Syntheses of cellulose derivatives via <i>O</i>‐triorganosilyl celluloses, 1. Effective synthesis of organic cellulose esters by acylation of trimethylsilyl celluloses

Stein, A.; Klemm, Dieter

doi:10.1002/marc.1988.030090811

Cited by 38 publications

(20 citation statements)

References 5 publications

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“…Figure 4 shows the size exclusion chromatogram of the palmitoyl cellulose after different reaction times. In contrast to the experimental procedure of Stein [10] no chlorotrimethylsilane distilled from the nitrobenzene reaction mixtures up to 160 8C. They do not contain trimethylsilyl groups to a significant degree and the amount of hydroxy groups is estimated to be lower than 0.3.…”

Section: Cellulosementioning

confidence: 72%

“…The high temperature reactions were made in nitrobenzene at 150 8C or higher temperature adopting the reaction conditions which had been used in the literature [10]. Starting materials in this series were glycerol (1), 1,3-bis(trimethylsiloxy)-2-propanol (2), 1,2,3-tris(trimethylsiloxy) propane (3), methyl-2,3,4-tris-O-trimethylsilyl-a-D-glucopyranoside (11), and methyl-2,3,4,6-tetrakis-O-trimethylsilyl-a-D-glucopyranoside (10).…”

Section: Model Compoundsmentioning

confidence: 99%

“…From the benzoylation only oligomeric products with a molar mass below 1000 are left. After 30 min at this temperature (identical to [10]) most of the nitrobenzene and unreacted 4-nitrobenzoyl chloride were removed at 0.01 mbar under anhydrous conditions. During acylation with palmitoyl chloride the molar mass decreases by a factor of 100 from almost one million to 10 000 (against polystyrene standards).…”

Section: Cellulosementioning

confidence: 99%

“…Klemm and coworkers described selective esterification of the free hydroxy groups in trimethylsilyl cellulose by acid chlorides in the presence of an acid acceptor like triethylamine and 4-N,N-dimethylaminopyridine (DMAP) as catalyst at room temperature. At elevated temperature, e. g. nitrobenzene at 160 8C, without any added catalyst trimethylsiloxy groups are reported to react selectively while the hydroxy groups are not affected under these conditions [10] (Scheme 1). At elevated temperature, e. g. nitrobenzene at 160 8C, without any added catalyst trimethylsiloxy groups are reported to react selectively while the hydroxy groups are not affected under these conditions [10] (Scheme 1).…”

Section: Introductionmentioning

confidence: 99%

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Selectivity in the acylation of partially silylated hydroxy polymers - a study with trimethylsilyl cellulose and model compounds

Mörmann¹,

Demeter

Wagner

1999

Acta Polym.

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Acylation of partially trimethylsilylated cellulose, glycerol (1), 1,3‐bis(trimethylsiloxy)‐2‐propanol (2), methyl‐2,3,4,6‐tetrakis‐O‐trimethylsilyl‐α‐D‐glucopyranoside (10) and methyl‐2,3,4‐tris‐O‐trimethylsilyl‐α‐D‐glucopyranoside (11) either with acyl chlorides/triethylamine at room temperature or with acyl chlorides at elevated temperature in the absence of an acid scavenger has been studied. Selective acylation of free hydroxy groups has been found with acyl chloride/amine, though complete conversion of free hydroxy groups of cellulose could not be achieved under these conditions. High temperature acylation, however, results in an unselective reaction of free hydroxy groups and trimethylsilyloxy groups. Trans‐silylation takes place and chlorination is found in the reaction of 1 and 2. Carbohydrates were not chlorinated under these conditions, silyl cellulose, however, is strongly depolymerized.

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Section: Cellulosementioning

confidence: 72%

Section: Model Compoundsmentioning

confidence: 99%

Section: Cellulosementioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Selectivity in the acylation of partially silylated hydroxy polymers - a study with trimethylsilyl cellulose and model compounds

Mörmann¹,

Demeter

Wagner

1999

Acta Polym.

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“…In previous papers we have reported on syntheses of organic cellulose esters via trialkylsilylcelluloses [37]. In previous papers we have reported on syntheses of organic cellulose esters via trialkylsilylcelluloses [37].…”

Section: Trialkylsilylethermentioning

confidence: 99%

New approaches to advanced polymers by selective cellulose functionalization

et al. 1997

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The uniform structure of cellulose, combined with its hydrophilicity, biocompatibility, chirality, and structure-forming capacity, as well as its broad synthetic potential, make the design of cellulose-based advanced materials a challenge for polysaccharide research. The synthesis of new cellulose products with regiocontrolled pattern of functionalization and of well defined supramolecular nanoscale architectures is a highlight in recent cellulose chemistry. The present feature will discuss regioselective functionalization of cellulose and cellulose derivatives with respect to reactivity of the polymer depending on molecular and supramolecular structure. Experimental examples of functionalization via ester intermediates of controlled stability as well as via protecting or activating ether groups are described and the efficiency of the reaction routes and procedures is evaluated. Moreover, problems and progress in techniques of product analysis and structure-property relationships as well as potential applications of regioselectively functionalized cellulosics are presented together with a discussion of possible future developments in cellulose chemistry. Acta Polymer., 48,277-297 0 VCH Verlagsgesellschaft mbH, D-6945 1 Weinheim 1997 0323-7648/97/0808-0277$17.50+.50/0 ' 278 Klemm, Heinze, Philipp, Wagenknecht Acta Polymer., 48,277-297 (1997) Fig. 5. Electron microscopic pictures (TEM) of typical cellulose samples: acotton linters, b -spruce sulfite pulp (from Fink et al.

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Selectivity in the acylation of partially silylated hydroxy polymers – a study with trimethylsilyl cellulose and model compounds

Mormann¹,

Demeter²,

Wagner³

1999

Acta Polym.

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Acylation of partially trimethylsilylated cellulose, glycerol (1), 1,3-bis(trimethylsiloxy)-2-propanol (2), methyl-2,3,4,6-tetrakis-O-trimethylsilyl-a-D-glucopyranoside (10) and methyl-2,3,4-tris-O-trimethylsilyl-a-D-glucopyranoside (11) either with acyl chlorides/triethylamine at room temperature or with acyl chlorides at elevated temperature in the absence of an acid scavenger has been studied. Selective acylation of free hydroxy groups has been found with acyl chloride/amine, though complete conversion of free hydroxy groups of cellulose could not be achieved under these conditions. High temperature acylation, however, results in an unselective reaction of free hydroxy groups and trimethylsilyloxy groups. Trans-silylation takes place and chlorination is found in the reaction of 1 and 2. Carbohydrates were not chlorinated under these conditions, silyl cellulose, however, is strongly depolymerized.

show abstract

Syntheses of cellulose derivatives via O‐triorganosilyl celluloses, 1. Effective synthesis of organic cellulose esters by acylation of trimethylsilyl celluloses

Cited by 38 publications

References 5 publications

Selectivity in the acylation of partially silylated hydroxy polymers - a study with trimethylsilyl cellulose and model compounds

Selectivity in the acylation of partially silylated hydroxy polymers - a study with trimethylsilyl cellulose and model compounds

New approaches to advanced polymers by selective cellulose functionalization

Selectivity in the acylation of partially silylated hydroxy polymers – a study with trimethylsilyl cellulose and model compounds

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