摘要:

AbstractRecent advances in the synthesis and reaction chemistry of fluorine‐containing tri‐ and tetracoordinate sulfur(IV)and pentacoordinate sulfur(VI)compounds are presented. Each molecule included contains sulfur bonded to fluorine or to a fluorinated gr

ISSN:0021-2148    

DOI:10.1002/ijch.197800002

出版商:WILEY‐VCH Verlag    

年代:1978

数据来源: WILEY

摘要:

AbstractRecent research on oxyfluorides of bromine is reviewed. This work is the first on the subject since 1963 when BrO2F was the only known oxyfluoride of bromine. Since then a number of other oxyfluoro compounds have been prepared, and a considerable amount of information on the structure and properties of all these compounds including additional information on BrO2F has been obtained. This review attempts to summarize all the data reported up to mid‐197

ISSN:0021-2148    

DOI:10.1002/ijch.197800003

出版商:WILEY‐VCH Verlag    

年代:1978

数据来源: WILEY

摘要:

AbstractThe reactions of simple chlorine containing compounds of the general composition XCl are reviewed and discussed. The compounds included for review are ClF, RfOCl, SF5OCl, CF3OOCl, SF5OOCl, ClOSO2F, ClOClO3and ClONO2. It is concluded that most of the known reaction chemistry of electropositive chlorine compounds can be rationalized in terms of either addition of Cl‐X across multiple bonds or oxidative addition to atoms, such as iodine or sulfur in their lower oxidation states. The observed variety of final reaction products can be explained by a multitude of secondary reactions which can involve either eliminations, further additions or degradations. The observed reactions are easily moderated and controlled and only seldom is no reaction encountere

ISSN:0021-2148    

DOI:10.1002/ijch.197800004

出版商:WILEY‐VCH Verlag    

年代:1978

数据来源: WILEY

摘要:

AbstractThe principles of electric deflection spectroscopy and its relevance to molecular structure are reviewed. Application of this technique to gain insights into the structures of binary fluorides and oxide fluorides are described in detail. In particular, knowledge gained about nonrigid fluoride structures is described and some thoughts concerning future applications of electric deflection spectroscopy are presented.

ISSN:0021-2148    

DOI:10.1002/ijch.197800005

出版商:WILEY‐VCH Verlag    

年代:1978

数据来源: WILEY

摘要:

AbstractRecent advances in the field of fluorohalogenate chemistry are reviewed. Areas considered include their preparation, properties and structure. It is concluded that while many of the expected anions formed by the various halogen fluorides can be isolated and identified, full understanding of their structures is hindered by their extremely reactive properties and the fact that their existence is mostly limited to the solid state.

ISSN:0021-2148    

DOI:10.1002/ijch.197800006

出版商:WILEY‐VCH Verlag    

年代:1978

数据来源: WILEY

摘要:

AbstractResults of high pressure fluorination (300–3000 bar F2) are given and discussed, e.g. fluorides of CrIV, MnIV, NiIV, CuIV, PtIV, PrIV, NdIV(?), DyIV(?) and RhV, AuV. Newly prepared were BaNiF6(monoclinic, a = 9.465Å, b = 4.950Å, c = 6.655Å, β = 103.3O), Cs2‐xRbxNiF6, Rb2‐xKxNiF6(K2PtCl6‐type) all carmine‐red; BaPrF6(RbPaF6‐type, a = 8.027Å, b = 11.593Å, c = 5.617Å), SrPrF6(LaF6‐type, a = 7.090Å, c = 7.290Å), both colourless powders; Cs2KNdF7(a = 9.605Å), Cs2KDyF7(a = 9.479Å), both cubic, orange‐yellow powders, (NH4)3, ZrF7‐type; MnF4(trig., a = 19.53 Å, c = 12.59 Å), ultramarine‐blue single crystals, O+2[MnF5]−(monoclinic, a = 17.55 Å, b = 8.43 Å, c = 9.10 Å, β = 101.8°), bright‐red single crystals, and yellow single crystals, O+2[AuF6]−, which dec

ISSN:0021-2148    

DOI:10.1002/ijch.197800007

出版商:WILEY‐VCH Verlag    

年代:1978

数据来源: WILEY

摘要:

AbstractSince 1970 we developed three novel methods of fluoro‐organic synthesis in our laboratory, namely: photofluorination (R‐H→‐F); fluorodehydrozylation (R‐OH→‐F); fluorodesulfurization (R‐SH→‐F). The general idea suggesting the development of the first two of these reactions was to find one‐step methods for transforming readily available and relatively complex organic compounds into the corresponding fluorine derivatives. The third method emerged as a chance discovery in an attempt to photofluorinate penicillamine, an amino acid with an SH group. The primary motivation of our search was to develop straightforward and routine syntheses of fluorine‐containing antimetabolites including enzyme inhibitors. Therefore, it was very attractive to find methods of fluorination capable of transforming a metabolite into an antimetabolite in one single step. The general concept that C‐fluorinated metabolites can represent antimetabolites was already established. However, F analogs of metabolites in general were considered probes for understanding the behavior of the desfluoro metabolites rather than compounds of practical use, e.g., as drugs. In contrast, introduction of F for improvement of drugs was well established before 1970. By that time, the pioneering discovery of Josef Fried of the beneficial effect of introducing F into corticosteroids had already led to a widely accepted and employed approach for the “molecular manipulation” of a wide range of drugs. A striking advance in organofluorine synthesis occurred shortly before our own concentrated effort commenced when Sir Derek Barton and co‐workers published the first general method for the direct introduction of F into olefins and aromatic compounds of nucleophilic character so as to react with the electrophilic fluorinating reagent, fluoroxytrifluoromethane (CF3OF). Nonetheless, it appeared to us that the “state of art” of organofluorine synthesis was not yet advanced enough for the routine synthesis of fluorinated metabolites and for the direct introduction of F into drugs.Two objectives determined our efforts from the beginning: Our first goal was to elevate the “state of art” in respect to synthesis. The second was to attempt to sharpen the selection process in the choice of metabolites which were to serve as substrates for generation of drugs, that is of antimetabolites of great selectivity and practical utility. Both photofluorination and fluorodehydroxylation were developed to serve a particular principle in design of antimetabolites and drugs, namely the principle of isogeometric modification of metabolites with maximal shift of electron‐distribution to generate specific and active antimetabolites. The work to be reviewed here led to the discovery of an antimetabolite (3‐fluoro‐D‐alanine‐2d(code‐named MK‐641)) which is the unorthodox component of the experimental antibacterial combination drug, MK‐641/MK‐642. Analysis of the mechanism of action of this antimetabolite suggests that it belongs to the class of “suicide

ISSN:0021-2148    

DOI:10.1002/ijch.197800008

出版商:WILEY‐VCH Verlag    

年代:1978

数据来源: WILEY

摘要:

AbstractFluoroxy reagents are versatile and useful electrophilic fluorinating reagents. Having wide applicability in a variety of solvents they display great potential for the synthesis of specifically fluorinated analogs of bioactive molecules.

ISSN:0021-2148    

DOI:10.1002/ijch.197800009

出版商:WILEY‐VCH Verlag    

年代:1978

数据来源: WILEY

摘要:

AbstractXenon fluorides, especially XeF2and the intercalates of XeF4and XeF6in graphite, react with a broad range of aromatic compounds to provide a convenient direct route to fluoroaromatic compounds, many of which are otherwise difficult to prepare. Some of the products are of medicinal and biological interest. Highly colored radical cations are generated in the reactions by one‐electron oxidation. XeF2also serves as a useful source of fluorine by reacting readily with carbon‐carbon double and triple bonds to yield difluoro‐ and tetrafluoro‐ addition products, as well as products resulting from rearrangements (especially in the case of norb

ISSN:0021-2148    

DOI:10.1002/ijch.197800010

出版商:WILEY‐VCH Verlag    

年代:1978

数据来源: WILEY

摘要:

AbstractIntramolecular nucleophilic displacement in organic fluorine compounds takes place if a fluorine atom is located in the molecule at such a distance from a nucleophilic functional group as to allow cyclization to three‐membered rings (in aliphatic compounds only), five‐membered rings, six‐membered rings, and, exceptionally, seven‐ and polymembered rings (in aromatic series only). The nucleophilic functions can be hydroxyl groups of alcohols, enols, phenols and carboxylic acids, sulfhydryl groups, primary or secondary amino groups, and carbanionic carbon atoms. The reaction is common with aliphatic monofluorides and aromatic polyfluorides, and rare with geminal and trigeminal fluorides. Whereas in the aliphatic series it is usually an undesirable side‐reaction, in the aromatic series it is useful as a means of synthesizing carbocyclic and heterocyclic polynuclear

ISSN:0021-2148    

DOI:10.1002/ijch.197800011

出版商:WILEY‐VCH Verlag    

年代:1978

数据来源: WILEY