Download PDF
Synthesis 2002(9): 1147-1156
DOI: 10.1055/s-2002-32524
PAPER
© Georg Thieme Verlag Stuttgart · New York

Conjugated Materials: Problems and Prospects for Synthesis Using Carbohydrate Reagents

Daniel J. Sandman*, Ik-Bum Kim, Monica A. Rixman, Zo-Hong Tsai, Jeffrey Njus, Myunghwan Kim
Center for Advanced Materials, Department of Chemistry, University of Massachusetts Lowell, Lowell, Massachusetts 01854-5046 USA
Fax: 0019789343013; e-Mail: Daniel_Sandman@uml.edu;
Further Information

Publication History

Received 25 February 2002
Publication Date:
28 June 2002 (online)

    Permissions and Reprints All articles of this category

Abstract

General considerations related to the use of sugars and closely related compounds as reagents for molecular and macromolecular synthesis are presented. For the first time, we have used unprotected carbohydrates to initiate polymerizations. A variety of dicyanoalkenes and -arenes react with sugars in the presence of alkali to give conjugated polymers. Both cyclopolymerization and polymerization at only one of two cyano groups are observed, and some qualitative mechanistic issues related to these observations are discussed. In some cases, a sugar alkoxide is the active initiating reagent. Characterization of the resulting polymers is reported. Alkaline sugar reagents have also been used in Knoevenagel reactions to synthesize CN-PPV oligomers and a related conjugated polymer in good yields. The use of the polysaccharide chitosan as a polycation allows the absorption spectrum of the polythiophene HPURET to shift to longer wavelengths than other polycations in electrostatically assembled films.

Key words

polymers - carbohydrates - oligosaccharides - Knoevenagel reactions - polysaccharides - polycations

    References

  • 1 Shirakawa H. Angew. Chem. Int. Ed.  2001,  40:  2574 
    CrossrefSearch in Google Scholar
  • 2 MacDiarmid AG. Angew. Chem. Int. Ed.  2001,  40:  2581 
    CrossrefSearch in Google Scholar
  • 3 Heeger AJ. Angew. Chem. Int. Ed.  2001,  40:  2591 
    CrossrefPubMedSearch in Google Scholar
  • 4 Groenendaal L. Jonas F. Freitag D. Pielartzik H. Reynolds JR. Adv. Mater.  2000,  12:  481 
    CrossrefSearch in Google Scholar
  • 5 Electronic Materials: The Oligomer Approach   Müllen K. Wegner G. Wiley; Weinheim: 1998. 
  • 6 Phthalocyanines: Properties and Applications   Vol. 1-4:  Leznoff CC. Lever ABP. VCH; New York: 1989-1995. 
  • 7 McKeown NB. Phthalocyanine Materials   Cambridge University Press; New York: 1998. 
  • 8 Thomas AL. Phthalocyanine Research and Applications   CRC; Boca Raton, Florida: 1990. 
  • 9 Matsuoka M. In Infrared Absorbing Dyes   Matsuoka M. Plenum; New York: 1990.  Chap. 5.
  • 10 Moser FH. Thomas AL. The Phthalocyanines   CRC; Boca Raton, Florida: 1983. 
  • 11 Kobayashi S. J. Polym. Sci. Part A: Polym. Chem  1999,  37:  3041 
    Search in Google Scholar
  • 12 Gross RA. Kumar A. Kalra B. Chem. Rev.  2001,  101:  2097 
    CrossrefSearch in Google Scholar
  • 13 Kothakota S. Mason TL. Tirrell DA. Fournier MJ. J. Am. Chem. Soc.  1995,  117:  536 
    CrossrefSearch in Google Scholar
  • 14 Lichtenthaler FW. Cuny E. Martin D. Rönninger S. Weber T. Carbohydrates as Organic Raw Materials   Lichtenthaler FW. VCH; Weinheim: 1991.  p.207-246  
  • 15 Frost JW. Draths KM. Chem. Br.  1995,  31:  206 
    Search in Google Scholar
  • 16 Frost J. The Chem. Engineer  1996,  16:  32 
    Search in Google Scholar
  • 17 Robyt JF. Essentials of Carbohydrate Chemistry   Springer; New York: 1998.  p.80 
  • 18 Robyt JF. Essentials of Carbohydrate Chemistry   Springer; New York: 1998.  p.50-60  
  • 19 Daub J. Rapp KM. Salbeck J. Schöberl U. In Carbohydrates as Organic Raw Materials   Lichtenthaler FW. VCH; Weinheim: 1991.  p.323-350  
  • 20 Synthesis  2001,  312-343 
  • 21 Bigelow HE. Palmer A. Opolonick N. Org. Synth. Coll. Vol. 2   Wiley; New York: 1943.  p.57 
  • 22 Galbraith HW. Degering EF. Hitch EF. J. Am. Chem. Soc.  1951,  73:  1323 
    CrossrefSearch in Google Scholar
  • 23 Kornblum N. In Organic Reactions   Vol. II:  Wiley; New York: 1944.  p.262-340  
    Search in Google Scholar
  • 25 Sauter HP. Makowka C. Res. Discl.  1989,  302:  411 ;Chem. Abstr. 1990, 112, 7093x
    Search in Google Scholar
  • 26 Robyt JF. Essentials of Carbohydrate Chemistry   Springer; New York: 1998.  p.63 
  • 27 Lubineau J. Auge J. Bienayme H. Queneau Y. Scherrmann MC. Carbohydrates as Organic Raw Materials II   Descotes G. VCH; Weinheim: 1993.  p.99-112  
  • 28 Lubineau J. Auge J. Bienayme H. Lubin N. Queneau Y. In Cycloaddition Reactions in Carbohydrate Chemistry   Vol. 494:  Giuliano RM. American Chemical Society Symposium Series; Washington, D.C. 1992.  p.147-157  
    Search in Google Scholar
  • 29 Aoi K. Suzuki H. Okada M. Macromolecules  1992,  25:  7073 
    CrossrefSearch in Google Scholar
  • 30 Bisht KS. Deng F. Gross RA. Kaplan DL. Swift G. J. Am. Chem. Soc.  1998,  120:  1363 
    CrossrefSearch in Google Scholar
  • 31 Bon SAF. Haddleton DM. Polymer Preprints  1999,  40(2):  248 
    Search in Google Scholar
  • 32 Haddleton DM. Ohno K. Biomacromolecules  2000,  1:  152 
    CrossrefSearch in Google Scholar
  • 33 Butler GB. J. Polym. Sci. Part A: Polym. Chem.  2000,  38:  3451 
    Search in Google Scholar
  • 34 Nagasaki Y. Yasugi K. Yamamoto Y. Harada A. Kataoka K. Biomacromolecules  2001,  2:  1067 
    CrossrefSearch in Google Scholar
  • 35 Miles MG. Wager JS. Wilson JD. Siedle AR. J. Org. Chem.  1975,  40:  2577 
    Search in Google Scholar
  • 36 Rixman MA. Sandman DJ. Macromolecules  2000,  33:  248 
    CrossrefSearch in Google Scholar
  • 37 Butler GB. In Encyclopedia of Polymer Science and Technology   2nd ed., Vol. 4:  Mark HF. Bikales NM. Overberger CG. Menges G. Wiley-Interscience; New York: 1986.  p.566 
    Search in Google Scholar
  • 38 Wöhrle D. Adv. Polym. Sci.  1972,  10:  35 
    Search in Google Scholar
  • 39 Naito K, and Ikezaki T. inventors; Japanese Kokai, JP  6191912.  ; Chem. Abstr. 1986, 105, 217629h
  • 40 Keller TM. CHEMTECH  1988,  18:  635 
    Search in Google Scholar
  • 41 Hanack M. Lang M. Chemtract, Org. Chem.  1995,  8:  131 
    Search in Google Scholar
  • 43 Kim I.-B. Rixman MA. Tsai Z.-H. Wu D. Njus JM. Stark JC. Hankins J. Sandman DJ. Macromolecules  2001,  34:  7576 
    CrossrefSearch in Google Scholar
  • 44 Tsai Z.-H. Sandman DJ. J. Porphyrins Phthalocyanines  2001,  5:  564 
    CrossrefSearch in Google Scholar
  • 45 Horiguchi E. Shirai K. Jaung J. Furusyo M. Takagi K. Matsuoka M. Dyes and Pigments  2001,  50:  99 
    CrossrefSearch in Google Scholar
  • 47 Mague JT. Eduok EE. J. Chem. Crystallogr.  2000,  30:  311 
    CrossrefSearch in Google Scholar
  • 48 Hassner A. Stumer C. Organic Syntheses Based on Name Reactions and Unnamed Reactions   Pergamon; Oxford, UK: 1994.  p.205 
  • 49 House HO. Modern Synthetic Reactions   2nd ed.:  Benjamin/Cummings; Menlo Park, California: 1972.  p.646-653  
    Search in Google Scholar
  • 50 Schlick U. Teichert F. Hanack M. Synthetic Metals  1998,  92:  75 
    CrossrefSearch in Google Scholar
  • 51 Moratti SC. In Handbook of Conducting Polymers   2nd ed.:  Skotheim TA. Elsenbaumer RL. Reynolds JR. Marcel Dekker; New York: 1998.  p.343-361  
    Search in Google Scholar
  • 52 Kraft A. Grimsdale AC. Holmes AB. Angew. Chem. Int. Ed.  1998,  37:  402 
    CrossrefPubMedSearch in Google Scholar
  • 53 Kauffman H. Ber. Dtsch. Chem. Ges.  1917,  50:  515 
    Search in Google Scholar
  • 54 Holm MJ. Zienty FB. Terpstra MA. J. Chem. Eng. Data  1968,  13:  70 
    CrossrefSearch in Google Scholar
  • 55 Kim D.-J. Kim S.-H. Zyung T. Kim J.-J. Cho I. Choi SK. Macromolecules  1996,  29:  3657 
    CrossrefSearch in Google Scholar
  • 56 Kim M. Sandman DJ. J. Macromol. Sci.-Pure Appl. Chem.  2001,  A38:  1291 
    Search in Google Scholar
  • 57 Lehn J.-M. Supramolecular Chemistry   VCH; Weinheim: 1995.  p.139 
  • 58 Decher G. Science  1997,  277:  1232 
    CrossrefSearch in Google Scholar
  • 59 Kim M. Sandman DJ. In Electrical, Optical, and Magnetic Properties of Organic Solid State Materials V, In Materials Research Society Symposium Proceedings   Vol. 598:  Ermer S. Reynolds JR. Perry JW. Jen AK.-Y. Bao Z. Materials Research Society; Warrendale, PA 2000.  p.Paper BB 3.12 
    Search in Google Scholar
  • 60 Kuball H.-G. Höfer T. In Circular Dichroism: Principles and Applications   Berova N. Nakanishi K. Woody RW. Wiley-VCH; Weinheim 2000.  p.133-158  
  • 61 Okada S. Peng S. Spevak W. Charych D. Acc. Chem. Res.  1998,  31:  229 
    CrossrefSearch in Google Scholar
  • 62 Baek M.-G. Sevens RC. Charych DH. Bioconjugate Chem.  2000,  11:  777 
    CrossrefSearch in Google Scholar
  • 63 Madison PH. Long TE. Biomacromolecules  2000,  1:  615 
    CrossrefSearch in Google Scholar
24

Wassmundt, F. W.; Plourde, D. M.; Pedemonte, R. P. presented at the 203rd National Meeting of the American Chemical Society, San Francisco, California, 1992, April 5-10; Book of Abstracts, ORGN 310.

42

Jones, M. T. unpublished experiments 1994.

46

Kim, I.-B.; Njus, J.; Sandman, D. J.; Macromolecules, to be submitted.