Diels-Alder reactions in ethylammonium nitrate, a low-melting fused salt

doi:10.1016/S0040-4039(00)99579-0

Tetrahedron Letters

Volume 30, Issue 14, 1989, Pages 1785-1788

https://doi.org/10.1016/S0040-4039(00)99579-0 Get rights and content

Abstract

Relative to nonpolar organic solvents, ethylammonium nitrate gave endo stereoselectivity enhancements for the Diels-Alder reactions of cyclopentadiene with methyl acrylate and methyl vinyl ketone.

Relative to nonpolar organic solvents, ethylammonium nitrate gave endo selectivity enhancements for the illustrated reactions.

References (15)

D.F. Evans et al.
J. Phys. Chem.
(1983)
T.J. O'Leary et al.
J. Phys. Chem.
(1984)
W. Tamura-Lis et al.
J. Phys. Chem.
(1987)
J.A. Berson et al.
J. Am. Chem. Soc.
(1962)
R. Breslow et al.
J. Am. Chem. Soc.
(1988)
A. Ray
Nature (London)
(1971)
A. Ray
J. Am. Chem. Soc.
(1969)
L.G. Ionescu et al.
J. Chem. Soc.
(1981)
I. Rico et al.
J. Phys. Chem.
(1986)
D.F. Evans et al.
J. Am. Chem. Soc.
(1981)
M. Allen et al.
J. Solution Chem.
(1985)
D. Mirejovsky et al.
J. Am. Chem. Soc.
(1983)
D.K. Magnuson et al.
J. Solution Chem.
(1984)

There are more references available in the full text version of this article.

Cited by (140)

Solvent effects on Diels–Alder reaction in ionic liquids: A reaction density functional study
2024, Chinese Journal of Chemical Engineering
Extensive experimental studies have been performed on the Diels–Alder (DA) reactions in ionic liquids (ILs), which demonstrate that the IL environment can significantly influence the reaction rates and selectivity. However, the underlying microscopic mechanism remains ambiguous. In this work, the multiscale reaction density functional theory is applied to explore the effect of 1-butyl-3-methylimidazolium hexafluorophosphate ([BMIM][PF₆]) solvent on the reaction of cyclopentadiene (CP) with acrolein, methyl acrylate, or acrylonitrile. By analyzing the free energy landscape during the reaction, it is found that the polarization effect has a relatively small influence, while the solvation effect makes both the activation free energy and reaction free energy decrease. In addition, the rearrangement of local solvent structure shows that the cation spatial distribution responds more evidently to the reaction than the anion, and this indicates that the cation plays a dominant role in the solvation effect and so as to affect the reaction rates and selectivity of the DA reactions.
Ionic liquids with microwave-assisted extraction of natural products
2023, Extraction of Natural Products from Agro-industrial Wastes: A Green and Sustainable Approach
The concept of “green chemistry” conducted the researches towards the development of new, modern and sustainable equipment and solvents. Nowadays different types of ILs are used as solvents in modern extraction processes, mainly in microwave-assisted extraction (MAE) to obtain target compounds. The tandem ILs/microwave-assisted extraction can be considered to be in the development stage. Validation of the multitude of ILs applicable for the extraction of a wide range of phytocomponents of potential interest, inevitably will lead to an explosive development on this field in the coming years.
Effects of Ionic Liquids on the Nucleofugality of Chloride
2022, Journal of Organic Chemistry
The nucleofugality of chloride has been measured in solvent mixtures containing ionic liquids for the first time, allowing reactivity in these solvents to be put in context with molecular solvents. Using well-described electrofuges, solvolysis rate constants were determined in mixtures containing different proportions of ethanol and the ionic liquid 1-butyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide; the different solvent effects observed as the mixture changed could be explained using interactions of the ionic liquid with species along the reaction coordinate, determined using temperature dependent kinetic studies. The solvolysis data allowed determination of the nucleofugality of chloride in these mixtures, which varied with the proportion of salt in the reaction mixture, demonstrating quantitatively the importance of the amount of ionic liquid in the reaction mixture in determining reaction outcome. Nucleofugality data for chloride were determined in seven further ionic liquids, with the reactivity shown to vary over more than an order of magnitude. This outcome illustrates that the components of the ionic liquid are critical in determining reaction outcome. Overall, this work quantitatively extends the understanding of solvent effects in ionic liquids and demonstrates the potential for such information to be used to rationally select an ionic liquid to control reaction outcome.
A review on alternative lubricants: Ionic liquids as additives and deep eutectic solvents
2021, Journal of Molecular Liquids
Citation Excerpt :
ILs are defined as organic salts comprised entirely of ions, which exhibit melting points below 100 °C [6]. They were first reported in the literature in the beginning of the last century, but with higher impact in the 1980s [7]. ILs have unique properties such as high chemical and thermal stability, almost negligible vapor pressure, non-flammability, high ionic conductivity and ease in dissolving organic, inorganic and polymeric materials [8].
The growing concern with environmental issues and the rapid development of new engines accentuated the need for more efficient and green lubricants. Ionic liquids (ILs) have emerged as promising alternatives to the conventional lubricants due to their interesting properties. However, the manufacturing costs of ILs are usually high, making their application as neat lubricants impracticable. A viable solution to overcome this drawback is the application of ILs as additives to commonly used base oils. Another very attractive alternative is related to the deep eutectic solvents (DES), which have similar properties to ILs but are much cheaper and simple to prepare. This paper aims at reviewing the most relevant research done in the field of lubrication using IL additives and DES in the last 10 years (from 2011 to 2020).
Green Chemistry for Green Solvent Production and Sustainability Toward Green Economy
2021, Biomass, Biofuels, Biochemicals: Circular Bioeconomy-Current Developments and Future Outlook
Green economy aims to assist in the development of societies while reducing environmental risks. In this regard, various environmental dimensions, such as renewable resources and energies, as well as different economic features like growth, development, and cost, are considered. Green solvent utilization leads to lessening the environmental risks caused by the solvent used in the chemical industry. Green solvents refer to solvents that are in agreement with the concepts of green chemistry and mainly used in the recovery of chemical/biological products. These solvents are environmentally friendly and, in some cases, can originate from the processing of agricultural crops. Conventional solvents such as chloroform, methanol, hexane, etc. (derived from the chemical/petrochemical industry), are toxic to human health as well as the environment. Recently, much research has been performed to develop nontoxic or less-toxic solvents to extract different chemicals, which are known as green solvents. In this chapter, different types and applications of the green solvents in use nowadays, such as ionic liquids, natural deep eutectic solvents, supercritical solvents, and renewable solvents, are reviewed by considering challenges, perspectives, and how they are correlated with respect to the circular economy and green chemistry.
Microwave assisted organic syntheses (MAOS): The green synthetic method
2021, Handbook of Greener Synthesis of Nanomaterials and Compounds: Volume 1: Fundamental Principles and Methods
Nowadays, chemists all over the world have the biggest challenge to search for synthetic methods and strategies that allow the innovation, effectiveness and efficiency of any chemical transformation for the construction of organic molecules, not only reducing preparation costs but also considerably reducing the environmental impact. The green synthetic methods such as mechanosynthesis, sonosynthesis, electrosynthesis, and microwave (MW) assisted synthesis during the time have been excellent options for the above mentioned. In the early 90s until now, microwave assisted organic synthesis (MAOS) publications have increased tremendously due to fast, easy, and clean chemical routes. This chapter gives an overview of the recent advances in microwave-assisted organic synthesis for the formation of CC, CN, and CO bonds as a strategy for the construction of biologically active molecules in different media reaction such as ionic liquids, glycol, vegetal oil, and water. Also, the free-solvent reactions are report. The last section of this chapter describes the most recent reports about multicomponent of organic reaction under microwave irradiation.

View all citing articles on Scopus

View full text

Diels-Alder reactions in ethylammonium nitrate, a low-melting fused salt

Abstract

J. Phys. Chem.

J. Phys. Chem.

J. Phys. Chem.

J. Am. Chem. Soc.

J. Am. Chem. Soc.

Nature (London)

J. Am. Chem. Soc.

J. Chem. Soc.

J. Phys. Chem.

J. Am. Chem. Soc.

J. Solution Chem.

J. Am. Chem. Soc.

J. Solution Chem.