Trichloroisocyanuric Acid–KF as an Efficient Reagent for One-Pot Synthesis of Dialkylfluorophosphates from Dialkylphosphites

Acharya, Jyotiranjan; Gupta, Arvind; Pardasani, Deepak; Dubey, D. K.; Kaushik, M. P.

doi:10.1080/00397910802215880

Cited by 12 publications

(4 citation statements)

References 6 publications

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“…The dialkyl fluorophosphates, DMFP and DEFP, were synthesized from dialkyl phosphites following the procedure of Acharya et al The synthetic approach depicted in Scheme uses trichloroisocyanuric acid (TCICA) in combination with potassium fluoride (KF) in a one-pot reaction.…”

Section: Methodsmentioning

confidence: 99%

“…Note that fluorinated organophosphates are extremely toxic and should be handled only by skilled persons using a full-face respirator and chemical resistant gloves. 10 The dialkyl fluorophosphates, DMFP and DEFP, were synthesized from dialkyl phosphites following the procedure of Acharya et al 31 The synthetic approach depicted in Scheme 1 uses trichloroisocyanuric acid (TCICA) in combination with potassium fluoride (KF) in a one-pot reaction.…”

Section: Methodsmentioning

confidence: 99%

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Impact of Selected LiPF₆ Hydrolysis Products on the High Voltage Stability of Lithium-Ion Battery Cells

Wagner

Korth

Streipert

et al. 2016

ACS Appl. Mater. Interfaces

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Diverse LiPF hydrolysis products evolve during lithium-ion battery cell operation at elevated operation temperatures and high operation voltages. However, their impact on the formation and stability of the electrode/electrolyte interfaces is not yet investigated and understood. In this work, literature-known hydrolysis products of LiPF dimethyl fluorophosphate (DMFP) and diethyl fluorophosphate (DEFP) were synthesized and characterized. The use of DMFP and DEFP as electrolyte additive in 1 M LiPF in EC:EMC (1:1, by wt) was investigated in LiNiMnCoO/Li half cells. When charged to a cutoff potential of 4.6 V vs Li/Li, the additive containing cells showed improved cycling stability, increased Coulombic efficiencies, and prolonged shelf life. Furthermore, low amounts (1 wt % in this study) of the aforementioned additives did not show any negative effect on the cycling stability of graphite/Li half cells. DMFP and DEFP are susceptible to oxidation and contribute to the formation of an effective cathode/electrolyte interphase as confirmed by means of electrochemical stability window determination, and X-ray photoelectron spectroscopy characterization of pristine and cycled electrodes, and they are supported by computational calculations.

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Section: Methodsmentioning

confidence: 99%

Section: Methodsmentioning

confidence: 99%

Impact of Selected LiPF₆ Hydrolysis Products on the High Voltage Stability of Lithium-Ion Battery Cells

Wagner

Korth

Streipert

et al. 2016

ACS Appl. Mater. Interfaces

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“…As TCICA/KF conditions are likely not amenable to P−O bond cleavage of phosphine oxides, we considered seeking out another way in which the TCICA method would diverge from the oxalyl chloride method ( Scheme 2). In fact, Kaushik and coworkers have already established that dialkylphosphites can be converted to dialkylfluorophosphates using TCICA and KF [16] . Expanding upon their efforts, we now also report that a number of aryl‐ and alkyl‐substituted phosphinic fluorides are accessible ( 21 – 26 ; Table 2).…”

Section: Resultsmentioning

confidence: 60%

Examining Trichloroisocyanuric Acid and Oxalyl Chloride in Complementary Approaches to Fluorination of Group 15 Heteroatoms

Bornemann

Brüning

Bartalucci

et al. 2021

Helvetica Chimica Acta

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A mild, oxidative fluorination approach to a variety of fluorinated phosphorus compounds using trichloroisocyanuric acid (TCICA) and KF was developed as a complement to a recent study on deoxygenative fluorination using oxalyl chloride. Herein, the syntheses of several fluorinated organophosphorus compounds are reported, and both TCICA/KF and oxalyl chloride/KF conditions are compared and contrasted throughout. Initial investigations of the method on other group 15 heteroatoms (i. e., As, Sb, and Bi) are also reported, with varied success. This work notably extends the known TCICA/KF reactivity series to another group of elements beyond previously studied chalcogens (S, Se, and Te) and halogens (iodine) and expands the utility of the previously reported oxalyl chloride/KF method.

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“…10 These chlorination reactions can also be employed in strategies for the synthesis of phosphoric fluorides by simply adding a fluoride source. For example, in reactions with TCICA-KF, 11 trichloroacetonitrile-KF 12 or CuCl 2 -CsF, 13 the initially-formed chlorides are intercepted by the fluoride. Electrophilic fluorination of a phosphine oxide is achieved with reagents such as XeF 2 , 14 Selectfluor ®15 or DDQ/CuBr 2 /NaF.…”

mentioning

confidence: 99%

Direct, oxidative halogenation of diaryl- or dialkylphosphine oxides with (dihaloiodo)arenes

Eljo

Murphy

2018

Tetrahedron Letters

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The oxidative halogenation of diaryl-or dialkylphosphine oxides with the hypervalent iodine reagents (difluoroiodo)toluene (TolIF2, 1) and (dichloroiodo)benzene (PhICl2, 2) is reported. Phosphoric fluorides could be recovered in 32-75% yield, or they could be trapped with EtOH to give the corresponding phosphinate in typically good yield. Phosphoric chlorides were not readily isolable, and were trapped with alcohol and amine nucleophiles, giving diaryl-or dialkylphos-phinates and phosphinamides in up to 90% yield.

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Trichloroisocyanuric Acid–KF as an Efficient Reagent for One-Pot Synthesis of Dialkylfluorophosphates from Dialkylphosphites

Cited by 12 publications

References 6 publications

Impact of Selected LiPF₆ Hydrolysis Products on the High Voltage Stability of Lithium-Ion Battery Cells

Impact of Selected LiPF₆ Hydrolysis Products on the High Voltage Stability of Lithium-Ion Battery Cells

Examining Trichloroisocyanuric Acid and Oxalyl Chloride in Complementary Approaches to Fluorination of Group 15 Heteroatoms

Direct, oxidative halogenation of diaryl- or dialkylphosphine oxides with (dihaloiodo)arenes

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Trichloroisocyanuric Acid–KF as an Efficient Reagent for One-Pot Synthesis of Dialkylfluorophosphates from Dialkylphosphites

Cited by 12 publications

References 6 publications

Impact of Selected LiPF6 Hydrolysis Products on the High Voltage Stability of Lithium-Ion Battery Cells

Impact of Selected LiPF6 Hydrolysis Products on the High Voltage Stability of Lithium-Ion Battery Cells

Examining Trichloroisocyanuric Acid and Oxalyl Chloride in Complementary Approaches to Fluorination of Group 15 Heteroatoms

Direct, oxidative halogenation of diaryl- or dialkylphosphine oxides with (dihaloiodo)arenes

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Impact of Selected LiPF₆ Hydrolysis Products on the High Voltage Stability of Lithium-Ion Battery Cells

Impact of Selected LiPF₆ Hydrolysis Products on the High Voltage Stability of Lithium-Ion Battery Cells