Wagner-Meerwein rearrangement in the course of the ozonolysis of a bornene derivative

The ozonolysis of the bicyclo[2.2.1]heptene derivative 1 or 2 gave the octaline derivative 6 (the structure was confirmed by X-ray crystallographic analysis) or 7. The exo-addition of ozone to the double bond of 1 or 2 was followed by the fragmentation in carbonyl oxide and aldehyde. Then, the strong electrophilic character of the carbonyl oxide induces an unexpected Wagner-Meerwein rearrangement to give zwitterion 4. Finally, a fragmentation reaction with elimination of dioxygen gave the tetrasubstituted C-C double bonds of 6 or 7.     

A study of the ozonolysis of butadiene rubber in the presence of ethanol

The reaction of ozone with butadiene rubber (BR) having the microstructure: 90% 1,4-cis and 10% 1,4-trans and 1,2-cis, was investigated in pure chloroform and ethanol/chloroform mixture, respectively. Gel permeation chromatography was used to follow the molecular weight change of ozonolysed BR, and FT-IR and ¹H NMR were used to characterize the type and relative content of functional groups of ozonolysis products. It was found out that although the final ozonolysis products had almost the same functional groups whether ethanol was added or not, the addition of ethanol could efficiently prevent the cross-linking of ozonolysed BR.     

A new type of anomalous ozonolysis in strained allylic bicycloalkan-1-ols

7,7-Dimethyl-2-methylenenorbornan-1-ol, a fenchone-derived strained allylic bicycloalkan-1-ol, undergoes an unexpected new type of anomalous ozonolysis to yield a mixture of a rearranged β-hydroxyketone and a fragmented carboxylic acid. The proposed mechanisms involves two unusual different trappings for two different key Criegee’s intermediates.     

Novel synthesis of a strained para-cyclophane derivative

A [P. Rajakumar, A.M.A. Rasheed, Tetrahedron 61（22） （2005） 5351] para-cyclophane derivative was synthesized via intramolecular esterification of a dipeptide surrogate containing asparagine to form tetrahydropyrimidinone ring. The structures of the product and intermediates were characterized by 1H NMR, 13C NMR and mass spectrum.     

Unusual reactivity of bicyclo[2.2.1]heptene derivatives during the ozonolysis

This paper describes mechanistic studies on the ozonolysis of bicyclo[2.2.1]heptene derivatives 6 and 7 obtained from (R)-(+)-pulegone through the cyclopentadiene 5 and its Diels-Alder reaction with maleic anhydride. The ozonolysis of the tricyclic diol 7 led to the ketone 8 with the same skeleton while the anhydride 6 gave rise to the epoxide 10 and the bis-lactone 11. The structure of 8, 10 and 11 are confirmed by X-ray analysis. These unexpected results are discussed in terms of a π complex between ozone and the double bond.     

Stability of polyynes in air and their degradation by ozonolysis

Polyyne solutions in n-hexane or other aliphatic hydrocarbons having C₆H₂, C₈H₂ and C₁₀H₂ as main components were found to be unstable at relatively high concentration (≈10⁻² M) and to separate in few hours a brown precipitate. This phenomenon does not occur in more dilute solutions. The precipitate recovered from the mentioned solutions was analysed by FT-IR spectroscopy and thermogravimetry and found to be constituted by polyyne chains crosslinked and oxidized by oxygen resembling in some way the product obtained by photolysing acetylene in water solution and in presence of air. Polyynes react very quickly with ozone producing as main product polymeric ozonides which are insoluble in hydrocarbons and which have been studied with FT-IR spectroscopy. The oxidized nature of the chains highly crosslinked by ozonides, peroxide and oxygen bridges has been confirmed. The oxidized polyyne fraction remaining in solution after ozonolysis was studied by electronic absorption spectroscopy and by liquid chromatography. Extensive chain breaking was found as expected although some degree of unsaturation was preserved even in the final oxidized products.     

Unusual reactivity of bicyclo[2.2.1]heptene derivatives during the ozonolysis. Part 2

The ozonation of four bornene derivatives, prepared from (R)-(+)-pulegone, which possess a particularly hindered double bond, led to the formation of unexpected products depending on the nature of the solvent. The formation of the corresponding epoxides, ketones with the same skeleton, various lactones and even an allyl alcohol and an allyl chloride (allylic functionalisation) was observed. In two cases, products presenting a pulegone modified skeleton resulting from a Wagner-Meerwein rearrangement were obtained. The structure of three products was confirmed by crystallographic X-ray analysis. Mechanisms taking into account the rigid and congested structure of the reactants explain these results. The most striking steps were backed up by theoretical calculations.     

Synergistic effect of functional carbon nanotubes and graphene oxide on the anti‐corrosion performance of epoxy coating

In this work, we reported the synergistic effect of functional carbon nanotubes (CNTs) and graphene oxide (GO) on the anticorrosion performance of epoxy coating. For this purpose, the GO and CNTs were firstly modified by the 3‐aminophenoxyphthalonitrile to realize the nitrile functionalized graphene oxides (GO‐CN) and carbon nanotubes (CNTs‐CN). As modified GO‐CN and CNTs‐CN were characterized and confirmed by Fourier transform infrared spectroscopy, X‐ray photoelectron spectroscopy, and gravimetric analyzer. It was found that about 19 and 24 wt% of 3‐aminophenoxyphthalonitrile were grafted onto the surface of the GO and CNTs, respectively. The electrochemical impedance spectroscopy results showed that the GO‐CN&CNTs‐CN hybrid materials exhibit a remarkable superiority in enhancing the anticorrosion performance of epoxy coatings. Significant synergistic effect of the lamellar structural GO‐CN and CNTs‐CN on the anticorrosion performance of epoxy composite coatings was designed. Besides, the epoxy coating with 1 wt% of the GO‐CN&CNTs‐CN hybrid exhibited the best anticorrosion performance, in which the impedance showed the largest one (immersion in 3.5 wt% of NaCl solution for 168 hr). Copyright © 2016 John Wiley & Sons, Ltd.     

The direct determination of double bond positions in lipid mixtures by liquid chromatography/in-line ozonolysis/mass spectrometry

The direct determination of double bond positions in unsaturated lipids using in-line ozonolysis-mass spectrometry (O₃-MS) is described. In this experiment, ozone penetrates through the semi-permeable Teflon AF-2400 tubing containing a flow of a solution of fatty acid methyl esters (FAME). Unsaturated FAME are thus oxidized by the ozone and cleaved at the double bond positions. The ozonolysis products then flow directly into the atmospheric pressure photoionization (APPI) source of a mass spectrometer for analysis. Aldehyde products retaining the methyl ester group are indicative of the double bond positions in unsaturated FAME. For the first time, O₃-MS is able to couple directly to high performance liquid chromatography (HPLC), making the double bond localization in lipid mixtures possible. The application of LC/O₃-MS has been demonstrated for a fat sample from bovine adipose tissue. A total of 9 unsaturated FAME including 6 positional isomers were identified unambiguously, without comparison to standards. The in-line ozonolysis reaction apparatus is applicable to most mass spectrometers without instrumental modification; it is also directly compatible with various LC columns. The LC/O₃-MS method described here is thus a practical, versatile and easy to use new approach to the direct determination of double bond positions in lipids, even in complex mixtures.     

Formation of 1,2,4-oxadiazoles in the course of photooxidation of aromatic azides in acetonitrile

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Understanding the effect of allylic methyls in olefin cross-metathesis

A series of NMR spectroscopy experiments have been conducted with both the model compound, 3-methyl-1-pentene and the corresponding ADMET monomer 3,6,9-trimethylundeca-1,10-diene (11) to better understand the effect of allylic methyls during olefin metathesis chemistry. Traditional ADMET catalysts such as Schrock’s molybdenum (1), and Grubbs’ ruthenium 1st and 2nd generation (2 and 3) were examined under cross-metathesis and ADMET conditions. Regardless of catalyst selection, 50% or less metathesis conversion was observed for all reactions, especially in the case of the more sterically encumbered diene. With Schrock’s molybdenum catalyst 1, the reaction leads to an accumulation of the non-productive metallacyclobutane, trapping the catalyst in an inactive form. With Grubbs’ ruthenium catalysts 2 and 3, the substrate coordinates to the metal center primarily to yield non-productive metathesis, which results in a build-up of the methylidene complex leading to catalyst decomposition. These results are directly correlated to the orientation of the substrate’s bulk during the metallacyclobutane formation, the alkyl branch being adjacent to the metal center in the case of the molybdenum catalyst 1, and opposite to it in the case of ruthenium catalyst 2 and 3.     

Synthesis of a functionalized furan via ozonolysis—further confirmation of the Criegee mechanism

A new method for the synthesis of a tetrahydrofuran ring is described which involves ozonolysis of a diene possessing a free hydroxy group in the γ-position. The reaction proceeds via ozone attack on the terminal double bond, cleavage, and intramolecular cyclization through the free hydroxy group. The cyclization event can be rationalized through formation of Criegee’s carbonyl oxide, but not through the ‘unified’ mechanism, thereby lending support to the Criegee mechanism as a method of producing oxygen-containing heterocycles.     

Diisobutylaluminum hydride-promoted cyclization of silylated 1,3-dien-5-ynes: Application to total synthesis of a 20-norabietane derivative

The diisobutylaluminum hydride (DIBAL-H)-promoted benzocyclization, recently developed by this group, was adopted for the synthesis of a natural product containing a 9,10-dihydrophenanthrene skeleton to demonstrate its synthetic utility. One of the extracts from the roots of Salvia hydrangea DC. ex Bentham (Lamiaceae), a 20-norabietane derivative, was selected as the target molecule. The key step forming the 9,10-dihydrophenanthrene skeleton was achieved by the DIBAL-H-promoted cyclization of a silylated 1,3-dien-5-yne easily accessible from a substituted α-tetralone.     

Synthesis of 17-epi-calcitriol from a common androstane derivative, involving the ring B photochemical opening and the intermediate triene ozonolysis

An efficient synthesis of 17-epi-calcitriol 2, an epimer of natural hormone, via 17-epi-cholesterol 5a is described. Synthesis of 5a includes palladium-catalyzed cyclopropanation of the common androstane derivative 7 with an alkyl diazoacetate, reductive fission of the less shielded side of cyclopropane carboxylic acid esters 6, oxidation of the products into acid 11a, and alkylation of ester 11b. Photolysis of 7,8-dedydro-17-epi-25-hydroxycholesterol 19b and consecutive thermal rearrangement gave a mixture of several products that was subjected to ozonolysis to provide, after chromatography, hydroxy ketone 3a. The silyl derivative 3b was coupled with the respective ring A building block.     

Neighbouring group participation in formation of condensed azines. Formation of pyrazolo(3,4-b)pyrazines,isoxazolo(4,5-b)pyrazines and isothiazolo(5,4-b)pyridine

Pyrazine- and pyridinecarboxamidoximes with an amino, potentially tautomeric hydroxy or mercapto group inortho position could be transformed in the appropriate condensed azines. In this manner, representatives of pyrazolo(3,4-b)pyrazine, isoxazolo(4,5-b)pyrazine and isothiazolo(5,4-b)pyridine ring system were synthesized and some transformations investigated.Presented in part at the 8th International Congress of Heterocyclic Chemistry, Graz, 1981.     

Bicyclo[3.2.1]octanone catalysts for asymmetric alkene epoxidation: the effect of disubstitution

A series of 2-fluoro-8-oxabicyclo[3.2.1]octan-3-ones are prepared and tested as catalysts for alkene epoxidation with Oxone^®. These catalysts provide trans-stilbene oxide with up to 83% ee, but the highest ee value is obtained with the monofluorinated ketone 2: both 2,2- and 2,4-disubstituted catalysts afford epoxide of lower ee.     

The effect of humidity on the ozonolysis of unsaturated compounds in aerosol particles

Atmospheric aerosol particles are important in many atmospheric processes such as: light scattering, light absorption, and cloud formation. Oxidation reactions continuously change the chemical composition of aerosol particles, especially the organic mass component, which is often the dominant fraction. These ageing processes are poorly understood but are known to significantly affect the cloud formation potential of aerosol particles. In this study we investigate the effect of humidity and ozone on the chemical composition of two model organic aerosol systems: oleic acid and arachidonic acid. These two acids are also compared to maleic acid an aerosol system we have previously studied using the same techniques. The role of relative humidity in the oxidation scheme of the three carboxylic acids is very compound specific. Relative humidity was observed to have a major influence on the oxidation scheme of maleic acid and arachidonic acid, whereas no dependence was observed for the oxidation of oleic acid. In both, maleic acid and arachidonic acid, an evaporation of volatile oxidation products could only be observed when the particle was exposed to high relative humidities. The particle phase has a strong effect on the particle processing and the effect of water on the oxidation processes. Oleic acid is liquid under all conditions at room temperature (dry or elevated humidity, pure or oxidized particle). Thus ozone can easily diffuse into the bulk of the particle irrespective of the oxidation conditions. In addition, water does not influence the oxidation reactions of oleic acid particles, which is partly explained by the structure of oxidation intermediates. The low water solubility of oleic acid and its ozonolysis products limits the effect of water. This is very different for maleic and arachidonic acid, which change their phase from liquid to solid upon oxidation or upon changes in humidity. In a solid particle the reactions of ozone and water with the organic particle are restricted to the particle surface and hence different regimes of reactivity are dictated by particle phase. The potential relevance of these three model systems to mimic ambient atmospheric processes is discussed.     

p-Toluenesulfonic acid-promoted selective functionalization of unsymmetrical arylalkynes: a regioselective access to various arylketones and heterocycles

Regioselective hydration of a wide range of internal alkynes has been afforded in high to good yields by using PTSA in EtOH. The scope of the reaction of alkynes has been delineated. Arylaliphatic alkynes and diarylalkynes were regioselectively hydrated in good to excellent yields and short reaction times when the reaction was achieved under microwave irradiation. Moreover, diarylalkynes, arylenynes as well as diaryldiynes bearing a methoxy- or a thiomethyl substituent on the ortho position underwent a regioselective 5-endo-dig-cyclization to give a variety of 2-aryl- and 2-styrylbenzofuran or benzothiphene derivatives. We believe that, this new environmentally metal-free procedure combined to microwave irradiation would be in importance in the search of green laboratory-scale synthesis.