344-14-9Relevant articles and documents
FACILE SYNTHESIS OF DIALKYL FLUOROMALONATES AND THEIR DERIVATIVES
Ishikawa, Nobuo,Takaoka, Akio
, p. 107 - 110 (1981)
Dimethyl and diethyl fluoromalonates were prepared by the stepwise basic alcoholysis of hexafluoropropene in a total yield of 50 - 55 percent.These dialkyl fluoromalonates were alkylated with alkyl halides, and the resulting dialkyl α-fluoroalkylmalonates were cyclized with urea affording 5-fluorobarbituric acid derivatives.
Electrochemical Intermolecular Monofluoroalkylation of α,β-Unsaturated Carboxylic Acids and Heteroaromatics with 2-Fluoromalonate Esters
Hou, Zhong-Wei,Jiang, Ting,Wang, Lei,Wu, Ting-Xia
supporting information, p. 8585 - 8589 (2021/11/17)
An electrochemical approach for the preparation of monofluorides from α,β-unsaturated carboxylic acids and heteroaromatics with readily available 2-fluoromalonate esters as monofluoroalkyl radical precursors has been developed. The electrosynthesis employs ferrocene (Cp2Fe) as a catalyst in a simple undivided cell with a broad substrate scope, which obviates the need for sacrificial oxidizing reagents.
Process for fluorinating inorganic or organic compounds by direct fluorination
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Paragraph 0317-0322, (2020/07/14)
The invention relates to the use of a fluorinated gas, wherein the elemental fluorine (F2) is present at a high concentration, the present invention relates to a process for producing fluorinated compounds by direct fluorination using a fluorination gas in which elemental fluorine (F2) is present at a high concentration, such as a concentration of elemental fluorine (F2), in particular equal to much higher than 15 vol% or even 20 vol% (i.e., at least 15 vol% or even 20 vol%), and to a process for producing fluorinated compounds by direct fluorination using a fluorination gas. The process of the present invention relates to the manufacture of fluorinated compounds other than fluorinated benzene by direct fluorination, in particular to the preparation of fluorinated organic compounds, end products and intermediates for use in agricultural, pharmaceutical, electronic, catalyst, solvent and other functional chemical applications. The fluorination process of the invention can be carried outin batches or in a continuous manner. If the process of the invention is carried out in batches, a column (tower) reactor may be used. If the process of the invention is continuous, a microreactor may be used.
Preparation method of dimethyl 2-fluoromalonate
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Paragraph 0024-0041, (2019/06/30)
The invention belongs to the technical field of chemical synthesis, and particularly relates to a preparation method of dimethyl 2-fluoromalonate. The preparation method of the dimethyl 2-fluoromalonate comprises the following steps: (1) uniformly mixing and stirring 4-5 mol parts of dioxane, 1 mol part of dimethyl chloromalonate and 0.01-0.05 mol part of potassium iodide in a reaction vessel; (2)adding 1-1.5 mol parts of dried and activated potassium fluoride into the reaction vessel; (3) heating to carry out reflux reaction while stirring; (4) collecting fractions at the temperature of 74-78 DEG C; (5) stopping heating when the distillation temperature reaches 78 DEG C to obtain a crude product of dimethyl 2-fluoromalonate; and (6) refining the crude product of dimethyl 2-fluoromalonateto obtain a target product. The method is controllable in process, high in yield and low in cost.
Continuous synthesis method for 2-fluoroethyl malonate compound
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Paragraph 0074-0078, (2019/11/20)
The invention discloses a continuous synthesis method for a 2-fluoroethyl malonate compound. The continuous synthesis method comprises the following steps: taking a formula shown in the description asa raw material, and carrying out a continuous decarbonylation reaction in continuous reaction equipment, thereby obtaining the 2-fluoroethyl malonate compound represented by a formula shown in the description, wherein R and R' separately represent straight-chain or branched alkyl, substituted or unsubstituted aryl or substituted or unsubstituted heterocycle or cyclic alkyl and are the same or different. According to the method, the high-temperature decarbonylation reaction of 2-fluoro-3-oxo-disuccinate is achieved by adopting the continuous reaction equipment. Compared with the traditional pot type reaction, the amount of materials participating in reaction in unit time is reduced greatly, so that a high-temperature hazardous area is reduced, and the security risk is greatly lowered.
Preparation method for fluoromalonic acid diester
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Paragraph 0046-0048, (2018/06/15)
The invention especially relates to a preparation method for fluoromalonic acid diester, belonging to the field of organic synthesis. The preparation method comprises a step of subjecting fluoroacetate and dialkyl carbonate to a condensation reaction in the presence of alkali so as to prepare fluoromalonic acid diester. The preparation method provided by the invention is mild in reaction process;the preparation method has low toxicity and corrosivity due to elimination of conventional chlorination and fluorination steps; and the preparation method does not produce difluoromalonic acid diesterimpurities, has low requirements on factory equipment and is simple and safe to operate.
Protonation and transformations of α-diazo-β-dicarbonyl compounds in superacids: generation of the strongest carbon-centered cationic electrophiles at the protonation of diazomalonates in Friedel–Crafts reactions
Satumov, Eugeniy T.,Medvedev, Jury J.,Nilov, Denis I.,Sandzhieva, Maria A.,Boyarskaya, Irina A.,Nikolaev, Valerij A.,Vasilyev, Aleksander V.
, p. 4835 - 4844 (2016/07/18)
Protonation of diazodiketones N2C(COR)2in Br?nsted superacids (TfOH, FSO3H, TfOH–SbF5) gives rise to stable and non-reactive O,O-diprotonated at carbonyl oxygens species N2C(C(=OH+)R)2, which were studied by means of1H and13C NMR. Diazomalonates N2C(CO2Alk)2, contrary to diazodiketones, react with TfOH or HF, releasing nitrogen and producing triflates of oxymalonates TfOCH(CO2Alk)2or fluoromalonates FCH(CO2Alk)2, respectively. Diazoketoesters N2C(COR)(CO2Alk) react in the same way only with TfOH, but not with HF. The reactions of diazomalonates with arenes ArH (benzene, toluene, xylenes) in TfOH solution yield corresponding Friedel–Crafts reaction products ArCH(CO2Alk)2. According to performed DFT calculations, trication+CH(C(=OH+)OMe)2, a possible intermediate, which is derived from protonation of dimethyl diazomalonate, should be the strongest cationic carbon-centered electrophile known up to date.
METHOD FOR PRODUCING FLUOROMALONIC ESTER DERIVATIVE
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Paragraph 0023; 0024; 0029; 0030, (2017/02/24)
PROBLEM TO BE SOLVED: To provide a method for producing a fluoromalonic ester derivative, useful as a raw material of electronic materials and as a synthetic intermediate of an agrochemical, which does not use or waste an expensive fluorinating agent and also has a short process. SOLUTION: A fluoromalonic ester derivative represented by a formula (2) is produced by reacting a malonic ester derivative with the 2-position modified with R3 with N-fluoro-bis(methanesulfonyl)imide in the presence of a Lewis acid. (R1 and R2 are each independently a methyl group, an ethyl group, a C3-4 linear, branched or cyclic alkyl group, a phenyl group, or a benzyl group; and R3 is H, a methyl group or an ethyl group.) SELECTED DRAWING: None COPYRIGHT: (C)2016,JPO&INPIT
Fluorine gas for life science syntheses: Green metrics to assess selective direct fluorination for the synthesis of 2-fluoromalonate esters
Harsanyi, Antal,Sandford, Graham
supporting information, p. 3000 - 3009 (2015/05/27)
Optimisation and real time reaction monitoring of the synthesis of 2-fluoromalonate esters by direct fluorination using fluorine gas is reported. An assessment of green metrics including atom economy and process mass intensity factors, demonstrates that the one-step selective direct fluorination process compares very favourably with established multistep processes for the synthesis of fluoromalonates.
A Convenient Synthesis of 2-Fluoro- and 2-Chloromalonic Esters Mediated by Hypervalent Iodine
Kitamura, Tsugio,Muta, Kensuke,Oyamada, Juzo
, p. 3241 - 3245 (2015/10/19)
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.