Conseguences of soil crude oil pollution on some wood properties of olive trees Chemistry |195 https://doi.org/10.30526/30.3.1615 7302(عام 0العدد ) 03مجلة إبن الهيثم للعلوم الصرفة والتطبيقية المجلد Ibn Al-Haitham Jour. for Pure & Appl. Sci. Vol. 30 (3) 2017 Synthesis, Characterization and Study of Mesomorphic Behavior of New Bent and Liner Core Compounds Containing Heterocyclic Nisreen H. Karam Alaa K. Shanshal Dept. of Chemistry/College of Education For Pure Science ( Ibn Al- Haitham)/ University of Baghdad Received in:14/May/2017,Accepted in:21/June/2017 Abstract We described herein the synthesized and characterized of new bent and liner core compounds containing thiazolidin-4-one ring[XI-XIII] and [XIV-XVI] respectively. These compounds synthesized by sequence reactions starting from reaction resorcinol or hydroquinone with chloracetyl chloride to yield compounds [I] and [II] ,then the later compounds reactant with 4-hydroxybenzylaldehyde to product dialdehyde compounds [III] and [IV] .The Schiff bases compounds[V-VII] and [VIII-X] synthesized from reaction the compound [III] or [IV] with different aromatic amines, while the bent and liner core mesogens containing thiazolidin-4-one ring [XI-XIII] and [XIV-XVI] synthesized from reaction Schiff bases compounds[V-VII] or [VIII-X] with thioglycolic acid. In addition estrfecation of cinnamic acid with methanol to yield ester compound[XVII]which was converted to their acid hydrazid[XVIII] and the acid hydrazid reacted with glysine in phosphorous oxychloride to yield (5-styryl-1,3,4-oxadiazol-2-yl) methanamine [XIX]. Then reactant the1,3,4-oxadiazol compound[XIX] with dialdehyde compound [III] or [IV] to product new Schiff bases compounds [XX] and [XXI] , afterword added thioglycolic acid to give new thiazolidin-4-one derivatives [XXII] and [XXIII], respectively. The synthesized compounds were characterized by melting points , FTIR , 1 HNMR and mass spectroscopy (of some of them).The liquid crystalline properties were studied by hot stage polarized optical microscopy (POM) and differential scanning calorimetry(DSC).All the Schiff bases compounds [V-X] showed liquid crystals phases while thiazolidin-4-one derivatives[XI-XIII],[XIV-XVI]and [XXIII] didn’t show any liquid crystals properties except the compound [XXII] showed enantiotropic nematic phase. Keywords: liquid crystals; 1,3,4-oxadiazol; resorcinol and hydroquinone. Chemistry |196 https://doi.org/10.30526/30.3.1615 7302(عام 0العدد ) 03مجلة إبن الهيثم للعلوم الصرفة والتطبيقية المجلد Ibn Al-Haitham Jour. for Pure & Appl. Sci. Vol. 30 (3) 2017 Introduction In recent years, there has been interest study of liquid crystals resulting in the discovery of many applications in modern technologies, particularly in display devices due to their unusual optical and electrical properties. The banana- shaped liquid crystals are also interested widely, due to its unique electro-optic and photo-induced characteristics [1,2]moreover, these materials are also of significant interest for command surfaces and sensors[3] Many workers synthesized bent or liner core liquid crystals compounds containing1,3- disubstitutedphenylene or 1,4-disubstitutedphenylene from resorcinol or hydroquinone, respectively, as Ciobanu et. al.[4] synthesized and investigated liquid crystalline behavior of symmetrical non liner liquid crystal containing 1,3- disubstituted benzene ring as a central core also consisting of different linkage groups beside to terminal alkyloxy chain containing 6 to 10 carbon atoms(1).All compounds appeared enantiotropic mesophases (nematic and smectic phases). OO OO NN CH HC NN NN RO OR R = COCnH2n+1 , n = 5-9 (1) Also, Huzum et al.[5]synthesized and studied mesomorphic behavior of two new series of bent core liquid crystalline compounds based on a 1,3-dihydroxybezene core and containing a cholesteryl 6-oxyhexanoate wing. While, Alaasar et al[6]synthesized and investigated bent-core mesogens derived from 4-methylresorcinol with azobenzene wings and terminal group as (OCnH2n+1,n=6-22). The short homologues chain exhibit smectic phases and for the longes thomologue only a crystalline phase was observed. In addition ,Yuvaraj et al.[7]investigated the liquid crystalline and light-induced properties of resorcinol spacer based dimericazobenzene(2),the compound [2]showed nematic and smecticA phases OO OO NN NN O O (2) CH35 H3C 5 One the other hand ,synthesized liner core liquid crystals compounds containing 1,4- disubstitutedphenylene from hydroquinone as, synthesized three aromatic rigid mesogenicdiols(3) based on hydroquinone and 4-hydroxy benzoic acid as starting materials[8]. The experimental results reveal that hydroquinone based rigid triad mesogenicdiol have higher thermal stability. Chemistry |197 https://doi.org/10.30526/30.3.1615 7302(عام 0العدد ) 03مجلة إبن الهيثم للعلوم الصرفة والتطبيقية المجلد Ibn Al-Haitham Jour. for Pure & Appl. Sci. Vol. 30 (3) 2017 O O (3) O O HO OH In the literature, we did not found any studies of the effect of thiazolidin-4-one derivativeson the liquid crystals properties, therefore this paper presents the synthesis, structural characterization and mesomorphic properties of new bent and liner core liquid crystals containing thiazolidin-4-one unit as while as 1,3,4-oxadiazol ring. Experimental Chemicals All chemicals were supplied by Fluka, Merck and Aldrich chemicals Co. Techniques FT-IR spectra were recorded by 600 FT-IR spectrometer. 1 H-NMR spectra were carried out by company: Bruker ,500 MHz and were reported in ppm(δ), DMSO was used as a solvent with TMS as an internal standard, measurements were made at Central lab ,Tehran University. Massspectrum was determined by scan110(1.257min):direct prob-013777.d,at Central lab ,Tehran University.uncorrected melting points were determined by using Hot-Stage, Gallen Kamp melting point apparatus.The transition temperatures and textures of the mesophases were determined using polarized opticalmicroscope model Leica DM2500 Mand DSC measurements were conducted with STAPT-1000LINSIS. Chemistry |198 https://doi.org/10.30526/30.3.1615 7302(عام 0العدد ) 03مجلة إبن الهيثم للعلوم الصرفة والتطبيقية المجلد Ibn Al-Haitham Jour. for Pure & Appl. Sci. Vol. 30 (3) 2017 Synthesis New compounds are synthesized according to scheme1: CH CH C O OH CH CH C O OMe CH CH C O NHNH2 H 2 NCH 2 COOH/POCl 3 CH CH NN O CH2NH2 C C O O CH2Cl ClH2C C C O O CH2 H2CO O OHC CHO CH CH CH NN O CH2N CH NCH2 NN O CH H C MeOH Con. H 2 SO 4 2 ClCOCH 2 Cl 2 HOC6H4CHO NH2NH2.H2O EtOH HO OH O O O O 4-X-C6H4-NH2 X=CH3O , CH3 and OH C C O O CH 2 H2CO O N=HC CH=N O O X X C C O O CH2 H2CO O O OX C C O O CH 2 H2CO O O O H CN SO N H C S O X + [I],[II] [III],[IV] [V-VII],[VIII-X] 2HSCH2COOH Benzene Pyridine /DMF Sodium acetate/EtOH [XI-XIII],[XIV-XVI] [XVII] [XVIII] [XIX] [XX],[XXI] CH CH NN O H2 C NN O CH H C C C O O CH2 H2CO O O O [XXII],[XXIII] NHC S O H2 C CHN SO 2HSCH 2 COOH Benzene EtOH EtOH Scheme (1) Preparation of 1,3-phenylene bis(2-chloroacetate) [I]and 1,4-phenylene bis(2- chloroacetate)[II][9,10] Chloroacetyl chloride (0.002 mol) was slowly added to a stirred solution of resorcinol or hydroquinone (0.11 g ,0.001 mol) , pyridine 1 ml and DMF 2 ml at 0 ℃. Then, the reaction mixture was stirred for 3 hrs.atroom temperature then, neutralized with saturated sodium bicarbonate solution.The precipitate was filtered and washed with water, dried and the residue was recrystallized from ethanol. Data compound [I]: reddish color, Yield 70 %, m.p.= 66-68 0 C Data compound [II]: white color ,Yield 78 %, m.p.= 122-123 0 C Chemistry |199 https://doi.org/10.30526/30.3.1615 7302(عام 0العدد ) 03مجلة إبن الهيثم للعلوم الصرفة والتطبيقية المجلد Ibn Al-Haitham Jour. for Pure & Appl. Sci. Vol. 30 (3) 2017 Synthesis of1,3-phenylene bis(2-(4-formylphenoxy)acetate)[III] and1,4-phenylene bis(2- (4-formylphenoxy)acetate)[IV] A mixture of compound [I] or [II](0.001mol ) ,4-hydroxybenzylaldehyde (0.002 mol ) and fused sodium acetate (0.246 g , 0.003 mol ) in absolute ethanol 5 ml was refluxed for 4 hrs . then cooled and poured into cold water . The precipitate was filtered and recrystallized by ethanol . Data compound [III]: brown color , Yield 70 %, m.p = 86-88 0 C Data compound [IV]: dark brown color , Yield 68 %, m.p = 58-60 0 C Synthesis of Schiff base compounds [V-VII] and [VIII-X] A mixture of compound [III] or [IV] ( 0.001 mol ) and different aromatic amines (0.002 mol) were dissolved in 5ml ethanol absolute, refluxed for 3-4 hrs . and cooled to room temperature . the solid product was to give new Schiff bases . The physical properties are listed in Table(1). Synthesis of thiazolidin-4-onederivatives[XI-XIII] and [XIV-XVI] A mixture of Schiff bases [V-VII] or [VIII-X] (0.001mol) and thioglycolic acid (0.002 mol) was refluxed in dry benzene (3 ml) for 12 hrs . The solvent was evaporated and residue was neutralized with sodium bicarbonate solution then, the precipitate was filtered. The physical properties are listed in Table (1). Preparation of Methyl 3-phenyl-2-propenoate[XVII][11] A mixture of cinnamic acid ( 36.408 g , 0.246 mol ) in absolute methanol ( 100 ml ) and sulfuric acid ( 3 ml ) was refluxed for ( 6 hrs. ) after cooling the mixture was washed with sodium bicarbonate solution , then washed with water several times dried and recrystallized from ethanol. Yield 80 % ,m.p= (36- 38°C) Preparation of 3-Phenyl-2-propenohydrazide[XVIII] A mixture of ester compound [XVII] ( 0.006 mol ) and 80% hydrazine hydrate ( 3 ml ) in absolute ethanol ( 5 ml ) was refluxed for ( 3 hrs ) . The mixture was cooled at room temperature then solvent was evaporated and solid formed recrystallized from acetone.Yield76 %, m.p115−117. Synthesis of(5-styryl-1,3,4-oxadiazol-2-yl)methanamine [XIX] Compound [XVIII](1.62g, 0.01 mol) and glysine(0.75g, 0.01 mol) were refluxed with phosphorous oxychloride (5mL) for 24 hrs. and the reaction mixture was then treated with ice water carefully and made basic by adding concentrated sodium bicarbonate solution. The resulting solid was filtered, dried and recrystallized by ethanol.darkbrown color, Yield 65%,m.p = 166-168 °C Synthesis of 1,3-phenylene bis{2-[4-(((5-styryl-1,3,4-oxadiazol-2- yl)methylimino)methyl)phenoxy]acetate}[XX] and 1,4-phenylene bis{2-[4-(((5-styryl- 1,3,4-oxadiazol-2-yl)methylimino)methyl)phenoxy]acetate}[XXI] These compounds were synthesized by using the same procedure given for synthesis compounds[V-VII] and [VIII-X],except using the compound [XIX] as aromatic amines. Data compound [XX]:browncolor , Yield 77%, m.p =116-118 0 C Data compound [XXI]: brown color , Yield 70%, m.p = 68-70 0 C Chemistry |200 https://doi.org/10.30526/30.3.1615 7302(عام 0العدد ) 03مجلة إبن الهيثم للعلوم الصرفة والتطبيقية المجلد Ibn Al-Haitham Jour. for Pure & Appl. Sci. Vol. 30 (3) 2017 Synthesis of1,3-phenylene bis(2-(4-(4-oxo-3-((5-styryl-1,3,4-oxadiazol-2- yl)methyl)thiazolidin-2-yl)phenoxy)acetate) [XXII] and 1,4-phenylene bis(2-(4-(4-oxo-3- ((5-styryl-1,3,4-oxadiazol-2-yl)methyl)thiazolidin-2-yl)phenoxy)acetate) [XXIII] These compounds were synthesized by using the same procedure given for synthesizing compounds[XI-XIII] and [XIV-XVI], except using the compounds [XX],[XXI]instead of compounds [V-VII] and [VIII-X] Data compound [XXII]:brown color, Yield 63%, m.p = 125-127 0 C Data compound [XXIII]: brown color , Yield 65%, m.p = >300 0 C Results and discussion In order to obtain the compounds [I] and [II] ,we reacted the resorcinol or hydroquinone with two moles from chloroacyl chloride in pyridine and DMF. These compounds were identified by FTIR spectroscopy. The FTIR spectra of these compounds showed disappearance bands of the υ OH groups, which were observed in the starting materials and showed new absorption stretching bands at 1774 cm -1 and 1764cm -1 that are attributed to the C=O of ester groups[12],respectively. Also, showed stretching band at 793cm -1 and 758cm -1 for CH2Cl,respectively. The dialdehyde [III] and [IV] were prepared from reacted compound [I] or [II]with two moles from 4-hydroxybenzylaldehyde and fused sodium acetate in absolute ethanol .The FTIR spectra of these compounds showed new stretching bands at 1686cm -1 and1668 cm - 1 assigned to CHO groups , also showed new stretching bands at 1217cm -1 and1215cm -1 for ether groups( -CH2-O-),respectively. While the 1 HNMR spectrum (in DMSO-d6 as a solvent) of compound [III], Figure(1 )showed: a singlet signal at δ9.77 ppm for two protons of CHO groups, many signals in the region δ (6.17-7.75) ppm of twelve aromatic protons of benzene rings, a singlet signal at δ 3.45 ppm due to four protons of two (OCH2CO)groups. The Schiff bases [V-VII]and[VIII-X] were synthesized by condensation reaction of one mole from the dialdehyde compounds[III] or [IV]with different aromatic amine in ethanol. These Schiff bases were characterized by melting points and FTIR and 1HNMR spectroscopy. The characteristic FTIR spectra of these compounds showed the disappearance of absorption stretching bands due to NH2 and CHO for starting material together with the appearance of stretching bandsat range (1651-1654) cm -1 and (1638-1645)cm -1 assignable to C=N groups, respectively . The characteristics FTIR absorption bands of new Schiff bases are listed in Table'(2). The 1 HNMR spectra (in DMSO-d6 as a solvent) for compound [V] and [IX ]showed: a singlet signals at δ8.45 ppm and δ8.59 ppm for two protons of azomethine ( N=CH) groups, respectively , multiplet signals appear at δ (6.85-7.74)ppm and δ (6.54- 7.75)ppm for twenty aromatic protons of benzene rings , respectively. A sharp signal at δ3.75 ppmthat could be attributed to the four protons of two(OCH2CO) groups and six protons of two (CH3O) terminal groups for compound [V].while two protons of two(OCH2CO) groups and six protons of two (CH3) terminal groups for compound [IX] appear at δ3.32 ppm and δ2.92 ppm, respectively, the 1 HNMR spectrum of compound [V] as Figure( 2). The thiazolidin-4-one derivatives[XI-XIII] and [XIV-XVI] were synthesized by the reaction of two moles of thioglycolic acid with one mole of Schiff bases [V-VII]and [VIII-X] in dry benzene ,respectively. These compounds were characterized by their melting points and FTIR spectroscopy. The FTIR spectra showed the disappearance of a stretching band of imine groups and the appearance of a stretching band of carbonyl group of thiazolidinone moiety[13] around (1662-1678) cm -1 and(1654-1685) cm -1 ,while (C-S) groups[14] around ( 950- 993) cm -1 and ( 970- 997) cm -1 ,respectively. The FTIR spectral data for these compounds are listed in Table (3). 1 HNMR spectra of compounds [XII] and [XIV] (in DMSO-d6 as a solvent): showed signals at δ 2.18 ppm and δ 3.65 ppm for six protons of the two (CH3) and Chemistry |201 https://doi.org/10.30526/30.3.1615 7302(عام 0العدد ) 03مجلة إبن الهيثم للعلوم الصرفة والتطبيقية المجلد Ibn Al-Haitham Jour. for Pure & Appl. Sci. Vol. 30 (3) 2017 (CH3O) groups ,respectively, a singlet was observed at δ3.65 ppm and δ3.72 ppm for four protons of (OCH2CO ) groups ,respectively. Singlet signal appeared at δ 4.36ppm and δ 4.10ppm due to four protons of two(H-5 thiazolidinone) ,respectively. Also ,multiplet signals appear at δ (6.30-7.46)ppm and δ (6.85-7.51)ppm for twenty aromatic protons of benzene rings and two protons of two (H-2 thiazolidinone) respectively. Figure(3) showed the 1 HNMR spectrum of compound [XII]. The ester compound [XVII] was prepared from reaction of cinnamic acid in methanol with conc. H2SO4 (as a catalyst).The FTIR spectrum for compound [XVII] showed the disappearance of absorption stretching bands of O-H and C=O groups of (carboxylic moiety) in starting materials together with the appearance of a new stretching band at 1716cm - 1 assigned to C=O group of ester moiety. The condensation of one mole of ester compound [XVII] with excess of 80% hydrazine hydrate in ethanol produced the acid hydrazide [XVIII].The compound was characterized by FTIR spectroscopy ,the FTIR spectrum for this compound showed stretching vibration of (NH, NH2) groups in the region (3280-3188)cm -1 as well as stretching absorption at 1664cm -1 of υ C=O (amide) and disappearance of absorption stretching band due to υ C=O of ester moiety. The acid hydrazide[XVIII] and glysine compound could be smoothly cyclidehydrated by boiling in phosphorus oxychloride to produce the 1,3,4-oxadiazol compound[XIX]. The FTIR spectrum for this compound showed absorption stretching band at 1637cm -1 due to υ C=N group for oxadiazol ring.The mechanism[15] of dehydration in the presence of POCl3 is depicted in the following steps: (Scheme 2) C O OH CH CH C O NHNH2 CH CH NN O CH 2 NH 2 POCl3H2NCH2 C O ClH2NCH23 H3PO4 C O ClH2NCH2 CH CH C O NH-NH C O CH2NH2 CH CH C O NH-NH C O CH2NH2 CH CH C N C O CH2NH2OH NH CH CH C N C O CH2NH2OH NH H+ CH CH C N C O CH2NH2 OH NH H + CH CH C N C OH2 CH2NH2 O N H + -H3O + + + Scheme (2) Then, reactant the1,3,4-oxadiazol compound[XIX] with dialdehyde compound [III] or [IV] to synthesize new Schiff base compounds [XX] and [XXI] , respectively. These Schiff bases were characterized by melting points and FTIRand 1 HNMR spectroscopy. The characteristic FTIR spectra of these compounds showed the disappearance of absorption bands due to NH2 and CHO for stretching of starting material together with the appearance of stretching bandsat 1645cm -1 and1651cm -1 assignable to C=N groups,respectively . The 1 HNMR spectrum (in DMSO-d6 as a solvent) for compound [XX], as Figure(4) showed: a singlet signals at δ8.53 ppm for two protons of azomethine ( N=CH) Chemistry |202 https://doi.org/10.30526/30.3.1615 7302(عام 0العدد ) 03مجلة إبن الهيثم للعلوم الصرفة والتطبيقية المجلد Ibn Al-Haitham Jour. for Pure & Appl. Sci. Vol. 30 (3) 2017 groups ,multiplet signals appear at δ (6.40-7.75)ppm for twenty two aromatic protons of benzene rings, signals at δ(5.41-6.33) ppm that could be attributed to the four protons of two(-CH=CH-)groups. Also singlet signal appears at δ 3.51 ppm due to four protons of two (OCH2CO) groups and signal appears at δ2.08 ppm for four protons of two(CH2N) groups,. In addition to, synthesizing new thiazolidin-4-one derivatives [XXII] and [XXIII] by adding two moles of thioglycolic acid with one mole of Schiff bases [XX] and [XXI] in dry benzene as a solvent. The FTIR spectra for these compounds showed the disappearance of a stretching band of imine groups and the appearance of a stretching band of carbonyl group of thiazolidinone moiety at 1674cm -1 and 1655 cm -1 also C-S groups at 997 cm -1 and 968cm - 1 ,respectively. The mass spectrum of compound [XXIII] that molecular weight =948 , Figure (5) showed base peak at m/z=110 .Also the spectrum showed peak attributed to the presence of the oxadiazol ring (m/z=81 and 53) and peak at (m/z=149)of the thiazolidin-4- one ring ,as while as peaks at m/z= 77and 65 for aromaticity of this compound. The fragments of this compound were illustrated in Scheme (3). CH CH NN O H2 C NN O H C H CC C O O CH2H2CO OOO NHC S O H2 CCHN SO CH CH NN O H2 C CHN S NN O H2 C CHN m/z=334 m/z=110 NHN O CH m/z=82 NN m/z=53 NHN H2 C C C O O CH2H2CO OOO NHHC S O CHN SO m/z=647 NN H C NH m/z=81 N O H2 C H2COCHN SO m/z=277 H 3 C H2COCHN SO m/z=222 m/z=178 CHN S m/z=149 + . m/z=77 m/z=65 m/z=149 CH2 CH NN O CH3 m/z=110 C O C OO -28 -72 -12 -55 948 -224 -185 NHN H 2 C C C O O CH 2H2CO OOO NHHC S O CH2 H N m/z=575 NHHC S O -72 -494 -28 -426 -397 Scheme (3) Liquid crystalline properties The liquid crystalline properties were investigated by polarized optical microscopy (POM) in association with differential scanning calorimetry(DSC). All the schiff bases compounds [V-X] showed liquid crystals phases. The compound [V]showed monotropic droplets nematic texture under POM because the methoxy groups have a higher polarizability, this could be explained in term of terminal/lateral (t/l) interaction forces ratio, because the methoxy chain led to a higher ratio of t/l interaction forces and when this ratio is high, compound tend to give less ordered mesophases (nematic mesophase)[16] as Figure 6(a),while Figure(7) showed DSC thermogram for this compound. Chemistry |203 https://doi.org/10.30526/30.3.1615 7302(عام 0العدد ) 03مجلة إبن الهيثم للعلوم الصرفة والتطبيقية المجلد Ibn Al-Haitham Jour. for Pure & Appl. Sci. Vol. 30 (3) 2017 The compounds [VII] and [X] showed enantiotropic SmA phase as Figure 6(b) for compound [VII].Butthe compounds [VI],[VIII] and [IX] showed enantiotropic SmB phase[17] as Figures 6(c) and 6(d) for compounds [VIII] and [IX] ,respectively. Finally, all thiazolidin-4-one derivatives[XI-XIII],[XIV-XVI]and [XXIII] didn’t show any liquid crystals properties but simply changes from the crystalline solid state to the isotropic liquid except the compound [XXII] showed nematic phase ,this is may by presence of oxadiazole ring and geometric structure of this compound. The transition temperatures for Schiff bases compounds [V-X] and thiazolidin-4-one derivatives[XI-XIII],[XIV-XVI], [XXII]and compound [XXIII] are summarized in Table 4 and Table5, respectively. References 1- Lutfor, M.R; Hegde, G.; Kumar ,S.; Tschierske,C. and Chigrinov, V. G.; (2009)Synthesis and characterization of bent-shaped azobenzene monomers: guest–host effects in liquid crystals with azo dyes for optical image storage devices, Optical Materials 32 (1), 176-183. 2- Prasad, V.; Kang, S. W.; Qi X.; and Kumar, S. J.; ,(2004) Photo-responsive and electrically switchable mesophases in a novel class of achiral bent-core azo compounds, J. Mater. 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H. and AL-dujaili, A.H.; (2013) Synthesis and Characterization of Heterocyclic Compounds Derived From 4- Hydroxy and 4-AminoAcetophenone, Ibn Al-Haitham Jour. for Pure and Appl. Sci. , 26 (3) ,296-312. 15- Tomi ,I. H. R. ; Al-Qaisi, A. H. J. and Al-Qaisi, Z. H. J.; (2010) Synthesis, Characterization and Effect of bis-1,3,4-Oxadiazole Containing Glycine Moiety on the Activity of Some Transferase Enzymes ,Ibn Al-Haitham Jour. for Pure and Appl. Sci., 23 (3) . 16- Karam, N. H .; Tomi, I. H. R. and Tomma, J. H.; (2016) Synthesis, Characterization and Study of The Liquid Crystalline Behavior of Four and Six Heterocyclic Compounds, Iraqi Journal of Science, 57, 3B, 1876-1890. 17- Dierking, I.; ( 2003), Textures of Liquid Crystals, Wiley-VCH, Weinheim, Germany. Chemistry |205 https://doi.org/10.30526/30.3.1615 7302(عام 0العدد ) 03مجلة إبن الهيثم للعلوم الصرفة والتطبيقية المجلد Ibn Al-Haitham Jour. for Pure & Appl. Sci. Vol. 30 (3) 2017 Table (1): The physical properties for the compounds[V-XVI] Comp . No. X Nomenclature Molecular formula Yield % M. P 0 C Color [V] CH3O 1,3-phenylene bis(2-(4-((4- methoxyphenylimino)methyl)phenoxy)acetate) C38H32N2O8 85 212- 214 gold [VI] CH3 1,3-phenylene bis(2-(4-((p- tolylimino)methyl)phenoxy)acetate) C38H32N2O6 87 203- 205 Yellow [VII] OH 1,3-phenylene bis(2-(4-((4- hydroxyphenylimino)methyl)phenoxy)acetate) C36H28N2O8 73 65- 67 brown [VIII] CH3O 1,4-phenylene bis(2-(4-((4- methoxyphenylimino)methyl)phenoxy)acetate) C38H32N2O8 82 190- 192 gold [IX] CH3 1,4-phenylene bis(2-(4-((p- tolylimino)methyl)phenoxy)acetate) C38H32N2O6 75 209- 211 brown [X] OH 1,4-phenylene bis(2-(4-((4- hydroxyphenylimino)methyl)phenoxy)acetate) C36H28N2O8 86 >30 0 dark brown [XI] CH3O 1,3-phenylene bis(2-(4-(3-(4-methoxyphenyl)- 4-oxothiazolidin-2-yl)phenoxy)acetate) C42H36N2O10S2 82 gum my Pal yellow [XII] CH3 1,3-phenylene bis(2-(4-(4-oxo-3-p- tolylthiazolidin-2-yl)phenoxy)acetate) C42H36N2O8S2 72 gum my Pal yellow [XIII] OH 1,3-phenylene bis(2-(4-(3-(4-hydroxyphenyl)- 4-oxothiazolidin-2-yl)phenoxy)acetate) C40H32N2O10S2 68 gum my brown [XIV] CH3O 1,4-phenylene bis(2-(4-(3-(4-methoxyphenyl)- 4-oxothiazolidin-2-yl)phenoxy)acetate) C42H36N2O10S2 62 170- 172 Off white [XV] CH3 1,4-phenylene bis(2-(4-(4-oxo-3-p- tolylthiazolidin-2-yl)phenoxy)acetate) C42H36N2O8S2 67 gum my brown [XVI] OH 1,4-phenylene bis(2-(4-(3-(4-hydroxyphenyl)- 4-oxothiazolidin-2-yl)phenoxy)acetate) C40H32N2O10S2 74 133- 135 brown Chemistry |206 https://doi.org/10.30526/30.3.1615 7302(عام 0العدد ) 03مجلة إبن الهيثم للعلوم الصرفة والتطبيقية المجلد Ibn Al-Haitham Jour. for Pure & Appl. Sci. Vol. 30 (3) 2017 Table (2): Characteristics FTIR absorption bands of compounds[V-X] Table (3):Characteristics FTIR absorption bands of thiazoldin-4-ones [XI-XVI] Comp. No. Characteristic bands FTIR spectra(cm -1 ) Ʋ(O-H) Ʋ(C-H) aromatic Ʋ(C-H) aliphatic Ʋ(C=O) ester Ʋ(C=N) Ʋ (C=C) aromatic [V] _ 3003 2970-2841 1741 1653 1606 [VI] _ 3026 2970-2866 1732 1654 1604 [VII] 3415 3070 2966-2858 1707 1651 1604 [VIII] _ 3005 2972-2839 1720 1645 1606 [IX] _ 3026 2978-2866 1730 1640 1606 [X] 3415 3051 2981-2823 1714 1638 1608 Comp. No. Characteristic bands FTIR spectra(cm -1 ) Ʋ(C-H) aromatic Ʋ(C-H) aliphatic Ʋ(C=O) thiazoldinone Ʋ(C=C) aromatic Ʋ(C-S) [XI] 3095 2962-2833 1662 1603 950 [XII] 3030 2958-2858 1678 1608 964 [XIII] 3068 2962-2806 1678 1604 993 [XIV] 3010 2956-2837 1654 1600 970 [XV] 3030 2970-2830 1685 1608 997 [XVI] 3010 2966-2852 1681 1600 995 Chemistry |207 https://doi.org/10.30526/30.3.1615 7302(عام 0العدد ) 03مجلة إبن الهيثم للعلوم الصرفة والتطبيقية المجلد Ibn Al-Haitham Jour. for Pure & Appl. Sci. Vol. 30 (3) 2017 Table (4): Phase transition temperatures ( o C) of Schiff bases compounds[V-X] Cr, crystalline phase;SmB smectic B phase ;SmA smecticA phase; N, nematic phase; I, isotropic liquid Table (5): Phase transition temperatures ( o C) of thiazolidin-4-one derivatives [XI- XIII],[XIV-XVI], [XXII]and compound [XXIII] Cr, crystalline phase ;N, nematic phase; I, isotropic liquid Comp. No. Transition Temperatures ( o C) [V] Cr N I 224201 [VI] Cr N ISmB 175 200 220 [VII] Cr N ISmA 209150 185 [VIII] Cr N ISmB 160 205 225 [IX] Cr N ISmB 175 220 233 [X] Cr N ISmA 120 160 200 Comp. No. Transition Temperatures ( o C) [XI] Cr I 170 [XII] Cr I 150 [XIII] Cr I 160 [XIV] Cr I 179 [XV] Cr I 165 [XVI] Cr I 140 [XXII] Cr N I 110 175 [XXIII] Cr I 310 Chemistry |208 https://doi.org/10.30526/30.3.1615 7302(عام 0العدد ) 03مجلة إبن الهيثم للعلوم الصرفة والتطبيقية المجلد Ibn Al-Haitham Jour. for Pure & Appl. Sci. Vol. 30 (3) 2017 Figure (1 ):The 1 HNMR spectrum of compound [III] Figure(2):The 1 HNMR spectrum of compound [V] Figure (3):The 1 HNMR spectrum of compound [XII] Chemistry |209 https://doi.org/10.30526/30.3.1615 7302(عام 0العدد ) 03مجلة إبن الهيثم للعلوم الصرفة والتطبيقية المجلد Ibn Al-Haitham Jour. for Pure & Appl. Sci. Vol. 30 (3) 2017 Figure (4):The 1 HNMR spectrum of compound [XX] Figure (5):The mass spectrum of compound[XXIII] 5 0 1 0 0 1 5 0 2 0 0 2 5 0 3 0 0 3 5 0 4 0 0 4 5 0 5 0 0 5 5 0 6 0 0 6 5 0 0 5 0 0 0 0 0 1 0 0 0 0 0 0 1 5 0 0 0 0 0 2 0 0 0 0 0 0 2 5 0 0 0 0 0 3 0 0 0 0 0 0 3 5 0 0 0 0 0 4 0 0 0 0 0 0 4 5 0 0 0 0 0 5 0 0 0 0 0 0 5 5 0 0 0 0 0 6 0 0 0 0 0 0 6 5 0 0 0 0 0 m / z - - > A b u n d a n c e S c a n 1 1 0 ( 1 . 2 5 7 m i n ) : D I R E C T P R O B _ 0 1 3 7 7 7 . d \ d a t a . m s 1 1 0 . 1 5 3 . 1 1 7 8 . 1 2 7 7 . 1 2 2 2 . 1 3 3 2 . 3 4 2 9 . 2 6 4 7 . 75 1 5 . 63 7 9 . 5 5 7 5 . 5 4 0 6 0 8 0 1 0 0 1 2 0 1 4 0 1 6 0 1 8 0 2 0 0 2 2 0 2 4 0 2 6 0 2 8 0 3 0 0 0 5 0 0 0 0 0 1 0 0 0 0 0 0 1 5 0 0 0 0 0 2 0 0 0 0 0 0 2 5 0 0 0 0 0 3 0 0 0 0 0 0 3 5 0 0 0 0 0 4 0 0 0 0 0 0 4 5 0 0 0 0 0 5 0 0 0 0 0 0 5 5 0 0 0 0 0 6 0 0 0 0 0 0 6 5 0 0 0 0 0 m / z - - > A b u n d a n c e S c a n 1 1 0 ( 1 . 2 5 7 m i n ) : D I R E C T P R O B _ 0 1 3 7 7 7 . d \ d a t a . m s 1 1 0 . 1 8 1 . 1 5 3 . 1 1 4 9 . 0 1 7 8 . 1 1 2 9 . 1 2 7 7 . 1 2 0 0 . 1 2 2 1 . 1 3 1 2 . 22 4 6 . 2 Chemistry |210 https://doi.org/10.30526/30.3.1615 7302(عام 0العدد ) 03مجلة إبن الهيثم للعلوم الصرفة والتطبيقية المجلد Ibn Al-Haitham Jour. for Pure & Appl. Sci. Vol. 30 (3) 2017 Figure(6):Cross polarizing optical textures of (a) nematicphase for compound [V] at 210 o C(b)smectic A phase for compound [VII] at170 o C(c )smecticB phase for compound [VIII] at 190 o C (d) smectic B phase for compound [IX] at 210 o C Figure (7) : DSC thermogram for compound [V] (a ) (b ) (c) (C ) (d )