Chemische und pharmakologische Studien über Derivate des Benzo[de]chinolins. II. 10.Mitteilung über natürliche und synthetische Isochinolinderivate

Chemical and Pharmacological Studies on Derivatives of Benzo[de]quinoline, II Spirocompounds of type V ( 12–18 ) were synthesized by a carbenium ion cyclization reaction of the intermediates 7 and 11 , respectively. 7 was prepared from 2-oxocyclopentanepropionic acid via 1, 2 , and 4–6; 11 from the same starting material via 1, 2 , and 8–10 . - The spiro[7H-benzo[de]quinolin-7,1′-cyclohexan]-2′-one 27 and other compounds of type VI could be synthesized from the (1-isoquinolinyl)ethyl-cyclohexanone 25: 25 is hydroxylated to the hydroxyketone 26 ; treatment of 26 with a mixture of sulfuric acid and oleum gives 27 . The structure of 27 has been proved by transformation into the known spirocyclohexane 33 . - Aporphine analogues of type VII ( 38, 39 ) were synthesized from the cyclic ketone 34 via either the formylketone 35 and its methyl vinyl ketone adducts 36 and 37 or the methyl ethynyl ketone adduct 40 . Compound 40 has also been cyclized to the 10-hydroxy-aporphine 42 . 9 compounds of the types mentioned have been screened for hypotensive action in rats, and partly in cats and dogs. Only compound 13 · HCl proved to be (moderately) active in rats and dogs.     

Iron carbonyl complexes of 2,3,5,6-tetrakis(methylene)-7-oxabicyclo[2.2.1]heptane. Crystal and molecular structure of (C10H10O)Fe(CO)3 and (C9H10CO)Fe2(CO)6

The reaction of 2,3,5,6-tetrakis(methylene)-7-oxabicyclo[2.2.1]heptane (I) with iron carbonyls in various solvents yields the (η⁴-1,3-diene)Fe(CO)₃ isomers (II: exo; III: endo) and the bimetallic isomers bis[(η⁴-1,3-diene)Fe(CO)₃] (IV: bis(exo); V: endo,exo). In weakly coordinating solvents, a parallel rearrangement of I occurs through CO bond cleavage of the allylic ether by Fe₂(CO)₉ yielding an unsaturated ketone (VI) bonded to two Fe(CO)₃ groups through a trimethylenemethane and a 1,3-diene system, respectively. The geometries of III and VI have been ascertained by X-ray crystal structure determinations.     

Adsorption of a diverse set of organic vapors on the bulk water surface

The bulk water surface is of fundamental interest to physical as well as environmental chemistry. As there is a lack of wide-ranging adsorption data from the air to the bulk water surface, a large and diverse data set of adsorption coefficients of nonionic, organic compounds has been produced with inverse gas chromatography. The 61 compounds were chosen to cover a large range of properties, considering the intermolecular interactions between the compounds and the bulk water surface, i.e., van der Waals and electron-donor/acceptor interactions. The data set gained in this work was interpreted with a linear free energy relationship (LFER) based on these intermolecular interactions. From this LFER, a general adsorption model is derived, including compound (i) and surface (surf) properties: log K(i surf/air)(m(3)/m(2)) = 0.135(+/-0.003) log K(i hexadecane/air)(gamma(surf)(vdW))(0.5) + 5.11(+/-0.15)Sigma beta(i2)(H)EA(surf) + 3.60(+/-0.28)Sigma alpha(i2)(H)ED(surf) - 8.47. This adsorption model can be used for the characterization of adsorption to any other surface. The adsorption model for bulk water surface adsorption as well as the general adsorption model can be used as prediction tools in natural or technical systems.     

Stereoselective Double Friedel-Crafts Acylation of trans-μ-(2,3,6,7-Tetramethylidenebicyclo[3.2.1]octane)bis(tricarbonyliron). Crystal Structure of trans-μ-{(1RS,2RS,3SR,5RS,6SR,7SR)-C,2,3,C-η:C,6,7,C-η-[(Z,Z)-1,1′-(3,7-Dimethylidenebicyclo[3.2.1]octane-2,6-diylidene)di(2-propanone)]}bis(tricarbonyliron)

The Friedel-Crafts mono and double acylations of trans-μ-[(1RS,2RS,3SR,5RS,6SR,7SR)-C,2,3,C-η:C,6,7,C-η-(2,3,6,7-tetramethylidenebicyclo[3.2.1]octane)]bis(tricarbonyliron) ( 4 ) are highly stereoselective and yield trans-μ-{(1RS,2RS,3SR,5RS,6SR,7RS)-C,2,3,C-η :C,6,7,C-η-[(Z)-1-(3,6,7-trimethylidenebicyclo[3.2.1]-oct-2-ylidene)-2-propanone]}bis(tricarbonyliron) ( 5 ) and trans-μ-{(1RS,2RS,3SR,5RS,6SR,7SR)-C,2,3,C-η :C,6,7,C-η-[(Z,Z)-1,1′-(3,7-dimethylidenebicyclo [3.2.1] octane-2,6-diylidene)di(2-propanone)]}bis(tricarbonyliron) ( 6 ) whose structure has been established by single-crystal X-ray diffraction.     

High-throughput synthesis and characterization of bulk ceramics from dry powders

A high-throughput experimental (HTE) setup using conventional powders as raw materials was developed to synthesize and characterize ceramic bulk samples avoiding the customary liquid- or vapor-phase synthesis routes. Its functionality was verified using the well-known binary material system ZrO2-Y2O3. Libraries of 0.5 mol % yttria resolution were prepared using varying boundary systems as well as a number of liquid mixing aids. Automated powder X-ray diffraction (XRD) was applied to check the monoclinic phase content retained after heat-treatment on various positions for each sample. This phase information was used for comparison with a reference library comprising conventionally prepared samples by means of a regression analysis and mean deviation of monoclinic phase percentage. Out of the eight HTE libraries, three showed a significant comparability to the reference library.     

Folate content in sea buckthorn berries and related products (Hippophaë rhamnoides L. ssp. rhamnoides): LC-MS/MS determination of folate vitamer stability influenced by processing and storage assessed by stable isotope dilution assay

A stable isotope dilution assay was adopted for quantitation of folate vitamers in sea buckthorn berries, juice, and concentrate using fourfold labeled folate isotopologues of the folate derivatives as the internal standards and reversed-phase liquid chromatography-tandem mass spectrometry with electrospray ionization (LC-ESI-MS/MS). Processing effects and storage stability were investigated during juice and concentrate production from sea buckthorn berries (Hippopha? rhamnoides). The technological processing of the berries caused a total degradation of tetrahydrofolate and 5-formyltetrahydrofolate in the generated juice. The content of the main folate vitamer 5-methyltetrahydrofolate remained approximately unchanged during the whole processing from the berries to the concentrate. Sea buckthorn juice was stored under two household storage conditions (6 degrees C, 25 degrees C), and also under accelerated aging conditions (40 degrees C) for up to 7 days to determine the effects of storage temperature on the stability of 5-methyltetrahydrofolate. The content of 5-methyltetrahydrofolate was nearly unchanged during the storage at 6 degrees C after 7 days. The juice showed almost identical degradation of 5-methyltetrahydrofolate of about 17-20% at 25 degrees C and 40 degrees C after 7 days of storage. [figure: see text]     

Separation of betalains from berries of Phytolacca americana by ion-pair high-speed counter-current chromatography

The first preparative fractionation of betalain pigments by means of ion-pair high-speed counter-current chromatography (IP-HSCCC) from berry extracts of Phytolacca americana (Phytolaccaceae) is presented. A novel HSCCC solvent system consisting of 1-butanol-acetonitrile-water (5:1:6, v/v/v) was applied using ion-pair forming trifluoroacetic acid at low concentration (0.7%, v/v). Affinity of polar betacyanins and betaxanthins to the organic stationary phase of the biphasic HSCCC solvent mixture was considerably improved. Partitioning coefficient values and influence of increasing trifluoroacetic acid additions to the biphasic solvent mixture were measured for all identified betacyanins and betaxanthins. Gentle separation by IP-HSCCC of the injected pigment extract (900 mg) yielded sufficient amounts of the principal pigments 15S-betanin/15R-isobetanin. The pure epimers separated by C18-HPLC were immediately studied by one- and two-dimensional NMR. In the recovered fractions, minor concentrated betacyanins and betaxanthins were significantly enriched by IP-HSCCC and were detected for the first time in the extracts of P. americana. IP-HSCCC and C18-HPLC were shown to be complementary techniques in the isolation procedure of recovering minor concentrated, highly polar and chemically instable betacyanins and betaxanthin from complex plant matrices. Altogether, identification of 17 betalains was achieved by HPLC-diode array detection-electrospray ionization MS/MS in the HSCCC fractions with their respective isomers, also resulting in the tentative elucidation of betacyanins with novel salicylic acid substitution pattern in the berry extracts of P. americana.     

A Useful Extension of Ito＇s Formula with Applications to Optimal Stopping

Given a continuous semimartingale M = （Mt）t≥〉0 and a d-dimensional continuous process of locally bounded variation V = （V^1,……, V^d）, the multidimensional Ito Formula states that f（Mt, Vt） - f（M0, V0） = ∫[0, t] Dx0f（Ms, Vs）dMs＋∑i=1^d∫[0, t] Dxi F（Ms, Vs）dVs^i＋1/2∫[0, t] Dx0^2 f（Ms, Vs）d 〈M〉s if f（x0,……,xd） is of C^2-type with respect to x0 and of C^1-type with respect to the other arguments This formula is very useful when solving various optimal stopping problems based on Brownian motion. However, in such application the function f typically fails to satisfy the stated conditions in that its first partial derivative with respect to x0 is only absolutely continuous. We prove that the formula remains true for such functions and demonstrate its use with two examples from Mathematical Finance.