Exposure to the fumes and smoke from white phosphorus pastes in the strike-anywhere match industry was associated, in the latter half of the 19th century, with a low incidence of necrotic lesions of the jaw bones and/or a fragility of the mid-femur occasioning fractures after minor trauma. Hundreds of cases were reported in many countries. The plight of these workers was the subject of international social pressure eventually leading to the prohibition of the matches. The reappearance in the early 21st century of two similar maladies associated with bisphosphonic acid (BP) medications led us to investigate the potential connection between these two pairs of debilitating effects. The BP molecules were chosen for development beginning in the early 1970s as pharmacologically satisfactory analogs of a simple inorganic phosphorus compound, pyrophosphoric acid, which had been found to exert an inhibitory effect on bone dissolution in vitro. These BPs inhibited bone loss in vivo. Independently, chemical analyses published in the mid-1980s demonstrated that the original small inorganic phosphorus model molecule was the most prevalent substance in the complex fumes and smoke associated with the pair of legacy diseases, thus persuasively connecting it, mediated by a common biological mechanism, to the modern drug side-effects.

August Wilhelm Hofmann, 1818–1892, discovered many of the functional groups of organophosphorus chemistry, including primary, secondary, and tertiary phosphines, oxides and sulfides of the latter, phosphonic and phosphinic acids and their chloro derivatives, dithiophosphinic acids, tetraalkyl phosphonium hydroxides, and Lewis salts from both tertiary phosphines and their oxides. Some of his procedures are still in use today. Some fundamental properties of these groups were also discovered. In spite of these contributions, much current literature fails to recognize him as the founder of the field, generally giving credit to Carl Arnold August Michaelis and sometimes to Alexander E. Arbuzov, both of whom followed Hofmann chronologically. The contributions of Michaelis and Arbusov were indeed most impressive and extensive. However, the case made in this paper, established by studying the original German literature, will be that August W. Hofmann deserves recognition as the originator of the field of organophosphorus chemistry, indeed as the founding father of the field.

Today I want to reflect with you on the dramatic growth of the field of phosphorus chemistry that I have observed since my entry into it in 1950. At that time, phosphorus chemistry was scarcely kno...

The last five years have seen many advances in the chemistry of phospholes. Motivating much of the work has been the potential for discovering valuable applications of phospholes, especially as ligands in metal coordination compounds designed for use as homogeneous catalysts, and in the field of electro-optical substances. This review covers the research in the synthesis, properties and applications of phospholes that has been published since the last comprehensive review by the author in 1999. While prepared for the specialist, the review is designed to introduce some of the aspects of phosphole chemistry to the general reader.

B3LYP and MP2 calculations at the 6-311+G(nd,p) level (with n = 2 for second-row elements and n = 1 otherwise) were carried out using the atoms-in-molecules (AIM) approach to characterize the thiophosphoryl bond. A series of R3PS molecules were studied and compared with the corresponding R3PO systems. As with the phosphoryl bond, one cannot distinguish the thiophosphoryl bond from a standard P=S double bond by comparing bond distances. On the basis of the P=S bond in HP=S having a reference bond order of 2.0, the thiophosphoryl bond has a bond order of about 1.6. Examination of localized orbitals show that this bond is less polar than the corresponding PO bond. As with the phosphoryl bond, what sets the thiophosphoryl bond apart is the high degree of back-bonding that contributes to the delocalization index (and covalent bond order) and is the basis for its stronger than single bond character and short bond distance. S-33 NMR shielding calculations were also carried out and, in a few instances, compared directly with newly determined experimental shieldings. Copyright (C) 2004 John Wiley Sons, Ltd.

33 S NMR chemical shifts were calculated by the scaled DFT and EMPI approaches for the fluoride, chloride and bromide of trimethylsulfonium ion (1) and S ‐methyltetrahydrothiophenium ion (2), in addition to the free cations. Experimental values were obtained for the iodides of 1 (δ +48, CS 2 = 0 ppm) and 2 (δ +95), and were found to agree with the calculated values well within the standard deviation of 35 ppm (3.5% of the shielding range) established in earlier work for a great variety of sulfur compounds. An earlier literature value of δ +750 for the iodide of 2 is therefore to be replaced. Calculations provide a shift of δ +68 for S ‐methylthianium ion with equatorial methyl, indicating that the reported value of δ +670 for the iodide is also incorrect. Copyright © 2004 John Wiley & Sons, Ltd.

ChemInformVolume 33, Issue 40 p. 271-271 Reviews Five-Membered Rings: Phospholes (Literature from 1953-1994) Louis D. Quin, Louis D. Quin Dep. Chem., Univ. Mass., Amherst, MA 01003, USASearch for more papers by this author Louis D. Quin, Louis D. Quin Dep. Chem., Univ. Mass., Amherst, MA 01003, USASearch for more papers by this author First published: 19 May 2010 https://doi.org/10.1002/chin.200240271AboutPDF 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. Volume33, Issue40October 8, 2002Pages 271-271 RelatedInformation

Animals of hydrothermal vents live in a unique environment that conceivably could lead to modifications of the usual phosphorus functional groups of importance in living systems. To explore this possibility, specimens of a sea anemone (unidentified) from the TAG hydrothermal field, Mid-Atlantic Ridge, the mussel Bathymodiolus N. sp. from the Mid-Atlantic Ridge, and the tubeworm Riftia pachyptila from the East Pacific Rise were analyzed for compounds containing the carbonphosphorus bond. The analysis was based on the use of 31P-nuclear magnetic resonance, which gives signals for C–P compounds that are well separated from those of biological phosphoric acid derivatives. The animals were extracted to provide a lipid- and a water-soluble fraction, leaving an insoluble, largely proteinaceous solid residue. The lipid and residue fractions were subjected to hydrolysis to release bound forms of phosphonic acids. All fractions were analyzed by 31P-NMR. Aminophosphonic acids [primarily NH2CH2CH2PO(OH)2 (1) and CH3NHCH2CH2PO(OH)2 (2)] represented the only type of C–P compound detected. These are well-known constituents of coastal invertebrates. For the mussel and sea anemone, these compounds were present in bound form in both the lipid and insoluble residue. The tube worm contained C–P material only in the insoluble residue, but in quite small amounts. The 31P-NMR method is especially valuable in being able to discriminate between compounds 1 and 2. By this technique, two coastal sea anemones (Tealia felina and Bunadosoma cavernata), previously thought to have 1 as the dominant aminophosphonic acid, were in fact found to be much richer in originally undetected 2. This compound was also detected for the first time in a mussel (Genkensia demissa).

The Nature of Organophosphorus Chemistry. Some General Considerations of Organophosphorus Compounds. The Common 3-Coordinate Functions ( ~ 3, ~ 3). The 4-Coordinate Phosphine Oxides, Other Chalcogenides and Phosphonium Salts. The Acids of Organophosphorus Chemistry and Their Derivatives. Phosphorus-31 NMR Spectroscopy. Other Spectroscopic Techniques in Organophosphorus Chemistry. Heterocyclic Phosphorus Compounds. Optically Active Organophosphorus Compounds. The Low- and High-Coordination States of Phosphorus. Organophosphorus Chemistry in Biology, Agriculture, and Technology. Index.

ADVERTISEMENT RETURN TO ISSUEPREVBook ReviewNEXTHeterocyclic Chemistry. Third Edition By Thomas L. Gilchrist (University of Liverpool). Addison Wesley Longman: Essex. 1997. xvii + 414 pp. £22.99. ISBN 0-582-27843-0.Louis D. QuinView Author Information University of North Carolina at WilmingtonCite this: J. Am. Chem. Soc. 1998, 120, 17, 4257–4258Publication Date (Web):March 28, 1998Publication History Published online28 March 1998Published inissue 1 May 1998https://pubs.acs.org/doi/10.1021/ja9756376https://doi.org/10.1021/ja9756376book-reviewACS PublicationsCopyright © 1998 American Chemical SocietyRequest reuse permissionsArticle Views337Altmetric-Citations2LEARN ABOUT THESE METRICSArticle Views are the COUNTER-compliant sum of full text article downloads since November 2008 (both PDF and HTML) across all institutions and individuals. These metrics are regularly updated to reflect usage leading up to the last few days.Citations are the number of other articles citing this article, calculated by Crossref and updated daily. Find more information about Crossref citation counts.The Altmetric Attention Score is a quantitative measure of the attention that a research article has received online. Clicking on the donut icon will load a page at altmetric.com with additional details about the score and the social media presence for the given article. Find more information on the Altmetric Attention Score and how the score is calculated. Share Add toView InAdd Full Text with ReferenceAdd Description ExportRISCitationCitation and abstractCitation and referencesMore Options Share onFacebookTwitterWechatLinked InRedditEmail Other access optionsGet e-Alertsclose SUBJECTS:Aromatic compounds,Nuclear magnetic resonance spectroscopy,Phosphorus,Students,Undergraduates Get e-Alerts

Heteroatom ChemistryVolume 9, Issue 7 p. 601-604 Free to Read A tribute to Professor Robert R. Holmes on the occasion of his 70th birthday Professor Emeritus Louis D. Quin, Professor Emeritus Louis D. Quin University of Massachusetts, AmherstSearch for more papers by this authorProfessor Joan A. Deiters, Professor Joan A. Deiters Vassar CollegeSearch for more papers by this authorWilliam E. McEwen, Corresponding Author William E. McEwen Editor-in-Chief University of Massachusetts, AmherstUniversity of Massachusetts, Department of Chemistry, Amherst, MA 01003Search for more papers by this author Professor Emeritus Louis D. Quin, Professor Emeritus Louis D. Quin University of Massachusetts, AmherstSearch for more papers by this authorProfessor Joan A. Deiters, Professor Joan A. Deiters Vassar CollegeSearch for more papers by this authorWilliam E. McEwen, Corresponding Author William E. McEwen Editor-in-Chief University of Massachusetts, AmherstUniversity of Massachusetts, Department of Chemistry, Amherst, MA 01003Search for more papers by this author First published: 27 January 1999 https://doi.org/10.1002/(SICI)1098-1071(1998)9:7<601::AID-HC1>3.0.CO;2-HAboutPDF 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 onEmailFacebookTwitterLinkedInRedditWechat Volume9, Issue7Special Issue: Dedicated to Robert R. Holmes1998Pages 601-604 RelatedInformation

ADVERTISEMENT RETURN TO ISSUEPREVBook ReviewNEXTThe Chemistry of Functional Groups, Vol. 4: The Chemistry of Organophosphorus Compounds Edited by F. R. Hartley (Cranfield University). John Wiley & Sons, Inc. New York, NY. 1996. xiv + 945 pp. 15 × 22.5 cm. $375.00. ISBN 0-471-95706-2.Louis D. QuinView Author Information Department of Chemistry University of Massachusetts Amherst, Massachusetts 01003Cite this: J. Nat. Prod. 1997, 60, 3, 323Publication Date (Web):March 21, 1997Publication History Published online21 March 1997Published inissue 1 March 1997https://doi.org/10.1021/np960621zCopyright © 1997 American Chemical Society and American Society of PharmacognosyRIGHTS & PERMISSIONSArticle Views80Altmetric-Citations-LEARN ABOUT THESE METRICSArticle Views are the COUNTER-compliant sum of full text article downloads since November 2008 (both PDF and HTML) across all institutions and individuals. These metrics are regularly updated to reflect usage leading up to the last few days.Citations are the number of other articles citing this article, calculated by Crossref and updated daily. Find more information about Crossref citation counts.The Altmetric Attention Score is a quantitative measure of the attention that a research article has received online. Clicking on the donut icon will load a page at altmetric.com with additional details about the score and the social media presence for the given article. Find more information on the Altmetric Attention Score and how the score is calculated. Share Add toView InAdd Full Text with ReferenceAdd Description ExportRISCitationCitation and abstractCitation and referencesMore Options Share onFacebookTwitterWechatLinked InReddit Read OnlinePDF (35 KB) Get e-AlertsSUBJECTS:Chemical warfare,Functional groups,Organophosphorus compounds,Phosphorus,Reaction products Get e-Alerts

Heteroatom ChemistryVolume 8, Issue 5 p. 371-374 Free to Read A tribute to Prof. William E. McEwen on the occasion of his seventy-fifth birthday Alfred Schmidpeter, Alfred Schmidpeter Regional EditorSearch for more papers by this authorShigeru Oae, Shigeru Oae Regional EditorSearch for more papers by this authorLouis D. Quin, Louis D. Quin Guest EditorSearch for more papers by this author Alfred Schmidpeter, Alfred Schmidpeter Regional EditorSearch for more papers by this authorShigeru Oae, Shigeru Oae Regional EditorSearch for more papers by this authorLouis D. Quin, Louis D. Quin Guest EditorSearch for more papers by this author First published: 07 December 1998 https://doi.org/10.1002/(SICI)1098-1071(1997)8:5<371::AID-HC1>3.0.CO;2-C AboutPDF 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 Volume8, Issue51997Pages 371-374 RelatedInformation

ChemInform 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.

The structure of the title compound1 has been determined by X-ray crystallography analysis. The following crystal data were found: orthorhombic,Pca2l,a=9.60691),b=16.356(1),c=8.686(1) Å. Both the phospholane and phospholene rings involved in the 7-phosphabicyclo-[2.2.1] hept-2-ene system have almost regular envelope conformations, and the cyclohexene ring has a significantly deformed boat conformation. The low value of the C−P−C angle, 84.2(2)°, reflects the steric strain around the phosphorus bridge and may be responsible for the reactivity of esters and amides derived from1 in the O-insertion reaction with m-chloro-perbenzoic acid. The dihedral angle between the plane of the benzene and succinimide rings is 82.4(2)°.