Synthesis of Arylamines by Electrophilic Amination of Grignard Reagents with Acetone O-(2,4,6-trimethylphenylsulfonyl)oxime

Yıl 2008, Cilt: 12 Sayı: 1, 9 - 12, 09.04.2009

Tahir Daşkapan Ağca Cengiz

Öz

Arylamines constitute an important class of organic compounds which give rise to a broad spectrum of practical and useful applications. Arylamino group is a fundamental structural motif in Nature. Amongst modern methods, electrophilic amination of an easily available organometallic reagent appeared as an important method in the organic synthesis. In this work, an easily applicable method was developed for the preperation of arylamines which are used in synthetic organic, medicinal and agricultural chemistry by electrophilic amination of organomagnesium reagents with acetone O-(2,4,6-trimethylphenylsulsulphonyl)oxime under mild reaction conditions and in good yields.

Anahtar Kelimeler

Electrophilic Amination, Oximes, Amines, Organomagnesium Compounds

Grignard Reaktiflerinin Aseton O-(2,4,6-trimetilfenilsülfonil)oksim ile Elektrofilik Aminasyonuyla Arilaminlerin Sentezi

Öz

Arilaminler, birçok pratik ve yararlı uygulamalara imkan veren önemli bir organik bilesik sınıfıdır. Arilamino grubu dogada temel bir yapısal motiftir. Amin sentezi için gelistirilen modern yöntemler arasında kolay bulunabilen bir organometalik reaktifin elektrofilik aminasyonu yöntemi, organik sentezde önemli bir yöntem olarak ortaya çıkmıstır.Bu çalısmada, sentetik organik, ilaç ve tarım kimyasında kullanılan arilaminlerin, organomagnezyum reaktiflerinin aseton O-(2,4,6-trimetilfenilsülfonil)oksim ile elektrofilik aminasyonuyla ılımlı reaksiyon sartları altında ve iyi verimle hazırlanması için kolay uygulanabilir bir yöntem gelistirilmistir.

Anahtar Kelimeler

Elektrofilik Aminasyon, Oksimler, Aminler, Organomagnezyum Bileşikleri

Kaynakça

• Alvernhe, G., Laurent, A. 1972. Obtention d’amines Primaires par action d’organo-magnesiens sur l’acetoxime. Tetrahedron Letters, 11, 1007-1010.
• Ay, M. 1989. I. Grup ve II. Grup organometalik bileşiklerin ketoksimlerle elektrofilik aminasyonu Doktora Tezi, A. Ü. Fen Bilimleri Enstitüsü, Ankara, 92 sayfa
• Barber, H.J. 1943. Coprous Cyanide: A Note on its Preparation and Use. J. Chem. Soc., 1, 79.
• Boche, G., Bernheim, M., Schrott, W. 1982. Primary Amines via Electrophilic Amination of Organometallic Compounds with O- diphenylphosphinyl)hydroxylamine. Tetrahedron Letters, 23, 5399-53402.
• Brodkin, G.I., Shubin, V.G. 2005. Nitrenium Ions and Problem of Direct Electrophilic Amination of Aromatic Compounds. Russ. J. of Org. Chem., 41, 473-504.
• Brown, R., Jones, W.E. 1946. A Convenient Method of Preperation of Certain Primary Amines, J. Chem. Soc.,781-782.
• Chaabouni, R., Laurent, A., Mison, P. 1973. Formation d’aziridines Cyclaniques par Action de Reactifs de Grignard sur les Oximes: Determination des Configurations Relatives. Tetrahedron Letters. 16, 1343-1346.
• Coleman, G.H., Hauser, C.R. 1928. The Formation of Primary Amines from Grignard Reagents and Monochloroamine. J. Am. Chem. Soc., 50, 1193- 1196.
• Coleman, G.H., Yager, C.B. 1929. The Formation of Primary Amines from Grignard Reagents and Monochloroamine. II. J. Am. Chem. Soc., 51, 567- 569.
• Coleman, G.H., Buchanan, M.A. 1933. The Reaction of Nitrogen Trichloride with Grignard Reagents. J. Am. Chem. Soc., 55, 3669-3672.
• Coleman, G.H. 1933. The Reaction of Alkylchlorramines with Grignard Reagents. J. Am. Chem. Soc., 55, 3001-3005.
• Erdik, E., Ay, M. 1989. Electrophilic Amination of Carbanions. Chem. Review, 89, 1947-1980.
• Erdik, E., Ay, M. 1989. Effect of Copper (I) Iodide and Magnesium Chloride on Amination of Aryl Grignards with Ketoximes. Synth. React. Inorg. Metal.-Org. Chem., 19, 663-668.
• Erdik, E., Daşkapan, T. 2002. Can We Aminate Grignard Reagents Under Barbier Conditions?. Tetrahedron Letters, 43, 6237-6239.
• Gündüz, T. 1983. Kantitatif Analiz Laboratuar Kitabı III.baskı, Ankara Üniversitesi Fen Fakültesi Basımevi, Ankara, 312 sayfa.
• Hogopian, R.A., Terien, M.J. Murdoch, J.R. 1984. Synthesis of Amines Through Nucleophilic Addition on Nitrogen. J. Am. Chem. Soc., 106, 5753-5754.
• Keller, R.N., Wynocoff, H.D. 1946. Copper (I) Chloride. Inorg. Synth., 2, 1-4.
• Narasaka, K., Tsutsui, H., Ichikawa, T. 1999. Preparation
• of Primary Amines by the Alkylation of O
• Sulfonyloximes of Benzophenone Derivatives with
• Grignard Reagents. Bull. Chem. Soc. Jpn., 72, 1869-1878.
• Rappoport, Z. 1980 Handbook of Tables for Organic Compound Identification, CRC Press, Inc., Florida.
• Schverdina, N.I., Kotscheschkow, K.A. 1940. Die Reaktion Organomagnesium und Organolithium Verbindungen als Methode zur Synthese von Primaren Amine. Chem. Zentbl., I. 360: J. Gen. Chem. USSR, (Eng. Transl.), 1938, 8,1825-1827.
• Semon, W.L. 1923. The Preperation of Hydroxylamine Hydrochloride and Acetoxime. J. Am. Chem. Soc. 45, 188-190.
• Semon, W.L. 1924. Hydroxylamine Hydrochloride and Acetoxime. Org. Synth., III.,61-64.
• Smith, P.A.S., Rowe, C.P., Bruner, L.B. 1969. Azides and Amines from Grignard Reagents and Tosyl Azides. J. Org. Chem., 34, 11, 3430-3433.
• Wakefield, B.J. 1995. Organomagnesium Methods in Organic Synthesis, Best Synthetic Methods. Academic Pres Ltd., 249 p, Florida.
• Watson, S.C., Eastham, J.F. 1967. Colored Indicators for Simple Direct Titration of Magnesium and Lithium Reagents. J. Organometall. Chem., 9, 165-168.