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SYNTHESIS OF ISOXAZOLE DERIVATIVES IN REACTION OF 2-HYDROXYPHENYLCARBONYL COMPOUNDS OR 1,3-DIKETONES WITH HYDROXYLAMINE-O-SULFONIC ACID

2-Hydroxybenzaldehyde 1a and 2-hydroxyacetophenone 1b react with hydroxylamine-O-sulfonic acid (HSA) yielding the corresponding oxime hydrogensulfates 2a and 2b, separated as potassium salts.These salts undergo conversion with good yields to benzisoxazole 3a and 2-methylbenzoxazole 3b, respectively.In similar reaction of 1,3-diketones, both cyclic and acyclic 1c-k with HSA, isoxazole derivatives 3c-k were obtained.

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Isoxazole – Wikipedia,
Isoxazole | C3H3NO – PubChem

Discovery of 3-Methyl-5-phenylisoxazole

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Copper induced cyclization of alpha,beta-unsaturated carbonyl compounds to isoxazoles

An unusual synthesis of isoxazoles from alpha,beta-unsaturated ketoximes is reported. Using very inexpensive reagents, isoxazoles are isolated in good yields. Notably, a mixture of E and Z oxime isomers is employed. Initial studies indicate the oxidative cyclization reaction does not proceed via radical route; a copper insertion/elimation route is proposed.

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An efficient synthesis of isoxazoles and pyrazoles under ultrasound irradiation

A series of 5-arylisoxazole and 5-aryl-1H-pyrazole derivatives was synthesized by the reaction of 3-(dimethylamino)-1-arylprop-2-en-1-one with hydroxylamine hydrochloride or hydrazine hydrate under ultrasound irradiation without using any catalyst. This method has the advantages of easier work-up, mild reaction condition, high yields, shorter reaction time, and environmentally benign procedure.

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Generation of Nitrile Oxides via O-Tributylstannyl Aldoximes; Application to the Synthesis of Isoxazolines and Isoxazoles

Nitrile oxides were generated readily by the reaction of aldoximes 1, with tert-butyl hypochlorite and bis(tributyltin) oxide.The reaction proceeded efficiently under mild conditions, in which O-stannylated aldoximes 2 are thought to be key intermediates.This reaction system was applicable to the one-pot syntheses of isoxazole derivatives 4 and 5 in the presence of dipolarophiles via a <3 + 2> cycloaddition.

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An efficient one-pot synthesis of 3,5-disubstitueted isoxazoles from beta-diketones in room temperature ionic liquids (ILs) is described. Compared with the classical reaction conditions, this new synthetic method is environmentally friendly and has the advantages of recyclability of IL and very good to excellent yields.

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Coordination compounds of manganese(II) with isoxazole, 3,5-dimethylisoxazole and 3-methyl,5-phenylisoxazole

A series of compounds of general formula Mn(L)nX2 have been prepared where L = isoxazole (isox), 3,5-dimethylisoxazole (3,5-diMeisox), 3-methyl,5-phenylisoxazole (3-Me,5-Phisox); 1, 2, 4; X = Cl, Br, I, SCN.The i.r., E.S.R. and electronic spectra, the magnetic moments and the conductivities of the compounds have been used to elucidate their structure.The ligands are generally bridging N and O-bonded and the complexes are hexacoordinate.

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Metal-carbonyl-Induced Reaction of Isoxazoles. Ring Cleavage and Reduction by Hexacarbonylmolybdenum, Pentacarbonyliron, or Nonacarbonyldi-iron

In the presence of and water the isoxazoles (1a-f) undergo thermally induced reductive cleavage of the N-O bond to give beta-amino enones in good yield.Similar results were obtained by the use of and water with photoirradiation, or of and water with heating.A mechanism involving an N-complexed isoxazolepentacarbonylmolybdenum or isoxazoletetracarbonyliron, and a – or -complexed (beta-oxo vinyl)nitrene intermediate is proposed for the reactions.The complexed nitrene moiety could be reduced by the central metal in the presence of water to give amine.Furthermore, treatment of 2-benzoyl- 3-phenyl-2-H-azirine (8a), which is an isomer of 3,5-diphenylisoxazole, with the metal carbonyls and water also resulted in the formation of a beta-amino enone possibly via the corresponding complexed (beta-oxo vinyl)nitrene.An N-complexed isoxazole-pentacarbonylmolybdenum intermediate was prepared by the photoreaction of with 3,5-dimethylisoxazole.Its characterization, and chemical transformations, have been carried out to investigate the proposed mechanism.

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Isoxazole – Wikipedia,
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Convenient synthesis of 3,5-disubstituted isoxazoles

alpha,beta-Unsaturated oximes obtained from the corresponding alpha,beta-unsaturated ketones on treatment with 2 equivalents of manganese dioxide in refluxing chloroform gives 3,5-disubstituted isoxazoles in good yields. Copyright Taylor & Francis Group, LLC.

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Monohydrochloride Assisted Synthesis of Functionalized Isoxazoles and Pyrazoles from Allenic Ketones: First Synthesis of (Z)-2-Methyl-7H-benzo[b]pyrazolo[5,1-d][1,5]oxazocines

A facile hydrochloride promoted regioselective synthesis of isoxazoles and pyrazoles from 1,2-allenic ketones is reported. The reaction has been scaled up to gram scale. A direct 8-endo dig ring annulations towards the first synthesis of (Z)-2-methyl-7H-benzo[b]pyrazolo[5,1-d][1,5]oxazocine has been developed.

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SYNTHESIS AND REACTIONS OF 5-(TRIBUTYLSTANNYL)ISOXAZOLES

3-Substituted 5-(tributylstannyl)isoxazoles were synthesized in good yields by the 1,3-dipolar cycloaddition reaction of ethynyltributylstannane with nitrile oxides generated in situ. 3-Methyl-5-(tributylstannyl)isoxazole was easily converted to the corresponding 5-benzoyl- and 5-arylisoxazoles by the palladium-catalyzed reaction.

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