A Study of Some Fluorine-containing β-Diketones<sup>1</sup>

Park, J. D.; Brown, Harvey A.; Lacher, J. R.

doi:10.1021/ja01115a041

Cited by 69 publications

(18 citation statements)

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“…(4)) : (4) where the proton set free in Hacac is thought to act as follows (Eq. (5)): (5) Moreover, it was confirmed by mass spectrometry that hydrogen gas is formed during the process of the dissolution. In view of the above facts, the following reaction mechanism may be proposed for the dissolution of iron in Hacac: …”

Section: Phenomena Of Dissolutionmentioning

confidence: 74%

“…As the enol form of VII is preferred in the HTTA solution, the following equilibrium is also possible between HTTA and alcohol (Eq. (14)): (14) with water or alcohols are interesting even in the field of organic chemistry; moreover, the solubilities of metals in these solutions must also involve a large number of significant problems. The unique behavior of HTTA is seen not only in the dissolution of metal, but also in the solvent extraction.…”

Section: Acceleratingmentioning

confidence: 99%

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Studies of the Direct Dissolution of Metal in a β-Diketone Reagent

Sato¹,

Kammori²

1969

Bulletin of the Chemical Society of Japan

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As it was found that metallic iron is dissolved in acetylacetone (Hacac), the interaction between the solute and the solvent in the dissolution phenomena, together with the process of the dissolution of metal, were examined in detail in order to apply it to analytical techniques. The factors of the oxygen, the co-existing water, and the dissociated proton in acetylacetone were shown to be effective in the dissolution. With typical β-diketones, the exception of acetylacetone, such as trifluoroacetylacetone (HTFA), hexafluoroacetylacetone (HHFA), benzoyltrifluoroacetone (HBTA), 2-furoyltrinuoroacetone (HFTA), and 2-thenoyltrifluoroacetone (HTTA), were also employed; they were shown to have the same properties as the above one. The relationship between the solubilities of metals and the effect of adding an organic solvent, the equilibrium reactions of fluorine-containing β-diketones with water or alcohols, or the preferred enol forms of trifluorosubstituted β-diketones, were also discussed, paying attention to the accelerating effects of the solvents on the dissolution.

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Section: Phenomena Of Dissolutionmentioning

confidence: 74%

Section: Acceleratingmentioning

confidence: 99%

Studies of the Direct Dissolution of Metal in a β-Diketone Reagent

Sato¹,

Kammori²

1969

Bulletin of the Chemical Society of Japan

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“…Cyclocondensation of 1,3-diketones with hydrazines is a conventional synthetic route to pyrazoles, e. g., in the case 1b the pyrazole 4h is formed in less than 50 % overall yield (referring to the starting cyclohexanone [11,22]). Use of sodium salt 2h allowed us to obtain compound 4h in 70 % overall yield in a very simple two-step reaction sequence (Scheme 3).…”

Section: Resultsmentioning

confidence: 99%

“…100 %), m. p. 180 -182 • C (lit. : 182 -182.5 • C [22]). An analytical sample was recrystallized from methanol / water (1 : 1 by volume).…”

Section: Copper(ii) Bis-[2-(trifluoroacetyl)cyclohexanonate] (2b)mentioning

confidence: 99%

Metal and Boron Derivatives of Fluorinated Cyclic 1,3-Dicarbonyl Compounds

Sevenard

Khomutov

Boltachova

et al. 2009

Zeitschrift Für Naturforschung B

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Starting from the corresponding cyclic 1,3-diketones or other precursors (cyclic ketones as well as lactones), several new salts and chelate complexes of fluorinated 1,3-dicarbonyls were obtained. Their preparative significance was demonstrated by straightforward syntheses of fluorinated pyrazoles, benzimidazoles and 1,7-ketoesters. The structure of a boron chelate of 2-(trifluoroacetyl)-cyclohexanone was investigated by X-ray diffraction.

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“…General. The 2-(polyfluoroacyl)cycloalkanones 1a,f [13], 1b [24], 1c [21] [25], 1d [26], 1e,g [27], and 1h [25] were synthesized by a Claisen-type condensation of cyclopentanone or cyclohexanone and alkyl polyfluoroalkanoates. The 4-ene-1,3-diones 3 were prepared from the corresponding compounds 1 according to the procedure elaborated earlier by us [12].…”

Section: Experimental Partmentioning

confidence: 99%

Reaction of 2-(Polyfluoroacyl)cycloalkanones with Hydroxylamine

Sevenard¹,

Khomutov²,

Pashkevich³

et al. 2002

HCA

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The 2-acylcycloalkanones 1a ± g and 3a ± c, possessing a polyfluoroalkyl group, react with hydroxylamine regio-and stereoselectively to yield 4,5-dihydroisoxazol-5-ols 2a ± g and 4a ± c, respectively, i.e., products of Naddition to the oxo group at the cycloalkane ring (Schemes 1 and 2). The products 2 and 4 can be dehydrated under drastic conditions only (Schemes 3 and 4). The structure of one of the 4,5-dihydroisoxazol-5-ols was confirmed by X-ray crystal-structure analysis.Introduction. ± The interaction of 1,3-dicarbonyl compounds with hydroxylamine is considered to be one of the basic synthetic routes to isoxazole derivatives [1], which possess significant chemical potential [1] [2], as well as various biological activities [3].For a nonsymmetrical 1,3-dicarbonyl substrate in this reaction, the formation of regioisomers is possible. Thus, in the case of 2-acetylcyclohexanone, a mixture of isomeric 3-methyl-and 5-methylisoxazoles was obtained [4] [5]. The introduction of a polyfluorinated substituent in the 1,3-dicarbonyl compound results in a significant change of the electron-density distribution and consequently in a change of relative reactivity of the two carbonyl groups. The reaction of linear polyfluoroalkyl 1,3-diketones with hydroxylamine occurs unambigously affording 4,5-dihydro-5-(polyfluoroalkyl)isoxazol-5-ols exclusively ± an intermediate step in the 5-(polyfluoroalkyl)isoxazole formation. The dihydroisoxazolols represent stable compounds that may be dehydrated to the corresponding isoxazoles under drastic conditions only [6 ± 8]. Moreover, 2-(trifluoroacetyl)-and 2-(polychloroacetyl)-substituted cyclohexanones [5], triterpen-3-ones [9], and homoadamantanone [10] are known to give 4,5-dihydro-5-R Hal -isoxazol-5-ols, 5-(trifluoromethyl)isoxazoles, or 3-(trifluoromethyl)isoxazoles in the reaction with hydroxylamine, depending on the size of the carbocyclic ring in the 1,3-diketone molecule and on the reaction conditions.Among the 2-acyl-substituted cycloalkanones, the cyclopentanone derivatives represent a special case, forming an alternative product ± 4,5-dihydro-3-R-isoxazol-5-ols ± in the reaction with hydroxylamine, independent of the presence of F-atoms in the RCO moiety [11]. In the case of 2-(trifluoroacetyl)cyclopentanone, the dioxime [11], which cyclizes in acidic medium only, was also isolated.The present work aimed at the investigation of the chemical behavior of a variety of 2-(polyfluoroacyl)cycloalkanones in the reaction with hydroxylamine, the former differing in ring size, (polyfluoroalkyl)-radical length, and the presence of substituents at the cycloalkane ring. The expected products of such reactions can possess a set of

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A Study of Some Fluorine-containing β-Diketones¹

Cited by 69 publications

References 0 publications

Studies of the Direct Dissolution of Metal in a β-Diketone Reagent

Studies of the Direct Dissolution of Metal in a β-Diketone Reagent

Metal and Boron Derivatives of Fluorinated Cyclic 1,3-Dicarbonyl Compounds

Reaction of 2-(Polyfluoroacyl)cycloalkanones with Hydroxylamine

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A Study of Some Fluorine-containing β-Diketones1

Cited by 69 publications

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Studies of the Direct Dissolution of Metal in a β-Diketone Reagent

Studies of the Direct Dissolution of Metal in a β-Diketone Reagent

Metal and Boron Derivatives of Fluorinated Cyclic 1,3-Dicarbonyl Compounds

Reaction of 2-(Polyfluoroacyl)cycloalkanones with Hydroxylamine

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A Study of Some Fluorine-containing β-Diketones¹