IBN AL- HAITHAM J. FOR PURE & APPL. S CI. VOL. 24 (2) 2011 Synthesis and Characterization of New Schiffs Bases Derived from D-Erythroascorbic Acid and Pyrimidines A. A. Muk hlus , M.S. Al-Rawi , J. H. Tomma , A. H. Al-Dujaili Departme nt of Chemistry , College of Education I bn Al- Haitham Unive rsity of Baghdad. Received in : 3 April 2011 Accepted in : 22 May 2011 Abstract The new C-5 schiff bases derived from D-ery throascorbic acid contaning p y rimidine unit were sy nthesized by condensation of D-ery throascorbic acid with aromatic amine (containin g p y rimidine unit)in dry benzene using glacial acetic acid as a cataly st . D-erythroascorbic acid was sy nthesized by four steps(Schem 1), while the aromatic amine which is containin g o xop y rimidine or thiopy rimidine sy nthesized by the reaction of chalcon e urea or thiourea in acid or basic medium, resp ectively . The st ructure of sy nthesized comp ounds have been characterized by their melting p oints , FTIR , UV-Vis and 1 HNM R sp ectroscopy . All the sy nthesized comp ounds have been screened for their antibacterial activities. They exhibited good antibacterial activity against Escherich ia coli (G-) and Staphy lococus aureus (G+) , while the comp ounds [V]b , [VI]b and [VII]b did not show any biological activity against this type of bacteria. Key word : Shiff bases , L-Ascorbic acid , Pyrimidines Introduction L-Ascorbic ac id is one of the most important b iomo lecules . It acts as an antioxidant and radical s cavenger widely d istributed in aerobic organisms [1]. L-Ascorbic acid derivatives have been found to possess antitumorand antivira l activit ies [2-4]. IBN AL- HAITHAM J. FOR PURE & APPL. S CI. VOL. 24 (2) 2011 Py rimidines have a great interest due to the wide variety of interest ing biolo gical activities observed for these comp ounds such as antiviral [5] , antitumor [6] , antican cer , anti- inflammetory [7] and antimicrobial [8]activities. Py rimidine nucllos ides containin g C-5 alky ny l group s have been shown to p ossess significant antiviral and anticancer prop erties[9]. Herdewijn [9] sy nthesized many C-5 substituted pyrimidine deriv atives(1) and (2) of L-ascorbic acid . These compounds exhibited antivir al and c ytostatic evaluations. HN N O O O O PhC H 2O OCH 2Ph R N NO O O PhC H 2O OCH 2Ph O C R R = A lk yl or A r yl g ro up s [ 1] [ 2] Recently , M alic and et al [10] sy nthesized anti tumor pyrimidine der ivatives of L- ascorbic acid (3) and (4) . HN N O O O O Ph CH 2 O OCH 2Ph HN N O O O O OH R RO R HO [ 3] [ 4] R = H , F , C F 3 a nd R = H or C H 3 Ali et al [11] sy nthesized carbohy drate derivatives containin g imine group as antibacterial . M ore recently , El-Say ed et al [12] and EL- Sekily [13]sy nthesized L-ascorbic acid derivatives containin g imine group at 2- and 3- p osition ,comp ounds(5) and (6), resp ectivly . O O NNHP h [5] PhHNN [6] OHH OH OH O O NNHCOP hPhCOHNN OH IBN AL- HAITHAM J. FOR PURE & APPL. S CI. VOL. 24 (2) 2011 Here in this w ork (Scheme 1) , we reported the synthesis , characterization and antibacterial activity of novel im ines of L-ascorbic acid containing pyrmidine unit. O O C NH 2 O X HN N S NH2 HN N O NH2 X X O OOH C O O HO HO HO OH [ I] [ II] [II I] [ IV] [V]a -d [VI]a-d [VI I]a-d [VII I]a-d [IX]a-d O O O O HO OH Me Me O O O O HO Me Me O2 CAr O O HO CH CH T h io u r e a N a O H ace tone d ry HCl 65% G AA Na IO4 ansoyl chloride py X CHO + C NH 2 O C H3 N aOH U rea H C l N CH HN N S X O ON CH HN N X X = 4-NO2 , 4-C l , 4-Me2 N , 3 -NO2 ; Ar= 4-CH 3OC 6H4 - Scheme 1 ArCO 2 ArCO 2 Ar CO2 ArC O2 O2 CAr O2 CAr O2C Ar O 2C ArAr CO2 O + O OOH C [ IV] ArC O2 O2 CAr + Experime ntal Mate rials : All chemicals wer e sup p lied from M erck , GCC and Aldrich Chemicals Co. and used as received . Technique s : FT IR sp ectra were recorded using p otassium bromide discs on a 8400s Shimadzu sp ectrop hotometer and FTIR sp ectrop hotometer , Shimadzo (Ir p restige-21) . 1 HNM R sp ectra were carried out by : Bruker , model: ultra shield 300 M Hz , origin : Switzerland and are r eported in pp m(S), DM SO was used as a solvent with TM S as an IBN AL- HAITHAM J. FOR PURE & APPL. S CI. VOL. 24 (2) 2011 internal st andard . M eas urements wer e mad e at chemistry depart ment, A l-alby at univers ity , Uncorrected melting p oints were determined by using Hot -Stage, Gallen Ka mp meltin g p oint app aratus. UV sp ectra of solutions were p erformed on CECL 7200 Ingland Sp ectrop hotometer using CHCl3 as a s olvent . Synthesis preparation of 5,6-O-isopropyli dene-L-ascorbic acid[I]: This comp ound was p rep ared from the reaction of L-ascorbic acid with Acetone in a acid ic media , followin g Salo mon methode [14]. Synthesis of 2,3-O-dianisoyl-5,6-O-isopropylidene-L-ascorbic acid [II]: To a cold solution of [I](10gm , 0.046mol) in p y ridine(50 mL) , Anisoy l chloride was added (17.5mL , 0.129 mol) with st irring for 2 hrs, then kept in dark p lace at room temp erature for 24 hrs.The mixture was p oured into ice-water the oil layer was extracted with (150ml) chloroform,washed with water and drived over anhydrous magnesium sulfate [15]. Filtered and the solvent evaporated, p urified from chloroform:petroleum ether(1:5) to give[II] (15gm,76.5%) as a pale yellow solid ,m.p (102-104 0 C) Rf(0.80) (benzene:methanol) (5:5). Synthesis of 2,3-O-dianisoyl-L-ascorbic acid[III]: Compound[II] (10gm, 0.0236 mol) was dissolved in a mixture of (65%) acetic acid (30ml), absolute methanol(10mL) and st irred for 48 hrs at room temp erature. To t he resulting solution a benzene(40ml) was added and evap orated to y ield[III] [16], yield (7gm, 78%) as a white cry stals, m.p (130-132 0 C), Rf (0.42) (benzene:methanol) (4:6). Synthesis of pentulosono-Lacton-2,3-ene - dianisoate[IV]: To a st irred solution of sodium p eriodate (5.6gm) in distilled water (60mL) at (0 0 C), a solution of [III] (10 gm, 0.026 mol) in absolute ethanol (60mL) was added drop wise . Aft er stirring 15 min, ethy lene glycol (0.5mL) was added and st irring for on e hour. The mixture was extracted with ethy l acetate (3x50ml)[17]. The extracts dried over anhydrouse M gSO4 , filtered and the solvent evaporated , the residue recry st allized from benzene to y ield [IV] (4 gm, 45%) as a white cry st als , m.p (156-158 0 C), Rf(0.7) (benzene: methanol) (6:4). Synthesis of chalcone: 4-[3-(4`-substituted phenyl)-2-propene-1-one]-aniline [V]a-d: Equimolar quantities of 4-amino acetop henone (0.01 mol),(1.35 g) and 4- or 3- substituted benzaldehyde (0.01 mol) were dissolved in min imum amount of alcohol. Sod ium 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 became cold. Then the mixture was p oured slowly into 400 mL of ice water with constant st irring and kept in refrigerator for 24 hrs [18]. The precipitate obtained was filtered , washed and recry st allized from chloroform . Synthesis of 4[6-(4`- substituted phenyl)-2-oxo-1,2, -di -hydropyrimidine-4- yl] aniline [VI]a-d : A mixture of chalcone[ V]a- d (0.001 mol) and urea (0.06 gm, 0.001mol ) in ethanol (20mL) and conc.hy drochloric a cid (5 mL) was refluxed for 6 hrs .The reaction mi xture was then concentrated to half of its volume .Cooled and neutralized with ammonium hy droxide. The p recipitated solid was filtered off , washed with water [19] ، dried and recry st allized from ethanol . Synthesis of 4-[6-(4`-substitute d phenyl )-2-thioxo-1,2-dihydropyrimidine-4- yl) aniline [VII]a-d : A mixture of chalcone [VI]a- d (0.001mol), thiourea (0.076gm , 0.001mo l) and sodiu m hy droxide (0.1 g) in (25 mL) of 80% (v\v) ethanol was ref luxed for 6hrs. The reaction mixture was concentrated , cooled and the solid was filtered off , washed with water[19] , dried and then cry stallized from ethanol. Physical data of comp ound[V]a- d , [VI]a- d and [VII]a- d are given in Table 1. Synthesis of Schiff bases [VIII]a-d and [IX]a-d A mixture of new amino comp ounds [VI]a- d (0.01 mol) , aldehyde [IV] (0.012 mol) , dry benzene (15 mL) and 2 drop s of glacial acetic acid was refluxed for 6hrs . The solvent was evap orated under vaccum and the residue crystallized from chloroform. The p hy sical data of all Schiff b ases are listed in Table 2. Results and Discussion 5,6-O-isop ropy lidene-L-ascorbic acid[I] was p repared by the reaction of L-ascorbic acid with acetone in dry HCl (14) . The FT IR sp ectrum showed a broad st retching band at (3240-3074) cm -1 for(O-H) viny lic, st retching bands at (2993-2908) cm -1 for (C-H) aliphatic, acetal linkage st retching band at(1755) cm -1 due to (C=O) of Lactone ring , st retching b and at(1685) cm -1 for (C=C) and st retching bands at (1141-900) cm -1 for C-O stretching . Compound [I] reacts with excess of anisoy l chloride in dry py ridine to give the corresp onding ester [II]. The FT IR sp ectrum exhibited ap p earance of s tretching band IBN AL- HAITHAM J. FOR PURE & APPL. S CI. VOL. 24 (2) 2011 (C=O) of the ester , and disappearance of the st retching bands for (O-H) of comp ound [I] , st retching bands at( 2961-2935) cm -1 for (C-H) alip hatic group , finally st retching band at (1604) cm -1 could b e attributed to (C=C) aromatic. The hydrolysis of compound [II] in acid media r esult hy drolyzed of isop ropy lidene ring to y ield 2,3-O-dianisoy l-L-ascorbic acid [III] which characterized by melting p oint and FT IR .The FTIR sp ectrum showed a band at (3445 ) cm -1 for (O-H) , a stretching at (3074) cm -1 for (C-H) aromatic. Gly cols [III] oxidized by p eriodate, which is cleav es the C5- C6 bond (bearing OH group s) and formation the aldehy de compound D-ery throascorbic acid [I V].This comp ound is characterized by meltin g p oint , FTIR,UV-VIS, M ass and 1 HNMR sp ectroscopy . The FTIR sp ectrm showed two bands at (2839-2677)cm-1 for (C-H) aldehyde stretching, a st retching band at (1715) cm -1 for (C=0) of aldehydic group , UV-Vis showed λm ax at 300 nm. M ass sp ectrum showed M +1 =413. 1 HNM R sp ectrum( δ, DM SO) showed the followin g sin gal:a singlet sign al at δ( 12.5) p p m that could be att ributed to the aldehy dic p roton. Two doublet of doublets in the region δ (7.00 – 7.97) p p m due to eight aromatic p rotons, a singlet at δ( 3.86) pp m for p roton of lactone ring at C4 . A sharp singlet at δ(3.82) pp m for the (OCH3) group . Chalcones [ V]a- d are sy nthesized by Claisen-Schmidt condensation of 4-amino aceto p henone and 4- or 3- substituted benzaldehy de by base cataly zed followed by dehydration to y ield the desire chalcons .The st ructural assign ments of the chalcones are based on meltin g p oints and their sp ectral data of FT IR ,UV-Vis and 1 HNM R sp ectroscopy . The FT IR sp ectra indicated the app earance of two bands in the region (3483-3273) cm -1 which could be att ributed to a sy mmetric and sy mmetric stretching vibration of NH2 group , a weak band at (3119-3105) c m -1 due to st retching v ibration of (CH=CH) group , two p eaks at (1650) cm -1 and (1635) cm -1 are due to of (C=O) and (C=C) st retching vibration , resp ectively. The FTIR sp ectral data and UV-Vis data for the chalcones are listed in Table( 3).The 1 HNM R of chalcon [V]a (δ , DM SO) fig (1), shows t he following features: two p airs of doublet of doublets in the region δ (7.6-8.2) pp m which can be att ributed to eight p rotons of two p -substituted of benzene ring showing d ifferent substitut ed at p ositions 1,4 . A doublet band at δ ( 6.6)pp m is due to two p rotons of (COCH=CH) [19] moiety and a doublet band at δ (8.3) ppm for proton of (=CHAr). The two protons of amine group appear as a singlet band at δ( 6.24 ) ppm. The oxop y imidine was sy nthesized from reaction of chalcone [ V]a- d with urea in acidic medium. The st ructure of the o xop y rimidine [ VI]a- d characteristic by FT IR sp ectra which are showed the disapp earance of two absorption bands of new absorp tion bands for NH,C=O (amid) and C=N (endocyclic at ( 3433) cm -1 , (1639) cm -1 and (1610) cm -1 , resp ectively. FTIR characterist ic bands and UV-Vis data of the sy nthesized comp ounds [VI]a- IBN AL- HAITHAM J. FOR PURE & APPL. S CI. VOL. 24 (2) 2011 d list ed in Table (4) . 1 HNM R sp ectrum of comp ound [VI]b fig (2) , shows the following signals: eight aromatic p rotons app eared as t wo p airs of doublet at δ (6.7-7.5) pp m and δ (7.9- 8.0) pp m , a singlet sign al at δ( 7.6) p p m could be att ributed to the one p roton of 1H (oxo- py rimidine) and a singlet at δ (7.5) p p m due to the proton of CH(oxo-py rimidine) , as sin glet broad sign al two p rotons of NH2 group appeared as δ( 5.0) pp m [19]. Thiopyrimidiens[VII]a- d were sy nthesized from the reaction of chalcon es[V]a- d with thiourea in basic medium .The st ructure of the comp ounds [VII]a-d is characterized by FTIR, UV-VI S and 1 HNM R sp ectroscopy . The characterist ic FTIR adsorption band of thiopyrimidines showed the disapp earance of two absorption bands of the (CH=CH) and (C=O) group s in the chalcon es and app earance of n ew absorp tion bands for(NH, C=N and C=S) group s around (3341)cm -1 , (1620)cm -1 and (1305) cm -1 , resp ectively[19]. The FT IR sp ectral data and the UV-Vis data of these comp ounds are shown in Table 4 . 1 HNM R sp ectrum of thiopyrimidine [VII]a- d exhibited eight aromatic p rotons appeared as many p airs of doublet at δ (6.5-7.9)p p m,a singlet si gnal at δ (6.05)p p m could be att ributed to the NH(Thiopy rimidine) and asinglet at δ (6.55)pp m for p roton of –CH(Thiopy rimidine) , A sharp singlet at δ( 6.18)pp m due to two p rotons of NH2 group . The novel Schiff b ases[VIII]a- d and [IX]a- d were sy nthesized by refluxing equemolar e of D-ery throascorbic acid [VI] with amino comp ounds of p y rimidine[VI]a- d or [ VII]a- d in dry benzene with some drop s of glacial acetic the s ixteen aromat ic protons , and a singlet signal at δ( 3.86)ppm that could be attributed to the proton at C4 of Lactone ring. Biological Activity The antibacterial activity of the sy nthesized comp ounds was p erformed accordin g to the agar diffusion method [20]. The p rep ared comp ounds were tested against E.coli and Staph. aureus .Each compounds was dissolved in DM SO to give concentration 1p p m. The p lates were then incubated at 37 0 C and examined after 24 hrs. The zones of inhibition formed were measured in millimeter and are r epresented by (-), (+), (+ +) and (+ + +) dependin g up on the diameter and clarity as in Table (6). All the comp ounds exhibit the highest or low biolo gical activity while the comp ounds[V]b , [VI]b , and [VII]b showed no activity against both the organisms, and compound [VI]d d id not show activity against only (G+) . The comp ounds showed good inhibition against of the two types of the bacteria, this could be related to the p resence of the D-ery throascorbic acid , oxop y rimidine , thiopyrimidine and imine linkage. IBN AL- HAITHAM J. FOR PURE & APPL. S CI. VOL. 24 (2) 2011 Re ferences 1.Du ,c.; Liu , j.; Su, w.; Ren, y . and Wei, d. (2003) "The p rotective effect of ascorbic acid derivative on PC12 cells,Involvement of It s ROS scavenging ability " , Life Sci. , 74 :771-780. 2. Tanuma, S.; Sh iokawa, D.; Tanimoto,Y.; Ikekita, M . and Takeda , M .,(1993). "Benzy lidene ascorbate induces apop tosis in L929 Tumor cell, Biochem, Biop hy s, Rrs, Commun., 194 :29- 35. 3. Velr i, R.; Fodor, G.; Liu, C. and Woolv erton , C. (1986) "A new class of sy nthetic biolo gical r esp onse modifiers,t he methy lfuryl butyrolactones" , J. Biol, Res. M od. , 5: 444- 461. 4. Woolverton,C.; Veltri, R.and Sny der , I. (1986) "Stimulation of human p mn in vitroi by asuccinimide molecular comp lex of methy lfuryl butyrolactones", J.Biol,Res.M od., 5 :527-538 . 5. Nasr, M . and Gineinah, M . , (2002) "Py rido[2,3-d]py rimidin py rimido[5’,4’:5,6]- py rido[2,3-d] py rimidines as new antiviral agents: Sy nthesis and biolo gical activity " Arch.p harm., 335 :289-295. 6. Baraldi, P.; Pavani, M .; Nunez, M .; Brigidi, P. ; Vitali, B.; Gambari, R. and Romagnoli R. (2002)" Ant imicrobial and antitumor activity of N-heteroimine-1,2,3- diathiazoles and their transformation in triazolo-, imidazo- and py razolopy rimidines" .Bio.org.M ed.Chem. 10: 449-456. 7. Sondhi, S.; Johar, M .; Rajvanshi,S.; Dast idar, G. ; Shukla, R.; Raghubir , R. and Lown, J. (2001)" Ant icancer, anti-inflammatory and analgesic activity evaluation of heterocyclic comp ounds sy nthesized by the reaction of 4-isothiocy anato-4-methy lp entan-2-one with substituted o-p heny lenediamines, o-diaminop y ridine and (unsubstituted o-diamino- py rimidines". Austr. J. Chem. , 54: 69-74. 8. Chowdhury , A.; M atin , M .; and Anwar, M . (1997) "Sy nthesis and antimicrobial activities of fused py rimidines: Benzot hieno[2,3- d]imidazol[1,2-c] p y rimidine", Chitt agon g. Chitt agong Univ. st ud. Part(II) , 21 :79-83. 9. Herdewijn,P. (1994) "5-substituted-2-deoxy uridines as anti-HS V-1 Agents : synthesis and structure-activity relationship, Ant ivira l Chem,Chemother". 5: 131-146. 10. Malic, S.; Sverdnzic, D.; Gazivoda , T. and Marunovic, A.(2000) "Synthesis and antitumor ac tivities of novel pyrimidine der ivatives of 2,3-O,O-Dibenzyl-6- deoxy-L-Ascorbic ac id",J. Med. Chem. 43: 4806-4811. IBN AL- HAITHAM J. FOR PURE & APPL. S CI. VOL. 24 (2) 2011 11. Ali, U .; AL-Rawi , A. and AL-Rawi , M. (1998) "Sy nthesis of some new Schiff bases derived from glucosamine of p ossible anti microbial activity " J.Drrasat,Natural and Engineer ing scien ces,25(1):95. 12. El- Sayed , H. ; At ta , K. ; Aboul-Ela , S. and B eldi , R. (2007)" M icrowave Assist ant sy nthesis of M ono- and Bis- Pheny lhy drazones of L-Threo-and-D-Erythro-2,3- Hexodiulosono-1,4-Lactones for The Sy nthesis of an Array of Heterocy clic Compounds", Jordan J. of Chemist ry , 2(1): 117-124. 13. EL- Sekily , A. (2008) "Hy drogenation p roducts from dehydro-D-Ery thro- and L-Threo- Ascorbic acids mono- and b ishy drazones".,The Arabian Jou.for scien ce and engineer ing,33(1A), 7-13. 14. Salo mon, L.(1963) Exp erientia ,19(12) :619. 15. Jwad, R. (2006) "Sy nthesis of new oxazep ine derivatives st arting from L-ascorbic acid", Thesis , Education College Ibn Al-Haitham, University of Baghdad. 16. Loudon, G. (2002) "Organic Chemistry ",4th Ed.,Oxford University p ress,Inc.,New York, ,855-856,869 and 873. 17. Al-Ogiady , R. (2010)"Sy nthesis of new M alonate and Barbiturate derivatives of D- Erythroascorbic acid and their M etal comp lexes",Ph.D.Thesis, Education College Ibn Al- Haitham ,University of Baghdad. 18. Kalirajan , R.; Sivakumar, S. ; Gowramma , S. ; Jubic, B. and Saresh , B. (2009) International J. Chem.Tech Res.,1(1): 27-34. 19. Fathalla , O . ; Awad, S. and M ohamed, M . (2005) "Sy nthesis of new 2-Thiouracil-5- Sulphonamide d erivatives with Anty bacterial and Ant i Fungl activity ",Arch p harm Res.,28(11):1205-1212. 20. Allawy , H. (2000) "Sy nthesis of some new bis-1,4-substituted butane derivatives containin g 1,3,4-O xadiazole or 1,2,4-Trizole unit", M .Sc Thesis, Education Colle ge Ibn Al- Haitham,Baghdad University . IBN AL- HAITHAM J. FOR PURE & APPL. S CI. VOL. 24 (2) 2011 Table(1):The physical propertie s compounds[V]a-d,[VI]a-d and [VII]a-d. Color Yield % M.P C 0 Molecular Form ula Struc tural Form ula Nom enca lture Comp. No. Orange 90 210 C1 5 H12 N2 O3 CH NHC O CHO 2N 4[3- (4`-nitropheny l)-2- prope ne-1- one] a niline [V]a Ye llow 75 164 C1 5 H12 NOCl CH NHC O CHCl 4[3- (4`-chloropheny l)-2- prope ne-1- one] a niline [V]b Red 60 140 C1 7 H18N2 O CH NC O CHMe 2N 4[3- (4`-N,N- dim ethy lpheny l)- 2-pr opene- 1-one] aniline [V]c Da rk Orange 80 204 C1 5 H12 N2 O3 CH NC O CH O2N 4[3- (3`-nitropheny l)-2- prope ne-1- one] a niline [V]d Orange 70 214- 218 C1 6 H12 N4 O3 HN N NHO2N O 4[6- (4`-nitropheny l)-2-oxo- 1, 2-dihy dro- py rim idine-4- y l]aniline [VI] a Ye llow 55 208 C1 6 H12 N3 OC l HN N O NCl 4[6-(4`-chloropheny l)-2-oxo- 1,2-dihy dro- py rim idine-4- y l]aniline [VI]b Red 50 212 C1 8 H18 N4 O HN N NMe2 N O 4[6- (4`-N,N- dim ethy l pheny l)- 2-oxo- 1, 2-Dihy dro py rim idine -4-y l] aniline [VI] c Orange 70 197 C1 6 H12 N4 O3 HN N O O2N 4[6- (3`-nitropheny l)-2-oxo- 1, 2-Dihy dropy rim idine -4-y l] aniline [VI]d Pale brown 60 276 C1 6 H12 N4 O2 S HN N O2N S 4[6- (4`-nitropheny l)-2-thioxo- 1, 2-dihy dro- py rim idine-4- y l]aniline [VII]a Ye llow 65 200 C1 6 H12 N3 SCl HN N C l S 4[6- (4`-chloropheny l)-2- thioxo-1, 2-Dihy dro py rim idine -4-y l] aniline [VII] b Ye llow 50 162- 164 C1 8 H18 N4 S HN N NMe 2N S 4[6- (4`-N,N- dim ethy l pheny l)- 2-thioxo-1, 2-Di hy dro py rim idine -4-y l] aniline [VII]c Brown 50 150 C1 6 H12 N4 O2 S HN N S O2N 4[6- (3`-nitropheny l)-2-thioxo- 1, 2-Dihy dro py rim idine -4-y l] aniline [VII] d IBN AL- HAITHAM J. FOR PURE & APPL. S CI. VOL. 24 (2) 2011 Table(2):The physical propertie s compounds [VIII]a-d an d [IX]a-d. Col or Yield % M.P 0C Mol ecular formula Rf Stru ctu ral formul a Comp. No. Yello w 50 185- 187 C37H26O11N4 0.31 O O ArCO 2 O 2 CAr N CH HN N O O 2 N [VIII]a Brow n 55 190 C37H26O9N3Cl 0.35 O O ArCO 2 O 2 CAr N CH HN N O Cl [VIII]b Brow n 50 >30 0 C39H32O9N4 0.16 O O ArCO 2 O 2CAr N CH HN N O Me 2 N [VIII]c Oran g 60 124- 126 C37H26O11N4 0.36 O O ArCO 2 O 2 CAr N CH HN N O 2N O [VIII]d Brow n 55 >30 0 C37H26O10N4S 0.37 O O ArCO 2 O 2 CAr N CH HN N S O 2 N [IX]a Brow n 50 >30 0 C37H26O8N3Cl S 0.47 O O ArCO 2 O 2CAr N CH HN N Cl S [IX]b Red 60 170 C39H32O8N4S 0.28 O O ArCO 2 O 2 CAr N CH HN N S Me 2 N [IX]c Yello w 65 144 C37H26O10N4S 0.21 O O ArCO 2 O 2 CAr N CH HN N O 2N S [IX]d IBN AL- HAITHAM J. FOR PURE & APPL. S CI. VOL. 24 (2) 2011 Tabl e (3) :Ch arcte rrisiti c FTIR absorption band an d UV dat a ( λ m ax) of compound [V] Table(4):Characteristic FTIR a bsor ption bands and UV data (λmax) of compounds [ VI]a- d and[VII]a-d Characteristi c bands FTIR sp ectra (cm-1) UV data Comp. No. others νC=S νC=C aromatic νC=N endocycli c νC=O amid e νC-H aromat ic νNH 2 asy . , sy . and νNH λ ma x (nm)in CHCl 3 4-NO2 :1 508 ,1343 1589 1610 1640 3100 34 84,3387,3256 30 7 [VI]a 4-Cl:1080 1605 1630 1645 3053 34 60,3342,3217 31 8.5 [VI]b 4-N(Me)2:1168 1567 1610 1643 3036 34 25,3390,3213 33 9 [VI]c 3-NO2 :1346 1609 1636 1645 3094 34 72,3418,3341 27 9 [V I]d 4- NO2:1512,1338 1312 1597 1628 3067 34 60 , 33 33,3221 35 4.5 [VII]a 4-Cl:1087 1288 1597 1620 3050 34 56,3341,3221 31 9.5 [VII]b 4-N(Me)2:1168 1304 1597 1620 3053 34 76,3433,3329 40 8.5 [VII]c 3-NO2:1346 1308 1589 1628 3086 34 10,3383,3360 26 6 [VII]d Characteristi c bands FTIR sp ectra (cm-1) UV data Comp. No. others νCH=CH νC=O νNH 2 asy . , sy . λ ma x (nm) in CHCl3 4-NO2 :1504,1 342 1635 1650 3483 , 3387 30 6 [V]a 4-Cl:1089 1632 1670 3385-3273 34 1.5 [V]b 4-N(Me)2 :1165 1630 1662 3480-3236 34 2.5 [V]c 3-NO2:1346 1632 1651 3426-3333 28 4.5 [V]d IBN AL- HAITHAM J. FOR PURE & APPL. S CI. VOL. 24 (2) 2011 Tabl e (5):Ch aracte risti c FTIR abs orption ban ds and UV data (λmax) of compounds [VII]a-d and [IX]a-d Table(6): Anti bacterial activity of the prepared compounds Key to symbols: Highl y active = + + +(mor than)15 mm. Moderatel y active = + +(11-15) mm. and Slightly active = + (5-10) . Chara cter istic ba nds FTIR spec tra (cm-1) UVda ta Comp. No. νC- O νC=S νC= C ar o m . νC=N endocy c. νC=N exocy c . νC=O am id νC=O ester VC=O Lacton νC-H aliph. ν C-H ar om . νN H λmax(nm ) in CHCl3 1263 1602 1615 1637 1653 1738 1760 2982-2847 3052 3390 258 [VIII]a 1261 1590 1605 1630 1659 1735 1767 2962-2839 3059 3417 234 [VIII]b 1257 1585 1605 1640 1650 1715 1766 2978-2839 3060 3402 258.5 [VIII]c 1237 1580 1605 1632 1642 1724 1770 2984-2878 3059 3337 268.9 [VIII]d 1257 1310 1601 1610 1630 1645 1720 1766 2962-2843 3078 3348 252.6 [I X] a 1261 1300 1585 1605 1627 1650 1730 1766 2981-2843 3050 3406 261 [I X] b 1258 1305 1580 1600 1630 1642 1715 1766 2908-2949 3078 3383 258.5 [I X] c 1263 1304 1580 1605 1627 1645 1720 1769 2982-2843 3059 3368 252.4 [I X]d St aph.aureus (G+) E.Coli (G-) Comp. No. St aph.aurus (G+) E.Coli (G-) Comp. No. + + + + + [VIII]a + + + + + [V]a + + + + + + [VIII]b - - [V]b + + + + + + [VIII]c + + + + [V]c + + + + + + [VIII]d + + + + ++ [V]d + + + [IX]a + + + + [VI]a + + + + + + [IX] b - - [VI]b + + + + + + [IX] c + + + + + + [VI]c + + + + + + [IX]d - + [V I]d + + + + [IV] + + + + + [VII]a - - [VII]b + + + [VII]c + + + + + + [VII]d IBN AL- HAITHAM J. FOR PURE & APPL. S CI. VOL. 24 (2) 2011 Fig. (1): 1 HNMR- spectrum of compound[V]a Fig . (2): 1 HNMR-spectrum of compound[VI]b IBN AL- HAITHAM J. FOR PURE & APPL. S CI. VOL. 24 (2) 2011 Fig .(3): FTIR-s pectrum of compound[ VIII]d Fig .(4) : 1 HNMR-spectrum of compound[VIII]a 2011) 2( 24المجلد مجلة ابن الھیثم للعلوم الصرفة والتطبیقیة ارثرو اسكوربیك - Dتحضیر و تشخیص مشتقات جدیدة من قواعد شف لحامض و البیرمیدین عمار ھاني الدجیلي، جمبد ھرمز توما ، منى سمیر الراوي ، عبد الجبار عبد القادر مخلص جامعة بغداد ، ابن الھیثم –كلیة التربیة ، سم الكیمیاء ق 2011نیسان 3: في استلم البحث 2011آیار 22: قبل البحث في الخالصة ي - Dحضرت المركبات الجدیدة لقواعد شف المشتقة من حامض ارثرو اسكوربیك مع مركبات البیریمیدین الت ي البنزین ) المحتویة على وحدة البیرمیدین(ارثرواسكوربیك مع االمینات االروماتیة - Dحضرت من تكاثف حامض ف ي محفزا ت - Dحضر الحامض . الجاف وباستعمال قطرات من حامض الخلیك الثلج ارثرواسكوربیك باربع خطوا ل الجالكونات مع ) 1(متتالیة كما في المخطط رقم ط بینما حضر االمین االروماتي من تفاع الیوریا او الثایوریا في وس .حامضي او قاعدي وعلى التوالي FTشخصت جمیع المركبات المحضرة بقیاس درجات انصھارھا وبوساطة طیف IR UV-Vis, وطیف 1 HNM R . ة د نوعین من البكتریا واظھرت النتائج فعالیة بایولوجی محضرة ض درست الفعالیة البایولوجیة للمركبات ال Staphy.یدة ضد البكتریا بنوعیھا ج lococcus (G+) ,Echerichia coli (G-) ات بینما لم تظھر المركب[V]b , [VI]b , [VII]b نوع من البكتریا .اي فعالیة بایولوجیة ضد ھذا ال . بیرمیدین ,حامض االسكوربیك , قواعد شف : الكلمات المفتاحیة