The parent (H(2)N-S-F) and N,N-dialkyl-substituted fluorides of amidosulfoxylic acid (R(2)N-S-F, R=Me or R(2)N=Morph) as well as the related compounds X-S-F (X=CH(3), OH, F, SiH(3), PH(2), SH, Cl) have been investigated with quantum chemical calculations at the ab initio (MP2) level of approximation. The geometries, electronic structures, molecular orbital (MO) energies and NMR chemical shift values have been calculated to evaluate the role and extent of the polarization and delocalization effects in forming of the high-field fluorine NMR resonances within the series of interest. The deltaF magnitudes for all investigated fluorides of amidosulfoxylic acid as well as the deltaN value calculated for Me(2)N-S-F are in the good agreement with the (19)F and (14)N NMR chemical shift values measured experimentally. For the parent compounds, H(2)N-S-F and H(2)N-SO(2)-F, the orientation of principal axes of the magnetic shielding tensors and the corresponding principal sigma(ii) values along these axes have been qualitatively interpreted basing on the analysis of the MO interactions in the presence of the rotating magnetic field.

2-Benzothiazolyl-N-(arenesulfonyl)-sulfinimidoyl fluorides were synthesized by the treatment of benzothiazolyl-2-sulfur trifluoride with sulfonamides. The reaction of 2-benzothiazolyl-N(p-toluenesulfonyl)-sulfinimidoyl fluoride with tertbutylamine and morpholine gave 2-benzothiazolyl-N-(arenesulfonyl)-sulfinimidoyl amides. The reaction of 2-benzothiazolyl-N-(p-toluenesulfonyl)-sulfinimidoyl fluoride or 2-benzothiazolyl-N-15-(p-tosyl) sulfinimidoyl fluoride with S-trimethylsilylbenzenethiol gave di(benzothiazolyl-2) disulfide, fluorotrimethylsilane and N,N'-bis(p-toluenesulfonyl)-N,N'-bis(phenylthio)-hydrazine or N-15, N-15'-bis(p-toluenesulfonyl)-N-15,N-15'-bis(phenylthio)-hydrazine, respectively. (c) 2005 Wiley Periodicals, Inc.

Simple, convenient and universal method of the different types of organosulfur trifluorides synthesis, with common formula RSF3 where R = dialkylamino group, aromatic or heterocyclic radical, was elaborated. The method consists in the reaction of thiosulfurous acid diamides, diaryldisulfides or diheteryldisulfides with chlorine in the presence of potassium fluoride excess.

The evolution of the term fluorous is addressed first, then a concise terminology is proposed, including fluorous partition coefficient, specific fluorophilicity and fluorousness. Some examples are shown for the design of higher generation fluorophilic molecules, involving Class I to Class III ponytails. Fluorophilic ethers of the structure of ArC(CF(3))(2)O(CH(2))(m)(CF(2))(n)F (m = 1. n = 1. 7 m = 3, it = 8) are obtained in high yields, when 2-aryl- 1, 1, 1,3,3,3-hexafluoro-propanols are reacted either with trifluoroethyl- and 1H. 1H-perfluorooetyl triflates (NaH/ DMF, Williamson ether synthesis) or with 3-perfluorooctyl-propanol (Ph(3)P/EtO(2)CN=NCO(2)Et/PhCF(3). Mitsunobu reaction), respectively. Fluorophilic phenol- and perfluoro-tert-butyl ethers can also be prepared effectively by the latter method. In case of higher homologues (n = 7, 8) product isolation can be facilitated using fluorous extraction (C(6)F(14)/CH(3)OH). Specific fluorophilicity values of target molecules are estimated using a 2D method and compared with experimentally determined ones. (C) 2002 Elsevier Science B.V. All rights reserved.

Chalcogen tetrafluorides and the corresponding ionic structures and associates were simulated by the PM3 quantum-chemical method, and their stabilities were estimated. The ability of chalcogen tetrafluorides and their derivatives to form fluorine bridging bonds E-F...E increases in the series S, Se, Te. These bridging bonds, in keeping with their lengths, can be regarded as strong semipolar bonds. Chalcogen atoms in associated structures occur in pseudooctahedral hybridization.

(+/-)-15-Fluoro-11,15-dideoxyprostaglandin E(1) and its methyl and ethyl esters were synthesized. Dehydroxyfluorination reaction of (+/-)-11-deoxyprostaglandin E(1) esters with various reagents based on SF4 was studied. Along with the target 15-fluorides (mixtures of alpha- and beta-epimers), products of allylic shift and dehydration in a ratio dependent on the fluorination agent were shown to be formed. With a morpholinotrifluorosulfuran-tris(morpholine)sulfonium trimethyldifluorosilicate mixture, the maximal excess (70%) of one of the 15-fluoro epimers was achieved. Possible mechanisms of dehydroxyfluorination of(+/-)-11-deoxyprostaglandin E(1) esters with dialkylaminofluorosulfurans were proposed. Methyl esters of 15-alpha fluoro- and 15-beta fluoro-11,15-dideoxyprostaglandin E(1) exhibited moderate antiaggregation activity in rabbit platelet tests.

(+/-)-15-Fluoro-11,15-dideoxyprostaglandin E1 and its methyl and ethyl esters were synthesized. Dehydroxyfluorination reaction (+/-)-11-deoxyprostaglandin E1 esters with various reagents based on SF4 was studied. Along with the target 15-fluorides (mixtures of alpha- and beta-epimers), products of allylic shift and dehydration in a ratio dependent on the fluorination agent were shown to be formed. With a morpholinotrifluorosulfuran-tris(morpholine)sulfonium trimethyldifluorosilicate mixture, the maximal excess (70%) of one of the 15-fluoro epimers was achieved. Possible mechanisms of dehydroxyfluorination of (+/-)-11-deoxyprostaglandin E1 esters with dialkylaminoflluorosulfurans were proposed. Methyl esters of 15-alpha-fluoro- and 15-beta-fluoro-11,15-dideoxyprostaglandin E1 exhibited moderate antiaggregation activity in rabbit platelet tests.

AbstractChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 100 leading journals. To access a ChemInform Abstract of an article which was published elsewhere, please select a “Full Text” option. The original article is trackable via the “References” option.

AbstractChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 100 leading journals. To access a ChemInform Abstract of an article which was published elsewhere, please select a “Full Text” option. The original article is trackable via the “References” option.

AbstractThe title compound (III) acts as fluorating agent.

ChemInformVolume 20, Issue 14 Natural Products ChemInform Abstract: One-Step Synthesis of Pyrimidine 2′-Deoxy-5′-O-trityl-O2,3′-anhydronucleosides. G. V. ZAITSEVA, G. V. ZAITSEVA Inst. bioorg. khim. Akad. nauk Beloruss. SSR MinskSearch for more papers by this authorE. V. VAAKS, E. V. VAAKS Inst. bioorg. khim. Akad. nauk Beloruss. SSR MinskSearch for more papers by this authorV. E. PASHINNIK, V. E. PASHINNIK Inst. bioorg. khim. Akad. nauk Beloruss. SSR MinskSearch for more papers by this authorV. I. TOVSTENKO, V. I. TOVSTENKO Inst. bioorg. khim. Akad. nauk Beloruss. SSR MinskSearch for more papers by this authorL. N. MARKOVSKII, L. N. MARKOVSKII Inst. bioorg. khim. Akad. nauk Beloruss. SSR MinskSearch for more papers by this authorI. A. MIKHAILOPULO, I. A. MIKHAILOPULO Inst. bioorg. khim. Akad. nauk Beloruss. SSR MinskSearch for more papers by this author G. V. ZAITSEVA, G. V. ZAITSEVA Inst. bioorg. khim. Akad. nauk Beloruss. SSR MinskSearch for more papers by this authorE. V. VAAKS, E. V. VAAKS Inst. bioorg. khim. Akad. nauk Beloruss. SSR MinskSearch for more papers by this authorV. E. PASHINNIK, V. E. PASHINNIK Inst. bioorg. khim. Akad. nauk Beloruss. SSR MinskSearch for more papers by this authorV. I. TOVSTENKO, V. I. TOVSTENKO Inst. bioorg. khim. Akad. nauk Beloruss. SSR MinskSearch for more papers by this authorL. N. MARKOVSKII, L. N. MARKOVSKII Inst. bioorg. khim. Akad. nauk Beloruss. SSR MinskSearch for more papers by this authorI. A. MIKHAILOPULO, I. A. MIKHAILOPULO Inst. bioorg. khim. Akad. nauk Beloruss. SSR MinskSearch for more papers by this author First published: April 4, 1989 https://doi.org/10.1002/chin.198914319AboutPDF 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 onFacebookTwitterLinked InRedditWechat No abstract is available for this article. Volume20, Issue14April 4, 1989 RelatedInformation

The conformational equilibria in the series of 2-substituted 1,1-difluorocyclohexanes were investigated by comparison of the integral intensities of the signals of the conformers in the low-temperature /sup 19/F NMR and PMR spectra and from the averaged width of the signal for the methine proton ion the PMR spectra. It was found that the equilibrium is displaced toward the axial conformer compared with the corresponding monosubstituted cyclohexanes, and this was explained on the basis of dipole-dipole repulsion in the equatorial conformer. The structural characteristics of the 1,1,2-trisubstituted cyclohexanes prevent the appearance of the quantum-mechanical effect which stabilizes the gauche arrangement of the strongly electronegative substituents.