nach oben

Erschienen in:

01.10.2007

Studies on DMSO-containing carbanilation mixtures: chemistry, oxidations and cellulose integrity

verfasst von: Ute Henniges, Elisabeth Kloser, Anjan Patel, Antje Potthast, Paul Kosma, Martin Fischer, Klaus Fischer, Thomas Rosenau

Erschienen in: Cellulose | Ausgabe 5/2007

Einloggen

Aktivieren Sie unsere intelligente Suche, um passende Fachinhalte oder Patente zu finden.

search-config

KI-gestützte Suche

Aus

Abstract

The oxidative effect of carbanilation mixtures containing dimethylsulfoxide (DMSO) was demonstrated by means of alcohol model substances in which competitive carbanilation was prevented due to steric hindrance of the hydroxyl function, rendering those compounds specific probes for oxidation effects. Dimethylsulfonium ions and derived ylide species were shown to be the actually oxidizing species according to trapping methodology using lipophilic olefins which were converted into the corresponding cyclopropane and epoxide derivatives. The experimental data were in good agreement with DFT computations carried out on the B3LYP/6-311+G(d,p) level of theory. The direct interaction of cellulose and sulfoxide solvent was proven by means of methyl-(2-naphthyl)sulfoxide (MNSO) as a model for DMSO, which caused introduction of UV-detectable methylthionaphthyl ether moieties into the cellulose, formed in Pummerer-type side reaction paralleling the chemical behavior of DMSO. A facile color test—responding to sulfoxide-derived oxidizing species—was developed to assess the suitability of carbanilation conditions with regard to cellulose oxidation and degradation. DMSO-based carbanilation systems have to be used with great caution for determination of molecular weight parameters and for similar purposes which require complete maintenance of the cellulose integrity. Cellulose oxidation/degradation by DMSO-derived intermediates upon carbanilation can be minimized but cannot be avoided completely. Thus, if cellulose integrity is an issue as it is in cellulose analytics, it is recommended to replace DMSO by solvent components of similar solution behavior but without the inherent danger of generating oxidants, such as pyridine or DMAc, whenever possible.

Vorheriger Artikel Efficient synthesis of cellulose furoates in 1-N-butyl-3-methylimidazolium chloride

Nächster Artikel New class of carbohydrate-based nonionic surfactants: diblock co-oligomers of tri-O-methylated and unmodified cello-oligosaccharides

Sie haben noch keine Lizenz? Dann Informieren Sie sich jetzt über unsere Produkte:

Springer Professional "Technik"

Online-Abonnement

Mit Springer Professional "Technik" erhalten Sie Zugriff auf:

über 67.000 Bücher
über 390 Zeitschriften

aus folgenden Fachgebieten:

Automobil + Motoren
Bauwesen + Immobilien
Business IT + Informatik
Elektrotechnik + Elektronik
Energie + Nachhaltigkeit
Maschinenbau + Werkstoffe

Jetzt Wissensvorsprung sichern!

Jetzt informieren

Springer Professional "Wirtschaft+Technik"

Online-Abonnement

Mit Springer Professional "Wirtschaft+Technik" erhalten Sie Zugriff auf:

über 102.000 Bücher
über 537 Zeitschriften

aus folgenden Fachgebieten:

Automobil + Motoren
Bauwesen + Immobilien
Business IT + Informatik
Elektrotechnik + Elektronik
Energie + Nachhaltigkeit
Finance + Banking
Management + Führung
Marketing + Vertrieb
Maschinenbau + Werkstoffe
Versicherung + Risiko

Jetzt Wissensvorsprung sichern!

Jetzt informieren

Cellulosic hydroxyls were present in 10-fold molar excess relative to the alcoholic probe.

The oxidation is unable to convert aldehydes to carboxylic acids. The C-6 hydroxymethyl groups are thus oxidized to the aldehyde stage only, but not further to glucuronic acid moieties. Similarly, C-2 or C-3 keto groups are introduced without any further cleavage of adjacent carbon-carbon bonds (as for instance in periodate or permanganate oxidations).

The structure of this compound strongly resembles the naphthoquinones isolated as trace chromophores from cellulosic fiber material, see Rosenau et al. (2004, 2005).

Intrinsic reaction coordinates. This technique gives a full picture of the occurring transition states and intermediates between a starting geometry of molecules and the corresponding product geometry, provided that all elementary steps of the reaction are known.

A full set of computational data can be obtained from the authors upon request.

It should be noted that a precise determination of absolute thermodynamic data (enthalpies, energies, entropies) by computations is still difficult and requires application of time-consuming and computationally demanding high-accuracy methods. However, determination of the relative thermodynamic data as in the present case—comparing similar isodesmic reactions—affords very accurate results, as possible computational systematic errors are effectively cancelled out.

Becke A (1988) Density-functional exchange-energy approximation with correct asymptotic behavior. Phys Rev A38:3098–3100

Becke A (1993) Density-functional thermochemistry. III. The role of exact exchange. J Chem Phys 98:5648–5652CrossRef

Brownstein S, Ingold KU (1989) Chiral effects on the ¹³C resonances of α-tocopherol and related compounds. A novel illustration of Newman’s “rule of six”. J Org Chem 54:560-569CrossRef

Brückner R (1996) Reaktionsmechanismen. Organische Reaktionen, Stereochemie, moderne Synthesemethoden. Spektrum Akademischer Verlag, Heidelberg, pp 307–312

Burton GW, Doba T, Gabe EJ, Hughes L, Lee FL, Prasad L, Ingold KU (1985) Autoxidation of biological molecules. 4. Maximizing the antioxidant activity of phenols. J Am Chem Soc 107:7053–7065CrossRef

Dupont AL, Mortha G (2004) Comparative evaluation of size-exclusion chromatography and viscometry for the characterisation of cellulose. J Chromatogr A 1026(1–2):129–141CrossRef

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 37:3291–3303CrossRef

Evans R, Wearne RH, Wallis AFA (1991a) Pyridine-catalyzed depolymerization of cellulose during carbanilation with phenylisocyanate in dimethylsulfoxide. J Appl Polym Sci 42:813–820CrossRef

Evans R, Wearne RH, Wallis AFA (1991b) Effect of amines on the carbanilation of cellulose with phenylisocyanate. J Appl Polym Sci 42:821–827CrossRef

Fischer M (2005) Polymeranaloge Carbanilierung von Cellulose. Dissertation, Dresden University of Technology, Germany

Fischer M, Fischer K (2005) Polymer-analogous preparation of cellulose tricarbanilates: mechanisms of degradation in dimethylsulfoxide. Macromol Symp 223:121–135CrossRef

Francl MM, Pietro WJ, Hehre WJ, Binkley JS, Gordon MS, DeFrees DJ, Pople JA (1982) Self-consistent molecular orbital methods. XXIII. A polarization-type basis set for second-row elements. J Chem Phys 77:3654–3665CrossRef

Hall DM, Horne JR (1973) Preparation of cellulose triacetate and cellulose tricarbanilate by nondegradative methods. J Appl Polym Sci 17:3727CrossRef

Hariharan PC, Pople JA (1973) The influence of polarization functions on molecular orbital hydrogenation energies. Theor Chim Acta 28:213–222CrossRef

Hearon WM, Hiatt GD, Fordyce CR (1943a) Carbamates of cellulose and cellulose acetate. I. Preparation. J Am Chem Soc 65:829–833 CrossRef

Hearon WM, Hiatt GD, Fordyce CR (1943b) Carbamates of cellulose and cellulose acetate. II. Stability toward hydrolysis. J Am Chem Soc 65:833–836CrossRef

Lauriol JM, Froment P, Pla F, Robert A (1987) Molecular weight distribution of cellulose by on-line size exclusion chromatography – low angel laser light scattering. Part 1: basic experiments and treatment of data. Holzforschung 41:109–113CrossRef

Lee C, Yang W, Parr RG (1988) Development of the Colle-Salvetti correlation-energy formula into a functional of the electron density. Phys Rev B37:785–789

Lee TV (1991) Oxidation of alcohols by DMSO. Comp Org Syn 7:291–303

Mancuso AJ, Swern D (1981) Activated dimethyl sulfoxide: useful reagents for synthesis. Synthesis 1981(3) 165–185CrossRef

Mancuso AJ, Huang SL, Swern DJ (1978) Oxidation of long-chain and related alcohols to carbonyls by dimethyl sulfoxide “activated” by oxalyl chloride. J Org Chem 43:2480–2482CrossRef

Mancuso AJ, Brownfain DS, Swern DJ (1979) Structure of the dimethyl sulfoxide-oxalyl chloride reaction product. Oxidations of heteroaromatic and diverse alcohols to carbonyl compounds. Org Chem 44:4148–4150CrossRef

Miehlich B, Savin A, Stoll H, Preuss H (1989) Results obtained with the correlation energy density functionals of Becke and Lee, Yang and Parr. Chem Phys Lett 157:200–208CrossRef

Moffatt JG (1971) Sulfoxide-carbodiimide and related oxidations. In: Augustine RL, Trecker DJ (eds) Oxidation, vol. 2. Dekker, New York, pp 1–64

Omura K, Swern D (1978) Oxidation of alcohols by “activated” dimethyl sulfoxide. A preparative, steric and mechanistic study. Tetrahedron 34:1651–1660CrossRef

Parham WE, Huestis LD (1962) The reaction of dichlorocarbene with 2,3-chromene and 3,4-chromene. J Am Chem Soc 84:813–816CrossRef

Pfitzner KE, Moffatt JG (1963) A new and selective oxidation of alcohols. J Am Chem Soc 85:3027–3028

Potthast A, Schiehser S, Rosenau T, Sixta H, Kosma P (2004) Effect of UV radiation on the carbonyl distribution in different pulps. Holzforschung 58:597–602CrossRef

Röhrling J, Potthast A, Rosenau T, Lange T, Ebner G, Sixta H, Kosma P (2002) A novel method for the determination of carbonyl groups in cellulosics by fluorescence labeling. 1. Method development. Biomacromolecules 3:959–968CrossRef

Rosenau T, Potthast A, Ebner G, Hofinger A, Kosma P (2002) Novel tocopheryl compounds XII. On a novel chromanone-naphthalenetrione rearrangement related to vitamin E chemistry. Org Lett 4:1257–1258 CrossRef

Rosenau T, Potthast A, Milacher W, Hofinger A, Kosma P. (2004) Isolation and identification of residual chromophores in cellulosic materials. Polymer 45(19):6437–6443 CrossRef

Rosenau T, Potthast A, Milacher W, Adorjan I, Hofinger A, Kosma P (2005) Discoloration of cellulose solutions in N-methyl-morpholine-N-oxide (Lyocell). Part 2: Isolation and Identification of Chromophores. Cellulose 12(2):197–208CrossRef

Schroeder LR, Haigh FC (1979) Gel permeation chromatographic analysis of cellulose and wood pulp polysaccharides. Tappi J 62:103–105

Terbojevich M, Cosani A, Camilot M, Focher B (1995) Solution studies of cellulose tricarbanilates obtained in homogeneous phase. J Appl Polym Sci 55:1663–1671CrossRef

Tidwell TT (1990) Oxidation of alcohols by activated dimethyl sulfoxide and related reactions: an update. Org React 39:297–572

Urano S, Hattori Y, Yamanoi S, Matsuo M (1980) ¹³C nuclear magnetic resonance studies on α-tocopherol and its derivatives. Chem Pharm Bull 28:1992–1998

Valtasaari L, Saarela K (1975) Determination of the chain length distribution of cellulose by gel permeation chromatography using the tricarbanilate derivative. Paperi ja Puu 57:5–10

Wood BF, Conner AH, Hill CG (1986) The effect of precipitation on the molecular weight distribution of cellulose tricarbanilate. J Appl Polym Sci 32:3703–3712CrossRef

Yanagisawa M, Isogai A (2005) SEC-MALS-QELS study on the molecular conformation of cellulose in LiCl/amide solutions. Biomacromol 6(3):1258–1265CrossRef

Titel: Studies on DMSO-containing carbanilation mixtures: chemistry, oxidations and cellulose integrity
verfasst von: Ute Henniges
Elisabeth Kloser
Anjan Patel
Antje Potthast
Paul Kosma
Martin Fischer
Klaus Fischer
Thomas Rosenau
Publikationsdatum: 01.10.2007
Verlag: Springer Netherlands
Erschienen in: Cellulose / Ausgabe 5/2007
Print ISSN: 0969-0239
Elektronische ISSN: 1572-882X
DOI: https://doi.org/10.1007/s10570-007-9130-3

Springer Professional

Abstract

Bitte loggen Sie sich ein, um Zugang zu Ihrer Lizenz zu erhalten.

Sie haben noch keine Lizenz? Dann Informieren Sie sich jetzt über unsere Produkte:

Springer Professional "Technik"

Springer Professional "Wirtschaft+Technik"

Weitere Artikel der Ausgabe 5/2007

Sugar beet cellulose nanofibril-reinforced composites

Surface modification of cellulose with plant triglycerides for hydrophobicity

Morphological and structural development of hardwood cellulose during mechanochemical pretreatment in solid state through pan-milling

Preparation and characterization of cellulose β-ketoesters prepared by homogeneous reaction with alkylketene dimers: comparison with cellulose/fatty acid esters

Degradation processes in the cellulose/N-methylmorpholine-N-oxide system studied by HPLC and ESR. Radical formation/recombination kinetics under UV photolysis at 77 K

Enhanced degradation of cellulose acetate film containing diphenyliodonium salt–benzophenone