, 18:1305 | Cite as

Synthesis of regioselectively brominated cellulose esters and 6-cyano-6-deoxycellulose esters



The control of regiochemistry in the synthesis of polysaccharide derivatives is one of the most significant scientific challenges in the field. Its importance is only further highlighted by the individual successes in synthesis of regioselectively substituted derivatives, in particular cellulose esters and ethers, over the last 20 years. The availability of these samples and studies of their properties versus randomly substituted analogs has shown clearly that properties like solubility, aggregation phenomena, and optical properties depend heavily on the regiochemistry of substitution. We report here on the one-pot synthesis of novel 6-bromo-6-deoxy-2,3-O-acylcellulose derivatives, which as more organic soluble derivatives of 6-bromo-6-deoxycellulose should allow broader exploitation of the highly regioselective cellulose 6-bromination chemistry. We illustrate the potential of these new derivatives by conversion to 6-cyano-6-deoxycellulose esters.


Cellulose ester Regioselective synthesis 6-Bromo-6-deoxycellulose 6-Cyano-6-deoxycellulose Polysaccharide derivative 



This work was supported primarily by the Institute for Critical Technology and Applied Science (ICTAS) at Virginia Tech. The authors would also like to thank Mark Flynn for running the GPC analyses.


  1. Aoki N, Furuhata KI, Saegusa Y, Nakamura S, Sakamoto M (1996) Reaction of 6-bromo-6-deoxycellulose with thiols in lithium bromide-N, N-dimethylacetamide. J Appl Polym Sci 61:1173–1185CrossRefGoogle Scholar
  2. Aoki N, Fukushima K, Kurakata H, Sakamoto M, Furuhata K-i (1999) 6-Deoxy-6-mercaptocellulose and its S-substituted derivatives as sorbents for metal ions. React Funct Polym 42:223–233CrossRefGoogle Scholar
  3. Buchanan CM, Edgar KJ, Hyatt JA, Wilson AK (1991a) Preparation of cellulose [1-C-13] acetates and determination of monomer composition by NMR spectroscopy. Macromolecules 24:3050–3059CrossRefGoogle Scholar
  4. Buchanan CM, Edgar KJ, Wilson AK (1991b) Preparation and characterization of cellulose monoacetates—the relationship between structure and water solubility. Macromolecules 24:3060–3064CrossRefGoogle Scholar
  5. Edgar KJ (2007) Cellulose esters in drug delivery. Cellulose 14:49–64CrossRefGoogle Scholar
  6. Edgar KJ, Buchanan CM, Debenham JS, Rundquist PA, Seiler BD, Shelton MC, Tindall D (2001) Advances in cellulose ester performance and application. Prog Polym Sci 26:1605–1688CrossRefGoogle Scholar
  7. Evans R, Wearne RH, Wallis AFA (1989) Molecular weight distribution of cellulose as its tricarbanilate by high performance size exclusion chromatography. J Appl Polym Sci 37:3291–3303CrossRefGoogle Scholar
  8. Fox SC, Li B, Xu D, Edgar KJ (2011) Regioselective esterification and etherification of cellulose—a review. Biomacromolecules 12:1956–1972CrossRefGoogle Scholar
  9. Furuhata K-i, Ikeda H (1999) Ionic cellulose derivatives: synthesis of sodium 6-deoxycellulose-6-sulfonate with high degree of substitution. React Funct Polym 42:103–109CrossRefGoogle Scholar
  10. Furuhata K-i, Koganei K, Chang H-S, Aoki N, Sakamoto M (1992) Dissolution of cellulose in lithium bromide-organic solvent systems and homogeneous bromination of cellulose with N-bromosuccinimide-triphenylphosphine in lithium bromide-N, N-dimethylacetamide. Carbohydr Res 230:165–177CrossRefGoogle Scholar
  11. Heinze T, Liebert T, Koschella A (2006) Esterification of polysaccharides. Springer, BerlinGoogle Scholar
  12. Katoh Y, Tsujimoto Y, Yamamoto C, Ikai T, Kamigaito M, Okamoto Y (2011) Chiral recognition ability of cellulose derivatives bearing pyridyl and bipyridyl residues as chiral stationary phases for high-performance liquid chromatography. Polym J 43:84–90CrossRefGoogle Scholar
  13. Katritzky AR, Pilarski B, Urogdi L (1989) Efficient conversion of nitriles to amides with basic hydrogen peroxide in dimethyl sulfoxide. Synthesis 12:949–950CrossRefGoogle Scholar
  14. Klemm D, Shmauder H-P, Heinze T (2002) Cellulose. In: Vandamme EJ, Baets SD, Steinbüchel A (eds) Biopolymers, vol. 6, polysaccharides II: polysaccharides from eukaryotes. Wiley-VCH, Weinheim, pp 275–319Google Scholar
  15. Liebert T, Wotschadlo J, Gericke M, Köhler S, Laudeley P, Heinze T (2009) Modification of cellulose in ionic liquids towards biomedical applications. In: Polysaccharide materials: performance by design, vol 1017. ACS symposium series, vol 1017. American Chemical Society, pp 115–132Google Scholar
  16. Matsui Y, Ishikawa J, Kamitakahara H, Takano T, Nakatsubo F (2005) Facile synthesis of 6-amino-6-deoxycellulose. Carbohydr Res 340:1403–1406CrossRefGoogle Scholar
  17. McIsaac JE, Ball RE, Behrman EJ (1971) Mechanism of the base-catalyzed conversion of nitriles to amides by hydrogen peroxide. J Org Chem 36:3048–3050CrossRefGoogle Scholar
  18. Mormann W, Wezstein M (2009) Trimethylsilylation of cellulose in ionic liquids. Macromol Biosci 9:369–375CrossRefGoogle Scholar
  19. Okamoto Y (2009) Chiral polymers for resolution of enantiomers. J Polym Sci A Polym Chem 47:1731–1739CrossRefGoogle Scholar
  20. Perlack RD, Wright LL, Turhollow AF, Graham RL, Stokes BJ, Erbach DC (2005) Biomass as feedstock for a bioenergy and bioproducts industry: the technical feasability of a billion-ton annual supply. United States Department of Energy. doi: 10.2172/885984
  21. Rahn K, Diamantoglou M, Klemm D, Berghmans H, Heinze T (1996) Homogeneous synthesis of cellulose p-toluenesulfonates in N,N-dimethylacetamide/LiCl solvent system. Angew Makromol Chem 238:143–163CrossRefGoogle Scholar
  22. Rubo A, Kellens R, Reddy J, Steier N, Hasenpusch W (2000) Alkali metal cyanides. In: Ullmann’s encyclopedia of industrial chemistry. Wiley, New JerseyGoogle Scholar
  23. Saad GR, Sakamoto M, Furuhata Ki (1996) Dielectric study of β-relaxation in some cellulosic substances. Polym Int 41:293–299CrossRefGoogle Scholar
  24. Sata H, Murayama M, Shimamoto S (2004) Properties and applications of cellulose triacetate film. Macromol Symp 208:323–334CrossRefGoogle Scholar
  25. Tahiri C, Vignon MR (2000) TEMPO-oxidation of cellulose: synthesis and characterisation of polyglucuronans. Cellulose 7:177–188CrossRefGoogle Scholar

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© Springer Science+Business Media B.V. 2011

Authors and Affiliations

  1. 1.Department of Wood Science and Forest ProductsVirginia TechBlacksburgUSA

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