In support of the implementation of the European Union (EU) Water Framework Directive (WFD), the European Commission (EC) Joint Research Centre (JRC) organized a laboratory and sampling intercomparison study for the chemical monitoring of polyaromatic hydrocarbons (PAHs), polybrominated diphenyl ethers (PBDEs), and nonylphenol and octylphenol (NP/OP), priority substances of the WFD, in river water. EU Member State laboratories were invited to analyze a standard solution with unknown concentration levels and a river-water extract, as well as a real water sample from the River Po (Italy). For the standard solution and the river-water extract, good agreement was achieved for five laboratories. Triple-quadrupole liquid chromatography with tandem mass spectrometry (LC-MS2) and gas chromatography with MS (GC-MS) with or without derivatization proved to be comparable methods for the analysis of NP and OP. Fluorescence detection can also be used to analyze NP and OP, but it is less specific. The results of the River Po water sample showed that some laboratories have problems in analyzing NP at concentration levels below 100 ng/L due to contamination of laboratory blanks. Plastics materials should not be used during extraction and sample preparation.

According to the Water Framework Directive (WFD), EU Member States are now committed to monitor priority substances on a regular basis in all relevant water bodies and to check compliance with the environmental quality standards (EQS) proposed by the Commission. Methods for monitoring of priority substances were not specified in the WFD but reference was made to any relevant CEN/ISO Standards. Hence, the question arose whether the existing European and International Standards are actually fit for the purpose of compliance checking with the proposed environmental quality standards. For this reason, a European-wide survey of existing standard methods for the determination of priority substances according to WFD was carried out. It could be shown that for all priority substances, except C10-13 chloroalkanes, analytical standard methods exist. The comparison of the proposed EQS with the lower limits of application (LLOAs) stated in the scope of the standards revealed that compliance checking would only be possible for 58 % (marine waters) and 67 % (inland waters) of the priority substances. These percentages would still be lower if the recommended data quality requirement, LLOA < 30% of EQS, had been taken into account. Hence, a survey was conducted amongst European monitoring laboratories to collect information on LLOAs that can be achieved under realistic conditions applying European or International Standards methods. Referring to statements of 20 European laboratories from five countries, most standard methods are more sensitive than mentioned in their scopes. Taking this and data quality requirements into account, compliance checking would be possible for approximately 90% of the considered priority substances when applying European or International Standards. Exceptions are brominated diphenyl ethers, C10-13 chloroalkanes, hexachlorbutadiene, tributyl tin compounds in inland and marine waters as well as pentachlorobenzene in marine waters. No lower LLOAs than stated in the corresponding standard were reported for benzene, volatile halogenated compounds (e.g., 1,2-dichloroethane, dichloromethane), di(2-ethylhexyl)phthalate (DEHP), octylphenol, and nonylphenol. This confirms that recently released standards actually represent the best and most sensitive methods for analysing priority substances in water.Surveying the sample pre-treatment section of standard methods for technical details on how to deal with the Suspended Particulate Matter (SPM) present in the sample showed that in many cases none or only unqualified information (e.g. filtration of the sample where appropriate) was given. Also the data provided by the interviewed laboratories were inconsistent. These results document that there is no consistent procedure, how to deal with samples containing substantial amounts of SPM even when considering only information on a certain priority substance.

Mass Spectrometric Fragmentation of 4‐Substituted 5‐Hydroxynaphth[2,1‐d]1,3‐oxathiol‐2‐onesThe mass spectra of 5‐hydroxynaphth[2,1‐d]1,3‐oxathiol‐2‐ones 1a‐1x have been studied. They show characteristic fragmentations with participation of neighbouring groups. Investigations of isotopically labelled 4‐alkyl and 4‐acyl derivatives give evidence for the formation of cyclic ionic structures.

AbstractDie Umsetzung der Oxathiolone (I) mit den Nitrosoverbindungen (II) führt im Sinne einer Ehrlichb‐Sachs‐Reaktion zu den Titelverbindungen (III).

Chemischer InformationsdienstVolume 13, Issue 12 Heterocyclic Compounds ChemInform Abstract: OXIDATIVE COUPLING OF CH-ACID COMPOUNDS WITH P-PHENYLENEDIAMINES. VII. SYNTHESIS AND OXIDATIVE COUPLING OF 5-HYDROXYNAPHTH(2,1-D)-1,3-OXATHIOL-2-ONES G. MANN, G. MANNSearch for more papers by this authorH. WILDE, H. WILDESearch for more papers by this authorS. HAUPTMANN, S. HAUPTMANNSearch for more papers by this authorM. NAUMANN, M. NAUMANNSearch for more papers by this authorP. LEPOM, P. LEPOMSearch for more papers by this author G. MANN, G. MANNSearch for more papers by this authorH. WILDE, H. WILDESearch for more papers by this authorS. HAUPTMANN, S. HAUPTMANNSearch for more papers by this authorM. NAUMANN, M. NAUMANNSearch for more papers by this authorP. LEPOM, P. LEPOMSearch for more papers by this author First published: March 23, 1982 https://doi.org/10.1002/chin.198212245AboutPDF 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. Volume13, Issue12March 23, 1982 RelatedInformation

Oxidative Coupling of CH‐acid Compounds with p‐Phenylenediamines. VIII. Synthesis of 5H‐Benzo[a]phenothiazin‐5‐ones from Naphth[2,1‐d]1,3‐oxathiol‐2‐onesReaction of 5‐hydroxynaphth[2,1‐d]1,3‐oxathiol‐2‐ones with N,N‐diethyl‐quinone‐1,4‐diimine leads to 5H‐benzo[a]phenothiazin‐5‐ones 1–21. The same dyes are available by use of p‐substituted nitrosobenzenes in acetic acid, or in methanol in the presence of oxygen acceptors. The mechanisms of dye formation are discussed.

Oxidative Coupling of CH‐acid Compounds with p‐Phenylenediamines. V. Mass Spectrometric Fragmentation of 4‐Substituted 3‐Methyl‐1‐phenyl‐pyrazolin‐5‐onesThe mass spectra of 3‐methyl‐1‐phenyl‐pyrazolin‐5‐one 1 and 4‐substituted derivatives 2–18 have been studied and the fragmentation mechanisms are discussed. The major cleavages take place in three ways, whose significance is related to the properties of the substituents. The mass spectra permit the determination of the structure, purity and stability of the substituted colour couplers.

Oxidative Coupling of CH-acid Compounds with p-Phenylenediamines. V. Mass Spectrometric Fragmentation of 4-Substituted 3-Methyl-1-phenyl-pyrazolin-5-ones The mass spectra of 3-methyl-1-phenyl-pyrazolin-5-one 1 and 4-substituted derivatives 2–18 have been studied and the fragmentation mechanisms are discussed. The major cleavages take place in three ways, whose significance is related to the properties of the substituents. The mass spectra permit the determination of the structure, purity and stability of the substituted colour couplers.

Oxidative Coupling of CH‐acid Compounds with p‐Phenylenediamines. VII. Synthesis and Oxidative Coupling of 5‐Hydroxy‐naphth[2,1‐d] 1,3‐oxathiol‐2‐ones5‐Hydroxy‐naphth[2,1‐d]1,3‐oxathiol‐2‐ones with different substituents 1–21 were synthesized using the following procedures: Condensation of substituted naphthoquinones‐1,4 with thiourea (A); electrophilic substitution of 5‐hydroxy‐naphth[2,1‐d]1,3‐oxathiol‐2‐one (B); Fries‐reaction of 5‐acyloxy‐ and 5‐N‐phenylcarbamoyloxy‐naphth[2,1‐d]1,3‐oxathiol‐2‐ones (C). Oxidative coupling of the compounds with N,N‐diethyl‐quinone‐1,4‐diimine yielded thiazine dyes.

Heterocycles containing an integrated 2-nitrobenzaldehyde imine moiety produce ions of m/z 134 with high abundance under electron impact. As shown by kinetic energy release measurements these ions have the same structure in all the cases studied, identical to m/z 134 formed from the reference compound 2-nitrobenzoylpiperidide. The mechanism of formation of m/z 134 most probably involves isomerization of its precursor ion to give a spiro intermediate, from which m/z 134 arises either synchronously or after a second isomerization. Both alternatives formally represent an oxygen transfer from the nitro group to the imino carbon via a 5-membered transition state.

Chemischer InformationsdienstVolume 11, Issue 2 Physical Organic Chemistry ChemInform Abstract: OXIDATIVE COUPLING OF CARBON ACID COMPOUNDS WITH P-PHENYLENEDIAMINES. IV. MASS SPECTROMETRIC STUDIES OF 4-SUBSTITUTED 1-HYDROXY-2-NAPHTHOIC ACID DERIVATIVES G. MANN, G. MANNSearch for more papers by this authorH. WILDE, H. WILDESearch for more papers by this authorR. HERZSCHUH, R. HERZSCHUHSearch for more papers by this authorJ. LEHMANN, J. LEHMANNSearch for more papers by this authorP. LEPOM, P. LEPOMSearch for more papers by this author G. MANN, G. MANNSearch for more papers by this authorH. WILDE, H. WILDESearch for more papers by this authorR. HERZSCHUH, R. HERZSCHUHSearch for more papers by this authorJ. LEHMANN, J. LEHMANNSearch for more papers by this authorP. LEPOM, P. LEPOMSearch for more papers by this author First published: January 15, 1980 https://doi.org/10.1002/chin.198002061AboutPDF 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. Volume11, Issue2January 15, 1980 RelatedInformation

Chemischer InformationsdienstVolume 10, Issue 4 Heterocyclic Compounds ChemInform Abstract: TETRAZOLES. XXX. POLYAZACYCL(2.3.3)AZINE BY THERMOLYSIS OF S-TRIAZOLO(4,3-C)TETRAZOLO(1,5-A)PYRIMIDINE A. KOENNECKE, A. KOENNECKESearch for more papers by this authorE. LIPPMANN, E. LIPPMANNSearch for more papers by this authorR. DOERRE, R. DOERRESearch for more papers by this authorP. LEPOM, P. LEPOMSearch for more papers by this author A. KOENNECKE, A. KOENNECKESearch for more papers by this authorE. LIPPMANN, E. LIPPMANNSearch for more papers by this authorR. DOERRE, R. DOERRESearch for more papers by this authorP. LEPOM, P. LEPOMSearch for more papers by this author First published: January 23, 1979 https://doi.org/10.1002/chin.197904210Read the full textAboutPDF 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. Volume10, Issue4January 23, 1979 RelatedInformation

Oxidative Coupling of CH‐acid Compounds with p‐Phenylenediamines. IV. Mass Spectrometric Investigations of 4‐Substituted 1‐Hydroxy‐2‐naphthoic‐acid Derivatives.Mass spectrometric fragmentations of 4‐substituted 1‐hydroxy‐N‐3′, 5′‐(dimethoxy‐carbonyl)phenyl‐2‐naphthalene carboxamides and derivatives of 1‐hydroxy‐2‐naphthoic acid and 4‐bromo‐1‐hydroxy‐2‐naphthoic acid have been determined. All compounds undergo a characteristic fragmentation. The most important primary process is amide cleavage and hydrogen rearrangement. The relation of the primary fragments which compete for the charge depends on the substituents of the active methylene group and of the amide. The mass spectra permit determination of structure, purity and stability of the substituted colour couplers.

AbstractDie Tetrazole (I) setzen sich mit 1‐Fluor‐2,4‐dinitro‐benzol zu den Diaryltetrazolen (II) um.