VII]m in dry benzene with some drops of glacial acetic acid (GAA). These Schiff bases were identified by their melting points , FTIR , UV and ¹HNMR spectroscopy . FTIR absorption-spectra showed the disappearance of absorption bands due to NH2 and C=O groups of the starting materials together with appearance of new absorption band in the region (1625-1650) cm ˉ¹ which is assigned to C=N stretching. The other data of functional groups which are characteristic of these compounds and the UV-VIS spectroscopy data are given in Table 2. 1HMNR spectrum of Schiff base [X]12b the shows the following signals: twenty four aromatic protons appeared as doublets in the region δ 6.6-7.9 ppm , sharp singlet at δ 6.2 ppm that could be attributed to azomethine protons . A singlet signal at δ 6.1 ppm is due to one proton of (CH) isoxazoline rings , three protons triplet at δ 4.95-5.2 ppm that are attributed to OCH2 groups . Two protons of CH2 (isoxazoline) appears as doublet of doublet at δ 4.1-4.5 ppm , and a multiplet at the region δ 1.0-2.1 which were assigned to the ten aliphatic protons of (CH2)10 . References 1- Swamy ,P.and S. Agasimundin , Y. (2008) Synthesis and Antimicrobial Screening of Certain Substituted Chalcones and Isoxazolines bearing Hydroxy benzofuran , Rasayan J. Chem, 1(2):421- 428. 2- Al-Issa , S. and Hattab, A.A. (2008) “ Comparative study-reaction of 2`-Hydroxy chalcones with Hydroxyl amine Hydrochloride in different reaction medium” ,,J. Saudi Chem. Soc., 12(4): 537-542. 3- Sharma, P. ; Sharma, S.; Singh ,S. and Suresh , B. (2009) “ Synthesis of Some New Isoxazoline Derivatives Jain , as Possible Anti-Candida Agents ” , Acta Poloniae Pharmaceutica- Drug Research, 66(1) :101-104. 4- Desai, J.; Desai, C. and Desai, K. (2008) “ A convenient , Rapid and Eco- Friendly Synthesis of isoxazoline Heterocyclic Moiety Containing Bridge at 2°- Amine as Potential Pharmaological Agent ” J. Iran. Chem. Soc., 5(1): 67- 73. 5- Singhal, M. ; Verma, B.; Jhala, Y. and Dulawat, S. (2005) “ An efficient synthesis of some new fluorine containing acetyl pyrazoline and isoxazole derivatives and their antibacterial activity ” Indian J. Heterocycl. Chem., 14: 343. 6- Prajapati, A.; Bardia, R. ; Rao, T. and Verma, V. (2007) “An efficient synthesis of some new fluorine containing acetyl pyrazoline and isoxazole derivatives and their antibacterial activity” , J. Inst. Chemists , 79, 7. 7- Azarifar ,D. and Ghasemnejad, H. (2003), “Microwave-Assisted synthesis of some new 3,5- IBN AL- HAITHAM J. FOR PURE & APPL. SCI. VOL.24 (2) 2011 arylated 2-pyrazoline” , Molecules, 8:642-648. 8- Levai, A. and Jeko, (2007) “synthesis of carboxylic acid derivatives of 2-pyrazolines” , J. Arkivoc, (I),134-145 . 9- Li, J. ; Zhang X. and Lin, Z. (2007) “ an improved synthesis of 1,3,5-triaryl-2-pyrazolines in acetic acid aquieous solution under ultrasound irradiation” Beilstein Journal of Organic Chemistry, 3(13):1-4. 10- Ramesh ,B.; Prasad, Y. and Ahmed, S. (2009) “ Synthesis and antimicrobial Activity of Some Novel Pyrazoline derivatives” Pharmacologyonline 2: 327-330. 11- Rao,N. ; Kumar, R. and Srivastava , Y . (2009) “Microwave induced Synthesis and antimicrobial Activies of Some N1-morpholino ethanoyl-3,5-diaryl-2-Pyrazoline derivatives” , Rasayan J.Chem, 2(3) :716-719. 12- Venkataraman, S. ; Jain, Shah S. and Upmanyu , N. (2010) “ Synthesis and Biological Activity of Some Novel Pyrazolines” , Acta Poloniae Pharmaceutica-Drug Research , 67(4) :361- 366. 13- Dawane, S. ; Konda, G.; Shaikh, M. ;Chobe1, S. ; Khandare, T. ;Kamble T. and Bhosale , B. (2010), “ Synthesis and Invitro Antimicrobial Activity of Some New 1-thiazolyl-2- Pyrazoline Derivatives ” , Article, 1(2). 14- Jayashankara , B. and Lokanatha Rai , K. ,(2008), “ Synthesis and Evaluation of Antimicrobial Activity of A New Series of Bis (Isoxazoline) Derivatives ” , Arkivoc , (XI), 75- 85 . 15- Azarifar, D. and Shaebanzadeh , M. (2002) “ Synthesis and Characterization of New 3,5- Dinaphthyl Substituted 2-Pyrazolines and Study of Their Antimicrobial Activity” , Molecules, 7: 885-895. 16- Caramella, P. and Gruenanger , P. (1984) “1,3-Dipolar Cycloaddition Chemistry” , (Ed.), Vol. 1 Padwa, A., Wiley Interscience, New York , 337. 17- Vicini , P. ; Geronikaki , A. ; Incerti , M. ; Busonera , B. ; Ooni , G. Kabras , C. and Colla ,P. (2003) “ Synthesis and biological evaluation of benzo[d]isothiazole, benzothiazole and thiazole Schiff bases ” , Bioory .Med .Chem . 11: 4785-4789. 18- Tarafder , M. ; Kasbollah , A.; Saravan , N.; Crouse , K. ; Ali A. and Tin , O. (2002) “ S- methyldithiocarbazate and its Schiff bases: Evaluation of bondings and biological properties ” J. Biochem .Mol. Biol. Biophs , 6: 85-91. 19- Satyanarayana , V.; Srevani, P.; Sivakumar, A. and Vijayakumar, V. (2008) “ Synthesis and antimicrobial activity new Schiff bases containing coumarin moiety and their spectral characterization ”, Arkivoc , (xvii) , 221-233. 20- Kahveci , B.; Bekircan O. and Karaoglu , S. (2005) “ Synthesis and antimicrobial activity of some 3-alkyl-4-(arylmethyleneamino)-4,5-dihydro-1H-1,2,4-triazol-5-ones ” Indian J. Chem. ,44B , 2614-2617. 21- Betircan ,O.; Kahveei, B. and Kucuk , M. (2006) “Synthesis and anticancer evaluation of some new unsymmetrical 3,5-diaryl-4H-1,2,4-triazole derivatives” , Tur . J. Chem. 30:29- 40. 22- Singh ,W. and Dash , B. (1988) “Synthesis of some new Schiff bases containing thiazole and oxazole nuclei and their fungicidal activity ” , Pesticides 22:33-37 . 23- Kalirajan , R.; Sivakumar , S. ;Jubie , S. ; Gowramma, B. and Suresh, B. (2009) “ Synthesis and Biological Evaluation of Some Heterocyclic Derivatives of Chalcones” , International J. of Chem Tech Research 1(1) :27-34. 24- Abd El-Fattah, O . ;Fathalla , M.; Kassem , E. ; Ibrahem, N. and Kamel , M. (2008) IBN AL- HAITHAM J. FOR PURE & APPL. SCI. VOL.24 (2) 2011 “Synthesis and anticancer of some new quinazolin-4-one derivatives and evaluation of their antimicrobial and Anti-inflammatory effects” ,Acta Poloniae Pharm-Drug Res. 65(1):11- 20. 25- Tomma, J. and Al-Dujaili , A. (2002) “ Mesomorphic Behaviour of Some New Schiff – Bases Esters Containing 1,3,4- Oxadiazole Unit ” ,Iraqi J. Sci., 43(1) :35-57. 26- Vogel, A. (1974) “ Practical Organic Chem “Longman Group Ltd , London , 3rd Edition. 27- Al- Dujaili , A. And Tomma ,J, (2002), “ Synthesis and Liquid-Crystalline Properties Of some New 1,3,4-Thiadiazol Imines Derivatives” , J. Iraqi Journal of Chemistry , 28(2) :405-413. 28- Griffin , A. and Havens , S. (1981) “ M esogenic Polymers . III . Thermal Properties and Synthesis of Three Homologus Series of Thermotropic Liquid Crystalline “Backbone”Polyesters” , J. of Polym. Sci. Polymer Physics Edition , 19:951-969. 29- Shah ,T. and Desai , V. (2007) “Synthesis and antibacterial studies of some novel Schiff isoxazoline derivatives ” , J.Serb. Chem. So.,72(5) :443-449. 30- Al-Issa , S. A. (2007) “ Synthesis and Characterization of New 3,5-Dinaphthyl Substituted 2- Pyrazolines and Study of Their Antimicrobial Activity” , J kau. Sci , 19:67-77. IBN AL- HAITHAM J. FOR PURE & APPL. SCI. VOL.24 (2) 2011 Table (1): The physical properties of Chalcones [I] and compounds [II]-[V]. Comp. No. Nomenclature Structural formula Molecular formula M. P 0C Yield % Color [II]a 4[5-(4`-nitrophenyl)-4,5- dihydroisoxazol-3-yl]aniline O N O2N NH2 C15H13N3O3 230 50 Dark brown [II]b 4[5-(4`-chlorophenyl)-4,5- dihydroisoxazol-3-yl]aniline O N NH2Cl C15H13N2Ocl 152 55 Pale yellow [III]a 4[5-(4`-nitrophenyl)-4,5- dihy dro-1H-pyrazol-3-yl]aniline O2N HN N NH2 C15H14N4O2 150 65 Orange [VIII]1a 3[4-(p-methoxy benzoyloxy) benzylidene aminophenyl]-5-(p- nitrophenyl)-4,5- dihydroisoxazole CH3O CO2 NO2 N O CH=N C30H23N3O6 242 50 Dark orange [VIII]3a 3[4-(p-propoxy benzoyloxy) benzylidene aminophenyl]- 5-(p-nitrophenyl)-4,5- dihydroisoxazole C3H7 O CO2 NO2 N O CH =N C32H27N3O6 276 68 Dark orange [VIII]4a 3[4-(p-butoxy benzoyloxy) benzylidene aminophenyl]- 5-(p-nitrophenyl)-4,5- dihydroisoxazole C4H9 O CO2 NO2 N O CH=N C33H29N3O6 240 80 Dark orange [VIII]1b 3[4-(p-methoxyBenzoyloxy) benzylidene aminophenyl]- 5-(p-chlo ro phenyl)- 4,5dihydroisoxazole CH3O CO2 Cl N O C H=N C30H23N2O4Cl 256- 260 48 Pale yellow [VIII]3b 3[4-(p-propoxy benzoyloxy)benzy lidene aminophenyl]-5-(p-chloro phenyl)-4,5- dihydroisoxazole C3H 7O CO2 Cl N O CH=N C32H27N2O4Cl 260 80 Pale yellow [VIII]4b 3[4-(p-butoxy benzoyloxy)benzy lidene aminophenyl]-5-(p-chloro phenyl)-4,5- dihydroisoxazole C4H 9O CO2 Cl N O CH=N C33H29N2O4Cl 218- 222 50 Pale brown [IX]1a 3[4-(p-methoxy benzoyloxy) benz ylidene aminophenyl]-5-(p-nitro phenyl)-4,5-dihydro-1H- pyrazole CH3O CO2 NO2 N NH CH =N C30H24N4O5 224 70 Dark brown [IX]3a 3[4-(p-propoxy benzoyloxy) benz ylidene aminophenyl]- 5-(p-nitro phenyl)-4,5- dihydro-1H-pyrazole C3H7O CO2 NO2 N NH CH= N C32H28N4O5 248 50 Dark brown [IX]4a 3[4-(p-butoxy benzoyloxy) benzy lidene aminophenyl]- 5-(p-nitro phenyl)-4,5- dihydro-1H-pyrazole C4H9O CO2 NO2 N NH CH= N C33H30N4O5 244- 246 48 Dark brown [X]3a 1,3-bis{4-[5-(p- nitrophenyl)-4,5- dihydroisoxazol-3-yl] aniline-benzylidene -4oxy} propane O N N =CH O (CH2)3O2N ] 2[ C47H38N6O8 200 55 Brown [X]12a 1,12-bis{4-[5-(p- nitrophenyl)-4,5- dihydroisoxazol-3-yl] aniline benzylidene-4- oxy}dodecane O N N=CH O (CH 2)12O2N ] 2[ C56H56N6O8 186 70 Dark orange [X]3b 1,3-bis{4-[5-(p- chlorophenyl)-4,5- dihydroisoxazol-3-yl] aniline- benzylidene-4oxy}propane O N N=CH O (CH2)3C l ] 2[ C47H38N4O4Cl2 >300 51 Yellow [X]12 b 1,12-bis{4-[5-(p- chlorophenyl)-4,5- dihydroisoxazol-3-yl] aniline bezylidene- 4oxy}dodecane O N N=C H O (CH 2)12Cl ] 2[ C56H56N4O4Cl2 256 84 Pale yellow [XI]3a 1,3-bis{4-[5-(p- nitrophenyl)-4,5-dihydro- 1H-pyrazol-3-yl] aniline benzylidene-4oxy}propane HN N N=CH O (CH2)3O2N ] 2[ C47H40N8O6 202 53 Dark brown [XI]12a 1,12-bis{4-[5-(p- nitrophenyl)-4,5-dihydro- 1H-pyrazol-3-yl] aniline benzylidene-4oxy}propane HN N N =CH O (CH 2)12O2N ] 2[ C56H58N8O6 210 50 Dark brown IBN AL- HAITHAM J. FOR PURE & APPL. SCI. VOL.24 (2) 2011 Table (2): Characteristic FTIR absorption bands and UV data (λmax) of mono S chiff bases [XI]-[XIV]. Characteristic bands FTIR spectra (cm-1) UV data Comp. No. νC-O endocyc νC=C aromatic νC=N endoc yclic νC=N exocycli c νC=O ester νC-H aliphatic ν C-H aromatic νNH λmax (nm) in CHCl3 1261 1585 1605 1630 1724 2843-2950 3071 282 [VIII]1a 1258 1599 1601 1627 1728 2841-2969 3077 278.5 [VIII]3a 1261 1582 1601 1630 1728 2825-2959 3071 276.5 [VIII]4a 1261 1580 1601 1627 1728 2820-2960 3050 281.5 [VIII]1b 1259 1597 1600 1627 1724 2845-2960 3070 278 [VIII]3b 1261 1580 1607 1630 1726 2874-2961 3071 277.5 [VIII]4b 1582 1605 1627 1724 2871-2959 3050 3430 277.5 [IX]1a 1585 1600 1637 1724 2878-2970 3066 3418 275.5 [IX]3a 1590 1607 1627 1726 2872-2961 3071 3431 278.5 [IX]4a 1589 1600 1627 2850-2934 3050 290 [X]3a 1597 1601 1628 2851-2924 3070 287 [X]12a 1598 1605 1630 2853-2930 3055 334 [X]3b 1595 1607 1624 2851-2936 3050 294 [X]12b 1585 1600 1627 2850-2926 3050 3413 344 [XI]3a 1580 1601 1630 2851-2924 3070 3379 287 [XI]12a 2011) 2( 24المجلد والتطبیقیة الصرفة للعلوم الھیثم ابن مجلة تحضیر وتشخیص قواعد شف جدیدة تحوي على وحدة االوكسازولین او البایرازولین جمبد هرمز توما ،مصطفى سعد خزعل د ،كلیة التربیة ابن الهیثم ،قسم الكیمیاء جامعة بغدا 2011شباط 27:استلم البحث في 2011نیسان 12: قبل البحث في الخالصة ، حتوي على حلقات غیر متجانسة متنوعة مثل أوكزازولین جدیدة ت یتضمن هذا البحث تحضیر قواعد شف نایتروبنزالدیهاید -أمینو اسیتوفینون َمع بارا- 4من تفاعل] a,b]Iیحضر الجالكون ، الجالكون مادة اساسیة لاعمبایرازولین باست مع هایدروكسیل أمین ] a,b]Iیتفاعل الجالكون . شمدت-طة تفاعل كالیسیناكلوروبنزالدیهاید في وسط قاعدي بوس- َأو بارا مع الهایدرازین ] I[a، بینما یؤدي تفاعل أحد أ نواِع الجالكونات ] a,b]IIهایدروكلوراید مؤدیا الى تكوین مشتقات االیزوكزازولین a].[IIIالى تكوین البایرازولین ؛ من تفاعل مركبات حلقیة غیر متجانسة مختلفة ] XI[-m]X[mو ] n]IX[-n ]VIIIحضرت قواعد شف على التوالي في بنزین جاف ] VII[mو ألدیهایدات ثنائیة ] VI[nمع ألدیهایدات أحادیة ] III[aبایرازولین ، ] a,b]IIأوكزازولین .ید العكسي وقطرات من حامض الخلیك الثلجي مع التصع ق ائالطر فضال عن شخصت جمیع المركبات المحضرة في هذا البحث من خالل قیاس درجات أنصهارها وطیف الرنین النووي المغناطیسي البروتوني ،وطیف األشعة فوق البنفسجیة ،الطیفیة المتمثلة بطیف األشعة تحت الحمراء .)لبعض منها( قواعد شف ,بایرازولین ,اوكزازولین : الكلمات المفتاحیة للباحث االول مستل من رسالة ماجستیر