- 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 0087; 0088
(2019/02/21)
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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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- 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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- Perfluorination of Allene Derivatives by Direct Fluorination
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Perfluoropropane was prepared from allene with elemental fluorine in the presence of sodium fluoride in 84percent yield for the first time.The reaction of allene with elemental fluorine afforded 2,2-difluoropropane in the absence of sodium fluoride.Methoxyallene and cyanoallene were perfluorinated with elemental fluorine in the presence of sodium fluoride to give heptafluoropropyl trifluoromethyl ether and heptafluoropropyl cyanide in good yields respectively.In addition, the direct fluorination of cyanoallene in the presence of cesium fluoride afforded N,N-difluorononafluorobutylamine in 95percent yield.
- Arimura, Takashi,Shibakami, Motonari,Tamura, Masanori,Kurosawa, Shigeru,Sekiya, Akira
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p. 588 - 598
(2007/10/02)
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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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