115899-98-4Relevant articles and documents
A Convenient Synthesis of 2-Fluoro- and 2-Chloromalonic Esters Mediated by Hypervalent Iodine
Kitamura, Tsugio,Muta, Kensuke,Oyamada, Juzo
, p. 3241 - 3245 (2015)
Direct fluorination of malonic esters with a reagent system of iodosylbenzene and Et3N·5HF gave the corresponding 2-fluoromalonic esters in good to high yields. Direct chlorination using iodosylbenzene and hydrochloric acid also provided the 2-chloromalonates in high yields.
Elemental fluorine. Part 3 [1]. The preparation of dialkyl fluoromalonates by direct fluorination
Chambers,Hutchinson,Thomson
, p. 165 - 166 (1996)
Dialkyl fluoromalonates have been prepared by treating the sodium derivatives of the parent dialkyl malonates with elemental fluorine.
1-Fluoro-2-pyridone: A Useful Fluorinating Reagent
Purrington, Suzanne T.,Jones, Walda Ann
, p. 761 - 762 (1983)
1-Fluoro-2-pyridone (mp 50-53 degC) has been prepared by reaction of 5percent fluorine in nitrogen and 2-(trimethylsiloxy)pyridine in FCCl3 at -78 degC.After sublimation, the pyridone is used as a selective fluorinating agent in the preparation of some fl
A stable fluorinated and alkylated lithium malonatoborate salt for lithium ion battery application
Wan, Shun,Jiang, Xueguang,Guo, Bingkun,Dai, Sheng,Goodenough, John B.,Sun, Xiao-Guang
, p. 9817 - 9820 (2015)
A new fluorinated and alkylated lithium malonatoborate salt, lithium bis(2-methyl-2-fluoromalonato)borate (LiBMFMB), has been synthesized for lithium ion battery application. A 0.8 M LiBMFMB solution is obtained in a mixture of ethylene carbonate (EC) and ethyl methyl carbonate (EMC) (1:2 by wt). The new LiBMFMB based electrolyte exhibits good cycling stability and rate capability in LiNi0.5Mn1.5O4 and graphite based half-cells.
Induction of B- to Z-DNA transition by copper and zinc complexes with C(15) substituted macrocyclic pentaaza ligands
Spingler, Bernhard,Da Pieve, Chiara
, p. 1637 - 1643 (2005)
The new macrocyclic ligand 15-fluoro-15-methyl-l,4,7,10,13- pentaazacyclohexadecan-14,16-dione (2) was synthesised and its crystal structure determined together with the ones of the known analogues of 2, 15-fluoro-1,4,7,10,13-pentaazacyclohexadecan-14,16-dione (1) and 15,15-difluoro-1,4,7,10,13-pentaazacyclohexadecan-14,16-dione (3). The binding behaviour of all three ligands to copper and zinc was studied in the solid state. They can bind to the metal centre by either triple coordination (N3) with all secondary amines or after double deprotonation of the two amides with all five nitrogen atoms (N5). The N5 coordination mode is favoured by the presence of one or two fluorine substituents at the C(15) position and by a high pH in the case of aqueous solutions. Circular dichroism titrations of poly d(GC) with the metal complexes showed that only 4 and 5, that is the copper complexes of 1 and 2, induced a complete B- to Z-DNA transition. The degree of cooperativity of the transition was found to be 3.4 and 7.3 for 4 and 5 respectively. As a possible hypothesis to explain this difference, the additional methyl group in 5 compared with 4 may be involved in a hydrophobic interaction with the DNA. Ligand 2, the copper complex 6 of the bis fluoro substituted ligand 3, and the zinc complex 7 of ligand 1 did not induce any change in the direction of Z-DNA. In the case of 6, the CD spectrum of the DNA actually showed no change at all, indicating that the complex was even not interacting with the B form of DNA. Therefore it is assumed that the bis fluoro substitution is causing the complex to be in the neutral N5 coordination mode at the experimental conditions of pH 7. The electrostatic contribution together with the shielding effect of the ligand might explain the absence of any interaction with the DNA. The Royal Society of Chemistry 2005.
New promising lithium malonatoborate salts for high voltage lithium ion batteries
Sun, Xiao-Guang,Wan, Shun,Guang, Hong Yu,Fang, Youxing,Reeves, Kimberly Shawn,Chi, Miaofang,Dai, Sheng
, p. 1233 - 1241 (2017)
Three new lithium salts, lithium difluoro-2-methyl-2-fluoromalonatoborate (LiDFMFMB), lithium difluoro-2-ethyl-2-fluoromalonatoborate (LiDFEFMB), and lithium difluoro-2-propyl-2-fluoromalonatoborate (LiDFPFMB), have been synthesized and evaluated for application in lithium ion batteries. These new salts are soluble in a mixture of ethylene carbonate (EC) and ethyl methyl carbonate (EMC) (1:2 by wt) and 1.0 M salt solutions can be easily prepared. The ionic conductivities of these new salts are close to those of LiBF4 and LiPF6. Cyclic voltammograms reveal that these new salt based electrolytes can passivate both natural graphite and high voltage spinel LiNi0.5Mn1.5O4 (LNMO) to form effective solid electrolyte interphases (SEIs). In addition, these new salt-based electrolytes exhibit good cycling stability with high coulombic efficiencies in both LiNi0.5Mn1.5O4 and graphite based half-cells and full cells.
Are carboxylic esters really refractory to DAST? On the fluorination of α-hydroxyesters with DAST
Lepri, Susan,Buonerba, Federica,Maccaroni, Paola,Goracci, Laura,Ruzziconi, Renzo
, p. 82 - 91 (2015)
Diethyl 2-alkyl-2-hydroxymalonates react with DAST almost exclusively at the ester carbonyl giving a mixture of ethyl 2-(ethoxydifluoromethyl)-2-hydroxyalkanoates, 1,1-bis(ethoxydifluoromethyl)alkan-1-ols when administered at room temperature in dichloromethane. The reaction was exploited in the synthesis of nucleus- and side-chain polyfluorinated indoles. The fluorination of substituted diethyl 2-[(1-tert-butoxycarbonylindol-3-yl)methyl]-2-hydroxymalonates with DAST gave a mixture of ethyl 2-(ethoxydifluoromethyl)-2-hydroxy-3-(1-tert-butoxycarbonylindol-3-yl)propionate, diastereomeric 1′-tert-butoxycarbonyl-2′-hydroxy-2,2-diethoxycarbonylspiro(cyclopropane-1,3′-indoline) and only traces of 1,1-bis(ethoxydifluoromethyl)-2-(1-tert-butoxycarbonylindol-3-yl)ethanol. The composition of these mixtures changes depending on the reaction conditions. Regioselectively substituted ethyl 2-hydroxy-2-[(1-tert-butoxycarbonylindol-3-yl)methyl]-3,3,3-trifluoropropionate reacts with DAST at 0 °C in dichloromethane giving satisfactory yields of the corresponding 1-ethoxy-2-[(1-tert-butoxycarbonylindol-3-yl)methyl]-1,1,3,3,3-pentafluoropropan-2-ols as the exclusive reaction products. In the same reaction conditions, ethyl 3-(1-tert-butoxycarbonylindol-3-yl)-2-hydroxypropionate mainly provides 1′-tert-butoxycarbonyl-2′-hydroxy-2,2-diethoxycarbonylspiro(cyclopropane-1,3′-indoline) together with the “normal” fluorination product ethyl 3-(1-tert-butoxycarbonylindol-3-yl)-2-fluoropropionate. A plausible mechanism of this process is proposed in the following.
Carbanion Fluorination with Xenon Difluoride in the Presence of Sulfur (II) Derivatives
Patrick, Timothy B.,Nadji, Sourena
, p. 415 - 420 (1988)
An electrophilic fluorination reagent capable of fluorinating carbanions in moderate yield is obtained from the reaction of xenon difluoride with Sulfur II derivatives such as dimethyl sulfide.
A Unified and Desymmetric Approach to Chiral Tertiary Alkyl Halides
Huang, Zhongxing,Low, Kam-Hung,Zhang, Suihan,Zheng, Yin,Zi, Weiwei
supporting information, p. 1951 - 1961 (2022/02/09)
Enantioenriched tertiary alkyl halides are prevalent in bioactive molecules and can serve as versatile synthetic intermediates to construct complex structures. While conventional access to these motifs often hinges on stereoselective carbon-halogen or carbon-carbon bond formation reactions, desymmetric approaches using halogenated and prochiral tetrasubstituted carbons are largely elusive in comparison. Here, we report that a suite of dinuclear zinc catalysts with a prolinol- or pipecolinol-derived tetradentate ligand can reductively desymmetrize a large collection of easily available halomalonic esters to α-halo-β-hydroxyesters. These polyfunctionalized tertiary alkyl fluorides, chlorides, and bromides proved to be useful intermediates toward fluorinated drug analogs and polyhalogenated monoterpenes. The facile intramolecular epoxidation of the chiral chloride and bromide products has also enabled expeditious access to natural products containing tertiary alcohol motifs.
HETEROARYL COMPOUNDS AS IRAK INHIBITORS AND USES THEREOF
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Paragraph 00180, (2017/05/02)
The present invention relates to compounds of Formula (I) and pharmaceutically acceptable compositions thereof, useful as IRAK inhibitors.
