Book Reviews

Abstract

TROUBLESHOOTING IN DER HPLC (Fehlersuche in der HPLC) by N. Vonk, B. G. J. Baars and H. Schaller, Birkhauser Verlag, Therwill (Switzerland), 140 pages, ISBN 3-7643-2400-7, SFr 44.80.

WATER SAMPLING, ed., J. M. Krajca, Ellis Horwood Ltd., Chichester, U.K., 212 pages. £39.95, ISBN 0-853128138.     

Books Section

Abstract

Colombo, A.G. (1992). Environmental Impact Assessment. Kluwer Academic Publishers, Dordrecht, p. 334 + xii pp., Hardcover, ISBN: 0-7923-1589-8, Dfl180.00; £61.00.

Martin, G. and Laffort, P. (1991). Odeurs et Désodorisation dans l'Environnement. (Odors and Desodorisation in the Environment). TEC & DOC – Lavoisier, Paris. p. 452 + xxiv pp., Hardcover, In French, ISBN: 2-85206-605-X, FF 565.00.

Yalkowsky, S. H. and Banerjee, S. (1992). Aqueous Solubility: Methods of Estimation for Organic Compounds. Marcel Dekker, Inc., New York. p. 264 + vi pp., Hardcover, ISBN: 0-8247-8615-7, US$99.75 (U.S. and Canada) US$114.50 (all other countries).     

Book Review

Abstract

ENVIRONMENTAL SOIL AND WATER CHEMISTRY, by V.P. Evangelou, 564 pages, Wiley Interscience, New York (1998). ISBN 0-471-16515-8. £ 51.95.

ENVIRONMENTAL TRANSPORT PROCESSES, by B.E. Logan, 654 pages, Wiley Interscience, New York (1999). ISBN 0-471-18871-9. £58.50

MERCURY CONTAMINATED SITES. Characterization, risk assessment and remediation, edited by R. Ebinghaus, R.R. Turner, L.D. de Lacerda, O. Vasiliev and W. Salomons, 538 pages, Springer-Verlag, Berlin (1999). ISBN 3-540-63731-1. DM 198.00. USD 129.00

ENVIRONMENTAL PHOTOCHEMISTRY, edited by P. Boule, 359 pages, Springer-Verlag, Berlin (1999). ISBN 3-540-62913-0. DM 298.00

A BEGINNER'S GUIDE TO MASS SPECTRAL INTERPRETATION, by T. A. Lee, 186 pages, John Wiley & Sons, Chichester, (1998). ISBN 0-471-97629-6 USD 19.99

TECHNIQUES IN AQUATIC TOXICOLOGY, edited by Gary K. Ostrander, 686 pages, CRC Press, Boca Raton, Florida. (1996). ISBN 1-56670-149-X, £ 65.00

HANDBOOK OF CHEMOMETRICS AND QUALIMETRICS. Part B, by D.L. Massart, L.M.C. Buydens, S. de Jong, P.J. Lewi and J. Smeyers-Verbeke, 732 pages, Elsevier, Amsterdam (1998). ISBN 0-444-82853-2. USD 201.00     

Book Reviews

Abstract

WATER AND WATER ANALYSIS (in German: Wasser und Wasseruntersuchung), 2nd revised edition in the Series “Laboratory Books in Chemistry”, by Leonhard A. Hiitter, A-6060 Hall in Tirol, Austria, 344 pages (including 38 figures, 34 tables, 43 pages with newest literature references and other informations (regulations, addresses) mainly from Germany, Austria and Switzerland, and a good index of nine pages), carton cover, format 227 × 165 mm, ISBN 3-425-05075-3, Verlag Diesterweg/Salle, D-6000 Frankfurt/Main and Sauerlander, CH-5000 Aarau (1984), DM 48.00

AQUATIC TOXICOLOGY, Volume 2 of a Series, edited by Laverne J. Weber, Marine Science Center, Oregon State University, Newport, Oregon, U.S.A., 236 pages (including 7 tables, 33 figures, references (mainly of the 1970's) added to each chapter, and a valuable subject index of 6 pages), linen, format 243 × 163 mm, ISBN 0-89004-439-2, Raven Press, New York 10036 (1984), US $55.00

TOXICITY TESTING, NEW APPROACHES AND APPLICATIONS IN HUMAN RISK ASSESSMENT, edited by Dr. A. P. Li et al., Enviromental Health Laboratory Monsanto Company, St. Louis, Missouri, U.S.A., 295 pages (including 37 tables, 49 figures, newest references added to each contribution, discussion statements, a good subject index of six pages, and an address list of contributors), linen, format 241 × 162mm, ISBN 0-88167-083-9, Raven Press, New York (1983/1985), US $50.50

HEALTH RISKS TO FEMALE WORKERS IN OCCUPATIONAL EXPOSURE TO CHEMICAL AGENTS, by Prof. Dr. Reinier L. Zielhuis et al., Coronel Laboratorium, Universiteit van NL-1054 BW Amsterdam, The Netherlands, 132 pages (including 30 tables, references added to each chapter, an appendix on recent data, but no subject index), soft cover, format 242 × 165mm, ISBN 3-540- 13579-0, Springer-Verlag, Berlin-Heidelberg-New York-Tokyo (1984), DM 70.00, or approximately US $24.60

IS THE SOIL DYING (in German: Stirbt der Boden)? GDI-Series Man-Nature-Environment, by Dr. Volker Hauff et al., D-5300 Bonn, 250 pages (including 49 figures, 34 tables, an author index of two pages, but no subject index), soft cover, format 241 × 171 mm, no ISBN-number, GDI-Buchhandlung, CH-8803 Riischlikon, Switzerland (1985), SFr. 50.00

THE HANDBOOK OF ENVIRONMENTAL CHEMISTRY, PARTS C and D, edited by Prof. Dr. Otto Hutzinger, Chair of Ecological Chemistry and Geochemistry, D-8580 Bayreuth, linen, format 248 × 170 mm, Springer-Verlag Berlin-Heidelberg-New York-Tokyo (1985).     

Book Reviews

Abstract

Neure Methoden zur Analyse von Tensiden, H. Konig, Springer-Verlag, Berlin-Heidelberg-New York. 25Abb., VII, 239 pages. 1971, DM 58.00. ISBN 3-540-05581-9. Reviewed by T. Rihs, Instituto Nacional de Investigaciones Agropecuarias, Apartado 340, Quito, Ecuador.

P. P. FIETZEK und K. KUHN, H. CLEVER, H. KRECH, W. MARKS, F. OEHME: “Automation in Analytical Chemistry” 32 Abb., 103 Seiten, 1972, DM 28, -, U.S. $8.90. Springer-Verlag, Berlin-Heidelberg-New York. ISBN 3-540-05758-7. Begutachtet von S. Wolf, Hoffman-La Roche, Basle, Switzerland.     

Book Reviews

Abstract

HANDBOOK FOR ESTIMATING PHYSICOCHEMICAL PROPERTIES OF ORGANIC COMPOUNDS, by M. Reinhard and A. Drefal, 228 pages, J. Wiley, New York (1999). ISBN 0—471—172634. UK £ 210.00

THE CHEMISTRY OF POLLUTION, by G. Fellenberg, 192 pp. J. Wiley & Sons, Chichester, U.K. (1999). ISBN 0—471—980889. UK£ 24,95.

NATURAL ATTENUATION OF FUELS AND CHLORINATED SOLVENTS IN THE SUBSURFACE, by T.H. Wiedemeier, H.S. Rifai, C.J. Newell and J.T. Wilson, 617 pages, J. Wiley, New York (1999). ISBN 0—471—19749—1. UK £ 58.50

UNDERSTANDING OUR ENVIRONMENT, 3^rd, edition, edited by R.M. Harrison, 445 pages, The Royal Society of Chemistry, Cambridge (UK) (1999). ISBN 0—85404—584—8. UK£ 19.95

ENDOCRINE DISRUPTING CHEMICALS, Vol. 12 of Issues in Environmental Science and Technology, edited by R.E. Hester and R.H. Harrison, 152 pages, Royal Society of Chemistry, Cambridge (U.K.) (1999). ISBN 0—85404—255—5. UK£ 25,00

METHOD PERFORMANCE STUDIES FOR SPECIATION ANALYSIS. by P. Quevauviller, 271 pages, The Royal Society of Chemistry, Cambridge (U.K.) (1998). ISBN 0—85404—467—1. UK£ 59.50

GLOBAL AQUATIC AND ATMOSPHERIC ENVIRONMENT, by H.D. Kumar and D.P. Häder, 393 pages, Springer, Berlin (1999). ISBN 3—540—65369—4. USD 229.00

BIOACCUMULATION. New Aspects and Developments, edited by B. Beek, 284 pages, Springer, Heidelberg, 2000. ISBN 3—540—62575. USD 143.00

INTERLABORATORY STUDIES AND CERTIFIED REFERENCE MATERIALS FOR ENVIRONMENTAL ANALYSIS. The BCR approach, by Ph. Quevauviller and E.A. Maier, 558 pages, Elsevier Science, Amsterdam NL, (1999). ISBN 0—444—82389—1. USD 251.50 (Euro 224.62).     

A review of: “From Chemical Topology to Three-Dimensional Geometry”

Abstract

Balaban, A. T. (1997). Plenum Press, New York. 420 pp. Hardcover, ISBN: 0-306-45462-9, US$125.00. (ordering information can be obtained from: http://www.plenum.com)     

Book Review

Abstract

A Guide to Organophosphorus Chemistry, by Louis D. Quin, an internationally recognized authority, published by John Wiley and Sons (http://www.wiley.com/chemistry) ISBN 0-471-31824-8, $94.95, 394pp.

Aminophosphonic and Aminophosphinic Acids: Chemistry and Biological Activity. Editors: Valery P. Kukhar (Ukrainian Academy of Sciences) and Harry R Hudson (University of North London). Published by John Wiley and Sons Ltd., Chichester, UK, on 31 March, 2000. ISBN 0 471-89149-5, 175.00 Pounds sterling, 634 pages.

Phosphorus Ylides. Chemistry and Application in Organic Synthesis, by Oleg I. Kolodiazhnyi. Published by Wiley-VCH, 1999, ISBN 3-527-29531-3, 220SF, 555 pages.     

Book Reviews

Glossary On Air Pollution, Who Regional Publications European Series No. 9 (Director, Promotion of Environmental Health, WHO Regional Office for Europe, Scherfigsvej 8, DK-2100 Copenhagen θ) 1980, 114 pages (including an introduction, a list of reviewers and a list of the sources of definitions), stiff paper cover, format 239 ± 159 mm, ISBN 92-9020-109-6, WHO Health and Biomedical Information Programme, CH-1211 Geneva 27, SFr. 12.

Spektroskopische Methoden in Der Organischen Chemie (in German), by Manfred Hesse, Herbert Meier and Bernd Zeeh, 478 pages, including 169 figures and 86 tables, flexible paper cover, ISBN 3-13-576101-0, Georg Thieme Verlag, Stuttgart 1979, price DM 26.80.

Analysis of Polycyclic Aromatic Hydrocarbons in Environmental Samples, World Health Organisation/International Agency for Research on Cancer, IARC Publication No. 29 (Series: Environmental Carcinogens, Selected Methods of Analysis, Volume 3, edited by H. Egan, Laboratory of the Government Chemist, London, U.K. et al.) 1980, 240 pages (including 17 figures, 18 tables, many formulae, an annex with 8 methods of analysis and 29 pages of valuable references in two sections), linen, format 242 ± 186 mm, ISBN 92-8-321129-4, WHO Health and Biomedical Information Programme, CH-1211 Geneva 27, US$30 or SFr. 50.

Toxic Metals and Their Analysis by Eleanor Berman, Cook County Hospital, Chicago, Illinois, U.S.A., 304 pages (including an index of 5 pages, 29 tables and 5 figures), linen, format 241 × 163 mm, ISBN 0-85501-468-7, published 1980 by Heyden International Topics in Science, Spectrum House, Hillview Gardens, London NW4 2JQ, U.K., prices £12, US$27 or DM 56.     

Perkin-Elmer introduce new gas chromatograph

Abstract

APPLICATIONS OF MASS SPECTROMETRY TO TRACE ANALYSIS. Ed. S. Facchetti, Elsevier, US $78.75, Dfl. 185.00.

QUANTITATIVE AQUATIC BIOLOGICAL INDICATORS. by David J. H. Phillips, Fisheries Research Station Aberdeen, Hong Kong, POLLUTION MONITORING SERIES (1980), 488 pages (including 99 figures, 103 tables, 44 pages of literature references up to 1978, an author index of 10 pages, a species index of 4 pages, and a subject index of 18 pages), linen, format 228 × 148 mm, ISBN 0-85334-884-7, Applied Science Publishers Ltd., London, £26.

DIRECTORY OF POLLUTION CONTROL EQUIPMENT COMPANIES IN WESTERN EUROPE, Third Edition (1980), 588 pages (including an index of 127 pages, which is however-structured somewhat arbitrarily according to types of equipment and according to countries), stiff paper cover, format 210 × 147 mm, ISBN 0 906685 00 1, European Directories, a Division of Inter Company Comparisons Ltd., 23, City Road, London EC1Y 1AA, £30.

HALOGENATED BIPHENYLS, TERPHENYLS, NAPHTHALENES, DIBENZODIOXINS AND RELATED PRODUCTS, by R. D. Kimbrough (ed.) (Elsevier Biomedical Press, R.V., Amsterdam, NL. U.S. $95.00, Dfl 195.

CHROMATOGRAPHY AND THE ENVIRONMENT, Environmental problem solving using gas and liquid chromatography, R. L. Grob and M. A. Kaiser, Elsevier, Amsterdam, 1982, XII + 240 pages, ISBN 0-444-42065-7     

High performance liquid chromatography

Ohne Zusammenfassung

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High performance liquid chromatography Fallstricke und Fehlerquellen der HPLC in Bildern by Dr. V. R. Meyer. Hüthig Verlag, Heidelberg, Germany 1996. 128 S. ISBN 37785-2417-8. Preis: DM 38.-/?S 278.-/sFr 38.-

     

Bioanalytik für Einsteiger.Diabetes,Drogen und DNA. Von Reinhard Renneberg.

Spektrum Akademischer Verlag, Heidelberg 2008. 284 S., geb., 34.95 €.—ISBN 978‐3827418319

     

Book Reviews

Abstract

Aquatic Chemistry: An Introduction Emphasizing Chemical Equilibria in Natural Waters. Werner Stumm and James L. Morgan. Wiley-Interscience, New York, London, Sydney, Toronto 1971. XV+582 pages. Reviewed by R. P. Walser, Quality Control, Pharmaceutical Division, Sandoz Ltd., Basle, Switzerland

Residue Reviews. Edited by F. A. Günther, Springer Verlag, New York, Vols. 34, 38, and 40, 1971. Reviewed by O. Hutzinger, Atlantic Regional Laboratory, National Research Council of Canada, Halifax, Nova Scotia, Canada.

Determination of organophosphorus pesticide residues in fruits and vegetables, on the Swedish market from 1964 to 1968, by S. Renvall and M. Âkerblom (Vol. 34, p. 1).

Pesticide residue analysis in the presence of Polychlorobiphenyls (PCB), by L. M. Reynolds (Vol. 34, p. 27).

Development of the Food and Drug Administration's method of analysis for multiple residues of organochlorine pesticides in foods and feeds, by J. A. Burke (Vol. 34, p. 59).

Carbamate insecticide residues in plant material: Determination by gas chromatography, by I. H. Williams (Vol. 38, p. 1).

Analytical methods for the determination of fumigants, by B. Malone (Vol. 38, p. 21).

Recent applications of mass spectrometry and combined gas chromatographymass spectrometry to pesticide residue analysis, by F. J. Biros (Vol. 40, p. 1).     

4-Methylisocamphenilansäure und 4-(3,3,4-Trimethyl-2-exo-norbornyl)-3-buten-2-on

The synthesis of 4-methylisocamphenilanic acid (7) and of the unsaturated ketone 4-(3,3,4-trimethyl-2-exo-norbornyl)-3-buten-2-one (2), an analogue of -irone (1), are described. The preparation of2 has been accomplished by: catalyzedDiels—Alder reaction of methylcyclopentadiene and mesityl oxide, hydrogenation and isomerization of the resulting ketone mixture to theexo-ketone6, oxidation of6 to the acid7, reduction of7 to the corresponding aldehyde8 and aldol reaction of8 with acetone. The structure of the key intermediate6 was established by mass, 100 MHz¹H-NMR and¹³C-NMR spectra. The odour of2 is discussed briefly.

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Teil der Diplomarbeit vonI. Schmidmayer.

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9. Mitt.,G. Buchbauer undM. Wiltschko. J. Soc. Cosmet. Chem., im Druck.

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8. Mitt.,G. Buchbauer undE. Klissenbauer, Mh. Chem.109, 499 (1978).     

Books

Abstract

“CHROMATOGRAPHY OF ANTIBIOTICS”, G. H. Wagman & M. J. Weinstein, Elsevier Science Publishers, Amsterdam, 1984, 510pp., $113.50 (US).

“STERIC EXCLUSION LIQUID CHROMATOGRAPHY OF POLYMERS”, J. Janca, Ed., Marcel Dekker, Inc., New York & Basel, 1984, 329pp., $55.00 (US).

“CHROMATOGRAPHIC STUDIES OF BIOGENESIS OF PLANT VOLATILES”, P. Schreier, Dr. Alfred Huthig Verlag GmbH., Heidelberg, 1984, 165pp., $34.00 (US).     

Book Reviews

Ion-Selective Electrodes in Analytical Chemistry, VOL. 2, H. Freiser (ed.), Plenum Press, New York, 1980.

Pesticide Analytical Methodology by John Harvey, Jr. (E. I. Du Pont de Nemours and Company) and Gunter Zweig (U.S. Environmental Protection Agency), ACS Symposium Series 136, 406 pages (including 177 figures, 54 tables and an index of 18 pages), linen, format 235 × 160mm, ISBN 0-8412-0581-7, American Chemical Society, 1155 Sixteenth Street, N.W. Washington, D.C. 20036, 1980, US38.00.

Particulates in Water, Characterization, Fate, Effects, and Removal by Michael C. Kavanaugh (James M. Montgomery, Consulting Engineers, Inc., Pasadena) and James O. Leckie (Stanford University, Stanford) ACS Advances in Chemistry Series 189, 401 pages (including 145 figures, 56 tables and an index of 11 pages), linen, format 235 × 160mm, ISBN 0-8412-0499-3, American Chemical Society, 1155 Sixteenth Street, N.W. Washington, D.C. 20036, 1980, USS59.50.

Pesticide Manufacturing and Toxic Materials Control Encyclopedia Editor, M. Sittig; 810 pages, $96; 1980, Noyes Data Corporation, Park Ridge, N.J., U.S.A. ISBN 0-8155-0814-X. Reviewed by A. de Kok, Section of Environmental Chemistry, Free University, Amsterdam, The Netherlands.

Dictionary of Chemical Terminology (In Five Languages–English, German, French, Polish and Russian. Edited by D. Kryt, Warsaw, Poland). Elsevier Scientific Publishing Company, Amsterdam and New York. 1980, 612 pages, Price: US $95.00/Dfl. 195.00 ISSBN 0-444-99788-1.     

PHOSPHORORGANISCHE VERBINDUNGEN 851 SYNTHESE UND ANWENDUNG OPTISCH AKTIVER TERTIÄRER PHOSPHINE ALS CO-KATALYSATOREN DER HOMOGENHYDRIERUNG MIT RHODIUM-PHOSPHIN-KOMPLEXEN

Abstract

Die Darstellung der optisch aktiven Methyl-n-propyl(bzw.-isopropyl)arylphosphine 1 bis 8 wird beschrieben. Hierbei ist Aryl: p-Methoxyphenyl (1 und 2), p-Dimethylaminophenyl (3 und 4), o-Methoxyphenyl (5 und 6), o-Dimethyl-aminophenyl (7) und o-Aminophenyl (8).

Die Phosphine 1 bis 8 werden als optisch aktive Co-Katalysatoren bei der Homogenhydrierung von α- und ß-Methylzimtsäureethylester, der α-Acetaminoacrylsäure und der α-Acetaminozimtsäure mit Rhodium-Phosphinkomplexen eingesetzt und jeweils die optische Induktion bestimmt. Folgende Ergebnisse (Vgl. die Tabellen 1 bis 4) wurden erhalten:

1) Die CH₃O-Gruppe und N(CH₃)₂-Gruppe verändern unabhängig von ihrer Stellung die optische Induktion bei der Homogenhydrierung von α- und ß-Methylzimtsäureethylester nur unwesentlich im Vergleich zu den entsprechenden Methyl-n-propyl (bzw.-isopropyl)-phenylphosphinen.

2) Bei der Homogenhy drierung von α-Acetaminoacrylsäure und α-Acetaminozimtsäure üben para-ständige OCH₃- und (CH₃)₂N-Gruppen in den optisch aktiven Co-Katalysatoren (Verbindungen 1 bis 4) keinen Einfluß auf die Höhe der optischen Induktion aus.

3) In ortho-Stellung verknüpfte OCH₃- und (CH₃)₂N-Gruppen (Verbindungen 5 bis 7) führen jedoch bei der Homogenhydrierung von α-Acetaminoacrylsäure und α-Acetaminozimtsäure zu einer beachtlichen Erhöhung der optischen Induktion. Bei α-Acetaminozimtsäure und 7 als Co-Katalysator beträgt die optische Induktion 80%! Hierbei übertrifft die (CH₃)₂N-Gruppe die CH₃O-Gruppe an Wirksamkeit.

4) Methyl-n-propyl-o-aminophenylphosphin 8 ist als Co-Katalysator unbrauchbar, da es offenbar durch Wechsel-wirkung der NH₂-Gruppe mit Rhodium die Koordinierung des prochiralen Olefins mit dem Komplex unterdrückt.

5) Eine experimentell begründete Deutung für das Zusammenwirken der am Aufbau der Homogenkatalysatoren beteiligten Komponenten konnte nicht gegeben werden.

Tabelle 5 zeigt die Abhängigkeit der Hydriergeschwindigkeit von Art und Stellung der Substituenten im Phenylrest. Die Hydriergeschwindigkeit ist bei den induktionsstarken Co-Katalysatoren 5 bis 7 deutlich vermindert.

The preparation of the optically active methyl-n-propyl(isopropy) aryl phosphines 1 ± 8 is described, whereby the aryl group is p-methoxyphenyl (1, 2), p-dimethylaminophenyl (3, 4), o-methoxyphenyl (5, 6), o-dimethylaminophenyl (7) and o-aminophenyl (8).

The phosphines 1–8 were used as chiral co-catalysts at the rhodium complex in the homogeneous hydrogenation of α- and ß-methyl cinnamic acids, α-acetaminoacrylic acid and α-acetaminocinnamic acid. The optical induction in the products was measured. The following results (see Tables 1–4) were obtained:

1) The methoxy and dimethylamino groups, independent of their site, have only negligible influence on the optical yield in the reduction of α- and ß-methylcinnamic acids compared with the parent methyl-propylphenylphosphine.

2) In the hydrogenation of acetaminoacrylic acid and α-acetaminocinnamic acid, para methoxy- or dimethylamino groups (compounds 1–4) show likewise no special influence on the optical yield.

3) Ortho methoxy or dimethylamino groups (compounds 5–7), however, result in a measurable increase in optical yield in the reduction of α-acetaminoacrylic- and α-acetaminocinnamic acids. In the case of compound 7 with α-acetaminocinnamic acid, an optical purity of 80% was obtained! The dimethylamino group is in this case more effective than the methoxy group.     

Die IR-Spektren von Kobalt-, Nickel- und Zink-Orthovanadat

Infrared spectra of crystalline Co₃(VO₄)₂, Ni₃(VO₄)₂ and Zn₃(VO₄)₂ as well as the laser-Raman spectrum of the last mentioned compound are reported and discussed. A series of solid solutions of the type (Zn/Ni)₃(VO₄)₂ have also been prepared and investigated, in order to obtain a wider insight into the spectroscopic behaviour of this class of compounds in the 500-250 cm^–1 region. Comparisons with the formerly investigated isotypic Mg₃(VO₄)₂ allows to confirm some of the earlier statements and assignments in the light of additional experimental information.

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26. Mitt. der Reihe Orthovanadate und verwandte Verbindungen. 25. Mitt.:E. J. Baran, J. Mol. Struct., im Durck; 24. Mitt.:E. J. Baran undI. L. Botto; J. inorg. nucl. Chem., im Druck; 23. Mitt:M. E. Escobar undE. J. Baran, Z. anorg. allg. Chem., in Druck.     

PHOSPHORORGANISCHE VERBINDUNGEN 921

Abstract

Optisch aktive Phosphinigsäureamide R¹R²PNR₂ 4 (R¹ [dbnd] Ph, R² [dbnd] Me bzw. Et, R [dbnd] Et) sind durch kathodische Spaltung bzw.Cyanolyse optisch aktiver Amidophosphoniumsalze [R¹R²R³PNR₂]X (R¹ [dbnd] Ph. R² [dbnd] Me bzw. Et. R³ [dbnd] Bz bzw. All, R [dbnd] Et) unter Erhaltung der Konfiguration in hohen Ausbeuten zugänglich.

Optisch aktive Amidophosphoniumverbindungen, z.B. Ethyl-methyl-phenyl-diethylamido-phosphoniumiodid 10 oder Benzyl-ethyl-phenyl-diethylamido-phosphoniumbromid 12 werden erhalten:

a) aus den optisch aktiven tertiären Phosphinen, z.B. R-(+)Benzyl-methyl-phenyl-phosphin 6 bzw. S-(-)Ethyl-methyl-phenyl-phosphin 13 durch Umsetzung mit Alkyl- oder Arylaziden über die Phosphinimine 7 mit anschließender Alkylierung.

b) durch Alkylierung der optisch aktiven Phosphinigsäureamide 4. Die unter a) und b) genannten Umsetzungen verlaufen unter Erhaltung der Konfiguration.

c) Bei der Umsetzung optisch aktiver tertiärer Phosphine mit N-Halogenaminen entstehen nur racemische Amidophosphoniumsalze.

Optisch aktive Amidophosphoniumsalze, z.B. S(+)-Benzyl-methyl-phenyl-diethylamido-phosphoniumbromid 8 oder R-(-)-Ethyl-methyl-phenyl-diethylamido-phosphoniumiodid 10 werden bei der Einwirkung wäßriger Alkalien unter Inversion zu den entsprechenden Phosphinoxiden 9 bzw. 11 abgebaut. Optisch aktive Amidophosphoniumsalze, z.B. S(+)-Benzyl-ethyl-phenyl-diethylamido-phosphoniumbromid 12, werden mit LiAlH₄ retentiv unter Abspaltung des Aminliganden in die zugrundeliegenden optisch aktiven tertiären Phosphine übergeführt. Die Olefinierung von Benzaldehyd mit S(+)-Benzyl-ethyl-phenyl-diethylamido-phosphoniumbromid 5 ergibt unter Retention Stilben und optisch aktives Ethyl-phenyl-phosphinsäure-diethylamid 17, das auch durch Oxidation von R(-)-4 mit H₂O₂ erhalten wird. Schwefelung von R(-)-4 liefert das optisch aktive Ethyl-phenyl-thiophosphinsäure-diethylamid 18.

Das optisch aktive Phosphinigsäure-diethylamid 4 racemisiert allein und in Kohlenwasserstoffen gelöst bei 130°C nach einer Reaktion nullter Ordnung. Die Racemisierung wird durch Austausch der sekundären Aminogruppe über cyclische Assoziate verursacht. Beweis: Verbindungen mit unterschiedlichen. Substituenten am Phosphor- und Stickstoff tauschen beim dreistündigen Erhitzen auf 200°C die sekundären Aminogruppen aus. Es entstehen neue Phosphinigsäureamide in annähernd äquivalenten Mengen.

In Nitrobenzol bildet sich mit Phosphinigsäureamiden ein Charge-Transfer-Komplex, der im Falle des optisch aktiven Ethyl-phenyl-phosphinigsäure-diethylamids 4 bereits bei Zimmertemperatur eine schnelle Racemisierung bewirkt.

Optisch aktives Ethyl-phenyl-phosphinigsäure-diethylamid 4 liefert als Co-Katalysator bei der Homogenhydrierung von α-Ethylstyrol mit (RhCl-Hexadien-1,5)₂ 2-Phenylbutan mit einer optischen Ausbeute von 34%.     

Power‐Law Kinetic Models for Synthesis of Ammonia Borane

In the past few years, there have been increasing numbers of studies for the production and dehydrogenation of ammonia borane (NH₃BH₃, AB), which has become a significant hydrogen storage material. However, kinetic model studies based on the synthesis of AB in the literature have not been encountered, though there are many kinetic modeling studies on dehydrogenation of AB (Akbayrak et al., Appl Catal B 2016, 198, 162–170; Choi et al., Phys Chem Chem Phys 2014, 16(17), 7959–7968; Esteruelas et al., Inorg Chem 2016, 55(14), 7176–7181; Park et al., Int J Hydrogen Energy 2015, 40(46), 16316–16322; Rakap, Appl Catal B 2015, 163, 129–134; Tonbul et al., Int J Hydrogen Energy 2016, 41(26), 11154–11162; Zhang et al., Int J Hydrogen Energy 2016, 41(39), 17208–17215). The paper describes the development of a kinetic model for synthesis of ammonia borane by using borohydride (NaBH₄) and ammonium salt (NH₄)₂SO₄. The synthesis of AB experiments was carried out at different temperature ranges between 25 and 50°C, different inlet molar ratios (NaBH₄/(NH₄)₂SO₄ = 1–4), and different molarities with respect to NaBH₄ (0.11–0.67 M NaBH₄). After the parametric experiments were conducted, empirical power law was evaluated for the synthesis reaction. The power‐law model represented the trends of the kinetics of the synthesis reaction and was reproduced as .