Pentafluorophenyl Compounds Research Articles

Synthesis of Sulfur Perfluorophenyl Compounds Using a Pentafluorobenzenesulfonyl Hypervalent Iodonium Ylide.

A novel pentafluorobenzenesulfonyl hypervalent iodonium ylide 3 was designed and synthesized as a useful tool for the preparation of sulfur pentafluorophenyl compounds containing a C6F5S or C6F5SO2 unit. Electrophilic pentafluorophenylthiolation of enamines, formal [3+2] cycloaddition reaction of nitriles and alkynes, and intramolecular SNAr cyclization were achieved using iodonium ylide 3. The fluoro-click reaction was also demonstrated using one of the products via an intermolecular SNAr reaction with heterocentered nucleophiles.

Homoleptic Heavy Alkaline Earth and Europium Triazenides

The sigma-bond metathesis reaction between PhSiH(3) and the heteroleptic metal pentafluorophenyl compounds [Dmp(Tph)N(3)MC(6)F(5)(thf)(n)] (Dmp = 2,6-Mes(2)C(6)H(3) with Mes = 2,4,6-Me(3)C(6)H(2); Tph = 2-TripC(6)H(4) with Trip = 2,4,6-(i)Pr(3)C(6)H(2); n = 1, 2; M = Sr, Ba, Eu) supported by sterically crowded, biphenyl- and terphenyl-substituented triazenido ligands afforded the first homoleptic stontium, barium, and europium triazenides [M{N(3)Dmp(Tph)}(2)] {M = Sr (2), Ba (4), Eu (5)}. Crystallization of 2 from an n-heptane/1,2-dimethoxyethane mixture gave the complex [Sr{N(3)Dmp(Tph)}(2)(dme)] (3). All new compounds have been characterized by (1)H and (13)C NMR spectroscopy (not 5), elemental analysis, IR spectroscopy (5 only), and X-ray crystallography. In the solid-state structures, the first coordination sphere of the metal cations consists of four nitrogen atoms of the two bidentate triazenide ligands. Additional metal-eta(n)-pi-arene-interactions of different hapticity n (n = 3-6) are observed to the flanking arms of the terphenyl substituents.

Synthesis and Reactivity of Mononuclear Anionic Pentafluorophenyl Compounds of Rhodium(I) and Iridium(I). X-ray Structure of [{P(OPh)3}2(C6F5)2RhAg(PPh3)

Synthesis and Reactivity of Mononuclear Anionic Pentafluorophenyl Compounds of Rhodium(I) and Iridium(I). X-ray Structure of [{P(OPh)3}2(C6F5)2RhAg(PPh3)

Pentafluorophenyl compounds of rhodium(III) with bidentate phosphorus or nitrogen ligands

Treatment of [P(CH 2Ph)Ph 3] 2[Rh(μ-Cl)(C 6F 5) 3 2] with tertiary diphosphine ligands gives anionic compounds of the type [P(CH 2Ph)Ph 3][RhCl(C 6F 5) 3L 2] (L 2=(bis(diphenylphosphino)methane (I), bis(diphenylphosphino)amine (II) and bis(diphenylphosphino)ethane (III)) and neutral compounds of stoichiometry [Rh(C 6F 5) 3L 2] (IV-VI); dichloromethane solutions of IV-VI react with carbon monoxide or tert-butyl isocyanide yielding complexes of the type [Rh(C 6F 5) 3L' 2] (L'= CO or tBuCN) (VII-X)). In a similar way, addition of nitrogen ligands to solutions of [P(CH 2Ph)Ph 3] 2[Rh(μ-Cl)(C 6F 5) 3 2] or [Rh(C 6F 5) 3(OEt 2) x] gives dinuclear complexes [Rh(C 6F 5) 3 2L 2] (L 2 = 2,2′-bipyrimidine (XIII), L = 4,4′-bipyridine (XIV)) and mononuclear complexes [Rh(C 6F 5) 3L 2] (L 2 = 1,10-phenanthroline (XV) or 2,2′-biimidazole (XVI)).

ChemInform Abstract: GAS‐PHASE ELECTRON ATTACHMENT REACTIONS AND NEGATIVE‐ION MASS SPECTRA OF SUBSTITUTED PENTAFLUOROPHENYL COMPOUNDS

Chemischer InformationsdienstVolume 15, Issue 23 Physical Organic Chemistry ChemInform Abstract: GAS-PHASE ELECTRON ATTACHMENT REACTIONS AND NEGATIVE-ION MASS SPECTRA OF SUBSTITUTED PENTAFLUOROPHENYL COMPOUNDS I. K. GREGOR, I. K. GREGORSearch for more papers by this authorM. GUILHAUS, M. GUILHAUSSearch for more papers by this author I. K. GREGOR, I. K. GREGORSearch for more papers by this authorM. GUILHAUS, M. GUILHAUSSearch for more papers by this author First published: June 5, 1984 https://doi.org/10.1002/chin.198423069Read the full textAboutPDF ToolsRequest permissionExport citationAdd to favoritesTrack citation ShareShare Give accessShare full text accessShare full-text accessPlease review our Terms and Conditions of Use and check box below to share full-text version of article.I have read and accept the Wiley Online Library Terms and Conditions of UseShareable LinkUse the link below to share a full-text version of this article with your friends and colleagues. Learn more.Copy URL Share a linkShare onFacebookTwitterLinkedInRedditWechat No abstract is available for this article. Volume15, Issue23June 5, 1984 RelatedInformation

Gas phase electron attachment reactions and negative ion mass spectra of substituted pentafluorophenyl compounds

Abstract Compounds of the type C 6 F 5 ·R (R = F, CH 3 , NH 2 , OH, SH, OCH 3 , COCH 3 , CHO, NO 2 , CN) undergo low energy electron attachment reactions in the gas phase under negative chemical ionisation (NCI) conditions which can result in the production of intense negative ion beams. Long-lived molecular negative ions are formed when R is highly electron withdrawing and this correlates in certain cases (R = F, CN, CHO) with reported [M] − · autodetachment times. Compounds with R = COCH 3 , CHO, CN which exhibit minimal fragmentation of [M] − · are useful negative ion mass calibrants.

The thiolate anion as a nucleophile Part IV. Reactions of some pentafluorophenyl compounds

Direct nucleophilic substitution with sodium methanethiolate of the pentafluorophenyl compounds C 6F 5X (X = Cl, Br, I. NO 2, NH 2, CO 2H, SC 6F 5, OMe, OH) has given varying amounts of XC 6F 4(SMe), XC 6F 3(SMe) 2, C 6F 4(SMe) 2, XC 6F 2(SMe) 3 and C 6F 2(SMe) 4. In some cases cleavage of the aromatic carbon-X bond (X = Br, I, CO 2H, SC 6F 5) forming C 6F 4(SMe)H and C 6F 2(SMe) 3H, and the O-Me bond forming HOC 6F 2(SMe) 3 was observed. The new compounds isolated have been characterized by elemental analyses, infrared and mass spectra and their stereochemistries have been from their 1H and 19F NMR spectra.

Reaktionen von Pentafluorbenzolsulfen-, -sulfin- und -sulfonsäurechlorid mit Natrium-bis(trimethylsilyl)-amid / Reactions of Pentafluorobenzenesulfenyl, -sulfinyl, and -sulfonyl Chlorides with Sodium-bis(trimethylsilyl) Amide

By reaction with NaN[Si(CH3)3]2, the chlorides C6F5SCl, C6F5S(O)Cl, and C6F5SO2Cl are converted into C6F5SN[Si(CH3)3]2, C6F5S(O)N[Si(CH3)3]2, and Na+[C6F5SO2]-, respectively. In this instance the reactivity pattern of the pentafluorophenyl compounds does not differ from that of similar phenyl derivatives.

Fluorine NMR spectra of pentafluorophenyl derivatives

AbstractThe fluorine chemical shifts and spin‐spin coupling constants of 65 pentafluorophenyl derivatives with widely varying organic substituents were examined. Useful correlations of the three meta coupling constants with the chemical shifts of the para fluorine were found. It is suggested that these relationships be extended to all compounds of the type considered in order to determine the signs and approximate values of meta coupling constants.Equations for correlation of the fluorine chemical shifts with the Taft constants are presented. The possibility of calculating the Taft constants from the 19F NMR spectra of pentafluorophenyl compounds is being discussed.

Inter-ring coupling in the 19F NMR spectra of pentafluorophenyl compounds of Group IV elements

The mechanism of inter-ring coupling in the nuclear magnetic resonance spectra of pentafluorophenyl compounds of Group IV elements is considered.

Chemical shifts and coupling constants in pentafluorophenyl derivatives. IIi. Application to a study of bonding in selected compounds

Abstract : The pi interactions within molecules containing the pentafluorophenyl group are examined using the coupling constant-chemical shift relationship as proposed in the preceding paper. The following series, selected from the 73 pentafluorophenyl compounds studied, are discussed: pentafluorophenylphosphines and some of their complexes including metal carbonyl derivates: compounds of the type C6F5XMR3, where X = O or S,M = Si,Ge,Sn, or Pb, and R = Ch3 or C6H5; and of the type C6H5NHR where R = B(C6H5)2,CH3,H,Si(CH3)3. Estimates of (p to d) pi bonding between group IV elements and oxygen, sulfur, and nitrogen are given. The influence of a sigma-bond polarity upon back donation by halogens is considered. (Author)

The 19F NMR spectra of some pentafluorophenyl compounds of group IV elements

Accurate chemical shifts have been determined for the pentafluorophenyl fluorine nuclei of a number of group IV pentafluorophenyl compounds by the use of an extended lock in the HA mode. All the compounds studied have a very large ortho shift, the trends of which can be predicted by both the Van der Waals electric field theory [1] and the through bond theory of Hruska et al. [2]. The meta- and para- 19F chemical shifts have been used to predict the π-electron accepting ability of the various substituents attached to the group IV atom. The coupling constants obtained from those compounds which give resolvable spectra supports the chemical shift work.

Highly fluorinated analogues of pharmacologically active compounds.

The pentafluorophenyl analogues of noradrenaline, adrenaline, and N-methyladrenaline [C6F5·CH(OH)·CH2·NR1R2 with R1= R2= H; R1= H, R2= Me; R1= R2= Me, respectively] have been prepared by reduction with sodium borohydride of the corresponding amino-ketones obtained by standard methods. 3-(N-2-Chloroethyl-N-ethyl)-aminomethyl-4,5,6,7-tetrafluorobenzo[b]thiophen has also been synthesised as a potential catecholamine antagonist and anti-tumour agent, by a method involving the cyclisation with polyphosphoric acid of 2,3,4,5-tetra-fluorophenylthiopropanone to give the expected 4,5,6,7-tetrafluoro-3-methylbenzo[b]thiophen, and thence by standard methods. The above pentafluorophenyl compounds are only very weak catecholamine antagonists.

Steric hindrance in pentafluorophenyl compounds of group IV elements

The first page of this article is displayed as the abstract.

The SN mechanism in aromatic compounds. XXXII. Reactivity of some perhalogenobenzenes

Substituent effects in a series of pentafluorophenyl compounds (C6F5X) ranging from powerful activating to powerful deactivating substituents are considered, both as regards orientation and rates, and shown to be simply and reliably predicted by considering the change as made up of two components, viz. from C6F6 to C6F5H and from C6F5H to C6F5X. The same principle applies generally to C6Hal5X compounds, and the necessary orientation and rate data are obtainable from the existing large body of substituent effects in aromatic SN reactions. Comparisons are thus also easily possible with substituent effects in aromatic SE reactions, and more generally. The reasons for predominant para direction for almost all groups, except the more powerful deactivating substituents which are meta directing, and the expectation of a few borderline cases, emerge clearly from discussion. While orientation is largely known already, there have been very few precise rate determinations apart from the present work. Some brief consideration of the admixture of dioxan with protic solvent is given. The reactivities of hexafluorobenzene and hexachlorobenzene are compared. The substantially greater reactivity reported with the former is regarded as due solely to the greater mobility of fluorine than chlorine, with first row nucleophdes in protic solvents; whereas in contrast it is predicted that the C6Cl5 group is slightly more activating for aromatic S, reactions than the C,F, group. The relative reactivities of C6F6 and C6H5F, and C6Cl6 and C6H5Cl are also compared. Rate ratios are c.108; ΔΔE? c.15 kcal mole-1; and Δlog10B c.+1.