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Full-Text Articles in Physical Sciences and Mathematics
Alkene Ozonolysis In The Academic Lab, Patrick Dussault
Alkene Ozonolysis In The Academic Lab, Patrick Dussault
Organic Peroxides: Safety Issues
The following information is offered as a guide based upon our experience with application of ozone for organic oxidations and hydroperoxide synthesis. Please send suggestions, requests, or corrections to pdussault1@unl.edu.
Introduction and leading references
Overview of ozonolysis: Mechanism, Substrate reactivity, Typical reaction conditions, Reaction monitoring, Reaction work-ups
Safety Issues
Acknowledgements:
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The following provides a brief introduction to the application of ozonolysis within academic labs. Ozonolysis remains among the most frequently used of methods for oxidative cleavage of alkenes. While best known as a means by which to introduce aldehydes and ketones, ozonolysis can also be used to generate other …
Working With Organic Peroxides In The Academic Lab, Patrick Dussault
Working With Organic Peroxides In The Academic Lab, Patrick Dussault
Organic Peroxides: Safety Issues
ABSTRACT: The following is a brief introduction to peroxide safety from the viewpoint of a synthetic chemist. Major topics include: classes of organic peroxides; peroxide reactivity; hazard identification and minimization; reaction monitoring; and, hazards associated with auto-oxidation of peroxidizable solvents.
KEYWORDS: peroxide, hydroperoxide, hydroperoxyacetal, ozonide, perester, dihydroperoxide, monoperoxyacetal, active oxygen, peroxide strips, TLC indicator, self-accelerating decomposition, radical, exothermicity, transition metals.
CONTENTS: 1. Literature resources 2. Major classes of peroxides 3. Basis for peroxide reactivity 4. Determining reactivity and minimizing hazards a. Steps to take before an experiment b. Minimizing hazard during reactions c. Monitoring reactions d. Working with isolated peroxides …
Developing Functionalized Peroxide Precursors For The Synthesis Of Cyclic And Spirocyclic Ethers, Anna J. Diepenbrock
Developing Functionalized Peroxide Precursors For The Synthesis Of Cyclic And Spirocyclic Ethers, Anna J. Diepenbrock
Department of Chemistry: Dissertations, Theses, and Student Research
There is increasing interest in the development of methods for the synthesis of oxetanes and spirocyclic oxetanes, a class of molecules of interest to chemists as they synthesize libraries of possible drug target scaffolds with tunable physiochemical and biological properties.1,2 Although most ethers are prepared through reaction of nucleophilic oxygen with electrophilic carbon, this work explores new reagents and routes for the synthesis of spirocyclic oxetanes based upon an application of "umpolung" or polarity reversal involving attack of nucleophilic carbon on the electrophilic oxygen of a peroxide (Scheme 1). In this work, a 2-carbon peroxide synthon for reverse etherification …
Spiroadamantyl 1,2,4-Trioxolane, 1,2,4-Trioxane, And 1,2,4-Trioxepane Pairs: Relationship Between Peroxide Bond Iron(Ii) Reactivity, Heme Alkylation Efficiency, And Antimalarial Activity, Xiaofang Wang, Darren J. Creek, Charles E. Schiaffo, Yuxiang Dong, Jacques Chollet, Christian Scheurer, Segio Wittlin, Susan A. Charman, Patrick Dussault, James K. Wood, Jonathan L. Vennerstrom
Spiroadamantyl 1,2,4-Trioxolane, 1,2,4-Trioxane, And 1,2,4-Trioxepane Pairs: Relationship Between Peroxide Bond Iron(Ii) Reactivity, Heme Alkylation Efficiency, And Antimalarial Activity, Xiaofang Wang, Darren J. Creek, Charles E. Schiaffo, Yuxiang Dong, Jacques Chollet, Christian Scheurer, Segio Wittlin, Susan A. Charman, Patrick Dussault, James K. Wood, Jonathan L. Vennerstrom
Patrick Dussault Publications
These data suggest that iron(II) reactivity for a set of homologous spiroadamantyl 1,2,4-trioxolane, 1,2,4-trioxane, and 1,2,4-trioxepane peroxide heterocycles is a necessary, but insufficient, property of animalarial peroxides. Heme alkylation efficiency appears to give a more accurate prediction of antimalarial activity than FeSO4-mediated reaction rates, suggesting that antimalarial activity is not merely dependent on peroxide bond cleavage, but also on the ability of reactive intermediates to alkylate heme or other proximal targets.
Spiroadamantyl 1,2,4-Trioxolane, 1,2,4-Trioxane, And 1,2,4-Trioxepane Pairs: Relationship Between Peroxide Bond Iron(Ii) Reactivity, Heme Alkylation Efficiency, And Antimalarial Activity, Xiaofang Wang, Darren J. Creek, Yuxiang Dong, Jacques Chollet, Christian Scheurer, Sergio Wittlin, Susan A. Charman, Patrick H. Dussault, James K. Wood, Jonathan L. Vennerstrom
Spiroadamantyl 1,2,4-Trioxolane, 1,2,4-Trioxane, And 1,2,4-Trioxepane Pairs: Relationship Between Peroxide Bond Iron(Ii) Reactivity, Heme Alkylation Efficiency, And Antimalarial Activity, Xiaofang Wang, Darren J. Creek, Yuxiang Dong, Jacques Chollet, Christian Scheurer, Sergio Wittlin, Susan A. Charman, Patrick H. Dussault, James K. Wood, Jonathan L. Vennerstrom
Chemistry Faculty Publications
These data suggest that iron(II) reactivity for a set of homologous spiroadamantyl 1,2,4-trioxolane, 1,2,4-trioxane, and 1,2,4-trioxepane peroxide heterocycles is a necessary, but insufficient, property of animalarial peroxides. Heme alkylation efficiency appears to give a more accurate prediction of antimalarial activity than FeSO4-mediated reaction rates, suggesting that antimalarial activity is not merely dependent on peroxide bond cleavage, but also on the ability of reactive intermediates to alkylate heme or other proximal targets.
Asymmetric Synthesis Of 1,2-Dioxanes: Approaches To The Peroxyplakoric Acids, Chunping Xu, Chris Schwartz, Joseph Raible, Patrick Dussault
Asymmetric Synthesis Of 1,2-Dioxanes: Approaches To The Peroxyplakoric Acids, Chunping Xu, Chris Schwartz, Joseph Raible, Patrick Dussault
Patrick Dussault Publications
The stereospecific intramolecular alkylation of a hydroperoxyacetal provides the basis for the first asymmetric synthesis of the dioxane propionate core of the peroxyplakorates. Chemoselective hydrometallation of an alkyne in the presence of a peroxide is used to introduce a synthon for the polyunsaturated side chains of the peroxyplakorates. The route suggests a general solution for the 1,2-dioxane unit in many peroxide natural products.
The 14N Quadrupole Coupling In Hexamethylene Triperoxide Diamine (Hmtd), John Persons, Gerard S. Harbison
The 14N Quadrupole Coupling In Hexamethylene Triperoxide Diamine (Hmtd), John Persons, Gerard S. Harbison
Gerard Harbison Publications
Using high-field NMR, we have determined the magnitude of the nuclear quadrupole interaction in hexamethylene triperoxide diamine (HMTD), the explosive allegedly used in the London bombings of July 2005. The experimental quadrupolar coupling constant, 5.334 MHz, is in good agreement with quantum chemical calculations. The predicted single zero-field transition frequency should lie in a relatively empty part of the 14N nuclear quadrupole resonance (NQR) spectrum; the spin relaxation rate is reasonably fast.
Stereoselective Allylation Of Chiral Monoperoxyacetals, Aqeel Ahmed, Patrick Dussault
Stereoselective Allylation Of Chiral Monoperoxyacetals, Aqeel Ahmed, Patrick Dussault
Patrick Dussault Publications
Neighboring iodo-, alkoxy-, acetoxy- and silyl groups impart useful levels of diastereoselection in the Lewis acid-mediated allylation of monoperoxyacetals. Although monoperoxyacetals are found to be considerably less reactive than corresponding nonperoxidic acetals, similar stereochemical trends are observed in the two series.