New selective approach to p-chlorocalix[4]arenes synthesis / Mitin V.V., Ivanova E.A., Prokhorova P.E., Morzherin Y.Y. // Letters in Organic Chemistry. - 2016. - V. 13, l. 9. - P. 625-628.

ISSN:

15701786

Type:

Article

Abstract:

Background: Calixarenes are well-known building blocks in supramolecular chemistry. Introduction of the halogen atom at the upper rim of the molecule allows to obtain very promising synthons for synthesis of more complex calixarene structures. Each halogen is specific for the certain types of reactions. It is known that chlorine derivatives are preferable for the Kumada, Hiyama, Stille, Negishi, Suzuki cross-coupling reaction and Buchwald-Hartwig amination. para-?hlorinated derivatives of calix[4]arene were described in the literature even less than other halogenated ones because of their synthesis complication (low yield construction from chlorophenols). Methods: To increase the yield of p-chlorinated calix[4]arene and to reduce the number of synthetic steps ipso-chlorination reactions were tried. Reactions were carried out in dry tetrachloromethane with sulfuryl chloride in the presence of Lewis acids (AlCl3, FeCl3, PCl5). Results: It was shown that PCl5 presence led to the best yield (57%). It was almost two times higher than in the case of aluminum chloride use. Unfortunately, the reaction with FeCl3 did not give the individual product. Conclusion: A new method for synthesis of dichlorinated at the upper rim calix[4]arenes via ipsochlorination with sulfuryl chloride in the presence of phosphorous pentachloride was developed. The influence of other Lewis acids was studied. The number and position of chlorine atoms in the structure of obtained compounds were confirmed. © 2016 Bentham Science Publishers.

Author keywords:

Chlorination; Chlorocalix[4]arene; Halogenated calix[4]arene; Ipso-Substitution; Sulfuryl chloride

Index keywords:

нет данных

DOI:

10.2174/1570178613666161013144

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https://www.scopus.com/inward/record.uri?eid=2-s2.0-85009063013&doi=10.2174%2f1570178613666161013144841&partnerID=40&md5=5464390280f9aa4e6aed9858b3ffe2d1

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Link	https://www.scopus.com/inward/record.uri?eid=2-s2.0-85009063013&doi=10.2174%2f1570178613666161013144841&partnerID=40&md5=5464390280f9aa4e6aed9858b3ffe2d1
Affiliations	Department of Technology for Organic Synthesis, Chemical Technology Institute, Ural Federal University, 19 Mira St., Yekaterinburg, Russian Federation
Author Keywords	Chlorination; Chlorocalix[4]arene; Halogenated calix[4]arene; Ipso-Substitution; Sulfuryl chloride
References	Ivanova, E.A., Prokhorova, P.E., Morzherin, Y.Y., Synthesis methods for halogenated calix[4]arenes (2016) Mini-Rev. Org. Chem., 13, pp. 245-254; De Mendoza, J., Nieto, P.M., Prados, P., Sanchez, C., A stepwise synthesis of functionalized calix[4]arenes and a calix[6]arenes with alternate electron-withdrawing substituents (1990) Tetrahedron, 46, pp. 671-682; Moshfegh, A.A., Badri, R., Hojjatie, M., Kaviani, M., Naderi, B., Nazmi, A.H., Ramezanian, M., Hakimelahi, G.H., The synthesis of 4,11,18,25 - Tetrachloro[ 14]metacyclophane - 7,14,21,28 - tetrol. Structural analogues of phloglucides (1982) Helv. Chim. Acta, 65, pp. 1221-1228; Bohmer, V., Merkel, L., Kunz, U., Assimetrically-substituted calix[4]arenes (1987) J. Chem. Soc. Chem. Commun., 12, pp. 896-897; Bohmer, V., Jung, K., Schoen, M., Wolff, A., Direct synthesis of calix[4]arenes with two different phenolic units in alternating order (1992) J. Org. Chem., 57, pp. 790-792; Bohmer, V., Marschollek, F., Zetta, L., Calix[4] arenes with four differently substituted phenolic units (1987) J. Org. Chem., 52, pp. 3200-3205; Kuhnert, N., Le-Gresley, A., On the scope and limitations of the Heck reaction of upper rim tetraiodocalix[4]arenes (2001) J. Chem. Soc. Perkin Trans., 24, pp. 3393-3398; Arduini, A., Pochini, A., Rizzi, A., Sicuri, A.R., Ungaro, R., A novel synthesis of p-phenylcalix[4]arenes via tetraiodo derivatives (1990) Tetrahedron Lett., 31, pp. 4653-4656; Kumar, S., Chawla, H.M., Varadarajan, R., One step facile synthesis of bromocalix[n]arenes (2002) Tetrahedron Lett., 43, pp. 7073-7075; Ivanova, E.A., Prokhorova, P.E., Mitin, V.V., Glukhareva, T.V., Morzherin, Y.Y., Chlorination of calix[4]arene derivatives (2015) Synt. Commun., 45, pp. 1592-1597; Bohmer, V., Rathay, D., Kammerer, H., The t-butyl group as a possible protective group in the synthesis of oligo [hydroxy-1,3- phenylene]methylenes (1978) Org. Prep. Proced. Int., 10, pp. 113-121; Kammerer, H., Happel, G., Bohmer, V., Rathay, D., Stepwise synthesis of 4,11,18,25-tetra-t-butyl-[1.1.1.1]metacyclophane-7,14, 21,28-tetraol and 4,11-dimethyl-[1.1.1.1]metacyclophane-7,14,21, 28-tetraol (1978) Monatsh. Chem., 109, pp. 767-773; Silverstein, R.M., Webster, F.X., Kiemle, D.J., (2005) Spectrometric Identification of Organic Compounds, , John Wiley & Sons: Hoboken, NJ
Correspondence Address	Ivanova, E.A.; Department of Technology for Organic Synthesis, Chemical Technology Institute, Ural Federal University, 19 Mira St., Russian Federation; email: e.a.ivanova@urfu.ru
Publisher	Bentham Science Publishers B.V.
CODEN	LOCEC
Language of Original Document	English
Abbreviated Source Title	Lett. Org. Chem.
Source	Scopus