Reaction Of Hexafluoroacetone Research Articles

Simultaneous Formation of Cage and Spirane Pentaalkoxyphosphoranes in Reaction of 5,5-Dimethyl-2-(2-oxo-1,2-diphenylethoxy)-1,3,2-dioxaphosphorinane with Hexafluoroacetone

The reaction of hexafluoroacetone with 5,5-dimethyl-2-(2-oxo-1,2-diphenylethoxy)-1,3,2-dioxaphosphorinane occurs in two simultaneous directions: through the formation of cage phosphorane and spirophosphorane—1,1-(2,2-dimethylpropylenedioxy)-4,5-diphenyl-3,3-bis(trifluoromethyl)-2,6,7-trioxa-1-phosphabicyclo[2.2.11.4]heptane and 2-(2,2-dimethylpropylenedioxy)-2-hexafluoroisopropoxy-4,5-diphenyl-1,3,2-dioxaphospholene, respectively. The latter was obtained by authentic synthesis from 2-hexafluoroisopropoxy-5,5-dimethyl-1,3,2-dioxaphosphorinane and benzil. The mild hydrolysis of the compounds obtained leads to the formation of cyclic phosphates. The structure of the obtained compounds was determined by the NMR and mass spectrometry methods.

Reaction of 2-R-benzo[d]-1,3,2-oxazophosphorin-8-one with hexafluoroacetone. Synthesis and steric structure of 3-phenyl-9,9-bis(trifluoromethyl)-2-ethoxybenzo[d]-1,3,2-oxazaphosphepine-2,8-dione

Reaction of hexafluoroacetone with 2-R-benzo[d]-1,3,2-oxazophosphorin-8-ones leads to the formation of seven-membered nitrogen-containing heterocycles, the derivatives of 3-phenyl-9,9-bis (trifluoromethyl)benzo[d]-1,3,2-oxaza-phosphepine-2,8-diones. Steric structure of 2,3-diphenyl-9,9-bis (trifluoromethyl)-benzo[d]-1,3,2-oxazaphosphepine-2,8-di-one was established by X-ray structural analysis. By hydrolysis of the phosphepines a functionally substituted fluorinated ketone, 2-hydroxy-1-(2′-phenylamino)phenyl-2-trifluoromethyl-3,3,3-trifluoro)propan-1-one, was obtained.

One-Pot Synthesis of 3-Fluoro-4-(trifluoromethyl)quinolines from Pentafluoropropen-2-ol and Their Molecular Modification

Pentafluoropropen-2-ol (PFP) was prepared by the reaction of hexafluoroacetone (HFA) with Mg/TMSCl. The one-pot tandem sequential reactions of PFP via Mannich addition with aldimines followed by Friedel-Crafts cyclization and aromatization afforded the title quinolines. A variety of corresponding 3-substituted quinolines were derived from the title quinoline by nucleophilic substitution of 3-fluorine with nucleophiles. A defluorinative transformation of the 4-trifluoromethyl group of the title quinoline with hydrazine afforded pyrazoloquinoline.

The Cross‐Aldol Reaction of Hexafluoroacetone (HFA) with Ketones Catalyzed by an Acid.

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Reaction of hexafluoroacetone with 2,7-diethoxybenzo-[1,2-d:4,5-d′]bis[1,3,2]dioxaphosphinine-4,9-dione derived from 2,5-dihydroxyterephthalic acid

Reaction of hexafluoroacetone with 2,7-diethoxybenzo-[1,2-d:4,5-d′]bis[1,3,2]dioxaphosphinine-4,9-dione derived from 2,5-dihydroxyterephthalic acid

1,3,2(1,4,2)-Dioxaphosphepins annelated with naphthalene fragment: Synthesis and steric structure

Reaction of hexafluoroacetone and chloral with 2-R-naphtho-1,3,2-dioxaphosphorin-4-ones yields 2-R-2,5-dioxo-4,4-bis(trifluoromethyl)naphthol-1,3,2-and 2-R-2,5-dioxo-3-trichloromethylnaphtho-1,4,2λ5-dioxaphosphepins. Hydrolysis of the fluorophosphepins gives naphthyl-substituted fluorinated hydroxy ketones. The steric structure of the dioxaphosphepins and some fluorinated ketones was confirmed by single crystal X-ray diffraction. A competition between the π-π and halogen-halogen interactions and hydrogen bonds of classic type in the formation of crystal packing and supramolecular structure was revealed.

Preparation and steric structure of 2-Alkoxy-2,5-dioxo-4,4-bis(trifluoromethyl)-7(8)-chloro-1,3,2λ5-benzodioxaphosphepins

The reaction of hexafluoroacetone with 2-alkoxy-6(7)-chloro-1,3,2-benzodioxaphosphorin-4-ones yielded 7-and 8-chloro-substituted 2-alkoxy-2,5-dioxo-4,4-bis(trifluoromethyl)-1,3,2λ5-benzodioxaphosphepines. Their steric structure was studied by single-crystal X-ray diffraction. The effect of fluorinated substituents on the crystal packing of the benzophosphepines was demonstrated. Hydrolysis of these compounds gave the corresponding 4-and 5-chloro-substituted 2-(2-hydroxyphenyl)-2-oxo-1,1-bis(trifluoromethyl)-ethanols; the structure of 2-(2-hydroxy-5-chlorophenyl)-2-oxo-1,1-bis(trifluoromethyl)ethanol was also proved by single-crystal X-ray diffraction.

Reactive E=C(p-p)π-Systems. 56 [1] Attempted Preparation of PhE=C(CF3)2 by Reactions of Hexafluoroacetone with PhE(SiMe3)2 (E = As, P)

The chance to prepare sterically and inductively stabilized arsa- and phosphaalkenes of the type PhE=C(CF3)2 (E = As, P) by reacting phenyl-bis(trimethylsilyl)-arsane (1) and -phosphane (5), respectively, with hexafluoroacetone (HFA) was investigated. The insertion of the carbonyl function in one of the Si–E bonds was found to occur at temperatures between −78 and 20 °C. The elimination of hexamethyldisiloxane, which in case of acylamides and ketones spontaneously follows the insertion and in case of RE(SiMe3)–CR′2(OSiMe3) at least can be initiated by solid sodium hydroxide as catalyst, turned out to be impossible for the primary products PhE(SiMe3)–C(CF3)2-OSiMe3 [E = As (2), P (6)]. 2 and 6 were characterized by analytical (C, H) and spectroscopic methods (IR, NMR, MS).

Benzamidines in cyclocondensation with hexafluoroacetone and methyl trifluoropyruvate acyl- and ethoxycarbonylimines

The reactions of hexafluoroacetone and methyl trifluoropyruvate acyl- and ethoxycarbonylimines with benzamidines afford fluoro containing heterocycles of four structural types: dihydrotriazines, dihydrotriazinones, imidazoles, and imidazooxazoles.

Hexafluoroacetone as Protecting and Activating Reagent: Reactions of Hexafluoroacetone with α‐Keto Acids.

AbstractFor Abstract see ChemInform Abstract in Full Text.

Hexafluoroacetone as protecting and activating reagent: reactions of hexafluoroacetone with α-keto acids

Hexafluoroacetone and α-keto acids react to give 5,5-bis(trifluoromethyl) substituted 2(5H)-furanones and/or 2,2-bis(trifluoromethyl)-1,3-dioxolan-4-ones depending upon the substituent pattern of the side chain of the acid. A fluoroanalogue of the natural product zymonic acid was obtained from ethyl 3,3,3-trifluoropyruvate and 2-oxosuccinic acid in one step.

Oxidative Addition of Hexafluoroacetone, Perfluorinated 1,2-Diketones and Tetrachloro-O-Benzoquinone to Compounds of Low-Valent Phosphorus-New Modes of Addition and Unusual Products

Abstract The reaction of hexafluoroacetone (HFA) with the benzoxazaphosphorinone 1 leads to the λ5-oxazaphosphepinone 2. In several cases unusual products, 3, 8 - 14, 16, and 17, were isolated in the reactions of 1, 4 - 7, and 15 with HFA, tetrachloroorthobenzoquinone (TOB) and perfluorinated 1,2-diketones. X-Ray crystal structure analyses were carried out for the derivatives 2, 3, and 8 - 10.

Struktur des 2,2,4,4-Tetrakis(trifluormethyl)-1,3-diselenetans / Structure of 2,2,4,4-Tetrakis(trifluoromethyl)-1,3-diselenetane

The reaction of hexafluoroacetone with triphenylphosphane selenide proceeds with elimination of triphenylphosphane oxide to yield 2,2,4,4-tetrakis(trifluormethyl)-1,3-diselenetane (1). Crystals of 1 that are suitable for X -ray crystal structure analysis have been obtained by recrystallization from hexane.

ChemInform Abstract: Reactions of Hexafluoroacetone and Trifluoroacetylimines of Polyfluorocarbonyl Compounds with Pyrimidine Derivatives.

AbstractThe 4‐aminopyrimidines (I) and the 4‐aminopyrazolopyrimidines (VI) are coupled with hexafluoroacetone (II) to give the pyrimidooxazines (III) and the pyrazolopyrimidooxadiazines (VII) respectively.

Reaction of hexafluoroacetone and trifluoroacetylimines of polyfluorocarbonyl compounds with derivatives of pyrimidine

1. 4-Aminopyrimidines react with hexafluoroacetone to give pyrimidooxazines and pyrimidooxadiazines. 2. An account is given of the C5 aminoalkylation of 1,3-dimethyluracil by the trifluoroacetylimines of hexafluoroacetone and of the methyl ester of trifluoropyruvic acid.

Reaction of hexafluoroacetone with azacyclohexanes

Piperidine and its C-methyl derivatives are aromatized by hexafluoroacetone with simultaneous C-alkylation at one or both of the Β-positions of the ring, and in the case of α- and γ-methylpyridines also at the CH3 group.

Reductive defluorination of hexafluoroacetone and the synthesis of halopentafluoroacetones

1. Hexafluoroacetone undergoes reductive defluorination upon the action of metals to form perfluoro-2-propenolates of the metals and the products of their subsequent transformations. 2. A new preparative method was proposed for the synthesis of pentafluoro-2-propenol and halopentafluoroacetones based on the reaction of hexafluoroacetone with aluminum.

ChemInform Abstract: Inorganic Chemistry of Hexafluoroacetone

Publisher Summary This chapter presents a study on the inorganic chemistry of hexafluoroacetone (HFA). The difference in reactivity compared to organic ketones is caused by the strong electron-withdrawing effect of the fluorine atoms in HFA that leads to an electron-deficient carbonyl group. This is manifested in the inability to protonate the oxygen atom in super acidic media. Depending on the nature of the reaction partners, there are various pathways leading to different products. The chapter focuses on synthetic “inorganic” aspects of HFA chemistry, with attention to literature coverage since 1966. Reaction conditions and spectroscopic data are mentioned if necessary for structural and mechanistic considerations. Hydroxy- and alkoxysilanes are attacked by HFA to form hemiketals and ketals. The reaction of HFA with substituted vinyltrimethylsilyl ethers in the presence of Lewis acids with subsequent hydrolysis provides a good route to alcohols containing the hexafluoroisopropyl group. The reactions of germanium and tin compounds with HFA are very similar to those of silicon compounds. But because of differences in polarity and bond strengths some reactions yield products different from those of their silicon analogues. Reactions of open-chain and cyclic germoxanes and cyclic germadioxanes with HFA, and others have been investigated.

Reaction of hexafluoroacetone and pentafluoronitroacetone with methyl propargyl ether

The reaction of hexafluoroacetone and pentafluoronitroacetone with metkyl propargyl ether was studied. The intermediate methoxyallenylcarbinols give [2+2]-cycloadducts with the starting fluoroketones and also cyclize to give substituted 2,5-dihydrofurans.

ChemInform Abstract: Reaction of Hexafluoroacetone with Sodium p‐Cresolate.

ChemInformVolume 18, Issue 38 Preparative Organic Chemistry ChemInform Abstract: Reaction of Hexafluoroacetone with Sodium p-Cresolate. V. I. DYACHENKO, V. I. DYACHENKO Inst. elementoorg. soedin. im. Nesmeyanova Akad. nauk SSSR MoskvaSearch for more papers by this authorA. F. KOLOMIETS, A. F. KOLOMIETS Inst. elementoorg. soedin. im. Nesmeyanova Akad. nauk SSSR MoskvaSearch for more papers by this authorA. V. FOKIN, A. V. FOKIN Inst. elementoorg. soedin. im. Nesmeyanova Akad. nauk SSSR MoskvaSearch for more papers by this author V. I. DYACHENKO, V. I. DYACHENKO Inst. elementoorg. soedin. im. Nesmeyanova Akad. nauk SSSR MoskvaSearch for more papers by this authorA. F. KOLOMIETS, A. F. KOLOMIETS Inst. elementoorg. soedin. im. Nesmeyanova Akad. nauk SSSR MoskvaSearch for more papers by this authorA. V. FOKIN, A. V. FOKIN Inst. elementoorg. soedin. im. Nesmeyanova Akad. nauk SSSR MoskvaSearch for more papers by this author First published: September 22, 1987 https://doi.org/10.1002/chin.198738111Read the full textAboutPDF ToolsRequest permissionExport citationAdd to favoritesTrack citation ShareShare Give accessShare full text accessShare full-text accessPlease review our Terms and Conditions of Use and check box below to share full-text version of article.I have read and accept the Wiley Online Library Terms and Conditions of UseShareable LinkUse the link below to share a full-text version of this article with your friends and colleagues. Learn more.Copy URL Share a linkShare onFacebookTwitterLinked InRedditWechat No abstract is available for this article. Volume18, Issue38September 22, 1987 RelatedInformation