untitled ISSN 215 Synthes 3,5‐bis(4 Malki Sou Mahmoud Laboratory of A M’hidi University * Corresponding Material Science Tel.: +213.32558 ARTICLE IN DOI: 10.5155/e Received: 13 Oc Received in rev Accepted: 14 No Published onlin Printed: 31 Mar KEYWORDS Amine Synthesis 1,3,5‐Triazinan NMR spectrosc Hexahydrotriaz Infrared spectr 1. Introduct Hexahyd membered r 3 and 5 po hexahydrotr One of partic industrial ch 1,3,5‐triazina of N‐heteroc ligands in ho In the pr of the title co diffractomet sized title c using variou and UV spect 2. Experime 2.1. Instrum 53‐2249 (Print) sis and sp 4‐chlorop uhila *, Leila d Chebbah a Applied Chemistry a ty, Oum El Bouaghi, g author at: Labora es, Larbi Ben M’hid 8609. Fax: +213.32 FORMATION eurjchem.7.1.137‐1 ctober 2015 vised form: 14 Nov ovember 2015 ne: 31 March 2016 rch 2016 S ne opy zines oscopy tion drotriazines be ring compounds sitions [1]. Ov iazines have re cular interest is hemistry [3], as anes can be us cyclic carbenes omogenous cata revious researc ompound was c ter [5]. In this compound was s spectral techn troscopy. ental mentation E / ISSN 2153‐225 htt Europ ectral stu phenyl)‐1 Lefrada, Ah nd Assia Sid and Materials Techn i, 04000, Algeria atory of Applied Ch di University, Oum E 2424213. E‐mail ad 138.1337 ember 2015 elong to a w s having three ver the years, eceived consid s the use of thes s an example N ed as reactants , which are a alysis [4]. ch work, the sin characterized by work, the stru s confirmed an niques like FT‐ uropean Journal Europ 57 (Online)  20 tp://dx.doi.org/ pean Jo Journal web udies of 1‐propyl‐1 hcene Bouch d nology, Faculty of E emistry and Mater El Bouaghi, 04000, ddress: souhila.malk ABSTRACT A hexahydro chloroaniline, confirmed an NMR and UV s Cite this: Eur. wide range of nitrogen atoms N‐substituted erable attentio se type of produ N,N′,N′′‐trisubst s for the prepar substantial cl ngle crystal stru y X‐ray single c ucture of the sy nd characterize IR, 1H NMR, 13C l of Chemistry 7 pean Journal of C 016 Atlanta Pub 10.5155/eurjche ournal bpage: www. 1,3,5‐triaz hemma, Mus Exact Sciences and ials Technology, Fa Algeria. ki@gmail.com (M. S otriazine deriva , propylamine a nd characterized spectroscopy. . J. Chem. 2016, f six‐ s in 1, 1,3,5‐ on [2]. ucts in tituted ration ass of ucture crystal ynthe‐ ed by C NMR app an per und an 400 inte The FT‐ spe pho 2.2. 1:2 in 2 °C. eva lize pro (1) (2016) 137‐ Chemistry lishing House LL em.7.1.137‐138. of Che .eurjchem.co zinane stapha Bouh Natural Sciences a aculty of Exact Scie Souhila). ative was synt and formalin. Th d by using vario 7(1), 137‐138 Melting point w paratus. The pu analytical thin rcolated TLC p der UV light and eluent. 1H and 0 MHz spectro ernal reference e infrared spect IR 8201 PC (4 ectra were rec otometer (190‐1 . Synthesis An excess of fo stoichiometric 25 mL of ethano The resulting aporator to dry ed from cycloh opyl‐1,3,5‐triaza ‐138 LC ‐ All rights re .1337 emistry m henguel, and life, Departmen nces and Natural S thesized via a he structure of ous spectral tec was determine urity of the title layer chromat plates (Silica g d using CH2Cl2: 13C NMR spect meter at room and chemical tra was record 4000‐400 cm‐1) corded on a S 1100 nm). ormalin was ad c ratio of n‐pro ol. The mixture g solution wa yness and the hexane to affor acyclohexane in served ‐ Printed y nt of Material Scien Sciences and life, De a condensation the synthesized chniques like FT ed on a capillary e compound w tography (TLC) gel 60F254, Mer : Petroleum eth tra were recor m temperature shifts are expre ed in KBr pelle ) spectrophotom SPECORD 200 dded dropwise t pylamine and 4 was stirred for as evaporated white residue rd 3,5‐bis(4‐ch n 89% yield [3‐6 d in the USA ces, Larbi Ben epartment of reaction of d compound wa T‐IR, 1H NMR, 1 y melting point as screened by ) conducted on rck) visualized her (4:1, v:v) as rded on Bruker using TMS as essed as δppm. et on Shimadzu meter. The UV plus spectro‐ to a solution of 4‐chloroaniline r 12 hours at 20 on a rotary was recrystal‐ hlorophenyl)‐1‐ 6]. 4‐ as 3C t y n d s r s . u V ‐ f e 0 y ‐ ‐ 138 Souhila et al. / European Journal of Chemistry 7 (1) (2016) 137‐138 Scheme 1 M.p.: 135‐137 °C. FT‐IR (KBr, ν, cm‐1): 3089‐3033 (νC‐H, Ar‐ H), 2954‐2805 (CH3, CH2), 1276 (C‐N), 815 (C‐Cl), 752 (δC‐ H,Ar). 1H NMR (400 MHz, CDCl3, δ, ppm): 0.90 (t, 3H, CH3), 1.50 (m, 2H, CH2), 2.52 (t, 2H, CH2), 4.25 (s, 4H, C3H7‐N‐CH2‐N‐Ar), 4.71 (s, 2H, Ar‐N‐CH2‐N‐Ar), 6.91 (d, 4H, Ar), 7.18 (d, 4H, Ar). 13C NMR (100 MHz, CDCl3, δ, ppm): 11.81 (CH3‐CH2), 20.88 (CH3‐CH2), 53.99 (C2H5‐CH2‐N), 68.63 (C3H7‐N‐CH2‐N‐Ar), 71.27 (Ar‐N‐CH2‐N‐Ar), 118.75 (CH, Ar), 125.64 (CAr‐Cl), 129.13 (CH,Ar), 147.93 (N‐CAr). UV (λmax, nm): 327‐328 (π‐* transitons), 194‐197 (n‐* transitons). 3. Results and discussion An unsymmetrically substituted 1,3,5‐hexahydrotriazine, 3,5‐bis(4‐chlorophenyl)‐1‐propyl‐1,3,5‐triazacyclohexane (I), was synthesized via a mixed condensation reaction of 4‐chloro aniline and n‐propylamine with formaldehyde (formalin) [7,8] (Scheme 1). This compound is stable at room temperature and obtained in high yield (89%). Recrystallized from cyclohexane gave transparent colorless plaques. The synthesis mechanism is probably pass through imines, which trimerizes to give the title compound I [3]. The characterization of the title compound has been interpreted by FT‐IR, 1H‐NMR and 13C‐NMR including 2D measurements. The infrared spectrum reveals a strong sharp band at 815 cm‐1 resulting from the stretching vibration of C‐Cl band. Two absorption bands at 1492 and 1590 cm‐1 are shown by the six‐membered aromatic system (νC=C), another absorption band at 752 cm‐1 characteristic of the C‐H out of plane vibration of the aromatic system. The 1H NMR spectrum of the title compound shows protons of the methyl group resonate as a three proton triplet centered at δ 0.90 ppm. The two protons of CH2 group adjacent to both CH2 and CH3 groups appear as sexlet at δ 1.50 ppm (CH3‐CH2‐CH2). A triplet peak centered at δ 2.52 ppm shows the two protons of the CH2 group attached to the nitrogen atom (CH2‐CH2‐N). The protons of the heterocyclic triazine appear at δ 4.25 and 4.71 ppm. The protons of the aromatic system appear as a two doublets at δ 6.91 and 7.18 ppm. In the 13C NMR spectra of the title compound, the chemical shift values of different carbon atoms of the propyl group appear at δ 11.81, 20.88 and 53.99 ppm. The 13C NMR spectrum display two signals at δ 68.63 and 71.27 ppm corresponding to two carbon atoms of the triazinane cycle. Those of the aryl groups appear at δ129.13 and 118.75 ppm, and the C‐Cl atom appears at δ 125.64 ppm. The ultra‐violet (UV) spectrum of the crystalline form shows two weak signals at 194 and 197 nm characteristic the n → π* transition. The other signals appear as intense at 327 and 328 indicating the π→π* transitions. 4. Conclusion In this manuscript, we have described the synthesis of a triazacyclohexane derivative by the condensation of 4‐chloro aniline and n‐propylamine with formalin in the presence of ethanol. The desired product was obtained with good yield and characterized by the usual spectroscopic methods IR, NMR and UV. Acknowledgements We thank Prof. Mustapha Bouhenguel director of the Laboratory of Applied Chemistry and Materials Technology of the University Larbi Ben M’hidi of Oum El Bouaghi, Algeria. References [1]. Arshad, M.; Khan,T. A.; Khan, M. A. Int. J. Pharm. Sci. Res. 2014, 5(4), 149‐162. [2]. Afonso, C. A. M.; Lourenco, N. M. T.; Rosatella, A. A. Molecules 2006, 11(1), 81‐102. [3]. Lefrada, L.; Bouchemma, A.; Bouhenguel, M.; Ferhati, A.; Chebbah, M. Eur. J. Chem. 2012, 3(4), 404‐405. [4]. Poethig, A.; Ahrens, S.; Strassner, T. Acta Crystallogr. E 2007, 63(5), o2398‐o2399. [5]. Lefrada, L.; Bouchemma, A.; Bouacida, S.; Claiser, N.; Souhassou, M. Acta Crystallogr. E 2007, 70(9), o1061‐o1062. [6]. Chebbah, M.; Bouchemma, A.; Bouacida, S.; Lefrada, L.; Bouhenguel, M. Acta Crystallogr. E 2007, 69(6), o976‐o976. [7]. Bouchemma, A.; McCabe, P. H.; Sim, G. A. J. Chem. Soc., Perkin Trans. 2 1989, 6, 583‐587. [8]. Latreche, S.; Mousser, A.; Kociok‐Kohn, G.; Kohn, R. D.; Schaper, F. Polyhedron 2010, 29(5), 1399‐1404.