Reducing the use of solvents is an important aim of green chemistry. Using micelles self-assembled from amphiphilic molecules dispersed in water (considered a green solvent) has facilitated reactions of organic compounds. When performing reactions in micelles, the hydrophobic effect can considerably accelerate apparent reaction rates, as well as enhance selectivity. Here, we review micellar reaction media and their potential role in sustainable chemical production. The focus of this review is applications of engineered amphiphilic systems for reactions (surface-active ionic liquids, designer surfactants, and block copolymers) as reaction media. Micelles are a versatile platform for performing a large array of organic chemistries using water as the bulk solvent. Building on this foundation, synthetic sequences combining several reaction steps in one pot have been developed. Telescoping multiple reactions can reduce solvent waste by limiting the volume of solvents, as well as eliminating purification processes. Thus, in particular, we review recent advances in “one-pot” multistep reactions achieved using micellar reaction media with potential applications in medicinal chemistry and agrochemistry. Photocatalyzed reactions in micellar reaction media are also discussed. In addition to the use of micelles, we emphasize the process (steps to isolate the product and reuse the catalyst).
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Amphiphilic Polymer Nanoreactors for Multiple Step, One-Pot Reactions and Spontaneous Product Separation
Performing multiple reaction steps in “one pot” to avoid the need to isolate intermediates is a promising approach for reducing solvent waste associated with liquid phase chemical processing. In this work, we incorporated gold nanoparticle catalysts into polymer nanoreactors via amphiphilic block copolymer directed self-assembly. With the polymer nanoreactors dispersed in water as the bulk solvent, we demonstrated the ability to facilitate two reaction steps in one pot with spontaneous precipitation of the product from the reaction mixture. Specifically, we achieved imide synthesis from 4-nitrophenol and benzaldehyde as a model reaction. The reaction occured in water at ambient conditions; the desired 4-benzylideneaminophenol product spontaneously precipitated from the reaction mixture while the nanoreactors remained stable in dispersion. A 65% isolated yield was achieved. In contrast, PEGylated gold nanoparticles and citrate stabilized gold nanoparticles precipitated with the reaction product, which would complicate both the isolation of the product as well as reuse of the catalyst. Thus, amphiphilic nanoreactors dispersed in water are a promising approach for reducing solvent waste associated with liquid phase chemical processing by using water as the bulk solvent, eliminating the need to isolate intermediates, achieving spontaneous product separation to facilitate the recycling of the reaction mixture, and simplifying the isolation of the desired product.
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- Award ID(s):
- 1651957
- NSF-PAR ID:
- 10312159
- Date Published:
- Journal Name:
- Polymers
- Volume:
- 13
- Issue:
- 12
- ISSN:
- 2073-4360
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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- Free Publicly Accessible Full Text
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Accepted Manuscript1.0
- Journal Article:
- https://doi.org/10.3390/polym13121992
