- SYNTHESIS OF 3,3,3-TRIFLUOROPROPIONIC AND 4,4,4-TRIFLUORO-2-KETOBUTYRIC ACIDS
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Trifluoroethyl cyclohexyl ketone (4) is prepared by acylation of difluoroethylene (2) with cyclohexanecarboxylic acid chloride (1), followed by Cl->F exchange with potassium fluoride in the presence of triethylbenzylammonium chloride.Bayer-Villinger oxidation of ketone (4) with trifluoroperacetic acid gives cyclohexyl trifluoropropionate (5). 3,3,3-trifluoropropionic acid (6) is obtained by treatment of (5) with trimethylsilyl iodide.Condensation of 2,2,2-trifluorodiazoethane (7) with ethyl glyoxylate (8) gives mainly ethyl 4,4,4-trifluoro-2-ketobutyric acid ester (9) which leads after hydrolysis to the corresponding acid (12).
- Wakselman, C.,Tordeux, M.
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- UV absorption cross sections between 230 and 350 nm and pressure dependence of the photolysis quantum yield at 308 nm of CF3CH2CHO
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Ultraviolet (UV) absorption cross sections of CF3CH 2CHO were determined between 230 and 350 nm by gas-phase UV spectroscopy. The forbidden n → π* transition was characterized as a function of temperature (269-323 K). In addition, the photochemical degradation of CF3CH2CHO was investigated at 308 nm. The possible photolysis channels are: CF3CH2 + HCO (R1a), CF3CH3 + CO (R1b), and CF3CH2CO + H (R1c). Photolysis quantum yields of CF3CH2CHO at 308 nm, Φλ=308nm, were measured as a function of pressure (25-760 Torr of synthetic air). The pressure dependence of Φ λ=308nm can be expressed as the following Stern-Volmer equation: 1/Φλ=308nm = (4.65 ± 0.56) + (1.51 ± 0.04) × 10-18 [M] ([M] in molecule cm-3). Using the absorption cross sections and the photolysis quantum yields reported here, the photolysis rate coefficient of this fluorinated aldehyde throughout the troposphere was estimated. This calculation shows that tropospheric photolysis of CF3CH2CHO is competitive with the removal initiated by OH radicals at low altitudes, but it can be the major degradation route at higher altitudes. Photodegradation products (CO, HC(O)OH, CF 3CHO, CF3CH2OH, and F2CO) were identified and also quantified by Fourier transform infrared spectroscopy. CF3CH2C(O)OH was identified as an end-product as a result of the chemistry involving CF3CH2CO radicals formed in the OH + CF3CH2CHO reaction. In the presence of an OH-scavenger (cyclohexane), CF3CH2C(O)OH was not detected, indicating that channel (R1c) is negligible. Based on a proposed mechanism, our results provide strong evidences of the significant participation of the radical-forming channel (R1a).
- Antinolo, Maria,Jimenez, Elena,Albaladejo, Jose
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- Preparation method of 3, 3, 3-trifluoropropionic acid
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The invention relates to a preparation method of 3, 3, 3-trifluoropropionic acid, and belongs to the technical field of organic fluorine chemical industry. The preparation method of the 3, 3, 3-trifluoropropionic acid comprises the following steps: reacting a Grignard reagent CF3CH2MgCl with carbon dioxide; and hydrolyzing under an acidic condition to obtain the 3, 3, 3-trifluoropropionic acid. According to the invention, the related raw materials are cheap and easy to obtain, and the preparation process is safe and convenient to operate; the whole reaction process is high in conversion rate, few in by-products, recyclable in solvent, safe and environment-friendly; and the reaction process is short, continuous feeding can be realized, and large-scale industrial co-production is easy to realize.
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Paragraph 0020-0047
(2022/03/18)
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- Novel preparation method of 3, 3, 3-trifluoropropionic acid
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The invention discloses a novel preparation method of 3, 3, 3-trifluoropropionic acid, and relates to the field of medical pesticides. 1, 1-dichloroethylene is used as a raw material to be subjected to an addition reaction with chloroformate or ester under the catalysis of iron powder to obtain trichloropropionate or salt thereof, the trichloropropionate or salt thereof is smoothly subjected to afluorination reaction under proper conditions to efficiently obtain trifluoropropionate or fluorine trifluoropropionate, and the trifluoropropionate or fluorine trifluoropropionate is hydrolyzed to obtain 3, 3, 3-trifluoropropionic acid. In conclusion, the method for preparing trifluoropropionic acid has the advantages of cheap and easily available initial raw materials, simple reaction operation,mild reaction conditions, few steps and high conversion rate, and the conversion rate of the raw material 1, 1-dichloroethylene exceeds 78%.
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Paragraph 0025; 0026; 0029; 0030; 0033-0034; 0037-0038; 0040
(2020/04/02)
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- Preparation method of 3, 3, 3-trifluoropropionic acid
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The invention discloses a preparation method of 3, 3, 3-trifluoropropionic acid. The preparation method comprises the following steps: firstly, taking 2-chloro-1-1-difluoroethylene (a) as a raw material and carrying out a carbonylation reaction between the raw material and carbon monoxide to obtain 3, 3-difluoro-2-allyl chloride (b); carrying out a fluorination reaction on 3, 3-difluoro 2-allyl chloride by using hydrogen fluoride (HF) to obtain 3, 3, 3-trifluoropropionyl fluoride (c); and finally hydrolyzing the 3, 3, 3-trifluoropropionyl fluoride to obtain trifluoropropionic acid (d). The preparation method has the advantages as follows: the raw materials are cheap and easily available; conditions are mild; conversion rate of the starting material is high; and the total yield of the three-step reactions can reach 50% or above.
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Paragraph 0036; 0039; 0040; 0044; 0045; 0049; 0050; 0054
(2020/05/02)
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- A 3, 3, 3 - three fluorine propionic acid high efficient synthesis method
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The invention discloses a 3, 3, 3 - three fluorine propionic acid preparation method, relates to pharmaceutical intermediates preparation field, specifically comprises the following steps: first preparing a walnut shells powder, and then mixed with the tetrabutyl titanate, access with water-nitrogen, reaction at certain temperature, the produced solid with the molybdate mixed sintering treatment, to obtain the catalyst, finally to 3, 3, 3 - trifluoro propionaldehyde as raw materials, in order to hydrogen peroxide as the oxidizing agent, the above mentioned catalyst under the catalysis of the reaction, to obtain the target product, 3, 3, 3 - trifluoro propionaldehyde. The method of the invention process is simple, less catalyst levels, high product yield.
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Paragraph 0021-0052
(2019/03/23)
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- (Trifluoromethyl) malonic acid ester (by machine translation)
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[Problem] pharmaceuticals (trifluoromethyl) malonic acid ester compound is important as a fluorine-containing building blocks, a method of efficiently manufacturing. [Solution] the iron compound, in the presence of hydrogen peroxide and a sulfoxide, 3 - trifluoromethyl 3 - amino or alkoxy amino -3 - -2 - propenoic acid ester iodide -3 - -2 - alkoxy trifluoromethyl-propene imine acid ester, followed by hydrolysis in the presence of acid, formula (4) (trifluoromethyl) malonic acid ester represented. (R2 , R3 Is, C1 - C4 alkyl group independently)[Drawing] no (by machine translation)
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Paragraph 0059-0061
(2017/12/01)
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- Method for producing 3, 3, 3 - [...] (by machine translation)
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PROBLEM TO BE SOLVED: To provide a simple, efficient and inexpensive method capable of manufacturing a 3,3,3-trifluoro propionyl compound useful as a pharmaceutical and agricultural synthetic intermediate in an industrial scale.SOLUTION: There is provided a method of manufacturing a compound represented by the formula [1] by reacting a compound represented by the formula [2] with a polar compound after hydrolysis with using sulfuric acid. In the formula [1], X is Cl, OH, ORor NRR, Ris a Cto Calkyl group, a Cto Chalogenated alkyl group or phenyl group, Rand Rmay be same or different and are each independently a hydrogen, a Cto Calkyl group, a Cto Chalogenated alkyl group or phenyl group and each may together form a ring structure.
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Paragraph 0057; 0058; 0074-0076
(2019/10/19)
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- Synthesis of 3,3,3-trifluoroethyl isocyanate, carbamate and ureas. Anticancer activity evaluation of N-(3,3,3-trifluoroethyl)-N′-substituted ureas
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A new method is described for producing 3,3,3-trifluoroethyl isocyanate from perfluoroisobutene (PFIB). Isocyanate was used for synthesis of carbamates and ureas. A series of trifluoroethyl-substituted ureas has been tested in the National Cancer Institute (NCI, Bethesda, USA) by the NCI-60 DTP Human Tumor Cell Line Screening Program at a single high dose (10-5 M). The moderate anticancer activity was shown against some types of cancer on the individual human cell lines for leukemia, non-small cell lung cancer and renal cancer.
- Luzina, Elena L.,Popov, Anatoliy V.
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- Monitoring biocatalytic transformations mediated by polyketide synthase enzymes in cell lysate via fluorine NMR
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The biocatalytic employment of modular polyketide synthase enzymes in cell lysate has become a viable route to preparative quantities of synthetically valuable polyketide fragments. We report the quantitative, uninvasive, and continuous monitoring of such biocatalytic reactions by observing trifluoromethyl-bearing substrates via 19F NMR spectroscopic analysis. To demonstrate the utility of this technique, we followed reactions catalyzed by a thioesterase and several ketoreductases.
- Piasecki, Shawnk.,Keatinge-Clay, Adrian T.
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supporting information; experimental part
p. 1840 - 1842
(2012/09/05)
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- PROCESS FOR PRODUCING 3,3,3-TRIFLUOROPROPIONIC ACID
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A benzyl vinyl ether represented by the following formula is hydrolyzed in the presence of a catalyst selected among Arrhenius acids and Lewis acids to obtain 3,3,3-trifluoropropionaldehyde. Subsequently, the 3,3,3-trifluoropropionaldehyde is oxidized with an oxidizing agent. Thus, 3,3,3-trifluoropropionic acid can be more advantageously produced than in conventional techniques from an inexpensive starting material.
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Page/Page column 16-20
(2008/12/07)
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- METHOD FOR PRODUCING 3,3,3-TRIFLUOROPROPIONIC ACID CHLORIDE
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There is provided a process for producing 3,3,3-trifluoropropionyl chloride, which is characterized in that 3,3,3-trifluoropropionaldehyde is chlorinated by a chlorinating agent selected from the group consisting of chlorine (Cl2), sulfuryl chloride (SO2Cl2) and organic N-chloro compounds.
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Page/Page column 14
(2009/01/24)
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- Convenient synthesis of 3,3,3-trifluoropropanoic acid by hydrolytic oxidation of 3,3,3-trifluoropropanal dimethyl acetal
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A convenient and efficient method for preparing 3,3,3-trifluoropropanoic acid (1) is reported. The starting material is 1-chloro-3,3,3-trifluoropropene (2) that can be easily transformed into 3,3,3-trifluoropropanal dimethyl acetal (4) on treatment with methanol and KOH followed by acid-catalyzed addition of methanol. Direct transformation of 4 into 1 was efficiently achieved with 30% aqueous hydrogen peroxide (4.0 equiv.) in the presence of FeCl3 (0.025 equiv.) and hydrochloric acid (0.5 equiv.).
- Komata, Takeo,Akiba, Shinya,Hosoi, Kenji,Ogura, Katsuyuki
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- Preparation of carboxylic acids
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Carboxylic acids can be prepared by reacting compounds comprising a -CCl 2 F group, a CCIF 2 group or a CCl 3 group with sulfur trioxide and sulfuric acid. The reaction is especially suitable for the preparation of 3,3,3-trifluoropropionic acid from CF 3 -CH 2 -CCl 2 F, CF 3 -CH 2 -CCIF 2 , CF 3 -CH 2 -CCl 3 or a mixture of one or two thereof as starting material. Usually, oleum is used as the source for sulfur trioxide. In a preferred embodiment, the starting material comprises CF 3 -CH 2 -CCl 2 F and/or CF 3 -CH 2 -CCIF 2 which is or are prepared in a fluorination reaction between CCl 3 -CH 2 -CCl 3 and HF. As a source for CCl 3 -CH 2 -CCl 2 , the product of the reaction between CH 2 =CCl 2 and CCl 4 is advantageously used.
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Page/Page column 4-5
(2008/06/13)
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- METHOD FOR PRODUCING 3,3,3-TRIFLUOROPROPIONIC ACID
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A trifluoromethyl group-containing enamine is produced by reacting 1-halogeno-3,3,3-trifluoropropene with a cyclic secondary amine. This trifluoromethyl group-containing enamine is hydrolyzed, thereby obtaining 3,3,3-trifluoropropionaldehyde. Then, the thus-obtained 3,3,3-trifluoropropionaldehyde is oxidized with an oxidant, thereby obtaining 3,3,3-trifluoropropionic acid.
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Page/Page column 18-19
(2008/06/13)
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- The photochemical wolff rearrangement of 3-diazo-1,1,1-trifluoro-2-oxopropane revisited
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Ethyl 2-diazo-4,4,4-trifluoroacetoacetate (1a) and 3-diazo-1,1,1-trifluoro-2-oxopropane (1b) exhibit a deviating behavior in solution photolysis (hydrogen abstraction for la; Wolff rearrangement for 1b) [(a) F. Weygand, W. Schwenke and H. J. Bestmann, Angew, Chem., 1958, 70, 506; (b) F. Weygand, H. Dworschak, K. Koch and S. Konstas, Angew. Chem., 1961, 73, 409], As shown by 13C-labelling of Ib this difference is not caused by rearrangement of the primarily formed a-oxocarbene to an isomeric a-oxocarbene presenting a hydrogen atom as a migrating substituent for the Wolff rearrangement. It is discussed that the singlet a-oxocarbene generated from 1a .rapidly undergoes spin equilibration followed by hydrogen abstraction of the triplet a-oxocarbene. In contrast, due to a larger singlet-triplet splitting in the singlet a-oxocarbene generated from 1b, the intramolecular Wolff rearrangement on the singlet surface can efficiently compete with the singlet-triplet interconversion.
- Haiss, Peter,Zeller, Klaus-Peter
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p. 2556 - 2558
(2007/10/03)
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- Preparation of novel β-trifluoromethyl vinamidinium salt and its synthetic application to trifluoromethylated heterocycles
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β-Trifluoromethylated vinamidinium salt (1) was prepared in high yield by the reaction between 3,3,3-trifluoropropanoic acid and phosphorus oxychloride in N,N,-dimethylformamide at 70°C for 1h. This salt 1 reacted readily with bifunctional nitrogen nucleophiles, such as amidine and hydrazine derivatives, in acetonitrile or dimethyl sulfoxide to furnish the corresponding trifluoromethylated azaheterocycles in good yields.
- Yamanaka, Hiroki,Takekawa, Tadashi,Morita, Kenji,Ishihara, Takashi,Gupton, John T.
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p. 1829 - 1832
(2007/10/03)
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- Novel reactions of perfluoro-2-(trifluoromethyl)-propene
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Unlike its hydrocarbon counterpart, perfluoro-2-(trifluoromethyl)propene is a highly reactive compound.It participates in both heterolytic and homolytic reactions.It readily reacts with nucleophiles and sluggishly with electrophiles.It reacts as well with common organic solvents, such as dimethylformamide, ethanol and others.In this communication we describe its reactions with trifluoromethylthiocopper, sulfur trioxide and tributyltin cyanide, the mechanism of formation of the various products and their mass spectral data.
- Munavalli, S.,Lewis, E. O.,Muller, A. J.,Rossman, D. I.,Rohrbaugh, D. K.,Ferguson, C. P.
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p. 253 - 264
(2007/10/02)
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- 2-(2,2,2-Trifluoroethylidene)-1,3-dithianes. New Intermediates for the Preparation of CF3-Containing Compounds
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A simple and efficient synthesis of 2-(2,2,2-trifluoroethylidene)-1,3-dithianes is described.The title compounds are versatile intermediates for the preparation of trifluoromethyl derivatives.
- Solberg, Jan,Benneche, Tore,Undheim, Kjell
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- ALPHA-ACYLATION AND -ALLYLATION OF β,β,β-TRIFLUOROPROPIONIC ESTERS VIA THE KETENE SILYL ACETALS
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α-Acylation of the ketene silyl acetal of methyl β,β,β-trifluoropropionate and α-allylation via the ester enolate Claisen rearrangement of the 2-alkenyl trifluoropropionates are described which provide the corresponding α-CF3 β-ketoesters and α-CF3 γ,δ-unsaturated acids, respectively.
- Yokozawa, Tsutomu,Nakai, Takeshi,Ishikawa, Nobuo
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p. 3991 - 3994
(2007/10/02)
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