- FACILE SYNTHESIS OF DIALKYL FLUOROMALONATES AND THEIR DERIVATIVES
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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.
- Ishikawa, Nobuo,Takaoka, Akio
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- Electrochemical Intermolecular Monofluoroalkylation of α,β-Unsaturated Carboxylic Acids and Heteroaromatics with 2-Fluoromalonate Esters
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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.
- Hou, Zhong-Wei,Jiang, Ting,Wang, Lei,Wu, Ting-Xia
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supporting information
p. 8585 - 8589
(2021/11/17)
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- Process for fluorinating inorganic or organic compounds by direct fluorination
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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.
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Paragraph 0317-0322
(2020/07/14)
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- Continuous synthesis method for 2-fluoroethyl malonate compound
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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.
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Paragraph 0074-0078
(2019/11/20)
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- Preparation method of dimethyl 2-fluoromalonate
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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.
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Paragraph 0024-0041
(2019/06/30)
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- Preparation method for fluoromalonic acid diester
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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.
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Paragraph 0046-0048
(2018/06/15)
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- METHOD FOR PRODUCING FLUOROMALONIC ESTER DERIVATIVE
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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
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Paragraph 0023; 0024; 0029; 0030
(2017/02/24)
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- 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
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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.
- Satumov, Eugeniy T.,Medvedev, Jury J.,Nilov, Denis I.,Sandzhieva, Maria A.,Boyarskaya, Irina A.,Nikolaev, Valerij A.,Vasilyev, Aleksander V.
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p. 4835 - 4844
(2016/07/18)
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- Fluorine gas for life science syntheses: Green metrics to assess selective direct fluorination for the synthesis of 2-fluoromalonate esters
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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.
- Harsanyi, Antal,Sandford, Graham
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p. 3000 - 3009
(2015/05/27)
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- A Convenient Synthesis of 2-Fluoro- and 2-Chloromalonic Esters Mediated by Hypervalent Iodine
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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.
- Kitamura, Tsugio,Muta, Kensuke,Oyamada, Juzo
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p. 3241 - 3245
(2015/10/19)
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- METHOD OF PRODUCING MONOFLUOROMALONIC ACID DERIVATIVE
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PROBLEM TO BE SOLVED: To provide a method of producing a monofluoromalonic acid ester derivative that has a high yield, facilitates separation of a product, and allows industrial production. SOLUTION: A malonic acid ester derivative (1) is reacted with a hydrogen fluoride source in the presence of an iodosylbenzene derivative or an iodobenzene derivative and an oxidizing agent, to produce a monofluoromalonic acid derivative (4). COPYRIGHT: (C)2015,JPOandINPIT
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Paragraph 0032-0034
(2017/02/24)
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- (Re)Investigation of the reactivity of uranium hexafluoride toward several organic functions at room temperature
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The annual worldwide production of UF6 is very large and this compound is not used. Consequently, it could be interesting to find some applications as organic reagent. UF6 could be considered as an oxidizer of various functions. However, it seems also present some possibilities as a fluorinating reagent in mild conditions.
- Roy, Olivier,Marquet, Bernard,Alric, Jean-Paul,Jourdan, Alex,Morel, Bertrand,Langlois, Bernard R.,Billard, Thierry
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- An efficient method for α-monofluorination of carbonyl compounds with molecular fluorine: Use of α-hydroxymethylene substituent as directing and activating groups
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Molecular fluorine efficiently reacts with α-hydroxymethylene carbonyl compounds to give α-fluoro-α-formyl compounds in a highly site-specific manner. The fluorinated compounds mostly isolated as their hemiacetals with methanol are readily deformylated just by treatment with weak bases affording α-monofluorinated carbonyl compounds. In this fluorination method, the hydroxymethylene group serves not only as a directing group but also as the activating group of carbonyl compounds for fluorination. By this method, a series of α-fluoro carbonyl compounds including esters was synthesized in high yields.
- Kamaya, Hiroshi,Sato, Masayuki,Kaneko, Chikara
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p. 587 - 590
(2007/10/03)
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- N-Fluorobisimides. Efficient reagents for the fluorination of 1,3-dicarbonyl derivatives
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Fluorination of 1,3-dicarbonyl derivatives with N-fluorobisimides, (CF3SO2)2NF (1), results in the formation of 2-fluoro- or 2,2-difluoro-1,3-dicarbonyl analogs, depending on the reaction conditions.High yields are obtained for a variety of structural types.In the case of 1,3-dicarbonyl derivatives with low enol content, only the sodium enolates react with 1.Thus 1 has been demonsrtated to be perhaps the best fluorinating reagent for the fluorination of 1,3-dicarbonyl derivatives.All of the 2-fluoro-1,3-dicarbonyl products exist predominantly as keto tautomers.
- Xu, Ze-Qi,DesMarteau, Daryl D.,Gotoh, Yoshihiko
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- N-Fluoro Perfluoroalkylsulphonimides: Efficient Reagents for the Fluorination of 1,3-Dicarbonyl Derivatives
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Fluorination of 1,3-dicarbonyl derivatives with N-fluoro sulphonimides afforded either 2-fluoro or 2,2-difluoro products in high yields.
- Xu, Ze-Qi,DesMarteau, Darryl D.,Gotoh, Yoshihiko
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p. 179 - 181
(2007/10/02)
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- A NOVEL ROUTE TO 5-FLUOROURACILS FROM CHLOROTRIFLUOROETHENE
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Diethyl fluoromalonate was prepared in one-pot from chlorotrifluoroethene via trifluoroacrylic acid lithium salt in 79percent yield.Diethyl fluoromalonate was easily converted to 5-fluoro-6-chlorouracils, reductions of which gave 5-fluorouracils in good yields.
- Fuchikami, Takamasa,Yamanouchi, Akiko,Suzuki, Yasuyuki
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p. 1573 - 1576
(2007/10/02)
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- Acetyl Hypofluorite, a New Moderating Carrier of Elemental Fluorine and Its Use in Fluorination of 1,3-Dicarbonyl Derivatives
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Elemental fluorine and most of the fluoroxy reagents do not react efficiently or cleanly with 1,3-dicarbonyl derivatives or with their corresponding metal enolates even at -75 degC.It has been found that a suspension of sodium acetate in CFCl3 or in CFCl3-AcOH, when treated with elemental fluorine, forms a new electrophilic fluorinating reagent, CH3COOF (1), which reacts with substrates without further isolation or purification.This reagent is milder than F2, CF3OF, or CF3COOF and reacts successfully where the other reagents fail.When 1 reacts with 1,3-dicarbonyl compounds, the main product is the 1,3-dioxo-2-fluoro derivative in reasonable yields.When, however, the corresponding sodium enolates were treated with 1, the yields of the monofluoro derivatives were considerably higher.In the case of 1,3-dicarbonyl derivatives with low enol content, only the sodium enolates react with 1 to produce good to very good yields of the corresponding 2-monofluoro derivatives.Thus 1 can be considered as a moderating carrier of the highly reactive F2.
- Lerman, Ori,Rozen, Shlomo
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p. 724 - 727
(2007/10/02)
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- REACTION OF CHLORODIFLUOROPROPENOATES WITH POTASSIUM FLUORIDE
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Reaction of methyl 3-chlorodifluoropropenoate (I) with potassium fluoride afforded methyl trifluoropropenoate (II) which was dimerized to dimethyl perfluoro-4-methyl-2-pentenedioate (III).The reaction rate of I was not affected by the presence of the monomer II.Methyl 2-chlorodifluoropropenoate (VII) on treatment with potassium fluoride underwent dimerization and the unstable dimer X was transformed at -20 deg C into methyl 2-chloro-3,5,5-trifluoro-4-methoxycarbonyl-2,4-pentadienoate (XIII) and dimethyl 2-chloro-3-fluoro-4-trifluoromethyl-2-pentenedioate (XIV).These reactions involve a transfer of chlorine atom from the dimer X to the primarily formed 1-chloro-3,3,3-trifluoro-1-methoxycarbonylethanide (VIIa) which is transformed by this carbanion interconversion into methyl 2,2-dichlorotrifluoropropanoate (XI).The propenoate VII adds methanol in the presence of potassium fluoride whereas the propenoate I does not react under these conditions.
- Svoboda, Jiri,Paleta, Oldrich,Dedek, Vaclav
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p. 1272 - 1279
(2007/10/02)
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