Synthesis, Structure and Selective Upper Rim Functionalization of Long Chained Alkoxythiacalix[4]arenes OLEG KASYAN 1 , ELISABETH R. HEALEY 2 , ANDRIY DRAPAILO 1 , MIKE ZAWOROTKO 2 , SEBASTIEN CECILLON 3 , ANTHONY W. COLEMAN 3 and VITALY KALCHENKO 1, * 1 Institute of Organic Chemistry, National Academy of Sciences of Ukraine, Kyiv-94, Murmanska str. 5, Kyiv, Ukraine; 2 Department of Chemistry, The University of South Florida, 4202 E. Fowler Avenue, SCA 400, Tampa, Florida, 33620, USA; 3 IBCP, CNRS UMR 5086, 7 passage du Vercors, Lyon, F69367, France (Received: 13 June 2006; in final form: 13 July 2006) Key words: amphiphilic calixarene, Langmuir–Blodgett film, thiacalixarene, X-ray analysis Abstract The synthesis and X-ray structure investigation of the cone shaped monodecyloxythiacalix[4]arene, as well as the introduction of the reactive bromide or chloromethyl groups on it’s upper rim are described. Preparation of the amphiphilic derivative of thiacalixarene bearing three hydrophilic diethoxyphosphoryl groups at the upper rim and lipophilic decyloxy group at the lower rim is presented. Introduction Thiacalix[4]arenes, as the new members of the well- known calix[4]arene family [1], have been intensively studied during the last decade [2–6]. The presence of four bridging sulfur atoms in the thiacalix[4]arene macrocyclic skeleton, instead of four methylene groups in the classical calix[4]arenes, increases the size of the molecular cavity and enables supplementary modifica- tion of the macrocyclic skeleton by the oxidation of the sulfur atoms [4, 7–9]. Calixarenes possessing long chain alkyl groups are promising platforms in the design of self-assembled systems such as: Langmuir or Langmuir–Blodgett films; nanoparticles; biomembrane modifiers etc. [1]. Some examples of the lower rim total or partial alkylation of thiacalix[4]arenes 1a,b with methyl-, ethyl-, propyl- or butyl haloids are described in the literature [6, 10–13]. However, there is no example of the thiacalixa- rene lower rim functionalization with the long chain alkyl substituents. In this article we describe the syntheses and struc- tural examinations of the long chain (C 10 ,C 12 ) O- substituted thiacalix[4]arenes which can be used as the suitable platforms for the design of self-assembled systems. Regioselective functionalization of the cone shaped monodecyloxythiacalix[4]arene upper rim with three bromide, chloromethyl or diethoxyphosphoryl groups is presented. Experimental Synthesis of 2a, 2b and 2c Decylbromide (8.91 g, 40.32 mmol, 8.40 ml) was added to a suspension of 1a (1.00 g, 2.02 mmol) and K 2 CO 3 (5.57 g, 40.40 mmol) in dry acetone (40 ml). The reac- tion mixture was refluxed at stirring for 40 h. About 1 N HCl was added to the mixture (pH < 7). Water layer was washed with chloroform (3·30 ml). The combined organic layers were dried over Na 2 SO 4 and evaporated. Isopropyl alcohol (10 ml) was added and the crystalline residue was filtered, washed with isopropyl alcohol (2·5 ml) and dried for 2 h under vacuum (0.01 mmHg) at 50 °C. Compound 2a (0.53 g, 25%) was obtained as a colorless crystalline product. Mp 75–80 °C. 1 H NMR (300 MHz, CDCl 3 ): d 0.91 (t, 12H, J = 6.7 Hz, CH 3 ), 1.08 (m, 16H, (CH 2 ) 2 –CH 3 ), 1.14–1.38 (m, 48H, (CH 2 ) 6 –(CH 2 ) 2 –CH 3 ), 3.86 (t, 8H, J = 6.6 Hz, O– CH 2 ), 6.81 (t, 4H, J = 7.7 Hz, H-arom.), 7.34 (d, 8H, J = 7.7 Hz, H-arom.); 13 C NMR (75 MHz, CDCl 3 ): d 14.13 (s, CH 3 ), 22.73 (s, CH 2 –CH 3 ), 25.75 (s, CH 2 –CH 2 – CH 3 ), 28.94 (s, CH 2 –(CH 2 ) 2 –CH 3 ), 29.50 (s, CH 2 – (CH 2 ) 3 –CH 3 ), 29.75 (s, (CH 2 ) 3 –(CH 2 ) 4 –CH 3 ), 32.01 (s, CH 2 –(CH 2 ) 7 –CH 3 ), 69.14 (s, O–CH 2 ), 122.67 (s, C- arom.), 128.86 (s, C-arom.), 131.59 (s, C-arom.), 159.84 (s, C-arom.). Anal. calcd for C 64 H 96 O 4 S 4 , %: C, 72.68; H, 9.15; S, 12.13. Found, %: C, 72.61; H, 8.88; S, 11.85. In the same conditions, compound 2b (68%) was obtained as a colorless crystalline product. Mp 165– 170 °C. 1 H NMR (300 MHz, CDCl 3 ): d 0.90 (t, 12H, * Author for Correspondence. E-mail: vik@bpci.kiev.ua Journal of Inclusion Phenomena and Macrocyclic Chemistry (2007) 58:127–132 Ó Springer 2006 DOI 10.1007/s10847-006-9134-x