Stereochemie von Metallocenen, 20. Mitt.: Die Ermittlung der optischen Reinheit der Methylferrocen-α-carbonsäure (40. Mitt. über Ferrocenderivate)

Zusammenfassung Die optische Reinheit der Methylferrocen--carbonsäure (1) wurde mit Hilfe zweier Methoden ermittelt. Die Isotopenverdünnung unter Verwendung von (²H₁-Methyl)ferrocen--carbonsäure sowie ein Verfahren, das auf der Auswertung der Intensitätsverhältnisse diastereotoper Protonen in denNMR-Spektren der -Phenäthylamide von1 (verschiedener Drehung) beruht, lieferten übereinstimmende Ergebnisse: [] _d für optisch reines1 beträgt 55,6±1,0° bzw. 54±3°. Der durch Racematspaltung von1 gefundene Wert beträgt 51,5±0,8° (bzw. 53±2°)³. Damit sind die Drehungen aller 90, mit1 bereits früher chemisch korrelierten Ferrocenderivate, wenn überhaupt, nur geringfügig zu korrigieren.

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The optical purity of methylferrocene--carboxylic acid (1) was determined by two methods: isotope dilution, employing (²H₁-methyl)ferrocene--carboxylic acid, and a procedure based on the evaluation of the relative intensities of diastereotopic protons in theNMR-spectra of the -phenethylamides of1 having different rotations. By both methods corresponding results were obtained: optically pure1 has an []d of 55.6±1.0° and 54±3°, resp. The value for1 as found by optical resolution is 51.5±0.8° and 53±2°, resp.³. Hence, the rotations of all 90 ferrocene derivatives previously correlated with1 by unambiguous chemical methods have—if at all—to be corrected only slightly.

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Mit 2 Abbildungen

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19. Mitt.:H. Falk undG. Haller, Mh. Chem.99, 1103 (1968).

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39. Mitt.:K. Schlögl undHeidelore Soukup, Mh. Chem.99, 927 (1968).     

Cardiac glycosides ofAcokanthera venenata

Six cardenolides have been isolated from the leaves ofAcokanthera venenata G. Don: AV-1, mp 252–255°C, [] _D ²⁰ +39.4° (MeOH); AV-2, mp 199–208°C, [] _D ²⁰ -59.3° (MeOH); AV-3, mp 269–275°C/300–304°C, [] _D ²¹ –69.8° (MeOH); AV-4, mp 279–289°C; AV-5, mp 222–225°, [] _D ²⁰ -64.3° (MeOH); and AV-6, mp 193–196°C [] _D ²⁰ –23.8° (MeOH — CHCl₃). AV-5 has been identified as acovenoside A. AV-3 is a new cardiac glycoside: it is 1-acetoxy-3-(4-O--D-glucosyl-3-O-methyl--L-talomethylosyloxy)-14-hydroxy-5, 14-card-20(22)-enolide (glucoacovenoside B).Khar'kov State Pharmaceutical Institute. All-Union Scientific Research Institute of Drug, Chemistry and Technology, Khar'kov. Translated from Khimiya Prirodnykh Soedinenii, No. 3, pp. 372–376, May–June, 1987.     

Determination of lead and cadmium using a polycyclodextrin-modified carbon paste electrode with anodic stripping voltammetry

This work reports the use of and -cyclodextrin-modified carbon paste electrodes (CPE_-CD and CPE_-CD) to determine simultaneously Pb(II) and Cd(II) by means of the electrochemical technique known as anodic stripping voltammetry (ASV). Both modified electrodes displayed good resolution of the oxidation peaks of the said metals. Statistic analysis of the results strongly suggests that the CPE_-CD exhibited a better analytical response that the CPE_-CD, while the detection limits obtained for Pb(II) were 6.3×10^–7 M for the CPE_-CD and 7.14×10^–7 M for the CPE_-CD, whereas for Cd(II) they were 2.51×10^–6 M for the CPE_-CD and 2.03×10^–6 M for the CPE_-CD.     

Certification of bilirubin SRM 916a

Summary The process used to certify Standard Reference Material (SRM) 916a Bilirubin is described. The certification involved the use of various analytical techniques to detect or quantitate impurities, as well as to characterize the SRM itself. Bilirubin (BR) is believed to exist, in human serum, as the IX isomer. Samples prepared commercially, including this SRM, also contain the III and XIII isomers which are believed to be formed during purification. For the SRM, the three isomers were measured by HPLC and TLC. ¹H NMR was used to detect and quantitate chloroform in the BR. Biliverdine and mesobilirubin were not detected. Impurities insoluble in chloroform, the residue from the ashing of BR, and volatiles were measured, in addition to non-acidic impurities and impurities more acidic than BR. The absorptivity of BR in chloroform was measured. A pink fluorescent impurity was detected and measured by TLC. From these analyses, a best estimate of the total amount of impurities was determined, and the BR was issued as SRM 916a with a certified purity of 98.3±0.3%.     

Infrarotspektroskopische Charakterisierung von Carbons?uren durch ihre Trimethylsilylester

Zusammenfassung 91 Carbonsäuren wurden mit Dialkoxytrimethylsiloxy-N-trimethylsilylphosphoriminen (besonders Diäthoxytrimethylsiloxy-N-trimethylsilylphosphorimin, DASPI) oder mit Trimethylsilylmethyl acetamid, TMSMA, silyliert. Die C=O-Frequenzen der entsprechenden Trimethylsilylester können zur Ermittlung des Substitutionstyps am-C-Atom der Carbonsäuren dienen.-Aminosäuren bilden eine Ausnahme. Diese Säuren wurden wegen ungenügender Silylierung mit DASPI nur mit TMSMA silyliert. Folgende Frequenzbereiche der Silylesterbande wurden gefunden: aliphatisch, aliphatisch-verzweigt 1713 bis 1733 (1722±4) cm^–1;-heterosubstituiert, einschließlich-Acylamino- 1721–1754 (1737±11) cm^–1, in den meisten Fällen von einer zweiten, längerwelligen Bande begleitet im Abstand von 10–25 cm^–1:-unge-sättigt 1687–1736 (1701±13) cm^–1; aromatisch 1673–1721 (1705+10) cm^–1;-Amino- 1702–1731 (1719±7) cm^–1. (In Klammern: Mittelwerte mit Standardabweichung.)

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Infrared-spectroscopic characterisation of carboxylic acids by their trimethylsilyl esters

91 Carboxylic acids were silylated by dialkyltrimethylsilyl-N-trimethylsilyl phosphorimidates (mainly diethyltrimethylsilyl-N-trimethylsilyl phosphorimidate, DESPI) or trimethylsilylmethyl acetamide, TMSMA, and the C=O frequencies of the corresponding trimethylsilyl esters were investigated. Exceptions were -amino acids. Due to uncomplete silylation by DESPI these were silylated by TMSMA, but investigations in the region lower than 1690 cm^–1 could not be made because of the strong absorption by the amide I band of TMSMA.The following frequency regions of the silyl ester band were found: aliphatic, aliphatic-branched 1713–1733 (1722±4) cm^–1;-heterosubstituted, including-acylamino- 1721–1754 (1737±11) cm^–1 and, in most cases a second, lower frequency band at a distance of 10–25 cm^–1 originating from conformational isomers:-unsa-turated 1687–1736 (1701±13) cm^–1; aromatic 1673–1721 (1705±10) cm^–1;-amino-1702–1731 (1719±7) cm^–1. (In brackets: mean value ± standard deviation.)

     

Structure of the X-ray emission CuLα-line in YBa2Cu3O7−δ and CuO based on the SCFXα-SW calculation

Using the SCF X-SW method we have calculated the final states of the X-ray L-transition of the CuO ₄ ^–6 cluster modeling the nearest environment of the copper atom (one of two types) in YBa₂Cu₃O_7- and the nearest environment of copper in CuO. The energies of transitions forming the L-spectrum (with or without many-electron excitations) have been calculated. It has been shown that for interpretation of the main singularities of the X-ray emission L-spectrum, not only should the Coster-Kronig transitions be considered but also the shake-up excitation 2b_1g3b_1g processes and the multiple ionization satellites 3p^–1. An experimental schame has been suggested that allows separation of the effects of different many-electron processes on the L-spectrum.Institute of Inorganic Chemistry, Siberian Branch, Russian Academy of Sciences. Translated fromZhurnal Strukturnoi Khimii, Vol. 34, No. 4, pp. 3–9, July–August, 1993.Translated by L. Smolina     

Chemical transformations and evaluation of the basicities of 4,5-dihydropyrrolo[1,2,3-e,f][1,5]benzodiazepin-6(7h)-ones

The alkaline hydrolysis, amidation, and methylation of 4,5-dihydropyrrolo[1,2,3-e,f][1,5]benzodiazepin-6(7H)-one derivatives under various conditions were investigated. The ionization constants (pK) for 1,2-dimethyl-4,5-dihydro[1,2,3-e,f][1,5]benzodiazepin-6(7H)-one were calculated by the Hammett indicator method, and two values, viz., pK ¹ = –2.37 and pK ² = 5.53, which were ascribed to protonation of the diazepine ring and the indole ring of the molecule, respectively, were obtained.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 7, pp. 983–986, July, 1981.     

Environmental radioactivity in Uyo //5° N, 7° 50 E/, nigeria/

A survey of the environmental radioactivity in Uyo /5° N, 7° 50 E/, Nigeria has been done for the period 1981 to 1986. An overall average of 8.5±0.5 pCi is the environmental radioactivity for the surrounding air and 8.2±0.4 pCi for the top soil. Airborne -particles were also measured using CR-39 plastic detectors. The University Campus in Uyo had an overall average -activity of 75.3±0.8 fmCi while other sectors of the town had an average of 95.2±1.1 fmCi. Our results show a non-uniform distribution of - and other radioactivity in Uyo.     

Negativer linearer thermischer Ausdehnungskoeffizient von verstrecktem Polyäthylen

Zusammenfassung Der lineare thermische Ausdehnungskoeffizient von linearem Polyäthylen hoher Dichte wurde im Temperaturbereich –20 °C bis + 40°C bestimmt. Bei isotropen Proben besteht eine lineare Beziehung zwischen Dichte bzw. Kristallisationsgrad _v und. Die gemessenen Koeffizienten liegen fürT ₀ = 20 °C im Bereich = 110 ... 130 · 10^–6 K^–1.Kalt verstreckte Proben mit Verstreckungsgraden = 8 ... 15 haben beiT ₀ = 20 °C in Verstreckrichtung den Koeffizienten _l = –24 · 10^–6 K^–1. Der negative Zahlenwert von _tl ist unabhängig von und weiteren Herstellungsparametern. Seine Ursache ist einerseits die Orientierung derc-Achsen der Kristallite in Verstreckrichtung mit _c = –12 · 10^–6 K^–1 und andererseits der negative Koeffizient _am * –50 · 10^–6 K^–1 der verspannten amorphen Phase, der auf dem gummielastischen Verhalten der tie-molecules beruht.Beim Tempern oberhalb von +40 °C schrumpfen die Proben irreversibel, wobei _| ansteigt und nach dem Aufschmelzen der Proben wieder den Wert des isotropen Materials annimmt. Nach dem Tempern wenig unterhalb der Schmelztemperatur der Kristallite wurden überhöhte Koeffizienten _| gemessen, die eine Rotation der Kristallite um dieb-Achsen erkennen lassen.

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Summary The linear thermal coefficient of expansion,, of high density linear polyethylene has been determined in the temperature range of –20 ° ... + 40 °C. For isotropic samples a linear relationship between density or crystallinity _v and is valid. Measured values of forT ₀ = 20 °C amount to = 110 ... 130 · 10^–6 K^–1.Cold drawn samples of draw ratios = 8 ... 15 yield _| = –24 · 10^–6 K^–1 atT ₀ = 20 °C parallel to the draw axis. The negative value of _| does not depend on draw ratio or other parameters of sample processing. It is caused byc-axis orientation of the crystallites in draw direction with _c = –12 · 10^–6 K^–1 and by a negative coefficient _am * = –50 · 10^–6 K^–1 of the stressed amorphous phase, which is due to rubber elastic behaviour of the tie molecules.When annealed above 40 °C the samples shrink irreversibly and _| is augmented. After melting the samples the value of isotropic material is restored. Annealing the samples little below the melting temperature of the crystallites leads to superelevated values all which reflect| rotation of the crystallites around theb-axis.

     

Withasteroids ofPhysalis VI.1H and13C NMR spectra of withasteroids ixocarpalactone A and ixocarpanolide

The¹H and¹³C NMR spectra of two withasteroids isolated fromPhysalis ixocarpa Brot. have been studied in detail. Their spectral characteristics are discussed. A comparison of the results obtained has led to the identification of a withasteroid with the composition C₂₈H₄₀O₈, mp 291–292°C (from methanol) as ixocarpalactone A, in spite of some difference in its physical constants. The other compound, with mp 252–253°C (from methanol), had the composition C₂₈H₄₀O₆, [] _D ²⁰ +27±4°, is new and has been called ixocarpanolide. The structure of 5,20R-dihydroxy-1-oxo-6, 7-epoxy-22R-witha-2-enolide has been proposed for it.Institute of the Chemistry of Plant Substances, Academy of Sciences of the Uzbek SSR, Tashkent. Translated from Khimiya Prirodnykh Soedinenii, No. 3, pp. 326–332, May–June, 1986.     

Nuclear magnetic resonance spectra of furan derivatives of IV B group elements (review)

Electronic and steric effects in furan derivatives were studied by the method of ¹H, ¹³C, ¹⁷O, and ²⁹Si NMR spectroscopy. The characteristic features of the influence of substituents on the screening and spin-spin interaction of ring nuclei in -substituted derivatives of furan in the presence of a second -substituent have been noted.Dedicated to Prof. A. R. Katritsky on his 65th birthday.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 7, pp. 879–890, July, 1993.     

Steroid glycosides of the seeds ofNicotiana tabacum. II. The structures of nicotianosides C and F

From the seeds of tobacco Nicotiana tabacumL. we have isolated two new steroid glycosides, nicotianosidesC andF. The structures of the glycosides have been shown on the basis of chemical transformations and spectral characteristics. Nicotianoside C is a steroid glycoside of the spirostan series and has the structure of (25S)-5-spirostan-3ß-ol3-O-[-L-rhamnopyranosyl-(1 2)]-[-L-rhamnopyranosyl-(1 4)]-ß-Dglucopyranoside), and nicotianoside F is (25S)-5 furostan-3ß, 22, 26-triol 3-O-[-L-rhamnopyranosyl-(1 2)1-[-L-rhamnopyranosyl-(1 4)1-ß D-glucopyranoside) 26-O-ß-D-glucopyranoside.Institute of Genetics, Academy of Sciences of the Republic of Moldova, 277022, Kishinev, ul. Pédurilor, 20. Translated Khimiya Prirodnykh Soedinenii, No. 3, pp. 396–401, May–June, 1995. Original article submitted August 29, 1994.     

Neubestimmung der Gitterparameter,Dichten und thermischen Ausdehnungskoeffizienten von Silber und Gold,und Vollkommenheit der Struktur

Zusammenfassung Die neu bestimmten Gitterparameter des Ag und Au sinda ₂₅=4,08626±0,00004 (Ag) bzw. 4,07894±0,00005 Å (Au), die Brechungskorrektur+0,00035 einbezogen. Die Dichten beider Metalle sindd ₂₅=10,4976±0,0003 (Ag) bzw. 19,2779±0,0018 (Au) g cm^–3. Die thermischen Ausdehnungskoeffizienten sind _Ag=18.73·10^-6 and _Au=13.4·10^-6°C^-1 zwischen 10 und 65°. Beide Metalle weisen einen vollkommenen Aufbau (innerhalb der Fehlergrenzen) auf.Die vollständige Erholung der reinen, 99,999proz. Metalle von den Folgen der Kaltbearbeitung (Feilen) erfolgt sogar bei Zimmertemperatur: Ag-in ungefähr 24 Stdn., Au-in 5 Tagen. Die Verschiebung (Platzwechsel) der Atome wird stark durch Verunreinigungen verzögert.Der dicht unter dem Schmelzpunkt abgeschreckte Silberkristall zeigte eine geringe Dichte, die beim Tempern zunahm, was durch das Herausdiffundieren von Leerstellen erklärt werden kann.

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Redetermination of lattice parameters, densities and thermal expansion coefficients of silver and gold, and the perfection of their structures

The redtermined lattice parameters of Ag and Au are as follows:a ₂₅=4.08626±0.00004 and 4.07894±0.00005 Å, resp., including the refraction correction of 0.00035; the densities ared ₂₅=10.4976±0.0003 and 19.2779±0.0018 gcm^–3, resp. The thermal expansion coefficients between 10 and 65°C are: _Ag=18.73·10^-6 and _Au=13.4·10^-6°C^-1. Both metals showed a perfect structure (within the error limits).A complete recovery of the 99.999% pure metals from the consequences of cold work (filing) occurred at room temperature in about 24 hr. (Ag) and in 5 days (Au). The displacement of atoms is strongly retarded by the presence of impurities.A silver crystal quenched just below the melting point showed a lower density which increased during the heat treatment. This behavior can be explained by vacancies diffusing out of the crystal.

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Herrn Prof. Dr.H. Nowotny gewidmet.

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Mitteilung Nr. 132 aus dem GCMR, Univ. of Mo-Rolla.     

Die Acetalgruppe, 1. Mitt. Acetale von Halogenmethyl-arylcarbinolen

Several halomethyl-arylcarbinols were prepared, and the influence of substituents on enantiomer selectivity in the acetalisation reaction with [2S-(2,3a,4,7,7a)]-octahydro-7,8,8-trimethyl-4,7-methanobenzofuran-2-ol was examined.

Unserem sehr verehrten Lehrer, Herrn Prof. Dr.Otto Hromatka, mit den besten Wünschen zum 80. Geburtstag gewidmet.     

Simultaneous flow measurement of specific heats and thermal expansion coefficients of liquids: Aqueoust-BuOH mixtures and neat alkanols and alkanediols at 25°C

A flow method is described for the simultaneous measurement of volumetric specific heat capacities c _p ^v and thermal expansion coefficients of liquids, using a Picker heat capacity microcalorimeter. the method involves a simple sequence of operations in which the calorimeter unit is used alternately to measure a difference in volumetric specific heats at constant flow rate and temperature, or a flow rate variation resulting from a temperature scan on a flow cell. The precision of the method in measurements is close to 1% which is comparable to that of current dilatometric methods; the overall time for the combined c _p ^v - measurement is less than 30 minutes. Typical uses and reliability of the method are illustrated through results for aqueous NaCl solutions, t-BuOH-water mixtures, and ,-diols (C₂–C₅) at 25°C. The and c _p ^v values in homologous series of normal alkanes, alcohols and diols appear well represented by equations comprising two contributions, one related to the hydrocarbon chain length, the other dependent on the number density of –OH groups. The general trends in these data and comparison with similar results for H₂O₂ and H₂O illustrate the magnitude of the c _p ^v and anomalies in liquid water.     

Structure of N,N-disubstituted α,β-unsaturated α-amino aldehydes

Study of the IR and¹H and¹³C NMR spectra of N,N-disubstituted ,-unsaturated -amino aldehydes showed that in the nature of the electron density distribution these compounds occupy an intermediate position between -unsubstituted amino olefins and ,-unsubstituted aldehydes, being significantly closer to the latter.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 9, pp. 2031–2034, September, 1991.     

Reaction of diazomethane with some α-substituted acrylates

The reaction of methyl -methoxy-, -acetoxy-, and -chloroacrylate with diazomethane proceeds in conformity with the -M orienting effect of the ester group. The resulting ¹-pyrazolines are converted to 3(5)-carbomethoxypyrazole at room temperature (the reaction proceeds more readily on heating).Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 4, pp. 545–546, April, 1973.     

<Superscript>1</Superscript>H and <Superscript>13</Superscript>C NMR spectra of some drimanic sesquiterpenoids

One- and two-dimensional homo- and heteronuclear correlation proton, carbon, proton—proton, and proton—carbon NMR spectra of fifteen drimanic sesquiterpenoids: 11,12-dibromodrima-5,8-dien-7-one, drim-8-en-7-one, 11-hydroxydrim-8-en-7-one, 11,12-dihydroxydrim-8-en-7-one, 11-hydroxy-11,12-epoxydrim-8-en-7-one, 11-hydroxy-11,12-epoxydrim-8-en-7-one, 8,9-epoxydriman-7-one, 8,9-epoxydriman-7-ol, 11,12-diacetoxydrim-8-en-7-ol, drimane-7,8,11-triol, 7,8-isopropylidenedioxydriman-11-al, 9, 11-dihydroxydrim-7-en-6-one, drimane-7,8,9-triol, drimane-7,8,11-triol, and drim-8-ene-7,11,12-triol were studied. The proton and carbon chemical shifts were assigned.__________Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 12, pp. 2589–2594, December, 2004.     

Volumetric study on a Co(III) rotaxane complex in aqueous solutions at 25°C

Résumé The standard partial molar volumes have been determined for [(en)₂ClCo(III)(don) Co(III)CL(en)₂] Br₄-[-CDX]-rotaxane (Rotaxane) and its component compounds, [(en)₂ClCo(III)(don)Co(III)Cl(en)₂] Br₄ (Co(III)-II), and -CDX, in aqueous solution at 25°C V^o (Rotaxane) is smaller than the sum of V^o (CO(III)-II) and V^o (-CDX) by about 28 cm³-mol^–1. Some estimations were attempted; the number of methylene groups in the cavity of -CDX, was estimated to be six and the number of water molecules expelled from -CDX cavity by hydrocarbon chain of the Rotaxane, is around four.