IBN AL- HAITHAM J. FOR PURE & APPL. S CI. VOL. 24 (2) 2011 Synthesis and Characterization of Novel Schiff Bases Containing Isoxazoline or Pyrazoline Unit M. S. Khazaal and J. H. Tomma Departme nt of Chemistry , College of Education I bn Al- Haitham Unive rsity of Baghdad Received in : 27 February 2011 Accepte d in : 12 April 2011 Abstract This work involves sy nthesis of novel Schiff bases derivatives contining isoxazoline or py razoline units starting with chalcons . 4-Aminoacetop henone was react with p - nitrobenzaldehyde or p -chlorobenzaldehy de in basic med ium givin g chalcones [I]a,b by claisen- schemidt reactions. The chalcones [I]a,b were r eacted with hy droxy lamin e hy drochloride givin g isoxazolines [II]a,b in basic medium. The chalcone [I]a could also reacted with hy drazine hydrate to give p y razolines [III]a . The novel Schiff b ases with st ructural formula [ VIII]n , [IX]n , [X]m and [XI]m were prep ared by the reaction of amino compounds ; isoxazoline [II]a,b and py razolines [III]a with monoaldehy des [VI]n and dialdehy des [VII]m , resp ectively in dry benzene using drops of glacial acetic acid as a cataly st with reflux . All the sy nthesized comp ounds have been characterized by meltin g p oints , FTIR , UV-Vis and 1 HMNR (of some of theme) sp ectroscopy . Key word : isoxazoline , py razoline , Schiff bases. Introduction Isoxazolines are heterocyclic or ganic comp ounds that contain oxy gen and n itrogen atoms at p osition 1 and 2 . N O 4 5 3 2 1 The classical sy nthesis of the isoxazolines involves the base-cataly zed condensation of substituted aromatic ketone and subst itut ed aldehy des to give α,β-unsaturated ketones (chalcone), which on cyclization with hy droxy lamine hy drochloride in alk aline medium give the corresp onding iso xazoline d erivatives. (1-3). Desai et .al (4) sy nthesized of isoxazoline deriv atives [2] from substituted chalcon es [1] using hy droxy lamin e hydrochloride in NaOH medium usin g microwave . IBN AL- HAITHAM J. FOR PURE & APPL. S CI. 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 -OCH 3 , 4 -CH3 , 2-Cl Microwav e py razolines are heterocyclic comp ound of five membered unsaturated ring st ructure comp osed of three carbon atoms and two nitrogen atoms at p osition 1 and 2 . N N H 4 3 2 1 5 Sy nthesis and characterization of py razoline(5,6) derivatives has been a developing field within the realm of heterocyclic chemistry , because of their diverse p rop erties, fairly assessable p ath of sy nthesis, wide range of therap eutic activities and variety of industrial application, the py razoline and ring b ecame a center of attraction for organic chemists. Various methods were used for the p rep aration of py razolines , treatment of α,β- unsaturated ketones with hy drazines seems to be the most p op ular p rocedure for this p urp ose , this reaction has been conducted under various conditions (7-12). Py razoline derivatives are imp ortant electron rich nitrogen heterocycles which p lay an imp ortant role in the diverse biolo gical activities. T hese nitrogen heterocycles wid ely occur in nature in the form of alkaloids, vitamins, p igments and as constituents of p lant and animal cells. Isoxazoline and py razoline derivatives re main a main focus of medicinal chemist, due to their diverse p harmacological activity . Isoxazoline and py razolines derivatives have been reported to p ossess antibacterial(11), antifun gal(4,13), and antimicrobial(14,15) activity . In addition, iso xazoline d erivatives h ave p lay ed a crucial role as intermediates in the or ganic sy nthesis of number of heterocyclic p harmacological active compounds(16). Schiff bases att ract much interest both for sy nthetic and biological p oint of view (17) . Through literature survey revals that Schiff bases derived from various heterocyclic p ossess cytotoxic (18) , anticonvulsant , antimicrobial (19, 20) , antip roliferative (17) , anticancer (21) , and antifungal (22) activities . Dep ending on the above finding , we decided to sy nthesize novel Schiff b ases containin g iso xazoline or p y razoline units. Experime ntal Materials : All the chemicals were sup p lied from M erck , GCC and Aldr ich Ch emicals Co. and used as receiv ed . Technique s : FTIR sp ectra were recorded using p otassium bromide discs on a 8400s Shimadzu sp ectrop hotometer and FT IR sp ectrop hotometer , Shimadzo (Ir p restige-21) . 1 HNM R sp ectra were carried out by comp any : Bruker , model: ultra shield 300 M Hz , origin : Switzerland and are reported in pp m(S), DM SO was used as a solvent with TM S as an internal st andard . Measurements w ere made at chemistry depart ment, Al-albyat univ ers ity , Uncorrected IBN AL- HAITHAM J. FOR PURE & APPL. S CI. VOL. 24 (2) 2011 meltin g p oints were determined by using Hot -Stage, Gallen Kamp meltin g p oint apparatus. UV sp ectra of solutions were p erformed on CECL 7200 Ingland Sp ectrop hotometer using CHCl3 as a s olv ent . Gene ral pr oce du res Compounds [VIII]n , [IX]n , [X]m and [XI]m w ere synth es iz ed 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 2 NH 2E tOH 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 ,C l A(H eterocyclic unit)= , R=CnH2n+ 1 , n= 1 , 3 a nd 4 m= 3 , 12 Dry benzene G.AA OH [II]a,b CO 2 RO CHO O (C H2 ) m O C H O C H O Base Scheme 1 Preparation of (chalcone) 4-[3-(4`-substi tuted phe nyl )-2-propene - 1-one]-aniline [I]a,b Equimolar quantities of 4-amino acetop henone (1.35gm , 0.01 mol) and 4-chloro benzaldehy de or 4- nitro benzaldehyde (0.01 mol) were dissolved in minimum amount of alcohol. Sodium IBN AL- HAITHAM J. FOR PURE & APPL. S CI. VOL. 24 (2) 2011 hy droxide solution (0.02 mol) was added slowly and the mixture b ecomes cold. Then the mixture was p oured slowly into 400mL of ice water with const ant stirring and kept in refrigerator for 24 hrs (23) .T he precipitate obtained was f iltered ,washed and recry st allized from chloroform . The physical prop erties are given in table 1. Preparation of 4[5-(4`-substi tuted phe nyl)-4,5-dihydroisoxazol-3-yl ] aniline [II]a,b A mixture of chalk one [I]a or[I]b (0.02 mol), hydroxy lamine hy drochloride (1.39gm , 0.02 mol) and sodium hy droxide solution (0.5 gm NaOH in 25 mL of water) in ethanol (60mL) was reflu xed for 6hrs. The mixture was concentrated under vaccum and poured into ice water . The p recipitate obtained was filtered , washed and recry st allized from ethanol (24) p hysical data are list ed in Table (2.1). Prep aration of 4[5-(4̀ -nitro p heny l )-4,5-dihy dro-1H-py razol -3-y l]-aniline [III]a A mixture of chalcone [I]a , (0.01 mol) and hy drazine hy drate (05g , 0.01 mol ) in ethanol (15 mL) was heated under reflux for 6hrs . m After coolin g the separated solid was fi ltered off ,dried and crystallized from ethanol(24) phy sical prop erties list ed in Table (2.1). preparation of n-alkoxy benzoic acid [IV]n : This comp ound was p rep ared accordin g to references (25) . n-al koxybenz oyl Chloride [V]n : General p rocedure for p reparation of carboxy lic acid chlorides was described by A. vogel (26). Preparation of 4(4`-n-al koxy benz oyloxy) benzaldehyde [VI]n Acid chloride [V]n (10 mmo l) was added to a stirred solution of 4-hy droxy benzaldehy de (10 mmol)and dry py ridine (1mL) in dry dimethy l formamid e (DM F) (10 mL) at (5-10°C). Stirring was continued for 3hrs at the same temp erature . The resulting mixture was p oured into 100 mL of 10% HCl . The p recipitate was filtered and washed with solution of 10% NaHCO3 and water for several times (27) ,dried and recry st alized from ethanol . Preparation of polymethylene-α,ω-bis-4-oxybenzaldehydes [VII] m . These comp ounds were prep ared following the p rocedure described by A. Griffin et al. (28). S ynthesis of Shiff bases. Mono Shiff bases [VIII]n – [ IX] n A mixture of new amino comp ounds [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 ref luxed for 3hrs . The solvent was evap orated under vaccum and the residue crystallized from chloroform . The physical data of these Schiff bases are listed in Table (1) . Bis S chiff bases [X]m – [XI]m These comp ounds [X]m – [XI]m were obtained by using the same p rocedure given for the sy nthesis of 4chiff bases [VIII]n –[IX]n excep t the dialdehy de [VII]m was used instead of monoaldehy de [VI]n .The phy sical prop erties of all these bis 4chiff bases are given in Table (1). IBN AL- HAITHAM J. FOR PURE & APPL. S CI. VOL. 24 (2) 2011 Results and Discussion Chalcone was chosen as the st arting material for the sy nthesis of different heterocyclic comp ounds , such as : iso xazolines ,p y razolines d erivatives by usin g app rop erative reagents for that p urp ose . The chalcon es [I]a,b are sy nthesized by claisen-schmidt condensation of 4- amino acetop henone and p-substituted benzaldehyde by base catalyzed followed by dehydration to y ield the desire chalcones. The st ructural assi gnments of the chalcones [I]a,b based on melting p oints and their sp ectral data of FT IR,UV and ¹HNM R sp ectroscopy . The FT IR sp ectra indicated the appearance two bands in the region (3273-3483) cm ˉ¹ which could be att ributed to asy mmetric and sy mmetric st retching vibration of NH2 group ,a week band at 3105-3119 cm ˉ¹ due to st retching vibration of (=C-H) group , Two p eaks at 1650 cm ˉ¹ and 1635 cm ˉ¹ du e to of C=O and C=C (CH=CH) st retching vibrations,resp ectively. The UV-VI S sp ectroscopy of two chalcones [I]a and [I]b exhibited λm ax at 306 nm and 341.5 nm ,resp ectively. The 1 HNM R of chalcone [I]a shows the folloing features: two p airs of doublet of doublets in the region δ7.6-8.2 p p m which can be att ributed to eight p roton of two p -substituted benzene rin gs h avin g d ifferent subst ituents at p ositions I,4 . A doubl et band at δ 6.6 p p m due to two p roton of COCH= moiety and a doublet band at δ 8.3 pp m for p roton of =CHAr (1). The two p rotons of amine group app ear as a singlet band at δ 6.24 pp m. This comp ound [II]a,b was sy nthesized from the reaction of chalcones [I]a,b with hy droxy lamine hy drochloride 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 N H2 N H2 NH2 O2N O N H2 NH2 O2N O NH2 OH NH2 O2N N H2 N HHN CH 2 O2N NH2 O H CH 2 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 OH CH2 NHHN CH C [E ] IBN AL- HAITHAM J. FOR PURE & APPL. S CI. VOL. 24 (2) 2011 The reaction p roceeds via nucleophilic att ak of the hy droxy l (OH) group of hy droxy l amine up on the carbon-carbon double bond in the basic medium (NaOH) to give the carbonion intermediate [A]. Prot on transfer y ielded [B],followed by intramolecular addition of the amino group on carbony l carbon of [B] whole y ield the intermediate [D]. Loss of H2O gives the isoxazoline compounds [E]. The structure of the isoxazolines [II]a,b have been characterized by melting p oint , FT IR,UV and 1 HNM R sp ectroscopy . The FT IR sp ectra of isoxazolines [II]a,b showed the disappearance of two absorp tion bands of the CH=CH and C=O group in the st arting material [I]a,b together with appearance of new absorp tion bands for C=N and C-O (cy clic ether) group s around 1628 cm ˉ¹ and 1180 cm ˉ¹ , resp ectively. The UV-VI S sp ectroscopy of isoxazolines [II]a and [II]b exh ibited λm ax at 301.5 nm and 293.5 nm ,resp ectively. The 1 HNM R sp ectrum of comp ound [II]b shows the following sin gals : eight aromatic p roton appeared as mu ltip late at δ7.2-7.9 pp m , a sin glet at δ 5.76 p p m due to the two p rotons of amino group . One p roton of CH-(isoxazoline) app eared as doublet at δ 6.0-6.3 p p m. While the two p rotons of CH2 (isoxazoline) app ears as doublet of doublet at δ 2.5 pp m (29). The chalcone [I]a was furt her reacted with hy drazine hydrate in ethanol absolute to y ield the corresp onding py razoline derivatives by the following reaction mechanism (30) , scheme 3. O H N N NH2O2N H HN H O2N NH 2 NH 2NH 2 O2N O NH2 NH2 O2N O NH2 O NH2 O2N NH 2 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 hy drazine hy drate in abs.ethanol under r eflu x affored the addition p roduct [C] which followed by closure reaction led to formation new py razoline [F] . The st ructure of the py razoline [III]a was identified by meltin g p oint , FT IR,UV and ¹HNM R sp ectroscopy . The FTIR sp ectrum of this comp ound showed the disapp earce of two absorption bands of the CH=CH and C=O group ,in the chalcone [I]a ,and app earance of new absorption bands of NH and C=N group at 3379 cm ˉ¹ and 1620 cm ˉ¹ ,resp ectively. The UV-VIS sp ectroscopy of py razoline [III]a exhibited λm ax at 302.5 nm . IBN AL- HAITHAM J. FOR PURE & APPL. S CI. VOL. 24 (2) 2011 The 1 HNM R sp ectrum of comp ound [III]a shows the following si gnals : eight aromatic p rotons app eared as doublets at δ 7.3-8.2 p p m,a doublet at δ 6.5-6.6 p p m that could be att ributed to the one p roton of NH (py razoline). Sh arp singlet at δ 5.3 pp m due to the two p rotons of amino group . One p roton Hx of CH-(py razoline) appeared as triplet (24) at δ 4.8-4.95 pp m, while the p rotons of CH-(py razoline) ap p ears as one p air doublet of doublets at δ 3.4-3.5 pp m and δ 2.5-2.8 pp m due to two p rotons of Ha and Hb,resp ectively . The new Schiff bases [ VIII]n-[XI]m were sy nthesized by refluxing aromatic p rimary amine [II]a,b or [III]a and mono-aldehyde [VI]n or di-aldehyde [VII]m in dry benzene with some drop s of glacial acetic acid (GAA). These Schiff bases were identified by their melting p oints , FTIR , UV and ¹HNMR sp ectroscopy . FTIR absorp tion-sp ectra showed the disappearance of absorption bands due to NH2 and C=O group s of the starting materials together with app earance of new absorption band in the region (1625-1650) cm ˉ¹ whi ch is assigned to C=N stretching. The other data of functional group s which are char acterist ic of these compounds and the UV-VI S sp ectroscopy data are given in Table 2. 1 HM NR sp ectrum of Schiff base [X]12b the shows the followin g si gn als: twenty four aromatic p rotons appeared as doublets in the region δ 6.6-7.9 p p m , sharp singlet at δ 6.2 pp m that could be att ributed to azomethine p rotons . A singlet signal at δ 6.1 pp m is due to one proton of (CH) isoxazoline rings , three p rotons t rip let at δ 4.95-5.2 pp m that are att ributed to OCH2 group s . T wo p rotons of CH2 (isoxazoline) app ears as doublet of doubl et at δ 4.1-4.5 pp m , and a multiplet at the region δ 1.0-2.1 which were assigned to t he ten aliphatic protons of (CH2)10 . Re ferences 1- Swamy ,P.and S. Agasimundin , Y. (2008) Sy nthesis and Antimicrobial Screen ing of Certain Subst itut ed Chalcones and Isoxazolines bearing Hy droxy benzofuran , Rasayan J. Chem, 1(2):421- 428. 2- Al-Issa , S. and Hatt ab, A.A. (2008) “ Comparative study -reaction of 2`-Hy droxy chalcones with Hy droxy l amine Hy drochloride in diff erent reaction medium” ,,J. Saudi Chem. Soc., 12(4): 537-542. 3- Sharma, P. ; Sh arma, S.; Singh , S. and Suresh , B. (2009) “ Sy nthesis of Some New Isoxazoline Der ivatives Jain , as Possible Ant i-Candida A gents ” , Acta Poloniae Pharmaceutica- Drug R esearch, 66(1) :101-104. 4- Desai, J.; Desai, C. and Desai, K. (2008) “ A convenient , Rap id and Eco- Fri endly Sy nthesis of isoxazoline Heterocyclic M oiety Containing Bridge at 2°- Amine as Potential Pharmaological A gent ” J. Iran. Chem. So c., 5(1): 67- 73. 5- Singhal, M . ; Verma, B.; Jhala, Y. and Dulawat, S. (2005) “ An efficient sy nthesis of some new fluorine contain ing acety l py razoline and isoxazole deriv atives and their antibacterial activity ” Indian J. Heterocy cl. Chem., 14: 343. 6- Prajap ati, A.; Bardia, R. ; Rao, T. and Verma, V. (2007) “An efficient sy nthesis of some new fluorine contain ing acety l py razoline and isoxazole deriv atives and their antibacterial activity ” , J. Inst. Chemists , 79, 7. 7- Az arifar ,D. and Ghasemnejad, H. (2003), “M icrowave-Assisted sy nthesis of some new 3,5- IBN AL- HAITHAM J. FOR PURE & APPL. S CI. VOL. 24 (2) 2011 arylated 2-pyrazoline” , M olecules, 8:642-648. 8- Levai, A. and Jeko, (2007) “sy nthesis of carboxy lic acid d erivatives of 2-p y razolines” , J. Arkivoc, (I),134-145 . 9- Li, J. ; Zhang X. and Lin, Z. (2007) “ an improved sy nthesis of 1,3,5-triary l-2-py razolines in acetic acid aqu ieous solution under ultrasound irradiation” Beilstein Journal of Organic Chemistry , 3(13):1-4. 10- Ramesh ,B.; Prasad, Y. and Ahmed, S. (2009) “ Sy nthesis and antimicrobial Activity of Some Nove l Py razoline derivatives” Pharmacolo gy online 2: 327-330. 11- Rao,N. ; Kumar, R. and Srivast ava , Y . (2009) “M icrowave induced Sy nthesis and antimicrobial Activies of Some N 1 -morpholino ethanoy l-3,5-diaryl-2-Py razoline derivatives” , Rasay an J.Chem, 2(3) :716-719. 12- Venkataraman, S. ; Jain, Shah S. and Up many u , N. (2010) “ Sy nthesis and Biological Activity of Some Novel Py razolines” , Acta Poloniae Pharmaceutica-Drug R esearch , 67(4) :361- 366. 13- Dawane, S. ; Konda, G.; Shaikh, M . ;Chobe1, S. ; Khandar e, T. ;Kamble T. and Bhosale , B. (2010), “ Sy nthesis and Invitro Antimicrobial Activity of Some New 1-t hiazolyl-2- Py razoline Derivatives ” , Article, 1(2). 14- Jay ashankara , B. and Lokanatha Rai , K. ,(2008), “ Sy nthesis and Evaluation of Ant imicrobial Activity of A New Series of Bis (Isoxazoline) Derivatives ” , Arkivoc , (XI), 75- 85 . 15- Az arifar, D. and Shaeb anzadeh , M . (2002) “ Sy nthesis and Characterization of New 3,5- Dinaphthy l Subst ituted 2-Py razolines and Study of Their Antimicrobial Activity ” , M olecules, 7: 885-895. 16- Caramella, P. and Gruen anger , P. (1984) “1,3-Dip olar Cy cloaddition Chemist ry ” , (Ed.), Vol. 1 Padwa, A., Wiley Interscience, New York , 337. 17- Vicini , P. ; Geronik aki , A. ; Incerti , M . ; Busonera , B. ; Ooni , G. Kabras , C. and Colla ,P. (2003) “ Sy nthesis and biological evaluation of benzo[d]isot hiazole, benzot hiazole and thiazole Schiff b ases ” , Bioory .M ed .Chem . 11: 4785-4789. 18- Tarafder , M . ; Kasbollah , A.; Sarav an , N.; Crouse , K. ; Ali A. and Tin , O. (2002) “ S- methy ldithiocarbazate and its Schiff bases: Evaluation of bondings and b iolo gical p rop erties ” J. Biochem .M ol. Biol. Biop hs , 6: 85-91. 19- Saty anarayana , V.; Srevan i, P.; Sivakumar, A. and Vijayakumar, V. (2008) “ Sy nthesis and antimicrobial activity new Schiff bases containin g coumarin moiety and their sp ectral characterization ”, Arkivoc , ( xv ii) , 221-233. 20- Kahveci , B.; B ekircan O. and Karao glu , S. (2005) “ Sy nthesis and antimicrobial activity of some 3-alkyl-4-(ary lmethy leneamino)-4,5-dihydro-1H-1,2,4-t riazol-5-ones ” Indian J. Chem. ,44B , 2614-2617. 21- Betircan ,O.; Kahveei, B. and Kucuk , M . (2006) “Sy nthesis and anticancer evaluation of some new unsy mmetrical 3,5-diaryl-4H-1,2,4-triazole derivatives” , Tur . J. Chem. 30:29- 40. 22- Singh ,W. and Dash , B. (1988) “Sy nthesis of some new Schiff bases containin g thiazole and oxazole nuclei and their fun gicidal activity ” , Pesticides 22:33-37 . 23- Kalirajan , R.; Sivaku mar , S. ;Jubie , S. ; Gowramma, B. and Suresh, B. (2009) “ Sy nthesis and Biological Evaluation of Some Heterocyclic Derivatives of Chalcones” , International J. of Chem Tech Research 1(1) :27-34. 24- Abd El-Fatt ah, O . ;Fathalla , M .; Kassem , E. ; Ibrahem, N. and Kamel , M . (2008) IBN AL- HAITHAM J. FOR PURE & APPL. S CI. VOL. 24 (2) 2011 “Sy nthesis and anticancer of some n ew quinazolin-4-one derivatives and evaluation of their antimicrobial and Ant i-inflammatory effects” ,Acta Poloniae Pharm-Drug Res. 65(1):11- 20. 25- Tomma, J. and Al-Dujaili , A. (2002) “ M esomorphic Behaviour of Some New Schiff – Bases Esters Containing 1,3,4- Oxadiazole Unit ” ,Iraq i J. Sci., 43(1) :35-57. 26- Vo gel, A. (1974) “ Practical Or ganic Chem “Longman Group Ltd , London , 3 rd Edition. 27- Al- Dujaili , A. And Tomma ,J, (2002), “ Sy nthesis and Liquid-Cry stalline Prop erties Of some New 1,3,4-Thiadiazol Imines Deriv atives” , J. Iraqi Journal of Chemistry , 28(2) :405-413. 28- Griffin , A. and Havens , S. (1981) “ M esogenic Polymers . III . T hermal Prop erties and Sy nthesis of Three Homologus Series of T hermotrop ic Liquid Crystalline “Backbone”Poly esters” , J. of Poly m. Sci. Poly mer Phy sics Edition , 19:951-969. 29- Shah ,T. and Desai , V. (2007) “Sy nthesis and antibacterial studies of some novel Schiff isoxazoline derivatives ” , J.Serb. Chem. So.,72(5) :443-449. 30- Al-Issa , S. A. (2007) “ Sy nthesis and Characterization of New 3,5-Dinap hthy l Subst ituted 2- Py razolines and Study of Their Antimicrobial Activity ” , J kau. Sci , 19:67-77. IBN AL- HAITHAM J. FOR PURE & APPL. S CI. VOL. 24 (2) 2011 Table (1): The physical propertie s of Chalcones [I] and compounds [II]-[V]. Comp. No. Nomenclatu re Stru ctu ral formul a Mol ecular formul a M. P 0C Yield % Col or [II]a 4[5-(4`-nitrophenyl)-4,5- dihydroisoxazol-3-yl]aniline O N O 2N NH2 C15H13N3O3 230 50 Dark brown [II]b 4[5-(4`-chloroph enyl)-4,5- dihydroisoxazol-3-yl]aniline O N NH2C l C15H13N2Ocl 152 55 Pale yellow [III]a 4[5-(4`-nitrophenyl)-4,5- dihy dro-1H-py razol -3-yl]aniline O2N HN N NH 2 C15H14N4O2 150 65 Orange [VIII]1a 3[4-(p-m ethoxy 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-p ropoxy 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 C 4H9 O CO 2 NO2 N O CH=N C33H29N3O6 240 80 Dark orange [VIII]1b 3[4-(p-m ethoxyBenzoyloxy) benzylidene aminophenyl]- 5-(p-chlo ro phenyl)- 4,5dihydroisoxazole CH3 O CO2 Cl N O C H=N C30H23N2O4Cl 256- 260 48 Pale yellow [VIII]3b 3[4-(p-p ropoxy benzoyloxy)ben zy 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)ben zy 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-m ethoxy 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-p ropoxy benzoyloxy) benz ylidene aminophenyl]- 5-(p-nitro phenyl)-4,5- dihydro-1H-pyrazole C3H7 O 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 C4H9 O 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-benzyliden e -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) 12O2 N ] 2[ C56H56N6O8 186 70 Dark orange [X]3b 1,3-bis{4-[5-(p- chlorophenyl)-4,5- dihydroisoxazol-3-yl] aniline- benzylidene-4oxy}propan e 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}propan e 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}propan e HN N N =CH O (CH 2) 12O2N ] 2[ C56H58N8O6 210 50 Dark brown IBN AL- HAITHAM J. FOR PURE & APPL. S CI. VOL. 24 (2) 2011 Table (2): Characteristic FTIR absor ption bands and UV data (λmax) of mono S chiff base s [XI]-[ XIV]. Ch aracte ri sti c bands FTIR spe ctra (cm-1) UV data Com p. No. νC-O endocyc νC=C aromatic νC=N endoc yclic νC=N exocycli c νC=O ester νC-H aliph ati c ν C-H aromatic νNH λ ma x (nm) in CHCl3 12 61 15 85 16 05 16 30 17 24 2843-2950 3071 282 [VIII]1a 12 58 15 99 16 01 16 27 17 28 2841-2969 3077 27 8.5 [VIII]3a 12 61 15 82 16 01 16 30 17 28 2825-2959 3071 27 6.5 [VIII]4a 12 61 15 80 16 01 16 27 17 28 2820-2960 3050 28 1.5 [VIII]1b 12 59 15 97 16 00 16 27 17 24 2845-2960 3070 278 [VIII]3b 12 61 15 80 16 07 16 30 17 26 2874-2961 3071 27 7.5 [VIII]4b 15 82 16 05 16 27 17 24 2871-2959 3050 34 30 27 7.5 [IX]1a 15 85 16 00 16 37 17 24 2878-2970 3066 34 18 27 5.5 [IX]3a 15 90 16 07 16 27 17 26 2872-2961 3071 34 31 27 8.5 [IX]4a 15 89 16 00 16 27 2850-2934 3050 290 [X]3a 15 97 16 01 16 28 2851-2924 3070 287 [X]12a 15 98 16 05 16 30 2853-2930 3055 334 [X]3b 15 95 16 07 16 24 2851-2936 3050 294 [X]12b 15 85 16 00 16 27 2850-2926 3050 34 13 344 [XI]3a 15 80 16 01 16 30 2851-2924 3070 33 79 287 [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 جامعة بغداد ،كلیة التربیة ابن الهیثم ،قسم الكیمیاء 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 مستل من رسالة ماجستیر للباحث االول