Complex Reactions

Author(s):  
L. K. Doraiswamy

When a reactant or a set of reactants undergoes several reactions (at least two) simultaneously, the reaction is said to be a complex reaction. The total conversion of the key reactant, which is used as a measure of reaction in simple reactions, has little meaning in complex reactions, and what is of primary interest is the fraction of reactant converted to the desired product. Thus the more pertinent quantity is product distribution from which the conversion to the desired product can be calculated. This is usually expressed in terms of the yield or selectivity of the reaction with respect to the desired product. From the design point of view, an equally important consideration is the analysis and quantitative treatment of complex reactions, a common example of which is the dehydration of alcohol represented by We call such a set of simultaneous reactions a complex multiple reaction. It is also important to note that many organic syntheses involve a number of steps, each carried out under different conditions (and sometimes in different reactors), leading to what we designate as multistep reactions (normally called a synthetic scheme by organic chemists). This could, for example, be a sequence of reactions like dehydration, oxidation, Diels-Alder, and hydrogenation. This chapter outlines simple procedures for the treatment of complex multiple and multistep reactions and explains the concepts of selectivity and yield. For a more detailed treatment of multiple reactions, the following books may be consulted: Aris (1969) and Nauman (1987). We conclude the chapter by considering a reaction with both catalytic and noncatalytic steps, which also constitutes a kind of complex reaction. Because both chemists and chemical engineers are involved in formulating a practical strategy for accomplishing an organic synthesis, it is important to appreciate the roles of each.

Molecules ◽  
2020 ◽  
Vol 25 (22) ◽  
pp. 5373
Author(s):  
Aneta Kurpanik ◽  
Marek Matussek ◽  
Piotr Lodowski ◽  
Grażyna Szafraniec-Gorol ◽  
Michał Krompiec ◽  
...  

PAHs (polycyclic aromatics hydrocarbons), the compound group that contains perylene and its derivatives, including functionalized ones, have attracted a great deal of interest in many fields of science and modern technology. This review presents all of the research devoted to modifications of PAHs that are realized via the Diels–Alder (DA) cycloaddition of various dienophiles to the bay regions of PAHs, leading to the π-extension of the starting molecule. This type of annulative π-extension (APEX) strategy has emerged as a powerful and efficient synthetic method for the construction of polycyclic aromatic hydrocarbons and their functionalized derivatives, nanographenes, and π-extended fused heteroarenes. Then, [4 + 2] cycloadditions of ethylenic dienophiles, -N=N-, i.e., diazo-dienophiles and acetylenic dienophiles, are presented. This subject is discussed from the organic synthesis point of view but supported by theoretical calculations. The possible applications of DA cycloaddition to PAH bay regions in various science and technology areas, and the prospects for the development of this synthetic method, are also discussed.


2018 ◽  
Vol 15 (2) ◽  
pp. 221-229 ◽  
Author(s):  
Shah Bakhtiar Nasir ◽  
Noorsaadah Abd Rahman ◽  
Chin Fei Chee

Background: The Diels-Alder reaction has been widely utilised in the syntheses of biologically important natural products over the years and continues to greatly impact modern synthetic methodology. Recent discovery of chiral organocatalysts, auxiliaries and ligands in organic synthesis has paved the way for their application in Diels-Alder chemistry with the goal to improve efficiency as well as stereochemistry. Objective: The review focuses on asymmetric syntheses of flavonoid Diels-Alder natural products that utilize chiral ligand-Lewis acid complexes through various illustrative examples. Conclusion: It is clear from the review that a significant amount of research has been done investigating various types of catalysts and chiral ligand-Lewis acid complexes for the enantioselective synthesis of flavonoid Diels-Alder natural products. The results have demonstrated improved yield and enantioselectivity. Much emphasis has been placed on the synthesis but important mechanistic work aimed at understanding the enantioselectivity has also been discussed.


2019 ◽  
Vol 16 (6) ◽  
pp. 527-543 ◽  
Author(s):  
Pedro M.E. Mancini ◽  
Carla M. Ormachea ◽  
María N. Kneeteman

During the last twenty years, our research group has been working with aromatic nitrosubstituted compounds acting as electrophiles in Polar Diels-Alder (P-DA) reactions with different dienes of diverse nucleophilicity. In this type of reaction, after the cycloaddition reaction, the nitrated compounds obtained as the [4+2] cycloadducts suffer cis-extrusion with the loss of nitrous acid and a subsequent aromatization. In this form, the reaction results are irreversible. On the other hand, the microwave-assisted controlled heating become a powerful tool in organic synthesis as it makes the reaction mixture undergo heating by a combination of thermal effects, dipolar polarization and ionic conduction. As the Diels-Alder (D-A) reaction is one of the most important process in organic synthesis, the microwave (MW) irradiation was applied instead of conventional heating, and this resulted in better yields and shorter reaction times. Several substituted heterocyclic compounds were used as electrophiles and different dienes as nucleophiles. Two experimental situations are involved: one in the presence of Protic Ionic Liquids (PILs) as solvent and the other under solvent-free conditions. The analysis is based on experimental data and theoretical calculations.


Author(s):  
Daiki Nakamizo ◽  
Seiya Kimura ◽  
Yuichi Koitabashi

<p>In order to use urban space effectively in Transit-Oriented Development (TOD), over-track buildings (built over railways), are becoming increasingly popular in Japan. From a construction and structural design point of view, the basement structure just beneath railways generally cannot be built while railway operations continue (interruption to operations is not permitted, In general).</p><p>This paper presents the structural design of a mid-story isolated high-rise building constructed over railways in Ikebukuro, Tokyo. The paper shows, not only the philosophy of the system, but also the structural design, full-scale experiments, and evaluation of the performance in each structural element. The authors believe that such a structural design will be one of the effective solutions to the over-track building.</p>


Synthesis ◽  
2020 ◽  
Author(s):  
Paolo Quadrelli ◽  
Marco Corti ◽  
Marco Leusciatti ◽  
Mattia Moiola ◽  
Mariella Mella

AbstractThe generation and trapping of two new nitrosocarbonyl intermediates bearing carbohydrate-based chiral substituents is achieved by the mild oxidation of the corresponding nitrile oxides with tertiary amine N-oxides. Their capture with suitable dienes and alkenes afforded the corresponding hetero Diels–Alder cycloadducts and ene adducts from fair to excellent yields. The entire methodology looks highly promising by the easy conversion of aldoximes into hydroxymoyl halides, widening the access to nitrosocarbonyls, versatile tools in organic synthesis.


Sign in / Sign up

Export Citation Format

Share Document