- Infrared and Raman spectra, vibrational assignment, and ab initio calculations of fluoromalononitrile
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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.
- Dakkouri,Grunvogel-Hurst,Guirgis, Gamil A.,Yu, Zhenhong,Jin, Yanping,Durig, James R.
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Read Online
- PPh3-catalyzed β-selective addition of α-fluoro β-dicarbonyl compounds to allenoates
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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.
- Liu, Yong-Liang,Wang, Xiao-Ping,Wei, Jie,Li, Ya
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supporting information
(2021/12/02)
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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 0039-0073; 0085-0114
(2019/11/20)
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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 0052-0054
(2018/06/15)
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- PROCESS FOR PREPARING (E)-(5,6-DIHYDRO-1,4,2-DIOXAZINE-3-YL) (2-HYDROXYPHENYL) METHANONE O-METHYL OXIME
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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);
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Paragraph 0069
(2016/12/22)
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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 0021-0024
(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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supporting information
p. 3000 - 3009
(2015/05/27)
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- PROCESS FOR PREPARING FLUOXASTROBIN
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A process for preparing fluoxastrobin, including: (i) reacting benzofuran-3(2H)-one O-methyl oxime (10) with an alkyl nitrite in the presence of an acid to form (3E)-2,3-benzofuran-dione O3-methyl dioxime (11A) as a predominant isomer; (ii) reacting(3E)-2,3-benzofuran-dione O3-methyl dioxime (11A) with 2-haloethanol to form (3E)-benzofuran-2,3-dione O2-(2-hydroxyethyl) O3-methyl dioxime (12A); and (iii) reacting(3E)-benzofuran-2,3-dione O2-(2-hydroxyethyl) O3-methyl dioxime (12A) with a base to form (E)-(5,6-dihydro-1,4,2-dioxazin-3-yl)(2-hydroxyphenyl)methanone O-methyl oxime (13) (iv) reacting a 4,6-di-halo-5-fluoro-pyrimidine (5), wherein X1 is halogen, with (E)-(5,6-dihydro-1,4,2-dioxazin-3-yl)(2-hydroxyphenyl)methanone O-methyl oxime (13), in the presence of a solvent and optionally in the presence of a base, to form an (E)-(2-((6-halo-5-fluoropyrimidin-4-yl)oxy)phenyl)(5,6-dihydro-1,4,2-dioxazin-3-yl)methanone O-methyl oxime (14): (v) reacting the (E)-(2-((6-halo-5-fluoropyrimidin-4-yl)oxy)phenyl)(5,6-dihydro-1,4,2-dioxazin-3-yl)methanone O-methyl oxime (14) with 2-chlorophenol, in the presence of a solvent and optionally in the presence of a base, to form fluoxastrobin:.
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Paragraph 0046
(2015/02/02)
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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 0028-0031
(2017/02/24)
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- FLUORINATED DERIVATIVES OF MELDRUM'S ACID, A METHOD FOR THE PREPARATION OF THE SAME, AND THEIR USE AS A SOLVENT ADDITIVE
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Disclosed are certain fluorinated derivatives of Meldrum's acid as novel compounds, preparation methods for the same, their use in Li ion batteries, Li air batteries and Li sulphur batteries as well as solvent compositions, electrolyte compositions and respective batteries containing them.
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Page/Page column 16
(2013/06/27)
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- Organocatalytic alkynylation of densely functionalized monofluorinated derivatives: C(sp3)-C(sp) coupling
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Organocatalytic alkynylation of nucleophilic fluorocarbons using hypervalent iodine compounds under cinchona-based catalysis, namely using O-allyl N-anthracenyl cinchona alkaloid derivative II, is described. The reaction gives the final fluoro-propargyl compounds in good to excellent yields (up to 91%) and with moderate to low enantioselectivity (up to 61% ee). The reaction represents the first example of the use of hypervalent iodine compounds for the construction of fluorinated compounds and opens access to the preparation of biologically attractive compounds such as 1,2,3-triazoles.
- Kamlar, Martin,Putaj, Piotr,Vesely, Jan
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supporting information
p. 2097 - 2100
(2013/04/24)
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- On the reaction of 4-substituted trimethyltin aromatics with perchlorylfluoride
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To evaluate the suitability of [18F]perchorylfluoride [18F]FClO3 as an electrophilic fluorination agent for the preparation of radiopharmaceuticals, the reactivity non-radioactive FClO3 towards 4-substituted trimethyltin aromatic compounds was studied. Contrary to the expectation, an electrophilic fluorination of the aromatic nucleus did not occur. The reaction of perchlorylfluoride with aromatic trimethylstannyl compounds resulted in the formation of trimethyltin fluoride and the respective destannylated aromatics in variable yields.
- Hiller, Achim,Patt, J?rg T.,Steinbach, J?rg
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p. 3737 - 3742
(2007/10/03)
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- METHOD FOR PRODUCING α-FLUOROMALONIC ACID DIALKYL ESTERS
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The invention relates to a novel advantageous method for producing α-fluoromalonic acid dialkyl esters.
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Page/Page column 5
(2008/06/13)
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- Catalyzed fluorination of carbonyl compounds
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The present invention provides a method of substituting a carbonyl compound with fluorine at the α-position, comprising reaching the carbonyl compound with a fluorinating present of a metal-containing catalyst. The reaction results in replacement of a hydrogen atom by fluorine. The catalyst, which is used in a catalytically effective amount, is preferably a transition metal. In one class of methods the catalyst is a transition metal compound. In another class of methods, the catalyst is an elemental metal, in which case the carbonyl compound has an activating group attached to the carbon atom which is substituted by fluorine.
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- A facile P-C bond cleavage of 2-fluoro2-phosphonyl-1,3-dicarbonyl compounds on silica gel
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α-Fluoro-β-keto esters and α-fluoromalonates were prepared by the P-C bond cleavage of 2-fluoro-2-phosphonyl-1,3-dicarbonyl compounds on wet silica gel.
- Kim, Dae Young
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p. 1205 - 1212
(2007/10/03)
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- A new synthesis of α-fluoromalonates from α-fluoro-α-phosphonyl malonates using P-C bond cleavage
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P-C bond cleavage of α-fluoro-α-phosphonyl malonates using magnesium chloride provides a new synthetic route to α-fluoro malonates.
- Kim, Dae Young,Kim, Joo Young
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p. 2483 - 2489
(2007/10/03)
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- Elemental fluorine. Part 9 : Catalysis of the direct fluorination of 2-substituted carbonyl compounds
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Catalysis of the reaction between fluorine and a range of 2-substituted carbonyl compounds has been investigated. Most notably, the preparation of diethyl-2-fluoromalonate has been achieved in high yield by fluorination of diethylmalonate in the presence of hydrated copper nitrate. Reactions between fluorine and carbanions derived from 2-substituted carbonyl compounds, including phosphonates, sulphones and nitriles, are also discussed.
- Chambers, Richard D.,Hutchinson, John
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- 15-deoxyspergualin analogs, their method of preparation and their use in therapeutics
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The present invention relates, by way of novel industrial products, to compounds which are structurally related to 15-deoxyspergualin and which have the formula STR1 in which: A is a single bond, a group --CH2 --, a group --CH2 O--, a group --CH2 NH--, a group --CH(OH)--, a group --CHF-- or a group --CH(OCH3)--, and n is equal to 6 or 8, and their addition salts. These novel compounds are useful especially as immunosuppressants. The invention further relates to the method of preparing said compounds.
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- Elemental fluorine. Part 3 [1]. The preparation of dialkyl fluoromalonates by direct fluorination
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Dialkyl fluoromalonates have been prepared by treating the sodium derivatives of the parent dialkyl malonates with elemental fluorine.
- Chambers,Hutchinson,Thomson
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p. 165 - 166
(2007/10/03)
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- Process for the preparation of α-fluoro-β-dicarbonyl compounds
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α-fluoro-β-dicarbonyl compounds are prepared by reacting a halogenated dicarbonyl compound at temperatures of 20° to 100° C. with an addition product of hydrogen fluoride and a trialkylamine. This process is easy to carry out in technical terms and can also be carried out on a large scale.
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- Fluorinated cyclobutyl purines and pyrimidines
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Antiviral activity is exhibited by compounds having the formula or a pharmaceutically acceptable salt thereof wherein R1 is a purinyl, substituted purinyl, pyrimidinyl, or substituted pyrimidinyl, R6 is -OH, -CH2OH, -OPO3H2, -CH2-O-PO3H2, or and R7 is hydrogen, -PO3H2, or
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- Acylation of Fluorocarbethoxy-Substituted Ylids: A Simple and General Route to α-Fluoro β-Keto Esters
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(Fluorocarbethoxymethylene)tri-n-butylphosphorane (3) reacts with acid chlorides and anhydrides to form the corresponding carbon acylated phosphonium salt 4, and hydrolysis of 4 under mild basic conditions provides RCOCFHCOOEt (8) in moderate yields.The reaction is applicable to primary, secondary, tertiary, cyclic, aromatic, and ester-substituted acid chlorides.Acylation with ethyl chloroformate and ethyl chlorothioformate leads to the diesters CFH(COOEt)2 and EtSCOCFHCOOEt.Extension of this reaction sequence to perfluorinated and partially fluorinated acid chlorides did not proceed cleanly to give the expected phosphonium salts.However, the anion derived from (EtO)2P(O)CFHC(O)OEt reacts with RFCOCl to form the corresponding C-acylated phosphonates 10, and hydrolysis of 10 gives RFCOCFHCOOEt.
- Thenappan, Alagappan,Burton, Donald J.
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p. 273 - 277
(2007/10/02)
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- 1-fluoro-1-halo-3,6-dioxabicyclo [4.1.0]heptane preparation, process and use
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A class of compounds, namely 1-fluoro-1-halo-3,6-dioxabicyclo[4.1.0]heptanes and a process using these compounds in the preparation of fluoromalonaldehyde acetals. The 1-fluoro-1-halo-3,6-dioxabicyclo[4.1.0]heptane is brought into contact with an alcohol in an acid medium. The fluoromalonaldehyde acetals obtained are also new products, which are useful for the synthesis of alkyl fluoromalonates or of fluorinated nitrogen-containing heterocycles.
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- Power and structure-variable fluorinating agents. The N-fluoropyridinium salt system
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The usefulness of the N-fluoropyridinium salt system as a source of fluorinating agents was examined by using substituted or unsubstituted N-fluoropyridinium triflates 1-11, N-fluoropyridinium salts possessing other counteranions 1a-d and 3a, and the counteranion-bound salts, N-fluoropyridinium-2-sulfonates 12 and 13. Electrophilic fluorinating power was found to vary remarkably according to the electronic nature of the ring substituents. This power increased as the electron density of positive nitrogen sites decreased, and this was correlated to the pKa values of the corresponding pyridines. By virtue of this variation, it was possible to fluorinate a wide range of nucleophilic substrates differing in reactivity. It is thus possible to fluorinate aromatics, carbanions, active methylene compounds, enol alkyl or silyl ethers, vinyl acetates, ketene silyl acetals, and olefins through the proper use of salts pentachloro 6 through 2,4,6-trimethyl 2, their power decreasing in this order. All the reactions could be explained on the basis of a one-electron-transfer mechanism. N-Fluoropyridinium salts showed high chemoselectivity in fluorination, the extent depending on the reactive moiety. In consideration of these Findings, selective 9α-fluorination of steroids was carried out by reacting 1 with tris(trimethylsilyl ether) 73 of a triketo steroid. Regio- or stereoselectivity in fluorination was determined by a N-fluoropyridinium salt structure. Steric bulkiness of the N-F surroundings hindered the ortho fluorination of phenols and aniline derivatives, while the capacity for hydrogen bonding on the part of the counteranions prompted this process, and the counteranion-bound salts 12 and 13 underwent this fluorination exclusively or almost so. Both bulky N-fluoropyridinium triflates 2 and 7 preferentially attacked the 6-position of the conjugated vinyl ester of a steroid from the unhindered β-direction to give a thermally unstable 6β-fluoro isomer. On the basis of these results, N-fluoropyridinium salts may be concluded to constitute a system that can serve as a source of the most ideal fluorinating agents for conducting desired selective fluorination through fluorinating capacity or structural alteration.
- Umemoto, Teruo,Fukami, Shinji,Tomizawa, Ginjiro,Harasawa, Kikuko,Kawada, Kosuke,Tomita, Kyoichi
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p. 8563 - 8575
(2007/10/02)
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- AN EXPEDIENT SYNTHESIS OF α-FLUORO-β-KETOESTERS
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Acylation of fluorocarboethoxymethylene tri-n-butylphosphorane (4) followed by hydrolysis under mild basic conditions provides the title compounds (6) in good yields.
- Thenappan, Alagappan,Burton, Donald J.
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p. 6113 - 6116
(2007/10/02)
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- Carbanion Fluorination with Xenon Difluoride in the Presence of Sulfur (II) Derivatives
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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.
- Patrick, Timothy B.,Nadji, Sourena
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p. 415 - 420
(2007/10/02)
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- 5-substituted-6-aminopyrimidines, composition and uses as cardiotonic agents for increasing cardiac contractility
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Herein is disclosed amino-pyrimidine derivatives, therapeutically acceptable acid addition salts thereof, processes for their preparation, methods of using the derivatives and pharmaceutical compositions. The derivatives are useful for increasing cardiac contractility in a mammal.
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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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- 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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p. 107 - 110
(2007/10/02)
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