Carbosilane Dendrimers with End-Grafted Silacrown- and Crown-Ether Units

Roy Buschbeck; Heinrich Lang; Shiva Agarwal; Vipin K. Saini; Vinod K. Gupta

doi:10.1055/s-2004-822349

PAPER

Carbosilane Dendrimers with End-Grafted Silacrown- and Crown-Ether Units

Roy Buschbeck^a, Heinrich Lang*^a, Shiva Agarwal^b, Vipin K. Saini^b, Vinod K. Gupta^b
^a Technische Universität Chemnitz, Fakultät für Naturwissenschaften, Institut für Chemie, Lehrstuhl Anorganische Chemie, Straße der Nationen 62, 09111, Chemnitz, Germany
e-Mail: heinrich.lang@chemie.tu-chemnitz.de;
^b Department of Chemistry, Indian Institute of Technology Roorkee, Roorkee - 247667, Uttaranchal, India

Abstract

All articles of this category

Abstract

The synthesis of the vinyl-functionalized silacrown ethers 1-methyl-1-vinylsila-8-crown-3 (3) and 1-methyl-1-vinylsila-11-crown-4 (4) by the reaction of (H₂C=CH)MeSi(OEt)₂ (1) with HO(CH₂CH₂O)_nH (2a, n = 2; 2b, n = 3) in presence of catalytic amounts of NaOMe is described. These species can be attached to 1^st and 2^nd generation carbosilane dendrimers by hydrosilylation. Treatment of Si(CH₂CH₂CH₂SiMe₂H)₄ (5) or Si[CH₂CH₂CH₂Si-Me(CH₂CH₂CH₂SiMe₂H)₂]₄ (8) with 3 or 4 produces the respective silacrown ether end-grafted carbosilane dendrimers 6, 7, 9 and 10 in nearly quantitative yield. In a similar manner 2-allyloxymethyl-12-crown-4 (11) gives with 5 and 8 the 12-crown-4 end-capped carbosilane dendrimers 12 and 13, respectively.

The formation of analytical pure and uniform carbosilane dendrimers with crown ethers at the periphery is based on elemental analysis, IR, ¹H, ¹³C{¹H} and ²⁹Si{¹H} NMR spectroscopy. ESI-TOF MS studies reveal that 7, 10, 12 and 13 form complexes with alkali ions, which enables such species to function as possible ionophores for chemical sensors.

Keywords

carbosilane dendrimers - hydrosilylation - crown ethers - silacrown ethers - chemical sensors

Full Text

References

1 Astruc D. Chardac F. Chem. Rev. 2001, 101: 2991

2a Twyman LJ. King ASH. Martin IK. Chem. Soc. Rev. 2002, 31: 69

2b King ASH. Twyman LJ. J. Chem. Soc., Perkin Trans. 1 2002, 2209

3a Van Heerbeek R. Kamer PCJ. van Leeuwen PWNM. Reek JNH. Chem. Rev. 2002, 102: 3717

3b Oosterom GE. Reek JNH. Kamer P.-CJ. van Leeuwen PWNM. Angew. Chem. 2001, 113: 1878

4a van Koten G. Kleij AW. van de Coevering R. Albrecht M. Hovestad NJ. Boersma J. Klein-Gebbink RJM. Polym. Mater. Sci. Eng. 2001, 84: 154

4b van Koten G. Jastrzebski JTBH. J. Mol. Catal. A: Chem. 1999, 146: 317

4c Gossage RA. van de Kuil LA. van Koten G. Acc. Chem. Res. 1998, 31: 423

5a Baars MWPL. Meijer EW. Top. Curr. Chem. 2000, 210: 131

5b Jansen JFGA. de Brabander-van den Berg EMM. Meijer EW. Science 1994, 266: 1226

6 Newkome GR. Pure Appl. Chem. 1998, 70: 2337

7 Guillena G. Kreiter R. van de Coevering R. Klein-Gebbink RJM. van Koten G. Mazon P. Chinchilla R. Najera C. Tetrahedron: Asymmetry 2003, 14: 3705

8 Shin H.-K. Kim J.-M. Kwon Y.-S. Park E. Kim C. Opt. Mater. 2003, 21: 289

9 Reineker P. Engelmann A. Yudson VI. J. Luminescence 2001, 94/95: 203

10 Jansen JFGA. Peerlings HWI. de Brabander-van den Berg EMM. Meijer EW. Angew. Chem., Int. Ed. Engl. 1995, 34: 1206

11 Balzani V. Ceroni P. Maestri M. Saudan C. Vicinelli V. Top. Curr. Chem. 2003, 228: 159

12 Tully DC. Fréchet JMJ. Chem. Commun. 2001, 1229

13 Fischer M. Voegtle F. Angew. Chem. Int. Ed. 1999, 38: 885

14 Albrecht M. van Koten G. Adv. Mater. 1999, 11: 171

15a Zhang G.-D. Harada A. Nishiyama N. Jiang D.-L. Koyama H. Aida T. Kataoka K. J. Controlled Release 2003, 93: 141

15b Zhang G.-D. Nishiyama N. Harada A. Koyama H. Aida T. Kataoka K. Macromolecules 2003, 36: 1304

15c Jiang D.-L. Aida T. Jasco Report 1999, 41: 1

16 Hecht S. Fréchet JMJ. J. Am. Chem. Soc. 2001, 123: 6959

17 Boiko N. Zhu X. Bobrovsky A. Shibaev V. Chem. Mater. 2001, 13: 1447

18a Kobiro K. Tobe Y. Watanabe K. Anal. Lett. 1993, 26: 49

18b Shen SL. Shibutani Y. Shono T. Fenxi Ceshi Xuebao 1998, 17: 47

19 Kim C. Kim H. Bull. Korean Chem. Soc. 2002, 23: 637

20 Ikeda I. Emura H. Okahara M. Synthesis 1984, 73

21 D’yakov VM. Kir’yanova AN. Kireeva LN. Chernyshev AE. Bochkarev VN. Androsenko SI. Zh. Obshch. Khim. 1988, 58: 539

22 Oddon G. Husseini MW. Tetrahedron Lett. 1993, 34: 7413