Final elucidation of the absolute configuration of the signal metabolite hormaomycin

The complete absolute configuration of hormaomycin 1 a has been established by HPLC and HPLC/MS experiments with appropriately derivatized 4-propylprolines, (2S,4S)-6 and (2R,4R)-6, as well as 4-(Z)-propenylprolines, cis-5 and trans-5, and also feeding experiments with enantiomerically pure samples of the deuterium-labeled 3-(2'-nitrocyclopropyl)alanine, (2S)-3,3-[D2]15 and (2S)-2,2'-[D2]15, and 4-(Z)-propenylproline 2',4-[D2]-(2S,4R)-5. The latter five amino acids were prepared for the first time and allowed one to unequivocally assign the hitherto unknown absolute configurations of the last four stereocenters in hormaomycin 1 a. As a bonus, some new information about the biosynthesis of this molecule has also been gathered.     

Photolysis of 2-dialkylamino-3-amino(or alkylamino)-1,4-naphthoquinones

Using¹H and¹³C NMR spectroscopy, naphthodihydroimidazolediols were identified as the primary products of photolysis of 2-dialkylamino-3-amino(alkylamino)-1,4-naphthoquinones. Their further non-photochemical (thermal) transformations depend on their structure and on the photolysis conditions.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 2, pp. 358–362, February, 1993.     

CAST/CNMR: highly accurate C NMR chemical shift prediction system considering stereochemistry

Accurate, practical prediction of ¹³C NMR chemical shifts has been achieved with a new system, CAST/CNMR, taking account of stereochemistry. The CAST/CNMR system has solved the critical problem of the accurate distinction of differences and similarities in stereochemical structures around a specific carbon, which has not yet been achieved by any other database-oriented system for prediction of ¹³C NMR chemical shifts. CAST/CNMR uses a three-dimensional structural database together with a ¹³C NMR spectral database. Absolute/relative configurational and conformational structural information are described by the CAST (CAnonical-representation of STereochemistry) coding method. This paper provides an overview of the CAST/CNMR system, and describes its application to two natural products as examples.     

Determination of heterocyclic aromatic amines (HAA) in commercially available meat products and fish by high performance liquid chromatography—Electrospray tandem mass spectrometry (HPLC-ESI-MS-MS)

Summary Ten heterocyclic aromatic amines (HAA) (1)–(10) were analyzed in commercially available meat products and fish. After sample preparation by Extrelut treatment and subsequent solid phase extraction applying propylsulphonic and C₁₈ silica cartridges, HPLC-ESI-MS-MS using selected reaction monitoring (SRM) and d₃-PhIP and d₃-MeIQx as internal and external standards, respectively, revealed the widely distributed presence of PhIP (8) and MeIQx (4), ranging from 0.1 to 5.3 ng g⁻¹ and 0.1 to 5.2 ng g⁻¹, respectively. Lower amounts were found for 4,8-DiMeIQx (5) and 7,8-DiMeIQx (6), ranging from 0.2 to 2.0 ng g⁻¹ and 0.1 to 0.2 ng g⁻¹, respectively. The other HAA under study, i.e. IQ, MeIQ, 4,7,8-TriMeIQx, Glu-P-1, and Glu-P-2 were not determinable under the experimental conditions used (determination limit 0.1 ng g⁻¹).     

Determination of the antifouling booster biocides irgarol 1051 and diuron and their metabolites in seawater by high performance liquid chromatography-diode array detector

A method for the simultaneous determination of two antifouling booster biocides, diuron (1-(3,4 dichlorophenyl) 3,3 dimethyl urea) and irgarol 1051 (2-methylthio-4-tert-butylamino-6-cyclopropylamino-s-triazine), and their metabolites, DCPMU (1-(3,4 dichlorophenyl)-3 methyl urea), DCPU (1-(3,4 dichlorophenyl) urea), DCA (3,4 dichloroaniline) and M1 (2-methylthio-4-tert-butylamino-s-triazine) in seawater by high performance liquid chromatography-diode array detector (HPLC-DAD) was developed. The optimization of the extraction procedure included the type of sorbent and the type of the organic solvent for the elution. Optimization of the liquid chromatography (LC) separation was also performed and the robustness of the developed separation was tested, in respect to the effect of three factors (column temperature, flow rate and initial strength of acetonitrile) on the retention times, peak resolution and peak area of the six compounds. The optimized procedure included off-line extraction of these compounds from seawater samples using C18 solid phase extraction (SPE) cartridges. The inter-day precision of the developed procedure was less than 14% (as R.S.D.s) for all the tested compounds. Satisfactory recoveries (higher than 82%) were obtained for all substances, except for DCA, for which low recovery was obtained (30.5%). The limits of detection (LODs) of the substances varied between 0.005 (DCPMU) and 0.026 (M1) μg L⁻¹.     

The effect of alcoholic mobile phase modifiers on retention and stereoselectivity on a commercially available cellulose-based HPLC chiral stationary phase: An unexpected reversal in enantiometric elution order

Summary High pressure liquid chromatographic methods for the determination of diphenylmethane-4,4-diisocyanate (MDI) and toluene diisocyanate (TDI) in chemical products are described. The MDI- and TDI monomers were determined as their urea derivative formed by the reaction with 9-(methyl aminomethyl)-anthracene. Using these methods MDI- and TDI monomer concentrations have been determined in 55 chemical products: sealing waxes, insulating- and adhesive foam, hardener, primer, adhesives and surface coatings. The recovery of both MDI and TDI monomers from various types of chemical product was found to be 92–97%, and the relative standard deviations of the methods was <5% for all types of products.     

Negative ion formation in compounds relevant to SF6 decomposition in electrical discharges

Dissociative and nondissociative electron attachment in the electron impact energy range 0–14 eV are reported for SOF₂ SOF₄, SO₂F₂, SF₄, SO₂, and SiF₄ compounds which can be formed by electrical discharges in SF₆. The electron energy dependences of the mass-identified negative ions were determined in a time-of-flight mass spectrometer. The ions studied include F^– and SOF ₂ ^–* from SOF₂; SOF ₃ ^– and F^– from SOF₄; SO₂F ₂ ^–* , SO₂F^–, F ₂ ^– , and F^– from SO₂F₂; SF ₄ ^–* and F^– from SF₄; O^–, SO^–, and S^– from SO₂; and SiF ₃ ^– and F^– from SiF₄. Thermochemical data have been determined from the threshold energies of some of the fragment negative ions. Lifetimes of the anions SOF ₂ ^–* , SO₂F ₂ ^–* , and SF ₄ ^–* are also reported.     

Crystal structures of 6-[(2-hydroxy-1,1-bis-hydroxymethyl-ethylamino)-methylene]-4-nitro-cyclohexa-2,4-dienone hydrate and 6-[(2-hydroxy-1,1-bis-hydroxymethyl-ethylamino)-methylene]-4-bromo-cyclohexa-2,4-dienone

Crystal structures of 6-[(2-hydroxy-1,1-bis-hydroxymethyl-ethylamino)-methylene]-4-nitro-cyclohexa-2,4-dienone hydrate (I) and 6-[(2-hydroxy-1,1-bis-hydroxymethyl-ethylamino)-methylene]-4-bromo-cyclohexa-2,4-dienone (II) have been determined. The crystals of I are monoclinic, a = 16.957(1) Å, b = 10.729(2) Å, c = 7.240(3) Å; β = 99.56(3)°, space group P2₁/c, Z = 4, R = 0.0492. The crystals of II are triclinic, a = 10.282(2) Å, b = 7.189(3) Å, c = 16.831(3) Å; α = 90.67(3)°, β = 100.10(3)°, γ = 95.87(3)°; space group P-1, Z = 4, R = 0.0591. The independent part of the unit cell of I contains one unique molecule and water of crystallization, while in II — two unique molecules A and B. C(CH₂OH)₃ fragment of the molecule B manifests the disordering of alcohol oxygen atoms. Both in I and II, the salicylidene fragment of the molecules exists in the quinoid tautomeric form.     

Determination of C1−C4 fatty acids as p-bromophenacyl esters using glass-capillary gas chromatography and electron-capture detection

Summary A method for the determination of low relative molecular mass carboxylic acids (C₁–C₄) in water is reported. The acids are converted to p-bromophenacyl esters prior to a glass-capillary gas chromatographic separation. By utilizing electron-caputre detection the detectability is substantially improved compared to flame-ionization detection. A comparison of three different ways to treat the water samples and to produce the derivatives is made. It is shown that the , p-dibromoacetophenone reagent decomposes to a small extent which limits the utility of the reagent. Nevertheless a detection limit for formic acid of approximately 2.5 mgl^–1 is obtained. The method is applied to the determination of formic and acetic acids in a paper kraft water sample.     

Stereoselective allyl amine synthesis through enantioselective addition of diethylzinc and [1,3]-chirality transfer: synthesis of lentiginosine and polyoxamic acid derivative

A new synthetic method for the preparation of allyl amines has been developed. The key steps of this method are enantioselective addition of diethylzinc and [1,3]-chirality transfer through the [3.3] sigmatropic rearrangement of allyl cyanates. Stereocontrolled syntheses of lentiginosine (1) and polyoxamic acid derivative 2 from a common intermediate 7 derived from D-tartaric acid (8), have been accomplished.