- Method for preparing perfluorinated nitrile through gas phase catalysis
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The invention discloses a method for preparing perfluorinated nitrile through gas phase catalysis. The method comprises the following steps: a, in the absence of a catalyst, enabling acyl fluoride R1COF or perfluor substituted ethylene oxide Cyclo-CF2-CR2R3-O- to perform a gas phase amination reaction with an ammonia gas or a primary amine compound, to obtain amide of which a general formula is R1CONH2 or CR2R3FCONH2, wherein general formulas of R1, R2 and R3 are CnF[2n+1], CxF[2x+1], and CyF[2y+1], wherein x and y are non-negative integer sets, x+y=n, and n is a positive integer set; and b, in the presence of the catalyst, dehydrating the amide R1CONH2, to obtain the perfluorinated nitrile R1CN. The method is short in reaction route, and the perfluor substituted ethylene oxide or the acylfluoride is easily obtained. A total yield of the perfluorinated nitrile is high, and the route is easy for continuous industrialization.
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Paragraph 0081; 0082
(2019/02/21)
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- Preparation method of perfluoronitrile
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The invention discloses a preparation method of perfluoronitrile. The preparation method comprises the following steps: a, performing a gas-phase addition reaction on perfluoroolefin R1R2C=CR3R4 and carbonyl fluoride to obtain acyl fluoride R1R2(COF)C-CFR3R4 (R1, R2, R3 and R4 have a general formula of a -CnF2n+1 group and n is a nonnegative integer set); b, aminating and dehydrating the acyl fluoride R1R2(COF)C-CFR3R4, acyl fluoride and alkali metal amide or an amine compound R-NH2 (R is lithium, sodium, potassium, rubidium, cesium or a -CmH2m+1 group and m is a nonnegative integer set) to obtain the perfluoronitrile R1R2(CN)C-CFR3R4. By the preparation method, a reaction route is short, the perfluoroolefin and the carbonyl fluoride are easy to obtain and low in price, the overall yield of the perfluoronitrile is high and the route is easy to industrialize.
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Paragraph 0067; 0068
(2018/09/08)
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- Process For Preparing Fluoroalkyl Nitriles
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The present invention relates to a process for preparing fluoroalkyl nitriles by reacting fluorinated carboxamides with halides and fluorinated carboxylic acids.
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Page/Page column 4
(2010/12/29)
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- Synthesis and antifungal activity of β mrifluoroalkyl aminovinyl ketone derivatives
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Ten β-trifluoroalkyl aminovinyl ketone derivatives were synthesized, and their inhibitory effects on several phytopathogenic fungi, an oomycete and plants were assessed. The various compounds were fungitoxic at the 10-100 μM range, with (Z)-3-amino-4,4,4-trifluoro-1-(4-chlorophenyl)but-2-en1-one exhibiting the highest inhibitory effect on most of the test pathogens. Alternarla alternata and Neurospora crassa were the most tolerant and sensitive fungi to the compounds, respectively. We propose that (Z)-3-amino-4,4,4- trifluoro-1-phenylbut-2-en-1-one is the minimal structural requirement for a β-trifluoroalkyl aminovinyl ketone fungitoxic derivative. 2009 American Chemical Society.
- Gellerman, Gary,Pariente, Natali,Zahi, Paz,Shnaiderman, Anat,Yarden, Oded
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experimental part
p. 8303 - 8307
(2010/07/15)
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- Synthesis and characterization of perfluorinated nitriles and the corresponding sodium 5-perfluoroalkyltetrazolate salts
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The high-yield syntheses of trifluoroacetonitrile (1a), pentafluoropropionitrile (1b) and heptafluorobutyronitrile (1c) under mild reaction conditions using readily available starting materials (trifluoroacetamide, pentafluoropropionamide, heptafluorobutanamide) are described. Furthermore, the reactions of the perfluoroalkyl nitriles with sodium azide in acetonitrile forming sodium 5-trifluoromethyltetrazolate (2a), sodium 5-pentafluoroethyltetrazolate (2b) and sodium 5-heptafluoropropyltetrazolate (2c) were undertaken. The 5-perfluoroalkyltetrazolate salts were characterized using vibrational (Raman and infrared) and multinuclear (13C, 14/15N, 19F) NMR spectroscopy, differential scanning calorimetry, mass spectrometry and elemental analysis. Additionally, the single crystal X-ray structure of the monohydrate of 2a was determined. Crystal data: 2a·H2O: monoclinic, C2/m, a = 18.8588(6) A?, b = 7.1857(2) A?, c = 9.3731(3) A?, β = 102.938(3)°, V = 1237.94(7) A?3, Z = 8, Dcalc = 1.911 g cm-3.
- Crawford, Margaret-J.,Klap?tke, Thomas M.,Radies, Hendrik
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experimental part
p. 1199 - 1205
(2009/04/07)
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- Aza-Wittig reaction of fluoroalkylated N-vinylic phosphazenes with carbonyl compounds. Usefulness of 2-azadienes for the preparation of fluoroalkyl pyridine derivatives
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A method for the preparation of 3-fluoroalkyl substituted 2-aza-butadienes 6 by aza-Wittig reaction of 3-fluoroalkyl-N-vinylic phosphazenes 4 and aldehydes 5 is reported. [4+2] Cycloaddition reaction of these heterodienes 6 with enamines 9 gives fluoroalkyl substituted pyridine 15, 16, 24-27 and isoquinoline 12-14, 20 derivatives.
- Palacios, Francisco,Alonso, Concepción,Rubiales, Gloria,Villegas, Maite
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p. 2779 - 2794
(2007/10/03)
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- Activated dimethyl sulfoxide dehydration of amide and its application to one-pot preparation of benzyl-type perfluoroimidates
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Various types of primary amides were treated under an activated dimethyl sulfoxide (DMSO) species, (COCl)2-DMSO and Et3N, as a dehydrating agent to obtain nitriles in excellent yield. This dehydration system was extended to a one-pot preparation of perfluoroimidates via volatile perfluoronitriles from perfluoroamides. Fifteen benzyl-type perfluoroimidates can be prepared in 70-90% yield as more stable imidates than the trichloro analogue. MPM- and DMPM-perfluoroimidates can be used to protect alcohols in place of the trichloroacetimidate with excellent chemical properties and in comparable yields.
- Nakajima, Noriyuki,Saito, Miho,Ubukata, Makoto
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p. 3561 - 3577
(2007/10/03)
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- Allyl, epoxy and glycosyl perfluoroimidates. One-pot preparation and reaction
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The one-pot preparation of allyl, epoxy and glycosyl perfluoroimidates and their reaction are described. Volatile perfluoronitriles were generated from perfluoroamides with an 'activated' dimethyl sulfoxide (DMSO) species at -78°C. Allyl, epoxy and glycosyl perfluoroimidates were prepared in 44-92% yield following in situ nucleophilic addition of alcohol and sugar derivatives to nitriles. The obtained trifluoroacetimidates were more stable than the trichloro analogue and were easily purified by SiO2 column chromatography and/or distillation. The 3,3-sigmatropic rearrangement of allylic analogues, acid-catalyzed cyclization of the epoxy analogues and glycosylation of sugar analogues were studied comparing with their corresponding trichloroacetimidates. The trifluoroacetimidates were considerably less reactive than trichloroacetimidates due to their electron-withdrawing substituents on the imidate carbon.
- Nakajima, Noriyuki,Saito, Miho,Kudo, Masabumi,Ubukata, Makoto
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p. 3579 - 3588
(2007/10/03)
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- Polyfluorinated Organic Compounds. X. Reaction of Perfluoro(2-methyl-2-pentene) with Sodium Azide
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Perfluoro(2-methyl-2-pentene) reacts with sodium azide in acetonitrile at -10°C to yield perluoro-(3-azido-2-methyl-2-pentene), which is stable only at low temperature. When the reaction is carried out in the presence of ethanol at the same temperature, stable 5-ethoxy-5-pentafluoroethyl-4,4-bis(trifluorornemyl)-4,5-dihydro-1H-1,2,3- triazole is formed. The reaction in the system acetonitrile-ethanol at 2°C yields ethyl pentafluoropropanimidate and bis(trifluoromethyl)diazomethane. Thermolysis and photolysis of perfluoro-(3-azido-2-methyl-2-pentene) in CCl4, as well as in C6H6, toluene, or pentane, results in fromation of 3-pentafluoroethyl-2,2-bis(trifluoromethyl)-2H-azirine.
- Zhuzhgov,Furin
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p. 710 - 714
(2007/10/03)
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- OXADIAZOLES WITH NF2-CONTAINING SUBSTITUENTS
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Oxalyl chloride was reacted with sodium-5-(difluoroamino)-difluoromethyltetrazolate or sodium-5-pentafluoroethyltetrazolate to form f = NF2CF2 (7)>, and with F2NCF2C(NH2)=NOH to give 2 (5) which may be dehydrated to the 1,2,4-oxadiazole (6).Both sodium salts can be reacted with perfluoroacyl acid chlorides to form 2,5-disubstituted 1,3,4-oxadiazoles, where Rf'=NF2CF2 and Rf = CF3 (8), C2F5 (9) or C3F7 (10); Rf'= C2F5 and Rf = CF3 (11) or C2F5 (12).
- John, Earnest Obed,Kirchmeier, Robert L.,Shreeve, Jean'ne M.
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p. 333 - 343
(2007/10/02)
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- Reaction of Pentafluoroethyl Radicals with Cyanogen Chloride
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The reaction of C2F5 radicals with cyanogen chloride was studied between 293 and 573 K, using perfluoroethyl iodide as the free-radical source. The main product, C2F5Cl is formed via an addition reaction or by abstraction of a chlorine atom by C2F5.The reactions involved are C2F5+ClCN->C2F5Cl+CN (2) C2F5+ClCN->/C2F5Cl+CN (4) C2F5+C2F5->C4F10 The Arrhenius plot shows pronounced curvature.The following rate constants were obtained for reactions (2) and (4) where kc is the rate constant for C2F5 combination. The results are compared with those for the reaction of CF3 with ClCN.
- Voehringer, Cecilia M. de,Staricco, Eduardo H.
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p. 3493 - 3498
(2007/10/02)
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