1-Butylacrylate, an industrial monomer, is rapidly metabolized by carboxylesterase-catalyzed hydrolysis to acrylic acid and 1-butanol. Acrylic acid enters the intermediary metabolism and is efficiently degraded to carbon dioxide as the metabolic end product. To obtain a virtually complete metabolic pattern, rats were dosed by a single intraperitoneal dose of 1 mmol/kg 1-butyl [3-13C]acrylate. The urine was then analyzed by a one-dimensional 1H-detected and two-dimensional 1H-13C shift-correlated heteronuclear multiple-quantum NMR experiment. In this experiment, three urinary metabolites, namely, 3-hydroxypropanoic acid, N-acetyl-S-(2-carboxyethyl)cysteine, and N-acetyl-S-(2-carboxyethyl)cysteine sulfoxide, were identified comparing their 1H and 13C chemical shifts with those of authentic standards. In another experiment, to enhance minor metabolic pathways, rats were dosed with 0.25 mmol/kg of a carboxylesterase inhibitor, tri-o-tolyl phosphate, prior to 0.5 mmol/kg butyl [3-13C]acrylate. Under these conditions, N-acetyl-S-(2-carboxyethyl)cysteine, N-acetyl-S-[2-(butoxycarbonyl)-ethyl]cysteine, and N-acetyl-S-(2-carboxyethyl)cysteine sulfoxide were found in urine. No metabolites which would arise from a possible metabolic activation of 1-butyl acrylate to 1-butyl oxiranecarboxylate and its subsequent hydrolysis or glutathione conjugation were found. It is estimated that any metabolite amounting to more than 1% of the dose should be detected under these conditions. To study the routes by which BA enters the intermediary metabolism, incorporation of the label into urinary carboxylic acids was followed by GC/MS. Significant enrichment was found in 3-hydroxypropanoic acid and citric and isocitric acid but not in lactic acid.(ABSTRACT TRUNCATED AT 250 WORDS)

A simple ion-suppression separation on reversed-phase columns, which is applicable for both analytical and semi-preparative work, is described. Six urinary metabolites of 1,3-diethenylbenzene (I), namely 1-(3-ethenylphenyl)-1,2-dihydroxyethane beta-D-glucosiduronates (two isomers, II and III), N-acetyl-S-[1-(3-ethenylphenyl)-2-hydroxyethyl]cysteine (IV), N-acetyl-S-[2-(3-ethenylphenyl)-2-hydroxyethyl]cysteine (V), 3-ethenylphenylmandelic acid (VI) and 3-ethenylphenylglyoxylic acid (VII), were isolated (Fig. 1). Four of them, IV-VII, have been identified in our previous work; the two glucosiduronates were identified for the first time by 1H NMR spectroscopy, fast atom bombardment mass spectrometry, and enzymic hydrolysis yielding 1-(3-ethenylphenyl)-1,2-dihydroxyethane as an aglycone. The method was reproducible the concentration range 0.05-5 mg/ml, the coefficient of variation being less than 7% (n = 5). Excretion of II-VI within 24 h in the urine of rats dosed with a single intraperitoneal injection of 100, 300 and 600 mg/kg I was determined quantitatively. The utility of the method is discussed in comparison with gas chromatographic-mass spectrometric techniques used previously.

1. Biotransformation of 1,3-diethenylbenzene (1) in rat gave four major metabolites, namely, 3-ethenylphenylglyoxylic acid (2), 3-ethenylmandelic acid (3), N-acetyl-S-[2-(3-ethenylphenyl)-2-hydroxyethyl]-L-cysteine (4) and N-acetyl-S-[1-(3-ethenylphenyl)-2-hydroxyethyl]-L-cysteine (5) were isolated from urine and identified by n.m.r. and mass spectrometry. 2. Four minor metabolites, 3-ethenylbenzoic acid (6), 3-ethenylphenylacetic acid (7), 3-ethenylbenzoylglycine (8) and 2-(3-ethenylphenyl)ethanol (9) were identified by g.l.c.-mass spectrometric analysis of urine extract derivatized in two different ways. 3. All identified metabolites are derived from 3-ethenylphenyloxirane (10), a reactive metabolic intermediate. No product of any metabolic transformation of second ethenyl group has been identified. However, several minor unidentified metabolites were detected by g.l.c.-mass spectrometry. 4. Total thioether excretion in 24 h urine after a single i.p. dose of 1 amounted to 28.3 +/- 3.5 dose (mean +/- SD). No significant differences in the thioether fraction were observed in the dose range 100-300 mg/kg. 5. Thioether metabolites consisted mainly of mercapturic acids 4 and 5. The ratio of metabolites 5 to 4 was 62:38. Each mercapturic acid consisted of two diastereomers. Their ratio, as determined by quantitative 13C-n.m.r. measurement was 95:5 and 79:21 for mercapturic acids 4 and 5, respectively.

Journal of High Resolution ChromatographyVolume 11, Issue 7 p. 541-542 Short Communication Conversion of bromoalkanes to chloroalkanes during closed loop stripping of chlorinated water samples V. Janda, Corresponding Author V. Janda Prague Institute of Chemical Technology, Suchbátarova 5, CS-166 28 Prague 6, CzechoslovakiaPrague Institute of Chemical Technology, Suchbátarova 5, CS-166 28 Prague 6, CzechoslovakiaSearch for more papers by this authorK. Marha, K. Marha Prague Institute of Chemical Technology, Suchbátarova 5, CS-166 28 Prague 6, CzechoslovakiaSearch for more papers by this authorJ. Mitera, J. Mitera Prague Institute of Chemical Technology, Suchbátarova 5, CS-166 28 Prague 6, CzechoslovakiaSearch for more papers by this author V. Janda, Corresponding Author V. Janda Prague Institute of Chemical Technology, Suchbátarova 5, CS-166 28 Prague 6, CzechoslovakiaPrague Institute of Chemical Technology, Suchbátarova 5, CS-166 28 Prague 6, CzechoslovakiaSearch for more papers by this authorK. Marha, K. Marha Prague Institute of Chemical Technology, Suchbátarova 5, CS-166 28 Prague 6, CzechoslovakiaSearch for more papers by this authorJ. Mitera, J. Mitera Prague Institute of Chemical Technology, Suchbátarova 5, CS-166 28 Prague 6, CzechoslovakiaSearch for more papers by this author First published: July 1988 https://doi.org/10.1002/jhrc.1240110712Citations: 3AboutPDF 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.Citing Literature Volume11, Issue7July 1988Pages 541-542 RelatedInformation

AbstractA series of gas chromatographic–mass spectrometric analyses was carried out on polyethylene, polypropylene, polystyrene and polyamide in CAB 4.5 and CAB 650 chambers in the flaming and non‐flaming combustion mode. The combustion products formed were identified and used to characterize the combustion process in both chambers; procedures were selected for testing polymeric materials for the dangerous effects of their combustion products.

The nature of the pyrolysis and thermoxidative decomposition products of a number of polyamides was investigated using thermogravimetry, gas chromatography and mass spectrometry. The degree of potential toxic effect has been assessed from qualitative evaluation of the results.

Mass spectrometry behaviour of monohydric phenols is discussed, and so far unpublished mass spectra of 32 monohydric C 9 to C 18 are given.

Copolymers of 1,2,2,2-tetrachloroethyl esters of unsaturated acids and halogenated N-phenyl maleimides with styrene were pyrolyzed; volatile products were analyzed with a mass spectrometer combined with a gas chromatograph. Hydrogen halide and carbon dioxide in the volatile products were determined during the thermal decomposition of copolymers in glass ampoules; the acyl chloride groups were determined in the residues. The thermal decomposition of copolymers of tetrachloroethyl esters with styrene sets in at ca. 230° by the release of chloral from the copolymer and splitting of some of the CCl bonds in the copolymer. The decomposition of copolymers of styrene with halogenated N-phenyl maleimides starts above 300° by depolymerization of the polystyrene chain sections and by splitting of some of the carbon-halogen bonds. At 310 and 500° for copolymers of tetrachloroethyl esters and at 500° for halogenated N-phenyl maleimides, there is radical dehydrohalogenation of the copolymers, with depolymerization of polystyrene blocks and splitting of carbon-carbon bonds in the main chain.

The methanolic extract of a copolymer of 6-caprolactam with 8-octanelactam was analyzed; cyclic oligomers were identified by mass spectroscopy. The cyclic homodimers and codimer were separated by thin-layer chromatography. The quantitative analysis of methanolic extract involved direct evaporation into the ion source of mass spectrometer.

Thermal and thermo-oxidative degradation of polyethylene and polypropylene is discussed. The products of thermal and thermo-oxidative degradation are analysed using a GC-MS after previous adsorption in a column containing a sorbent of styrene divinyl benzene copolymer type. Aldehydes are the products mostly resulting from the thermo-oxidation of polyethylene and methyl ketones are those resulting from the thermo-oxidation of polypropylene.

Chemischer InformationsdienstVolume 6, Issue 37 Preparative Organic Chemistry ChemInform Abstract: THERMAL DEGRADATION OF TRANS-POLYPENTENAMER J. ZACHOVAL, J. ZACHOVALSearch for more papers by this authorJ. KALAL, J. KALALSearch for more papers by this authorJ. KUBAT, J. KUBATSearch for more papers by this authorJ. MITERA, J. MITERASearch for more papers by this author J. ZACHOVAL, J. ZACHOVALSearch for more papers by this authorJ. KALAL, J. KALALSearch for more papers by this authorJ. KUBAT, J. KUBATSearch for more papers by this authorJ. MITERA, J. MITERASearch for more papers by this author First published: September 16, 1975 https://doi.org/10.1002/chin.197537093AboutPDF 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. Volume6, Issue37September 16, 1975 RelatedInformation

AbstractBei der Pb‐tetraacetat‐Oxidation von Adamantylmethanol (I) entstehen in Abhängigkeit vom Lösungsmittel in Pyridin als Hauptprodukte der Aldehyd (II) neben 48% Ausgangsprodukt und 8% des Acetats (IVa), in Benzol die Verbindungen (IIIa) und (IIIb) bzw. in Essigsäure die Acetate (IVa) (45% Ausbeute) und (IVb) (13%) sowie (IIIa) (21%).