Skip to main content
SpringerLink
Log in

Substituent effects on the kinetics of acid-catalyzed hydrolysis of methyl cellulose

  • Original Paper
  • Published:
Cellulose Aims and scope Submit manuscript

Abstract

The kinetics of the hydrolysis of methyl cellulose (MC, DS 1.27 and 1.95) was studied by a two-step procedure, comprising partial hydrolysis in 1 M TFA in water and water/acetone at 120 °C for various time periods, labeling of generated reducing ends by reductive amination, complete depolymerization by methanolysis followed by trimethylsilylation, and gas chromatographic analysis of the two sets of partially O-methylated glucose derivatives. Rate constants of MCs were all in the order of 10−4 s−1. In aqueous TFA, overall rate of hydrolysis of the MC with lower DS was faster than of the MC with higher DS. When substituting half of the water by acetone, reaction was slowed down while selectivity regarding different O-methyl glucosyl residues increased. Compared to the parent glucosyl unit methylation at O-2 and at O-6 decreased rate of hydrolysis, while 3-O-methyl favored it especially in the early stage of the conversion of the macromolecules. Beside slight differences between the two MCs and reaction conditions, rate constants k i (i = position of methyl) followed the order k 36 ≈ k 3 > k 0 ≈ k 23 > k 6 > k 2 ≥ k 236 > k 26. For the higher substituted MC2 an initial slow phase with more pronounced differences of k i, followed by a faster less selective period was observed. Regioselectivity of hydrolysis with respect to methyl positions was expressed as standard deviation of k i and was between 16 and 46% depending on MC and conditions. Findings are discussed with respect to electronic effects, solvent-effect, H-bonding pattern and solution state.

This is a preview of subscription content, log in via an institution to check access.

Access this article

Log in via an institution

Price excludes VAT (USA)
Tax calculation will be finalised during checkout.

Instant access to the full article PDF.

Institutional subscriptions

Fig. 1
Fig. 2
Fig. 3
Fig. 4
Fig. 5
Fig. 6
Fig. 7
Fig. 8

Similar content being viewed by others

References

  • Adden R, Knarr M, Huebner-Keese B, Sammler RL (2015) Methods and composition for inducing satiety. US20150045320 (A1)

  • Arisz P, Kauw JJJ, Boon JJ (1995) Substituent distribution along the cellulose backbone in O-methylcelluloses using GC and FAB MS for monomer and oligomer analysis. Carbohydr Res 271:1–14

    Article  CAS  Google Scholar 

  • Bochkov AF, Zaikov GE (1979) Chemistry of the O-glycosidic bond: formation and cleavage. Pergamon Press, Oxford

    Google Scholar 

  • Capon B (1969) Mechanism in carbohydrate chemistry. Chem Rev 69:407–498

    Article  CAS  Google Scholar 

  • Ciucanu I, Kerek F (1984) A simple and rapid method for the permethylation of carbohydrates. Carbohydr Res 131:209–217

    Article  CAS  Google Scholar 

  • Cuers J, Unterieser I, Burchard W, Adden R, Rinken M, Mischnick P (2012) Simultaneous determination of substituent patterns in partially acid hydrolyzed O-Me/O-Me-d 3 -cellulose and quantification of the obtained oligomers by HPLC-ESI-MS. Carbohydr Res 348:55–63

    Article  CAS  Google Scholar 

  • Cuers J, Rinken M, Adden R, Mischnick P (2013) Critical investigation of the substituent distribution in the polymer chains of hydroxypropyl methylcelluloses by LC-ESI-MS. Anal Bioanal Chem 405:9021–9032

    Article  CAS  Google Scholar 

  • De KK, Timell TE (1967) The acid hydrolysis of glycosides—III hydrolysis of O-methylated glucosides disaccharides. Carbohydr Res 4:72–77

    Article  CAS  Google Scholar 

  • Dean KES, Kirby AJ, Komarov IV (2002) Torsional effects on reactivity on glycosyl transfer. J Chem Soc Perkin Trans 2:337–341

    Article  Google Scholar 

  • Edward JT (1955) Stability of glycosides to acid hydrolysis—a conformational analysis. Chem Ind (Lond) 36:1102–1104

    Google Scholar 

  • Gibbons GC (1951) The homogeneous acid hydrolysis of methyl cellulose, part I—determination of reaction rate by reducing group measurement. J Text Inst Trans 43:T25–T37

    Article  Google Scholar 

  • Gibbons GC (1952) The homogeneous acid hydrolysis of methyl cellulose, part II—the change of the viscosity and the molecular weight during hydrolysis. J Text Inst Trans 43:T38–T52

    Article  CAS  Google Scholar 

  • Haworth WN (1932) Die Konstitution einiger Kohlenhydrate. Ber Dtsch Chem Ges A 65:43–65

    Article  Google Scholar 

  • Heuckendorff M, Pedersen CM, Bols M (2011) The influence of neighboring group participation on the hydrolysis of 2-O-methylated glucopyranosides. Org Lett 13:5956–5959

    Article  CAS  Google Scholar 

  • Höök JE, Lindberg B (1966) Acid hydrolysis of the mono-isopropyl ethers of methyl α- and β-d-glucopyranoside. Acta Chem Scand 20:2363–2369

    Article  Google Scholar 

  • Höök JE, Lindberg B (1968) Acid hydrolysis of the mono-hydroxyethyl ethers of methyl α- and β-d-glucopyranoside. Acta Chem Scand 22:921–926

    Article  Google Scholar 

  • Inamoto N, Masuda S (1982) Revised method for calculation of group electronegativities. Chem Lett 11:1003–1006

    Article  Google Scholar 

  • Jadhav V, Pedersen CM, Bols M (2011) A study of anhydrocelluloses—is a cellulose structure with residues in a 1C4-conformation more prone to hydrolysis? Org Biomol Chem 9:7525–7534

    Article  CAS  Google Scholar 

  • Jencks WP (1980) When is an intermediate not an intermediate? Enforced mechanisms of general acid-base catalyzed, carbocation, carbanion, and ligand-exchange reaction. Acc Chem Res 13:161–169

    Article  CAS  Google Scholar 

  • Jensen HH, Bols M (2003) Steric effects are not the cause of the rate difference in hydrolysis of Stereoisomeric glycosides. Org Lett 5:3419–3421

    Article  CAS  Google Scholar 

  • Jensen HH, Bols M (2006) Stereoelectronic substituent effects. Acc Chem Res 39:259–265

    Article  CAS  Google Scholar 

  • Jensen HH, Lyngbye L, Jensen A, Bols M (2002) Stereoelectronic substituent effects in polyhydroxylated piperidines and hexahydropyridazines. Chem A Eur J 8:1218–1226

    Article  CAS  Google Scholar 

  • Karst D, Yang Y (2007) Effect of structure of large aromatic molecules grafted onto cellulose on hydrolysis of the glycosidic linkages. Macromol Chem Phys 208:784–792

    Article  CAS  Google Scholar 

  • Kondo T, Koschella A, Heublein B, Klemm D, Heinze T (2008) Hydrogen bond formation in regioselectively functionalized 3-mono-O-methyl cellulose. Carbohydr Res 343:2600–2604

    Article  CAS  Google Scholar 

  • Lee JK, Bain AD, Berti PJ (2004) Probing the transition states of four glucoside hydrolyses with 13C kinetic isotope effects measured at natural abundance by NMR spectroscopy. J Am Chem Soc 126:3769–3776

    Article  CAS  Google Scholar 

  • Loerbroks C, Rinaldi R, Thiel W (2013) The electronic nature of the 1,4-β-glycosidic bond and its chemical environment: DFT insights into cellulose chemistry. Chem Eur J 19:16282–16294

    Article  CAS  Google Scholar 

  • Loerbroks C, Boulanger E, Thiel W (2015) Solvent influence on cellulose 1,4-β-glycosidic bond cleavage: a molecular dynamics and metadynamics study. Chem Eur J 21:5477–5487

    Article  CAS  Google Scholar 

  • McAllister JW, Lott JR, Schmidt PW, Sammler RL, Bates FS, Lodge TP (2015) Linear and nonlinear rheological behavior of fibrillar methylcellulose hydrogels. ACS Macro Lett 4:538–542

    Article  CAS  Google Scholar 

  • Mischnick P, Kühn G (1996) Correlation between reaction conditions and primary structure: model studies on methyl amylose. Carbohydr Res 290:199–207

    Article  CAS  Google Scholar 

  • Mischnick P, Momcilovic D (2010) Chemical structure analysis of starch and cellulose derivatives. Adv Carbohydr Chem Biochem 64:117–210

    Article  CAS  Google Scholar 

  • Mischnick P, Unterieser I, Voiges K, Cuers J, Rinken M, Adden R (2013) A new method for the analysis of the substitution pattern of hydroxyethyl (methyl) celluloses over the polysaccharide chain. Macromol Chem Phys 214:1363–1374

    Article  CAS  Google Scholar 

  • Moelwyn-Hughes EA (1929) The kinetics of the hydrolysis of certain glucosides, part II: trehalose, α-methylglucoside, and tetramethyl-α-methylglucoside. Transact Faraday Soc 25:81–92

    Article  CAS  Google Scholar 

  • Namchuk MN, McCarter JD, Becalski A, Andrews T, Withers SG (2000) The role of sugar substituents in glycoside hydrolysis. J Am Chem Soc 122:1270–1277

    Article  CAS  Google Scholar 

  • Reeve W, Erikson CM, Aluotto PF (1979) A new method for the determination of the relative acidities of alcohols in alcoholic solutions. The nucleophilicities and competitive reactivities of nucleophiles and phenoxides. Can J Chem 57:2747–2754

    Article  CAS  Google Scholar 

  • Rowland SP, Howley PS (1987) Influence of the location of substituents in substituted celluloses on solution hydrolysis of the d-glucosidic linkages. Carbohydr Res 165:69–76

    Article  CAS  Google Scholar 

  • Rowland SP, Howley PS (1989) Simplified hydrolysis of cellulose and substituted cellulose: observations on trifluoroacetic acid hydrolyses. J Appl Polym Sci 37:2371–2382

    Article  CAS  Google Scholar 

  • Saunders MD, Timell TE (1968) The acid hydrolysis of glycosides VI effect of substitution at C-3 and C-5. Carbohydr Res 6:12–17

    Article  CAS  Google Scholar 

  • Scanlon JT, Willis DE (1985) Calculation of flame ionization detector relative response factors using the effective carbon number concept. J Chromatogr Sci 23:333–339

    Article  CAS  Google Scholar 

  • Sinnott ML (1990) Catalytic mechanism of enzymic glycosyl transfer. Chem Rev 90:1171–1202

    Article  CAS  Google Scholar 

  • Timell TE (1964) Effects of substituents at C-5 on the acid hydrolysis of glycosides. Chem Ind (Lond) 12:503–504

    Google Scholar 

  • Unterieser I, Mischnick P (2011) Labeling of oligosaccharides for quantitative mass spectrometry. Carbohydr Res 346:68–75

    Article  CAS  Google Scholar 

  • Voiges K, Adden R, Rinken M, Mischnick P (2012) Critical re-investigation of the alditol acetate method for analysis of substituent distribution in methyl cellulose. Cellulose 19:993–1004

    Article  CAS  Google Scholar 

Download references

Acknowledgments

Financial support of the WoodWisdom-Net, the Bundesministerium für Bildung und Forschung (BMBF FKZ 0330837A), and of Dow Wolff Cellulosics GmbH, Germany, is gratefully acknowledged. We thank Dr. Roland Adden and Dr. Marian Rinken, Dow Wolff, now Dow Pharma and Food Solutions, for providing the MCs.

Author information

Authors and Affiliations

  1. Institute of Food Chemistry, Technische Universität Braunschweig, Schleinitzstr. 20, 38106, Braunschweig, Germany

    Kristin Voiges, Nico Lämmerhardt, Caroline Distelrath & Petra Mischnick

Authors
  1. Kristin Voiges
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Nico Lämmerhardt
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. Caroline Distelrath
    View author publications

    You can also search for this author in PubMed Google Scholar

  4. Petra Mischnick
    View author publications

    You can also search for this author in PubMed Google Scholar

Corresponding author

Correspondence to Petra Mischnick.

Rights and permissions

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Voiges, K., Lämmerhardt, N., Distelrath, C. et al. Substituent effects on the kinetics of acid-catalyzed hydrolysis of methyl cellulose. Cellulose 24, 555–569 (2017). https://doi.org/10.1007/s10570-016-1131-7

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1007/s10570-016-1131-7

Keywords

Search

Navigation