685-88-1Relevant academic research and scientific papers
Infrared and Raman spectra, vibrational assignment, and ab initio calculations of fluoromalononitrile
Dakkouri,Grunvogel-Hurst,Guirgis, Gamil A.,Yu, Zhenhong,Jin, Yanping,Durig, James R.
, p. 2001 - 2012 (1997)
The infrared spectra (3500-80 cm-1) of gaseous and solid and the Raman spectra (3500-30 cm-1) of liquid with quantitative depolarization values and solid fluoromalononitrile, FHC(CN)2, have been recorded. These spectra have been interpreted in detail and a complete vibrational assignment is proposed based on infrared band contours, depolarization values, and relative infrared and Raman intensities. The assignment is supported by a normal coordinate calculation based upon force constants obtained from MP2/6-31G* ab initio calculations. Also, from these calculations the predicted infrared and Raman spectra have been obtained. The C-H bond distance is predicted to be 1.096 A from the isolated carbon-hydrogen stretching frequency. Optimized geometric parameters have been obtained from RHF/6-31G*, MP2/6-31G* and MP2/6-311 + + G** ab initio calculations. These results are discussed and compared with those obtained for some similar molecules.
PPh3-catalyzed β-selective addition of α-fluoro β-dicarbonyl compounds to allenoates
Liu, Yong-Liang,Wang, Xiao-Ping,Wei, Jie,Li, Ya
supporting information, (2021/12/02)
A highly selective phosphine-catalyzed β-addition of α-fluoro β-dicarbonyl compounds to allenoates has been developed. Both α-fluoro β-diketones and α-fluoro β-keto esters prove to be competent fluorocarbon nucleophiles, giving a series of the β-addition products bearing a fluorinated quaternary carbon center in good to excellent yields and with excellent regioselectivities. A plausible reaction pathway is presented.
Continuous synthesis method for 2-fluoroethyl malonate compound
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Paragraph 0039-0073; 0085-0114, (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 0052-0054, (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.
METHOD FOR PRODUCING FLUOROMALONIC ESTER DERIVATIVE
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Paragraph 0021-0024, (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
PROCESS FOR PREPARING (E)-(5,6-DIHYDRO-1,4,2-DIOXAZINE-3-YL) (2-HYDROXYPHENYL) METHANONE O-METHYL OXIME
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Paragraph 0069, (2016/12/22)
A process for preparing (E)-(5,6-dihydro-l,4,2-dioxazin-3-yl)(2- hydroxyphenyl)methanone O-methyl oxime is described which includes: (i) reacting benzofuran-3(2H)-one O-methyl oxime (1) with at least one nitrite selected from n-butyl nitrite and tert-butyl nitrite, in the presence of a metal alkoxide to form (2Z,32)-2,3-benzofuran-dione O3-methyl dioxime (2) as the predominant isomer; (ii) reacting the (2Z,3Z)-2,3-benzofuran-dione O -methyl dioxime (2) with 2- haloethanol to form (2Z,3Z)-benzofuran-2,3-dione 02-(2-hydroxyethyl) O3 -methyl dioxime (3); and (iii) reacting the (2Z,3Z)-benzofuran-2,3-dione 02-(2-hydroxyethyl) and -methyl dioxime (3) with an acid to form (E)-(5,6-dihydro-l,4,2-dioxazin-3-yl)(2- hydroxyphenyl)methanone (9-methyl oxime (4);
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.
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.
METHOD OF PRODUCING MONOFLUOROMALONIC ACID DERIVATIVE
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Paragraph 0028-0031, (2017/02/24)
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
