Transformations of Di- and Tetrahydropyrimidine Derivatives into Condensed Heterocycles with Retention of their Partially Saturated Structure

2017 ◽  
Vol 54 (4) ◽  
pp. 2129-2154 ◽  
Author(s):  
Grigoriy Ya Remennikov
Synthesis ◽  
2021 ◽  
Author(s):  
Mikhailo Slivka ◽  
Mikhailo Onysko

AbstractCondensed heterocycles are well-known for their excellent biological effects and they are undeniably important compounds in organic chemistry. Electrophilic cyclization reactions are widely used for the synthesis of mono-heterocyclic compounds. This review highlights the utility of electrophilic cyclization reactions as an effective generic tool for the synthesis of various condensed heterocycles containing functional groups that are able to undergo further chemical transformations, such as nucleophilic substitution, elimination, re-cyclization, cleavage, etc. This review describes the reactions of unsaturated derivatives of different heterocycles with various electrophilic agents (halogens, arylsulfanyl chlorides, mineral acids) resulting in annulation of an additional partially saturated heterocycle. The electrophilic reaction conditions, plausible mechanisms and the use of such transformations in organic synthesis are also discussed. The review mainly focuses on research published since 2002 in order to establish the current state of the art in this area. 1 Introduction2 Electrophilic Cyclization Pathways Involving a Nitrogen Nucleo­philic Center3 Electrophilic Cyclization Pathways Involving a Chalcogen Nucleophilic Center3.1 Sulfur Centers3.2 Oxygen Centers3.3 Selenium Centers4 Strategies and Mechanisms5 Conclusion


Author(s):  
William Krakow

In recent years electron microscopy has been used to image surfaces in both the transmission and reflection modes by many research groups. Some of this work has been performed under ultra high vacuum conditions (UHV) and apparent surface reconstructions observed. The level of resolution generally has been at least an order of magnitude worse than is necessary to visualize atoms directly and therefore the detailed atomic rearrangements of the surface are not known. The present author has achieved atomic level resolution under normal vacuum conditions of various Au surfaces. Unfortunately these samples were exposed to atmosphere and could not be cleaned in a standard high resolution electron microscope. The result obtained surfaces which were impurity stabilized and reveal the bulk lattice (1x1) type surface structures also encountered by other surface physics techniques under impure or overlayer contaminant conditions. It was therefore decided to study a system where exposure to air was unimportant by using a oxygen saturated structure, Ag2O, and seeking to find surface reconstructions, which will now be described.


Author(s):  
Sudeep M. Rao ◽  
Joshua Samuel ◽  
Sai S. Prakash ◽  
C. Jeffrey Brinker

Ambient pressure silica aerogel thin films have recently been prepared by exploiting reversible drying shrinkage caused by derivatization of the internal gel surface. Aerogels have porosities of upto 99.9% and due to the small size of the pores (few nanometers), large capillary stresses are produced in gels that are partially saturated with a wetting liquid. As a result of these capillary stresses, the flexible silica network undergoes strain which has been observed using environmental microscopy. This technique allows variation of the equilibrium vapor pressure and temperature, and a simultaneous monitoring of the deformation of the unconstrained film thickness. We have observed >600% deformation during the pore-filling and pore-emptying cycles. In this presentation, we discuss the unique stress-strain behavior of these films.Ref.: Sai S. Prakash, C. Jeffrey Brinker, Alan J. Hurd & Sudeep M. Rao, "Silica aerogel films prepared at ambient pressure by using surface derivatization to induce reversible drying shrinkage", Nature. Vol. 374, 30 March, 1995, 439-443.


1986 ◽  
Vol 51 (10) ◽  
pp. 2167-2180 ◽  
Author(s):  
Lubor Fišera ◽  
Nadezhda D. Kozhina ◽  
Peter Oravec ◽  
Hans-Joachim Timpe ◽  
Ladislav Štibrányi ◽  
...  

3-Aryl-4-R-carbamoyl-5-hydroxymethylisoxazolines (IV) were synthesized by allowing R-NH2 amines with R = H, CH3, C3H7, C6H5C2H5, and NH2 to act on 3-(X-phenyl)-4-oxo-3a,4,6,6a-tetrahydrofuro[3,4-d]isoxazoles (III) with X = H, 4-CH3, 4-OCH3, 2-OCH3, 4-Cl, 2-Cl, 4-F, 2-F, 4-Br, 4-NO2, and 3-NO2. Exposed to radiation, the substances IV give Z-2-hydroxymethylamino-2-aryl-1-formylacrylamides (V) in good yields. The 4-Cl and 4-F substituted Z-derivatives V isomerize irreversibly to the E-derivatives VI if allowed to stand in solvent; the remaining derivatives V are stable. The quantum yields of the photoreaction are from 0.012 to 0.106 in dependence on the substituent X. In all cases where the compounds IV were used for the preparation of condensed heterocycles in conditions of acid-catalyzed reactions, lactones III were preferentially formed; the action of thionyl chloride on IV results in the formation of chloromethyl derivatives VIII, which do not undergo further cyclization.


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