In this paper , synthesis of a series of compounds from  hetero (Atoms, cycles) like  (5,6,7,8-membered )ring via cyclo addition reaction of anil compound to produce compound [1-13], this reactions involved addition of  carbonyl compounds like (( succinic acid , malonic acid , any compounds have  two terminal  from  amine  and  thiol or  carboxyl group)) to anil compounds  to  produce  various  membered  rings. The structure of the newly synthesized compounds [1-13] were confirmed with (C.H.N)- analysis &amp; substantiated with (FT.IR ,H.NMR) data  &amp; melting points. Keywords : eight membered , sulphur ,macrocycle , Imine ,heterocycle, five membered

Aljamali, Nagham .Mahmood.

English

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Chemistry and Materials Research                                                                                                                                                    www.iiste.org ISSN 2224- 3224 (Print) ISSN 2225- 0956 (Online) Vol.6 No.9, 2014  52 Synthesis of (5,6,7,8)-Membered Rings of (Sulfur ,Nitrogen) via  Cyclization of Imine Compounds   Dr. Nagham .Mahmood.Aljamali Assist. Professor ,Chem.Dept., Kufa Univ., Iraq E.mail :Dr.Nagham_mj@yahoo.com  Abstract In this paper , synthesis of a series of compounds from  hetero (Atoms, cycles) like  (5,6,7,8-membered )ring via cyclo addition reaction of anil compound to produce compound [1-13], this reactions involved addition of  carbonyl compounds like (( succinic acid , malonic acid , any compounds have  two terminal  from  amine  and  thiol or  carboxyl group)) to anil compounds  to  produce  various  membered  rings. The structure of the newly synthesized compounds [1-13] were confirmed with (C.H.N)- analysis & substantiated with (FT.IR ,H.NMR) data  & melting points. Keywords : eight membered , sulphur ,macrocycle , Imine ,heterocycle, five membered.  Introduction : Hetromacrocycles by far are the largest classical division of organic chemistry . Hetero cycles bearing nitrogen ,sulphur ,oxygen, constitute the core structure of a number of biologically interesting compounds ,some of them are pyrazoles , imidazoles ,which are structural subunits of several biologically active compounds(1-4) . Heterocycles have been used a scaffold to synthesize numerous therapeutic molecules , which are known for their medicinal importance as anticancer  antibacterial ,antiseptics, & are known to be involved in a number of biological reactions such as inhibition of DNA ,RNA  & protein synthesis(5-8). The utility of anil compounds lay in their usefulness as synthons in the synthesis of bio active molecules , it has ben found that the activity of hetero cycles increases on the incorporation of anil groups (9-13) .  Experimental:    All chemicals used were supplied from BDH & Fluka- company , purity 99.5 % .   All measurements were carried out by : 1 – Melting points : electro thermal 9300 , melting point engineering LTD , U.K  2 – FT . IR spectra : fourrier transform infrared shimadzu 8300 – (FT . IR ), KBr disc was performed by CO.S.Q.C. Iraq  3 – H.NMR-spectra and (C.H.N) – analysis : in center lab – institute of earth and environmental science , al –byat university , Jordan .  Synthesis of compound [1]. Condensation reaction by refluxing ethanolic mixture of equimolar amounts (0.1 mole ,12.0 gm) of p-methyl benzaldehyde & (0.1 mole ,9.7 gm) of 2-amino thiophene were react for (2hrs), the precipitate was filtered  & recrystallized from ethanol to produce 83% of anil compounds [1].  Synthesis of compounds [2-5]: A mixture of compound [1] (0.01 mole , 2.01 gm)was reacted with one of {(0.01 mole,1.38 gm )of 2-mercapto benzaldehyde ), (0.01mole, 1.19 gm of 2-amino benzaldehyde ), (0.01 mole , 1.20 gm of salicyldehyde ) ,(0.01mole , 0.75 gm of alanine )}, respectively , under reflux for (10hrs) in presence of anhydrous 1,5-dioxan (100) ml , the precipitate was filtered , dried ,& crystallized from absolute ethanol to produce % (86,84,82,86) respectively from compounds [2,3,4,5].  Synthesis of compounds [6-9]: A mixture of compound [5] (0.01 mole , 2.58 gm)was reacted with one of {(0.01 mole,1.18 gm )of succinic acid ), (0.01mole,1.04 gm of malonic acid ), (0.01 mole , 0.78 gm of acetyl chloride ) ,(0.01mole , 1.06 gm of benzaldehyde )}, respectively , with reflux for (6hrs) in presence of absolute ethanol (100) ml with drops of sodium ethoxide.  the precipitate was filtered , dried ,& crystallized from absolute ethanol to give  % (82,85,87,86) respectively, from compounds [6,7,8,9].   Chemistry and Materials Research                                                                                                                                                    www.iiste.org ISSN 2224- 3224 (Print) ISSN 2225- 0956 (Online) Vol.6 No.9, 2014  53 Synthesis of compounds [10,11]: A mixture of compound [8] (0.01 mole , 3 gm)was reacted with one of {(0.01 mole,1.04 gm )of malonic acid ), (0.01mole,1.18 gm of succinic acid )} respectively under reflux for (6hrs) in presence of absolute ethanol (100) ml with drops of sodium ethoxide, the precipitate was filtered , dried ,& crystallized from absolute ethanol to produce  % (87,85) respectively, from compounds [10,11].  Synthesis of compounds [12,13]: A mixture of p-methyl benzal dehyde (0.1mole ,1.2 gm)with P-chloro acetanilide(0.1 mole , 1.69gm) in ethanol (100) ml& 2ml of (3% sodium hydroxide solution )with stirring for (5hrs) at room temperature ,then refluxed for (8hrs), , the precipitate was filtered , dried ,& crystallized from ethanol to produce 88 %  of compounds [12]. To prepare compound [13], mixture of compound [12] (0.01 mole , 2.71 gm) & hydrazine(0.01 mole , 0.50 gm) under reflux for (7hrs) in presence of absolute ethanol (100) ml, the precipitate was filtered , dried ,& crystallized from ethanol to produce  % 86 of compound [13]. Scheme Reaction : SNH2 +CH3 CHOref .(1hrs)EthOHSN CH CH3r ef.(7hrs)DioxanNH2CH2 COOHSN CH CH3C NHOSN CH CH3COOSN CH CH3CNHOSN CH CH3CSOCHOSHNH2CHOOHCHOCHOSN CH CH3C NHOSN CH CH3C NOC OCH3SN CH CH3C NOC OCOSN CH CH3C NOC OCOCH3COCLCOOHCOOHCOOHCOOH[1]refluxEthOH[5](f ive-membered[4](six-membered)[3](six-membered)[2](six-membered)[9][8][7](f ive-membered)[6](six-membered) Chemistry and Materials Research                                                                                                                                                    www.iiste.org ISSN 2224- 3224 (Print) ISSN 2225- 0956 (Online) Vol.6 No.9, 2014  54 SN CH CH3C NOC OCH3[8]ref luxEtOH , EtoNaCOOHCOOHCOOHCOOHSN CH CH3C NOC OCOCCH2OSN CH CH3C NOC OCOCH2C O[10(seven-membered)[11](eight-membered)CL NHOC CH3 +CHCH3OEtOH , NaOH(2ML)StirringCL NHOCCH3ref luxNH2 NH2. H2OSNH CCH3NNH[13](f ive-membered)[12] Results & Discussion : In this study , we wish to report on anew approach for preparation of hetero atoms cycles (S,N,O) & hetero cycles (5,6,7,8-membered) ring from compounds [1-13]. Their FT.IR-Spectrum showed an absorption band at (1620) cm-1 in compound [1] due to the (CH=N) anil group ,which disappear & other bands are appear at {(1685-1698) cm-1 for amide(15) group ( C NO),(1530-1545) cm-1 for (C-N) endocycle & bands due to(C-S , C-NH , C-O , CH-NH )} in formed compounds [2-13] also new bands appeared such as (C=CH) due to alkene in compounds [9,12] ,bands at (1710-1725)cm-1 due to carbonyl of ketone in forned cycles in compounds [6-11] , & other bands are summarized in table (1) & figure (1-4). Their H.NMR-Spectra showed signal at 8.89 ʆ for proton of azomethine group (CH=N) in compound [1] which disappear & new signals appear at (5.96 ʆ for CH-S)(16) in compound [2] , (3.9 ʆ for CH-O) in Chemistry and Materials Research                                                                                                                                                    www.iiste.org ISSN 2224- 3224 (Print) ISSN 2225- 0956 (Online) Vol.6 No.9, 2014  55 compound[4] ,(3.09 ʆ - 3.19 ʆ for CH-NH in cyclic compounds[3,5-11,13] , (9.72 ʆ for proton of amide ) in compound [12] as result of formed cycles ,& other data of functional groups show in the following , Table (2) & figure (5-8) . Their (C.H.N)- analysis & melting points , it was found from compared the calculated data with experimentally data of these compounds ,the results were compactable , the data of analysis , M.F & melting points are listed in table (3) .  Acknowledgment : I would like to express my thanks to Mr.Samer  in Jordan for providing (C.H.N) element analytical , and H.NMR –spectra & melting points And express my thanks to(United Arabic Company) & ((Zaidan Company of Chemical )) for supplied some materials .  Table (1): (FT.IR)-data (cm-1) of compounds [1-13]. ComP.  no. I.R(KBR)    (Important Groups) [1] (CH=N) azomethine group : 1620  [2] (O=C-N) amide of endocyclic :1698,(C-N) endocyclic :1537 ,(C-S) endocyclic :675 ,1404, (C=C) aromatic:1581 . [3] (O=C-N) amide of endocyclic :1690,(C-N) endocyclic :1540 ,(NH): 3320 . [4] (O=C-N) amide:1698,(C-N) endocyclic :1540 ,(C-O-C): 1050 . [5] (O=C-N) amide:1685,(C-N) endocyclic :1535 ,(NH): 3330, (CH) aliphatic :2930  . [6] (O=C-N) amide:1690,(C-N) endocyclic :1530 ,( ) ketone: 1725, (CH) aliphatic :2950  . [7] (O=C-N) amide:1680,(C-N) endocyclic :1498 ,( ) ketone: 1717, (CH) aliphatic :2925  . [8] (O=C-N) amide:1690,(C-N) endocyclic :1544 ,(CH) aliphatic :2930.   [9] (O=C-N) amide:1695,(C-N) endocyclic :1545 ,(NH):3320,(=CH) alkene:3080 . [10] (O=C-N) amide:1686,(C-N) endocyclic :1537 ,( ) ketone: 1720, (CH) aliphatic :2920  . [11] (O=C-N) amide:1690,(C-N) endocyclic :1540 ,( ) ketone: 1725, (CH) aliphatic :2940  . [12] (O=C-N) amide:1695,(=CH) alkene: 3050  . [13] (C=N) azomethine:1620,(N-N) endocyclic :1400 ,(NH) : 3330, (CH) aliphatic :2940  .  Table (2): H.NMR-data(ɓppm) of compounds [1-13] . Comps H.NMR(DMF)   (Important peaks ) [1] 8.89 {1H ,(CH=N)} proton of azomethine group. [2] 6.34-7.8 (Ar-H) , 5.96 (CH-S). [3] 6.6-7.8 (Ar-H) ,3.11 (CH-NH) . [4] 6.36-7.3 (Ar-H) , 3.9 (CH-O) . [5] 3.09 (CH-NH) , 9.96 ( C NOCH2 ) . [6] 3.1 (1H ,CH-N), 12.2 (O=C-CH2-) ,10.2 ( C NOCH2 ) .  [7] 3.19 (1H ,CH-N) , 12.79 (2H , O=C-CH2 ). [8] 3.1 (1H , CH-N), 10.1 ( C NOCH2 ), 10.5 ( C NOCH3 ) . [9] 2.3 (1H ,CH=C), 3.4 (CH-NH), 6.4-7.2 (Ar-H). [10] 3.12 (1H,CH-N), 12.3 (2H, O=C-CH2-C=O) . [11] 3.3(1H,CH-N) ,12.59 ( COCCH2 ), 12.72(O=C-CH2-C=O) . [12] 9.72 ( ), 2.63 (CH=CH), 6.34-7.56 (Ar -H) , 1.01 (CH3) . [13] 1.2 (2H,CH2 –C) , 3.2 (CH-NH) , 6.4- 7.2 (Ar- H) , 1.2 (CH3) .    Chemistry and Materials Research                                                                                                                                                    www.iiste.org ISSN 2224- 3224 (Print) ISSN 2225- 0956 (Online) Vol.6 No.9, 2014  56 Table (2): physical properties & (C.H.N)- analysis of compounds [1-13]. Comps M.F M.P (C◦) Name of compounds          Calculation/Found C% H% N% [1] C12H11N1S1 161 2-(4—Toluine)- thiophenidine . 71.641 71.342 5.472 5.211 6.965 6.654 [2] C19H15NOS2 242 2-(4—Toluine)- 3-thiophenidine-5,6- benzo-1,3-Thiazane-4-one.  67.655 67.462 4.451 4.318 4.154 4.310 [3] C19H16N2OS 218 2-(4—Toluine)- 3-thiophenidine-5,6- benzo-pipyrimidine-4-one.  71.25 71.012 5.00 5.021 8.750 8.592 [4] C19H15NO2S 235 2-(4—Toluine)- 3-thiophene-1-oxo-5,6- benzo-pipyrimidine-4-one.  71.028 71.320 4.672 4.711 4.361 4.451 [5] C14H14N2OS 195 2-(4-- Toluine)- 3-thiophene Imidazoline-4-one.  65.116 65.014 5.426 5.201 10.852 10.312 [6] C18H16N2O3S 238 3-(2-- Thiophene) -2-(4--Toluine)-1,5-(2-,5-- dione–azane)– imadazol-4-one.  63.529 63.342 4.705 4.611 8.235 8.301 [7] C17H14N2O3S 222 3-(2-- Thiophene)-2-(4--Toluine)-1,5-(2-,4--di one –azolidine)–imadazol-4-one.  62.576 62.328 4.294 4.271 8.588 8.401 [8] C16H16N2O2S 200 2-(4-- Toluine)-3-thiophene-1-aceto- Imidazoline-4-one.  64.00 64.018 5.333 5.350 9.333 9.114 [9] C21H18N2OS 210 3-(2-- Thiophene) -2-(4--Toluine)-1,5-(2-,4- ,6--Tri one –azecane)–imadazol-4-one.  72.832 72.672 5.202 5.151 8.092 8.001 [10] C19H16N2O4S 240 3-(2-- Thiophene)-2-(4--Toluine)-1,5-(2-,4- ,6- -Tri one –azepane)–imadazol-4-one.  61.956 61.813 4.347 4.238 7.608 7.516 [11] C20H18N2O4S 229 2-(4-- Toluine)- 3-thiophene-5-styrene- Imidazoline-4-one.  62.827 62.719 4.712 4.623 7.329 7.113 [12] C16H14N1O1Cl 165 N-(4-Chloro phenyl)-3-Toluine acrylamide. 70.718 70.651 5.156 5.08 5.156 5.201 [13] C16H16N3Cl 176 4-[(5- -Toluine-4-,5- -dihydro pyrazol-3- -yl)amino] chloro benzene. 67.250 67.161 5.604 5.587 14.711 14.511  References  1. Shridhar .A , Keshavayya . J, Joy .H & Shoukat . R., (2011) , International .Res.J of pure . Appl.Chem., 1,3, 119-129. 2. Kumar .K, Reddy . K , Vamsikauth .A, Omprakash . G and Dubey .P., (2011).,Der.Pharma . Chemica .,3,5,113-122. 3. Faid allah .M ,Rostom . A and mohamm .S  ., (2010) .,J.K .A.U .Sci .,22 ,1 ,177 -191 . 4. Coquerel .Y , Bensa . D , Doutheau . A and Rodriguez . J .,(2006) ., org . lett ., 8,21, 4819 -4822 . 5. Hatem . G and mark . B ., (2011) , European . J .chem ., 2 ,2 ,214 -222 . 6. Parameswaran . M , Thengungal .K and Gopalakrish. S. ,(2009) , Acta . Pharma ., 59,159-170.  7. Singaravel .M , Sarkkarai. A & Kambikudi. R.,(2010)., International .J.pharma.Sci & Res., 1,9,391-398. 8. Smaail .R, Souad. S & Amal .R.,(2010), Lett. Drug . Design   . Discovery .,7,27-30. 9. Vibhute .A,Mokle .S,Nalwar .Y &Gurav .,(2009).,Bulletin .Cata.Soci . India ,8,164-168. 10. Ahasan .N & Islam . M.,(2007)., Bangladesh. J.Pharma., 2,81-87. 11. Palak. P ,Hiran. M & Dhrubo. 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Synthesis of (5,6,7,8)-Membered Rings of (Sulfur ,Nitrogen) via  Cyclization of Imine Compounds

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Synthesis of (5,6,7,8)-Membered Rings of (Sulfur ,Nitrogen) via Cyclization of Imine Compounds

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