SO2ClF Research Articles

Selected reactions of fluorine-fluorosulfate, FOSO 2F

The reactions of fluorine-fluorosulfate, FOSO 2F, with SSF 2, SeF 4, AsF 3 and MoF 5 have been studied, and its previously reported reactions with SF 4, Br 2 and I 2 re-investigated in order to test its suitability as a synthetic reagent. All substrates reacted exothermically, and sometimes explosively, between 80–298 K. The presence of the byproducts obtained may be rationalized by the thermal decomposition of some of the FOSO 2F, which proceeds along two pathways, i.e. FOSO 2F→1/2O 2+SO 2F 2 and FOSO 2F→1/2F 2+1/2S 2O 6F 2, during the extremely exothermic reactions via radical intermediates. The fluorine formed gives rise to fully fluorinated products, and the SO 3F· radicals, initially formed, either dimerize to give S 2O 6F 2 or decompose to O 2 and S 2O 5F 2. Element fluoride-fluorosnlfates, when formed at all, were obtained in low yields only when SO 2F 2 or SO 2FCl were used as suitable moderators. The complete vibrational spectra of EF 5OSO 2F (E=S, Se or Te) have been studied and assigned. The reactions of I 2, Br 2 and AsF 3 with FOSO 2F yielded viscous liquids of the approximate, non-stoichiometric composition EF n (SO 3F) 5− n (E=As or I) and EF n (SO 3F) 3− n (E=Br), with n=non-integral number. All compounds were characterized by their vibrational and 19F NMR spectra, and in the case of SeF 5OSOe 2F by 77Se NMR methods.

A convenient preparation of sulfuryl chloride fluoride

The reaction of either ammonium fluoride or potassium fluoride with sulfuryl chloride in the presence of trifluoroacetic acid at ambient temperature gave sulfuryl chloride fluoride in good to moderate yields.

Fluorination of trimethylsilyl phosphites and their structural analogues by sulfuryl chloride fluoride: simple preparation of phosphorofluoridates and related compounds, including deoxynucleoside phosphorofluoridates

Trimethylsilyl esters of general formula RR′POSiMe3 react in a quantitative and fully chemoselective way with sulfuryl chloride fluoride, ClSO2F, under extremely mild conditions to give phosphorofluoridates RO(R′O)P(O)F of high purity. This work provides easy access to all type of fluoridates from non-toxic starting materials. The synthetic usefulness of this method is illustrated by the synthesis of 3′- and 5′-mononucleoside phosphorofluoridates 10 and 3′,5′-dinucleoside phosphorofluoridates 11 from the corresponding nucleoside trimethylsilyl phosphites.

Janusene and tetrafluorojanusene in superacid media; radical cation formation and chemistry

Both janusene 1 and the facial tetrafluorojanusene undergo one electron oxidation in FSO 3H.SbF 5 (1:1) ‘magic acid’/SO 2ClF and in HF.SbF 5 (1:1)/SO 2ClF at low temperature to give persistent radical cations. Rapid dimerization → polymerization follows. Stable σ-complexes of protonation were not observed at all. In the less oxidizing milder superacid FSO 3H/SO 2, neither 1 nor 2 are fully protonated or oxidized. Radical cation-mediated condensation of 1 is much more rapid than for the fluorinated analog. Two structurally different dimeric compounds could be isolated in quenching experiments. The extent of transannular donor-acceptor interactions in the facially fluorinated janusenes were compared with those for the tropylium-containing janusene, fluorinated [2.2] paracyclophane and its stable σ-complex.

Silyloxyphosphanes. New Phosphitylating Reagents in Nucleotide Chemistry

Abstract Letsinger et al. developed a phosphite method of synthesis of oligonucleotides. This method was further improved by Carruthers et al. Our present work is a useful extension of the Letsinger-Carruthers type reagents. Recently, we have been able to demonstrate that bis- (N, N-diisopropylamino)trimethylsilyloxy phosphane exhibit phosphitylating properties in the presence 1-H-tetrazole.1 Preparation of this reagent and its ability to undergo selective nucleophilic substitution at the tricoordinate phosphorus atom without affecting the silicon center under conditions which are commonly used for the phosphite triester approach has been recently described.1 In the same paper we reported remarkable chemical properties of dinucleosidetrimethyl-siloxyphosphanes. Namely their participation in Michaelis-Arbuzov type reactions under extremely mild conditions and reactions with oxalylazolides and sulfuryl chloride fluoride which are unique for these reagents.

Metallocen-chemie hochfluorierter ligand-systeme XII. Synthese und charakterisierung von Cp 2Ti(BiF 6) 2

The preparation of the first fluorine-coordinated metallocene hexafluorobismutahte complex is reported. Cp 2Ti(BiF 6) 2 ( 1) was prepared from the reaction of Cp 2TiF 2 with BiF 5 in SO 2ClF in the presence of anhydrous HF, followed by recrystallization of 1 from liquid SO 2. IR investigations clearly indicate that the BiF 6 unit is not octahedral but is strongly distorted, and that both bridging (Ti···F···Bi) and nonbridging (BiF) fluorines are present.

A reassignment of the vibrational fundamentals of sulfuryl chloride fluoride

Low temperature Raman spectroscopy has led to a significant revision in the assignment of the vibrational fundamentals of sulfuryl chloride fluoride (SO 2FCl). The fundamentals in cm −1 are: ( a′) 1230, 826, 632, 503, 422, 295; ( a″) 1469, 476, 303. All are from gas-phase i.r. spectra except 295 cm −1, which is from the liquid-phase Raman spectrum. The revised assignments are consistent with the predictions of Pfeiffer's normal coordinate calculations [Z. phys. chem., Leipzig 240, 380 (1969)].

Ionization current detection of soft X-ray photoabsorption: Sulfur and chlorine k-shell spectra of SO 2F 2, SO 2FCl and SO 2Cl 2

An apparatus for recording inner-shell excitation spectra by detecting currents produced by the X-ray ionization of gases is described. The equivalence of ion current and true photoabsorption (log( I 0/ I)) detection for the case of S 1s spectroscopy of molecules is demonstrated. The ion current detection has been used to record the S 1s and Cl 1s spectra of SO 2FCl and SO 2Cl 2 and the S 1s spectrum of SO 2F 2. The spectral features are analysed in terms of excitations to σ* orbitals characteristic of the local bonding to the K-shell excited atom. The correlation between SX bond lengths and the positions of S 1s→σ*(SX) excitations relative to the S 1s ionization threshold is discussed and related to corresponding correlations for OX bonds.

ChemInform Abstract: Fluorination of Trimethylsilyl Phosphites and Their Structural Analogues by Sulfuryl Chloride Fluoride. A Facile Preparation of Phosphorofluoridates and Related Compounds.

AbstractThe phosphorofluoridates (III) are prepared by treatment of the trimethylsilyl esters (I) with sulfuryl chloride fluoride (II).

Synthetic methods and reactions. 123. Preparation of .alpha.-chloro ketones from enol silyl ethers with sulfuryl chloride fluoride and sulfuryl chloride

Synthetic methods and reactions. 123. Preparation of .alpha.-chloro ketones from enol silyl ethers with sulfuryl chloride fluoride and sulfuryl chloride

Onium ions. 25. Oxidation of tertiary phosphines and arsines with sulfur trioxide and sulfuryl chloride fluoride: demonstration of ambident reactivity

Onium ions. 25. Oxidation of tertiary phosphines and arsines with sulfur trioxide and sulfuryl chloride fluoride: demonstration of ambident reactivity

Reactions of chlorine monofluoride with tetrasulphur tetranitride, thiazyl chloride and thiazyl fluoride

Chlorine monofluoride reacts with tetrasulphur tetranitride to give thiazyl chloride (monomer and trimer) and thiazyl fluoride; with further ClF, NSCl reacts to form NSF then ClNSF 2, and finally N 2, Cl 2 and SF 4. The reaction NSCl/ClF to give NSF/Cl 2 reverses in SO 2 solvent due to removal of ClF as SO 2ClF. NSF was prepared, in a new method, by passing NSCl through a column of CsF at 110°.

Photoabsorption spectra of gaseous CH 3SO 2Cl, CCl 3SCl, SO 2ClF and (CH 3O) 2SO

The UV-visible absorption spectra of CH 3SO 2Cl, CCl 3SCl, SO 2ClF and (CH 3O) 2SO were quantitatively analyzed at 298 K. The threshold wavelengths for photodissociation of these molecules and SO 2F 2 were calculated from thermochemical data and estimates were made of their atmospheric photodissociation rate coefficients.

Organophosphorus compounds: the first applications of sulfuryl chloride fluoride SO2FCl in synthesis

Organophosphorus compounds: the first applications of sulfuryl chloride fluoride SO2FCl in synthesis

Synthetic Methods and Reactions; 921. A New Method of Dethioacetalization with Sulfuryl Chloride Fluoride

Synthetic Methods and Reactions; 92¹. A New Method of Dethioacetalization with Sulfuryl Chloride Fluoride

Aromatic protonation—4 : On the 1H- 2H exchange of three 9-n-alkylanthracenes on reaction with CF 3CO 2[ 2H] and FSO 3[ 2H

The reactions of 9-methyl-, 9-ethyl- and 9-propyl-anthracene with CF 3CO 2[ 2H] in C[ 2H]Cl 3 and with FSO 3[ 2H] in SO 2ClF have been investigated. Using 4 equivalents of CF 3CO 2[ 2H] at 50° 1H- 2H exchange was observed only for the 10-H and the side-chain α-hydrogens, and on using 8 and 12 equivalents at 50° also for the aromatic α-hydrogens. Treatment of the substrates with FSO 3[ 2H] at -60° leads to the stable 9-alkyl-[10- 2H]-10-anthracenium ions. On warming up to −25° a slow 1H- 2H exchange of only the 10- 1H of these anthracenium ions is observed. A mechanism for the 1H- 2H exchange of the aromatic and the side-chain α-hydrogens of the 9-alkylanthracenes is presented.

Reactions and energy distribution in dissociative electron capture processes in sulfuryl halides

The sulfuryl halides, SO 2F 2, SO 2Cl 2, and SO 2ClF form several ions by dissociative electron capture. The ionization efficiency curves are determined for each process. Where the ion intensity was great enough, the kinetic energy of the ion was measured over the greater part of the electron energy of the resonance. In most instances the kinetic energy of the ion increased linearly with electron energy over the range of the resonance. Extrapolation to zero kinetic energy release give the electron energy corresponding to the heat of the dissociation reaction. The kinetic energy released in the formation of F 2 − and Cl 2 − was only slightly greater than that predicted by the quasi-equilibrium theory, as would be expected from the fact that the molecule had to change its configuration during dissociation. Essentially all the excess energy was released in translation when SO 2F − was formed. The ions F − from SO 2F 2 and Cl − from SO 2Cl 2 are formed in two separate resonances, and the kinetic energy lines extrapolate to thermal appearance potentials (Δ H r) corresponding to the formation of SO 2 and the halogen atom. The Δ H r values for these reactions as well as that for Cl 2 − at their higher energy resonances appear to correspond to an electronic transition for SO 2 of 2.5 eV.

Synthetic Methods and Reactions; 831. Sulfuryl Chloride Fluoride, a Mild Dehydrating Agent in the Preparation of Nitriles from Aldoximes

Synthetic Methods and Reactions; 83¹. Sulfuryl Chloride Fluoride, a Mild Dehydrating Agent in the Preparation of Nitriles from Aldoximes

Synthetic Methods and Reactions; 881. Sulfuryl Chloride Fluoride, a Convenient Reagent for the Preparation of Amides from Carboxylic Acids and Primary Amines Under Mild Conditions

Synthetic Methods and Reactions; 88¹. Sulfuryl Chloride Fluoride, a Convenient Reagent for the Preparation of Amides from Carboxylic Acids and Primary Amines Under Mild Conditions

Radical cotelomerization of hexafluoropropene and ethylene with sulfuryl chloride fluoride

1. The cotelomerization of ethylene and hexafluoropropene with sulfuryl chloride fluoride occurred at 90°C with initiation by benzoyl peroxide. Cotelomers were isolated which consisted of two monomeric ethylene units and one of hexafluoropropene, and also of three monomeric units of ethylene and one of hexafluoropropene. 2. Due to the high electrophilicity of hexafluoropropene, the first and last monomeric units of the chain are always ethylene.