- Rearrangement in a Tripodal Nitroxide Ligand to Modulate the Reactivity of a Ti-F Bond
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The tripodal nitroxide ligand [(2-tBuNO)C6H4CH2)3N]3- (TriNOx3-) binds the Ti(IV) cation and prevents inner-sphere coordination of chloride in the complex [Ti(TriNOx)]Cl (1). The ligand undergoes an η2-NO to κ1-O rearrangement to enable a fluoride ion to bind in the related complex Ti(TriNOx)F (2). Computational and reactivity studies demonstrated that the ligand rearrangement contributed to the enthalpy change in the transfer of a fluoride anion.
- Boreen, Michael A.,Bogart, Justin A.,Carroll, Patrick J.,Schelter, Eric J.
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- C-F Bond Activation of P(C6F5)3 by Ruthenium Dihydride Complexes: Isolation and Reactivity of the missing Ru(PPh3)3H(halide) Complex, Ru(PPh3)3HF
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The major product of the reaction between Ru(IMe4)2(PPh3)2H2 (1; IMe4 = 1,3,4,5-tetramethylimidazol-2-ylidene) and P(C6F5)3 (PCF) is the five-coordinate complex Ru(IMe4)2(PF2{C6F5})(C6F5)H (2), which is formed via a complex series of C-F/P-C bond cleavage and P-F bond formation steps. In contrast, hydrodefluorination of all six ortho C-F bonds in PCF occurs with Ru(PPh3)4H2 to afford Ru(PPh3)3HF (3). NaBArF4 abstracted the fluoride ligand in 3 to give [Ru({η6-C6H5}PPh2)(PPh3)2H][BArF4], while B2pin2 reacted with 3 in C6D6 to yield a mixture of [Ru({η6-C6D6)(PPh3)2H]+ and Ru(PPh3)4H2. The treatment of 3 with HBpin (5 equiv) and HSiR3 (R = Et, Ph; 2 equiv) afforded Ru(PPh3)3(σ-HBpin)H2 and Ru(PPh3)3(SiR3)3H3, respectively. No stable substitution products were generated when 3 was reacted with Me3SiX (X = CF3, C6F5).
- Cybulski, Mateusz K.,Davies, Caroline J. E.,Lowe, John P.,Mahon, Mary F.,Whittlesey, Michael K.
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- A Facile Preparation of Rubidium and Caesium Selenocarboxylates
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Treatment of O-trimethylsilyl selenocarboxylates with rubidium and caesium fluorides affords rubidium and ceasium selenocarboxylates in good yields.
- Kawahara, Yasuyuki,Kato, Shinzi,Kanda, Takahiro,Murai, Toshiaki,Ishihara, Hideharu
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- Synthesis and characterization of (2,6-difluorophenyl)xenone(II) and bis(2,6-difluorophenyl)iodine(III) trifluoromethanesulfonates
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The reactions of bis (2,6-difluorophenyl)iodine(III) and 2,6-difluorophenylxenon(II) tetrafluoroborates with trimethylsilyl trifluoromethanesulfonate yield the corresponding bis (2,6-difluorophenyl)iodine(III) and (2,6-difluorophenyl)xenon(II) trifluoromethanesolfonates.The products were identified by NMR and vibrational spectroscopy as well as by mass spectrometry.The cation peak of an organoxenon compound has been detected for the first time by FAB mass spectrometry. - Keywords: Synthesis: (2,6-Difluorophenyl)xenon(II) trifluoromethanesulfonate; Bis(2,6-difluorophenyl)iodine(III) trifluoromethanesulfonate; NMR spectroscopy; FAB mass spectrometry
- Naumann, Dieter,Gnann, Robert,Padelidakis, Vasilios,Tyrra, Wieland
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- A Convenient Synthesis of Trimethylsilyl Fluoride
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Trimethylsilyl fluoride 1 is conveniently prepared by the reaction of trimethylsilyl trifluoromethanesulfonate with potassium fluoride in dimethylformamide containing 18-crown-6 ether.
- Della, Ernest W.,Tsanaktsidis, John
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- ON THE NON-EXISTENCE OF TRIMETHYLSILYL TETRAFLUOROBORATE IN ACETONE AND ACETONITRILE : THE GENERATION OF BORON TRIFLUORIDE IN WEAKLY COORDINATING SOLVENTS
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The recently proposed preparation of trimethylsilyl tetrafluoroborate actually gives trimethylfluorosilane and boron trifluoride coordinated to acetone or acetonitrile.
- Bassindale, Alan R.,Stout, Tim
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- Infrared Laser Photodetachment of Electrons from Vibrationally Excited Allyl Anions
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Infrared laser photodetachment of allyl anions has been investigated using the techniques of ion cyclotron resonance (ICR) spectroscopy.Facile detachment of vibrationally excited anions occurs with a phenomenologically defined cross section, ?* = (6.5 +/- 2) x 1E-20 cm2 at 945 cm-1, using a low-power CW CO2 laser.The detachment yield decreases with increasing photon energy in the range 900-1100 cm-1.Photodetachment from vibrationally relaxed anions also occurs but whit a much lower cross section, ? = (6.3 +/- 3) x 1E-23 cm2.When fluoride ion reacts with allyltrimethylsilane, about 30percent of the nascent allyl anions are vibrationally excited.The predominant relaxation mechanism below 1E-6 torr is radiative emission with a measured rate constant of 53 +/- 10 s-1.
- Wight, Charles A.,Beauchamp, J. L.
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- BEITRAEGE ZUR CHEMIE DES IODPENTAFLUORIDS TEIL II. IOD(V)-VERBINDUNGEN MIT α,ω-DIFUNKTIONELLEN ALKOHOLATEN
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Nucleophilic subsitution reactions if iodine pentaflurode with a series of homologous bifunctional alcoholates -(CH2)nO- (n=2,3,4,5,6,12), a geminal dialcoholate CCl3CH(O-)2 and a trifunctional alcoholate CH3C(CH2O-)3 protected by (CH3)3Si - groups are reported.Systems with short CH2 - chains (nX (X = SiMe3, IF4) which rearrange to mononuclear chelates IF3 of high stability.Dialcoholates with long CH2-chains (n>4) behave as bridging ligands forming stable multinuclear compounds IF4IF4 and (IF3)m (m>2). 1,4-Butanediolate is on the border line of the two systems.Products with greater subsitution IF2 (n=2,3) and IF2(OCH2)3CCH3 are also characterized.The dependence of 19F-NMR-shifts on the nature and arrangement of ligands is discussed.
- Frohn, Hermann Josef,Pahlmann, Wolgang
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- (CF3)2Cd*D UND (CF3)2Zn*D: NEUE REAGENZIEN FUER DIFLUORCARBEN-REAKTIONEN
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During the thermal decomposition of (CF3)2Cd and (CF3)2Zn complexes primarily difluorocarbene is eliminated.The formation of CF2 is unambiguously proved by matrix i.r. spectroscopy.Both (CF3)2Cd*D and (CF3)2Zn*D are excellent CF2 sources, which can easily be prepared and handled, and which undergo CF2 reactions even at low temperature.CF2 insertion was found during the reaction of (CF3)2Te with (CH3)2Cd via the intermediate formation of a CF3Cd compound to form CH3TeCF2CH3. (CF3)2Cd*glyme reacts with (CH3)3Si(OCOCF3) to CF3Cd(OCOCF3)*glyme; during this reaction CF2 is also eliminated.
- Lange, Horst,Naumann, Dieter
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- Synthesis of [1-14C]-2,2-difluoroethene from [14C]-formaldehyde
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[1-14C]-2,2-Difluoroethene was synthesized from [14C]-formaldehyde using a modification of the Wadsworth-Emmons reaction, via formation of the intermediate (EtO)2P(O)CF214CH2OSiMe3. This highly volatile product was collected in a liquid nitrogen trap at a purity of >97% and specific activity of 0.2 mCi/mmol, with yields of 10-15%.
- Ruzicka,Qiu,Baker,Burton
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- Indium(III) promoted oxidative P-P coupling of silylphosphines
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The reaction of indium(III) salts with Ph2PSiMe3 and PhP(SiMe3)2 gives rise to a one- and two-electron reductive P-P coupling respectively, with the formation of new P-P bonds resulting in the preparation of (Ph2P)2 and the cyclicoligophosphane compounds (PhP)4 and (PhP)6.
- Cartlidge, Ashleigh J.,Matthews, Peter D.
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supporting information
(2022/01/28)
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- A NEW METHOD OF 18F LABELLING AND INTERMEDIATE SALTS
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Disclosed herein is a salt of formula I: where R1, X, n, R, R1, Y, m, p, q, Z and o are as defined herein. Also disclosed herein are methods of using said salts in chemical synthesis, such as to prepare compounds isotopically enriched in 18F for use in PET imaging, as well as methods to make the compounds of formula I.
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(2021/06/26)
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- Direct amidation of acid fluorides using germanium amides
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Amide functional groups are an essential linkage that are found in peptides, proteins, and pharmaceuticals and new methods are constantly being sought for their formation. Here, a new method for their preparation is presented where germanium amides Ph3GeNR2convert acid fluorides directly to amides. These germanium amides serve to abstract the fluorine atom of the acid fluoride and transfer their amide group -NR2to the carbonyl carbon, and so function as amidation reagents.
- Hayatifar, Ardalan,Elifritz, Emily A.,Bloom, Molly B.,Pixley, Kaitlyn M.,Fennell, Christopher J.,Weinert, Charles S.
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supporting information
p. 4490 - 4493
(2021/04/12)
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- Difluorocarbene Generation from TMSCF3: Kinetics and Mechanism of NaI-Mediated and Si-Induced Anionic Chain Reactions
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The mechanism of CF2 transfer from TMSCF3 (1), mediated by TBAT (2-12 mol %) or by NaI (5-20 mol %), has been investigated by in situ/stopped-flow 19F NMR spectroscopic analysis of the kinetics of alkene difluorocyclopropanation and competing TFE/c-C3F6/homologous perfluoroanion generation, 13C/2H KIEs, LFERs, CF2 transfer efficiency and selectivity, the effect of inhibitors, and density functional theory (DFT) calculations. The reactions evolve with profoundly different kinetics, undergoing autoinhibition (TBAT) or quasi-stochastic autoacceleration (NaI) and cogenerating perfluoroalkene side products. An overarching mechanism involving direct and indirect fluoride transfer from a CF3 anionoid to TMSCF3 (1) has been elucidated. It allows rationalization of why the NaI-mediated process is more effective for less-reactive alkenes and alkynes, why a large excess of TMSCF3 (1) is required in all cases, and why slow-addition protocols can be of benefit. Issues relating to exothermicity, toxicity, and scale-up are also noted.
- García-Domínguez, Andrés,West, Thomas H.,Primozic, Johann J.,Grant, Katie M.,Johnston, Craig P.,Cumming, Grant G.,Leach, Andrew G.,Lloyd-Jones, Guy C.
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supporting information
p. 14649 - 14663
(2020/10/13)
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- Frustrated Lewis-Pair-Meditated Selective Single Fluoride Substitution in Trifluoromethyl Groups
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Single fluoride substitution in trifluoromethylarenes is an ongoing synthetic challenge that often leads to "over-reaction", where multiple fluorides are replaced. Development of this reaction would allow simple access to a vast range of difluoromethyl derivatives of current interest to pharmaceutical, agrochemistry, and materials sciences. Using a catalytic frustrated Lewis pair approach, we have developed a generic protocol that allows a single substitution of one fluoride in trifluoromethyl groups with neutral phosphine and pyridine bases. The resulting phosphonium and pyridinium salts can be further functionalized via nucleophilic substitution, photoredox coupling, and electrophilic transfer reactions allowing the generation of a vast array of difluoromethyl products.
- Gupta, Richa,Jaiswal, Amit K.,Mandal, Dipendu,Young, Rowan D.
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supporting information
p. 2572 - 2578
(2020/03/03)
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- METHOD FOR PREPARING HYDROGEN BIS(FLUOROSULFONYL)IMIDE AND METHOD FOR PREPARING LITHIUM BIS(FLUOROSULFONYL)IMIDE
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A method for preparing hydrogen bis(fluorosulfonyl)imide including contacting sulfonyl fluoride with hexamethyl disilazane in an organic solvent. The disclosure also provides a method for preparing lithium bis(fluorosulfonyl)imide (LiFSI). The method includes contacting sulfonyl fluoride with hexamethyl disilazane in an organic solvent and yielding hydrogen bis(fluorosulfonyl)imide; and contacting hydrogen bis(fluorosulfonyl)imide with a lithium compound and yielding lithium bis(fluorosulfonyl)imide.
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Paragraph 0051
(2020/06/07)
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- PROCESS FOR PRODUCING SULFONIC ACID GROUP-CONTAINING MONOMER
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The present disclosure is directed to provide a process capable of producing a sulfonic acid group-containing monomer in a good yield, which can be used as a raw material of fluorine-based polymer electrolytes, such as membranes for fuel cells, catalyst binder polymers for fuel cells, and membranes for chlor-alkali electrolysis. A process for producing a sulfonic acid group-containing monomer represented by the general formula (3) includes the step of mixing and stirring a cyclic compound represented by the general formula (1) and a silanol compound represented by the general formula (2).
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- NONAQUEOUS ELECTROLYTE COMPOSITIONS COMPRISING SILYL OXALATES
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Disclosed herein are electrolyte compositions comprising a fluorinated solvent, at least one silyl oxalate represented by the formulas RR′Si(C2O4), wherein R and R′ are each the same or different from each other and independently selected from C1-C8 alkyl, C2-C8 alkenyl, C2-C8 alkynyl, or C6-C10 aryl radical, optionally comprising at least one substituent selected from halogen, hydroxyl, alkoxy, carbonyl, and carboxyl groups; and LiPF6. Also disclosed herein are electrolyte compositions comprising a fluorinated solvent and a lithium oxalato phosphate salt represented by the formula LiPF(6-2q)(C2O4)q, wherein q is 1, 2 or 3; wherein the oxalato phosphate salt comprises at least a portion that is derived from at least one silyl oxalate as defined herein. The electrolyte compositions are useful in electrochemical cells, such as lithium ion batteries.
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Paragraph 0277-0283
(2019/08/20)
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- Preparation of NHC Stabilized Al(III)fluorides: Fluorination of [(SIMes)AlMe3] with SF4 or Me3SnF
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Various reaction routes have been developed to synthesize the N-heterocyclic carbene (NHC) stabilized Al(III) fluorides [(SIMes)Al(F)3] (2) and [(SIMes)Al(F)Me2] (3) through fluorination of [(SIMes)AlMe3] (1) (SIMes: 1,3-bis(2,4,6-trimethylphenyl)-imidazolidin-2-ylidene) with fluorinating agents such as SF4, SF6 and Me3SnF. The reactivity of 2 was investigated towards a F/Cl exchange reaction by treating it with Me3SiCl.
- Tomar, Pooja,Braun, Thomas,Kemnitz, Erhard
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p. 4735 - 4739
(2019/11/19)
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- Facile and systematic access to the least-coordinating WCA [(RFO)3Al-F-Al(ORF)3]- and its more Lewis-basic brother [F-Al(ORF)3]- (RF = C(CF3)3)
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By reaction of the Lewis acid Me3Si-F-Al(ORF)3 with a series of [PF6]- salts, gaseous PF5 and Me3Si-F are liberated and salts of the anion [F-Al(ORF)3]- ([f-al]-; RF = C(CF3)3) can be obtained. By addition of another equivalent of Me3Si-F-Al(ORF)3 to [f-al]-, gaseous Me3Si-F is released and salts of the least coordinating anion [(RFO)3Al-F-Al(ORF)3]- ([al-f-al]-) are formed. Both procedures work for a series of synthetically useful cations including Ag+, [NO]+, [Ph3C]+ and in very clean reactions with 5 g batch sizes giving excellent yields typically exceeding 90%. In addition, the synthesis of Me3Si-F-Al(ORF)3 has been optimized and scaled up to 85 g batches in an one-pot procedure. These anions could previously only be obtained by difficult to control decomposition reactions of [Al(ORF)4]- or by halide abstraction reactions with Me3Si-F-Al(ORF)3, generating relatively large countercations that are unsuited for further use as universal starting materials. Especially [al-f-al]- is of interest for the stabilization of reactive cations, since it is even weaker coordinating than [Al(ORF)4]- and more stable against strong electrophiles. This bridged anion can be seen as an adduct of [f-al]- and Al(ORF)3. Thus, it is similarly Lewis acidic as BF3 and eventually reacts with nucleophiles (Nu) from the reaction environment to yield Nu-Al(ORF)3 and [f-al]-. This prevents working with [al-f-al]- salts in ethereal or other donor solvents. By contrast, the [f-al]- anion is no longer Lewis acidic and may therefore be used for reactions involving stronger nucleophiles than the [al-f-al]- anion can withstand. Subsequently it may be transformed into the [al-f-al]- salt by simple addition of one equivalent of Me3Si-F-Al(ORF)3.
- Martens, Arthur,Weis, Philippe,Krummer, Michael Christian,Kreuzer, Marvin,Meierh?fer, Andreas,Meier, Stefan C.,Bohnenberger, Jan,Scherer, Harald,Riddlestone, Ian,Krossing, Ingo
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p. 7058 - 7068
(2018/09/25)
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- Synthesis and kinetics of disassembly for silyl-containing ethoxycarbonyls using fluoride ions
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In this study, a series of silyl-containing ethoxycarbonates and ethoxycarbamates on electron poor anilines and phenols were synthesized and their kinetics of disassembly determined in real-time upon exposure to fluoride ion sources at room temperature. The results provide a greater understanding of stability and kinetics for silyl-containing protecting groups that eliminate volatile molecules upon removal, which will allow for simplification of orthogonal protection in complex organic molecules.
- Camerino, Eugene,Daniels, Grant C.,Wynne, James H.,Iezzi, Erick B.
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p. 1884 - 1888
(2018/02/06)
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- METHOD FOR SYNTHESIS OF LITHIUM FLUORINATED BORATE SALTS
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An effective method to synthesize Li borate salt such as Li(RfO)aBFb, in which a and b are integers, and a+b=4, has been disclosed. Using RfO-TMS as the starting material enables a streamlined synthesis scheme and makes purification of the final product simple.
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Page/Page column 4
(2019/01/04)
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- Gram-Scale Synthesis of Amines Bearing a gem-Difluorocyclopropane Moiety
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The synthesis of monocyclic, spirocyclic and fused bicyclic secondary amines bearing a gem-difluorocyclopropane moiety via difluorocyclopropanation of unsaturated N-Boc derivatives using the trifluoromethyl(trimethyl)silane/sodium iodide [CF3SiMe3-NaI] system is described. The relative order of the substrate reactivity is established. It is shown that for the reactive alkenes the standard reaction conditions can be used, whereas for the substrates with low reactivity, slow addition of the Ruppert–Prakash reagent is necessary. (Figure presented.).
- Nosik, Pavel S.,Gerasov, Andrii O.,Boiko, Rodion O.,Rusanov, Eduard,Ryabukhin, Sergey V.,Grygorenko, Oleksandr O.,Volochnyuk, Dmitriy M.
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p. 3126 - 3136
(2017/09/25)
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- Enolonium Species—Umpoled Enolates
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Enolonium species/iodo(III)enolates of carbonyl compounds have been suggested to be intermediates in a wide variety of hypervalent iodine induced chemical transformations of ketones, including α-C?O, α-C?N, α-C?C, and α-carbon–halide bond formation, but they have never been characterized. We report that these elusive umpoled enolates may be made as discrete species that are stable for several minutes at ?78 °C, and report the first spectroscopic identification of such species. It is shown that enolonium species are direct intermediates in C?O, C?N, C?Cl, and C?C bond forming reactions. Our results open up chemical space for designing a variety of new transformations. We showcase the ability of enolonium species to react with prenyl, crotyl, cinnamyl, and allyl silanes with absolute regioselectivity in up to 92 % yield.
- Arava, Shlomy,Kumar, Jayprakash N.,Maksymenko, Shimon,Iron, Mark A.,Parida, Keshaba N.,Fristrup, Peter,Szpilman, Alex M.
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supporting information
p. 2599 - 2603
(2017/02/26)
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- Niobium(v)-catalyzed defluorinative triallylation of α,α,α-trifluorotoluene derivatives by triple C-F bond activation
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The catalytic defluorinative triallylation of α,α,α-trifluorotoluene derivatives via C-F bond activation has been achieved by the use of the NbCl5 catalyst and allyltrimethylsilane as a nucleophile. Several control experiments have suggested the importance of the conjugation between the fluorine atoms and the carbocation center in this reaction.
- Saito, Kodai,Umi, Taishi,Yamada, Takayuki,Suga, Takuya,Akiyama, Takahiko
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supporting information
p. 1767 - 1770
(2017/03/09)
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- Phenyliodonium diacetate mediated carbotrifluoromethylation of: N -acylhydrazones
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A concise, efficient and direct trifluoromethylation method of aldehyde-derived N-acylhydrazones has been firstly developed by using the combination of inexpensive, stable and commercially available TMSCF3 and PhI(OAc)2 as the CF3 source under mild reaction conditions. This method provides easy access to highly functionalized trifluoromethylated N-acylhydrazones, which could be used as trifluoromethyl synthetic building blocks to be further transformed into other valuable trifluoromethyl compounds.
- Zhang, Weigang,Su, Yingpeng,Chong, Siying,Wu, Lili,Cao, Guiyan,Huang, Danfeng,Wang, Ke-Hu,Hu, Yulai
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p. 11162 - 11175
(2016/12/07)
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- Depolymerization of end-of-life poly(dimethylsilazane) with boron trifluoride diethyl etherate to produce difluorodimethylsilane as useful commodity
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A straightforward protocol for the depolymerization of end-of-life poly(dimethylsilazane) using boron trifluoride diethyl etherate as depolymerization reagent to convert the Si-N to Si-F bonds was set-up. The application of the depolymerization reagent affords difluorodimethylsilane as major products, which can be a suitable synthon for the synthesis of new polymers (e.g., poly(dimethylsiloxanes) and allow an overall recycling of the [Me2Si]-unit.
- D?hlert, Peter,Pfrommer, Johannes,Enthaler, Stephan
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p. 1189 - 1193
(2016/08/31)
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- Syntheses of tricyanofluoroborates M[BF(CN)3] (M = Na, K): (CH3)3SiCl catalysis, countercation effect, and reaction intermediates
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Potassium tricyanofluoroborate, K[BF(CN)3], which is the starting material for tricyanofluoroborate room-temperature ionic liquids [N. Ignatev et al. J. Fluorine Chem., submitted] was obtained on a molar scale (140 g) from Na[BF4] and (CH3)3SiCN with a purity of up to 99.9%. The initial product of the reaction that was catalyzed by (CH3)3SiCl was Na[BF(CN)3]·(CH3)3SiCN that was characterized by multinuclear NMR and vibrational spectroscopy, elemental analysis, differential scanning calorimetry, and single-crystal X-ray diffraction. Na[BF(CN)3]·(CH3)3SiCN was converted to K[BF(CN)3] via a simple extraction protocol. The catalytic effect of (CH3)3SiCl was evaluated and some intermediates of the reaction, including the isocyanoborate anion [BF(NC)(CN)2]-, were identified using multinuclear NMR and vibrational spectroscopy. K[BF2(CN)2] also reacted with (CH3)3SiCN in the presence of (CH3)3SiCl, to result in K[BF(CN)3]. The interpretation of the experimental observations was supported by data derived from density functional theory (DFT) calculations. In addition, the influence of selected countercations of the tetrafluoroborate anion on the progress of the (CH3)3SiCl-catalyzed reaction was studied. The fastest reaction was observed for Na[BF4], while the conversion of [BF4]- to [BF(CN)3]- was slower with the countercation K+. Li[BF4] and [Et4N][BF4] were converted under the reaction conditions applied to Li[BF2(CN)2] and [Et4N][BF2(CN)2] only.
- Sprenger, Jan A. P.,Landmann, Johannes,Drisch, Michael,Ignatev, Nikolai,Finze, Maik
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p. 3403 - 3412
(2015/04/14)
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- Copper(I)-mediated direct trifluoromethylthiolation of allylic halides with elemental sulfur and (trifluoromethyl)trimethylsilane
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Abstract A new method has been developed for the copper-mediated trifluoromethylthiolation of allylic halides by using potassium fluoride, elemental sulfur, and (trifluoromethyl)trimethylsilane in anhydrous N,N-dimethylformamide. This protocol provides facile access to a variety of allylic trifluoromethyl thioethers in moderate to good yields under mild, ligand-free reaction conditions.
- Li, Jue,Wang, Peiqiang,Xie, Fei-Fei,Yang, Xi-Gang,Song, Xiao-Nan,Chen, Wei-Dong,Ren, Jiangmeng,Zeng, Bu-Bing
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supporting information
p. 3568 - 3571
(2015/06/08)
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- Approaches to prepare perfluoroalkyl and pentafluorophenyl copper couples for cross-coupling reactions with organohalogen compounds
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The reactions of iodoperfluoroalkanes CnF2n+1I (n = 2, 3, 4) and n-BuLi at low temperatures give NMR spectroscopic evidence for LiCnF2n+1 which were converted into LiCu(CnF2n+1)2 derivatives upon treatment with 0.5 mol copper(i) bromide, CuBr. An alternative route to obtain perfluoroorgano copper couples, Cu(Rf)2Ag (Rf = n-C3F7, n-C4F9, C6F5) was achieved from the reactions of the corresponding perfluoroorgano silver(i) reagents, AgRf, and elemental copper through redox transmetallations. The composition of the resulting reactive intermediates was investigated by means of 19F NMR spectroscopy and ESI mass spectrometry. Perfluoro-n-propyl and perfluoro-n-butyl copper-silver reagents prepared by the oxidative transmetallation route exhibited good properties in C-C bond formation reactions with acid chlorides even under moderate conditions. Substitution of bromine directly bound to aromatics for perfluoroalkyl groups was achieved at elevated temperatures, while success in halide substitution reactions using lithium copper couples remained poor.
- Kremlev, Mikhail M.,Mushta, Aleksej I.,Tyrra, Wieland,Yagupolskii, Yurii L.,Naumann, Dieter,Sch?fer, Mathias
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p. 19693 - 19699
(2015/11/27)
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- Stepwise addition of difluorocarbene to a transition metal centre
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The Ruppert-Prakash reagent (Me3SiCF3) is used to introduce difluorocarbene (CF2) and tetrafluoroethylene (TFE) ligands to cobalt(i) metal centres, whereby the TFE ligand is generated via [2+1] cycloaddition between [Co]CF2 and CF2.
- Lee, Graham M.,Harrison, Daniel J.,Korobkov, Ilia,Tom Baker
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supporting information
p. 1128 - 1130
(2014/01/17)
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- A janus-headed lewis superacid: Simple access to, and first application of Me3Si-F-Al(ORF)3
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Upon reaction of gaseous Me3SiF with the in situ prepared Lewis acid Al(ORF)3, the stable ion-like silylium compound Me3Si-F-Al(ORF)3 1 forms. The Janusheaded 1 is a readily available smart Lewis acid that differentiates between hard and soft nucleophiles, but also polymerizes isobutene effectively. Thus, in reactions of 1 with soft nucleophiles (Nu), such as phosphanes, the silylium side interacts in an orbital-controlled manner, with formation of [Me3Si-Nu]+ and the weakly coordinating [F-Al(ORF)3]-or [(FRO)3Al-F-Al(ORF)3]- anions. If exchanged for hard nucleophiles, such as primary alcohols, the aluminum side reacts in a charge-controlled manner, with release of FSiMe3 gas and formation of the adduct R(H)O-Al(ORF)3. Compound 1 very effectively initiates polymerization of 8 to 21 mL of liquid C4H8 in 50 mL of CH2Cl2 already at temperatures between -57 and -30 8C with initiator loads as low as 10 mg in a few seconds with 100 % yield but broad polydispersities.
- Rohde, Michael,Muller, Lutz O.,Himmel, Daniel,Scherer, Harald,Krossing, Ingo
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supporting information
p. 1218 - 1222
(2014/04/03)
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- Nitryl cyanide, NCNO2
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The elusive nitryl cyanide, NCNO2, has been synthesized and characterized. It was prepared in good yield, isolated by fractional condensation, characterized by NMR and vibrational spectroscopy, and studied by theoretical calculations. Nitryl cyanide holds promise as a high energy density material (HEDM) and might also prove useful as a HEDM building block. The simplicity and inherent stability of nitryl cyanide, together with the known multitude of nitriles in interstellar space, suggest that the compound might also be a potential candidate for observations in atmospheric and interstellar chemistry. Small yet feisty: The elusive small molecule nitryl cyanide, NCNO2, has been synthesized and characterized. It has a high kinetic stability, is extremely energetic, has a perfect oxygen balance with respect to combustion to CO2 and N2, and has potential as a building block for other energetic materials. Nitryl cyanide might also be of interest for atmospheric and interstellar chemistry. Isp=specific impulse.
- Rahm, Martin,Belanger-Chabot, Guillaume,Haiges, Ralf,Christe, Karl O.
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supporting information
p. 6893 - 6897
(2014/07/08)
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- Distinct mechanism of oxidative trifluoromethylation with a well-defined Cu(II) fluoride promoter: Hidden catalysis
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The fluoride [(bpy)CuF2(H2O)]·2H2O (1) reacts with CF3SiMe3 and PhB(OH)2 in DMF at rt to give PhCF3 in >95% yield within 15 min. Although 1 is a Cu(II) complex, this reaction occ
- Nebra, Noel,Grushin, Vladimir V.
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supporting information
p. 16998 - 17001
(2015/02/18)
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- On the feasibility of nickel-catalyzed trifluoromethylation of aryl halides
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A computational screening of 42 bidentate phosphines (PP) has yielded promising candidates for Ph-CF3 reductive elimination from Ni(II) complexes of the type [(PP)Ni(Ph)(CF3)]. The computed barriers and synthetic accessibility consid
- Jover, Jess,Miloserdov, Fedor M.,Benet-Buchholz, Jordi,Grushin, Vladimir V.,Maseras, Feliu
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p. 6531 - 6543
(2015/02/19)
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- C6F5XeY Molecules (Y = F and Cl): New synthetic approaches. first structural proof of the organoxenon halide molecule C 6F5XeF
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The arylxenonium salt [C6F5Xe][BF4] reacts with different sources of nucleophiles, Y (naked fluoride, [N(CH 3)4]F, the silanes, (CH3)3SiCl and (C2H5)3SiH, and the cadmiumorganyl, Cd(C 6F5)2), in coordinating solvents (C 2H5CN, CH3CN, CD3CN). While the products C6F5XeF, C6F5XeCl, and (C6F5)2Xe are well defined molecules, in reactions with (C2H5)3SiH only decomposition products presumably derived from 6F5XeH6F5XeC2H56F5XeF are discussed.
- Bilir, Vural,Frohn, Hermann-Josef
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p. 505 - 512
(2013/09/23)
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- An efficient method for the synthesis of symmetrical disiloxanes from alkoxysilanes using Meerwein's reagent
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We report here a new and efficient route to symmetrical disiloxanes from their corresponding alkoxysilanes using Meerwein's reagent as mediator and potassium carbonate as additive under mild reaction conditions in acetonitrile. Our methodology is very simple, economic, and high yielding. We have also proposed a reaction mechanism with the plausible silyloxonium intermediates. Georg Thieme Verlag Stuttgart · New York.
- Jorapur, Yogesh R.,Shimada, Toyoshi
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supporting information; experimental part
p. 1633 - 1638
(2012/08/07)
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- Convenient synthesis of fluoride-alkoxides of Nb(v) and Ta(v): A spectroscopic, crystallographic and computational study
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The synthesis and the spectroscopic characterization of fluoride-alkoxides of niobium and tantalum in the highest oxidation state are reported. Suspensions of MF5 (M = Nb, Ta) in a chlorinated solvent reacted with up to three equivalents of ROSiMe3 (R = Me, Et, Ph) to afford polynuclear derivatives and variable amounts of FSiMe3. Thus MF4(OR) (R = Et, Ph) and MF3(OR)2 were obtained by selective 1:1 and 1:2 reactions almost exclusively as single isomeric products; otherwise mixtures of MF4(OMe) species were afforded from the equimolar reactions of MF5 with MeOSiMe3. The 1:3 reaction of TaF5 with MeOSiMe3 led to different forms of TaF 2(OMe)3. The synthesis of TaF(OPh)4 was forced by high temperature conditions or the use of a large excess of PhOSiMe 3. DFT studies were carried out in order to predict, in the distinct cases, the most stable structures of the metal products. The molecular structures of [NbF2(OPh)2(μ-F)]3 and [TaF(OPh)3(μ-OPh)]2 were ascertained by X-ray diffraction.
- Bortoluzzi, Marco,Guazzelli, Nicola,Marchetti, Fabio,Pampaloni, Guido,Zacchini, Stefano
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p. 12898 - 12906
(2013/01/15)
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- Trip2C6H3SeF: The first isolated selenenyl fluoride
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Joining the stable: The first examples of the highly instable selenenyl fluorides RSeF are prepared from the reaction on the tin selenide RSeSnMe 3 with XeF2. Through the use of extremely large protecting groups (m-terphenyl ligands) which stabilizes the RSeF units against disproportionation, the compounds could be isolated and characterized by NMR spectroscopy and single-crystal structure analysis (see structure). Copyright
- Poleschner, Helmut,Ellrodt, Stefan,Malischewski, Moritz,Nakatsuji, Jun-Ya,Rohner, Christian,Seppelt, Konrad
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experimental part
p. 419 - 422
(2012/03/22)
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- ELECTROLYTE FORMULATIONS CONTAINING CYANO-ALKOXY-BORATE ANIONS
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The present invention relates to electrolyte formulations containing cyano-alkoxy-borate anions, their preparation and their use, in particular as part of electrolyte formulations for electrochemical or optoelectronic devices and special compounds containing cyano-alkoxy-borate anions.
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Page/Page column 58-59
(2012/04/17)
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- COMPOUNDS CONTAINING PERFLUOROALKYL-CYANO-ALKOXY-BORATE ANIONS OR PERFLUOROALKYL-CYANO-ALKOXY-FLUORO-BORATE ANIONS
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The present invention relates to compounds containing perfluoroalkyl-cyano-alkoxy-borate anions or perfluoroalkyl-cyano-alkoxy-fluoro-borate anions, ((per)fluoro)phenyl-cyano-alkoxy-borate anions or ((per)fluoro)phenyl-cyano-alkoxy-fluoro-borate anions or phenyl-cyano-alkoxy-borate anions which are monosubstituted or disubstituted with perfluoroalkyl groups having 1 to 4 C atoms or phenyl-cyano-alkoxy-fluoro-borate anions which are monosubstituted or disubstituted with perfluoroalkyl groups having 1 to 4 C atoms, the preparation thereof and the use thereof, in particular as part of electrolyte formulations for dye sensitized solar cells.
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Page/Page column 15-16
(2012/12/13)
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- Synthesis of 1,3-dialkyl imidazolium ionic liquids containing difunctional and tetrafunctional perfluoroalkylsulfonyl imide anions
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Direct methylation of imidazole using methylated difunctional or tetrafunctional perfluorosulfonyl imides renders excellent yields of the corresponding room temperature ionic liquids (RTILs). This methodology provides a simple, halide-free route to several novel RTILs containing multifunctional perfluorosulfonyl imide anions.
- Hickman, Tom,Desmarteau, Darryl D.
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experimental part
p. 11 - 15
(2012/03/10)
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- PALLADIUM NANOWIRES AND METHODS OF PREPARATION
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A one-dimensional palladium nanowire is provided. The nanowire includes a plurality of dipalladium complexes bonded to one another in a linear arrangement. In preparing the palladium nanowires, dipalladium complexes may be subject to an oxidizing treatment with an oxidizing agent in the presence of a solvent. From the step of oxidizing, bonds are formed between dipalladium complexes, resulting in the formation of a one-dimensional palladium nanowire. Depending on the process of preparing the palladium nanowire and components of the palladium nanowire itself, the nanowire may be tuned to exhibit varying levels of conductivity. In some cases, palladium nanowires are prepared based on metal (e.g., platinum). Various polymers may be attached to palladium nanowires, providing for enhanced solubility and stability.
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Page/Page column 38; 99
(2012/08/28)
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- Mild transition-metal-free amination of fluoroarenes catalyzed by fluoride ions
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Trimethylsilyl-protected heterocycles undergo N-C bond formation with a variety of electron-deficient fluoroarenes catalyzed by fluoride ions. This reaction avoids stoichiometric amounts of base and thus makes N-arylheterocycles accessible in a very mild and transition-metal-free way.
- Dehe, Daniel,Munstein, Isabel,Reis, Andreas,Thiel, Werner R.
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experimental part
p. 1151 - 1154
(2011/05/02)
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- Chloride ion-catalyzed generation of difluorocarbene for efficient preparation of gem-difluorinated cyclopropenes and cyclopropanes
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A chloride ion-catalyzed generation of difluorocarbene from a relatively non-toxic and inexpensive precursor, Me3SiCF2Cl (1), under mild and neutral conditions leads to an efficient preparation of gem-difluorocyclopropenes and difluorocyclopropanes through [2 + 1] cycloaddition reactions with alkynes and alkenes, respectively.
- Wang, Fei,Zhang, Wei,Zhu, Jieming,Li, Huaifeng,Huang, Kuo-Wei,Hu, Jinbo
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scheme or table
p. 2411 - 2413
(2011/04/15)
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- Reaction of 10,10-dimethyl-9-trimethylsiloxy-9,10-dihydrophenanthrene-9- carbonitrile with acids
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The behavior of 10,10-dimethyl-9-trimethylsiloxy-9,10-dihydrophenanthrene- 9-carbonitrile in trifluoromethanesulfonic acid and acid systems CF 3SO3H-CD2Cl2, HSO 3F-SO2ClF-CD2Cl2, and CF 3COOH-CD2Cl2 were studied by NMR spectroscopy. Principal reaction schemes were determined; the first step in these schemes is protonation of the initial compound at the oxygen or nitrogen atom.
- Bushmelev,Genaev,Sal'nikov,Shubin
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body text
p. 1057 - 1061
(2011/11/12)
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- METHOD OF PREPARING 1-METHYLCYCLOPROPENE AND APPLYING THE SAME TO PLANTS
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Disclosed is a method for directly preparing in situ 1-methylcyclopropene which inhibits the action of ethylene of accelerating the ripening process of plants, which comprises reacting a predetermined 1-methylcyclopropene precursor represented by the following Formula 2 or 3 with a base or fluoride anion material, and applying the 1-methylcyclopropene to plants: wherein Me, Et, R1, R2 and X are defined in the specification.
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Page/Page column 7-8
(2010/04/23)
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- Bis(perfluoroorganyl)bromonium salts [(RF)2Br]Y (RF = aryl, alkenyl, and alkynyl)
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Bromonium salts [(RF)2Br]Y with perfluorinated groups RFC6F5, CF3CFCF, C 2F5CFCF, and CF3C≡C were isolated from reactions of BrF3 with RFBF2 in weakly coordinating solvents (wcs) like CF3CH2CHF2 (PFP) or CF3CH2CF2CH3 (PFB) in 30-90% yields. C6F5BF2 formed independent of the stoichiometry only [(C6F5)2Br][BF 4]. 1:2 reactions of BrF3 and silanes C6F 5SiY3 (Y = F, Me) ended with different products - C 6F5BrF2 or [(C6F5) 2Br][SiF5] - as pure individuals, depending on Y and on the reaction temperature (Y = F). With C6F5SiF3 at ≥-30 °C [(C6F5)2Br][SiF5] resulted in 92% yield whereas the reaction with less Lewis acidic C 6F5SiMe3 only led to C6F 5BrF2 (58%). The interaction of K[C6F 5BF3] with BrF3 or [BrF2][SbF 6] in anhydrous HF gave [(C6F5) 2Br][SbF6]. Attempts to obtain a bis(perfluoroalkyl) bromonium salt by reactions of C6F13BF2 with BrF3 or of K[C6F13BF3] with [BrF2][SbF6] failed. The 3:2 reactions of BrF3 with (C6F5)3B in CH2Cl2 gave [(C6F5)2Br][(C6F 5)nBF4-n] salts (n = 0-3). The mixture of anions could be converted to pure [BF4]- salts by treatment with BF3·base.
- Frohn, Hermann-Josef,Giesen, Matthias,Welting, Dirk,Bardin, Vadim V.
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experimental part
p. 922 - 932
(2010/10/03)
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- Explored routes to unknown polyfluoroorganyliodine hexafluorides, R FIF6
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Two routes to RFIF6 compounds were investigated: (a) the substitution of F by RF in IF7 and (b) the fluorine addition to iodine in RFIF4 precursors. For route (a) the reagents C6F5SiMe3, C6F 5SiF3, [NMe4][C6F 5SiF4], C6F5BF2, and 1,4-C6F4(BF2)2 were tested. C 6F5IF4 and CF3CH2IF 4 were used in route (b) and treated with the fluoro-oxidizers IF7, [O2][SbF6]/KF, and K2[NiF 6]/KF. The observed sidestep reactions in case of routes (a) and (b) are discussed. Interaction of C6F5SiX3 (X = Me, F), C6F5BF2, 1,4-C6F 4(BF2)2 with IF7 gave exclusively the corresponding ring fluorination products, perfluorinated cyclohexadiene and cyclohexene derivatives, whereas [NMe4][C6F 5SiF4] and IF7 formed mixtures of C 6FnIF4 and C6FnH compounds (n = 7 and 9). CF3CH2IF4 was not reactive towards the fluoro-oxidizer IF7, whereas C6F 5IF4 formed C6FnIF4 compounds (n = 7 and 9). C6F5IF4 and CF 3CH2IF4 were inert towards [O 2][SbF6] in anhydrous HF. CF3CH 2IF4 underwent C-H fluorination and C-I bond cleavage when treated with K2[NiF6]/KF in HF. The fluorine addition property of IF7 was independently demonstrated in case of perfluorohexenes. C4F9CFCF2 and IF7 underwent oxidative fluorine addition at -30 °C, and the isomers (CF 3)2CFCFCFCF3 (cis and trans) formed very slowly perfluoroisohexanes even at 25 °C. The compatibility of IF7 and selected organic solvents was investigated. The polyfluoroalkanes CF 3CH2CHF2 (PFP), CF3CH 2CF2CH3 (PFB), and C4F9Br are inert towards iodine heptafluoride at 25 °C while CF3CH 2Br was slowly converted to CF3CH2F. Especially PFP and PFB are new suitable organic solvents for IF7.
- Frohn, Hermann-Josef,Bardin, Vadim V.
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experimental part
p. 1000 - 1006
(2010/11/16)
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- Fluorodecarboxylation, rearrangement and cyclisation: the influence of structure and environment on the reactions of carboxylic acids with xenon difluoride
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The reactions of structurally diverse carboxylic acids with XeF2 in both CH2Cl2/Pyrex and CH2Cl2/PTFE have been studied. Pyrex appears to be a very effective heterogeneous catalyst for an electrophilic mode of reaction of polarised XeF2, leading to rearrangement, cyclisation and cationic products. In CH2Cl2/PTFE, fluorodecarboxylation is the main mode of reaction, in accordance with previous studies, and may occur via a SET reaction of unpolarised XeF2.
- Ramsden, Christopher A.,Shaw, Maxine M.
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body text
p. 3321 - 3324
(2009/08/09)
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- Reaction of the Ruppert-Prakash reagent with perfluorosulfonic acids
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A new property of Me3SiCF3 to undergo C-F bond activation upon interaction with perfluorosulfonic acids is described. The reaction is catalyzed by titanium tetrachloride and affords difluoromethyl perfluorosulfonates in good yields.
- Levin, Vitalij V.,Dilman, Alexander D.,Belyakov, Pavel A.,Struchkova, Marina I.,Tartakovsky, Vladimir A.
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experimental part
p. 667 - 670
(2009/12/22)
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- One-pot synthesis of 3-fluoro-4-(trifluoromethyl)quinolines from pentafluoropropen-2-ol and their molecular modification
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(Chemical Equation Presented) Pentafluoropropen-2-ol (PFP) was prepared by the reaction of hexafluoroacetone (HFA) with Mg/TMSCl. The one-pot tandem sequential reactions of PFP via Mannich addition with aldimines followed by Friedel-Crafts cyclization and aromatization afforded the title quinolines. A variety of corresponding 3-substituted quinolines were derived from the title quinoline by nucleophilic substitution of 3-fluorine with nucleophiles. A defluorinative transformation of the 4-trifluoromethyl group of the title quinoline with hydrazine afforded py razoloquinoline.
- Hosokawa, Tsuyoshi,Matsumura, Akemi,Katagiri, Toshimasa,Uneyama, Kenji
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p. 1468 - 1474
(2008/09/16)
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- Process for the production of trialkylsilyl(fluorosulfonyl)difluoroacetate
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A process for the production of trialkylsilyl (fluorosulfonyl)difluoroacetate by contacting (fluorosulfonyl)difluoroacetyl fluoride with siloxane. The amount of (fluorosulfonyl)difluoroacetic acid by-product in trialkylsilyl(fluorosulfonyl)difluoroacetate is reduced by contacting said mixture with trialkylsilyl halide.
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Page/Page column 3-4
(2008/06/13)
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- Novel perfluoroalkanesulfonamide compounds
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The present invention provides compounds represented by the formula Y+?N(SO2Rf)(CF3). Such a compound can be manufactured through a reaction between M+?N(SO2Rf)(CF3) and Y+?B. The present invention also provides compounds represented by the formula Y+?N(SO2Rf)(CN). Such a compound can be manufactured through a reaction between M+?N(SO2Rf)(CN) and Y+?B. Rf in the above formulae is a perfluoroalkyl group. Y+ is an organic or inorganic cation. ?B is an organic or inorganic anion. M+ is an alkali metal cation or a silver cation.
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Page/Page column 23
(2008/06/13)
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- New anions of pentacoordinate phosphorus containing fluorine and trifluoromethyl groups
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The unique pseudo-trigonal-bipyramidal CF3PF3O - and (CF3)2PF2O- anions were obtained and characterised for the first time. They were formed by the reactions of (PhO)3P(O), Me3SiCF3 and the fluoride ion sources [Me4N]F and CsF, respectively, in glyme. These anions represent the stable transition states postulated for nucleophilic substitution at a tetrahedral phosphorus atom. The salt Cs[(CF3) 2PF2O] (7) is stable at room temperature for a month, while [Me4N][CF3PF3O] (1) dismutates into [Me4N][CF3PF(O)O] (2) and [Me4N][CF 3PF5] (3) above 0°C. Wiley-VCH Verlag GmbH & Co. KGaA, 2007.
- Pavlenko, Natalya V.,Babadzhanova, Lesya A.,Gerus, Igor I.,Yagupolskii, Yurii L.,Tyrra, Wieland,Naumann, Dieter
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p. 1501 - 1507
(2008/02/06)
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- The binary selenium(IV) azides Se(N3)4, [Se(N 3)5]-, and [Se(N3)6] 2-
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(Figure Presented) Black, red, gold: The reaction of SeF4 with Me3SiN3 at low temperatures results in the formation of the first binary selenium(IV) azide Se(N3)4. The decomposition in an NMR tube shows the colors of gray selenium, red selenium, and the desired yellow selenium tetraazide (see picture). The reactions of [SeF5]- and [SeF6]2- with Me 3SiN3 furnish the corresponding polyazidoselenites [Se(N3)5]- and [Se(N3) 6]2-. All materials are extremely temperature-sensitive.
- Klapoetke, Thomas M.,Krumm, Burkhard,Scherr, Matthias,Haiges, Ralf,Christe, Karl O.
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p. 8686 - 8690
(2008/09/18)
-
- Synthesis, NMR spectroscopic characterisation and reactions of 2,6-difluorophenylxenon fluoride, 2,6-F2C6H3XeF
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[2,6-F2C6H3Xe][BF4] is quantitatively transferred into 2,6-F2C6H3XeF in reactions with [NMe4]F. The latter has been isolated as a colourless solid which is stable in dichloromethane solution at room temperature for approximately 1 h. 2,6-F2C6H3XeF readily reacts with Me3SiX (X = Cl, Br, CN, NCO, OCOCF3, OSO2CF3, C6F5, 2,6-F2C6H3) to give compounds of general compositions 2,6-F2C6H3XeX which were identified by multinuclear NMR experiments. Evidence was found for C6H5Xe(2,6-F2C6H3) as a product of the reaction with C6H5SiF3.
- Bock, Harald,Scherer, Harald,Tyrra, Wieland,Naumann, Dieter
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p. 1440 - 1445
(2008/09/19)
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