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Synthesis of 3-Hydroxy-4-Substituted Picolinonitriles from 4-Propargylaminoisoxazoles via Stepwise and One-Pot Isoxazolopyridine Formation/N-O Bond Cleavage Sequence

A unique synthetic approach to 3-hydroxy-4-substituted picolinonitriles is achieved via gold(I)-catalyzed cyclization of 4-propargylaminoisoxazoles and subsequent N-O bond cleavage of isoxazolopyridines under mild reaction conditions in a stepwise and one-pot fashion.

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Isoxazole – Wikipedia,
Isoxazole | C3H3NO – PubChem

Discovery of 5-Phenylisoxazole

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Oxidation of alkylarenes by nitrate catalyzed by polyoxophosphomolybdates: Synthetic applications and mechanistic insights

Alkylarenes were catalytically and selectively oxidized to the corresponding benzylic acetates and carbonyl products by nitrate salts in acetic acid in the presence of Keggin type molybdenum-based heteropolyacids, H3+xPVxMo12-xO40 (x = 0-2). H 5PV2Mo10O40 was especially effective. For methylarenes there was no over-oxidation to the carboxylic acid contrary to what was observed for nitric acid as oxidant. The conversion to the aldehyde/ketone could be increased by the addition of water to the reaction mixture. As evidenced by IR and 15N NMR spectroscopy, initially the nitrate salt reacted with H5PV2Mo10O 40 to yield a NVO2+[H 4PV2Mo10O40] intermediate. In an electron-transfer reaction, the proposed NVO2 +[H4PV2Mo10O40] complex reacts with the alkylarene substrate to yield a radical-cation-based donor-acceptor intermediate, NIVO2[H4PV 2Mo10O40]-ArCH2R+.. Concurrent proton transfer yields an alkylarene radical, ArCHR., and NO2. Alternatively, it is possible that the NVO 2+[H4PV2Mo10O 40] complex abstracts a hydrogen atom from alkylarene substrate to directly yield ArCHR. and NO2. The electron transfer-proton transfer and hydrogen abstraction scenarios are supported by the correlation of the reaction rate with the ionization potential and the bond dissociation energy at the benzylic positions of the alkylarene, respectively, the high kinetic isotope effect determined for substrates deuterated at the benzylic position, and the reaction order in the catalyst. Product selectivity in the oxidation of phenylcyclopropane tends to support the electron transfer-proton transfer pathway. The ArCHR. and NO2 radical species undergo heterocoupling to yield a benzylic nitrite, which undergoes hydrolysis or acetolysis and subsequent reactions to yield benzylic acetates and corresponding aldehydes or ketones as final products.

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Isoxazole – Wikipedia,
Isoxazole | C3H3NO – PubChem

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Reactivity in the Gas Phase. Behaviour of Isoxazoles under Negative Ion Chemical Ionization Conditions

– ions of isoxazole (1a), 3-methylisoxazole (1b), 5-methylisoxazole (1c), 5-phenylisoxazole (1d) and benzoylacetonitrile (2a) are generated using NICI/OH- or NICI/NH2- techniques.Their fragmentation pathways are rationalized on the basis of collision-induced dissociation and mass-analysed ion kinetic energy spectra and by deuterium labelling studies. 5-Substituted isoxazoles 1c and 1d, after selective deprotonation at position 3, mainly undergo N-O bond cleavage to the stable alpha-cyanoenolate NC-CH=CR-O- (R=Me, Ph) that fragments by loss of R-CN, or R-H, or H2O.The same alpha-cyanoenolate anion (R=Ph) is obtained from 2a with OH-, or NH2-, confirming the structure assigned to the – ion of 1d.On the contrary, 1b is deprotonated mainly at position 5 leading, via N-O and C(3)-C(4) bond cleavages, to H-C<*>-O- and CH3CN.Isoxazole (1a) undergoes deprotonation at either position and subsequent fragmentations.Deuterium labelling revealed an extensive exchange between the hydrogen atoms in the ortho position of the phenyl group and the deuterium atom in the alpha-cyanoenolate NC-CD=CPh-O-.

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Isoxazole – Wikipedia,
Isoxazole | C3H3NO – PubChem

Final Thoughts on Chemistry for 5-Phenylisoxazole

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I2-Mediated Oxidative C-O Bond Formation for the Synthesis of Isoxazoles

A variety of mono-, di-, and tri-substituted (aryl, alkyl, and/or alkenyl) isoxazoles were synthesized from readily accessible alpha,beta-unsaturated oximes via I2-mediated oxidative C-O bond formation. The features of this synthetic approach include no use of transition metals, simple operation, mild reaction conditions, short reaction time, and broad substrate scope.

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Isoxazole – Wikipedia,
Isoxazole | C3H3NO – PubChem

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New Synthesis of Pyrazole and Isoxazole Derivatives

A convenient synthesis of 5-aryl-1-phenylpyrazoles and 5-arylisoxazoles, from readily available ketimine 1 dimethylformamide dimethylacetal and phenylhydrazine or hydroxylamine, is described.

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Isoxazole – Wikipedia,
Isoxazole | C3H3NO – PubChem

Archives for Chemistry Experiments of 5-Phenylisoxazole

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A Photoinduced Cobalt-Catalyzed Synthesis of Pyrroles through in Situ-Generated Acylazirines

Tetrasubstituted pyrroles can be synthesized in a one-pot procedure from isoxazoles. The process includes the photoinduced in situ formation of acylazirines combined with a subsequent cobalt(II)-catalyzed ring expansion with 1,3-diketones.

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Isoxazole – Wikipedia,
Isoxazole | C3H3NO – PubChem

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Isoxazole-azirine isomerization as a reactivity switch in the synthesis of heterocycles

[Figure not available: see fulltext.] This review contains a generalized and systematically arranged data about thermal, photochemical, and catalytic transformations of isoxazole?2-carbonyl-2H-azirine that were published in the period from 1969 to 2015, and considers the possibilities for using these compounds in the synthesis of nitrogen heterocycles. Radical and pericyclic steps of isomerization reactions have been discussed. Density functional theory calculations of the relative thermodynamic stability of isomeric isoxazoles and azirines have been performed. A total of 76 references are given.

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Isoxazole – Wikipedia,
Isoxazole | C3H3NO – PubChem

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Design of novel meso-CF3-BODIPY dyes with isoxazole substituents

The two approaches for the synthesis of meso-CF3 substituted BODIPY dyes bearing isoxazole substituents at the position 3 of boradiazaindacene core have been developed. The key stages of the approaches are cycloaddition of hydroxylamine to the triple bond of available ethynyldipyrromethanes (1) and synthesis of isoxazoles from ethynylpyrrole and their further condensation with 2,2,2-trifluoro-1-(pyrrol-2-yl)-1-ethanols (2). The novel BODIPY dyes exhibit prospective optical features and fluorescence in the 611?646 nm with high (up to 0.94) quantum yield. Spectroscopic results have been rationalized with quantum mechanics calculation.

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Isoxazole – Wikipedia,
Isoxazole | C3H3NO – PubChem

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SYNTHESIS AND STRUCTURE OF 5-HYDRAZINO- AND 5-HYDROXYAMINO-3-ARYL-2-PYRAZOLINES AND -2-ISOXAZOLES

It was established by the methods of 1H and 13C NMR spectroscopy that the oximohydrazones and bis(hydrazones) of aroylacetic aldehydes exist in the form of the corresponding 5-hydrazino- and 5-hydroxyamino-3-aryl-pyrazolines and -2-isoxazolines.The features of the aromatization of these compounds to the corresponding pyrazoles and isoxazoles were studied.Data on the mass-spectral study of the 5-hydroxyamino-2-pyrazoline-5-hydrazino-2-isoxazoline tautomerism in the gas phase are presented.

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Isoxazole – Wikipedia,
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THE CHEMISTRY OF FULMINIC ACID REVISED

The availability of a new synthesis of fulminic acid by hydrolysis of trimethylsilanecarbonitrile oxide allowed a reinvestigation of the chemistry of the title compound.Thus, cycloadditions to olefinic and acetylenic dipolarophiles are improved with respect to previous results and the oligomerisation is proved to occur via the reactive species hydroxyiminoacetonitrile oxide 7 and hydroxyiminomethyl-hydroxyimino-acetonitrile oxide 8.The Z-configuration, found for the oxime groups in these intermediates, is maintained in their derivatives, under kinetic control.

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Reference£º
Isoxazole – Wikipedia,
Isoxazole | C3H3NO – PubChem