Although fire is now rarely used in synthetic chemistry, it was not until Robert Bunsen invented the burner in 1855 that the energy from this heat source could be applied to a reaction vessel in a focused manner. The Bunsen burner was later superseded by the isomantle, oil bath, or hot plate as a source for applying heat to a chemical reaction. In the past few years, heating and driving chemical reactions by microwave energy has been an increasingly popular theme in the scientific community. This nonclassical heating technique is slowly moving from a laboratory curiosity to an established technique that is heavily used in both academia and industry. The efficiency of "microwave flash heating" in dramatically reducing reaction times (from days and hours to minutes and seconds) is just one of the many advantages. This Review highlights recent applications of controlled microwave heating in modern organic synthesis, and discusses some of the underlying phenomena and issues involved.

https://onlinelibrary.wiley.com/doi/pdf/10.1002/anie.200400655

Controlled microwave heating in modern organic synthesis.

4.2.8. Reductive Coupling 3109 5. Reaction of Aromatic Compounds 3110 5.1. Electrophilic Substitutions 3110 5.2. Radical Substitution 3111 5.3. Oxidative Coupling 3111 5.4. Photochemical Reactions 3111 6. Reaction of Carbonyl Compounds 3111 6.1. Nucleophilic Additions 3111 6.1.1. Allylation 3111 6.1.2. Propargylation 3120 6.1.3. Benzylation 3121 6.1.4. Arylation/Vinylation 3121 6.1.5. Alkynylation 3121 6.1.6. Alkylation 3121 6.1.7. Reformatsky-Type Reaction 3122 6.1.8. Direct Aldol Reaction 3122 6.1.9. Mukaiyama Aldol Reaction 3124 6.1.10. Hydrogen Cyanide Addition 3125 6.2. Pinacol Coupling 3126 6.3. Wittig Reactions 3126 7. Reaction of R,â-Unsaturated Carbonyl Compounds 3127

Organic Reactions in Aqueous Media with a Focus on Carbon−Carbon Bond Formations: A Decade Update

Hydrothermal technologies are broadly defined as chemical and physical transformations in high-temperature (200–600 °C), high-pressure (5–40 MPa) liquid or supercritical water. This thermochemical means of reforming biomass may have energetic advantages, since, when water is heated at high pressures a phase change to steam is avoided which avoids large enthalpic energy penalties. Biological chemicals undergo a range of reactions, including dehydration and decarboxylation reactions, which are influenced by the temperature, pressure, concentration, and presence of homogeneous or heterogeneous catalysts. Several biomass hydrothermal conversion processes are in development or demonstration. Liquefaction processes are generally lower temperature (200–400 °C) reactions which produce liquid products, often called “bio-oil” or “bio-crude”. Gasification processes generally take place at higher temperatures (400–700 °C) and can produce methane or hydrogen gases in high yields.

/pdf/thermochemical-biofuel-production-in-hydrothermal-media-a-57itjyvhnt.pdf

Thermochemical biofuel production in hydrothermal media: A review of sub- and supercritical water technologies

8.4.5. Nitromercuration Reactions 3878 9. Hydroamination of Alkenes and Alkynes under Microwave Irradiation 3878 * To whom correspondence should be addressed. Phone: +49 241 8

Hydroamination: direct addition of amines to alkenes and alkynes.

Sterically encumbered Lewis acid and Lewis base combinations do not undergo the ubiquitous neutralization reaction to form "classical" Lewis acid/Lewis base adducts. Rather, both the unquenched Lewis acidity and basicity of such sterically "frustrated Lewis pairs (FLPs)" is available to carry out unusual reactions. Typical examples of frustrated Lewis pairs are inter- or intramolecular combinations of bulky phosphines or amines with strongly electrophilic RB(C(6)F(5))(2) components. Many examples of such frustrated Lewis pairs are able to cleave dihydrogen heterolytically. The resulting H(+)/H(-) pairs (stabilized for example, in the form of the respective phosphonium cation/hydridoborate anion salts) serve as active metal-free catalysts for the hydrogenation of, for example, bulky imines, enamines, or enol ethers. Frustrated Lewis pairs also react with alkenes, aldehydes, and a variety of other small molecules, including carbon dioxide, in cooperative three-component reactions, offering new strategies for synthetic chemistry.

Frustrated Lewis pairs: metal-free hydrogen activation and more.

Understanding of the reactivity of organic molecules in hot water is developing from studies aimed at explaining how organic matter (kerogen) forms in natural environments and then breaks down into energy source materials. In natural systems where kerogens are depolymerized, hot water is ubiquitous and usually contains salt and minerals. Reactions such as ionic condensation, cleavage, and hydrolysis are facilitated by changes in the chemical and physical properties of water as temperature increases. These changes make the solvent properties of water at high temperature similar to those of polar organic solvents at room temperature, thus facilitating reactions with organic compounds. An understanding of aqueous organic chemistry may lead to potential applications in areas as diverse as the recycling of plastics, the synthesis of chemicals, and coal liquefaction.

https://science.sciencemag.org/content/sci/254/5029/231.full.pdf

Reactivity of organic compounds in hot water: geochemical and technological implications.

Disclosed is a process for converting organic material of oil-shale to predominantly liquids. The oil-shale is first heated to a temperature from about 360° C. to 475° C. in an anionic atmosphere. The resulting liquids and gases are collected and the residue is extracted with a microemulsion capable of extracting organic material from the heat treated oil-shale.

In situ shale-oil recovery process

Aquathermolysis: Reactions of Organic Compounds with Superheated Water

Reactions in High-Temperature Aqueous Media

A series of closely related primary, secondary, and tertiary alkanolamine model compounds were monitored in real time in aqueous solution via in situ nuclear magnetic resonance (NMR) spectroscopy while purging CO2-rich gas through the solution over a range of temperatures. The real-time in situ spectroscopic monitoring of this reaction chemistry provides new insight about reaction pathways through identification of primary products and their transformations into secondary products. New mechanistic pathways were observed and elucidated. The effects of CO2 loadings, relative absorption and desorption kinetics, pH, temperature, and other critical features of the amine/CO2 reaction system are discussed in detail. The effect of amine basicity and structure on these parameters was further elucidated by studying complementary electron-rich and -poor amines (pKa ∼ 4.5–11) and guanidines (pKa ∼ 14–15). While tertiary amines act only as simple proton acceptors, primary and secondary amines function as both bases an...

In Situ Nuclear Magnetic Resonance Mechanistic Studies of Carbon Dioxide Reactions with Liquid Amines in Aqueous Systems: New Insights on Carbon Capture Reaction Pathways

Michael Siskin

Papers

Reactivity of organic compounds in hot water: geochemical and technological implications.

In situ shale-oil recovery process

Aquathermolysis: Reactions of Organic Compounds with Superheated Water

Reactions in High-Temperature Aqueous Media

In Situ Nuclear Magnetic Resonance Mechanistic Studies of Carbon Dioxide Reactions with Liquid Amines in Aqueous Systems: New Insights on Carbon Capture Reaction Pathways