Evaluation of the Synthesis of Soluble Aromatic Cellulose Carbonates of Low Degree of Substitution

Abstract

The synthesis of soluble cellulose phenyl carbonates of low degree of substitution (DS, as low as 0.3) can be realized by using phenyl chloroformates with reactivity‐controlling moieties in the aromatic ring or by conversion of 6‐O‐triphenylmethyl cellulose. It is assumed that the primary hydroxyl group may yield to cross‐linking during the introduction of the phenyl carbonate moieties. Thus, for the first time soluble cellulose phenyl carbonates of low DS are accessible that are useful for the preparation of novel cellulose derivatives by reaction with nucleophilic reagents in particular amines.

Synthesis by carbonate aminolysis and chiral recognition ability of cellulose 2,3-bis(3,5-dimethylphenyl carbamate)-6-(α-phenylethyl carbamate) selectors

“…The absence of IR bands from free OH groups at 3400 cm −1 , the presence of bands assigned to C=O at 1763 cm −1 , C=C aromatic rings at 1592, 1492, 1457, 835 cm −1 , as well as C-O at 1236 and 1205 cm −1 indicate that microcrystalline cellulose, the starting material used, was quantitatively oxycarbonylated. The FTIR spectrum of cellulose derivative 1 was fully consistent with literature data (Ganske and Heinze 2018). The solid-state 13 C CP/MAS NMR spectrum with carbon signals assigned to the C=O group at 152.9 ppm and the aromatic ring at 120.…”

“…Cellulose tris(phenyl carbonate) was synthesized according to a protocol by (Ganske and Heinze 2018) with modification. Microcrystalline cellulose (1.0 g) was immersed and vigorously stirred in anhydrous DMAc (30 mL) under a dry nitrogen atmosphere.…”

“…Cellulose carbonates are a convenient platform for synthesizing cellulose derivatives, which is especially true for cellulose carbamate synthesis via aminolysis of the carbonates with simple primary and secondary alkyl amines (Pourjavadi et al 2011;Elschner et al 2013;Ganske and Heinze 2018). Cellulose aryl carbonates were shown to be more reactive than alkyl carbonates (Elschner and Heinze 2015).…”

“…Cellulose aryl carbonates were shown to be more reactive than alkyl carbonates (Elschner and Heinze 2015). For details on carbonate aminolysis to obtain cellulose carbamates see the comprehensive studies by T. Heinze and others (Pourjavadi et al 2011;Elschner et al 2013;Elschner and Heinze 2015;Ganske and Heinze 2018). Different phenyl chloroformates have inter alia been evaluated as reagents for cellulose aryl carbonate synthesis and it was reported that most phenyl chloroformates react regioselectively (but not regiospecifically) with C6-OH, rather than with C2-OH and C3-OH groups of cellulose (Elschner et al 2014;Ganske and Heinze 2018).…”

Synthesis of Polyanionic Cellulose Carbamates by Homogeneous Aminolysis in an Ionic Liquid/DMF Medium

“…A third strategy for the introduction of carbamate groups is the aminolysis of carbonate derivatives 4 (see also Figure 1), which can be obtained by the reaction of cellulose with chloroformates 3. The aminolysis of cellulose phenyl carbonates as (active) intermediates is an efficient method to introduce carbamate groups onto the cellulose backbone, a reaction that was extensively investigated inter alia by Heinze and others [17][18][19]. One of the most common reaction media for the homogeneous aminolysis of cellulose carbonate derivatives is N,N-dimethylformamide (DMF), with 24 h of reaction time, due to the good solubility of cellulose carbonate intermediates and reactants in this solvent [18].…”