Microsoft Word - 4 350 | Chemistry 2014) عام 3(العدد 27المجلد مجلة إبن الھيثم للعلوم الصرفة و التطبيقية Ibn Al-Haitham Jour. for Pure & Appl. Sci. Vol. 27 (3) 2014 Synthesis and Characterization of Some New Thiazine , Azetidine and Thiazolidine Compounds Containing 1,3,4- Thiadiazole Moiety And Their Antibacterial Study. Ali H. Samir Khalid F. Ali Ruwaidah S. Saeed Dept. of Chemistry/College of Education for Pure Science (Ibn Al- Haitham)/University of Baghdad Received in: 17 March 2014,Accepted in: 22 june 2014 Abstract 2-amino-5-mercapto-1,3,4-thiadiazole [I] were prepared by the cyclization of thiosemecarbazide with carbon disulphide and anhydrous sodium carbonate in ethanol as a solvent. The reaction of compound [I] with alkyl halides yielded 2- amino-5-thioalkyl-1,3,4- thiadiazole [II] and [III] . Compound [II] and [III] were reacted with different aromatic aldehydes to yieled 2-[(substituted benzyliden ) amino] -5- thioalkyl-1,3,4- thiadiazole [IV]a-c , [V]a-d and [VI]a-d . Schiff ,s bases [IV]a-c , [V]a-d and [VI]a-d were found to react with 2- mercapto benzoic acid in the triethyl amine to give 3-[ 5-( alkylthio) -1,3,4- thiadiazol-2-yl] - 2,3- dihydro- 2- (aryl) benzo [e] [1,3] thiazine -4-one [VII]a-c and [VIII]a . The Schiff ,s bases reacted with chloro acetyl chloride in the triethyl amine to give 3-chloro-1-(5-alkylthio)-1,3,4- thiadiazole-2-yl)-4-(aryl)azetidine-2-one[IX]a,b , [X]c and [XI]c,d .Also Schiff ,s bases reacted with 2-mercapto acetic acid in dry benzene to give 3-(5-mercapto-1,3,4-thiadiazole-2-yl)-2- (aryl)thiazolidine-4-one[XII]a,c ,[XIII]d and [XIV]]c,d. The structures of the newly synthesized compounds were confirmed by physical properties and spectral (UV-Vis , FT-IR and 1H-NMR) analysis. Key Words: 1,3,4-Thiadiazole , Thiazine-4-one, Azetidine-2-one , Thiazolidine-4-one . *This paper is part of master thesis of the third author . 351 | Chemistry 2014) عام 3(العدد 27المجلد مجلة إبن الھيثم للعلوم الصرفة و التطبيقية Ibn Al-Haitham Jour. for Pure & Appl. Sci. Vol. 27 (3) 2014 Introducation A heterocyclic compound is one which possesses a cyclic structure with at least two different of hetero atoms in the ring. Nitrogen , Oxygen and Sulphur are the most common heteroatoms . Heterocyclic compounds are very widely distributed in nature and the essential to life in various ways. Most of the sugars and their derivatives , including vitamin C , for instance , exist in the form of five-membered(Furan) or six-membered(Pyran) rings containing one oxygen atom . Most members of vitamin B group possess heterocyclic ring containing nitrogen . One example is vitamin B6 (Pyridoxine) , which is a derivative of Pyridine , essential in amino acid metabolism[1]. Thiadiazoles have occupied an important place in drug industry ; 1,3,4-thiadiazoles have wide applications in many fields . The earliest uses were in the pharmaceutical area some of the later uses are as antitumor and anti-inflammatory agents . Pesticides , dyes , lubricants and analytical reagents [2]. Azetidine is a hydrolytically sensitive , four membered cyclic amide , which is present in clinically useful penicillins and cephalosporin . The N-CO distance of 1.38 Ao this has been attributed to ring strain and to inhibition of normal amide interaction. They are commonly known as β-lactams , are well known heterocyclic compounds among the organic and medicinal chemists . Azetidine is an important four-membered heterocyclic β-lactam compound because it is a part of penicillin group compounds which fused with thiazolidine compound[3]. Thiazolidinones are an importartant group of heterocyclic compounds , having diverse biological uses as antibacterial[4] anticonvulsant[5] , anti-inflammatory[6,7] , FSH receptor agonist[8] , anticancer[9] , antiviral[10] , antifungal [11] and antihistaminic activities [12,13] . Materials and Methods Experimental All the chemicals used in the synthesis were of analytical grade . The melting points were determined in open capillary on Digimelt MPA 161 (MSRS) electronic apparatus and are uncorrected. The IR spectra of synthesized compounds were recorded on Shimadzu FT-IR 8400 spectrophotometer using potassium bromide. To monitor the reactions , as well as , to establish the identity and purity of reactants and products , thin layer chromatography was performed on microscopic glass slides coated with silica gel , using toluene-acetone , benzene-ether and chloroform-methanol , as the solvent systems and spots were visualized under UVradiation. Nuclear magnetic resonance spectra were recorded on Bruke, model:Ultra shield 300 MHZ , model spectrometer using DMSO as a solvent and TMS as internal reference (chemical shifts in δ ppm) . General Procedure for the Synthesis of Compounds. Preparation of 2-amino-5-mercapto-1,3,4-thiadiazole[I][14]. A mixture of (2g, 0.02 mol.) of thiosemicarbazide and (2.33g, 0.02 mol.) of anhydrous sodium carbonate was dissolved in 25ml. abs. ethanol. To this solution (3.2g, 0.04 mol.) of carbon disulphide was added. The resulting mixture was heated under reflux for 10 hrs. , the reaction mixture was then allowed to cool down to room temperature. Most of solvent was removed under reduced pressure and the residue was dissolved in 20ml. distilled water and then acidified with cold concentration hydrochloric acid to give pale yellow precipitate .The crude product was filtered and washed with cold water, recrystallized from water to give yellow product,yield (75%) , m.p (230-232)Co . Preparation of 2- amino-5 - thioalkyl-1,3,4-thiadiazole [II] , [III][15]. 352 | Chemistry 2014) عام 3(العدد 27المجلد مجلة إبن الھيثم للعلوم الصرفة و التطبيقية Ibn Al-Haitham Jour. for Pure & Appl. Sci. Vol. 27 (3) 2014 Compound [1] containing(-SH) group (0.001mol.) was dissolved in 10ml. dioxan , which contained (0.001mol.) potassium hydroxide. Ethyl iodide and isopropyl bromide(0.001mol.) were added using separating funnel dropwise with stirring . The reactants were refluxed for 3 hrs. The solvent was evaporated under reduced pressure ,water was added , and the crude product was extracted with ethyl acetate and dried with anhydrous magnesium sulphate . Evaporation of the organic layer gave solid products , recrystallized from dioxan to give 2-amino-5-thioethyl-1,3,4-thiadiazole[II] , yield (68%) , m.p (120-121)Co and 2-amino-5- thioisopropyl-1,3,4-thiadiazole[III] yield(80.5%) m.p (139-140)Co . Preparation of Schiff bases [IV]a-c , [V]a-d , [VI]a-d from the 2-amino-5-lthioalky-1,3,4- thiadiazole[16]. A mixture of compound [II]and compound [III] (0.01mol.) of appropriate aromatic aldehyde (0.01) in 15ml absolute ethanol . Three drops of glacial acetic acid were added and refluxed in water bath for 8hrs. The reaction mixture was then allowed to cool at room temperature, and the precipitate was filtered and dried , recrystallized from ethanol to give colored crystals. Table (1) shows the m.p. , yield and synthesized compounds [IV]a-c , [V]a-d , [VI]a-d . Preparationof 3 - (5-(substitutedthio)-1,3,4-thiadiazole-2-yl)-2,3-dihydro-2-(Aryl)benzo[e] [1,3] thiazine-4-one[VII]a,c , [VIII]a [17]. A mixture of Schiff base (0.01mol.) and 2-mercaptobenzoic acid (0.01mol.) were mixed with 30ml. dry benzene and 3drops of triethylamine were added . The mixture was refluxed for 6 hrs. Then the solvent was removed under reduced pressure . The residue was washed with 10% of sodium bicarbonate then filtered and recrystallized with dioxan. Table (2) shows the m.p. , yield and synthesized compounds [VII]a,c , [VIII]a . Preparation of 3- chloro -1- (5-mercapto-1,3,4-thiadiazole-2-yl) - 4 -(aryl) azetidine-2- one [X]c , [IX]a,b , [XI]c,d [18]. Chloro acetyl chloride (0.01mol.) in 10ml of dioxan cooled at (0-5) Co , to this , triethylamine (0.01mol.) in(10ml.) dioxane was added , and Schiff bases (0.01mol.) in 10ml of dioxane was slowly added and refluxed in water bath for (12hrs) . After the reaction had been completed- (detectad by TLC) , the reaction mixture poured into ice-cold water to give solid precipitate , which was filtered and dried , recrystallized by benzene-ether(50-50). Table (3) shows the m.p. , yield and synthesized compounds [X]c [IX]a,b , , [XI]c,d . Preparation of 3- (5-mercapto-1,3,4-thiadiazole-2-yl) - 2 -(aryl) thiazolidin-4-one [XII]a,c , [XIII]d , [XIV]c,d [19]. To mercapto acetic acid (0.001mol. , 0.09g) in dry benzene (30ml) `was added slowly to (0.001mol.) of Schiff bases .The addition continued about(5min) with continous stirring then for about 3 hrs. Followed by refluxing on a steam bath for about 18 hrs. Excess solvent was evaporated and the residue was treated with sodium bicarbonate , filtered and recrystallized with dioxan. Table (4) shows the m.p. , yield and synthesized compounds[XII]a,c , [XIII]d , [XIV]c,d . Biological evaluation[20] Some of synthesized compounds have been screend for antibacterial activities using cup-plate agar diffusion method. Pencilin and azthromycin (50µg /ml) were used as a standard drug for antibacterial activity. The compounds were screened for antibacterial activity against (Staphylococcus and Escherichia coli) in nutrient agar medium. These sterilized agar media were poured into petri- dishes and allowed to solidify. On the surface of the media microbial suspensions were spread with the help of sterilized triangular loop. A stainless steel cylinder of 8mm diameter (pre- sterilized) was used to bore cavities. All the synthesized compounds (50µg /ml) were placed serially in the cavities with the help of micropipette and allowed to diffuse for 1 hr. DMSO was used as a solvent for all the compounds , and as a control. These plates were incubated at 353 | Chemistry 2014) عام 3(العدد 27المجلد مجلة إبن الھيثم للعلوم الصرفة و التطبيقية Ibn Al-Haitham Jour. for Pure & Appl. Sci. Vol. 27 (3) 2014 37Co for 24 hr for antibacterial activities. The zone of inhibition observed around the cups after respective incubation was measured in mm . Result and Discussion The structure of compound [I] was identified by it,s melting point and FT-IR spectroscopy . The FT-IR spectrum of compound [I] , figure(1) , shows the following characteristic bands , two bands at 3396 cm-1 and 3278 cm-1 were due to asymmetric and symmetric stretching vibration of (-NH2) group respectively , an absorption band at 3091 cm- 1 was due to the (N-H) stretching (tautomeric form).The (-SH) stretching band found as very weak shoulder at 2331cm-1 , a band at 1604cm-1 was due to (C=N) stretching of the thiadiazole ring moiety .The sharp band at 1533cm-1 and 1330cm-1 are due to the (N-H) bending and (C-N) stretching vibration respectively . Also , the absorption band at 1055cm-1 for the (C=S) group which gives an evidence that compound [I] can exist in two tautomeric forms , thiol (A) and thione form (B) [14] . NN S SH2N H (A) NN SH2N S H .. (B) The compounds [II] and [III] were identified by m.p , T.L.C. , FT-IR and UV spectroscopy. The FT-IR for compound [II] and [III] respectively showed disappearance of band at 2358 cm-1 which due to (S-H). Also disappearance of the very weak band at 1055 cm-1 of (C=S) group , and remaining the two functional group due to (C=N) exocyclic , (C=N)[21] endocyclic , at(1622,1633) cm-1 , (1525,1554) cm-1 respectively , and appearance band at(1321,1421) cm-1 due to (S-CH2CH3) , and appearance band at (1328,1411) cm-1 due to (S- CH(CH3)2)[22] . The UV-Vis spectrum of [II] shows the absorption peaks at (343-286 ) nm may attributed to (n- π*) and(π-π*) transitions. FT-IR spectrum of compound [IV]a-c , [V]a-d , [VI]a-d , showed the disappearance of two absorption band at (3396 ,3278)cm-1 due to the (-NH2) stretching of amino group . On the other hand, the FT-IR spectra showed bands for (C-H) olefinic, (C=C) aromatic,(C=N) endocyclic and exocyclic imine (C=N) group stretching vibration[14] . FT- IR absorption for these compounds are shown in table (1) . Thiazine derivatives were prepared by the reaction of Schiff bases and 2- mercaptobenzoic acid in dry benzene . The products were identified by FT-IR ,UV-Vis spectroscopy , their melting points and checked by T.L.C. for compounds appearance of carbonyl group of the thiazines at (1662-1683) cm-1 and disappearance of the (C=N) group in (1610-1620) cm-1 and the disappearance of (O-H) broad band stretching vibration at 3450 cm-1 of 2-mercapto benzoic acid. Also all the spectral data for these compounds are listed in table (2). The Schiff bases compounds were treated with chloroacetyl chloride followed by the addition of triethyl amine The FT-IR spectra of compounds [XI]c , Figure ( 2 ) showed the appearance of the characteristic absorption band in region (1683-1707) cm-1 due to stretching vibration of carbonyl group of azetidine ring. Also the FT-IR spectrum showed the suggested band for olefinic (C-H) , (C=C) aromatic . All the spectral data for these compounds are listed in table (3). The1H-NMR spectrum for compounds [XI]c [23] , Figure (3) showed the following characteristic chemical shifts , (DMSO)ppm , (CH) proton in azetidione ring for compound[XI]c appeared as two signals (doublet) at δ (3.77-3.79) ppm and (CH) proton fused 354 | Chemistry 2014) عام 3(العدد 27المجلد مجلة إبن الھيثم للعلوم الصرفة و التطبيقية Ibn Al-Haitham Jour. for Pure & Appl. Sci. Vol. 27 (3) 2014 with chloro (doublet) at δ (4.27-4.46) ppm and δ (8.1-8.4) ppm for aromatic ring proton , multiplet signal at δ (3.02-3.5)ppm for proton of (C-H) in (CH(CH3)2) group. The doublet signal at δ (1.2) ppm for proton of methyl group.The (UV-Vis) spectrum of [XI]c , shows the absorption peaks at (332-285) may attributed to(n - π*) and (π-π*) transition. The thiazolidine-4-one derivatives [XII]a,c , [XIII]d , [XIV]c,d were synthesized by refluxing equimolar amounts from the imine compounds with thioglycolic acid in dry benzene . The FT-IR spectra for compounds[XII]a , Figure (4) showed the appearance of the characteristic absorption bands in the region (1689-1707) cm-1 due to stretching vibration of carbonyl group of thiazolidinone ring [24] .Also the FT-IR spectrum showed the suggested band for olefinic (C-H) , (C=C) aromatic. All the spectral datd for these compounds in table (4). The1H-NMR spectrum for compound[XII]a Figure(5) showed the following characteristic chemical shifts , (DMSO)ppm: the aromatic ring protons of compound[XII]a appeared as multiplet at δ (6.8-7.8)ppm , singlet signal at δ (2.9) ppm due to (S-H) proton , signal at δ (8.4) ppm due to the (C-H) proton in thiazolidinone as singlet and protons of (CH2) of thiazolidinone appeared at δ (3.35) ppm . The singlet signal at δ (3.07) ppm is for proton of ((CH3)2N) group . The (UV-vis) spectrum of compound [XII]a , Figure(6) shows the absorption peaks at(340-264) nm which may attributed to (n- π*) and (π-π*) transition Biological Activity The results revealed that compounds showed varying degrees of inhibition against the tested microorganism.In general,the compounds [I,II,III] thiadiazole and thioalkyl compounds exhibited potent activity against E.coli and S. aureus bacteria. The compound [I] showed high activity among these compounds against E. coli more than standard drugs , while compound [III] showed high activity against S. aureus more than standard drugs .The results also showed that some of schiff base compounds exhibited good activity against S. aureus (+ Gr) such as [(IV)b , (IV)c, (V)a,(V)b,(VI)a,(VI)d],while compounds [(IV)a, (IV)b,(VI)a, ,(VI)d] did not show any activity against E. coli (-Gr) when compared with the two standard drugs. The other Schiff base compounds showed moderate inhibitory against S. aureus and E.coli . The compounds [(IX)a,(XII)a,(VII)a] showed good activity against gram positive than gram negative bacteria. Also the results showed that the compounds [(XI)c , (XI)d ,(XIV)c , (XIV)d] showed good activity against the two microorganisms , when the –SH group substituted by alkyl group. In comparsion , azetidine compounds exhibited the highest biological activity than thiazolidine and thiazine compounds , respectively. Thus , it is concluded from the screening results that the most of azetidine compounds and its derivatives have higher antibacterial activity more than the standard drugs against S. aureus than E.coli in a concentration of 50µg/ml[25]. 355 | Chemistry 2014) عام 3(العدد 27المجلد مجلة إبن الھيثم للعلوم الصرفة و التطبيقية Ibn Al-Haitham Jour. for Pure & Appl. Sci. Vol. 27 (3) 2014 References 1-Achson , A. (2009) An introduction to the chemistry of heterocyclic compounds 3th ed. , Willy-Intersciences , India . 2-Vasoya , S. L. ; Paghdar , D. J. ; Chovatia, P. T. and Joshi , H. 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(1996)"Synthesis and characterization f some dioxadiazole and their methyl and ethyl thioether ", Mu,tah J. Res. Stud. 11(5)1022. 16-Mohmoud , M. J. ; Al-Rubaiy, Z. M. ;Al-Kubaisy , R. K. ; Al-Najafi, M. M. and Al- Jumaily, H. M. (2004)"Synthesis and antimicrobial evaluation of 2-amino-5-thiol-1,3,4- thiadiazole derivatives" ; Ibn-Al-Haitham. J. For pure and Appl. Sci. ,.17(1) ,. 103-110. 17- Majeed , I. Y. (2012) , Ph. D. Thesis , College of education for a Pure Science (Ibn-Al- Haitham) , University of Baghdad 18-Ritu S. , Pushkal S. , Srivastava S. .D. , Srivastava S. K. (2012),''Synthesis and pharmaceutical importance of 2-azetidinone derivatives of phenothiazine'', J. Chem. Sci.. 124,.3:633-637. 356 | Chemistry 2014) عام 3(العدد 27المجلد مجلة إبن الھيثم للعلوم الصرفة و التطبيقية Ibn Al-Haitham Jour. for Pure & Appl. Sci. Vol. 27 (3) 2014 19-Al-Masry, A. H. ; Fahmy, H. H. and Abdel Wahed, A. S. H. (2000); Molecules ;.5,.1429. 20-Barry A. L. (1977). ; The Antimicrobial Susceptibility Test: Principle and practices , (Len and Febiger , Philadelphia , USA) , 1976 ,180 ; Bio Abstr , 64,25183. 20-Barry A. L. (1977) ''The Antimicrobial Susceptibility Test: Principle and practices , (Len and Febiger , Philadelphia , USA) , 1976 ,180 ; Biol Abstr , 64,25183 21- Aly, A. A. and El-Ayed , R. (2006) "Synthesis and biological activity of new 1,3,4- thiadiazole derivatives", Chem..60(1)56-60 22- Mustaf , I. F. (1997) "Synthesis and characterization f some oxadiazole and triazole derivatives ", Muʼtah Journal for Research and Studies ,. 12(3) , 23-Jubie , S. ; Gowramma , B. ; Nitin , K. ; Muthal ; Kalirajan , R. ; Gomathi , S. and Elango , K.,(2009) ,''Synthesis and antimicrobial evaluation of some 2-azetidinone derivatives '', Int. J. ChemTech Res ,1(2) ,.153-157. 24-Al-Rubaiy ,Z. M. (1998) , M. Sc. Thesis, College of Science Baghdad University. 25- Rabasseda , X. (2010) Drugs Today (Barc.) ,46..7 ,.533. 357 | Chemistry 2014) عام 3(العدد 27المجلد مجلة إبن الھيثم للعلوم الصرفة و التطبيقية Ibn Al-Haitham Jour. for Pure & Appl. Sci. Vol. 27 (3) 2014 Scheme No. (1) H2N�NH�C�NH2 S CS2 , EtOH.abs.Na2CO3 NN S SHH2N NN S SHNHC � NN S S�CH�CH3H2N NN S S�CH2CH3H2N CH3 NN SNHC � NN S S�CH2CH3NHCAr � S�CH�CH3 CH3 S C NHC NN S SH O ArNN S SHNHC Cl O [XII]a,c NN S SH C NHC S O Ar NN S C NHC S O S�CH�CH3 CH3NN SNHC Cl O S�CH�CH3 CH3 [IX]a,b [VII]a,c [IV]a-c [VI]a-d[V]a-d S C NHC NN S SCHCH3 O Ar [XIV]c,d S C NHC NN S SCH2CH3 O Ar NN S SCH2CH3NHC Cl O CH3CH2I Drydioxane KOH KOH Drydioxane (CH3)2CHBr ArCHOArCHOArCHO EtOH.abs. EtOH.abs.EtOH.abs. (CH3)2CHBr DrydioxaneDrydioxane CH3CH2I KOH KOH [X]c [XI]c,d [VIII]a N H3C H3C O2N O2N , , ,Ar = CH3 drybenzene drybenzene drybenzene SH COOH HS�CH2COOH HS�CH2COOH d ry be n ze n e Dioxane Cl�CH2C�Cl O Et3N , drybenzeneCl�CH2C�Cl O Et3N , Dioxane Et3N, Cl�CH2C�Cl Dioxane Br .. .. Ar � O + H S C H 2 C O O H SH COOH �Ar Ar� � �Ar Ar Ar [I] [II][III] [XIII]d 358 | Chemistry 2014) عام 3(العدد 27المجلد مجلة إبن الھيثم للعلوم الصرفة و التطبيقية Ibn Al-Haitham Jour. for Pure & Appl. Sci. Vol. 27 (3) 2014 Table No.(1) :Physical properties and FT-IR spectral data of compounds [IV]a-c , [V]a-d , Com. No Structral Formula M.P υ(C-H) arom.cm- 1 υ(C-H) aliph.cm- 1 υ(C=N) exo cm- 1 Others cm-1 [IV]a NN S SHNN H3C H3C HC 220- 222 3089 2953 1614 υ (S-H) 2349 [IV]b NN S SHNHC O2N 216- 218 3128 2976 1612 υ (NO2)1348- 1531 [IV]c NN S SHNHCO2N 195- 197 3134 2978 1610 υ (NO2)1348- 1521 [V]a NN S SCH2CH3NHCN H3C H3C 160- 161 3084 2962 1616 υ (N- Me)1367 [V]b NN S SCH2CH3NHC O2N 130- 132 3086 2970 1614 υ (NO2)1354- 1527 [V]c NN S SCH2CH3NHCO2N 136- 138 3138 2987 1612 υ (NO2)1367- 1523 [V]d NN S SCH2CH3NHCBr 169- 170 3147 2966 1614 υ (C-Br)821 [VI] a NN S SCHCH3NHCN H3C H3C CH3 180- 181 3088 2960 1616 υ (N- Me)1371 [VI] b NN S SCHCH3NHC CH3 O2N 116- 118 3151 2972 1616 υ (NO2)1340- 1523 [VI] c NN S SCHCH3NHC CH3 O2N 150- 151 3109 2972 1616 υ (NO2)1340- 1525 [VI] d NN S SCHCH3NHC CH3 Br 113- 114 3086 2964 1614 υ (C-Br)821 359 | Chemistry 2014) عام 3(العدد 27المجلد مجلة إبن الھيثم للعلوم الصرفة و التطبيقية Ibn Al-Haitham Jour. for Pure & Appl. Sci. Vol. 27 (3) 2014 Table No. (2): Physical properties and FT-IR spectral data of compounds [VII]a,c , [VIII]a [VI]a-d. Comp.N o Structral Formula M.P υ(C-H) arom. cm-1 υ(C-H) aliph.cm-1 υ (C=O) cm-1 Others bands cm-1 [VII]a NN S SHN C NHC S O H3C H3C 240-242 3159 2978 1662 (υ S-H) 2376 [VII]c NN S SHO2N C NHC S O 211-212 3105-3007 2866 1678 (υ S-H) 2358 [VIII]a NN S SCHCH3 N CH3 C NHC S O H3C H3C 142-144 3050 2960 1681 (υ C-S-C) 680 Table No. (3) : Physical properties and FT-IR spectral data of compounds[X]c [IX]a,b , , [XI]c,d Comp.No Structral Formula M.P υ(C-H) aliph. cm-1 υ (C-H) arom.cm-1 υ(C=O) cyclic cm-1 Others Bands cm-1 [IX]a NN S SHN H C Cl O N H3C H3C 200-202 2978 3099 1683 υ(C-Cl)850, (υ C-N)1257 [IX]b NN S SHN H C Cl O O2N 240 dec. 2949 3049 1687 (υ S-H)2351 [X]c NN S SCH2CH3N H C Cl O O2N 187-189 2966 3045 1705 υ(C-Cl)850 υ(C- N)1232 [XI]c NN S SCH2CH3N H C Cl O O2N 110-112 2964 3045 1707 υ(C-Cl)825 [XI]d NN S SCHCH3N H C Cl O Br CH3 185-187 2914 3167 1685 υ(C-Cl)845 360 | Chemistry 2014) عام 3(العدد 27المجلد مجلة إبن الھيثم للعلوم الصرفة و التطبيقية Ibn Al-Haitham Jour. for Pure & Appl. Sci. Vol. 27 (3) 2014 Table No. (4) : Physical properties and FT-IR spectral data of compounds [XII]a,c , [XIII]d , [XIV]c,d Comp.No Structral Formula M.P υ(C-H) aliph. cm-1 υ(C-H) arom. cm-1 υ(C=O) Cyclic cm-1 Others Bands cm-1 [XII]a S C NHC NN S S O N H3C H3C 210-212 2978 3140 1693 (υ C-N) 1172 [XII]c S C NHC NN S SH O O2N 182-184 2978 3105 1691 υ(S-H) 2360 [XIII]d S C NHC NN S SCH2CH O Br 189-190 2978 3093 1689 (υ C-S-C) 682 [XIV]c S C NHC NN S SCHCH O O2N CH3 122-124 2920 3107 1707 υ(NO2)1346- 1521 [XIV]d S C NHC NN S SCHCH O Br CH3 105-107 2968 3151 1697 (υ C-Br) 831 Figure No. (1): FTIR-Spectrum of compound [I] 361 | Chemistry 2014) عام 3(العدد 27المجلد مجلة إبن الھيثم للعلوم الصرفة و التطبيقية Ibn Al-Haitham Jour. for Pure & Appl. Sci. Vol. 27 (3) 2014 Figure No. (2): FTIR-Spectrum of compound [XI]c Figure No.(3): 1H-NMR Spectrum of compound [XI]c 362 | Chemistry 2014) عام 3(العدد 27المجلد مجلة إبن الھيثم للعلوم الصرفة و التطبيقية Ibn Al-Haitham Jour. for Pure & Appl. Sci. Vol. 27 (3) 2014 Figure No. (4): FTIR-Spectrum of compound [XII]a NMR Spectrum of compound [XII]a-H1 Figure No.(5): 363 | Chemistry 2014) عام 3(العدد 27المجلد مجلة إبن الھيثم للعلوم الصرفة و التطبيقية Ibn Al-Haitham Jour. for Pure & Appl. Sci. Vol. 27 (3) 2014 Figure No. (6): UV-Vis Spectrum of compound [XII]a 364 | Chemistry 2014) عام 3(العدد 27المجلد مجلة إبن الھيثم للعلوم الصرفة و التطبيقية Ibn Al-Haitham Jour. for Pure & Appl. Sci. Vol. 27 (3) 2014 ن الجديدة بعض مركبات الثيازين و االزيتيدين والثيازولديتحضير و تشخيص البايولوجية لھاالفعالية ثياديازول ودراسة -4و3و1الحاوية على الوحدة علي حمادي سمير خالد فھد علي رويدة سمير سعيد جامعة بغداد )/ابن الھيثم (كلية التربية للعلوم الصرفة /قسم الكيمياء 2014حزيران 22,قبل في: 2014اذار 17استلم البحث في: الخالصة بتحولق الثايوسميكاربازايد مع ثنائي كبريتيد الكاربون [I]ثياديازول -4,3,1-مركبتو -5-امينو - 2حضرالمركب امينو -2مع ھاليدات االلكيل ليعطي المركب [I]بوجود كاربونات الصوديوم الالمائية وفي مذيب كحولي. تفاعل المركب الديھايدات اروماتية مختلفة اعطى مع [II] , [III] . تفاعل المركب [III] [II] , ثياديازول-4,3,1-ثايوالكايل - 5- ان .وجد , a-d [V]a-d , [IV]a-c[VI]ثياديازول -4,3,1-ثايو الكايل-5-](بنزلدين معوض ) امينو [-2المركب مركبتو حامض البنزويك بوجود ثالثي اثيل امين لتعطي -2. تتفاعل مع , a-d [[V]a-d , [IV]a-c[VI]قواعد شف - 4-ثيازين ][3,1] [e] [(اريل ) بنزو-2-داي ھايدرو -3,2- ]يل - 2-ثياديازول –4,3,1–( ثايوالكايل ) –5 [ -3المركب -5(- 1-كلورو-3. وتفاعلت قواعد شف مع كلورو اسيتايل كلورايد بوجود ثالثي اثيل امين لتعطي a,c [VII]a[VII]ون . , c,d [X]c , [IX]a,b[XI]ون - 2-(اريل) ازيتيدين - 4-يل )-2- ثياديازول - 4,3,1-ثايوالكايل ) - 2-ثياديازول- 4,3,1-مركبتو - 5(- 3مركبتو حامض الخليك في البنزين الجاف لتعطي - 2كذلك تتفاعل قواعد شف مع ).1كما ھو موضح في المخطط ( , c,d [XIII]d , [XII]a,c[XIV]ون - 4-(اريل) ثيازولدين- 2-يل ) شخصت المركبات الجديدة المحضرة من خالل القياسات الفيزيائية واطياف االشعة فوق البنفسجية و االشعة تحت ناطيسي.الحمراء وطيف الرنين النووي المغ ازيتيدين , ثيازولدين . , الثيازين , ثياديازول4,3,1-: الكلمات المفتاحية