Salisilaldehitten Sentezlenen Schiff Bazlarının Kütle Spektrumlarında Orto Substituentlerin Etkisi

Yıl 2013, Cilt: 8 Sayı: 1, 106 - 113, 10.06.2013

Gökhan Denizli Sevi Öz , Arda Atakol Emine İnal , Mehmet Akay

Öz

Orto, meta ve para substitue, hidroksi, metoksi, floro, kloro, bromo, iyodo anilinler, benzil amin, 2- hidroksi benzil amin ve salisilaldehit kullanılarak 21 tane Schiff bazı hazırlandı. Bu Schiff bazları 20-140 eV’luk elektronlarla direkt iyonlaştırıldı ve kütle fragmantleri belirlendi. Tüm Schiff bazlarında 20-140 eV’luk elektronlarla iyonlaşmada moleküler pik temel pik olarak gözlendi, 20-140 eV’luk elektronlarla iyonlaştırılmış Schiff bazlarında fragmentasyonun çok düşük olduğu spektrumda tek güçlü pikin moleküler pik olduğu görüldü. Anilin tarafında orto pozisyonunda substituent bulunması durumunda, temel pik M-X (m/z=196) olarak gözlendi. Brom içeren bileşiklerde gözlenen M+HX piklerinin, oluşan HBr’nin moleküle katılması sonucunda ortaya çıktığı sonucuna varıldı.

Anahtar Kelimeler

o-etkisi, Schiff bazı, salisilaldimin, Direk Inlet, HX katılması

The Effect of o-Substituents on Mass Spectra of Schiff Bases Synthesized from Salicylaldehyde

Öz

21 Schiff bases were prepared from orto, meta and para substituted hydroxy, metoxy, floro, chloro, bromo, iodo anilines, benzyl amines, 2-hydroxy benzyl amines and salicylaldehyde. The Schiff bases were ionized with 20-140 eV electrons using Direct Inlet to determine their mass fragments. In the cases where the substituents are in meta or para position and in the range of 20 to 140 eV, the molecular peaks were observed as the base peaks. The base peak in the spectra of the substances, in which the substituent close to the aniline side is in ortho position, was found to be the M-X (m/z=196) peak. M+HX peaks were also observed in the spectrum of the bromine substituted compound which is probably due to that the formed HBr attacked the molecule and was added to it.

Anahtar Kelimeler

o-effect, Schiff bases, salicylaldimine, Direct Inlet, HX addition

Kaynakça

• Paryzek W.R., Kaczmarek S.M., Patroniak V., Pospieszna-Markiewicz L., 2003. New Supramolecular dinuclear rare earth Schiff base Podands, Inorganic Chemistry Communications, 6: 26-29.
• Przybylski P., Schroeder G., Pankiewicz R., Brzezinski B., Bartl F., 2003. Complexes of Schiff base of gossypol with n-butylamine and some monovalent or bivalent cations studied by ESI-MS, NMR, FTIR as well as PM5 semiemprical methods, Journal of Molecular Structure, 658: 193- 205.
• Przybylski P., Kolodziej B., Leniec G., Kaczmarek M.T., Grech E., Typek J., Brzezinski B., 2007. ESI-MS Spectroscopic and semiemprical characterization of macrobicyclic complex with Er(III) cation, Journal of Molecular Structure, 878: 95-103.
• Przybylski P., Pyta K., Wicher B., Gdaniec M., Brzezinski B., 2008. Structure of a new Schiff base of gossypol with 1-(3-aminopropyl)2-pyrrolidinone studied by X-ray, FTIR, NMR, ESI-MS, and PM5 method, Journal of Molecular Structure, 889: 332-343.
• Zeng Q.L., Chen W.Z., Zhao Y.F., 2007. Electrospray ionisation mass spectral fragmentation study of amino acid derived oxovanadium Schiff base complexes and oxovanadium Schiff base complexes, International Journal of Mass Spectrometry, 262: 161-167.
• Jirasco R., Holčapek M., Koláŕová L., Nádvornik M., Popkov A., 2008. Characterization of Ni(II) complexes of Schiff bases of amino acids and (S)-N-(2-benzoylphenyl)-1-benzylpyrrolidine-2- carboxamide using ion trap QqTOF electrospray ionization tandem mass spectrometry, Journal of Mass Spectrometry, 43: 1274-1284.
• Przybylski P., Pyta K., Brezinski B., Bartl F., 2009. Complexes of heterocyclic aza derivatives of phytoalexin from cotton plant-gossypol with alkali metal cations and perchlorate anion studied by ESI mass spectrometric method in the positive and negative modes, Journal of Mass Spectrometry, 44: 838-846.
• Kantilal S.P., Rinehart K.L., Bailar J.C., 1970. Mass spectral studies of Schiff bases and their metal complexes, Organic Mass Spectrometry. 4: 441-451.
• Morris M.L., Koob R.D., 1983. Mass Spectral Analysis of Schiff Bases Derived from l,l,l-Trifluoro- 2,4-pent anedione and 1,2-Diaminoethane, 1,3-Diaminopropane,1,4-Diaminobutane and 1,2- Diaminobenzene and their Copper (II) and Nickel(II) Complexes, Organic Mass Spectrometry, 18: 305-314.
• Tarnburini S., Vigato P.A., Traldi P., 1986. Electron Impact Mass Spectrometry of Some Macrocyclic and Acyclic Aldimines, Organic Mass Spectrometry. 21: 183-192.
• Ma Y.C., Munson B., 1991. Thermal Effects on the Mass Spectra of Benzophenone Oximes Obtained by Gas Chromatography Electron Ionization, Organic Mass Spectrometry. 26: 821- 825.
• Vijfhuizen P.C., Terlouw J.K., 1977. The Electron Impact Induced Fragmentation of Aromatic Aldoximes, Organic Mass Spectrometry. 12: 245-253.
• Isse A.A., Abdurahman A.M., Vianello E., 1997. Role of Proton Transfer in the Electrochemical Reduction Mechanism of Salicylideneaniline, Journal of Electroanalytical Chemistry. 431: 249- 255.
• Issa Y.M., Hassib H.B., Abdelaal H.E., Kenawi I.M., 2011. Spectral investigation of the intramolecular Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy, 79: 1364-1374.
• Johnston D., Smart G.W., Smith D.M., 1976. o-Nitrobenzylidene Compounds, Organic Mass Spectrometry, 11: 609-622.
• Błachut D., Danikiewicz W., Olejnik M., Czarnocki Z., 2004. Electron ionization mass spectrometry as a tool for the investigation of the ortho effect in fragmentation of some Schiff bases derived from amphetamine analogs, Journal of Mass spectrometry, 39: 966-972.
• Ebara N., 1961. Benzylideneaniline, Bulletin of the Chemical Society of Japan, 34: 1151-1157.
• Carril M., Altmann P., Drees M., Bonrath W., Netscher T., Schütz J., Kuhn F.E., 2011. Methyltrioxorhenium-catalysed oxidation of pseudocumene for vitamin E synthesis, Journal of Catalysis, 283: 55-67.
• Karakaş A., Elmalı A., Ünver H., Svoboda I., 2004. Nonlinear optical properties of some derivatives of salicylaldimine-based ligands, Journal of Molecular Structure, 702: 103-110.
• Song D.P., Li Y.G., Lu R., Hu N.H., Li Y.S., 2008. Synthesis and characterization of novel neutral nickel complexes bearing their catalytic behaviour for vinylic polimerization of norbornane. Applied Organometallic Chemistry. 22: 333-340.
• Elmalı A., Karakaş A., Ünver H., 2005. Nonlinear optical properties of bis[(p- bromophenylsalicylaldiminato)chloro]iron(III) and its ligand N-(4-bromosalicylaldimine), Chemical Physics, 309: 251-257.
• Elerman Y., Elmalı A., Atakol O., Svoboda I., 1995. N(2-hydroxyphenyl)salicylaldimine, Acta Crystallographica, C51: 2344-2346.
• Golubev N.S., Smirnov S.N., Tolstoy P.M., Sharif S., Toney M.D., Denisov G.S., Limbach H.H., 2007. Observation by NMR of the tautomerism of an intramolecular OHOHN-charge relay chain in a model Schiff base. Journal of Molecular Structure, 844–845: 319-327.
• Užarević K., Rubčić M., Stilinović V., Kaitner B., Cindrić M., 2010. Keto–enol tautomerism in asymmetric Schiff bases derived from p-phenylenediamine, Journal of Molecular Structure, 984: 232-239.
• Türkoğlu G., Berber H., Dal H., Öğretir C., 2011. Synthesis, characterization, tautomerism and
• theoretical study of some new Schiff base derivatives, Spectrochimica Acta Part A: Molecular and
• Biomolecular Spectroscopy, 79: 1573-1583.
• Gündüz T., Gündüz N., Kılıç E., Atakol O., Köseoğlu F., 1991. Potentiometric Investigations of
• intramolecular nine and ten membered ring hydrogen bonds observed in Schiff bases, Analytica
• Chimica Acta, 249: 427-431.
• Gökhan Denizli e-mail: [e-mail]
• Arda Atakol e-mail: [e-mail]
• Emine Kübra İnal e-mail: [e-mail]
• Mehmet Abdülkadir Akay e-mail: [e-mail]