Reactions of halodeoxycelluloses with inorganic nucleophiles in aprotic amide solvents.

Furuhata, Ken-ichi; Chang, Hu-Sheng; Koganei, Katsuya; Sakamoto, Munenori

doi:10.2115/fiber.48.11_602

Cited by 9 publications

(3 citation statements)

References 4 publications

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“…These tests also enabled us to determine the minimum time required for complete conversion, which is expected to depend on the halogen. For example, Furuhata et al [39] studied the reactivity of halide ions in nucleophilic substitution reactions involving halodeoxycelluloses in aprotic solvents. They concluded that the ease of cleavage of the C─X bond in substitution reactions decreases in the following order: C─I > C─Br > C─Cl.…”

Section: Kinetic Studies and Quantitivity Of The Dissolution-reaction...mentioning

confidence: 99%

Structural Characterization of 6‐Halo‐6‐Deoxycelluloses by Direct‐Dissolution Solution‐State NMR Spectroscopy

Dryś,

Koso,

Kilpeläinen

et al. 2024

Macromol. Rapid Commun.

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Regioselective modifications of cellulose using activated cellulose derivatives such as 6‐halo‐6‐deoxycelluloses provide a convenient approach for developing sustainable products with properties tailored to specific applications. However, maintaining precise regiochemical control of substituent distribution in 6‐halo‐6‐deoxycelluloses is challenging due to their insolubility in most common solvents and the resulting difficulties in precise structure elucidation by modern instrumental analytical techniques. Herein, we present an accessible NMR‐based approach toward detailed characterization of 6‐halo‐6‐deoxycelluloses, including the determination of the degrees of substitution at carbon 6 (DS6). We show that the direct‐dissolution cellulose solvent, tetrabutylphosphonium acetate:DMSO‐d6, converts 6‐halo‐6‐deoxycelluloses to 6‐monoacetylcellulose, enabling in situ solution‐state NMR measurements. We employ a range of one‐ and two‐dimensional NMR experiments to demonstrate the quantitivity of the conversion and provide optimum dissolution conditions. In comparison with other NMR‐based derivatization protocols for elucidating the structure of 6‐halo‐6‐deoxycelluloses, the presented approach offers major advantages in terms of accuracy, speed and simplicity of analysis, and minimal requirements for reagents or NMR instrumentation.This article is protected by copyright. All rights reserved

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Section: Kinetic Studies and Quantitivity Of The Dissolution-reaction...mentioning

confidence: 99%

Structural Characterization of 6‐Halo‐6‐Deoxycelluloses by Direct‐Dissolution Solution‐State NMR Spectroscopy

Dryś,

Koso,

Kilpeläinen

et al. 2024

Macromol. Rapid Commun.

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“…A good data set for the fixed parameters of LiCl and LiBr in DMAc is a 1 = 2 kg 1/2 AE mol À1/2 , a 2 = 10 kg 1/2 AE mol À1/2 , a 3 = 1 kg 1/2 AE mol À1/2 and b = 3.2 kg 1/2 AE mol À1/2 . For both systems the values of b (1) and b (2) become negative between temperatures 333 and 423 K, see table 6. In PitzerÕs model b (1) and b (2) are related to the second virial coefficient of the electrolyte, but due to the large number of (probably not independent) parameters, it seems difficult to assign any physical reason to these values.…”

Section: The Extended Pitzer Model Of Archermentioning

confidence: 99%

“…Bromine is a better leaving group than chlorine and the C-Br bond is higher in stability than the C-I bond, as was observed in the nucleophilic substitutions of halodeoxycelluloses [6]. DMAc is known to interact strongly with metal cations to leave non-solvated anions.…”

Section: Introductionmentioning

confidence: 95%

Thermodynamic properties of (LiCl+N,N-dimethylacetamide) and (LiBr+N,N-dimethylacetamide) at temperatures from (323.15 to 423.15) K

Nasirzadeh

Neueder

Kunz

2005

The Journal of Chemical Thermodynamics

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Cationic graft copolymerization of tetrahydrofuran onto bromodeoxycellulose

Aoki

Furuhata

Sakamoto

1994

J of Applied Polymer Sci

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SYNOPSISCationic graft copolymerization of tetrahydrofuran onto halodeoxycelluloses, which were prepared under homogeneous conditions, was studied with silver tetrafluoroborate as a n initiator. 6-Bromo-6-deoxycelluloses gave graft copolymers, insoluble but swollen in tetrahydrofuran, whereas chlorodeoxycelluloses gave no graft copolymer. The graft copolymers were hydrolyzed in 2N HCl to give hydrolyzate solutions and insoluble solids. The hydrolyzate was found to be composed of 6-0-(4-hydroxybutyl) glucose and 6-0-(9-hydroxy-5-oxanonyl) glucose as well as oligomers of tetrahydrofuran by gas chromatography and gas chromatography-mass spectrometry after trifluoroacetylation. The insoluble solid was cross-linked polyoxytetramethylene, which could be hydrolyzed only very slowly in 2N HCl to yield oligomers of tetrahydrofuran. Thermal behavior of the graft copolymer was compared with t h a t of cellulose and of homopolymer of tetrahydrofuran. 0 1994

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Reactions of halodeoxycelluloses with inorganic nucleophiles in aprotic amide solvents.

Cited by 9 publications

References 4 publications

Structural Characterization of 6‐Halo‐6‐Deoxycelluloses by Direct‐Dissolution Solution‐State NMR Spectroscopy

Structural Characterization of 6‐Halo‐6‐Deoxycelluloses by Direct‐Dissolution Solution‐State NMR Spectroscopy

Thermodynamic properties of (LiCl+N,N-dimethylacetamide) and (LiBr+N,N-dimethylacetamide) at temperatures from (323.15 to 423.15) K

Cationic graft copolymerization of tetrahydrofuran onto bromodeoxycellulose

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