Synthese et reactivite des F-alkyl sulfures et sulfones actives

In this paper we report syntheses of F-alkyl compounds such as R_FC₂H₄S(O)_nCH₂Z (with n=0,2 and Z=H,Ø(C₆H₅),COØ,COOEt,COCH₃,CN). Using the carbanionic reactivity of these compounds, we would like to use them as precursors of surfactants, grafting hydrophilic functions on the carbons α or α′ to the sulfur atom. The compounds were not very reactive. Alkylation or acylation on this site could only be obtained with a ‘pseudo malonic’ CH₂ (R_FC₂H₄SO₂CH₂Z with Z=COØ, COOEt,COCH₃,CN). Only methyl iodide and acetyl chloride led to positive results.     

Reactivity of perfluoroalkenylmagnesium halides : Application to the synthesis of new α-β unsaturated polyfluorinated alcohols and organometallic compounds

The reactivity of perfluoroalkenylmagnesium bromides R_FCFCFMgBr (R_FC₄F₉, C₆F₁₃), obtained from the corresponding l-bromo-perfluoroalkenes, has been investigated.These Grignard reagents react with carbonyl compounds to give, with good yields, a series of new α-β unsaturated polyfluorinated alcohols R_FCFCFC(OH)RR′ (1). The synthesis and spectrographic characteristics of these compounds are reported and discussed.Perfluoroalkenyl mercuric and tin derivatives are obtained from the reaction of the perfluorinated Grignard reagents with mercuric salts and organotin halides respectively :

Spectroscopic identification and some chemical properties of these new perfluorinated organometallic compounds are given.The good reactivity of these unsaturated derivatives towards protic acids and electrophiles, leading to the cleavage of the perfluoroalkenyl group, is used to study the possibilities of transmetallation reactions.Somes examples of these reactions are reported.     

Synthese et application de nouveaux sulfures a chaine perfluoree

Metallation of thiols R_FC₂H₄SH followed by alkylation with iodides R′_FC₂H₄I leads either to symmetrical or to unsymmetrical sulphides R_FC₂H₄SC₂H₄R′_F (with R_F=R′_F or R_F ≠ R′_F). All compounds obtained are good solvents of gases (particularly O₂, CO, CO₂, N₂).This property allows their application as biological carriers of dissolved gases.     

Synthese d'ethers et de thioethers allyliques fluores par catalyse par transfert de phase

Several fluorinated allylic ethers, thioethers and diethers have been prepared in excellent yields by phase transfer catalysis (CTP). The used halogenated compounds are allyl chloride and bromide, p-chloromethylstyrene. The used fluorinated alcohols are aromatic pentafluorophenol and various aliphatics: CF₃CH₂OH, CF₂HCF₂CH₂OH ClCF₂CF₂CH₂OH,C₆F₁₃C₂H₄OH, HOCH₂CF₂CFClCF₂CH₂OH and HOC₆H₄C(CF₃)₂C₆H₄OH. All these new compounds have been characterized by ¹H and ¹³C NMR. We conclude that CTP is the best method to obtain allylic and diallylic compounds.     

Bis(fluorbenzoyloxy)methylphosphanoxide

Bis(fluorbenzoyloxy)methyl phosphane oxides CH₃P(O)[OC(O)R]₂ [R = C₆H₄2F (1), C₆H₄3F (2), C₆H₄4F (3), C₆H₃2,6F₂ (4), C₆H2,3,5,6F₄ (5)] were prepared by treating silver salts of carboxylic acids AgOC(O)R with CH₃P(O)C?₂ (IR-, ¹H-, ¹⁹?F-and ³¹P{¹H}-NMR-data). The mixed anhydrides 1–5 show unusual thermal stability at room temperature. Stability against hydrolysis decreases with increasing number of fluorine-atoms. The reaction of R′P(O)C?₂ [R′ = CH₃, C₆H₅, (CH₃)₃C] with M^IOC(O)R_F [R_F = CF₃, C₂F₅, C₆F₅; M^I = Ag^I, Na^I T?^I] was investigated.     

Strukturen von neuen Bis(pentafluorophenyl)halogenomercuraten [{Hg(C6F5)2}3(μ‐X)]— (X = Cl,Br, I)

Structures of New Bis(pentafluorophenyl)halogeno Mercurates [{Hg(C₆F₅)₂}₃(μ‐X)]^— (X = Cl, Br, I) From the reactions of [PNP]Cl or [PPh₄]Y (Y = Br, I) with Hg(C₆F₅)₂ crystals of the composition [Cat][{Hg(C₆F₅)₂}₃X] (Cat = PNP, X = Cl ( 1 ); Cat = PPh₄, X = Br ( 2 ), I ( 3 )) are formed. 1 crystallizes in the triclinic space group P1¯, 2 and 3 crystallize isotypically in the monoclinic space group C2/c. In the crystals the halide anions are surrounded by three Hg(C₆F₅)₂ molecules. The reaction of [PPh₄]Br with Hg(C₆F₅)₂ under slightly changed conditions gives the compound [PPh₄]₂[{Hg(C₆F₅)₂}₃(μ‐Br)][{Hg(C₆F₅)₂}₂(μ‐Br)] ( 4 ).     

Synthese regiospecifique et identification spectrale de nouveaux amino pyrazoles F-alkyl substitues

In this paper the regiospecific synthesis of new amino-3 (-5)pyrazoles substituted, by a long perfluoroalkyl chain (C₇F₁₅) in the 5 or 3 position is reported. These compounds were obtained by condensation of a hydrazine (substituted or not) with a 2-F-alkyl propynonitrile (R_FCCCN). This reaction gives only one isomer. Each isomer (amino-3 pyrazole or amino-5 pyrazole) was identified by ¹H N.M.R. and ¹⁹F.N.M.R.     

Cyclometallation reactions in complexes of the type Rh(oq)(CO)(P(o-BrC6F4)Ph2): II. The molecular structure of [Rh(oq)Br(P(o-C6F4)Ph2)(H2O)]2 (oq = 8-oxyquinolinate)

The complex [uRh(oq)Br(P(o-Cu₆F₄)Ph₂)(H₂O)]₂ is obtained by refluxing a solution of Rh(oq)(CO)(P(o-BrC₆F₄)Ph₂) (oq = 8-oxyquinolinate) in toluene. The structure of this compound has been determined by X-ray diffraction and refined to R = 0.061 and R_w = 0.065 factors. The cell has monoclinic symmetry, space group P2₁/n; a 19.513(2), b 17.049(1), c 16.898(1) Å and β 99.69(1)°. The structure consists of two independent Rh(oq)Br(P(o-C₆F₄)Ph₂)H₂O) units linked by hydrogen bonds between the coordinated water molecules and oq ligands to form a distorted boat (six atom ring of junction between the two units). In each unit the metal atom has a distorted octahedral coordination, with a four-atom metallocyclic ring (uRhPCCu) with CRhP and RhPC angles 69.3(2) and 85.3(3)°, respectively, in one unit, and 70.0(2) and 81.1(2)° in the other. The water molecule is readily displaced by a variety of phosphorus donor ligands to form the complexes uRh(oq)Br(P(o-Cu₆F₄)Ph₂)P′, P′ = PPh₃, P(p-CH₃C₆H₄)₃ and P(OCH₃)₃, in which the P atoms are in trans-dispositions.     

Neue Synthesen und Kristallstrukturen von Bis(fluorphenyl)quecksilber,Hg(Rf)2 (Rf = C6F5, 2, 3, 4, 6‐F4C6H, 2, 3, 5, 6‐F4C6H, 2, 4, 6‐F3C6H2, 2, 6‐F2C6H3)

New Syntheses and Crystal Structures of Bis(fluorophenyl) Mercury, Hg(R_f)₂ (R_f = C₆F₅, 2, 3, 4, 6‐F₄C₆H, 2, 3, 5, 6‐F₄C₆H, 2, 4, 6‐F₃C₆H₂, 2, 6‐F₂C₆H₃) Bis(fluorophenyl) mercury compounds, Hg(R_f)₂ (R_f = C₆F₅, C₆HF₄, C₆H₂F₃, C₆H₃F₂), are prepared in good yields by the reactions of HgF₂ with Me₃SiR_f. The crystal structures of Hg(2, 3, 4, 6‐F₄C₆H)₂ (monoclinic, P2₁/n), Hg(2, 3, 5, 6‐F₄C₆H)₂ (monoclinic, C2/m), Hg(2, 4, 6‐F₃C₆H₂)₂ (monoclinic, P2₁/c) and Hg(2, 6‐F₂C₆H₃)₂ (triclinic, P1) are described.     

Organomercury compounds XX Reactions of lithium polyfluorobenzenesulphinates with mercuric salts

The lithium polyfluorobenzenesulphinates, Li O₂SR (R = C₆F₅, $\text{p}$-HC₆F₄, $\text{m}$-HC₆F₄, or $\text{o}$-HC₆F₄), and the dilithium tetrafluorobenzenedisulphinates, $\text{p}$- and $\text{o}$-(LiO₂S)₂C₆F₄, have been prepared by reaction of the appropriate polyfluoroaryllithium compounds with sulphur dioxide. All compounds were isolated as hydrates and gave the corresponding $\text{S}$-benzylthiouronium salts on treatment with $\text{S}$-benzylthiouronium chloride. From reactions of the lithium sulphinates with suitable mercuric salts in water, generally at room temperature, the derivatives RHgX (R = C₆F₅, X = Cl, Br, CH₃CO₂, or PhSO₂; R = $\text{p}$-HC₆F₄, X = Cl, Br, or CH₃CO₂; R = $\text{m}$-HC₆F₄, X = Cl or Br; R = $\text{o}$-HC₆F₄, X = Cl), $\text{p}$-(XHg)₂C₆F₄ (X = Cl, Br, or CH₃CO₂), and $\text{o}$-(XHg)₂C₆X₄ (X = Cl or Br) have been prepared. Similarly, the bispolyfluorophenylmercurials R₂Hg (R = C₆F₅, $\text{p}$-HC₆F₄, or $\text{m}$-HC₆F₄) have been prepared from the corresponding lithium sulphinates and either mercuric salts or polyfluorophenylmercuric halides in aqueous $\text{t}$-butanol. A possible mechanism for the sulphur dioxide elimination reactions is discussed.     

Organomercury compounds : XXVI. Thermal decomposition of mercuric 2,6-disubstituted benzoates

The main thermal decomposition path for mercuric 2,6-disubstituted benzoates, (RCO₂)₂Hg (R = 2,6-X₂C₆H₃; X = F, Cl, Br, or Me), can be varied considerably. In boiling dimethyl sulphoxide, decarboxylation occurs giving the corresponding diarylmercurial (X = F or Cl) or RHgO₂CR derivative (X = Me or Br). There is considerable competition from reaction of the mercuric salt with the solvent in the last three cases. With boiling pyridine as medium, the 2,6-difluorobenzoate yields a mixture of R₂Hg and RHgO₂CR derivatives, but the 2,6-dichlorobenzoate only gives (RCO₂)₂Hg(py)₂. Thermal decomposition of the mercuric benzoates under vacuum yields the carboxylic acids and complex mercuration products, mainly based on 3-mercurated 2,6-disubstituted benzoates, with partial additional mercuration and/or decarboxylation. Pyrolysis of mercuric 2,6-dichlorobenzoate at atmospheric pressure results in both mercuration and decarboxylation, giving m-dichlorobenzene as the main volatile product and a complex mercurial with 1,3-dimercurated-2,6-dichlorobenzene repeating units and 2,6-dichlorophenyl terminal groups.     

Nucleophilic aromatic substitution; kinetics of fluorine-18 substitution reactions in polyfluorobenzenes. Isotopic exchange between 18F− and polyfluorobenzenes in dimethylsulfoxide. A kinetic study

Nucleophilic aromatic substitution reactions of C₆F₆, C₆XF₅ (XH, Cl, Br), C₆H₂F₄, oC₆H₄FNO₂ and pC₆H₄FNO₂ by the fluoride anion were studied in DMSO utilizing fluorine-18. Substitution of fluorine by fluorine-18 is the only reaction observed with a C₆F₆ substrate. With other substrates fluorine substitution is predominant. The kinetic studies provide results consistent with a S_NAr two step mechanism and suggest an intermediate analogous to that for electrophilic aromatic substitution. Consideration of σ^? indicates consistency with methoxide ion substitution results with similar substrates. The possible utility of these reactions in labeling aromatic compounds is noted.     

Darstellung und schwingungsspektroskopische Untersuchungen von Alkyl- und Arylborhalogeniden

Preparation and Vibrational Spectra of Alkyl- and Arylboronhalides Organohaloboranes R_mBX_3?m (R = CH₃, C₂H₅; X = Cl, Br; m = 1–3) can be prepared from BX₃ and tetraalkyllead as alkylating agent Data of the vibrational spectra (i.r. and Raman) of R_nBY_3?n (Y = F, Cl and Br; n = 1–3) and C₆H₅BY₂ are tabulated and assigned. Mixed halides i. e. RBXY compounds are spectroscopically characterized.     

Etude de l''addition des organomagnesiens satures et benzyliques aux enynes conjugues, simples et fonctionnels

Saturated and benzylic organomagnesium compounds are shown to readily undergo addition reactions with the conjugated enynes H$\text{C}\text{4}$$\text{C}\text{3}$C$\text{H}\text{2}$$\text{C}\text{1}$HCH₂R′, with R′ = alkyl, OH, OC₄H₉, NHC₂₅, N(C₂H₅)₂, by refluxing for several hours in benzene or toluene.This reaction leads to both υ-acetylenic compounds (1,2-addition) and β-allenic compounds (1,4-addition).     

Compounds containing CSF4 and CS+F4

The preparations of CH₂SF₄ and CH₃CHSF₄ are presented and the structures are discussed. Addition reactions of polar species give a wide range of new compounds, like Hg(CH₂SF₅)₂, F₄AsCH₂SF₅, cisBrSF₄CH₃, cisF₅SeOSF₄CH₂Br, a.o. While CH₂SF₄ decomposes at room temperature slowly to CH₂CH₂ and SF₄, at high temperatures HF and CSF₂ are formed. CH₃CHSF₄ gives mainly CH₃CHF₂ at room temperature. The “saturated” compounds CH₃SF₅ and C₂H₅SF₅ have been prepared. They react with SbF₅ in SO₂ at low temperatures to form the cations CH₃SF₄⁺ and C₂H₅SF₄⁺. The CH₃SF₄⁺ ion has been investigated in detail by nmr methods at low temperatures. It decomposes to CH₃ and SF₄, which react further in the SO₂/SbF₅ system to CH₃OSO⁺ and SF₃⁺.     

K2Br(OH) und Rb2Br(OH): Zwei neue ternäre Alkalimetallhalogenidhydroxide mit ausgeprägter Strukturverwandtschaft zu KOH bzw. RbOH

K₂Br(OH) and Rb₂Br(OH): Two New Ternary Alkali Metal Halide Hydroxides with a Pronounced Structural Relationship to KOH resp. RbOH Two isotypic compounds K₂Br(OH) and Rb₂Br(OH) were prepared in the systems KOH/KBr and RbOH/RbBr. Their structures were determined by single crystal X-ray methods: K₂Br(OH): P2₁/m, Z = 2, a = 6.724(1) Å, b = 4.272(4) Å, c = 8.442(2) Å, β = 108.14(2)°, Z(F_o) = 651 with (F_o)² ≥ 3σ(F_o)², Z(parameter) = 28, R/R_w = 0.041/0.047 Rb₂Br(OH): P2₁/m, Z = 2, a = 6.918(3) Å, b = 4.483(2) Å, c = 8.850(5) Å, β = 108.08(6)°, Z(F_o) = 326 mit (F_o)² ≥ 3σ(F_o)², Z(parameter) = 27, R/R_w = 0.074/0.082. The compounds are built up by chains of [M₂(OH)⁺] connected via Br^?. The structure of the chains as well as their orientation to one another show a pronounced relationship to the structures of the room temperature modifications of the isotypic binary hydroxides KOH and RbOH.     

Preparation and synthetic utility of fluorinated phosphonium salts,bisphosphonium salts and phosphoranium salts

The synthesis and mechanism of formation of phosphonium salts of the type [R₃$\text{P}\text{+}$CFXY]Z^? (where X = F, Cl, Br; Y = Br, Cl; Z = Br, Cl), $\text{bis}$-phosphonium salts of the type [R₃$\text{P}\text{+}$CF₂$\text{P}\text{+}$R₃]2Br^?, and phosphoranium salts of the type [R₃$\text{P}\text{+}$$\text{C}\text{?}$F$\text{P}\text{+}$R₃]X^? (X = Br, Cl) will be presented. The applicability of these substrates in the generation of useful nucleophilic or electrophilic synthetic intermediates will be discussed.     

Cyclische Diazastannylene. XXXII. Zur Synthese und Reaktivität difunktionalisierter Cyclosilagermadiazane—Bildung von Digermanen

Cyclic Diazastannylenes. XXXII. On the Synthesis and Reactivity of Difunctional Cyclosilagermadiazanes—Formation of Digermanes The cyclic bisaminostannylene Me₂Si(t-BuN)₂Sn 1 reacts with tetrahalides of germanium GeX₄(X = Cl, Br, I) forming the bisaminodihalogengermanes 2a, 2b and 2c. The halogen atoms of the compounds 2 may be substituted by alkyl-, amino- and pseudohalide groups: Me₂Si(t-BuN)₂GeXY (X = Y = N₃ 3 ; X = Br, Y = Me 4 , Y = t-Bu 6 , Y = N(SiMe₃)₂ 8a , Y = NEt₂ 9 ; X = Me, Y = N₃ 5a , Y = CN 5b ; X = N₃, Y = t-Bu 7 , Y = N(SiMe₃)₂ 10 ; X = I, Y = N(SiMe₃)₂ 8b ). Reduction of the compounds 2b and 4 with sodium naphthalide generates the digermanes (Me₂Si(t-BuN)₂GeR)₂ (with R = Br 11 , R = Me 12 ) Compound 8b crystallizes in the monoclinic space group P2₁/c with Z = 8 and lattice constants a = 16.205(8), b = 19.854(9), c = 17.537(9) Å, β = 107.50(9)°. Compound 11 crystallizes in the triclinic space group P1 with Z = 2 and lattice constants a = 8.921(4), b = 11.091(5), c = 17.590(8) Å, α = 80.5(1), β = 89.2(1), γ = 71.4(1)°.     

Reactions of some fluoroaromatics with the ethoxide anion

The reactions of sodium ethoxide in ethanol with various fluoroaromatics, C₆F_6?nH_n, C₆F_5?nH_nNO₂, C₆F₅X (X = CF₃, C₆F₅, COCH₃, CH₂Br), C₆Cl₆ and $\text{m}$H₂C₆Cl₄ have been studied. Partial substitution of the aromatic halogen was observed. The new products have been characterized by elemental analysis, NMR (H?1 and F?19), infrared and mass spectroscopy.     

Synthese und Eigenschaften von Diethyldithiocarbaminsäureperfluororganylestern, (C2H5)2NC(S)SRf (Rf = CF3, C2F5, i‐C3F7, n‐C4F9, C6F5)

Syntheses and Properties of Perfluoroorgano Esters of the Diethyldithiocarbamic Acid, (C₂H₅)₂NC(S)SR_f (R_f = CF₃, C₂F₅, i‐C₃F₇, n‐C₄F₉, C₆F₅) Tetraethylthiuram disulfide reacts under different conditions with perfluoroorgano silver(I), AgR_f, and perfluoroorgano cadmium compounds, Cd(R_f)₂, to give the corresponding perfluoroorgano esters of diethyldithiocarbamic acid, (C₂H₅)₂NC(S)SR_f (R_f = CF₃, C₂F₅, i‐C₃F₇, n‐C₄F₉, C₆F₅), and metal diethyldithiocarbamates, AgSC(S)N(C₂H₅)₂ and Cd[SC(S)N(C₂H₅)₂]₂. The mechanisms of the reactions with AgR_f and Cd(R_f)₂ are discussed.