Library

Notes: 3-O-benzyl (and 3-O-methyl)-1,2-O-isopropylidene-α-D-xylo-dialdo-1,4-furanoses treated with bromocyanomethylidene- or bromoacylmethylidene-triphenylphosphoranes gave in good yields the corresponding olefinic sugars. These compounds, which bear three adjacent electrophilic carbon atoms (C(5), C(6), C(7)) constitute useful synthetic intermediates in carbohydrate chemistry. They represent, for example, good starting materials for the preparation of 3-glycosylisoxazoles, 5-glycosylisoxazoles and 2-glycosylthiophenes.

Notes: Formation of strongly colored complexes of Cu+ with glyoxal-bis-(N-t-butylimin) (GLI) is observed in acetonitrile. Optical measurements reveal two complexes, Cu(GLI)+ (ṽmax = 26.0 kK, δ = 2800) and Cu(GLI)2+ (ṽmax = 19.3 kK, ε = 8530). The equilibrium constants (0.1M tetraethylammoniumperchlorate) are logK1 = 3.9 and logK2 = 2.5. The equilibrium data are confirmed by potentiometric measurements with a copper electrode. In O-donor solvents, only the 1:2 complex is observed. Cu(GLI)2CIO4 can be crystallized as a dark red solid which is stable towards atmospheric oxygen.

Notes: The orientation of the cycloaddition of diazomethane on unsaturated branchedchain sugars has been studied. For 3-C-cyanomethylidene-3-deoxy-1,2-O-isopropylidene-α-D-glycero-tetrofuranose the orientation was ‘normal’ and did not depend on the configuration at the double bond. The same situation prevailed with derivatives of 3-deoxy-1,2:5,6-di-O-isopropylidene-3-C-methylidene-α-D-xylo-hexofuranose. For the 3-C-acylmethylidene- and the 3-C-cyanomethylidene-3-deoxy-1,2:5,6-di-O-isopropylidene-α-D-ribo-hexofuranoses, the trans-(H-C(3′)-C(2))-isomer gave the ‘normal’ cycloadduct whereas the cis-isomer gave predominantly the αabnormal spiro-pyrazoline. This observation represents the first instance where the regioselectivity of a cycloaddition reaction is affected by the geometrical isomerism of the dipolarophile. The most probable explanation of the phenomenon is the conformational perturbation about the C(4)--C(5) bond of the unsaturated sugars induced by a change in the configuration at C(3). The consequence of that ‘conformational transmission’ of a difference in configuration at C(3) is that the steric crowding on the cis- than in the trans-isomer. Several novel examples of a new series of C-glycosylidenic derivatives, the spiro-pyrazolines, are described.

Notes: The stability constants of the Ni2+ and Co2+ complexes with 1,5-diazacyclooctane-N,N′-diacetic acid (H2DACODA) have been determined potentiometrically in 0.5M KNO3 at 25°. Only M(DACODA) and M(DACODA)OH- were observed.In addition the formation and dissociation kinetics of the pentacoordinate complexes M(DACODA) has been studied in aqueous solution using a stopped-flow technique. Formation follows the rate law vf = kf [M2+] [HDACODA-]/[H+], which can be interpreted as a bimolecular process either between M2+ and DACODA2- (kM,LML) or between MOH+ and HDACODA- (kMOH,HLML). The second order rate constants kM,LML are much higher than those expected from water exchange and can only be explained by a strong internal conjugate base effect. In the limiting case, however, this is equivalent to the second possible explanation, which assumes MOH+ and HDACODA- as reactive species. The dissociation rate is given by vd = (kML + kHML [H+]) · [M(DACODA)].

Notes: The 13C-NMR. spectra of a series of tri-n-alkyl arsenic complexes of platinum and palladium have been measured. In these complexes it is suggested that the carbon chemical shift of the atom bound directly to the arsenic is a useful structural probe. The chemical shift of the second carbon atom in the chain is interpreted in terms of interactions within the chains of anyone ligand. The values 2J(Pt, C) and 3J(Pt, C) are presented.

Notes: 3,5-Diamino-4-phenylazo-pyrazoles (1a-1c) react with acetylacetone and with ethyl acetoacetate to yield the corresponding pyrazolo[1,5-a]pyrimidine derivatives 2a-2c and 3a-3c, respectively.Whereas 1a-1c add readily to methyl acrylate yielding the 4,5,6,7-tetrahydropyrazolo[1,5-a]-pyrimidine derivatives 5a-5c, 1a-1c add to methylacrylonitrile or methyl methacrylate only under drastic conditions to yield 5d-5f. The pyrimido[1,2:2′,3′]pyrazolo[1,5-a]pyrimidine derivatives 10a-10c are prepared by the action of acrylonitrile on 2a-2c. Compounds 10a-10c are readily converted into the corresponding oxo derivatives 12a-12c on treatment with acetic acid-hydrochloric acid mixture.

Notes: 2-Aza-1,3-dienes. 2. Synthesis and Structure of a Stable Azomethine-ylid.Thermal treatment of 2-(2′-cyano-2′-methoxycarbonyl)methylide-amino-1-morpholino-cyclohexene results in the formation of a stable isomere. Its azomethine-ylid structure is demonstrated from the spectroscopic data (UV., IR., 1H- and 13C-NMR.). 1,3-dipolar cycloaddition reactions of this ylid leads to spiropyrrolines.

Notes: Synthesis of Nonactin.The macrotetrolide antibiotic nonactin (I), containing four units of a C10 hydroxy acid, has been synthesized starting from two adequately protected derivatives (III and IV) of nonactic acid (II). The 32-membered ring of the macrotetrolide is built up by a sequence of condensation and deprotection steps leading first to a product with two, and subsequently to one with four nonactic acid residues (VIII) which is then cyclized in the presence of Ag+-ions. Two reactions forming ester bonds have been developed to condense the hydroxy acids and to effect the final cyclization. In one the activation of the carboxyl group is achieved by conversion into the mixed anhydride with 2,4,6-trimethylbenzene sulfonyl chloride in pyridine. In the other the Ag+-ion induced reaction of a S-(2-pyridyl) hydroxy carbothioate is used to form the corresponding macrocyclic lactone. In the case of nonactin the ring closure is promoted by the coordinating effect of Ag+-ions present in the reaction mixture.

Notes: The results of this study show that three parameters are sufficient to describe the selectivity behaviour of nitrations influenced by mixing as long as a fast combination of the reactant solutions takes place and fast agitation is employed. This is in full agreement with the prediction of the mixing-reaction model developed previously [1]. Furthermore, the results show clearly that in nitromethane the formation rate of nitronium ions from nitric acid is slower than the mixing rate and the rate of the electrophilic substitution proper. From the mixing-disguised selectivity curves for the nitrations of durene and prehnitene with nitronium hexafluorophosphate in nitromethane the ratio of the rate constants k2 for the second nitrations can be estimated to be 1:2. For the two aromatic compounds the k1/k2 ratios are ≥ 104. Finally it could also be shown that small impurities in the solvent (e.g. water) can influence strongly the selectivity curves, depending on the method used for mixing.

Notes: The oxidation of β-pinene with aqueous alkaline potassium periodate and catalytic amounts of potassium permanganate gave, in addition to the expected oxidation product nopinone, a β-ketol. The structure of the latter was shown to be 1-(2-hydroxyisopropyl)bicyclo[3.1.0]hexan-2-one. The formation of this anomalous side-product represents a new type of rearrangement of the pinane skeleton.

Notes: Phytochemistry of genus Gentiana XIII. Study of flavocic and xantonic compounds in the leaves of Gentiana campestris L. 2nd communication.By means of column chromatography on polyamide, we have isolated from the leaves of Gentiana campestris L. a new xanthone-O-glucoside, the 3,4-dimethoxy-5, 8-dihydroxy-xanthone-1-O-β-D-glucopyranoside (2) and its aglucone, the 3,4-dimethoxy-1,5,8-trihydroxy-xanthone (1). The C-glucosides mangiferin (3) and swertisin (4) have also been isolated and identified.

Notes: ESR.-spectra are reported for the radical anion and the radical cation of benzo[b]-biphenylene (III). Comparison of the proton coupling constants (aHμ) for III · ⊖ and III · ⊕ with π-spin populations (ϱμ), calculated by the McLachlan procedure, permits a lower limit of 0.77 to be set for the parameter κ = β′/β where β′ represents a reduced value of the HMO integral for the two essentially single bonds linking the benzene with the naphthalene π-system. The differences in the aHμ values for III · ⊖ and III · ⊕ are substantially larger than those generally found for the two corresponding radical ions of alternant, purely benzenoid hydrocarbons, but they closely parallel the analogous differences observed for the radical anion and the radical cation of biphenylene.

Notes: The radical anion and the radical cation of azuleno[1,2,3-cd]phenalene (III) have been investigated by ESR. spectroscopy, along with the radical anion of 2-phenylazulene (IV). Also studied has been the neutral radical obtained by one-electron reduction of cyclohepta[cd]phenalenium-cation (VI⊕). Assignment of the proton coupling constants for the radical ions III. ·⊖, III ·⊕ and IV·⊕, and the radical VI · is supported by comparison with the ESR. spectra of specifically deuteriated derivatives III-d5 ·⊖, III-d5 ·⊕, IV-d2 ·⊖ and VI-d1′. The experimental results are in full accord with qualitative topological arguments and predictions of HMO models. Whereas the radical anion III ·⊖ exhibits α-spin distribution similar to that of IV ·⊖the corresponding radical cation III ·⊕ and the neutral radical VI · are related in this respect to phenalenyl (V·). It is noteworthy that oxidation of III by conc. H2SO4 yields a paramagnetic species (IIIa ·⊕) which has a similar - but not an identical - structure as the radical cation III ·⊕ produced from III with AlCl3 in CH3NO2.

Notes: Radioactive deoxaphomin (1) which was obtained by feeding [4′-3H, U-14C]-L-phenylalanine to cultures of Phoma sp. (S298) was shown to be well incorporated into cytochalasin B (phomin) (2). The results demonstrate that 1 is an immediate biogenetic precursor of 2.

Notes: Transcyclopropanation during the Tetrabromination of a Tricyclic Ketone to 3 exo, 4 endo, 6exo-Tribromo-7-bromomethyl-1,5-dimethyl-tricyclo[3.2.1.02,7]octan-8-oneBromination of the tricyclic ketone 1 with an excess of bromine at low temperature gives in approximately 30% yield the highly crystalline tricyclic tetrabromide 2 (Scheme 1). The structure of 2 was established by NMR.- and especially X-ray-analysis (Fig.1).Treatment of 1 with 1 mol-equ. of bromine gives an unstable dibromide, to which the structure 3 was assigned on the basis of its NMR.-spectrum and its further bromination to 2 (Scheme 1). In the course of the tetrabromination of 1 the original cyclopropane ring is opened in the first step (1 → 3) and another cyclopropane ring is formed in the second step (3 → 2) (cf. Scheme 3).

Notes: The photochemical behaviour of the title compound (7) is described. The obtained results indicate the high reactivity of the enamidic Δ5 double bond.

Notes: Fluoroorganic Syntheses IV: 1-Fluoro-1-organyl-cyclopropanes and other Cyclopropane Derivatives by Addition of „Successor-Carbenes“Treatment of chlorodifluormethane or dichlorodifluoromethane with methyllithium in the presence of an olefin affords 1-fluoro-1-methylcyclopropanes in fair yields. Depending on the particular reaction conditions, 1,1-difluorocyclopropanes, 1,1-dimethylcyclopropanes and 1-chloro-1-methylcyclopropanes may be obtained as well. Butyllithium and phenyllithium give rise to analogous products.

Notes: He(I) and He(II) photoelectron spectra of benzo[b]selenophene and benzo[b]telluropheneThe photoelectron spectra of benzo[b]selenophene (2) and benzo[b]tellurophene (1) have been recorded with He(I) and He(II) radiation and been compared to those of benzo[b]thiophene (3), benzo[b]furan (4), indole (5) and indene (6). The first four bands are correlated with π-orbitals, of which the highest occupied one is strongly localized on the heteroatom in the case of 1. The results are in agreement with semi-empirical PPP-calculations.

Notes: Pterobiline and neopterobilines, reactivity and structuresPterobiline (biliverdine IX γ) and the two neopterobilines: phorcabiline and sarpedobiline, are the three main bile pigments found in Lepidopters. Studies on the reactivity of pterobiline (1) and phorcabiline esters are reported. Preparation of derivatives, in vitro transformation of pterobiline into phorcabiline, analysis of the pigments and their derivatives by field desorption mass spectrometry and Fourier transform NMR., lead to the structure 5 for the dimethyl ester of phorcabiline. By a similar reaction, biliverdine IX δ (15) affords the neobiliverdine IX δ (16). Possibility of an easy formation of new tetrapyrrolic compounds in the IX γ and IX δ series is thus reported for the first time.

Notes: Photochemical Generation and Reactions of Benzonitrile-benzylideThe low temperature irradiation of 2,3-diphenyl-2H-azirine (1) in DMBP-glass at -196° has been reinvestigated. It was possible to convert 1 nearly quantitatively into the dipolar species benzonitrile-benzylide (3, Φ3 = 0,78), which exhibits UV.-absorptions at 344 (∊ = 48000) and 244 nm (∊ = 28500) (Fig. 1, Tab. 1). Irradiation of 3 with 345 nm light at -196° resulted in almost complete reconversion to the azirine 1 (Φ = 0,15; Fig. 2). When the solution of 3 in the DMBP-glass was warmed up to about -160° a quantitative dimerization to 1,3,4, 6-tetraphenyl-2,5-diaza-1,3,5-hexatriene (8) occurred. This proves that 8 is not only formed by the indirect route 3 + 1 → 7 \documentclass{article}\pagestyle{empty}\begin{document}$ \mathop {\longrightarrow }\limits^{hv} $\end{document} 11 → 8 known before (Scheme 1), but also by dimerization of 3 either by direct head to head coupling or via the intermediate e (p. 2675), followed by a fast thermal hydrogen transfer reaction.The occurrence of the dipolar intermediate 11 in the photochemical conversion of the bicyclic compound 7 to 8 could also be demonstrated by low temperature experiments: On irradiation at -196° 7 gave the cherry red dipolar intermediate 11 (λmax = 520 nm), which at -120° isomerizes to 8. It should be noted, that neither 7 nor 11 are formed by dimerization reactions of 3.Experiments carried out at room temperature demonstrate, that both processes for the formation of 8 may compete: Irradiation of a solution of 1 (DMBP, c = 8 × 10-4 to 5 × 10-3M) with 350 nm light of high intensity (which does not excite the bicyclic compound 7) leads to a relative high photostationary concentration of the dipolar species 3. Under these conditions the formation of 8 is due to dimerization of 3 (Φ8 = 0,19). With low light intensity only a very low stationary concentration of 3 can be obtained. Therefore the reaction of 3 with 1, leading to the bicyclic intermediate 7, becomes now predominant (Φ-1 = 1,55, which corresponds with the expected value of 2 × 0,8). Irradiation of 1 at -130° with 350 nm light of high intensity gives 8 with a quantum yield of 0,44. This is in agreement with the theoretical value Φ8 = 0,4 for an exclusive formation of 8 by dimerization of 3. The lower quantum yield for the formation of 8 at room temperature makes probable that under these conditions 3 not only dimerizes to 8, but also to another, so far unidentified dimer, e.g. 2,3,5,6-Tetraphenyl-2,5-dihydropyrazine.By flash photolysis of a solution of 1 (cyclohexane, c = 10-4M, 25°) the disappearance of 3 could directly be measured by UV.-spectroscopy: At relative high concentrations (c ≥ 10-7M) 3 disappeared according to a second order reaction with the rate constant k = 5 × 107M-1S-1. At lower concentrations (c ≤ 10-7M) the rate of disappearance of 3 follows first order kinetics. The rate constant of this pseudo first order reaction (3 + 1 → 7) has been determined to be 1 → 104M-1S-1.Using Padwa's table of relative rates for the cycloaddition of the dipolar species 3 to various dipolarophiles, including the azirine 1, an absolute rate constant of k ≈ 8 × 108M-1S-1 for the addition of 3 to the most active dipolarophile fumaronitrile could be estimated. In cyclohexane at room temperature, the diffusion controlled rate constant equals 6,6 × 109M-1S-1.In Table 1 the UV.-maxima of several nitrile-ylides, among them a purely aliphatic one, are given.

Notes: Adsorption potentials of simple molecules on various active carbons have been calculated directly from GSC. measurements, by using the procedure of Hansen et al. The model of slot-like micropores developed earlier, and based on a 3-9 adsorption potential, leads to consistent results. It reveals the existence of micropores having widths between 6.5 and 7.5 Å, in agreement with other methods.

Notes: Bei Verwendung von Rh-Alox-Katalysatoren lassen sich p-Aminophenyl-2-hydroxyäthyl-äther unter sorgfältig definierten Bedingungen ohne starke Hydrogenolyse zu cis-/trans-(4-Aminocyclohexyl)-(2-hydroxyäthyl)-äthern reduzieren; durch selektive Reduktion erhält man 4-Benzyl-cyclohexylamin aus 4-Benzylanilin sowie 1-(4-Aminocyclohexyl)-2-phenyl-äthan aus 1-(4-Aminophenyl)-2-phenyl-äthan.Rh- und Ru-Katalysatoren sind imstande, die bisher als nicht hydrierbar geltenden Methyl-, Amino- und Hydroxy-benzolsulfonsäuren quantitativ in die Methyl-, Amino- und Hydroxy-cyclohexansulfonsäuren überzuführen. Die Hydrierparameter werden ausführlich diskutiert.Wie sich aus 13C-NMR.-Daten herleiten lässt, entstehen bevorzugt die cis-Stereoisomeren. Die 4-Methyl-cyclohexansulfonsäure liegt bei Raumtemperatur zu 〉 90% in der Konformation mit axialer CH3- und äquatorialer SO3Θ-Gruppe vor (als Na-Salz in D2O gemessen).

Notes: Crystal Structure of a Dinuclear Peroxotitanium(IV)-Nitrilotriacetate ComplexThe structures of four peroxotitanium(IV) dipicolinates, with colours ranging from deep red to yellow orange, have been reported earlier, and a correlation between their colours and the variations of certain bond lengths has been proposed. This paper describes the pale yellow dinuclear peroxotitanium nitrilotriacetate complex Na4[Ti2O5(C6H6O6N)2]11 H2O. The monoclinic structure, space group B2/b, contains 25 independent non-hydrogen atoms and 17 hydrogen atoms. It has been determined from diffractometer data and refined to R = 3.2%. Titanium is again coordinated approximately pentagonal-bipyramidally. The μ-oxygen bridge occupies an axial position. The short (1.819 Å), nearly linear Ti-O-Ti bonds show double bond character. The titaniumperoxide bonds, however, are relatively long, thus confirming the rule proposed before: the more basic the axial ligands, the higher is the frequency of the absorption band, the longer are the Ti-peroxide bonds and the shorter are the axial distances. This is confirmed by electron density maps, which are to be discussed elsewhere in detail, showing bent Ti-peroxide bonds enclosing an angle of about 70° and a strong electron bridge on the μ-oxygen bond. Hydrogen bonding and the packing of the complexes is discussed.

Notes: New β-lactam antibiotics. Cephem derivatives with electron withdrawing substituents at position 3Oxidation of the 3-formyl-2-cephem compound 1 according to Corey [6] gave 2-cephem-3-carboxylic esters 4a, b, c (Scheme 1), which proved to be useful intermediates for the synthesis of cephalosporins bearing in position 3 a methoxycarbonyl group (10a, b, c, d / Scheme 2) or a carboxy group (20, 25, 30/Schemes 3, 4). The 3-formyl-3-cephem compounds 31a, b could be transformed into cyano- (33a) or methoxyiminomethyl- (36a, c, d) cephems (Scheme 5), which represent further examples of cephalosporins with electron withdrawing groups in position 3.

Notes: Es wird eine neue Synthese von β-Lactamen durch Umsatz von 4-Alkylazlactonen mit acyclischen Iminen beschrieben. Mit einem cyclischen Imin wird dagegen ein Imidazolin-Derivat erhalten.

Notes: How valid is the proof of existence of intermediates with pentacoordinated C-atoms in aliphatic SN2-reactions?Retention of configuration in the preparative conversion of cis-3-ethoxycyclobutylbrosylate (4) with sodium iodide and with lithium bromide in boiling acetone for 5 days to cis-3-ethoxycyclobutyliodide (6) and bromide (8), respectively, has been published by Ugi et al. to be the basis of a proof that species with pentacoordinated C-atoms exist sufficiently long during aliphatic SN2-reactions that they can undergo ligand reorganizations.It is now shown that the conditions used lead to a thermodynamic control, inasmuch as the cis- and trans-halides 6 and 7, as well as 8 and 9 isomerize to ∼2:1 equilibrium mixtures. Furthermore it is shown that the reaction of kinetic control occurs with inversion, inasmuch as the trans-: cis-halide ratio during the course of the reaction starts with high values and falls slowly to the equilibrium.Thus the nucleophilic substitutions on the examined four-membered ring system do not contravene previous experience with other aliphatic and alicyclic systems, so that the existence of pentacoordinated carbon species as intermediates in aliphatic SN2-reactions cannot be considered as proven.

Notes: The photo-oxidation of the title compound (1) is described. The isolated products are the result of a [2 + 2] oxygen addition to the olefinic double bond of the enamide.

Notes: Fluoroorganic Syntheses V. Preparation and Transformation of Chlorofluorocyclopropanes. - A Selective Approach to Fluoroallylic AlcoholsChlorofluorocarbene addition to unsaturated compounds is particularly convenient and efficient in a two-phase system. This method works satisfactorily even if the olefin carries base-sensitive substituents. The resultant chlorofluorocyclopropanes can be ring-opened by silver-salt assisted acetolysis affording 2-fluorallylacetates, which yield 2-fluorallylic alcohols upon saponification.

Notes: The ionisation energies and the HeI photoelectron spectra of the N-oxides of diazabenzenes are presented. The valence electronic structures of the N-oxides are discussed in view of the ionisation energies, and the profiles, of the bands. The interpreted data are compared to calculations which are in good agreement. The results are correlated to the physicochemical studies, and particularly to the electronic absorption spectroscopy, of the N-oxides. The assignment of the photoelectron spectra of the azabenzenes are considered with reference to the spectra of their N-oxides.

Notes: The synthesis and characterization of (±)-coralydine and (±)-O-methylcorytenchirine and their optical isomers are described.

Notes: S-Methylation of 6-S-benzyl-6-deoxy-1,2-O-isopropylidene-3-O-methyl-α-D-xylo-6-thiohexofuranos-5-ulose (1) gave the expected sulfonium salt 2 which on alcaline treatment yielded the stable sulfur ylide 3. This compound constitutes an useful synthetic intermediate in carbohydrate chemistry. On heating in 1,2-dimethoxyethane, it underwent a Stevens rearrangement which led to an extension of the carbon chain of the sugar and, reacted with Michael acceptors, it gave cyclopropanation reactions.

Notes: Acid-catalyzed rearrangement of 7-hydroxyroyleanone into a 20(10→9) abeo-abietane derivative and two phenalenonesShort treatment of either horminone (1b), taxoquinone (1a), 6,7-dehydroroyleanone (3) or 6β-hydroxyroyleanone (1c) with 80% H2SO4 at 0° leads to a mixture of rearranged products. Two of the structures, determined by X-ray-cristallography, were found to be (9R, 10R)-20(10→9)-abeo-12-hydroxy-5,7, 12-abietatriene-11,14-dione (4) and 9-isopropyl-2,2,5-trimethyl-8H-phenaleno[1,9-bc]furan-8-one (5), and the third compound, isolated in very small amounts, has been provisionally identified as 3-hydroxy-9-isopropyl-2,2,5-trimethyl-8H-phenaleno[1,9-bc]furan-8-one (6) from the spectroscopic data.

Notes: Intramolecular cyloadditions of binaphtyl compoundsThree new bridged ketones, 7,8 and 9, have been isolated in 44%, 3% and 19% yields respectively (Scheme 2) by heating 2,2′-bis-allyloxy-1,1′-binaphthyl (5) at 215° for 16 hours. These compounds could be epimerized about C(16) by bases, and in particular 9 yielded the new epimer 10. The structures of the alcohols obtained by reduction of the keto group are also given (Scheme 2). The constitution of all compounds was derived from spectroscopic data, chiefly from their 1H-NMR, spectra (tab. 2, 3 and fig. 1). The assignments were based on the observed long-range coupling constant between H(endo)-C(16) and H(endo)-C(5) in 7 and 10 and on the analysis of chemical shifts and coupling constants in both the ketones and their derivatives. Moreover, the structures of the compounds investigated have been proved by x-ray analysis of ketone 8 (chap. 3, fig. 2). The thermal conversion of binaphthylether 5 to the bridged ketones proceeds via an intramolecular Diels-Alder reaction, followed by Claisen rearrangement (Scheme 8). On heating, the bis-beta-methylallyl ether 20 yielded the ketone 21 and a small amount of the ether 23 (Schemes 5 and 7). Ether 23 and binaphthyl monoallyl ether 26 were converted thermally to the bridged ketones 31 (Scheme 7) and 27 (Scheme 6) respectively. In addition, 26 underwent an intramolecular ene-reaction to give the spiroketone 28 (Schemes 6 and 9). The structures of these compounds were also established, mainly by analysis of their 1H-NMR. spectra.

Notes: N-Isobutyl-11-(3, 4-methylenedioxyphenyl)-undeca-2,4,6-trans, trans, trans-trienoic amide (II) and N-isobutyl-11-(3,4-methylenedioxyphenyl)-undeca-2,8,10-trans, trans, trans-trienoic amide (III), two of the three possible structures of the alkaloid piperstachine, have been synthesized. Compound (III) has been found to be identical with piperstachine. The 1H- and 13C-NMR. spectra of the compound (II) are discussed.

Notes: Synthesis and Absolute Confifguration of the Enantiomers of Verapamil.Starting from the acids IV-(+) and IV-(-), a synthesis of the enantiomers I-(+) and I-(-) of the coronary vasodilator Verapamil is described and their absolute configuration determined through a chemical filiation with the acid XII-(S)-(+).

Notes: The He I photoelectron spectra of tetramethylcyclopentane-1,2,3-trione 1, 4,4,6,6-tetramethylcyclohexane-1,2,3-trione 2, bicyclo[1.2.3]octane-2,3,4-trione 3, bicyclo[2.2.3]nonane-2,3,4-trione 4 and anhydrous ninhydrine 5 are presented. The assignment of the first two bands is discussed using semiempirical calculations together with a qualitative band shape analysis. It is shown that the first two bands in 1 to 4 are due to the ionization of an electron from lone pair combinations of the 2p-oxygen orbitals.

Notes: The mass spectra of the three cyclopentane-1,2,3-triols, six cyclopentane-tetrols and four cyclopentane-pentols stereoisomers have been studied. Complex processes, especially regarding the H2O eliminations, were detected by extensive deuterium labelling.

Notes: Phenylpropionamides acylated in the ortho position with aralkanecarboxylic acids were cyclised to give, after reduction, 1-aralkyl-tetrahydro-2-benzazepines.

Notes: Structure of a Stable Dipolar Compound from 2,2-Dimethyl-3-dimethylamino-2H-azirine and Benzoylisothiocyanate.Benzoylisothiocyanate and 2,2-dimethyl-3-dimethylamino-2H-azirine (1) react to given the dipolar compound 4,4-dimethyl-2-thiazolin-5-dimethylimminium-2-benzcarboxamidate (2), whose structure has been proved by X-ray analysis. Compound 2, upon addition of water, yields the thiourea derivative 3, whereas by acid catalyzed hydrolysis the thiazolinone derivative 4 is formed. The dipolar structure 2 is also existent in organic solvents like dimethylsulfoxide or chloroform.

Notes: One the Reactivity of π-(η5-)-Cyclopentadienylpalladium-δ-(η1-)-allyl- and π-(η5-)-Cyclopentadienylpalladiumhalide Complexes; New ortho-Metallation Reactions of Trio-o-tolylphosphitTeil des Hauptvortrages von H. W. an der Jahrestagung der Chemical Society, York (U.K.), 7.-11.4.1975. 20.Mitt. der Reihe «Untersuchungen zur Reaktivität von Metall-π-Komplexen»; 19.Mitteilung siehe [1].(η5-C5H5)Pd(η3-2-ClC3H4) reacts with Lewis bases L[PPh3, P(OPh)3, P(O-p-Tol)3, P(O-o-Tol)3, CO] in a 1:1 molar ratio to give the η1-2-chloroallyl complexes 2a-2e. (η5-C5H5)-Pd(η1-2-ClC3H4)P(O-o-Tol)3 (2d) which is stable at room temperature has been isolated as a red oil. It represents the first well-characterized η1-allylpalladium derivative.2a-2d eliminate allene to form (η5-C5H5)PdClL (5a-5d). The tri-o-tolylphosphite complex 5d reacts with NaI to give (η5-C5H5)PdIP(O-o-Tol)3 (6) and on Al2O3 to give (η5-C5H5)Pd[P(OC6H3-o-Me)(OC6H4-o-Me)2] (7). Elimination of HCl leading to ortho-metallation of one of the six-membered rings of tri-o-tolylphosphite also occurs in the reaction of PdCl42- and P(O-o-Tol)3 to form Pd2Cl2[P(OC6H3-o-Me)(OC6 H4-o-Me)2]2 (9). This reacts with TlC5H5 to give 7. The preparation of Pd2Cl4[P(O-o-Tol)3]2 (8) and Pd2I2[P(OC6H3-o-Me)(OC6H4-o-Me)2]2 (10) is also reported.

Notes: On Reactions of oxygenated Cobalt(II) Complexes. V. Reactivity of diastereoisomeric μ-peroxo-μ-hydroxo-dicobalt(III) IonsThe kinetics of dissociation of μ-peroxo-μ-hydroxo-dicobalt(III) chelates have been reinvestigated using a stopped flow technique. The binuclear cations [(trien)Co(O2, OH) Co(trien)]3+, [(tren)Co(O2, OH)Co(tren)]3+ and [(en)2Co(O2, OH)Co(en)2]3+ dissociate on acidifying to Co2+ and the protonated ligand and up to 100% of the bound O2 is evolved. The dissociation is H+-catalyzed and first order in complex. The observed rate constants at pH 2 are in the range of 10-3 to 10-1 s-1 (20°). They depend not only on the nature of the ligand and on ligand configuration but also on the diastereoisomeric structure of the binuclear cation.In the case of trien there are 8 possible chemically different isomers. On oxygenation of Co(trien)2+ in dilute solution 3 of those isomers seem to be formed preferentially. Their rate constants are separated over a factor of 50. For [(en)2 Co(O2, OH)Co(en)2]3+ there exist a meso form and a chiral structure. On oxygenation of Co(en)22+ in dilute solution the meso form and the racemate are formed to about equal amounts. The racemate dissociates about 5 times slower. Of the 3 possible achiral isomers of [(tren)Co(O2, OH)Co(tren)]3+ one is formed stereoselectively by oxygenation in solution.

Notes: The 1H-decoupled 13C-NMR. spectra of 35 all-trans, 17 mono-cis vitamin A compounds (acetates, alcohols, aldehydes, acids and esters) and of one 11, 13-di-cis compound (11, 13-di-cis retinol) are reported. Included in this investigation are desmethyl-, desmethylethyl, and aryl-vitamin A analogues and others as well as 30 reference compounds of smaller molecular weight. Furthermore, the 13C-NMR. spectra of 23 β-apo- and other carotenoids were studied. A complete assignment of the signals of all 106 compounds to the specific carbon atoms was achieved by extensive application of lanthanide shift reagents, mainly Yb(dpm)3, by CW-offset and selective 1H-decoupling experiments, by comparison of the shifts of related compounds, and in three cases by utilization of specifically deuteriated compounds (11, 12-D2-retinol and retinyl acetate, 15, 15′-D2-β-carotene). The chemical shift differences between the cis- and trans-vitamin A compounds and the applicability of the shift reagents for the assignment of the 13C-NMR. spectra are discussed.

Notes: Enol derivatives in the chlorophyll series. 132-Desmethoxycarbonyl-173-desoxy-132,173-cyclochlorophyllide a-enol and a method for the introduction of magnesium into porphinoid ligands under mild conditionsMagnesium transfer from the iodo-magnesium salt of 3,5-di-t-butyl-4-hydroxy-toluene (BHT) into methyl pheophorbide a is a fast process in methylenechloride/ether solution at ambient temperature. This procedure for the introduction of magnesium into labile chlorin ligands has made possible the preparation of a crystalline 132, 173-cyclochlorophyllide a-enol. Concomitant use of the lithium salt of BHT facilitates the more critical insertion of magnesium into methyl bacteriopheophorbide a. The preparative success of these magnesium transfers depends crucially upon the solvent system used. Under conditions where the complexation of methyl pheophorbide a with iodo-magnesium-BHT is essentially complete within 2 minutes at 12° in methylenechloride/ether solution, strong inhibition of the magnesium transfer is observed by cosolvents such as pyridine, dimethylacetamide, dioxan or tetrahydrofuran.

Notes: Application of Ring Expansions for the Preparation of rac-Muscone and Exaltone®4,6-Undecamethylene-2-pyrone (8), prepared from 1-morpholino-cyclododec-1-ene (7) according to Hünig et al., was saponified and decarboxylated to a mixture of the 3-methyl-cyclotetradecenones 11, 12, 13 and 14, which was hydrogenated to 3-methyl-cyclotetradecanone (3). Similarly, 4,6-dodecamethylene-2-pyrone (16) was prepared from 1-morpholino-cyclotridec-1-ene (15) and ketene, saponified to a mixture of the 3-methyl-cyclopentadecenones 19, 20, 21 and 22 and the latter hydrogenated to rac-muscone (6).The ratios of the four regio- and stereoisomers in the above mentioned two mixtures of 3-methyl-cycloalkenones were derived from the 1H-NMR.-spectra.From the reactions of the enamines 7 and 15 were also isolated small amounts of 4,5-decamethylene- (9) and 4,5-undecamethylene-6-methyl-2-pyrone (17) respectively. Saponification and partial decarboxylation of 9 lead to (2-acetyl-cyclododec-1-enyl)-acetic acid (23) and methyl-(2-methyl-cyclododec-1-enyl)-ketone (24), the latter possessing an incense-like odor.The keton homologation method of Mock & Hartman (reaction of alkanones with diazoacetic ester in the presence of triethyl oxonium fluoroborate, followed by saponification and decarboxylation) was applied three times in succession, starting with cyclododecanone (1). This furnished, after the first stage, the cyclotridecanone (4) required for the above described synthesis of rac-muscone (6) and, after the third stage, cyclopentadecanone (5 = exaltone®).Application of this reaction to 2-methyl-cyclododecanone (28) resulted in a low yield of 2-methyl- (30) and 3-methyl-cyclotridecanone (31) in the ratio of 2:1.

Notes: Neue Cephalosporine, die in 3-Stellung eine Fluormethylgruppe aufweisen (9, 17/Schema 1), wurden ausgehend von 2b unter Verwendung von 2-Chlor-1,1,2-trifluor-triäthylamin als Fluorierungsmittel hergestellt. Mit Piperidin-schwefeltrifluorid erhielt man ferner aus 18 die 3-Difluormethyl-cephemverbindung 19 (Schema 2), die nach bekannten Methoden in antibakteriell wirksame Cephalosporine (20a, b) übergeführt wurde. 3-Fluor-cephemderivate, z.B. 23b, liessen sich ausgehend von entsprechenden 3-Hydroxy-cephemverbindungen, mit diesem Reagens jedoch nur in sehr geringer Ausbeute herstellen.

Notes: The Rǒle of Paliclavine in the Biosynthesis of Ergot AlkaloidsFeeding of [N-14CH3]-paliclavine to submersed cultures of Claviceps paspali Stevens et Hall and to surface cultures of the ergot fungus from Pennisetum typhoideum Rich. has shown that paliclavine is not involved in the biosynthesis of either the ergolene carboxylic acids or the tri- and tetra-cyclic clavines.

Notes: The structure elucidation of C-β-glucuronides of sulfinpyrazone (Anturan®) and phenylbutazone (Butazolidin®) by spectroscopic means is reported. These conjugates represent a novel type of drug metabolites.

Notes: Nous avons synthétisé une série de spiropyrannes benzoxathioliques par un processus en deux étapes: obtention de perchlorates styryliques en milieu acide par condensation simultanée de trois substrats intermédiaires, puis cyclisation en milieu basique. Un mécanisme est proposé.Ces spiropyrannes benzoxathioliques sont photochromes et nous avons étudié la cinétique de décoloration thermique ainsi que l'absorption visible de leurs photomérocyanines. Des observations comparables à celles enregistrées en série benzodithiolique nous ont amenés ici encore à envisager une structure de type quinonique pour la mérocyanine.

Notes: Tetrammine-copper(II)-tetraiodide Cu(NH3)4I4 crystallizes in the monoclinic space group C 2/m. The crystal structure has been determined from X-ray diffractometer data and refined to Rw = 2.2%. Four coplanar nitrogen atoms and two axial iodine atoms form an octahedral coordination around Cu(II) with a pronounced 4 + 2 tetragonal distortion. A connection of the Cu(II) atoms by linear, centrosymmetric I42- polyiodide ions results in infinite chains of [Cu(NH3)42+ I42-]-units. The central I-I-bond distance in I42- is 2.802(1) Å; a considerable amount of I-I bonding is indicated by the distance of 3.342(1) Å found for the terminal bonds. These intramolecular bond distances correspond to calculated I-I-bond orders of 0.80 and 0.43.

Notes: Template-Reactions II. Syntheses of tricyclic and tetracyclic metal complexes from aliphatic diamines and phenylazo-malondialdehyde-derivativesA template synthesis of metal complexes with 14- and 16-membered macrocycles 6 resp. 10 has been devised. These compounds are obtained in high yield by the condensation of aliphatic 1,2-or 1,3-diamines with phenylazo-malon-dialdehydes in the presence of divalent metal ions such as Cu(II) and Ni(II). This is the first reported one-step synthesis of tetraaza-annulenes with aliphatic diamines. The formation of the intermediate tricyclic complexes 5 and 9, obtained either by a template or a nontemplate synthesis, is also described. Ring closure with diamines leads again to 6 and 10 or to asymmetric tetraaza-macrocyclic systems such as 7 or 11.

Notes: ESR.-spectra are reported for the radical anion I · Θ of 2,7-diazapyrene (I), along with those for the radical cations I(2H) · ⊕ and I(2 CH3) · ⊕ of 2,7-dihydro-2,7-diazapyrene and its 2,7-dimethyl-derivative, respectively. In contrast to the analogous radical ions of 4,4′-bipyridyl (II) and other previously studied diazaaromatic compounds, there is a striking change in the 14N and proton coupling constants on going from the radical anion I · Θ to the radical cations I(2H) · ⊕ and I(2 CH3) · ⊕. This change can be rationalized in terms of the HMO model of the pyrene π-system. A reversal in the energy sequence of the lowest antibonding orbitals is predicted upon an increase in the absolute value of the Coulomb integral for the azasubstituted π-centres, such an increase simulating the enhanced electronegativity of the azanitrogen atoms 2 and 7 on protonation.

Notes: Addition-elimination reactions from germanium heterocycles I. Germadioxolanes (X=Y=O)The reactivity of 2-germa-1,3-dioxolanes is studied with unsaturated compounds such as carbonyl compounds (aldehydes and ketones) or heterocumulenes (PhNCO, PhNCS). The formation of mono- and di-insertion derivatives is observed. The structure of these adducts is established and their decomposition process, at atmospheric pressure or at high pressure, is precised.The mechanism of these addition-elimination reactions is established from 4,5-disubstitued germadioxolanes. The reaction takes place under steric control. The consecutive elimination reaction proceeds by a mechanism of intramolecular nucleophilic substitution.

Notes: Benzo[b]thiophene-2,3-diones (1) react with Grignard reagents to yield 2,3-dihydroxy-2,3-diaryl(aralkyl)benzo[b]-thiophenes (2). The latter compounds yield 3,3-diaryl(aralkyl)-benzo[b]thiophene-2-ones (3) by pinacolone rearrangement. Treatment of 3 by hot ethanolic sodium hydroxide solution yields the corresponding carboxylic acids by hydrolytic heteroring opening.

Notes: Die Kristallstruktur von K3JO5, tetragonal, Raumgruppe P4/ncc-D4h8, wurde durch Röntgen- und Neutronenbeugungsversuche an Pulverpräparaten bestimmt. Sie ist eng verwandt mit der von (NH4)3FeF6, wobei unter tetragonaler Verzerrung und Verdoppelung der c-Gitterkonstante die FeF6-Komplexe durch tetragonal-pyramidale JO5-Gruppen ersetzt sind.

Notes: Die Struktur der Titelsubstanz wurde röntgenographisch aus Diffraktometer-Einkristalldaten bestimmt und bis zu einem konventionellen R von 0,048 verfeinert. Der 8-Ring besitzt Wanne-Sessel-Konformation. PITZER- und BAEYER-Spannung sind gegenüber Cyclooctan verringert, und an die Stelle der transannularen 1, 5-H…H-Abstoßung im Cyclooctan ist eine stabilisierende 1, 5-As…O-Anziehung getreten. Die Koordination am As-Atom ist ψ-trigonal-bipyramidal mit axialen Abständen As—Cl 2,27 Å, As—O 2,45 Å und äquatorialen Abständen As—S 2,25 Å. Die Struktur besteht aus 12-fach koordinierten Molekülen.Die Kristalldaten der analogen Sb-Verbindung 5-Chlor-1-oxa-4, 6-dithia-5-stibaocan werden mitgeteilt.

Notes: Es wurde das IR-Spektrum von festem Diimin bei 5°K aufgenommen. Außerdem wurden die Stickstoff-Matrixspektren von Diimin, Mono- und Dideutero-diimin registriert und ein Zuordnugsvorschlag für die gemessenen Frequenzen gemacht. Danach hat Diimin eine trans-Struktur und gehört zur Punktgruppe C2h.

Notes: Kaliummetathiostannat K2SnS3 · 2 H2O wurde aus wäßriger Lösung rein dargestellt und durch eine Röntgenstrukturanalyse charakterisiert. Danach besteht das Thioanion aus SnS4-Tetraedern, die über gemeinsame Ecken zu unendlichen Ketten verknüpft sind (Sn—S 2,345…2,458 Å), so daß die Verbindung als K2n(SnS3)n · 2 nH2O zu formulieren ist. Das Poly-metathiostannat (SnS32-)n ist isomer zu dem kürzlich dargestellten dimeren Sn2S64-. Das Salz kristallisiert orthorhombisch (Pnma) mit den Gitterkonstanten a = 6,429, b = 15,621, c = 10,569 Å. Das Wasserstoffbrückensystem wurde vollständig analysiert. Die Verbindung wurde schwingungsspektroskopisch untersucht; die ermittelten Frequenzen wurden teilweise zugeordnet.

Notes: Die P2p-Bindungsenergien zahlreicher Phosphoryl- und Thiophosphorylverbindungen sind tabelliert und diskutiert. In vielen Fällen sind auch die Bindungsenergien innerer Elektronen anderer Atome verzeichnet.

Notes: An Hand der 117/119Zinn-Satelliten im 1H-Kernresonazspektrum von 2,2-disubstituierten 1,3,2-Dithiastannolanen wird versucht, die Schwierigkeiten in der Konformationsanalyse zu überwinden, die mit sehr schneller Ringinversion verbunden sind. Die Enthalpie des Übergangszustandes wird berechnet.

Notes: Ausgehend von den 0°C, -5°C und -10°C-Isothermen des quinären Systems Na+, K+, Mg2+/Cl-, SO42-//H2O bei Sättigung an NaCl und KCl bzw. Carnallit wird die Polytherme zwischen 25°C und -10°C dargestellt. Innerhalb des neu bestimmten Bereiches der Polytherme befindet sich bei -7,2°C die invariante Fünfsalzparagenese NaCl, KCl, Glaubersalz (Na2SO4 · 10 H2O), Bittersalz (MgSO4 · 7 H2O), Schönit (K2SO4 · MgSO4 · 6 H2O). Sie stellt gleichzeitig die untere Bildungstemperatur des Schönits in diesem System dar.Außerdem war es notwendig, im Bereich zwischen 25°C und 0°C weitere univariante und invariante Gleichgewichtslösungen zu überprüfen.

Notes: Reaktionen von M2(NCS)10 führen mit Ammoniak sowie primären und sekundären aliphatischen Aminen zu Verbindungen des Typs [M(NCS)(NH2)2NH]x bzw. M(NCS)3(NHR)2 [H2NR] und [M(NCS)3(NR′2)2 HNR′2], mit N-heterocyclischen Aminen zu [M(NCS)5L]-Komplexen, die jedoch Redoxumwandlungen unterliegen und [M(NCS)4L2]-Komplexe bilden. Reaktionen von [M(NCS)5(CH3CN)] mCH3CN mit Ammoniak und aliphatischen primären Aminen ergeben in Acetonitril Acetamidin, das amidinolytische Spaltung von M-NCS-Bindungen bewirkt und zu Verbindungen des Typs [M(NCS)a(NC(NHR″)CH3)b(CH3C(NH)NHR″)]x führt. Die dargestellten Komplexe werden durch derivatographische Untersuchungen und IR- bzw. VIS-Absorptionsspektren näher charakterisiert (M = Nb, Ta; x = 2; R = n-C4H9; R′ = C2H5; L = Pyridin, 4-Methylpyridin; m = 0, 1, 2; a = 1 oder 4; b = 4 bzw. 1; R″ = H, C4H9).

Notes: Es wird die Darstellung von Vanadatgranaten folgender drei Typen beschrieben: (I) {Na3}[B2III](V3)O12 (BIII = Cr, Sc), (II) {LiCa2}[B2II](V3)O12 (BII = Mg), (III) {Ca2AIII}[Li2](V3)O12 (AIII = In, Sc). Die Cr-Verbindung des Typs (I) zerfällt oberhalb 690°C in ein Gemisch von Cr2O3 und NaVO3. Die analoge Fe-Verbindung zersetzt sich in entsprechender Weise bereits bei 400°C, so daβ die Reindarstellung durch Festkörperreaktion nicht möglich ist. Bei größeren BIII-Ionen (Y, Yb, Lu) entstehen keine Granate des Typs (I), sondern Gemische aus BIIIVO4 (Zirkonstruktur) und Na3BIIIV2O8. Granate des Typs (II) sind für BII = Co und Ni nicht existenzfähig. Es entstehen Gemische aus {Ca3}[LiBII](V3)O12 (Granatstruktur), LiBIIVO4 (Spinellstruktur) und B3II(VO4)2. Beim Typ (III) erfolgt für AIII = Y eine Ausweichreaktion unter Bildung eines Gemisches aus YVO4, Ca3(VO4)2 und Li3VO4.

Notes: 1,2,4-Triphenyl-1-thio-cyclo-3,5-dithia-1,2,4-triphosphan (C6H5PS)3 (1) wird durch Reaktion von Dikalium-triphenyl-triphosphid (4) mit Dichlortrisulfan sowie durch Umsetzung von Phenylphosphin mit Schwefeldichlorid in sehr guter Ausbeute erhalten. Außerdem bildet sich 1 - zusammen mit dem Cyclo-thia-phosphan (C6H5P)4 (3) - bei der Umsetzung von 1,2-Diphenyl-1,2-dihalogen-diphosphanen mit Schwefelwasserstoff oder Disulfan sowie aus 4 und Dischwefeldichlorid. - Die Gesamtheit der spektroskopischen Befunde, insbesondere das 31P-Kernresonanzspektrum, ergibt für 1 eindeutig die Heterocyclophosphan-Struktur V mit fünfgliedrigem P3S2-Ring, in dem die S-Atome isoliert stehen und eines der direkt miteinander verbundenen P-Atome außer der Phenylgruppe noch ein exoständiges S-Atom trägt.

Notes: In the La—Pb system the heats of formation were measured, using a differential direct isoperibol calorimeter, and checking composition and state of the samples by chemical, metallographic and X-ray analyses. For the various compounds the H (for the reaction among solid phases at 300 K) correspond to the following values (Kcal/g · at.): La5Pb3 = -17.25 ± 0.5, La4Pb3 = -16.7 ± 0.5, La5Pb4 = -16.5 ± 0.5, La3Pb4 = -15.3 ± 0.5, LaPb2 = -14.4 ± 0.5, LaPb3 = -13.7 ± 0.5.The results obtained are briefly discussed and compared with those calculated using the method suggested by MIEDEMA.

Notes: Das durch Umsetzung von Chinolin mit Quecksilber(I)-nitrat aus wäßrigen Lösungen erhaltene [C18H14Hg2N2](NO3)2 kristallisiert monoklin (a = 1 062,8(9) pm, b = 1 021,9(8) pm, c = 1 823,6(15) pm, β = 100,35 ± 0,06°) in der Raumgruppe C2/c—C2h6 (Nr. 15) mit Z = 4. Die Struktur wurde röntgenographisch mittels Patterson- und Fourier-Synthesen gelöst und nach der Methode der kleinsten Fehlerquadrate bis zu einem R-Wert von 0,091 verfeinert.Die Substanz ist aufgebaut aus isolierten []-Gruppen, zwischen denen die Nitrationen liegen.

Notes: Die Systeme Li2O/CoO und Li2O/ZnO sind insofern analog. als beiden die Li-reichste Phase nach Pulveraufnahmen bei „Li4MO3“ liegt. Einkristalluntersuchungen führten auf eine pseudokubische, trigonale Elementarzelle mit a = 13,14, c = 7,99 Å (Zn) bzw. a = 13,10, c = 7,98 Å (Co). Überraschend ist, daß bei kubisch dichtester Kugelpackung von O2- offensichtlich keine vollständige Ordnung der Kationen vorliegt. Unklar bleibt trotz der Einkristalldaten, wie groß die Phasenbreiten sind.

Notes: Nou dargestellt wurden PbPtF6 (hellgelb), hex. BaGeF6-Typ, [a = 7,227, c = 7,071 Å]; CaPtF6 (hellgelb) [a = 5,245, c = 14,784 Å]; ZnPtF6 (hellgelb) [a = 4,980, c = 13,828 Å], CdPtF6 (hellgelb) [a = 5,118, c = 14,623 Å], HgPtF6 (hellgelb) [a = 5,132, c = 14,814 Å], MnPtF6 (ocker) [a = 5,094, c = 14,231 Å], CoPtF6 (hellbraun) (a = 5,002, c = 13,815 Å); NiPtF6 (eigelb) [a = 4,937, c = 13,687 Å], diese kristallisieren hexagonal im LiSbF6-Typ. Von CuPtF6 (hellgelb) ist die Struktur bislang unbekannt.

Notes: Die Verbreitung der Gaskomplexe MClm · xAlCl3 (FeCl3) mit x = 1, 2 oder 3 über weite Bereiche des Periodensystems wird dargelegt. Die thermodynamische Erörterung zeigt die große Stabilität der Komplexe bei Temperaturen 〈1200°K. Die ΔH°-Bilanz der stufenweisen Komplexbildung MCl2/MAlCl5/MAl2Cl8 wird diskutiert. ΔH° wird entscheidend durch die Auffüllung der Koordinationssphäre bestimmt.

Notes: Studies on the complexes of transition metals with the tridentate imine ligand bis(2′-quinolyl)-2, 6-pyridine have been carried out. On the basis of the elemental analysis data and the molar electrical conductivities, the chelates have been assigned the general formula [Me(C23H15N3)2](ClO4)2, where Me was Fe(II), Co(II), Mn(II), Cu(II) and Ni(II). Their electronic spectra in the solid state and in acetonitrile solution, as well as their infrared spectra have been reported and discussed.

Notes: Es wird über Gläser im System K2O—SiO2—VO2 berichtet. Der Glasbildungsbereich wird mit der im System K2O—SiO2—TiO2 auftretenden Glasbildung verglichen. Dichte und elektrische Leitfähigkeit der Gläser werden in Abhängigkeit von der Zusammensetzung diskutiert.

Notes: The thermal decompositions of Nb3O7Cl in atmosphere of argon and oxygen were carried out and the decomposition formulae were determined as follows: The decomposition products in each atmospheres were found to be the T-form Nb2O5 and H-form Nb2O5. It was, however, observed that if an amount of special polymorphic form of Nb2O5 has been added to the starting material, Nb3O7Cl, the decomposition product came to contain a larger proportion of the seeded form.NbO2F was decomposed in the oxygen atmosphere. The decomposition product appeared as the P-form Nb2O5 and transformed into the N-form Nb2O5. In the case of the thermal decomposition of NbO2F, no appreciable seeding effect was observed.

Notes: Durch Si—N-Spaltungsreaktion von Pentafluoroschwefelschwefeldi-fluoridimid 1 mit Silylaminen entstehen die Verbindungen SF5—N=S(F)NR2 und SF5—N=S(NR2)2. 1 gibt mit PCl5 SF5—N=SCl2. Die IR-, MS- und insbesondere die NMR-Spektren der neu dargestellten Verbindungen werden mitgeteilt und mit anderen SF6-Derivaten verglichen.

Notes: Es werden die Schwingungsspektren (IR und Raman) von XP(N(CH3)2)2CH3 und XP(N(CH3)2)(CH3)2 (X = O, S) mitgeteilt und den Grundschwingungen zugeordnet. Auf dieser Basis werden nach einem Näherungsverfahren die Valenzkraftkonstanten und die Bindungsordnungen berechnet und diskutiert. Die Ergebnisse werden mit denen der Kernresonanz-Spektroskopie verglichen.

Notes: Die Komplexe (RCHS)nM(CO)5 (R = H, CH3, n = 3; R = H, n = 4; M = Cr, Mo, W) wurden aus den Tetrahydrofuran-pentacarbonylmetallverbindungen und dem jeweiligen Liganden dargestellt. Die Cotton-Kraihanzel-Kraftkonstanten dieser Komplexe weisen die Schwefelliganden als geringfügig schwächere Akzeptoren, verglichen mit Triphenyl-phosphin, aus. Die Komplexe des Trimethyltrithians (R = CH3, n = 3) zeigen einen raschen intramolekularen Austausch der M(CO)5-Gruppe über die drei Koordinationsstellen des Liganden.

Notes: Erstmals wurden Einkristalle von LiMnO2 und β-NaMnO2 erhalten [LiMnO2: a = 2,805 Å, b = 5,757 Å, c = 4,572 Å, β-NaMnO2: a = 2,859 Å, b = 6,338 Å, c = 4,785 Å, beide Pmnm, bezügl. Parameter s. Text]. Es liegt eine durch den Jahn-Teller-Effekt charakteristisch verzerrte NaCl-Variante vor; die Elongation der [MnO6]-“Oktaeder” beträgt 14,1% (LiMnO2) bzw. 25,2% (β-NaMnO2). Der Madelung-Anteil der Gitterenergie wird berechnet.

Notes: Nach Einkristalluntersuchungen kristallisiert Na4CoO4 triklin (P1, a = 8,648, b = 5,702, c = 6,400 Å, α = 123,9°, β = 98,1°, γ = 99,2°). Es liegen fast tetraedrische CoO4-Gruppen vor; die Koordinationszahlen von Na+ betragen 4 und 5.

Notes: Sr2CuO2Cl2 wurde dargestellt und an Einkristallen röntgenographisch untersucht (Raumgruppe D4h17-Immm, a = 3,975, c = 15,618 Å). Die zum K2NiF4-Typ gehörende Kristallstruktur zeigt ein durch Cl- transkonfiguriertes Sauerstoffoktaeder um Cu2+. Eine Diskussion mit anderen verwandten Verbindungen (Sr2SuO3, Nd2CuO4) erläutert die aufgefundene Verteilung von O2- und Cl-.

Notes: In Anlehnung an frühere Arbeiten werden erstmals Kaliumcyanoselenocyanatochromate(III) in reiner Form isoliert. Die anschließende Charakterisierung erfolgt an den Tetrabutylammoniumsalzen.

Notes: Die spektralen Eigenschaften der Komplexe Cu 3 (CN) 4 (NH 3) 3, Cu 5 (CN) 6 (NH 3) 4, Cu 3 (CN) 4 en 2 H 2 O, Cu 4 (CN) 6 en 2 H 2 O, Cu 5 (CN) 6 en 2 und Cu 3 (CN) 4 (H 2 O) 5 werden untersucht. Durch Vergleich der Spektren mit den Ergebnissen einer Röntgen-Strukturanalyse der ersten drei Komplexe wird die Bindungsmöglichkeit der Cyanidgruppe und die Art der Koordination des ein- und zweiwertigen Kupfers in den untersuchten Komplexen unbekannter Struktur diskutiert.

Notes: In den Systemen N(n-C4H9)OH—SiO2—H2O und N(i-C5H11)4OH—SiO2—H2O wurde in kristallinen Silicatgemischen ein neuer, bisher unbekannter Silicatanionentyp nachgewiesen, der aus Doppelfünfringsilicatanionen der Formel [Si10O25]10- aufgebaut ist. Der entsprechende Trimethylsilylester [(CH3)3Si]10[Si10O25] wurde synthetisiert, seine Eigenschaften werden mitgeteilt.

Notes: Durch Reaktion von Fluorphosphoranen RPF4 (R = F, C6H5) mit Bis(trimethylsilyl)aminodifluorphosphin, (Me3Si)2NPF2, erhält man unter Si—N-Bindungsspaltung Phosphazene vom Typ RF2P=N-PF2. Zu disubstituierten Tetracarbonylmolybdänkomplexen (RF2P=N—PF2)2Mo(CO)4 gelangt man durch Verdrängung des Cycloolefins aus C7H8Mo(CO)4 (C7H8 = Bicycloheptadien) mittels RF2P=N—PF2. (Me3Si)2NPF2 bildet ebenfalls einen Komplex [(Me3Si)2NPF2]2Mo(CO)4. Die genannten Verbindungen werden durch IR-, Massen-, 19F- und 31P-NMR-Spektren charakterisiert.

Notes: Die individuellen Komplexbildungskonstanten und die thermodynamischen Daten der letzten Stufe der Bildung von Tetrachlorokobaltat(II) \documentclass{article}\pagestyle{empty}\begin{document}$$ {\rm[CoCl}_{\rm 3} {\rm L]}^ - + {\rm Cl^ -} = [{\rm CoCl}_{\rm 4}]^{2 - } + {\rm L} $$\end{document} wurden spektrophotometrisch bei verschiedenen Temperaturen und Ionenstärken in folgenden Lösungsmitteln (L) bestimmt: Nitromethan, Benzonitril, Acetonitril, Aceton, Dimethylformamid und Dimethylacetamid. Bei Verwendung von Tetrabutylammoniumsalzen ist die Berechnung der Aktivitäten in den untersuchten Lösungsmitteln bis zu Gesamtelektrolytkonzentrationen von etwa 0,1 mol/l möglich. Die Extinktionskoeffizienten für die Tri- und Tetrachlorokomplexformen sind vom Lösungsmittel abhängig; die freien Reaktionsenthalpien stehen im Zusammenhang mit der Donizität der Lösungsmittel.

Notes: Die IR-Gasspektren und Raman-Flüssigkeitsspektren von (CF3)2AsX wurden aufgenommen; die IR-Untersuchung von (CF3)2PX wurde durch die Registrierung der IR-Spektren im Bereich von 200-400 cm-1 vervollständigt. Die Zuordnung für die untersucht en Phosphane und Arsane wird durch eine Normalkoordinatenanalyse auf der Basis eines MVFF gestützt.

Notes: Die Behandlung von s-Trithian mit n-Butyllithium führt zu Lithiumsalzen von Carbanionen. Bei der Umsetzung mit den halogenfunktionellen Verbindungen CH3J. (CH3)3SiCl, (CH3)3GeCl, (CH3)3SnCl und (CH3)2SiCl2 reagieren diese unter Abspaltung von LiCl zu ein- oder mehrfach substituierten s-Trithianen.

Notes: P2J4 und Na2Cr(CO)5 reagieren in Benzol zu dem monomeren, diamagnetischen Komplex (CO)4CrP2J3. Das 31P-NMR-Spektrum zeigt die Anwesenheit unterschiedlich gebundener Phosphoratome. Der Austausch eines Jodatoms zwischen den P-Atomen führt zu einem temperaturabhängigen Gleichgewicht, in dem ein symmetrischer Übergangszustand auftritt. Triphenyl- und Tricyclohexylphosphin reagieren mit (CO)4CrP2J3 zu (CO)4 · P(C6H5)3 bzw. (CO)4 CrPJ2 · P(C6H11)3, wahrscheinlich dimerer Natur.

Notes: The thermal expansion of GeSe has been studied above room temperature up to the melting point of 670 ± 5°C by X-ray diffraction techniques using a 190 mm Unicam high temperature camera. The thermal expansion of the crystallographic axes is linear with a distinct change of the expansion coeffients for all axes above 400°C. The relative changes of the axes indicate a rearrangement of the structure towards cubic symmetry with increasing temperature. The transformation of GeSe from the orthorhombic to a normal NaCl-type structure is observed at 651 ± 5°C. The lattice parameter of the cubic form of GeSe is a0 = 5.730 ± 0.003 Å at 656°C. The GeSe lattice remains cubic up to the melting point.

Notes: Die Nitrosylkomplexe Co(NO)L3 und Fe(NO)2L2 (L = CO bzw. PF3) gehen sowohl unter thermischen Bedingungen in Tetrahydrofuran wie auch photochemisch induziert in Methylenchlorid mit [N(C2H5)4][SnCl3] L/SnCl3--Substitutionsreaktionen ein. Ausgehend von Co(NO)L3 erhält man die Tetraäthylammoniumsalze der Nitrosyltrichlorstannido-metallat-Komplexe [Co(NO)L2(SnCl3)]-. Bei Fe(NO)2L2 läuft die Reaktion stets zum allein isolierbaren [N(C2H5)4]2[Fe(NO)2(SnCl3)2] durch. Hingegen geht (π-C5H5)Mo(NO)(CO)2 weder mit [SnCl3]- noch mit PF3 unter UV-Bedingungen einen CO-Austausch ein. Aus den IR-spektroskopischen Daten wird für den Trichlorstannido-Liganden ein zumindest mit dem PCl3 vergleichbares π-Akzeptorvermögen abgeleitet.

Notes: The RAMAN spectra of solid polycristalline samples of peroxides of alkali metals, alkaline earths, and two group II transition metals have been measured. The O—O stretch vibration produces an intense band in the expected frequency region of 750 to 850 cm-1. The observation of a weak band at 815 cm-1 indicates the existence of BeO2. Frequency shifts in the hydrates of alkali and alkaline earth peroxides support different water association.

Notes: In der 2-Bis(carboxymethyl)-amino-5-hydroxy-terephthalsäure H5C sind eine Anthranilsäure-N,N-diessigsäure- und eine Salicylsäure-Gruppierung räumlich so angeordnet, daß eine koordinative Wechselwirkung mit dem gleichen Zentralatom nicht möglich ist. Mit Eisen(III) bildet H5C den mononuklearen Komplex (HC)Fe(OH)2-, in dem das Zentralatom in der Anthranilsäure-N,N-diessigsäure-Gruppierung gebunden ist. (HC)Fe(OH)2- geht im schwach sauren Gebiet unter Wasserabspaltung in die binukleare Species (HC)Fe(C)Fe(OH)4- über. In diesem tiefrot gefärbten Komplex fungiert als- Anion C5- als Brückenligand und koordiniert sowohl über die Anthranilsäure- als auch über die Salicylsäure-Gruppierung.Die Dimerisierung des Anions (HC)Fe(OH)2- kann durch die Komplexbildung im ternären System Eisen(III)/Nitrilotriessigsäure/5-Sulfosalicylsäure modelliert werden.

Notes: Les composés K3VO4, K3CrO4 et K3MnO4 existent sous deux formes allotropiques isotypes respectivement de K3Cr(O2)4 et de Na2CaSiO4. Des mesures magnétiques confirment le degré d'oxydation +V du chrome et du manganèse.

Notes: Trois types d'oxodérivés du titane(IV) contenant le groupe NCS ont été isolés. De formule globale {Ti3O4(NCS)4(AA)3}, {Ti2O(NCS)2(BB)4} et M2{TiO(NCS)4} (AA = phen, bpy; BB = acac, dbm), ces composés ont été analysés par diverses méthodes physiques (conductivité, infrarouge, rayons X). La valeur de la fréquence vTiO indique que, dans tous les cas, l'oxygène intervient dans la formation de pont.

Notes: Optimierungsverfahren innerhalb des Glassystems Alkalioxid/Erdalkalioxid/Tl2O/P2O5 führten zu einer Glaszusammnsetzung, bei der unter Erhalt guter glasbildender Eigenschaften eine hohe Strahlensensibilität (hoher strahlenchemischer Effekt) besteht. Durch UV-VIS-Spektroskopie in Abhängigkeit von der Zusammensetzung (auch unter Zugabe von Elektronendonatoren und -akzeptoren), Strahlendosis, Schmelzatomsphäre, durch das Verhalten der Gläser beim optischen bzw. thermischen Bleichen, durch Aufnahme von Fluoreszenz- und Thermolumineszenzspektren wurden Bandenzuordnungen getroffen und Aussagen über den Ablauf der strahlenchemischen Reaktionen des Thalliums gemacht.