About: Diethyl Fluoronitromethylphosphonate: Synthesis and Application in Nucleophilic Fluoroalkyl Additions

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Description	Diethyl fluoronitromethylphosphonate (3), a previously unknown compound, was synthesized by electrophilic fluorination of diethyl nitromethylphosphonate with Selectfluor. Base-induced decomposition of 3 was studied by NMR spectroscopy, which identified diethyl fluorophosphate and fluoronitromethane as the main decomposition products. C-H acidities [pK(a) values in dimethyl sulfoxide (DMSO)] of 3, 1-fluoro-1-phenylsulfonylmethanephosphonate (1; McCarthy's reagent), tetraethyl fluoromethylenebisphosphonate (2), and some nonfluorinated phosphonates were computed, and a good correlation between calculated and experimental pK(a) values was found. The calculated C-H acidities increased in the sequence 2<1<3. Diethyl fluoronitromethylphosphonate (3) was applied in the Horner-Wadsworth-Emmons reaction with aldehydes and trifluoromethyl ketones to provide new 1-fluoro-1-nitroalkenes with good to high stereoselectivities. Alkylation of 3 was successful only with iodomethane, however, conjugate additions of 3 to Michael acceptors such as alpha,beta-unsaturated carbonyl compounds, sulfones, and nitro compounds allowed access to variously modified diethyl 1-fluoro-1-nitrophosphonates. Diethyl fluoronitromethylphosphonate (3), a previously unknown compound, was synthesized by electrophilic fluorination of diethyl nitromethylphosphonate with Selectfluor. Base-induced decomposition of 3 was studied by NMR spectroscopy, which identified diethyl fluorophosphate and fluoronitromethane as the main decomposition products. C-H acidities [pK(a) values in dimethyl sulfoxide (DMSO)] of 3, 1-fluoro-1-phenylsulfonylmethanephosphonate (1; McCarthy's reagent), tetraethyl fluoromethylenebisphosphonate (2), and some nonfluorinated phosphonates were computed, and a good correlation between calculated and experimental pK(a) values was found. The calculated C-H acidities increased in the sequence 2<1<3. Diethyl fluoronitromethylphosphonate (3) was applied in the Horner-Wadsworth-Emmons reaction with aldehydes and trifluoromethyl ketones to provide new 1-fluoro-1-nitroalkenes with good to high stereoselectivities. Alkylation of 3 was successful only with iodomethane, however, conjugate additions of 3 to Michael acceptors such as alpha,beta-unsaturated carbonyl compounds, sulfones, and nitro compounds allowed access to variously modified diethyl 1-fluoro-1-nitrophosphonates. (en)
Title	Diethyl Fluoronitromethylphosphonate: Synthesis and Application in Nucleophilic Fluoroalkyl Additions Diethyl Fluoronitromethylphosphonate: Synthesis and Application in Nucleophilic Fluoroalkyl Additions (en)
skos:prefLabel	Diethyl Fluoronitromethylphosphonate: Synthesis and Application in Nucleophilic Fluoroalkyl Additions Diethyl Fluoronitromethylphosphonate: Synthesis and Application in Nucleophilic Fluoroalkyl Additions (en)
skos:notation	RIV/61388963:_____/14:00429485!RIV15-GA0-61388963
http://linked.open...avai/riv/aktivita	I P
http://linked.open...avai/riv/aktivity	I, P(GP203/08/P310)
http://linked.open...iv/cisloPeriodika	5
http://linked.open...vai/riv/dodaniDat	2015
http://linked.open...aciTvurceVysledku	Beran, Pavel Rulíšek, Lubomír Beier, Petr Opekar, Stanislav Pohl, Radek
http://linked.open.../riv/druhVysledku	J - Článek v odborném periodiku
http://linked.open...iv/duvernostUdaju	S - Úplné a pravdivé údaje nepodléhající ochraně podle zvláštních právních předpisů
http://linked.open...titaPredkladatele	Ústav organické chemie a biochemie AV ČR, v. v. i.
http://linked.open...dnocenehoVysledku	11400
http://linked.open...ai/riv/idVysledku	RIV/61388963:_____/14:00429485
http://linked.open...riv/jazykVysledku	eng - angličtina
http://linked.open.../riv/klicovaSlova	C1 building blocks; fluorine; nucleophilic addition; phosphanes; synthetic methods (en)
http://linked.open.../riv/klicoveSlovo	C1 building blocks phosphanes nucleophilic addition synthetic methods fluorine
http://linked.open...odStatuVydavatele	DE - Spolková republika Německo
http://linked.open...ontrolniKodProRIV	[3F2AA674AB19]
http://linked.open...i/riv/nazevZdroje	Chemistry - A European Journal
http://linked.open...in/vavai/riv/obor	CC
http://linked.open...ichTvurcuVysledku	5 (xsd:int)
http://linked.open...cetTvurcuVysledku	5 (xsd:int)
http://linked.open...vavai/riv/projekt	Nucleophilic introduction of fluorinated groups using organo-phosphorus compounds
http://linked.open...UplatneniVysledku	2014
http://linked.open...v/svazekPeriodika	20
http://linked.open...iv/tvurceVysledku	Beran, Pavel Beier, Petr Opekar, Stanislav Pohl, Radek Rulíšek, Lubomír
http://linked.open...ain/vavai/riv/wos	000336431100034
issn	0947-6539
number of pages	6 (xsd:int)
http://bibframe.org/vocab/doi	10.1002/chem.201303817

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