- Synthesis and Characterization of Bidentate (P^N)Gold(III) Fluoride Complexes: Reactivity Platforms for Reductive Elimination Studies
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A new family of cationic, bidentate (P^N)gold(III) fluoride complexes has been prepared and a detailed characterization of the gold-fluoride bond has been carried out. Our results correlate with the observed reactivity of the fluoro ligand, which undergoes facile exchange with both cyano and acetylene nucleophiles. The resulting (P^N)arylgold(III)C(sp) complexes have enabled the first study of reductive elimination on (P^N)gold(III) systems, which demonstrated that C(sp2)?C(sp) bond formation occurs at higher rates than those reported for analogous phosphine-based monodentate systems.
- Genoux, Alexandre,Biedrzycki, Micha?,Merino, Estíbaliz,Rivera-Chao, Eva,Linden, Anthony,Nevado, Cristina
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supporting information
p. 4164 - 4168
(2020/12/23)
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- Preparation method of fluorine-containing aryl compound
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The invention relates to the field of organic synthesis, and especially relates to a preparation method of a fluorine-containing aryl compound. The invention provides a preparation method of a compound as shown in a formula 1. The preparation method comprises the following steps: fluorination reaction: reacting a compound as shown in a formula 2 with alkali metal fluoride in the presence of a phase transfer catalyst to prepare the compound as shown in the formula 1. According to the preparation method of the fluorine-containing aryl compound provided by the invention, a reaction system does not contain a solvent, the boiling point of the phase transfer catalyst is relatively high, solvent interference is avoided during rectification or short steaming after the reaction is finished, the distillation yield is high, and the product purity is good.
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Paragraph 0143-0150
(2021/06/12)
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- Mechanistic Insights into C(sp2)?C(sp)N Reductive Elimination from Gold(III) Cyanide Complexes
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A new family of phosphine-ligated dicyanoarylgold(III) complexes has been prepared and their reactivity towards reductive elimination has been studied in detail. Both, a highly positive entropy of activation and a primary 12/13C KIE suggest a late concerted transition state while Hammett analysis and DFT calculations indicate that the process is asynchronous. As a result, a distinct mechanism involving an asynchronous concerted reductive elimination for the overall C(sp2)?C(sp)N bond forming reaction is characterized herein, for the first time, complementing previous studies reported for C(sp3)?C(sp3), C(sp2)?C(sp2), and C(sp3)?C(sp2) bond formation processes taking place on gold(III) species.
- Genoux, Alexandre,González, Jorge A.,Merino, Estíbaliz,Nevado, Cristina
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p. 17881 - 17886
(2020/08/19)
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- Method for preparing polyfluorobenzonitrile through catalytic fluorination of polychlorobenzonitrile
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The invention discloses a method for preparing polyfluorobenzonitrile through catalytic fluorination of polychlorobenzonitrile, and belongs to the field of preparation of fine chemical industry intermediates. The preparation method comprises the following steps: carrying out a heating activation reaction on a fluoride salt, an organic solvent and electron-withdrawing substituted phenylborate; andadding polychlorobenzonitrile, heating to 80-120 DEG C, rectifying while reacting, then supplementing polychlorobenzonitrile and potassium fluoride, and rectifying while reacting to obtain polyfluorobenzonitrile. According to the invention, the reaction system is high in catalytic activity, the technical problems of low conversion rate/medium selectivity and the like of the single nitrile compounds with low activity during fluoridation reactions are solved, the mode simultaneously performing reacting and product distilling in the reaction process promotes the continuous forward proceeding of the reaction so as to improve the reaction yield, and the method is suitable for industrial production.
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- Preparation method of pentafluorobenzonitrile
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The invention discloses a preparation method of pentafluorobenzonitrile. The method comprises the following steps: (1) introducing oxygen gas and ammonia gas into a mixed system of 2,6-dichloro-3-fluoroacetophenone, copper salt, a phase transfer catalyst and a solvent A to perform reaction to obtain 2,6-dichloro-3-fluorobenzonitrile; (2) perchlorinating the 2,6-dichloro-3-fluorobenzonitrile under the action of a catalyst to obtain 2,3,4,6-tetrachloro-5- fluorobenzonitrile; (3) adding the 2,3,4,6-tetrachloro-5-fluorobenzonitrile, KF and the phase transfer catalyst into a solvent B, and performing fluoridation to obtain the pentafluorobenzonitrile. The 2,6-dichloro-3-fluoroacetophenone used in the preparation method is a by-product in producing 2,4-dichloro-5-fluoroacetophenone, and the total yield of a single cycle can reach 83%; the raw materials are cheap and easy to obtain, the cost is reduced, and the environment is protected; and the synthetic process is simple, the operation is convenient, the yield is relatively high, the purity is good, and the pentafluorobenzonitrile is suitable for industrial production.
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Paragraph 0042; 0043; 0044; 0045; 0046; 0047; 0048; 0049
(2017/07/19)
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- Selective one-pot synthesis of aminopolyhalobenzonitriles from polyhalobenzotrichlorides in anhydrous ammonia
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Polyhalogenated benzotrichlorides (pentafluoro-, chlorotetrafluoro-, chlorotrifluoro-, and tetrafluorobenzotrichlorides) undergo one-pot ammonolysis?+?aminodefluorination by the action of anhydrous ammonia to form mono- and diamino derivatives of polyhalobenzonitriles. For the substrates comprising halogen at the para-position, the ammonolysis of the CCl3 group and the first aminodefluorination occur simultaneously in the temperature range from ?33 to 5?°C. The temperature of introducing the second NH2 group is higher by 60–100?°C, whereby conditions were found for the selective synthesis of mono- and diaminopolyhalobenzonitriles. The use of anhydrous ammonia as a reagent and a solvent minimizes side reactions and simplifies an isolation of the high purity products.
- Vaganova, Tamara A.,Rodionov, Vladimir I.,Chuikov, Igor P.,Chochrina, Ekaterina A.,Malykhin, Evgenij V.
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- Method for preparing 2,3,4,5,6-pentafluorophenol
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The invention discloses a method for preparing 2,3,4,5,6-pentafluorophenol. The method comprises the following step of in water, performing an oxidation reaction on 2,3,4,5,6-pentafluoro phenylboronic acid as shown in the formula (VI) and hydrogen peroxide, thereby obtaining 2,3,4,5,6-pentafluorophenol as shown in the formula (VII). According to the method, an oxidation reaction is implemented in the water, so that the method is low in cost, and environmental-friendly; and besides, the method is high in reaction yield and purity and relatively applicable to industrial production.
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Paragraph 0078; 0079
(2017/08/29)
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- Fluorobenzonitrile compound preparation method
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The present invention provides a fluorobenzonitrile compound preparation method, fluorobenzonitrile compounds are as shown in the general formula (I), an objective product can be prepared from a general-formula-(II)-shown chlorobenzonitrile compound as a raw material by reacting with an anhydrous fluoride in the presence of an inert gas under high temperature high pressure reaction conditions and flashing a reaction product, wherein the objective product itself is used as a solvent. Due to use of the objective product itself as the solvent, a main component of the fluorine exchange reaction product only comprises the objective product, due to use of an inert gas pressurization method to improve the fluorine exchange reaction and product separation conditions, the product is separated and purified in the flashing manner, the reaction residual heat is rationally used, and the whole process is simple and feasible. The method is readily available in raw materials, simple in process, energy-saving, consumption-reducing, and more suitable for industrial scale production.
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Paragraph 0082; 0083; 0084
(2016/12/01)
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- Pentafluorobenzonitrile production method
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The present invention discloses a pentafluorobenzonitrile production method which belongs to the field of fine chemical production, pentafluorobenzonitrile is prepared from the raw materials of pentachlorophenylformonitrile, anhydrous potassium fluoride, benzonitrile and polyethylene glycol in the ratio of 1.0-1.1: 5.0-5.2: 23-25: 0.2-0.3 by fluorination process, and key points of the production method are as follows: 1, selection of the raw material ratio; 2, selection of appropriate temperature, to be more specific, the temperature is as low as possible under possible conditions, and when a better effect cannot be achieved by reduction of the temperature, the reaction temperature is improved to obtain a higher yield; and 3, selection of reaction time, to be more specific, by the selection of the reaction time, the reaction is more full to obtain a highest yield; the pentafluorobenzonitrile produced according to the formula and the method has the advantages of simple production process, low production cost, and no pollution, the pentafluorobenzonitrile yield can reach 78%, the content can reach 95%, and the product is an important medicine and pesticide intermediate.
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Paragraph 0012
(2016/10/10)
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- Palladium(II) complexes with a phosphino-oxime ligand: Synthesis, structure and applications to the catalytic rearrangement and dehydration of aldoximes
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The treatment of [PdCl2(COD)] (COD = 1,5-cyclooctadiene) with 1 and 2 equivalents of 2-(diphenylphosphino)benzaldehyde oxime in dichloromethane at room temperature led to the selective formation of [PdCl2{κ2-(P,N)-2-Ph2PC6H4CHNOH}] (1) and [Pd{κ2-(P,N)-2-Ph2PC6H4CHNOH}2][Cl]2 (2), respectively, which represent the first examples of Pd(II) complexes containing a phosphino-oxime ligand. These compounds, whose structures were fully confirmed by X-ray diffraction methods, were active in the catalytic rearrangement of aldoximes. In particular, using 5 mol% complex 1, a large variety of aldoximes could be cleanly converted into the corresponding primary amides at 100 °C, employing water as solvent and without the assistance of any cocatalyst. Palladium nanoparticles are the active species in the rearrangement process. In addition, when the same reactions were performed employing acetonitrile as solvent, selective dehydration of the aldoximes to form the respective nitriles was observed. For comparative purposes, the catalytic behaviour of an oxime-derived palladacyclic complex has also been briefly evaluated.
- Menéndez-Rodríguez, Lucía,Tomás-Mendivil, Eder,Francos, Javier,Nájera, Carmen,Crochet, Pascale,Cadierno, Victorio
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p. 3754 - 3761
(2015/07/01)
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- Interaction of the electrophilic bis(pentafluorophenyl)iodonium cation [(C6F5)2I]+ with the ambident pseudohalogenide anions [SCN]- and [CN]-
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The iodonium pseudohalide compounds, [(C6F5) 2I][X] (X = SCN and CN) were synthesized by means of fluoride substitution in [(C6F5)2I][F] with the Lewis acidic reagents (CH3)3Si-NCS and (CH3) 3Si-CN. The isolated iodonium pseudohalides are intrinsically unstable solids. Decomposition resulted in equimolar amounts of C 6F5I and C6F5SCN or C 6F5I and C6F5CN, respectively. In case of [(C6F5)2I][SCN] single crystals could be grown from CH2Cl2. The crystal structure revealed a dimer with an eight membered ring formed by two ambident anions bridging the iodine atoms of two cations by N and S coordination. The favored dimerization of [(C6F5)2I][SCN] and [(C6F 5)2I][CN] in the gas phase is supported by ab initio computations.
- Hirschberg, Markus E.,Barthen, Peter,Frohn, Hermann-Josef,Bl?ser, Dieter,Tobey, Briac,Jansen, Georg
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- Reactions of a cyclopentadienyl-amidinate titanium benzimidamido complex
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We report the first reactivity study of a transition-metal benzimidamido complex, namely Cp Ti{PhC(NiPr)2}{NC(ArF 5NOtBu} (5, ArF5= C6F5). Reaction with CO2 and tBuNCO gave the cycloaddition products CpTi{PhC(NiPr)2}{OC(O)N(C{ArF5}NO tBu)} and CpTi{PhC(NiPr)2}{OC(N tBu)N(C{ArF5}NOtBu)} (10), respectively, whereas with CS2 slow extrusion of ArF5CN from 5 occurred to ultimately form CpTi{PhC(NiPr)2}{SC(S)N(O tBu)}. Reaction of 5 with ArC(O)H (Ar = Ph, 4-C6H 4Me, 4-C6H4tBu, 4-C 6H4OMe, 4-C6H4NMe2, 4-C6H4CF3) also gave the isolable metallacyclic complexes CpTi{PhC(NiPr)2}{N(C{ArF5}NO tBu)C(Ar)(H)O} (13) via reversible [2 + 2] cycloaddition reactions. In contrast, reaction with HC(O)NMe2 formed Me 2N{NC(ArF5)NOtBu}H (16) within 1 h at room temperature. Upon heating, 10 and 13 also underwent retrocyclization, forming the organic products tBuNCNC(ArF5)NOtBu and ArC{NC(ArF5)NOtBu}H (14), respectively. Selected examples of 14 and 16 were studied by DFT and UV-visible spectroscopy. Addition of isonitriles tBuNC and XylNC (Xyl = 2,6-C6H 3Me2) to CpTi{PhC(NiPr)2}{NC(Ar) NOtBu} (Ar = ArF5 (5), 2,6-C6H 3F2 (ArF2)) afforded the σ adducts CpTi{PhC(NiPr)2}{NC(Ar)NOtBu}(CNR) (Ar = ArF5, R = tBu, Xyl (19); Ar = ArF2, R = Xyl). Subsequently, 19 formed CpTi{PhC(NiPr)2}{NC(NO tBu)C6F4N(Xyl)C}(F) (20) via C-F bond activation. Reaction of 5 with 2 equiv of B(ArF5)3 gave CpTi{PhC(NiPr)2}{ON(B{ArF5}3) C(ArF5)N(H)(B{ArF5}3)} with elimination of 2-methylpropene.
- Groom, Laura R.,Russell, Adam F.,Schwarz, Andrew D.,Mountford, Philip
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p. 1002 - 1019
(2014/03/21)
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- Ruthenium-catalyzed one-pot synthesis of primary amides from aldehydes in water
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The readily available arene-ruthenium(ii) complex [RuCl2(η 6-C6Me6){P(NMe2)3}] (5 mol%) proved to be an efficient catalyst for the direct synthesis of primary amides from aldehydes and hydroxylamine hydrochloride (NH2OH· HCl) in water at 100 °C. The process, which requires the presence of NaHCO3 to catch the HCl released during the formation of the key aldoxime intermediates, was operative with both aromatic, heteroaromatic, α,β-unsaturated and aliphatic aldehydes, and tolerated several functional groups. A greener approach using commercially available NH 2OH solution (50 wt.% in water) is also presented.
- Garcia-Alvarez, Rocio,Diaz-Alvarez, Alba E.,Crochet, Pascale,Cadierno, Victorio
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p. 5889 - 5894
(2013/05/09)
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- METHOD FOR PRODUCING AROMATIC FLUOROCOMPOUND
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PROBLEM TO BE SOLVED: To provide a method for producing an aromatic fluorocompound, by which an corresponding aromatic fluorocompound (for example, pentafluorobenzonitrile) can be produced in a high yield by the halogen exchange reaction of an aromatic halogen compound (for example, pentachlorobenzonitrile) with a fluorinating agent (for example, potassium fluoride). SOLUTION: This method for producing the aromatic fluorocompound is characterized by supplying the aromatic halogen compound of raw material as particles having an average particle diameter of 20 to 200μm.
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Page/Page column 8-9
(2008/06/13)
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- Method for production of organic fluorine compound
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A method for the production of an aromatic fluorine compound is provided which is capable of preventing the occurrence of benzoic acid fluorides during the course of a halogenation exchange reaction or allowing removal of the benzoic acid fluorides formed at all. A method for the production of an organic fluorine compound is disclosed which comprises preventing the occurrence of acid fluorides of an aromatic compound during the production of the organic fluorine compound by the reaction of an organic chlorine or bromine compound with a fluorinating agent in benzonitrile as a solvent or allowing removal of the acid fluorides formed.
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Page column 14
(2008/06/13)
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- Photolytic and radical induced decompositions of O-alkyl aldoxime ethers
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Direct photolytic radical induced homolyses of O-alkyl arylaldoxime ethers (ArCH=NOR) were studied by EPR spectroscopy and by end product analyses. Initiating radicals (X·), including t-BuO·, t-BuS· , alkyl and Me3Sn·, added rapidly to the C=N double bond to give adduct oxyaminyl radicals (ArCHXN·OR) that could be observed and characterised by EPR spectroscopy. For O-alkyl arylaldoxime ethers containing H-atoms attached to the carbon adjacent to the ether oxygen (OR = OCHR12), t-BuO· radicals also abstracted this hydrogen to yield oxyalky radicals that underwent rapid β-scission to afford iminyl radicals (ArCHN·) and an aldehyde or ketone (R12CO). judged by the relative importance of ROH and ArCN amongst the products, abstraction of the iminyl hydrogen atom also took place to yield oximidoyl radicals (ArC·=NOR), although this could not be confirmed by EPR spectroscopic observation of these radicals. Thus, homolysis induced by t-BuO· radicals took place comparatively unselectively. Addition of the t-BuO· radical to the C=N double bond of oxime ethers was very fast, the rate constant being comparable to that for addition of the same radical to nitrones. Direct and photosensitised UV photolysis of O-alkyl arylaldoxime ethers gave alkoxyl and aryliminyl radicals in very low yields. Although traces of 2-methyl-tetrahydrofuran were detected from cyclisation of the pent-4-enyloxyl radical generated by direct photolysis of O-pent-4-enyl benzaldoxime, yields were too low for preparative purposes.
- McCarroll, Andrew J.,Walton, John C.
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p. 1868 - 1875
(2007/10/03)
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- Exploitation of aldoxime esters as radical precursors in preparative and EPR spectroscopic roles
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Photolyses of aldoxime esters, containing a considerable range of alkyl groups, lead to cleavage of their N-O bonds and formation of aryliminyl and alkyl radicals. The process was found to be favoured by 4-methoxyacetophenone as a photosensitiser and by methoxy substituents in the aryl rings. 4-Nitro- and pentafluoro-substitutions of the aryl rings were, on the other hand, deleterious. The intermediate iminyl radicals, together with primary, secondary and tertiary alkyl radicals were characterised by 9 GHz EPR spectroscopy. Cyclopropyl, CF3, and CCl3 radicals were probably also formed, but were too reactive for direct EPR spectroscopic detection. Photosensitised reaction of benzophenone oxime O-nonanoyl ester produced the diphenylmethaniminoxyl, as well as the expected n-octyl and iminyl radicals. This indicated that O-C bond scission accompanied O-N scission for this ketoxime ester. At higher temperatures the C-centred radicals added to the starting oxime esters to produce alkoxyaminyl radicals that were also spectroscopically detected in some cases. No evidence for abstraction of the iminyl hydrogen by tertbutoxyl radicals was obtained. Instead, the t-BuO radicals added to the C=N double bonds of the oxime esters. Similarly, chlorine abstraction from alkylbenzohydroximoyl chlorides by trimethyltin radicals did not take place. Preparative scale experiments with oxime esters containing suitably unsaturated alkyl groups showed that good yields of cyclised products could be obtained in the presence of the photosensitiser. This process constitutes a general method by which carboxylic acids or acid chlorides can be converted into alkyl radicals and hence to cyclised derivatives.
- McCarroll, Andrew J.,Walton, John C.
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p. 2399 - 2409
(2007/10/03)
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- Aromatic radical-anions. XII. A cyclic amperometric and ESR study of the transformations of polyfluorinated benzonitrile radical-anions
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Cyclic voltamperometry and ESR spectrometry were used to study the chemical transformations of radical-anions of benzonitrile derivatives containing from two to five fluorine atoms.Two types of transformations were found to be characteristic for such species, namely, the elimination of a fluoride anion and subsequent formation of defluorination products and dimerization with the subsequent formation of fluorinated derivatives of 4,4'-dicyanodiphenyl.The facility of these processes depends significantly on the number and arrangement of the fluorine atoms in the benzene ring.The relationship between the electronic structure and reactivity of fluorinated benzonitrile radical-anions was examined.
- Efremova, N. V.,Starichenko, V. F.,Shteingarts, V. D.
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- Entropy Changes and Electron Affinities from Gas-Phase Electron-Transfer Equilibria: A(-) + B = A + B(-)
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By measuring the electron-transfer equilibria 1, A(-) + B = A + B(-), at 150 deg C with a pulsed electron high-pressure mass spectrometer we determined the ΔGo1 values involving 12 new compounds.Measurements of the temperature dependence of K1 for 21 reactions involving some of the new compounds and many compounds whose ΔGo1 had been determined previously led, via van't Hoff plots, to ΔHo1 and ΔSo1 values.These were interconnecting such that ΔHo and ΔSo continuous scales (ladders) were obtained.These were anchored to SO2 whose electron affinity is accurately known.Available geometries and vibrational frequencies for SO2 and SO2(-) permit the evaluation of So(SO2(-)) - So(SO2).Through the ΔSo scale the So(B(-)) - So(B) for the other compounds B could be obtained also.Certain regularities in the So(B(-)) - So(B) data permitted entropy estimates to be made also for compounds for which no van't Hoff plots were made.In this manner a table of ΔHo, ΔSo, and ΔGo data for the electron capture e + B = B(-) was obtained, which contains some 50 compounds B.Most of the compounds are substituted benzenes, quinones, conjugated acid anhydrides, and perfluorinated organics.
- Chowdhury, Swapan,Heinis, Thomas,Grimsrud, Eric P.,Kebarle, Paul
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p. 2747 - 2752
(2007/10/02)
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- REACTION DES ORGANOMAGNESIENS FLUORES AVEC LES CYANATES. PREPARATION DE NITRILES PERFLUORES.
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The condensation of fluorinated Grinard reagents with phenyl cyanate produces perfluorinated nitriles.The isolation of an ester in the case of ethyl cyanate shows the existence of an imidic intermediate.
- Thoai, N.,Rubinstein, M.,Wakselman, C.
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p. 271 - 276
(2007/10/02)
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- Fluorination with Complex Metal Fluorides. Part 5. Fluorination of Nitriles over Caesium Tetrafluorocobaltate(III)
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Benzonitrile and the isomers of benzenedicarbonitrile (phthalo-, isophthalo-, and terephthalo-nitrile) have been fluorinated over caesium tetrafluorocobaltate(III) at elevated temperatures to give a mixtures containing undecafluorocyclohexanecarbonitrile.In addition the dinitriles gave decreasing yields (1,4- > 1,3- > 1,2-) of the corresponding cyclohexanedircarbonitriles.Some reactions (addition, defluorination, hydrolysis, and reduction) of undecafluorocyclohexanecarbonitrile are described.
- Phull, Gurjeet S.,Plevey, Raymond G.,Rendell, Richard W.,Tatlow, John Colin
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p. 1507 - 1511
(2007/10/02)
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