Reaction of some sympathomimetic amines with sodium 1,2-naphthoquinone-4-sulphonate

Summary The condensation products of 4 sympathomimetic amines with 1,2-naphthoquinone-4-sulphonic acid have been prepared and examined. A spectrophotometric procedure based on the chloroform-soluble orange-red condensation product is described. The same products were investigated fluorimetrically after reduction with sodium borohydride. The results obtained are satisfactory.

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Zusammenfassung Die Kondensationsprodukte vier sympathicomimetischer Amine mit 1,2-Naphthochinon-4-sulfonsäure wurden dargestellt und untersucht. Ein spektralphotometrisches Verfahren auf der Grundlage des chloroformlöslichen, orangeroten Kondensationsproduktes wurde beschrieben. Die gleichen Produkte wurden auch fluoreszenzanalytisch nach ihrer Reduktion mit Natriumborhydrid untersucht. Die Ergebnisse sind befriedigend.

     

1-Alkoxy-2-azaallenyl-komplexe von chrom und wolfram

The successive reaction of (CO)₆M with Na[NCR₂¹] and [Et₃O]BF₄ yields (CO)₅M[C(NCR₂¹)OEt] (II: M = Cr; III: M = W; CR₂¹ = C(C₆H₄Br-p)₂ (a), CPh₂ (b), C(C₆H₄OMe-p)₂ (c), C(C₆H₄)₂O (d), CBu₂^tt (e)). Hexacarbonyltungsten, (CO)₆W, reacts with Na[NCPh₂] and MeOSO₂F to give (CO)₅W[C(NCPh₂) OMe] (IV). X-Ray analysis of IIe shows that: (1) the CNC fragment is almost linear (171.7°); (2) the two NC bond lengths are equal within experimental error; and (3) the O,C,Cr,N plane is perpendicular to the C(Me₃),C,N,C(Me₃) plane (90.0°). Therefore compounds II–IV are best described as 1-alkoxy-2-azaallenyl complexes.     

Anwendung mikroanalytischer Methoden zur Lösung kunst- und kulturgeschichtlicher Probleme

Zusammenfassung Mit bekannten mikroanalytischen Arbeitsmethoden — Oberflächenreaktionen, Abstrichuntersuchungen mit dem Korundstäbchen, Schutzschichtreaktionen sowie dem Abdruckverfahren — lassen sich archaeometrische Probleme einer Lösung näherbringen. Die Art der Korrosion kupferhaltiger Oberflächen wurde diskutiert.

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Application of microanalytical methods to the solution of artistic- and cultural historical problems

Summary Archeometrical problems are brought closer to a solution by means of known microanalytical procedures-surface reactions, surface scraping studies with the corundum rod, protective layer reactions as well as the imprint method. A discussion of the corrosion of copper-bearing surfaces is included.

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Vortrag anläßlich der Tagung Chemische Analysen — Kunst- und Kulturwissenschaften im Reiß-Museum in Mannheim, 19.–21. September 1974.     

Zur struktur von CaPdF4, CdPdF4, HgPdF4 und HpPdF2

Single crystals of CaPdF₄ (purple) and CdPdF₄ (dark blue) have been obtained by heating CaF₂ (CdF₂) with PdF₂ at 820°C (900°C) for ca. 20–30 d in sealed Pd (Pt) tubes. CaPdF₄ crystallizes tetragonal (KBrF₄-Type) with a = 5.52₁, c = 10.57₀ Å (space group I4/mcm ? D^18_4h, No. 140) Z = 4, 283 unique reflexions, R = 0.083; R_w = 0.079, CdPdF₄ cubic (CaF₂-variant) with a = 5.40₃ Å (space group Pa3 ? T^6_h, No. 205) Z = 4, 165 unique reflexions, R = 0.047, R_w = 0.032. The high pressure modification of PdF₂, obtained by heating PdF₂ in closed Pt-tubes under a pressure of ≈ 60 kbar and ‘HgPdF₄’, both black, a = 5.32₇ Å and a = 5.43 Å are isotypic. CaPdF₄ is diamagnetic, CdPdF₄ and HPPdF₂ are antiferromegnetic.     

The surface activity of the lower homologues of n-alkylammonium chlorides in aqueous solutions. Effect of hydrophobic hydration

Summary The surface tensions of aqueous solutions ofn-alkylammonium chlorides (methyl to hexyl) have been measured at 25 °C. With methylammonium chloride the surface tension increased with concentration, whereas with ethylammonium chloride and higher homologues, the surface tension decreased with concentration. The results suggest that this transition is attributed to the effect of hydrophobic hydration. For propylammonium chloride and higher homologues, the relation between the surface tension lowering da and the concentrationC in the range of 0–10 dyne/cm, can be expressed by the equation; = AC + BC, whereA andB are constants. The surface tension coefficientB has been found to increase approximately twofold for each additional CH₂ group of alkyl chain.

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Zusammenfassung Es wurden die Oberflächenspannungen wäßriger Lösungen vonn-Alkylammoniumchloriden (Methyl- bis Hexylammoniumchloride) bei 25 °C gemessen. Für Methylammoniumchlorid nimmt die Oberflächenspannung mit der Konzentration zu, aber bei allen höheren Homologen mit der Konzentration ab. Die Ergebnisse deuten darauf hin, daß dieser Übergang durch die hydrophobe Hydration bedingt wird. Für Propylammonium-chlorid und die höheren Homologen wird die Beziehung zwischen der Erniedrigung der Oberflächenspannung und der KonzentrationC in dem Bereich von 1 bis 10 dyn/cm durch die folgende Gleichung ausgedrückt: = AC + BC (A undB sind Konstanten). Es wurde gefunden, daß B für jede zusätzliche CH₂-Gruppe etwa um den Faktor 2 größer wird.

     

Synthese neuer N-Vinylpyrrole

Syntheses of New N-Vinylpyrroles The reactions of pyrrolyl potassium ( 1 ) with (ethoxymethylene)malonic acid derivatives 2a–e yielded the carbanions 3a–e , which could be hydrolyzed to 4a–e , but with the exception of 4b they were not isolated, because a transformation to the N-vinylpyrroles 5a , c–e by elimination of ethanol took place; 1 reacted with 2b at 80°C to give 4b and 6 . Hydrolysis of 4b with KOH yielded 4g , which eliminated 1 mol of ethanol to form 5f , decarboxylation of which led to N-vinylpyrrole 7 . By cyclization of 5e under various conditions the pyrrolizines 8a , b are obtained, the hydrolysis of which did not give ketone 9 but only amino alcohol 10 . Some other cyclizations of 11a–c and 13 yielded the 3H-pyrrolizine derivatives 12a–c and 14 , respectively.     

Wave mechanics - the first fifty years : edited by W.C. Price,S.S. Chissick and T. Ravensdale,Butterworths, London, 1973, pp. 435, price £12.00

The free NH₃ molecule and the [Zn(NH₃)₄]²⁺ ion were studied by the kinematic coupling approach. The pure effects of this coupling were found to be small, and some modifications had to be introduced in order to get a reasonable force field. The force constants deduced for the skeletal vibrations are comparable with those of a quasi-exact force field. Calculated frequencies for [⁶⁸Zn(NH₃)₄]²⁺ and [⁶⁴Zn(ND₃)₄]²⁺ are reported in addition to those of [⁶⁴Zn(NH₃)₄]²⁺. Mean amplitudes of vibration for [⁶⁴Zn(NH₃)₄]²⁺ are given.     

Is laser-ablation-ICP-MS an alternative to solution analysis of solid samples?

The basic obstacles for the general use of laser-ablation(LA)-ICP-MS in analytical laboratories are connected with its reproducibility and calibration. A mathematical relation deduced from the correlation function of the analytical signals allows the estimation of the number of craters needed for representative analyses. The procedure was applied to different samples such as manganese crusts and soils. The ion intensities of the major elements in the manganese crusts and nodules were used as internal standards, improving relative standard deviations by factors between 2 and 3. Selected samples of wood and manganese crusts were analyzed by LA-ICP-MS and the results compared with those obtained by solution ICP-MS. The agreement of the values is within the 95% confidence limits. Powdered reference materials and, in the case of wood analysis, cellulose doped with standard solutions were used for the calibration.     

Darstellung und Reaktionen des 3-Ethinyl-2,4-diformyl-pentandials

Preparation and physical and chemical properties of 3-ethinyl-2,4-diformyl-pentandial (3 a) and its salts are described.3 a contains 2 malonaldehyde groups. Starting from3 a, 4H-pyranes, 4H-dihydropyridines, dipyrazoles, diisoxazoles, bisdiazepines and vinamidine derivates are obtained.

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Mit 1 Abbildung     

Zur Umsetzung des 3,4,5,6-Tetrahydro-6-hydroxy-4,4,6-trimethyl-1,3-thiazin-2-thions mit sekundären Aminen

Tetrahydro-6-hydroxy-trimethyl-1,3-thiazine-2-thione (1) reacts with secondary amines via the dialkylammonium-3-oxoalkyldithiocarbamate3, either via isothiocyanates6 to 4-dialkylaminodihydro-2(1H)-pyridinethiones7 or to dialkylammonium dithiocarbamates (13), depending on the amine used and the reaction conditions. Subsequently, 6-dialkylaminotetrahydro-1,3-thiazine-2-thiones11 or tetrahydro-6-mercapto-1,3-thiazine-2-thione10 are formed. On being heated to reflux,11 reacts to pyridinethione7 and 4-dialkylaminodihydrothiopyranthione19. With secondary amines only13 is formed from tetrahydro-6-hydroxytetramethyl-1,3-thiazine-2-thione20. The reaction of dihydrotrimethyl-1,3-thiazine-2-thione21 with secondary amines leads to N,N-dialkylthioureas16 or dialkylammonium thiocyanates17 and with dialkylformamides 4-dialkylaminodihydropyridinethiones7 are formed. Dihydrotetramethyl-1,3-thiazine-2-thione24 reacts neither with secondary amines nor with dialkylformamides.