- GROUP ADDITIVITY FOR THE BAND STRENGTH OF THE CF-CHROMOPHORE FOR IR-PHOTOCHEMISTRY.
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Integrated band strengths for rovibrational absorption in the frequency range of the CF-chromophore (800 to 1300 cm** minus **1) have been obtained from vapor phase IR-spectra of twelve fluoroalkanes containing one or more CF groups. It is found that the chromophore band strength is about 1. 7 (pm)**2 for each CF group with some minor variations due to neighboring substituents at the CF carbon atom. These variations can be accounted for by a simple, empirical equation. The results are discussed in relation to the chromophore principle in IR-photochemistry. The frequency distribution of the chromophore absorption for primary, secondary, and tertiary alkyl fluorides is considered. The primary CF-chromophore (R-CH//2-F) is suggested to be a particularly useful general chromophore for CO//2-laser pumping. The foundations of the group additivity for chromophore band strengths and some further applications are discussed as well.
- Quack,Thoene
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Read Online
- Synthesis, Bonding, and Reactivity of Vanadium(IV) Oxido-Fluorido Compounds with Neutral Chelate Ligands of the General Formula cis-[VIV(=O)(F)(LN-N)2]+
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Reaction of the oxidovanadium(IV)-LN-N species (LN-N is bipy = 2,2′-bipyridine or bipy-like molecules) with either BF4- or HF and/or KF results in the formation of compounds of the general formula cis-[VIV(=O)(F)(LN-N)2]+. Structural and spectroscopic (electron paramagnetic resonance) characterization shows that these compounds are in the tetravalent oxidation state containing a terminal fluorido ligand. Density functional theory calculations reveal that the VIV-F bond is mainly electrostatic, which is reinforced by reactivity studies that demonstrate the nucleophilicity of the fluoride ligand in a halogen exchange reaction and in fluorination of various organic substrates.
- Passadis, Stamatis S.,Tsiafoulis, Constantinos,Drouza, Chryssoula,Tsipis, Athanassios C.,Miras, Haralampos N.,Keramidas, Anastasios D.,Kabanos, Themistoklis A.
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Read Online
- METHOD FOR PRODUCING FLUORINATED HYDROCARBONS
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Provided is a method for industrially advantageously producing a fluorinated hydrocarbon (3). The disclosed method for producing a fluorinated hydrocarbon represented by formula (3) includes bringing into contact, in a hydrocarbon-based solvent, a secondary or tertiary ether compound represented by formula (1) below with an acid fluoride represented by formula (2) in the presence of lithium salt or sodium salt (in the formulae, R1 and R2 each represent a C1-3 alkyl, and R1 and R2 may be bonded to each other to form a ring structure; R3 represents a hydrogen atom, methyl, or ethyl; and R4 and R5 each represent methyl or ethyl).
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Paragraph 0113-0115; 0127
(2020/01/12)
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- Catalytic Formation of C(sp3)-F Bonds via Heterogeneous Photocatalysis
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Due to their chemical, physical, and biological properties, fluorinated compounds are widely employed throughout society. Yet, despite their critical importance, current methods of introducing fluorine into compounds suffer from severe drawbacks. For example, several methods are noncatalytic and employ stoichiometric equivalents of heavy metals. Existing catalytic methods, on the other hand, exhibit poor activity, generality, selectivity and/or have not been achieved by heterogeneous catalysis, despite the many advantages such an approach would provide. Here, we demonstrate how selective C(sp3)-F bond synthesis can be achieved via heterogeneous photocatalysis. Employing TiO2 as photocatalyst and Selectfluor as mild fluorine donor, effective decarboxylative fluorination of a variety of carboxylic acids can be achieved in very short reaction times. In addition to displaying the highest turnover frequencies of any reported fluorination catalyst to date (up to 1050 h-1), TiO2 also demonstrates excellent levels of durability, and the system is catalytic in the number of photons required; i.e., a photon efficiency greater than 1 is observed. These factors, coupled with the generality and mild nature of the reaction system, represent a breakthrough toward the sustainable synthesis of fluorinated compounds.
- Tarantino, Giulia,Hammond, Ceri
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p. 10321 - 10330
(2018/11/21)
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- MANUFACTURING METHOD OF FLUORINATED HYDROCARBON
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PROBLEM TO BE SOLVED: To provide a method for industrially advantageously manufacturing fluorinated hydrocarbon (3). SOLUTION: There is provided a method for manufacturing fluorinated hydrocarbon represented by the formula (3), including contacting a secondary or tertiary ether compound represented by the formula (1) and acid fluoride represented by the formula (2) in the presence of a silver salt in a hydrocarbon solvent. R1 and R2 are each independently a C1 to 3 alkyl group, R1 and R2 may bind to form a ring structure, R3 is H, a methyl group or an ethyl group, R4 and R5 are each independently a methyl group or an ethyl group. SELECTED DRAWING: None COPYRIGHT: (C)2018,JPOandINPIT
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Paragraph 0066; 0090; 0091
(2018/05/08)
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- METHOD FOR PRODUCING FLUORINATED HYDROCARBON
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PROBLEM TO BE SOLVED: To provide a method for industrially advantageously producing a fluorinated hydrocarbon. SOLUTION: The method for producing a fluorinated hydrocarbon represented by formula (3) comprises bringing a secondary or tertiary ether compound represented by formula (1) into contact with an acid fluoride represented by formula (2) in the presence of a compound having an N-X bond (X is a halogen atom selected from a chlorine atom, a bromine atom, and an iodine atom) in a halogenated hydrocarbon-based solvent. (R1 and R2 are each independently a C1-C3 alkyl group; R3 is H, a methyl group, or an ethyl group; R4 and R5 are each a methyl group or an ethyl group; and R1 and R2 may be bonded together to form a ring structure.) SELECTED DRAWING: None COPYRIGHT: (C)2018,JPOandINPIT
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Paragraph 0064; 0068; 0072
(2018/03/09)
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- Catalytic formation of C(sp3)-F bonds via decarboxylative fluorination with mechanochemically-prepared Ag2O/TiO2 heterogeneous catalysts
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Mechanochemically-prepared, Ag2O-containing solid materials, are shown to be efficient heterogeneous catalysts for the synthesis of C(sp3)-F bonds via decarboxylative fluorination. Five catalytic cycles without loss of intrinsic activity could be performed with the optimal catalyst, composed of 1 wt% Ag2O supported on TiO2 (P25), despite the challenging conditions. The catalyst is easily prepared from the corresponding oxides in 20 minutes by simple mechanical mixing methods. In addition to ease of separation and re-use, the turnover numbers obtained over the solid catalyst are over one order of magnitude higher than those obtained with the state-of-the-art homogeneous catalyst, AgNO3, under otherwise identical conditions. To the best of our knowledge, this represents the first true heterogeneous catalyst for the selective formation of C(sp3)-F bonds with electrophilic fluorine donors, representing a major breakthrough in the field of catalytic fluorination.
- Tarantino,Botti,Dimitratos,Hammond
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p. 30185 - 30190
(2017/07/11)
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- Light-promoted metal-free cross dehydrogenative couplings on ethers mediated by NFSI: Reactivity and mechanistic studies
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Cross dehydrogenative couplings on ethers occur very effectively using N-fluorobis(phenyl)sulfonimide (NFSI) as oxidizing agent under UVA irradiation in the presence of 2 mol% benzophenone. The reaction was shown to proceed first by fast radical fluorination of the α-C-H bond of ethers, followed by HF elimination to yield the highly electrophilic oxocarbenium ion as a key intermediate.
- Beniazza, Redouane,Abadie, Baptiste,Remisse, Lionel,Jardel, Damien,Lastécouères, Dominique,Vincent, Jean-Marc
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supporting information
p. 12708 - 12711
(2017/12/02)
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- METHOD FOR PRODUCING FLUORINATED HYDROCARBON
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PROBLEM TO BE SOLVED: To provide an industrially advantageous method for producing a fluorinated hydrocarbon such as 2-fluorobutane useful as etching gas for a dry etching process. SOLUTION: There is provided a method for producing a fluorinated hydrocarbon represented by formula (3) by bringing an ether compound represented by formula (1) into contact with an acid fluoride represented by formula (2) in a halogenated hydrocarbon solvent in the presence of a metal halide represented by formula (4): MX3 (M represents a metal atom; X represents a chlorine atom or a bromine atom) (R1 and R2 each independently represent an alkyl group having 1-3 carbon atoms; R1 and R2 may be bonded to form a ring structure; R3 represents H, a methyl group or an ethyl group; R4 and R5 each independently represent a methyl group or an ethyl group.) SELECTED DRAWING: None COPYRIGHT: (C)2017,JPOandINPIT
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Paragraph 0054; 0072; 0077
(2017/10/31)
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- METHOD FOR PRODUCING FLUORINATED HYDROCARBON
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The present invention is a method for producing a fluorohydrocarbon represented by a structural formula (3) comprising bringing a secondary or tertiary ether compound represented by a structural formula (1) into contact with an acid fluoride represented by a structural formula (2) in a hydrocarbon-based solvent in the presence of a boron trifluoride complex. (In structural formulae (1) to (3), each of R1 and R2 represents an alkyl group having 1 to 3 carbon atoms, R3 represents a hydrogen atom, a methyl group, or an ethyl group, and each of R4 and R5 represents a methyl group or an ethyl group, provided that R1 and R2 are optionally bonded to each other to form a ring structure.)
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Paragraph 0072
(2017/07/14)
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- The fluorinated hydrocarbon production (by machine translation)
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2 - fluorobutane industrially advantageous production method [a]. (1) the ether compound represented by the formula [a], equation (2) as shown in the di-acid, a hydrocarbon-based solvent, in the presence of boron trifluoride catalyst is carried on a polyvinylpyrrolidone, contacting, formula (3) represented by the production of fluorinated hydrocarbons. (R1 And R2 The alkyl groups are independently C1 a-3; R1 And R2 The coupling may form a ring structure; R3 Is H, a methyl group or an ethyl group; R4 Is a methyl group or an ethyl group; R5 Is a methyl group or ethyl group)[Drawing] no (by machine translation)
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Paragraph 0066
(2017/09/02)
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- REMOVAL OF LIGHT FLUOROALKANES FROM HYDROCARBON STREAMS
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The removal of fluoroalkanes from fluoroalkane-containing hydrocarbon streams, preferably C3 to C5 hydrocarbon streams. The fluoroalkane-containing hydrocarbon stream is contacted with an adsorbent containing a strong acid function, preferably a silica gel or a strong cation ion-exchange resin having sulfonic acid functionality.
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Page/Page column 5
(2012/06/16)
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- Difluoroalkylamines from high temperature vapor phase reactions of nitrogen trifluoride with alkanes, ethers and benzene
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At temperatures around 400 °C, nitrogen trifluoride (NF3) readily reacts with alkanes and benzene as well as ethers. In all cases, products were N,N-difluoroamines. This is in contrast to difluoroamination of benzylic substrates where the initial N,N-difluoroamines underwent eliminations or rearrangements and were not isolated. Cyclic and acyclic alkanes generated N,N-difluoroaminoalkanes. Benzene substituted on the ring to form N,N-difluoroaniline. Ethers reacted to generate α-N,N-difluoroamino ethers. Little direct fluorination was observed.
- Belter, Randolph K.
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scheme or table
p. 961 - 964
(2011/11/06)
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- Removal of light fluoroalkanes from hydrocarbon streams
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The removal of fluoroalkanes from fluoroalkane-containing hydrocarbon streams, preferably C3 to C5 hydrocarbon streams. The fluoroalkane-containing hydrocarbon stream is contacted with an adsorbent containing a strong acid function, preferably a silica gel or a strong cation ion-exchange resin having sulfonic acid functionality.
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Page/Page column 2
(2010/07/04)
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- 1,1,3,3,3-Pentafluoropropene secondary amine adducts new selective fluorinating agents
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Addition of secondary amine SA (dimethylamine DMA, diethylamine DEA, pyrrolidine Pyr, piperidine Pip, morpholine Mor) to pentafluoropropene PFP gives rise to generation of mixtures of two products (1-dialkylamine-1,3,3,3-tetrafluoropropene and N,N-dialkyl-1,1,3,3,3-pentafluoropropylamine) in different ratios. Those reaction mixtures, however, were found to be efficient fluorinating agents replacing hydroxyl groups in alcohols into fluorine. In general, they react with alcohols yielding corresponding fluorides, equimolar amounts of appropriate 3,3,3-trifluoropropionamide and hydrogen fluoride. Aliphatic primary alcohols including octanol and benzylic alcohol yield only alkyl fluorides. The secondary and tertiary alcohols, beside the desired fluorides, give usually considerably amount of alkenes.
- Koroniak, Henryk,Walkowiak, Justyna,Grys, Krzysztof,Rajchel, Andrzej,Alty, Adam,Du Boisson, Rick
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p. 1245 - 1251
(2008/09/20)
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- 2,2-Dihydroperfluoropentane (HFC 4310 mf) synthesis from HFP dimer
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The thermodynamic dimer of hexafluoropropene (HFP) may be used for the one pot synthesis of 2H-perfluoro-2-pentene, which is the starting compound for preparation of 2,2-dihydroperfluoropentane (HFC 4310 mf).
- Cheburkov, Yuri,Moore, George G.I.
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p. 227 - 231
(2007/10/03)
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- Catalytic fluorination by halide exchange with 16-electron ruthenium(II) complexes. X-ray structure of [Tl(μ-F)2Ru(dppe)2]PF6
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The 16-electron ruthenium(II) complexes [RuCl(dppe)2]PF6 (2; dppe = 1,2-bis(diphenylphosphino)ethane), [RuCl(chiraphos)2]PF6 (3; chiraphos = (S,S)-3,4-bis(diphenylphosphino)butane), and [RuCl(PNNP)]PF6 (4; PNNP = (1S,2S)-N,N′-bis[2-(diphenylphosphino)-benzylidene]diaminocyclohexane) catalyze the nucleophilic fluorination of activated alkyl halides with a catalyst loading as low as 1 mol %. The alkyl halides (CH3)3CX (X = Br, 5c; X = I, 5d), Ph2CHBr (6c), and PhCH(Me)Br (7c) are converted to the fluoro analogues in the presence of TlF as the fluoride source. Yields are between 31 and 83%. The chiral complex 4 converts 7c to PhCH(Me)F (7a) with 49% yield after 24 h. At 1% conversion, 7a is nonracemic (16% ee), which indicates that kinetic resolution occurs, albeit at a low level. The fluorination of 1,2-dibromo-1,2,3,4-tetrahydronaphthalene (8c) is highly regioselective and gives 1-fluoro-2-bromo-1,2,3,4-tetrahydronaphthalene (8a) in 68% yield. The difluoro-bridged thallium adduct [Tl(μ-F)2Ru(dppe)2]PF6 (9) was observed by 31P NMR during catalysis with 2 and independently prepared by reaction of 2 with TlF (2 equiv). Complex 9 was characterized by 1H, 31P, 19F, and 205Tl NMR spectroscopy, as well as by X-ray diffraction.
- Barthazy, Peter,Togni, Antonio,Mezzetti, Antonio
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p. 3472 - 3477
(2008/10/08)
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- Toward metal-mediated C-F bond formation. Synthesis and reactivity of the 16-electron fluoro complex [RuF(dppp)2]PF6 (dppp = 1,3-bis(diphenylphosphino)propane)
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The five-coordinate fluoro complex [RuF(dppp)2]PF6 (1a) has been prepared by reacting [RuCl(dppp)2]PF6 (1b) with TlF (dppp = 1,3-bis(diphenylphosphino)propane). An X-ray investigation of 1a shows a distorted trigonal bipyramidal geometry (Y-shaped). The 16-electron complex 1a reacts with a number of donors, including CO, H2, and F-. The X-ray structure of trans-[RuF(CO)(dppp)2]PF6 (2aBPh4) suggests that the π-donor ability of the fluoro ligand is only slightly higher than that of chloride. The reaction of 1a with [Me4N]F gives cis-[RuF2(dppp)2] (3), a rare difluoro complex not stabilized by π-acidic co-ligands. The Ru-F bond of 1a is hydrogenolyzed upon reaction with H2 to give [RuH(η2-H2)(dppp)2]+. The coordinatively unsaturated complex 1a reacts with activated haloalkanes R-X (X = Cl or Br) in 1:1 molar ratio to give the fluorinated organic derivative and [RuX(dppp)2]+. The halide metathesis proceeds instantaneously and quantitatively with (E)-3-bromo-1,3-diphenylpropene and chlorotriphenylmethane. Substrate conversion decreases with decreasing substitution at the halogen-bearing carbon atom.
- Barthazy,Stoop,Worle,Togni,Mezzetti
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p. 2844 - 2852
(2008/10/08)
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- Carbon-fluorine bond formation via a five-coordinate fluoro complex of ruthenium(II)
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The 16-electron, five-coordinate fluoro complex [RuF(dppp)2]PF6 (1a; dppp = propane-1,3-diylbis[diphenylphosphine] smoothly reacts with 1,3- diphenylallyl bromide (=1,1'-(3-bromoprop-1-ene-1,3-diyl)bis[benzne]) in dry CDCl3 to give 1,3-diphenylallyl fluoride and [RuBr(dppp)2]+ in nearly quantitative yield. Under similar conditions, bromide (or chloride)/fluoride exchange also occurs with chlorotriphenylmethane, bromodiphenylmethane, and tert-butyl bromide. The crystal structure of 1a is reported.
- Barthazy, Peter,Hintermann, Lukas,Stoop, Robert M.,Woerle, Michael,Mezzetti, Antonio,Togni, Antonio
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p. 2448 - 2453
(2007/10/03)
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- Evidence for Carbocation Intermediates in the TiO2-Catalyzed Photochemical Fluorination of Carboxylic Acids
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Laser flash photolysis/transient absorbance spectroscopy was used to determine the mechanism of photo-Kolbe fluorination of carboxylic acids, RCOOH --> RF, at colloidal TiO2 suspensions in acetonitrile.Transient absorption spectra of Ph3C(+), Ph3C(*), Ph2CH(*) and Ph2CH(+) were observed from the photooxidation of Ph3CCOOH and Ph2CHCOOH at TiO2 using 355-nm excitation.Transient decays, monitored in the presence and absence of fluoride ions, showed that the carbocations reacted rapidly with fluoride, but the neutral radicals did not.By varying the laser intensity, it wa s found that the photooxidation of Ph3CCOOH to Ph3C(*) at TiO2 occured via a single-photon process, while the formation of of Ph3C(+) required two photons.This finding is in agreement with the parabolic light intensity dependence of initial reaction rates in bulk photolysis experiments.Although fluoride is strongly adsorbed on the TiO2 surface in acetonitrile solution, the oxidizing power of photogenerated holes could be increased by coordinating HF to F(-), and therefore the threshold for oxidative photochemical fluorination was extented to more positive potentials.In this way less easily oxidized carboxylic acids RCOOH could be converted to RF.
- Lai, Cuiwei,Kim, Yeong Il,Wang, Chong Mou,Mallouk, Thomas E.
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p. 1393 - 1399
(2007/10/02)
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- REACTIONS OF CHLORINE MONOFLUORIDE. VI. RELATIVE RATES OF SUBSTITUTIVE FLUORINATION OF BROMINE-SUBSTITUTED ALKANES. HYDRIDE SHIFTS AND OTHER MIGRATIONS DURING FLUORINATION
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The relative rates of substitutive fluorination of bromoalkanes with various structures by chlorine monofluoride in a nonpolar medium at 20-40 deg C were investigated by the method of competing reactions.Halogen atoms vicinal with the substituted bromine greatly reduce the fluorination rate.The reactivity of the secondary bromides decreases in the order (CH3)2CHBr>>CH3CHBrCH2Cl>>CH2ClCHBrCH2Cl.The geminal halogen atoms have little effect on the rate of substitutive fluorination.The fluorination rates of the bromoalkanes CH2BrCH2Br, CH2BrCHClBr, and CH2BrCCl2Br are in ratios 10:3:1 respectively, while the fluorination rate of CH3CHClBr is much higher than that of CH2ClCH2Br.As a rule the debromination of primary bromides containing vicinal halogens (Br, Cl) is accompanied by migration of the latter and gives fluorides with iso structures.Hydride shifts take place in cases where stable tertiary or secondary carbocations are formed as a result of migration of the hydride; for example, the fluorination of CH3CHFCH2Br leads to the geminal difluoroalkane CH3CF2CH3.The mechanism of substitutive fluorination is discussed.
- Morozova, T. V.,Chuvatkin, N. N.,Panteleeva, I. Yu.,Boguslavskaya, L. S.
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p. 1255 - 1263
(2007/10/02)
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- REACTIONS OF CHLORINE MONOFLUORIDE. SUBSTITUTION OF CHLORINE ATOMS BY FLUORINE IN CHLORINE-SUBSTITUTED ALKANES AND ESTERS
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In anhydrous hydrogen fluoride under mild conditions chlorine monofluoride selectively substitutes the chlorine atoms in chlorine-substituted alkanes and esters by fluorine with the formation of high yields of the corresponding fluorides.The presence of an alkoxycarbonyl group or difluoromethylene group at the α position to the CHCl group deactivates the chlorine atom, and substitution by fluorine does not occur.In chloroalkanes, from which elimination of the chloride ion leads to sufficiently stable carbocations, substitution by fluorine can be realized in the absence of hydrogen fluoride at temperatures between -20 and -60 deg C.The fluorinating capacity of chlorine monofluoride is increased in the presence of catalytic amounts (3-5percent) of antimony pentachloride.Here the reaction is less selective than in hydrogen fluoride.In certain cases substitution is accompanied by hydride transfers.
- Chuvatkin, N. N.,Panteleeva, I. Yu.,Boguslavskaya, L. S.
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p. 821 - 827
(2007/10/02)
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- Betylates. 2. The formation and high reactivity of alkylbetylates
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Unhindered primary alkyl N,N-dimethylsulfamates (1) react with methyl fluorosulfate to give the corresponding alkyl fluorosulfates (3) and the betaine, Me3N(1+)SO3(1-) (4), evidently by way of the intermediate alkylbetylate fluorosulfate (2); with certain other alkyl esters (1) products of substitution, elimination, and rearrangement are formed.The reaction not only provides a potentially useful route to simple alkyl fluorosulfates, but serves to demonstrate the powerful nucleofugality of the betylate group.To obtain a method for predicting the reactivity of betylates, we have compared substituent parameters with rate constants in four series of nucleophilic displacement involving esters of the general structure ROSO2Z; correlation (of log k) with ?* is mediocre but a new parameter, ?15* with a "15percent resonance" contribution as defined by Swain and Lupton, gives good to excellent agreement in the four reaction series.Evidence is presented for formation of the 7-norbornyl cation via the betylate from 7-norbornyl N,N-dimethylsulfamate and methyl fluorosulfate.Comparison with what is known of the reactivities of 7-norbornyl p-toluenesulfonate and trifluoromethanesulfonate esters serves to confirm that betylates are among the most nucleofugal functions of which a derivative has been fully characterized.
- King, James Frederick,Lee, Teresa Mee-Ling
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p. 362 - 372
(2007/10/02)
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