- A single-step one pot synthesis of dialkyl fluorophosphates from dialkylphosphites
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An efficient synthetic method has been developed to obtain dialkyl fluorophosphates from dialkylphosphites using inorganic reagent (CuCl2 and CsF) at room temperature.
- Purohit, Ajay Kumar,Pardasani, Deepak,Kumar, Ajeet,Goud, D. Raghavender,Jain, Rajiv,Dubey
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- Synthesis and Storage Stability of Diisopropylfluorophosphate
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Diisopropylfluorophosphate (DFP) is a potent acetylcholinesterase inhibitor commonly used in toxicological studies as an organophosphorus nerve agent surrogate. However, LD50 values for DFP in the same species can differ widely even within the same laboratory, possibly due to the use of degraded DFP. The objectives here were to identify an efficient synthesis route for high purity DFP and assess the storage stability of both the in-house synthesized and commercial source of DFP at the manufacturer-recommended storage temperature of 4°C, as well as -10°C and -80°C. After 393 days, the commercial DFP stored at 4°C experienced significant degradation, while only minor degradation was observed at -10°C and none was observed at -80°C. DFP prepared using the newly identified synthesis route was significantly more stable, exhibiting only minor degradation at 4°C and none at -10°C or -80°C. The major degradation product was the monoacid derivative diisopropylphosphate, formed via hydrolysis of DFP. It was also found that storing DFP in glass containers may accelerate the degradation process by generating water in situ as hydrolytically generated hydrofluoric acid attacks the silica in the glass. Based on the results here, it is recommended that DFP be stored at or below -10°C, preferably in air-tight, nonglass containers.
- Heiss, Derik R.,Zehnder, Donald W.,Jett, David A.,Platoff, Gennady E.,Yeung, David T.,Brewer, Bobby N.
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- Tetrabutylammonium tetra (tert-butyl alcohol) coordinated fluoride-an efficient reagent for the synthesis of fluorine derivatives of phosphorus(V) compounds
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Direct conversion of phosphorus(V) chlorides to the corresponding phosphorus(V) fluorides was achieved using a solid reagent, tetrabutylammonium tetra (tert-butyl alcohol) coordinated fluoride. The phosphorus(V) fluorides were directly synthesized and efficiently isolated in very good yields.
- Gupta, Hemendra K.,Pardasani, Deepak,Mazumder, Avik,Purohit, Ajay Kumar,Dubey, Devendra K.
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experimental part
p. 2697 - 2699
(2009/08/09)
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- Dichlorodimethylhydantoin-KF as an efficient reagent for one pot synthesis of dialkylfluorophosphates from dialkylphosphites
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Organic-inorganic hybrid reagent dichlorodimethylhydantoin-KF (DCDMH-KF) mixture was explored as an efficient reagent for the direct conversion of dialkylphosphites to their corresponding dialkylfluorophosphates at room temperature and in shorter reaction times through a facile electrophilic-nucleophilic metathesis.
- Gupta,Acharya,Dubey,Kaushik
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p. 226 - 229
(2008/09/16)
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- Trichloroisocyanuric acid-KF as an efficient reagent for one-pot synthesis of dialkylfluorophosphates from dialkylphosphites
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Trichloroisocyanuric acid-KF afforded dialkylfluorophosphates from dialkylphosphites at room temperature through a facile electrophilic- nucleophilic metathesis. Copyright Taylor & Francis Group, LLC.
- Acharya,Gupta,Pardasani, Deepak,Dubey,Kaushik
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p. 3760 - 3765
(2008/12/23)
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- Single step fluorination of dialkylphosphites: trichloroacetonitrile-KF as an efficient reagent for the synthesis of dialkyl fluorophosphates
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The use of trichloroacetonitrile and KF mixture is described as an efficient reagent for the direct conversion of dialkylphosphites to their corresponding dialkyl fluorophosphates via in situ formation of dialkyl chlorophosphates in one-pot.
- Gupta,Acharya,Pardasani,Dubey
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p. 2232 - 2235
(2008/09/19)
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- Rapid and efficient solid-supported reagent synthesis of fluorine derivatives of phosphorus(V) compounds
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Direct conversion of phosphorus(V) chlorides to the corresponding phosphorus(V) fluorides was achieved utilizing a solid-supported reagent. The phosphorus(V) fluorides were straightforwardly synthesized and efficiently isolated in very good yields.
- Sierakowski, Timothy,Kiddle, James J.
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p. 2215 - 2217
(2007/10/03)
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- PHOSPHORYLNITRILE OXIDES. 5. REACTIONS OF 3-(DIALKOXYPHOSPHORYL)ISOXAZOLES AND -ISOXAZOLINES WITH NUCLEOPHILIC REAGENTS
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3-Phosphorylated isoxazoles and isoxazolines react with nucleophiles either with cleavage of the P-C bond and subsequent ring opening or with retention of the heterocyclic ring depending on the structure of the ring substituents, nature of the nucleophile, and reaction conditions.This permits the selective chemical modification of the starting compounds.
- Pavlov, V. A.,Kurdyukov, A. I.,Gorin, B. I.,Sagitova, F. R.,Aristova, N. V.,et al.
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p. 718 - 723
(2007/10/02)
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- POLYHALOMETHANE REACTIONS WITH PHOSPHITE ANIONS: FLUOROPHILIC REACTIVITY OF PHOSPHORUS
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Di-isopropyl phosphite reacts with bromotrifluoromethane under basic conditions giving a mixture of some seven products.Identification of these by high-resolution NMR and MS shows that 80 percent of all products are formed by displacement of fluorine from
- Blackburn, G. Michael,Guo, Mao-Jun,Taylor, Steven
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p. 139 - 142
(2007/10/02)
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- Fluorination of Trimethylsilyl Phosphites and their Structural Analogues by Sulfuryl Chloride Fluoride: Simple Preparation of Phosphorofluoridates and Related Compounds, including Deoxynucleoside Phosphorofluoridates
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Trimethylsilyl esters of general formula RR'POSiMe3 react in a quantitative and fully chemoselective way with sulfuryl chloride fluoride, ClSO2F, under extremely mild conditions to give phosphorofluoridates RO(R'O)P(O)F of high purity.This work provides easy access to all type of fluoridates from non-toxic starting materials.The synthetic usefulness of this method is illustrated by the synthesis of 3'- and 5'-mononucleoside phosphorofluoridates 10 and 3',5'-dinucleoside phosphorofluoridates 11 from the corresponding nucleoside trimethylsilyl phosphites.
- Dabkowski, Wojciech,Cramer, Friedrich,Michalski, Jan
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p. 1447 - 1452
(2007/10/02)
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- THE FLUORINATION OF HYDROPHOSPHORYL COMPOUNDS USING 2-HYDROPERFLUOROPROPYL AZIDE
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2-Hydroperfluoropropyl azide efficiently fluorinates hydrophosphoryl compounds to give the corresponding P(V) acid fluorides.
- Lermontov, S. A.,popov, A. V.,Sukhozhenko, I. I.,Pushin, A. N.,Martynov, I. V.
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p. 839 - 841
(2007/10/02)
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- Alkylation of (Fluorocarbethoxymethylene)-tri-n-butylphosphorane: A Facile Entry to α-Fluoroalkanoates
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(Fluorocarbethoxymethyl)trialkylphosphonium bromides 6, prepared from ethyl bromofluoroacetate and tertiary phosphines, react with n-butyllithium in THF to give the corresponding phosphoranes 7.Reaction of the pregenerated (fluorocarbethoxymethylene)tri-n-butylphosphorane 7a with primary alkyl iodides and activated alkyl bromides followed by in situ hydrolysis of the alkylated salts provides the fluoroalkanoates 9 in a one-pot reaction.In the case of secondary alkyl halides, no substitution was observed, the main reaction being decomposition of the phosphorane.However, the anion obtained from diisopropyl (fluorocarbethoxymethyl)phosphonate 10 b reacts with CH3CH(Ph)Br and (CH3)2CHI to afford the corresponding alkylated phosphonates in good yields.Displacement of the phosphonate moiety either by base-induced hydrolysis or by reduction was unsuccessful.
- Thenappan, Alagappan,Burton, Donald J.
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p. 2311 - 2317
(2007/10/02)
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- Fluorination of Trimethylsilyl Phosphites and Their Structural Analogues by Sulphuryl Chloride Fluoride. A Facile Preparation of Phosphorofluoridates and Related Compounds
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Trimethylsilyl esters of general formula RR'POSiMe3 react in a quantitative and fully chemoselective way with sulphuryl chloride fluoride to give phosphorofluoridates RR'P(O)F of high purity under extremely mild conditions.
- Dabkowski, W.,Michalski, J.
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p. 755 - 756
(2007/10/02)
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