Synthesis of Polyanionic Cellulose Carbamates by Homogeneous Aminolysis in an Ionic Liquid/DMF Medium
Abstract
:1. Introduction
2. Materials and Methods
2.1. Materials
2.2. Instrumentation
2.3. Synthesis
2.3.1. General Information
2.3.2. Synthesis of Cellulose bis-2,3-O-(3,5-Dimethylphenyl Carbamate) 10
2.3.3. Synthesis of Cellulose 6-O-(Phenyl Carbonate)-bis-2,3-O-(3,5-Dimethyl Phenyl Carbamates) 11a–c (Oxycarbonylation Reaction)
2.3.4. Synthesis of Cellulose 6-O-(Propynyl Carbamate)-bis-2,3-O-(3,5-Dimethylphenyl Carbamate) 12 (Aminolysis)
2.3.5. Synthesis of Cellulose Derivatives 13a–b (Aminolysis)
- Procedure A—Heterogeneous Reaction
- Procedure B—Homogenous Reaction with N,O-bis(Trimethylsilyl)Acetamide (BSA)
- Procedure C—Two-Step, One-Pot Homogenous Reaction in DMF/[EMIM]OAc
- Procedure D—Two-Step, One-Pot Homogenous Reaction in DMF and DMF/[EMIM]OAc
3. Results and Discussion
3.1. Evaluation of the Oxycarbonylation (Carbonate Formation) Reaction
3.2. Aminolysis Reaction with Propargyl Amine
3.3. Aminolysis Procedures A–D
- Procedure A—Heterogeneous Comparison
- Procedure B—Silylation Followed by Aminolysis
- Procedure C—Two-Step, One-Pot Homogenous Reaction in DMF/[EMIM]OAc
- Procedure D—Two-Step, One-Pot Homogenous Reaction in DMF and DMF/[EMIM]OAc
4. Conclusions and Outlook
Supplementary Materials
Author Contributions
Funding
Institutional Review Board Statement
Informed Consent Statement
Data Availability Statement
Conflicts of Interest
Abbreviations
BSA | N,O-Bis-(trimethylsilyl)acetamide |
CS | Chiral selector |
DMAc | N,N-Dimethylacetamide |
DMF | N,N-Dimethylformamide |
DS | Degree of substitution |
EA | Elemental analysis |
[EMIM]OAc | 1-Ethyl-3-methylimidazolium acetate |
EtOH | Ethanol |
MeOH | Methanol |
IL | Ionic liquid |
RT | Room temperature |
TBAF | tetra-n-Butylammonium fluoride hydrate |
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Calculated (wt%) | Found (wt%) | |||||||||||
---|---|---|---|---|---|---|---|---|---|---|---|---|
C | H | O | N | Cl | S | C | H | O | N | Cl | S | |
10 | 63.15 | 6.18 | 24.53 | 6.14 | - | - | 59.90 ± 0.07 | 6.27 ± 0.05 | 25.96 ± 0.50 | 5.66 ± 0.07 | - | - |
11b | 60.93 | 5.11 | 23.57 | 4.58 | 5.80 | - | 59.43 ± 0.14 | 4.86 ± 0.18 | 25.96 ± 0.50 | 4.28 ± 0.12 | 6.11 ± 0.05 | - |
11c | 64.57 | 5.59 | 24.97 | 4.86 | - | - | 61.27 ± 0.10 | 5.08 ± 0.14 | 25.16 ± 0.34 | 4.48 ± 0.04 | - | - |
13aB | 58.84 | 5.82 | 27.99 | 7.35 | - | - | 57.79 ± 0.05 | 5.98 ± 0.09 | 28.34 ± 0.09 | 5.56 ± 0.03 | - | - |
13aC | 59.96 ± 0.18 | 5.98 ± 0.12 | 26.39 ± 0.50 | 6.03 ± 0.05 | - | - | ||||||
13aD | 55.04 ± 0.19 | 5.56 ± 0.12 | 29.48 ± 0.64 | 6.81 ± 0.06 | - | - | ||||||
13bB | 53.37 | 5.47 | 28.96 | 6.92 | - | 5.28 | 59.89 ± 0.14 | 6.13 ± 0.03 | 26.01 ± 0.72 | 6.11 ± 0.02 | - | 0.08 ± 0.04 |
13bC | 49.75 ± 0.19 | 5.15 ± 0.03 | 23.48 ± 0.52 | 5.41 ± 0.03 | - | 1.03 ± 0.02 | ||||||
13bD | 46.58 ± 0.02 | 5.48 ± 0.08 | 32.70 ± 1.17 | 6.27 ± 0.03 | - | 4.86 ± 0.04 |
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Bui, C.V.; Rosenau, T.; Hettegger, H. Synthesis of Polyanionic Cellulose Carbamates by Homogeneous Aminolysis in an Ionic Liquid/DMF Medium. Molecules 2022, 27, 1384. https://doi.org/10.3390/molecules27041384
Bui CV, Rosenau T, Hettegger H. Synthesis of Polyanionic Cellulose Carbamates by Homogeneous Aminolysis in an Ionic Liquid/DMF Medium. Molecules. 2022; 27(4):1384. https://doi.org/10.3390/molecules27041384
Chicago/Turabian StyleBui, Cuong Viet, Thomas Rosenau, and Hubert Hettegger. 2022. "Synthesis of Polyanionic Cellulose Carbamates by Homogeneous Aminolysis in an Ionic Liquid/DMF Medium" Molecules 27, no. 4: 1384. https://doi.org/10.3390/molecules27041384